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Toggle navigation Topics by WorldWideScience.org Home About News Advanced Search Contact Us Site Map Help Sample records for advanced nmr approaches « 1 2 3 4 5 » 1. Advanced solid-state NMR spectroscopy of natural organic matter Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially the systematic approach to NOM characterization, and their ... 2. Advanced solid-state NMR spectroscopy of natural organic matter. Mao, Jingdong; Cao, Xiaoyan; Olk, Dan C; Chu, Wenying; Schmidt-Rohr, Klaus 2017-05-01 Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state (13)C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on (13)C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used (15)N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided. Copyright © 2016 Elsevier B.V. All rights reserved. 3. A Guided Inquiry Approach to NMR Spectroscopy Parmentier, Laura E.; Lisensky, George C.; Spencer, Brock 1998-04-01 We present a novel way to introduce NMR spectroscopy into the general chemistry curriculum as part of a week-long aspirin project in our one-semester introductory course. Aspirin is synthesized by reacting salicylic acid and acetic anhydride. Purity is determined by titration and IR and NMR spectroscopy. Students compare IR and NMR spectra of their aspirin product to a series of reference spectra obtained by the class. Students are able to interpret the IR spectra of their aspirin using IR data from previous experiments. NMR is introduced by having students collect 1H NMR spectra of a series of reference compounds chosen to include some of the structural features of aspirin and compare spectra and structures of the reference compounds to develop a correlation chart for chemical shifts. This process is done in small groups using shared class data and is guided by a series of questions designed to relate the different kinds of hydrogen atoms to number and position of peaks in the NMR spectrum. Students then identify the peaks in the NMR spectrum of their aspirin product and relate percent purity by titration with spectral results and percent yield. This is an enjoyable project that combines the synthesis of a familiar material with a guided inquiry-based introduction to NMR spectroscopy. 4. LC-NMR coupling technology: recent advancements and applications in natural products analysis Exarchou, V.; Krucker, M.; Beek, van T.A.; Vervoort, J.J.M.; Gerothanassis, I.P.; Albert, K. 2005-01-01 An overview of recent advances in nuclear magnetic resonance (NMR) coupled with separation technologies and their application in natural product analysis is given and discussed. The different modes of LC-NMR operation are described, as well as how technical improvements assist in establishing LC-NMR 5. Advanced intelligence and mechanism approach ZHONG Yixin 2007-01-01 Advanced intelligence will feature the intelligence research in next 50 years.An understanding of the concept of advanced intelligence as well as its importance will be provided first,and detailed analysis on an approach,the mechanism approach.suitable to the advanced intelligence research will then be flolowed.And the mutual relationship among mechanism approach,traditional approaches existed in artificial intelligence research,and the cognitive informatics will be discussed.It is interesting to discover that mechanism approach is a good one to the Advanced Intelligence research and a tmified form of the existed approaches to artificial intelligence. 6. Recent advances in computational predictions of NMR parameters for the structure elucidation of carbohydrates: methods and limitations. Toukach, Filip V; Ananikov, Valentine P 2013-11-07 All living systems are comprised of four fundamental classes of macromolecules--nucleic acids, proteins, lipids, and carbohydrates (glycans). Glycans play a unique role of joining three principal hierarchical levels of the living world: (1) the molecular level (pathogenic agents and vaccine recognition by the immune system, metabolic pathways involving saccharides that provide cells with energy, and energy accumulation via photosynthesis); (2) the nanoscale level (cell membrane mechanics, structural support of biomolecules, and the glycosylation of macromolecules); (3) the microscale and macroscale levels (polymeric materials, such as cellulose, starch, glycogen, and biomass). NMR spectroscopy is the most powerful research approach for getting insight into the solution structure and function of carbohydrates at all hierarchical levels, from monosaccharides to oligo- and polysaccharides. Recent progress in computational procedures has opened up novel opportunities to reveal the structural information available in the NMR spectra of saccharides and to advance our understanding of the corresponding biochemical processes. The ability to predict the molecular geometry and NMR parameters is crucial for the elucidation of carbohydrate structures. In the present paper, we review the major NMR spectrum simulation techniques with regard to chemical shifts, coupling constants, relaxation rates and nuclear Overhauser effect prediction applied to the three levels of glycomics. Outstanding development in the related fields of genomics and proteomics has clearly shown that it is the advancement of research tools (automated spectrum analysis, structure elucidation, synthesis, sequencing and amplification) that drives the large challenges in modern science. Combining NMR spectroscopy and the computational analysis of structural information encoded in the NMR spectra reveals a way to the automated elucidation of the structure of carbohydrates. 7. A new laboratory approach to shale analysis using NMR relaxometry Washburn, Kathryn E.; Birdwell, Justin E.; Baez, Luis; Beeney, Ken; Sonnenberg, Steve 2013-01-01 Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T1 and T2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T1-T2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T1 and T2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T1-T2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T1 and T2 measurements were used to improve assessment of the solid organic phases, specifically 8. Recent Advances in Solution NMR: Fast Methods and Heteronuclear Direct Detection Felli, I.C. [CERM and Depatment of Chemistry, University of Florence, 50019 (Italy); Brutscher, B. [DSV-IBS, 38027 Grenoble (France) 2009-07-01 Today, NMR spectroscopy is the technique of choice to investigate molecular structure, dynamics, and interactions in solution at atomic resolution. A major limitation of NMR spectroscopy for the study of biological macromolecules such as proteins, nucleic acids, and their complexes, has always been its low sensitivity, a consequence of the weak magnetic spin interactions. Therefore many efforts have been invested in the last decade to improve NMR instrumentation in terms of experimental sensitivity. As a result of these efforts, the availability of high-field magnets, cryogenically cooled probes, and probably in the near future hyper-polarization techniques, the intrinsic NMR sensitivity has increased by at least one order of magnitude. Stimulated by new challenges in the life sciences, these technical improvements have triggered the development of new NMR methods for the study of molecular systems of increasing size and complexity. Herein, we focus on two examples of recently developed NMR methodologies. First, advanced multidimensional data acquisition schemes provide a speed increase of several orders of magnitude. Second, NMR methods based on the direct detection of low-gamma nuclei present a new spectroscopic tool, highly complementary to conventional NMR techniques. These new methods provide powerful new NMR tools for the study of short-lived molecules, large and intrinsically unstructured proteins, paramagnetic systems, as well as for the characterization of molecular kinetic processes at atomic resolution. These examples illustrate how NMR is continuously adapting to the new challenges in the life sciences, with the focus shifting from the characterization of single biomolecules to an integrated view of interacting molecular networks observed at varying levels of biological organization. (authors) 9. Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds Márcio S. Silva 2017-02-01 Full Text Available Nuclear magnetic resonance (NMR is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to 1H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds. 10. Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR Methodology Run-Cang Sun 2013-01-01 Full Text Available The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA, nitrobenzene oxidation (NBO, and derivatization followed by reductive cleavage (DFRC. Recent advances in nuclear magnetic resonance (NMR technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ, as well as their applications are reviewed. 11. Structural characterization of functionalized gold nanoparticles for drug delivery in cancer therapy: a NMR based approach. Coelho, SÃlvia C; Rangel, Maria; Pereira, Maria C; Coelho, Manuel A N; Ivanova, Galya 2015-07-15 In the present paper, we report results from a study of the structure and physicochemical properties of gold nanoparticles modified with poly(ethylene glycol) (PEG) designed for the drug delivery of the proteasome inhibitor Bortezomib (BTZ) in cancer therapy. A number of advanced analytical techniques were used to define important physicochemical characteristics such as composition, structure, surface properties, particle size and morphology. A new approach based on detailed NMR studies was employed to define specific intermolecular interactions and mechanisms of drug immobilization and location into surface modified gold nanoparticles (AuNPs). Particularly important information was gained from analysis of NMR spectroscopic parameters such as the spectral line shape, translation diffusion, the nuclear Overhauser effect (NOE) and spin-lattice relaxation (T1). The results confirmed the coexistence of two different types of BTZ inclusion into polyethylene glycol coated gold nanoparticles: (i) association with the polymer chains by weak H-bonds and/or dipole-charge interactions and (ii) adsorption on the surface of the gold nanoparticles. The results allowed for determination of the overall structure of Bortezomib loaded PEG coated AuNPs, which is related to the therapeutic drug efficacy and activity in the treatment of cancer. 12. Reorientation phenomena in imidazolium methyl sulfonate as probed by advanced solid-state NMR. Goward, Gillian R; Saalwächter, Kay; Fischbach, Ingrid; Spiess, Hans Wolfgang 2003-01-01 Evidence for reorientation of imidazolium rings in imidazolium methylsulfonate is demonstrated using solid-state NMR. This material is a model system for exciting new protonconducting materials based on imidazole. Two advanced NMR methods, including 1H-13C and 1H-15N recoupled polarization transfer with dipolar sideband pattern analysis and analysis of the coalescence of 13C lineshapes are used to characterize the ring reorientation. The process is found to occur at temperatures well below the melting point of the salt, between 240 and 380 K, and is described by a single activation energy, of 38+/-5 kJ/mol. This material is considered as a model system for quantifying the ring reorientation process, which is often proposed to be the rate-limiting step in proton transport in imidazole-based proton conducting materials. 13. A tracked approach for automated NMR assignments in proteins (TATAPRO) Atreya, H.S.; Sahu, S.C.; Chary, K.V.R.; Govil, Girjesh [Tata Institute of Fundamental Research, Department of Chemical Sciences (India) 2000-06-15 A novel automated approach for the sequence specific NMR assignments of {sup 1}H{sup N}, {sup 13}C{sup {alpha}}, {sup 13}C{sup {beta}}, {sup 13}C'/{sup 1}H{sup {alpha}} and {sup 15}N spins in proteins, using triple resonance experimental data, is presented. The algorithm, TATAPRO (Tracked AuTomated Assignments in Proteins) utilizes the protein primary sequence and peak lists from a set of triple resonance spectra which correlate {sup 1}H{sup N} and {sup 15}N chemical shifts with those of {sup 13}C{sup {alpha}}, {sup 13}C{sup {beta}} and {sup 13}C'/{sup 1}H{sup {alpha}}. The information derived from such correlations is used to create a 'master{sub l}ist' consisting of all possible sets of {sup 1}H{sup N}{sub i}, {sup 15}N{sub i}, {sup 13}C{sup {alpha}}{sub i}, {sup 13}C{sup {beta}}{sub i}, {sup 13}C'{sub i}/{sup 1}H{sup {alpha}}{sub i}, {sup 13}C{sup {alpha}}{sub i-1}, {sup 13}C{sup {beta}}{sub i-1} and {sup 13}C'{sub i-1}/ {sup 1}H{sup {alpha}}{sub i-1} chemical shifts. On the basis of an extensive statistical analysis of {sup 13}C{sup {alpha}} and {sup 13}C{sup {beta}} chemical shift data of proteins derived from the BioMagResBank (BMRB), it is shown that the 20 amino acid residues can be grouped into eight distinct categories, each of which is assigned a unique two-digit code. Such a code is used to tag individual sets of chemical shifts in the master{sub l}ist and also to translate the protein primary sequence into an array called pps{sub a}rray. The program then uses the master{sub l}ist to search for neighbouring partners of a given amino acid residue along the polypeptide chain and sequentially assigns a maximum possible stretch of residues on either side. While doing so, each assigned residue is tracked in an array called assig{sub a}rray, with the two-digit code assigned earlier. The assig{sub a}rray is then mapped onto the pps{sub a}rray for sequence specific resonance assignment. The program has been tested using 14. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material? Knicker, Heike; Lange, Sascha; van Rossum, Barth; Oschkinat, Hartmut 2016-04-01 Compared to solution NMR spectroscopy, solid-state NMR spectra suffer from broad resonance lines and low resolution. This could be overcome by the use of 2-dimenstional solidstate NMR pulse sequences. Until recently, this approach has been unfeasible as a routine tool in soil chemistry, mainly because of the low NMR sensitivity of the respective samples. A possibility to circumvent those sensitivity problems represents high-field Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy (Barnes et al., 2008), allowing considerable signal enhancements (Akbey et al., 2010). This is achieved by a microwave-driven transfer of polarization from a paramagnetic center to nuclear spins. Application of DNP to MAS spectra of biological systems (frozen solutions) showed enhancements of the factor 40 to 50 (Hall et al., 1997). Enhancements of this magnitude, thus may enable the use of at least some of the 2D solid-state NMR techniques that are presently already applied for pure proteins but are difficult to apply to soil peptides in their complex matrix. After adjusting the required acquisition parameters to the system "soil organic matter", lower but still promising enhancement factors were achieved. Additional optimization was performed and allowed the acquisition of 2D 13C and 15N solid-state NMR spectra of humified 13C and 15N enriched plant residues. Within the present contribution, the first solid-state DNP NMR spectra of humic material are presented. Those data demonstrate the great potential of this approach which certainly opens new doors for a better understanding of biochemical processes in soils, sediments and water. Akbey, Ãœ., Franks, W.T., Linden, A., Lange, S., Griffin, R.G., van Rossum, B.-J., Oschkinat, H., 2010. Dynamic nuclear polarization of deuterated proteins. Angewandte Chemie International Edition 49, 7803-7806. Barnes, A.B., De Paëpe, G., van der Wel, P.C.A., Hu, K.N., Joo, C.G., Bajaj, V.S., MakJurkauskas, M.L., Sirigiri, J.R., Herzfeld, J 15. NMR-based approach to the analysis of radiopharmaceuticals: radiochemical purity, specific activity, and radioactive concentration values by proton and tritium NMR spectroscopy. Schenk, David J; Dormer, Peter G; Hesk, David; Pollack, Scott R; Lavey, Carolee Flader 2015-06-15 Compounds containing tritium are widely used across the drug discovery and development landscape. These materials are widely utilized because they can be efficiently synthesized and produced at high specific activity. Results from internally calibrated (3)H and (1)H nuclear magnetic resonance (NMR) spectroscopy suggests that at least in some cases, this calibrated approach could supplement or potentially replace radio-high-performance liquid chromatography for radiochemical purity, dilution and scintillation counting for the measurement of radioactivity per volume, and liquid chromatography/mass spectrometry analysis for the determination of specific activity. In summary, the NMR-derived values agreed with those from the standard approaches to within 1% to 9% for solution count and specific activity. Additionally, the NMR-derived values for radiochemical purity deviated by less than 5%. A benefit of this method is that these values may be calculated at the same time that (3)H NMR analysis provides the location and distribution of tritium atoms within the molecule. Presented and discussed here is the application of this method, advantages and disadvantages of the approach, and a rationale for utilizing internally calibrated (1)H and (3)H NMR spectroscopy for specific activity, radioactive concentration, and radiochemical purity whenever acquiring (3)H NMR for tritium location. Copyright © 2015 John Wiley & Sons, Ltd. 16. Assigning the NMR Spectrum of Glycidol: An Advanced Organic Chemistry Exercise Helms, Eric; Arpaia, Nicholas; Widener, Melissa 2007-01-01 Various one- and two-dimensional NMR experiments have been found to be extremely useful for assigning the proton and carbon NMR spectra of glycidol. The technique provides extremely valuable information aiding in the complete assignment of the peaks. 17. Novel approaches for bond order assignment and NMR shift prediction Dehof, Anna Katharina 2011-01-01 Molecular modelling is one of the cornerstones of modern biological and pharmaceutical research. Accurate modelling approaches easily become computationally overwhelming and thus, different levels of approximations are typically employed. In this work, we develop such approximation approaches for problems arising in structural bioinformatics. A fundamental approximation of molecular physics is the classification of chemical bonds, usually in the form of integer bond orders. Many input data se... 18. Diffusion of light gases in advanced nanoporous membranes and catalysts via NMR diffusometry Mueller, Robert A. Diffusion in nanoporous gas separation membranes and catalysts plays an important role in their selectivity and performance. As a result, there is an intense effort towards development of novel membranes and catalysts with microstructures tailored for improved transport properties. Fundamental understanding and prediction of the mass transport properties of these materials can be obtained by studies of mass transport on a broad range of microscopic length scales. In this dissertation, a novel NMR diffusometry technique is employed to study the influence of the pore network properties on light gas diffusion for several nanoporous systems, which represent promising advanced gas separation membranes and catalysts. The following systems were investigated: (i) carbon molecular sieve membranes, (ii) mixed-matrix membranes and (iii) rare-earth aerogel catalysts. For carbon molecular sieve membranes, the self-diffusion properties of several light gases of industrial importance are characterized by investigating the dependences of the self diffusivity on displacement length scale, temperature, sorbate loading and composition. Analysis of these dependences and comparison of the measured microscopic transport data with the corresponding results of membrane permeation enabled the determination of membrane structural properties which lead to the remarkable diffusion selectivity of these membranes. For mixed-matrix membranes, detailed measurements of light gas sorbate diffusion over a broad range of microscopic length scales enables resolution of the different modes of sorbate self-diffusion inside mixed-matrix membranes. Finally for samaria-aerogel catalyst, the influence of catalyst packing is explored based on detailed microscopic diffusion measurements over a broad range of sorbate loading pressures and detailed data analysis. These studies were enabled by application of a novel pulsed-field gradient nuclear magnetic resonance technique, developed in part by this work 19. I. Advances in NMR Signal Processing. II. Spin Dynamics in Quantum Dissipative Systems Lin, Yung-Ya [Univ. of California, Berkeley, CA (United States) 1998-11-01 Part I. Advances in IVMR Signal Processing. Improvements of sensitivity and resolution are two major objects in the development of NMR/MRI. A signal enhancement method is first presented which recovers signal from noise by a judicious combination of a priordmowledge to define the desired feasible solutions and a set theoretic estimation for restoring signal properties that have been lost due to noise contamination. The effect of noise can be significantly mitigated through the process of iteratively modifying the noisy data set to the smallest degree necessary so that it possesses a collection of prescribed properties and also lies closest to the original data set. A novel detection-estimation scheme is then introduced to analyze noisy and/or strongly damped or truncated FIDs. Based on exponential modeling, the number of signals is detected based on information estimated using the matrix pencil method. theory and the spectral parameters are Part II. Spin Dynamics in body dipole-coupled systems Quantum Dissipative Systems. Spin dynamics in manyconstitutes one of the most fundamental problems in magnetic resonance and condensed-matter physics. Its many-spin nature precludes any rigorous treatment. ‘Therefore, the spin-boson model is adopted to describe in the rotating frame the influence of the dipolar local fields on a tagged spin. Based on the polaronic transform and a perturbation treatment, an analytical solution is derived, suggesting the existence of self-trapped states in the. strong coupling limit, i.e., when transverse local field >> longitudinal local field. Such nonlinear phenomena originate from the joint action of the lattice fluctuations and the reaction field. Under semiclassical approximation, it is found that the main effect of the reaction field is the renormalization of the Hamiltonian of interest. Its direct consequence is the two-step relaxation process: the spin is initially localized in a quasiequilibrium state, which is later detrapped by 20. The PAW/GIPAW approach for computing NMR parameters: a new dimension added to NMR study of solids. Charpentier, Thibault 2011-07-01 In 2001, Mauri and Pickard introduced the gauge including projected augmented wave (GIPAW) method that enabled for the first time the calculation of all-electron NMR parameters in solids, i.e. accounting for periodic boundary conditions. The GIPAW method roots in the plane wave pseudopotential formalism of the density functional theory (DFT), and avoids the use of the cluster approximation. This method has undoubtedly revitalized the interest in quantum chemical calculations in the solid-state NMR community. It has quickly evolved and improved so that the calculation of the key components of NMR interactions, namely the shielding and electric field gradient tensors, has now become a routine for most of the common nuclei studied in NMR. Availability of reliable implementations in several software packages (CASTEP, Quantum Espresso, PARATEC) make its usage more and more increasingly popular, maybe indispensable in near future for all material NMR studies. The majority of nuclei of the periodic table have already been investigated by GIPAW, and because of its high accuracy it is quickly becoming an essential tool for interpreting and understanding experimental NMR spectra, providing reliable assignments of the observed resonances to crystallographic sites or enabling a priori prediction of NMR data. The continuous increase of computing power makes ever larger (and thus more realistic) systems amenable to first-principles analysis. In the near future perspectives, as the incorporation of dynamical effects and/or disorder are still at their early developments, these areas will certainly be the prime target.

« 1 2 3 4 5 » « 1 2 3 4 5 » 21. Comprehensive multiphase NMR spectroscopy: Basic experimental approaches to differentiate phases in heterogeneous samples Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G.; Simpson, Myrna J.; Maas, Werner E.; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J.; Hume, Alan; Simpson, André J. 2012-04-01 Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate 1H and 13C spectra for the different phases. In addition, 19F performance is also addressed. To illustrate the capability of 19F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state. 22. A high-resolution solid-state NMR approach for the structural studies of bicelles. Dvinskikh, Sergey; Dürr, Ulrich; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy 2006-05-17 Bicelles are increasingly being used as membrane mimicking systems in NMR experiments to investigate the structure of membrane proteins. In this study, we demonstrate the effectiveness of a 2D solid-state NMR approach that can be used to measure the structural constraints, such as heteronuclear dipolar couplings between 1H, 13C, and 31P nuclei, in bicelles without the need for isotopic enrichment. This method does not require a high radio frequency power unlike the presently used rotating-frame separated-local-field (SLF) techniques, such as PISEMA. In addition, multiple dipolar couplings can be measured accurately, and the presence of a strong dipolar coupling does not suppress the weak couplings. High-resolution spectra obtained from magnetically aligned DMPC:DHPC bicelles even in the presence of peptides suggest that this approach will be useful in understanding lipid-protein interactions that play a vital role in shaping up the function of membrane proteins. 23. A High Resolution Solid State NMR Approach for the Structural Studies of Bicelles Dvinskikh, Sergey; Dürr, Ulrich; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy 2008-01-01 Bicelles are increasingly being used as membrane mimicking systems in NMR experiments to investigate the structure of membrane proteins. In this study, we demonstrate the effectiveness of a 2D solid-state NMR approach that can be used to measure the structural constraints such as heteronuclear dipolar couplings between 1H, 13C and 31P nuclei in bicelles without the need for isotopic enrichment. This method does not require a high radio frequency power unlike the presently used rotating-frame separated-local-field (SLF) techniques like PISEMA. In addition, multiple dipolar couplings can be measured accurately and the presence of a strong dipolar coupling does not suppress the weak couplings. High resolution spectra obtained from magnetically aligned DMPC:DHPC bicelles even in the presence of peptides suggest that this approach will be useful in understanding lipidprotein interactions that play a vital role in shaping up the function of membrane proteins. PMID:16683791 24. Advanced computational approaches to biomedical engineering Saha, Punam K; Basu, Subhadip 2014-01-01 There has been rapid growth in biomedical engineering in recent decades, given advancements in medical imaging and physiological modelling and sensing systems, coupled with immense growth in computational and network technology, analytic approaches, visualization and virtual-reality, man-machine interaction and automation. Biomedical engineering involves applying engineering principles to the medical and biological sciences and it comprises several topics including biomedicine, medical imaging, physiological modelling and sensing, instrumentation, real-time systems, automation and control, sig 25. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory Gonzalez, Elizabeth; Dolino, Drew; Schwartzenburg, Danielle; Steiger, Michelle A. 2015-01-01 A laboratory experiment was developed to introduce students in either an organic chemistry or biochemistry lab course to two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy using simple biomolecules. The goal of this experiment is for students to understand and interpret the information provided by a 2D NMR spectrum. Students are… 26. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory Gonzalez, Elizabeth; Dolino, Drew; Schwartzenburg, Danielle; Steiger, Michelle A. 2015-01-01 A laboratory experiment was developed to introduce students in either an organic chemistry or biochemistry lab course to two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy using simple biomolecules. The goal of this experiment is for students to understand and interpret the information provided by a 2D NMR spectrum. Students are… 27. Compositional analysis of multi-element magnetic nanoparticles with a combined NMR and TEM approach Gellesch, Markus; Hammerath, Franziska; Süß, Vicky; Haft, Marcel; Hampel, Silke; Wurmehl, Sabine; Büchner, Bernd 2017-09-01 The increasing interest in nanoscale materials goes hand in hand with the challenge to reliably characterize the chemical compositions and structural features of nanosized objects in order to relate those to their physical properties. Despite efforts, the analysis of the chemical composition of individual multi-element nanoparticles remains challenging—from the technical point of view as well as from the point of view of measurement statistics. Here, we demonstrate that zero-field solid-state nuclear magnetic resonance (NMR) complements local, single particle transmission electron microscopy (TEM) studies with information on a large assembly of chemically complex nanoparticles. The combination of both experimental techniques gives information on the local composition and structure and provides an excellent measurement statistic through the corresponding NMR ensemble measurement. This analytical approach is applicable to many kinds of magnetic materials and therefore may prove very versatile in the future research of particulate magnetic nanomaterials. 28. Fine refinement of solid state structure of racemic form of phospho-tyrosine employing NMR Crystallography approach. Paluch, Piotr; Pawlak, Tomasz; Oszajca, Marcin; Lasocha, Wieslaw; Potrzebowski, Marek J 2015-02-01 We present step by step facets important in NMR Crystallography strategy employing O-phospho-dl-tyrosine as model sample. The significance of three major techniques being components of this approach: solid state NMR (SS NMR), X-ray diffraction of powdered sample (PXRD) and theoretical calculations (Gauge Invariant Projector Augmented Wave; GIPAW) is discussed. Each experimental technique provides different set of structural constraints. From the PXRD measurement the size of the unit cell, space group and roughly refined molecular structure are established. SS NMR provides information about content of crystallographic asymmetric unit, local geometry, molecular motion in the crystal lattice and hydrogen bonding pattern. GIPAW calculations are employed for validation of quality of elucidation and fine refinement of structure. Crystal and molecular structure of Ophospho-dl-tyrosine solved by NMR Crystallography is deposited at Cambridge Crystallographic Data Center under number CCDC 1005924. 29. Metabolic response to exogenous ethanol in yeast: An in vivo statistical total correlation NMR spectroscopy approach Maso Ricci; Marianna Aggravi; Claudia Bonechi; Silvia Martini; Anna Maria; Claudio Rossi 2012-09-01 In vivo NMR spectroscopy, together with selectively 13C-labelled substrates and ‘statistical total correlation spectroscopy’ analysis (STOCSY), are valuable tools to collect and interpret the metabolic responses of a living organism to external stimuli. In this study, we applied this approach to evaluate the effects of increasing concentration of exogenous ethanol on the Saccharomyces cerevisiae fermentative metabolism. We show that the STOCSY analysis correctly identifies the different types of correlations among the enriched metabolites involved in the fermentation, and that these correlations are quite stable even in presence of a stressing factor such as the exogenous ethanol. 30. Metabolic response to exogenous ethanol in yeast: an in vivo statistical total correlation NMR spectroscopy approach. Ricci, Maso; Aggravi, Marianna; Bonechi, Claudia; Martini, Silvia; Aloisi, Anna Maria; Rossi, Claudio 2012-09-01 In vivo NMR spectroscopy, together with selectively 13C-labelled substrates and 'statistical total correlation spectroscopy' analysis (STOCSY), are valuable tools to collect and interpret the metabolic responses of a living organism to external stimuli. In this study, we applied this approach to evaluate the effects of increasing concentration of exogenous ethanol on the Saccharomyces cerevisiae fermentative metabolism. We show that the STOCSY analysis correctly identifies the different types of correlations among the enriched metabolites involved in the fermentation, and that these correlations are quite stable even in presence of a stressing factor such as the exogenous ethanol. 31. Quantitative NMR Approach to Optimize the Formation of Chemical Building Blocks from Abundant Carbohydrates Elliot, Samuel Gilbert; Tolborg, Søren; Sádaba, Irantzu 2017-01-01 The future role of biomass-derived chemicals relies on the formation of diverse functional monomers in high yields from carbohydrates. Recently, it has become clear that a series of Î ±-hydroxy acids, esters and lactones can be formed from carbohydrates in alcohols and water using tin......-containing catalysts such as Sn-Beta. These compounds are potential building blocks for polyesters with additional olefin and alcohol functionalities. We employ an NMR approach to identify, quantify and optimize the formation these building blocks in the chemocatalytic transformation of abundant carbohydrates by Sn... 32. Solid-state NMR and Membrane Proteins Opella, Stanley J. 2015-01-01 The native environment for a membrane protein is a phospholipid bilayer. Because the protein is immobilized on NMR timescales by the interactions within a bilayer membrane, solid-state NMR methods are essential to obtain high-resolution spectra. Approaches have been developed for both unoriented and oriented samples, however, they all rest on the foundation of the most fundamental aspects solid-state NMR, and the chemical shift and homo- and hetero-nuclear dipole-dipole interactions. Solid-state NMR has advanced sufficiently to enable the structures of membrane proteins to be determined under near-native conditions in phospholipid bilayers. PMID:25681966 33. Recent advances and new strategies in the NMR-based identification of natural products. Halabalaki, Maria; Vougogiannopoulou, Konstantina; Mikros, Emmanuel; Skaltsounis, Alexios Leandros 2014-02-01 Nature comprises an untapped pool of unique compounds with high structural uniqueness and exceptional properties. At the core of natural products (NPs) discovery is the identification procedure and NMR remains the most efficient method. Technical improvements such as miniaturized and crycogenic NMR probes along with hyphenation capabilities and computational support are at the center of evolution. Concepts such as dereplication and metabolomics are increasingly adopted in NPs using the power of databases, currently fragmented. The introduction and utilization of these technical and computational implements could lead NPs research to more comprehensive structure identification and new holistic perspectives. 34. Metabolic response to exogenous ethanol in yeast: an in vivo NMR and mathematical modelling approach. Martini, Silvia; Ricci, Maso; Bartolini, Fiora; Bonechi, Claudia; Braconi, Daniela; Millucci, Lia; Santucci, Annalisa; Rossi, Claudio 2006-03-20 The understanding of the metabolic behaviour of complex systems such as eukaryotic cells needs the development of new approaches that are able to deal with the complexity due to a large number of interactions within the system. In this paper, we applied an approach based on the combined use of in vivo NMR experiments and mathematical modelling in order to analyze the metabolic response to ethanol stress in a wild-strain of Saccharomyces cerevisiae. Considering the cellular metabolic processes resulting from activation, inhibition, and feed-back activities, we developed a model able to describe the modulation of the whole system induced by an external stress due to increasing concentrations of exogenous ethanol. This approach was able to interpret the experimental results in terms of metabolic response to exogenous ethanol in the yeast. The robustness and flexibility of the model enables it to work correctly at different initial exogenous ethanol concentrations. 35. Advanced Approach of Multiagent Based Buoy Communication Gediminas Gricius 2015-01-01 Full Text Available Usually, a hydrometeorological information system is faced with great data flows, but the data levels are often excessive, depending on the observed region of the water. The paper presents advanced buoy communication technologies based on multiagent interaction and data exchange between several monitoring system nodes. The proposed management of buoy communication is based on a clustering algorithm, which enables the performance of the hydrometeorological information system to be enhanced. The experiment is based on the design and analysis of the inexpensive but reliable Baltic Sea autonomous monitoring network (buoys, which would be able to continuously monitor and collect temperature, waviness, and other required data. The proposed approach of multiagent based buoy communication enables all the data from the costal-based station to be monitored with limited transition speed by setting different tasks for the agent-based buoy system according to the clustering information. 36. Advanced Approach of Multiagent Based Buoy Communication Gricius, Gediminas; Drungilas, Darius; Andziulis, Arunas; Dzemydiene, Dale; Voznak, Miroslav; Kurmis, Mindaugas; Jakovlev, Sergej 2015-01-01 Usually, a hydrometeorological information system is faced with great data flows, but the data levels are often excessive, depending on the observed region of the water. The paper presents advanced buoy communication technologies based on multiagent interaction and data exchange between several monitoring system nodes. The proposed management of buoy communication is based on a clustering algorithm, which enables the performance of the hydrometeorological information system to be enhanced. The experiment is based on the design and analysis of the inexpensive but reliable Baltic Sea autonomous monitoring network (buoys), which would be able to continuously monitor and collect temperature, waviness, and other required data. The proposed approach of multiagent based buoy communication enables all the data from the costal-based station to be monitored with limited transition speed by setting different tasks for the agent-based buoy system according to the clustering information. PMID:26345197 37. Statistical Physics An Advanced Approach with Applications Honerkamp, Josef 2012-01-01 The application of statistical methods to physics is essential. This unique book on statistical physics offers an advanced approach with numerous applications to the modern problems students are confronted with. Therefore the text contains more concepts and methods in statistics than the student would need for statistical mechanics alone. Methods from mathematical statistics and stochastics for the analysis of data are discussed as well. The book is divided into two parts, focusing first on the modeling of statistical systems and then on the analysis of these systems. Problems with hints for solution help the students to deepen their knowledge. The third edition has been updated and enlarged with new sections deepening the knowledge about data analysis. Moreover, a customized set of problems with solutions is accessible on the Web at extras.springer.com. 38. An advanced phantom study assessing the feasibility of neuronal current imaging by ultra-low-field NMR Körber, Rainer; Nieminen, Jaakko O.; Höfner, Nora; JazbinÅ¡ek, Vojko; Scheer, Hans-Jürgen; Kim, Kiwoong; Burghoff, Martin 2013-12-01 In ultra-low-field (ULF) NMR/MRI, a common scheme is to magnetize the sample by a polarizing field of up to hundreds of mT, after which the NMR signal, precessing in a field on the order of several μT, is detected with superconducting quantum interference devices (SQUIDs). In our ULF-NMR system, we polarize with up to 50 mT and deploy a singlestage DC-SQUID current sensor with an integrated input coil which is connected to a wire-wound Nb gradiometer. We developed this system (white noise 0.50 fT/√{Hz}) for assessing the feasibility of imaging neuronal currents by detecting their effect on the ULF-NMR signal. Magnetoencephalography investigations of evoked brain activity showed neuronal dipole moments below 50 nAm. With our instrumentation, we have studied two different approaches for neuronal current imaging. In the so-called DC effect, long-lived neuronal activity shifts the Larmor frequency of the surrounding protons. An alternative strategy is to exploit fast neuronal activity as a tipping pulse. This so-called AC effect requires the proton Larmor frequency to match the frequency of the neuronal activity, which ranges from near-DC to ∼kHz. We emulated neuronal activity by means of a single dipolar source in a physical phantom, consisting of a hollow sphere filled with an aqueous solution of CuSO4 and NaCl. In these phantom studies, with physiologically relevant dipole depths, we determined resolution limits for our set-up for the AC and the DC effect of ∼10 μAm and ∼50 nAm, respectively. Hence, the DC effect appears to be detectable in vivo by current ULF-NMR technology. 39. Sensitivity of the NMR density matrix to pulse sequence parameters: a simplified analytic approach. Momot, Konstantin I; Takegoshi, K 2012-08-01 We present a formalism for the analysis of sensitivity of nuclear magnetic resonance pulse sequences to variations of pulse sequence parameters, such as radiofrequency pulses, gradient pulses or evolution delays. The formalism enables the calculation of compact, analytic expressions for the derivatives of the density matrix and the observed signal with respect to the parameters varied. The analysis is based on two constructs computed in the course of modified density-matrix simulations: the error interrogation operators and error commutators. The approach presented is consequently named the Error Commutator Formalism (ECF). It is used to evaluate the sensitivity of the density matrix to parameter variation based on the simulations carried out for the ideal parameters, obviating the need for finite-difference calculations of signal errors. The ECF analysis therefore carries a computational cost comparable to a single density-matrix or product-operator simulation. Its application is illustrated using a number of examples from basic NMR spectroscopy. We show that the strength of the ECF is its ability to provide analytic insights into the propagation of errors through pulse sequences and the behaviour of signal errors under phase cycling. Furthermore, the approach is algorithmic and easily amenable to implementation in the form of a programming code. It is envisaged that it could be incorporated into standard NMR product-operator simulation packages. 40. Uncertainty quantification approaches for advanced reactor analyses. Briggs, L. L.; Nuclear Engineering Division 2009-03-24 The original approach to nuclear reactor design or safety analyses was to make very conservative modeling assumptions so as to ensure meeting the required safety margins. Traditional regulation, as established by the U. S. Nuclear Regulatory Commission required conservatisms which have subsequently been shown to be excessive. The commission has therefore moved away from excessively conservative evaluations and has determined best-estimate calculations to be an acceptable alternative to conservative models, provided the best-estimate results are accompanied by an uncertainty evaluation which can demonstrate that, when a set of analysis cases which statistically account for uncertainties of all types are generated, there is a 95% probability that at least 95% of the cases meet the safety margins. To date, nearly all published work addressing uncertainty evaluations of nuclear power plant calculations has focused on light water reactors and on large-break loss-of-coolant accident (LBLOCA) analyses. However, there is nothing in the uncertainty evaluation methodologies that is limited to a specific type of reactor or to specific types of plant scenarios. These same methodologies can be equally well applied to analyses for hightemperature gas-cooled reactors and to liquid metal reactors, and they can be applied to steady-state calculations, operational transients, or severe accident scenarios. This report reviews and compares both statistical and deterministic uncertainty evaluation approaches. Recommendations are given for selection of an uncertainty methodology and for considerations to be factored into the process of evaluating uncertainties for advanced reactor best-estimate analyses. « 1 2 3 4 5 » « 1 2 3 4 5 » 41. Advanced Safeguards Approaches for New Fast Reactors Durst, Philip C.; Therios, Ike; Bean, Robert; Dougan, A.; Boyer, Brian; Wallace, Rick L.; Ehinger, Michael H.; Kovacic, Don N.; Tolk, K. 2007-12-15 This third report in the series reviews possible safeguards approaches for new fast reactors in general, and the ABR in particular. Fast-neutron spectrum reactors have been used since the early 1960s on an experimental and developmental level, generally with fertile blanket fuels to “breed†nuclear fuel such as plutonium. Whether the reactor is designed to breed plutonium, or transmute and “burn†actinides depends mainly on the design of the reactor neutron reflector and the whether the blanket fuel is “fertile†or suitable for transmutation. However, the safeguards issues are very similar, since they pertain mainly to the receipt, shipment and storage of fresh and spent plutonium and actinide-bearing â €œTRUâ€-fuel. For these reasons, the design of existing fast reactors and details concerning how they have been safeguarded were studied in developing advanced safeguards approaches for the new fast reactors. In this regard, the design of the Experimental Breeder Reactor-II “EBR-II†at the Idaho National Laboratory (INL) was of interest, because it was designed as a collocated fast reactor with a pyrometallurgical reprocessing and fuel fabrication line – a design option being considered for the ABR. Similarly, the design of the Fast Flux Facility (FFTF) on the Hanford Site was studied, because it was a successful prototype fast reactor that ran for two decades to evaluate fuels and the design for commercial-scale fast reactors. 42. Advances on interdisciplinary approaches to urban carbon Romero-Lankao, P. 2015-12-01 North American urban areas are emerging as climate policy and technology innovators, urbanization process laboratories, fonts of carbon relevant experiments, hubs for grass-roots mobilization, and centers for civil-society experiments to curb carbon emissions and avoid widespread and irreversible climate impacts. Since SOCCR diverse lines of inquiry on urbanization, urban areas and the carbon cycle have advanced our understanding of some of the societal processes through which energy and land uses affect carbon. This presentation provides an overview of these diverse perspectives. It suggests the need for approaches that complement and combine the plethora of existing insights into interdisciplinary explorations of how different urbanization processes, and socio-ecological and technological components of urban areas affect the spatial and temporal patterns of carbon emissions, differentially over time and within and across cities. It also calls for a more holistic approach to examining the carbon implications of urbanization and urban areas as places, based not only on demographics or income, but also on such other interconnected features of urban development pathways as urban form, economic function, economic growth policies and climate policies. 43. An algebraic geometry approach to protein structure determination from NMR data. Wang, Lincong; Mettu, Ramgopal R; Donald, Bruce Randall

2005-01-01 determination. An implementation of our algorithm has been applied to 6 different real biological NMR data sets recorded for 3 proteins. Our algorithm is combinatorially precise, polynomial-time, and uses much less NMR data to produce results that are as good or better than previous approaches in terms of accuracy of the computed structure as well as running time. In practice approaches such as restrained molecular dynamics and simulated annealing, which lack both combinatorial precision and guarantees on running time and solution quality, are commonly used. Our results show that by using a different "slice" of the data, an algorithm that is polynomial time and that has guarantees about solution quality can be obtained. We believe that our techniques can be extended and generalized for other structure-determination problems such as computing side-chain conformations and the structure of nucleic acids from experimental data. 44. Advanced Structural Determination of Diterpene Esters Using Molecular Modeling and NMR Spectroscopy. Nothias-Scaglia, Louis-Félix; Gallard, Jean-François; Dumontet, Vincent; Roussi, Fanny; Costa, Jean; Iorga, Bogdan I; Paolini, Julien; Litaudon, Marc 2015-10-23 Three new jatrophane esters (1-3) were isolated from Euphorbia amygdaloides ssp. semiperfoliata, including an unprecedented macrocyclic jatrophane ester bearing a hemiketal substructure, named jatrohemiketal (3). The chemical structures of compounds 1-3 and their relative configurations were determined by spectroscopic analysis. The absolute configuration of compound 3 was determined unambiguously through an original strategy combining NMR spectroscopy and molecular modeling. Conformational search calculations were performed for the four possible diastereomers 3a-3d differing in their C-6 and C-9 stereocenters, and the lowest energy conformer was used as input structure for geometry optimization. The prediction of NMR parameters ((1)H and (13)C chemical shifts and (1)H-(1)H coupling constants) by density functional theory (DFT) calculations allowed identifying the most plausible diastereomer. Finally, the stereostructure of 3 was solved by comparison of the structural features obtained by molecular modeling for 3a-3d with NMR-derived data (the values of dihedral angles deduced from the vicinal proton-proton coupling constants ((3)JHH) and interproton distances determined by ROESY). The methodology described herein provides an efficient way to solve or confirm structural elucidation of new macrocyclic diterpene esters, in particular when no crystal structure is available. 45. A tabu search approach for the NMR protein structure-based assignment problem. CavuÅŸlar, Gizem; Çatay, Bülent; Apaydın, Mehmet Serkan 2012-01-01 Spectroscopy is an experimental technique which exploits the magnetic properties of specific nuclei and enables the study of proteins in solution. The key bottleneck of NMR studies is to map the NMR peaks to corresponding nuclei, also known as the assignment problem. Structure-Based Assignment (SBA) is an approach to solve this computationally challenging problem by using prior information about the protein obtained from a homologous structure. NVR-BIP used the Nuclear Vector Replacement (NVR) framework to model SBA as a binary integer programming problem. In this paper, we prove that this problem is NP-hard and propose a tabu search (TS) algorithm (NVR-TS) equipped with a guided perturbation mechanism to efficiently solve it. NVR-TS uses a quadratic penalty relaxation of NVR-BIP where the violations in the Nuclear Overhauser Effect constraints are penalized in the objective function. Experimental results indicate that our algorithm finds the optimal solution on NVRBIP’s data set which consists of seven proteins with 25 templates (31 to 126 residues). Furthermore, it achieves relatively high assignment accuracies on two additional large proteins, MBP and EIN (348 and 243 residues, respectively), which NVR-BIP failed to solve. The executable and the input files are available for download at http://people.sabanciuniv.edu/catay/NVR-TS/NVR-TS.html. 46. Crude to leads: a triple-pronged direct NMR approach in coordination with docking simulation. Tanoli, Sheraz A K; Tanoli, Nazish U; Bondancia, Tatiani M; Usmani, Saman; Kerssebaum, Rainer; Ferreira, Antonio G; Fernandes, Joao B; Ul-Haq, Zaheer 2013-09-01 The screening of compounds that bind to the target of interest (specific proteins) plays a vital role in drug discovery. Usually, the identification of biologically active compounds is done from a library of structurally known compounds. However, we successfully illustrate here, that NMR techniques including saturation transfer difference (STD), transfer nuclear Overhauser spectroscopy (TrNOESY) and STD-TOCSY (total correlation spectroscopy) in combination with separation methods not only enable the rapid and comprehensive screening of active components, but also their unequivocal structural characterization. Furthermore, a time saving for the recognition of leads is also possible with this application. To probe the binding studies, a hydroethanolic fraction of crude extract (1 mg) from natural product (Rauia resinous) was used for the initial assessment with BSA protein. The docking simulation was performed with BSA in the region of Thr190, Arg198, Arg217, Trp213, Arg256, Ala290 and Tyr451 to further refine the active compound towards the leads. Docking results mimic binding as identified by STD, Tr-NOESY and STD-TOCSY. Isovetexine-2-rhamnosoide (2) was found to be most active through group epitope mapping results as well as the docking simulation with relative free energy of -7.2770. This experiment provided excellent results through the direct NMR screening method. Using Bovine Serum Albumin as a reference, we illustrate that this approach offers an excellent way for the first hand detection of the active constituents/inhibitors from natural remedies used in folk medicinal treatments. 47. NMR analysis of male fathead minnow urinary metabolites: A potential approach for studying impacts of chemical exposures Ekman, D.R. [Ecosystems Research Division, U.S. EPA, 960 College Station Road, Athens, GA 30605 (United States)], E-mail: [email protected]; Teng, Q. [Ecosystems Research Division, U.S. EPA, 960 College Station Road, Athens, GA 30605 (United States); Jensen, K.M.; Martinovic, D.; Villeneuve, D.L.; Ankley, G.T. [Mid-Continent Ecology Division, U.S. EPA, 6201 Congdon Boulevard, Duluth, MN 55804 (United States); Collette, T.W. [Ecosystems Research Division, U.S. EPA, 960 College Station Road, Athens, GA 30605 (United States) 2007-11-30 The potential for profiling metabolites in urine from male fathead minnows (Pimephales promelas) to assess chemical exposures was explored using nuclear magnetic resonance (NMR) spectroscopy. Both one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy was used for the assignment of metabolites in urine from unexposed fish. Because fathead minnow urine is dilute, we lyophilized these samples prior to analysis. Furthermore, 1D {sup 1}H NMR spectra of unlyophilized urine from unexposed male fathead minnow and Sprague-Dawley rat were acquired to qualitatively compare rat and fish metabolite profiles and to provide an estimate of the total urinary metabolite pool concentration difference. As a small proof-of-concept study, lyophilized urine samples from male fathead minnows exposed to three different concentrations of the antiandrogen vinclozolin were analyzed by 1D {sup 1}H NMR to assess exposure-induced changes. Through a combination of principal components analysis (PCA) and measurements of {sup 1}H NMR peak intensities, several metabolites were identified as changing with statistical significance in response to exposure. Among those changes occurring in response to exposure to the highest concentration (450 {mu}g/L) of vinclozolin were large increases in taurine, lactate, acetate, and formate. These increases coincided with a marked decrease in hippurate, a combination potentially indicative of hepatotoxicity. The results of these investigations clearly demonstrate the potential utility of an NMR-based approach for assessing chemical exposures in male fathead minnow, using urine collected from individual fish. 48. Quantitative NMR Approach to Optimize the Formation of Chemical Building Blocks from Abundant Carbohydrates. Elliot, Samuel G; Tolborg, Søren; Sádaba, Irantzu; Taarning, Esben; Meier, Sebastian 2017-07-21 The future role of biomass-derived chemicals relies on the formation of diverse functional monomers in high yields from carbohydrates. Recently, it has become clear that a series of Î ±-hydroxy acids, esters, and lactones can be formed from carbohydrates in alcohol and water solvents using tin-containing catalysts such as Sn-Beta. These compounds are potential building blocks for polyesters bearing additional olefin and alcohol functionalities. An NMR approach was used to identify, quantify, and optimize the formation of these building blocks in the Sn-Beta-catalyzed transformation of abundant carbohydrates. Record yields of the target molecules can be achieved by obstructing competing reactions through solvent selection. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. 49. On the reliability of NMR relaxation data analyses: a Markov Chain Monte Carlo approach. Abergel, Daniel; Volpato, Andrea; Coutant, Eloi P; Polimeno, Antonino 2014-09-01 The analysis of NMR relaxation data is revisited along the lines of a Bayesian approach. Using a Markov Chain Monte Carlo strategy of data fitting, we investigate conditions under which relaxation data can be effectively interpreted in terms of internal dynamics. The limitations to the extraction of kinetic parameters that characterize internal dynamics are analyzed, and we show that extracting characteristic time scales shorter than a few tens of ps is very unlikely. However, using MCMC methods, reliable estimates of the marginal probability distributions and estimators (average, standard deviations, etc.) can still be obtained for subsets of the model parameters. Thus, unlike more conventional strategies of data analysis, the method avoids a model selection process. In addition, it indicates what information may be extracted from the data, but also what cannot. 50. Multilayer Approach for Advanced Hybrid Lithium Battery Ming, Jun 2016-06-06 Conventional intercalated rechargeable batteries have shown their capacity limit, and the development of an alternative battery system with higher capacity is strongly needed for sustainable electrical vehicles and hand-held devices. Herein, we introduce a feasible and scalable multilayer approach to fabricate a promising hybrid lithium battery with superior capacity and multivoltage plateaus. A sulfur-rich electrode (90 wt % S) is covered by a dual layer of graphite/Li4Ti5O12, where the active materials S and Li4Ti5O12 can both take part in redox reactions and thus deliver a high capacity of 572 mAh gcathode -1 (vs the total mass of electrode) or 1866 mAh gs -1 (vs the mass of sulfur) at 0.1C (with the definition of 1C = 1675 mA gs -1). The battery shows unique voltage platforms at 2.35 and 2.1 V, contributed from S, and 1.55 V from Li4Ti5O12. A high rate capability of 566 mAh gcathode -1 at 0.25C and 376 mAh gcathode -1 at 1C with durable cycle ability over 100 cycles can be achieved. Operando Raman and electron microscope analysis confirm that the graphite/Li4Ti5O12 layer slows the dissolution/migration of polysulfides, thereby giving rise to a higher sulfur utilization and a slower capacity decay. This advanced hybrid battery with a multilayer concept for marrying different voltage plateaus from various electrode materials opens a way of providing tunable capacity and multiple voltage platforms for energy device applications. © 2016 American Chemical Society. 51. A systematic approach to obtain validated partial least square models for predicting lipoprotein subclasses from serum NMR spectra Mihaleva, V.V.; Schalkwijk, van D.B.; Graaf, de A.A.; Duynhoven, van J.P.M.; Dorsten, van F.A.; Vervoort, J.J.M.; Smilde, A.K.; Westerhuis, J.A.; Jacobs, D.M. 2014-01-01 A systematic approach is described for building validated PLS models that predict cholesterol and triglyceride concentrations in lipoprotein subclasses in fasting serum from a normolipidemic, healthy population. The PLS models were built on diffusion-edited (1)H NMR spectra and calibrated on HPLC-de 52. A systematic approach to obtain validated partial least square models for predicting lipoprotein subclasses from serum nmr spectra Mihaleva, V.V.; Schalkwijk, D.B. van; Graaf, A.A. de; Duynhoven, J. van; Dorsten, F.A. van; Vervoort, J.; Smilde, A.; Westerhuis, J.A.; Jacobs, D.M. 2014-01-01 A systematic approach is described for building validated PLS models that predict cholesterol and triglyceride concentrations in lipoprotein subclasses in fasting serum from a normolipidemic, healthy population. The PLS models were built on diffusion-edited 1H NMR spectra and calibrated on HPLC-deri 53. Advanced quantum communications an engineering approach Imre, Sandor 2012-01-01 The book provides an overview of the most advanced quantum informational geometric techniques, which can help quantum communication theorists analyze quantum channels, such as security or additivity properties. Each section addresses an area of major research of quantum information theory and quantum communication networks. The authors present the fundamental theoretical results of quantum information theory, while also presenting the details of advanced quantum ccommunication protocols with clear mathematical and information theoretical background. This book bridges the gap between quantum ph 54. Unambiguous metabolite identification in high-throughput metabolomics by hybrid 1D 1 H NMR/ESI MS 1 approach: Hybrid 1D 1 H NMR/ESI MS 1 metabolomics method Walker, Lawrence R. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Hoyt, David W. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Walker, S. Michael [Department of Ecology and Evolutionary Biology, University of Kansas, Lawrence KS 66045 USA; Ward, Joy K. [Department of Ecology and Evolutionary Biology, University of Kansas, Lawrence KS 66045 USA; Nicora, Carrie D. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Bingol, Kerem [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA 2016-09-16 We present a novel approach to improve accuracy of metabolite identification by combining direct infusion ESI MS1 with 1D 1H NMR spectroscopy. The new approach first applies standard 1D 1H NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in metabolomics library. This generates a list of candidate metabolites. The list contains false positive and ambiguous identifications. Next, we constrained the list with the chemical formulas derived from high-resolution direct infusion ESI MS1 spectrum of the same sample. Detection of the signals of a metabolite both in NMR and MS significantly improves the confidence of identification and eliminates false positive identification. 1D 1H NMR and direct infusion ESI MS1 spectra of a sample can be acquired in parallel in several minutes. This is highly beneficial for rapid and accurate screening of hundreds of samples in high-throughput metabolomics studies. In order to make this approach practical, we developed a software tool, which is integrated to Chenomx NMR Suite. The approach is demonstrated on a model mixture, tomato and Arabidopsis thaliana metabolite extracts, and human urine. 55. Compact NMR Bluemich, Bernhard; Haber-Pohlmeier, Sabina; Zia, Wasif [RWTH Aachen Univ. (Germany). Inst. fuer Technische und Makromolekulare Chemie (ITMC) 2014-06-01 Nuclear Magnetic Resonance (NMR) spectroscopy is the most popular method for chemists to analyze molecular structures, while Magnetic Resonance Imaging (MRI) is a noninvasive diagnostic tool for medical doctors that provides high-contrast images of biological tissue. In both applications, the sample (or patient) is positioned inside a large, superconducting magnet to magnetize the atomic nuclei. Interrogating radio-frequency pulses result in frequency spectra that provide the chemist with molecular information, the medical doctor with anatomic images, and materials scientist with NMR relaxation parameters. Recent advances in magnet technology have led to a variety of small permanent magnets to allow compact and low-cost instruments. The goal of this book is to provide an introduction to the practical use of compact NMR at a level nearly as basic as the operation of a smart phone. 56. Spectroscopic approaches to resolving ambiguities of hyper-polarized NMR signals from different reaction cascades Jensen, Pernille Rose; Meier, Sebastian 2016-01-01 The influx of exogenous substrates into cellular reaction cascades on the seconds time scale is directly observable by NMR spectroscopy when using nuclear spin polarization enhancement. Conventional NMR assignment spectra for the identification of reaction intermediates are not applicable in thes... 57. An Oil Spill in a Tube: An Accessible Approach for Teaching Environmental NMR Spectroscopy Simpson, Andre´ J.; Mitchell, Perry J.; Masoom, Hussain; Mobarhan, Yalda Liaghati; Adamo, Antonio; Dicks, Andrew P. 2015-01-01 NMR spectroscopy has great potential as an instrumental method for environmental chemistry research and monitoring but may be underused in teaching laboratories because of its complexity and the level of expertise required in operating the instrument and interpreting data. This laboratory experiment introduces environmental NMR spectroscopy to… 58. An Oil Spill in a Tube: An Accessible Approach for Teaching Environmental NMR Spectroscopy Simpson, Andre´ J.; Mitchell, Perry J.; Masoom, Hussain; Mobarhan, Yalda Liaghati; Adamo, Antonio; Dicks, Andrew P. 2015-01-01 NMR spectroscopy has great potential as an instrumental method for environmental chemistry research and monitoring but may be underused in teaching laboratories because of its complexity and the level of expertise required in operating the instrument and interpreting data. This laboratory experiment introduces environmental NMR spectroscopy to… 59. NMR imaging of the liver. Diagnostics, differential diagnostics, therapeutic approaches; MRT der Leber. Diagnostik, Differenzialdiagnostik, Therapieansaetze Fischbach, Frank; Fischbach, Katharina [Universitaetsklinikum Magdeburg A.oe.R. (Germany). Klinik fuer Radiologie und Nuklearmedizin 2017-03-01 The book on NMR imaging of the liver covers the following issues: Fundamentals of NMR imaging, T1-weighted imaging; T2-weighted imaging, diffusion-weighted imaging, cavernous hemangioma, focal nodular hyperplasy; hepatocellular adenoma, hepatocellulas carcinoma, cholangiocellular carcinoma, hepatic metastases. 60. Autonomous driving in NMR. Perez, Manuel 2017-01-01 The automatic analysis of NMR data has been a much-desired endeavour for the last six decades, as it is the case with any other analytical technique. This need for automation has only grown as advances in hardware; pulse sequences and automation have opened new research areas to NMR and increased the throughput of data. Full automatic analysis is a worthy, albeit hard, challenge, but in a world of artificial intelligence, instant communication and big data, it seems that this particular fight is happening with only one technique at a time (let this be NMR, MS, IR, UV or any other), when the reality of most laboratories is that there are several types of analytical instrumentation present. Data aggregation, verification and elucidation by using complementary techniques (e.g. MS and NMR) is a desirable outcome to pursue, although a time-consuming one if performed manually; hence, the use of automation to perform the heavy lifting for users is required to make the approach attractive for scientists. Many of the decisions and workflows that could be implemented under automation will depend on the two-way communication with databases that understand analytical data, because it is desirable not only to query these databases but also to grow them in as much of an automatic manner as possible. How these databases are designed, set up and the data inside classified will determine what workflows can be implemented. Copyright © 2016 John Wiley & Sons, Ltd. « 1 2 3 4 5 » « 2 3 4 5 6 » 61. In situ solid-state NMR for heterogeneous catalysis: a joint experimental and theoretical approach. Zhang, Weiping; Xu, Shutao; Han, Xiuwen; Bao, Xinhe 2012-01-07 In situ solid-state NMR is a well-established tool for investigations of the structures of the adsorbed reactants, intermediates and products on the surface of solid catalysts. The techniques allow identifications of both the active sites such as acidic sites and reaction processes after introduction of adsorbates and reactants inside an NMR rotor under magic angle spinning (MAS). The in situ solid-state NMR studies of the reactions can be achieved in two ways, i.e. under batch-like or continuous-flow conditions. The former technique is low cost and accessible to the commercial instrument while the latter one is close to the real catalytic reactions on the solids. This critical review describes the research progress on the in situ solid-state NMR techniques and the applications in heterogeneous catalysis under batch-like and continuous-flow conditions in recent years. Some typical probe molecules are summarized here to detect the Brønsted and Lewis acidic sites by MAS NMR. The catalytic reactions discussed in this review include methane aromatization, olefin selective oxidation and olefin metathesis on the metal oxide-containing zeolites. With combining the in situ MAS NMR spectroscopy and the density functional theoretical (DFT) calculations, the intermediates on the catalyst can be identified, and the reaction mechanism is revealed. Reaction kinetic analysis in the nanospace instead of in the bulk state can also be performed by employing laser-enhanced MAS NMR techniques in the in situ flow mode (163 references). 62. Lipid binding protein response to a bile acid library: a combined NMR and statistical approach. Tomaselli, Simona; Pagano, Katiuscia; Boulton, Stephen; Zanzoni, Serena; Melacini, Giuseppe; Molinari, Henriette; Ragona, Laura 2015-11-01 Primary bile acids, differing in hydroxylation pattern, are synthesized from cholesterol in the liver and, once formed, can undergo extensive enzyme-catalysed glycine/taurine conjugation, giving rise to a complex mixture, the bile acid pool. Composition and concentration of the bile acid pool may be altered in diseases, posing a general question on the response of the carrier (bile acid binding protein) to the binding of ligands with different hydrophobic and steric profiles. A collection of NMR experiments (H/D exchange, HETSOFAST, ePHOGSY NOESY/ROESY and (15) N relaxation measurements) was thus performed on apo and five different holo proteins, to monitor the binding pocket accessibility and dynamics. The ensemble of obtained data could be rationalized by a statistical approach, based on chemical shift covariance analysis, in terms of residue-specific correlations and collective protein response to ligand binding. The results indicate that the same residues are influenced by diverse chemical stresses: ligand binding always induces silencing of motions at the protein portal with a concomitant conformational rearrangement of a network of residues, located at the protein anti-portal region. This network of amino acids, which do not belong to the binding site, forms a contiguous surface, sensing the presence of the bound lipids, with a signalling role in switching protein-membrane interactions on and off. 63. Bottom-up and top-down solid-state NMR approaches for bacterial biofilm matrix composition Cegelski, Lynette 2015-04-01 The genomics and proteomics revolutions have been enormously successful in providing crucial "parts lists" for biological systems. Yet, formidable challenges exist in generating complete descriptions of how the parts function and assemble into macromolecular complexes and whole-cell assemblies. Bacterial biofilms are complex multicellular bacterial communities protected by a slime-like extracellular matrix that confers protection to environmental stress and enhances resistance to antibiotics and host defenses. As a noncrystalline, insoluble, heterogeneous assembly, the biofilm extracellular matrix poses a challenge to compositional analysis by conventional methods. In this perspective, bottom-up and top-down solid-state NMR approaches are described for defining chemical composition in complex macrosystems. The "sum-of-the-parts" bottom-up approach was introduced to examine the amyloid-integrated biofilms formed by Escherichia coli and permitted the first determination of the composition of the intact extracellular matrix from a bacterial biofilm. An alternative top-down approach was developed to define composition in Vibrio cholerae biofilms and relied on an extensive panel of NMR measurements to tease out specific carbon pools from a single sample of the intact extracellular matrix. These two approaches are widely applicable to other heterogeneous assemblies. For bacterial biofilms, quantitative parameters of matrix composition are needed to understand how biofilms are assembled, to improve the development of biofilm inhibitors, and to dissect inhibitor modes of action. Solid-state NMR approaches will also be invaluable in obtaining parameters of matrix architecture. 64. Evaluation of standard and advanced preprocessing methods for the univariate analysis of blood serum 1H-NMR spectra. De Meyer, Tim; Sinnaeve, Davy; Van Gasse, Bjorn; Rietzschel, Ernst-R; De Buyzere, Marc L; Langlois, Michel R; Bekaert, Sofie; Martins, José C; Van Criekinge, Wim 2010-10-01 Proton nuclear magnetic resonance ((1)H-NMR)-based metabolomics enables the high-resolution and high-throughput assessment of a broad spectrum of metabolites in biofluids. Despite the straightforward character of the experimental methodology, the analysis of spectral profiles is rather complex, particularly due to the requirement of numerous data preprocessing steps. Here, we evaluate how several of the most common preprocessing procedures affect the subsequent univariate analyses of blood serum spectra, with a particular focus on how the standard methods perform compared to more advanced examples. Carr-Purcell-Meiboom-Gill 1D (1)H spectra were obtained for 240 serum samples from healthy subjects of the Asklepios study. We studied the impact of different preprocessing steps--integral (standard method) and probabilistic quotient normalization; no, equidistant (standard), and adaptive-intelligent binning; mean (standard) and maximum bin intensity data summation--on the resonance intensities of three different types of metabolites: triglycerides, glucose, and creatinine. The effects were evaluated by correlating the differently preprocessed NMR data with the independently measured metabolite concentrations. The analyses revealed that the standard methods performed inferiorly and that a combination of probabilistic quotient normalization after adaptive-intelligent binning and maximum intensity variable definition yielded the best overall results (triglycerides, R = 0.98; glucose, R = 0.76; creatinine, R = 0.70). Therefore, at least in the case of serum metabolomics, these or equivalent methods should be preferred above the standard preprocessing methods, particularly for univariate analyses. Additional optimization of the normalization procedure might further improve the analyses. 65. Application of the AMPLE cluster-and-truncate approach to NMR structures for molecular replacement Bibby, Jaclyn [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Keegan, Ronan M. [Research Complex at Harwell, STFC Rutherford Appleton Laboratory, Didcot OX11 0FA (United Kingdom); Mayans, Olga [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Winn, Martyn D. [Science and Technology Facilities Council Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Rigden, Daniel J., E-mail: [email protected] [University of Liverpool, Liverpool L69 7ZB (United Kingdom) 2013-11-01 Processing of NMR structures for molecular replacement by AMPLE works well. AMPLE is a program developed for clustering and truncating ab initio protein structure predictions into search models for molecular replacement. Here, it is shown that its core cluster-and-truncate methods also work well for processing NMR ensembles into search models. Rosetta remodelling helps to extend success to NMR structures bearing low sequence identity or high structural divergence from the target protein. Potential future routes to improved performance are considered and practical, general guidelines on using AMPLE are provided.

66. Study of advanced ion conducting polymers by relaxation, diffusion and spectroscopy NMR methods Daniel Jardón Ãlvarez 2016-01-01 Advances on secondary lithium ion batteries imply the use of solid polymer electrolytes, which represent a promising solution to improve safety issues in high energy density batteries. Through dissolution of lithium salts into a polymeric host, such as poly(ethylene oxide) (PEO), ion conducting polymers are obtained. The Li+ ions will be localized in the proximity of the oxygen atoms in the PEO chains and thus, their motion strongly correlated with the segmental reorientation of the polymer. ... 67. NMR-based approach to measure the free energy of transmembrane helix-helix interactions. Mineev, Konstantin S; Lesovoy, Dmitry M; Usmanova, Dinara R; Goncharuk, Sergey A; Shulepko, Mikhail A; Lyukmanova, Ekaterina N; Kirpichnikov, Mikhail P; Bocharov, Eduard V; Arseniev, Alexander S 2014-01-01 Knowledge of the energetic parameters of transmembrane helix-helix interactions is necessary for the establishment of a structure-energy relationship for α-helical membrane domains. A number of techniques have been developed to measure the free energies of dimerization and oligomerization of transmembrane α-helices, and all of these have their advantages and drawbacks. In this study we propose a methodology to determine the magnitudes of the free energy of interactions between transmembrane helices in detergent micelles. The suggested approach employs solution nuclear magnetic resonance (NMR) spectroscopy to determine the population of the oligomeric states of the transmembrane domains and introduces a new formalism to describe the oligomerization equilibrium, which is based on the assumption that both the dimerization of the transmembrane domains and the dissociation of the dimer can occur only upon the collision of detergent micelles. The technique has three major advantages compared with other existing approaches: it may be used to analyze both weak and relatively strong dimerization/oligomerization processes, it works well for the analysis of complex equilibria, e.g. when monomer, dimer and highorder oligomer populations are simultaneously present in the solution, and it can simultaneously yield both structural and energetic characteristics of the helix-helix interaction under study. The proposed methodology was applied to investigate the oligomerization process of transmembrane domains of fibroblast growth factor receptor 3 (FGFR3) and vascular endothelium growth factor receptor 2 (VEGFR2), and allowed the measurement of the free energy of dimerization of both of these objects. In addition the proposed method was able to describe the multi-state oligomerization process of the VEGFR2 transmembrane domain. 68. Integrated optics approach for advanced semiconductor lasers Suematsu, Yasuharu; Arai, Shigehisa 1987-11-01 Recent advances in the field of semiconductor integrated optics are reviewed from the point of view of monolithic integration of semiconductor lasers and other optical components and/or devices. Emphasis is placed on dynamic-single-mode (DSM) lasers, such as DFB and DBR lasers, intended for highly stable single-wavelength light sources for such monolithic integration. The realization of high-performance DSM lasers and the fabrication techniques of monolithically integrated optical devices and circuits are briefly reviewed. A variety of potential applications is discussed. 69. Advances in studying order and dynamics in condensed matter by NMR Voda, M.A. 2006-07-13 In this thesis, molecular transport in liquid samples is studied in terms of susceptibility induced magnetic field inhomogeneities and spectral distortions for interdiffusion in binary mixtures. Molecular order and dynamics are topics for two different soft solids, natural rubber and polyurethane. The influence of the mixture heterogeneity on the magnetic field homogeneity was investigated in terms of a spatial and time-dependent magnetic susceptibility. The effect of the heterogeneous distribution of magnetic susceptibility in liquid mixtures on the static and rf field homogeneity was simulated together with the corresponding spectral distortions. The problem of low magnetic field homogeneity provided by the Halbach type of magnets is discussed. The design of modified Halbach magnets is studied in order to increase the field homogeneity. The work was focused on two types of Halbach magnets, consisting of 16 and 24 magnet blocks, respectively. Different modifications were applied to these magnet designs, and the field homogeneity was significantly improved. The changes induced in molecular dynamics and order in stretched elastomers was investigated using multispin moments edited by multiple-quantum NMR. The main purpose of this part is to investigate the changes in proton residual dipolar coupling and the sensitivity of multiple quantum coherences of higher order for cross-linked natural rubber under uniaxial deformation. The effect of uniaxial deformation of a natural rubber band was investigated by measurements of second van Vleck moments and fourth moments edited by doublequantum and triple-quantum coherences, respectively. A spin diffusion experiment was employed for the elucidation of the morphology and domain sizes of a series of polyurethane samples. A proton DQ dipolar filer was used to select the magnetization of the rigid phase. The most probable morphology is three-dimensional for the TPU samples with a high content in HS as was established by a 70. Improving the efficiency of quantitative (1)H NMR: an innovative external standard-internal reference approach. Huang, Yande; Su, Bao-Ning; Ye, Qingmei; Palaniswamy, Venkatapuram A; Bolgar, Mark S; Raglione, Thomas V 2014-01-01 The classical internal standard quantitative NMR (qNMR) method determines the purity of an analyte by the determination of a solution containing the analyte and a standard. Therefore, the standard must meet the requirements of chemical compatibility and lack of resonance interference with the analyte as well as a known purity. The identification of such a standard can be time consuming and must be repeated for each analyte. In contrast, the external standard qNMR method utilizes a standard with a known purity to calibrate the NMR instrument. The external standard and the analyte are measured separately, thereby eliminating the matter of chemical compatibility and resonance interference between the standard and the analyte. However, the instrumental factors, including the quality of NMR tubes, must be kept the same. Any deviations will compromise the accuracy of the results. An innovative qNMR method reported herein utilizes an internal reference substance along with an external standard to assume the role of the standard used in the traditional internal standard qNMR method. In this new method, the internal reference substance must only be chemically compatible and be free of resonance-interference with the analyte or external standard whereas the external standard must only be of a known purity. The exact purity or concentration of the internal reference substance is not required as long as the same quantity is added to the external standard and the analyte. The new method reduces the burden of searching for an appropriate standard for each analyte significantly. Therefore the efficiency of the qNMR purity assay increases while the precision of the internal standard method is retained. Copyright © 2013 Elsevier B.V. All rights reserved. 71. Advancing Instructional Communication: Integrating a Biosocial Approach Horan, Sean M.; Afifi, Tamara D. 2014-01-01 Celebrating 100 years of the National Communication Association necessitates that, as we commemorate our past, we also look toward our future. As part of a larger conversation about the future of instructional communication, this essay reinvestigates the importance of integrating biosocial approaches into instructional communication research. In… 72. A simple mathematical model and practical approach for evaluating citric acid cycle fluxes in perfused rat hearts by 13C-NMR and 1H-NMR spectroscopy. Tran-Dinh, S; Hoerter, J A; Mateo, P; Bouet, F; Herve, M 1997-04-15 We propose a simple mathematical model and a practical approach for evaluating the flux constant and the absolute value of flux in the citric acid cycle in perfused organs by 13CNMR and 1H-NMR spectroscopy. We demonstrate that 13C-NMR glutamate spectra are independent of the relative sizes of the mitochondrial and cytosolic compartments and the exchange rates of glutamates, unless there is a difference in 13C chemical shifts of glutamate carbons between the two compartments. Wistar rat hearts (five beating and four KClarrested hearts) were aerobically perfused with 100% enriched [2-(13)C]acetate and the kinetics of glutamate carbon labeling from perchloric acid extracts were studied at various perfusion times. Under our experimental conditions, the citric acid cycle flux constant, which represents the fraction of glutamate in exchange with the citric acid cycle per unit time, is about 0.350 +/- 0.003 min(-1) for beating hearts and 0.0741 +/- 0.004 min(-1) for KCl-arrested hearts. The absolute values of the citric acid flux for beating hearts and for KClarrested hearts are 1.06 +/- 0.06 micromol x min(-1) x mg(-1) and 0.21 +/- 0.02 micromol x min(-1) x g(-1), respectively. The fraction of unlabeled acetate determined from the proton signal of the methyl group is small and essentially the same in beating and arrested hearts (7.4 +/- 1.7% and 8.8 +/- 2.1%, respectively). Thus, the large difference in the Glu C2/C4 between beating and arrested hearts is not due to the important contribution from anaplerotic sources in arrested hearts but simply to a substantial difference in citric acid cycle fluxes. Our model fits the experimental data well, indicating a fast exchange between 2-oxoglutarate and glutamate in the mitochondria of rat hearts. Analysis of the flux constant, calculated from the half-time of glutamate C4 labeling given in the literature, allows for a comparison of the citric acid flux for various working conditions in different animal species. 73. Delivering advanced therapies: The big pharma approach. Tarnowski, J; Krishna, D; Jespers, L; Ketkar, A; Haddock, R; Imrie, J; Kili, S 2017-07-24 After two decades of focused development and some recent clinical successes, cell and gene therapy (CGT) is emerging as a promising approach to personalized medicines. Genetically engineered cells as a medical modality are poised to stand alongside or in combination with small molecule and biopharmaceutical approaches to bring new therapies to patients globally. Big pharma can play a vital role in industrializing CGT by focusing on diseases with high un-met medical need and compelling genetic evidence. Pharma should invest in manufacturing and supply chain solutions that deliver reproducible, high quality therapies at a commercially viable cost. Due to the fast pace of innovation in this field proactive engagement with regulators is critical. It is also vital to understand the needs of patients all along the patient care pathway and to establish product pricing that is accepted by prescribers, payers, and patients.Gene Therapy accepted article preview online, 24 July 2017. doi:10.1038/gt.2017.65. 74. Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy Mao, J.; Fang, X.; Lan, Y.; Schimmelmann, A.; Mastalerz, Maria; Xu, L.; Schmidt-Rohr, K. 2010-01-01 We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved. 75. Advanced drug delivery approaches against periodontitis. Joshi, Deeksha; Garg, Tarun; Goyal, Amit K; Rath, Goutam 2016-01-01 Periodontitis is an inflammatory disease of gums involving the degeneration of periodontal ligaments, creation of periodontal pocket and resorption of alveolar bone, resulting in the disruption of the support structure of teeth. According to WHO, 10-15% of the global population suffers from severe periodontitis. The disease results from the growth of a diverse microflora (especially anaerobes) in the pockets and release of toxins, enzymes and stimulation of body's immune response. Various local or systemic approaches were used for an effective treatment of periodontitis. Currently, controlled local drug delivery approach is more favorable as compared to systemic approach because it mainly focuses on improving the therapeutic outcomes by achieving factors like site-specific delivery, low dose requirement, bypass of first-pass metabolism, reduction in gastrointestinal side effects and decrease in dosing frequency. Overall it provides a safe and effective mode of treatment, which enhances patient compliance. Complete eradication of the organisms from the sites was not achieved by using various surgical and mechanical treatments. So a number of polymer-based delivery systems like fibers, films, chips, strips, microparticles, nanoparticles and nanofibers made from a variety of natural and synthetic materials have been successfully tested to deliver a variety of drugs. These systems are biocompatible and biodegradable, completely fill the pockets, and have strong retention on the target site due to excellent mucoadhesion properties. The review summarizes various available and recently developing targeted delivery devices for the treatment of periodontitis. 76. 1H NMR- based metabolomics approaches as non- invasive tools for diagnosis of endometriosis Negar Ghazi 2016-01-01 Full Text Available Background: So far, non-invasive diagnostic approaches such as ultrasound, magnetic resonance imaging, or blood tests do not have sufficient diagnostic power for endometriosis disease. Lack of a non-invasive diagnostic test contributes to the long delay between onset of symptoms and diagnosis of endometriosis. Objective: The present study focuses on the identification of predictive biomarkers in serum by pattern recognition techniques and uses partial least square discriminant analysis, multi-layer feed forward artificial neural networks (ANNs and quadratic discriminant analysis (QDA modeling tools for the early diagnosis of endometriosis in a minimally invasive manner by 1H- NMR based metabolomics. Materials and Methods: This prospective cohort study was done in Pasteur Institute, Iran in June 2013. Serum samples of 31 infertile women with endometriosis (stage II and III who confirmed by diagnostic laparoscopy and 15 normal women were collected and analyzed by nuclear magnetic resonance spectroscopy. The model was built by using partial least square discriminant analysis, QDA, and ANNs to determine classifier metabolites for early prediction risk of disease. Results: The levels of 2- methoxyestron, 2methoxy estradiol, dehydroepiandrostion androstendione, aldosterone, and deoxy corticosterone were enhanced significantly in infertile group. While cholesterol and primary bile acids levels were decreased. QDA model showed significant difference between two study groups. Positive and negative predict value levels obtained about 71% and 78%, respectively. ANNs provided also criteria for detection of endometriosis. Conclusion: The QDA and ANNs modeling can be used as computational tools in noninvasive diagnose of endometriosis. However, the model designed by QDA methods is more efficient compared to ANNs in diagnosis of endometriosis patients. 77. Multimodality approach for locally advanced esophageal cancer Khaldoun Almhanna; Jonathan R Strosberg 2012-01-01 Carcinoma of the esophagus is an aggressive and lethal malignancy with an increasing incidence world-wide.Incidence rates vary internationally,with the highest rates found in Southern and Eastern Africa and Eastern Asia,and the lowest in Western and Middle Africa and Central America.Patients with locally advanced disease face a poor prognosis,with 5year survival rates ranging from 15ï¼…-34ï¼….Recent clinical trials have evaluated different strategies for management of locoregional cancer; however,because of stage migration and changes in disease epidemiology,applying these trials to clinical practice has become a daunting task.We searched Medline and conference abstracts for randomized studies published in the last 3 decades.We restricted our search to articles published in English.Neoadjuvant chemoradiotherapy followed by surgical resection is an accepted standard of care in the United States.Esophagectomy remains an essential component of treatment and can lead to improved overall survival,especially when performed at high volume institutions.The role of adjuvant chemotherapy following curative resection is still unclear.External beam radiation therapy alone is considered palliative and is typically reserved for patients with a poor performance status. 78. Advanced solid-state NMR techniques for characterization of membrane protein structure and dynamics: application to Anabaena Sensory Rhodopsin. Ward, Meaghan E; Brown, Leonid S; Ladizhansky, Vladimir 2015-04-01 Studies of the structure, dynamics, and function of membrane proteins (MPs) have long been considered one of the main applications of solid-state NMR (SSNMR). Advances in instrumentation, and the plethora of new SSNMR methodologies developed over the past decade have resulted in a number of high-resolution structures and structural models of both bitopic and polytopic α-helical MPs. The necessity to retain lipids in the sample, the high proportion of one type of secondary structure, differential dynamics, and the possibility of local disorder in the loop regions all create challenges for structure determination. In this Perspective article we describe our recent efforts directed at determining the structure and functional dynamics of Anabaena Sensory Rhodopsin, a heptahelical transmembrane (7TM) protein. We review some of the established and emerging methods which can be utilized for SSNMR-based structure determination, with a particular focus on those used for ASR, a bacterial protein which shares its 7TM architecture with G-protein coupled receptors. 79. Advanced solid-state NMR techniques for characterization of membrane protein structure and dynamics: Application to Anabaena Sensory Rhodopsin Ward, Meaghan E.; Brown, Leonid S.; Ladizhansky, Vladimir 2015-04-01 Studies of the structure, dynamics, and function of membrane proteins (MPs) have long been considered one of the main applications of solid-state NMR (SSNMR). Advances in instrumentation, and the plethora of new SSNMR methodologies developed over the past decade have resulted in a number of high-resolution structures and structural models of both bitopic and polytopic α-helical MPs. The necessity to retain lipids in the sample, the high proportion of one type of secondary structure, differential dynamics, and the possibility of local disorder in the loop regions all create challenges for structure determination. In this Perspective article we describe our recent efforts directed at determining the structure and functional dynamics of Anabaena Sensory Rhodopsin, a heptahelical transmembrane (7TM) protein. We review some of the established and emerging methods which can be utilized for SSNMR-based structure determination, with a particular focus on those used for ASR, a bacterial protein which shares its 7TM architecture with G-protein coupled receptors. 80. Efficient design of multituned transmission line NMR probes: the electrical engineering approach. Frydel, J A; Krzystyniak, M; Pienkowski, D; Pietrzak, M; de Sousa Amadeu, N; Ratajczyk, T; Idzik, K; Gutmann, T; Tietze, D; Voigt, S; Fenn, A; Limbach, H H; Buntkowsky, G 2011-01-01 Transmission line-based multi-channel solid state NMR probes have many advantages regarding the cost of construction, number of RF-channels, and achievable RF-power levels. Nevertheless, these probes are only rarely employed in solid state-NMR-labs, mainly owing to the difficult experimental determination of the necessary RF-parameters. Here, the efficient design of multi-channel solid state MAS-NMR probes employing transmission line theory and modern techniques of electrical engineering is presented. As technical realization a five-channel ((1)H, (31)P, (13)C, (2)H and (15)N) probe for operation at 7 Tesla is described. This very cost efficient design goal is a multi port single coil transmission line probe based on the design developed by Schaefer and McKay. The electrical performance of the probe is determined by measuring of Scattering matrix parameters (Sparameters) in particular input/output ports. These parameters are compared to the calculated parameters of the design employing the S-matrix formalism. It is shown that the S-matrix formalism provides an excellent tool for examination of transmission line probes and thus the tool for a rational design of these probes. On the other hand, the resulting design provides excellent electrical performance. From a point of view of Nuclear Magnetic Resonance (NMR), calibration spectra of particular ports (channels) are of great importance. The estimation of the Ï€/2 pulses length for all five NMR channels is presented. « 2 3 4 5 6 » « 3 4 5 6 7 » 81. Urinary metabolomics of pregnant women at term: a combined GC/MS and NMR approach. Caboni, Pierluigi; Meloni, Alessandra; Lussu, Milena; Carta, Emanuela; Barberini, Luigi; Noto, Antonio; Deiana, Sara Francesca; Mereu, Rossella; Ragusa, Antonio; Paoletti, Anna Maria; Melis, Gian Benedetto; Fanos, Vassilios; Atzori, Luigi 2014-10-01 Physiological changes leading to parturition are not completely understood while clinical diagnosis of labour is still retrospective. Gas chromatography mass spectrometry (GC/MS) and nuclear magnetic resonance spectroscopy (NMR) represent two of the main analytical platforms used in clinical metabolomics. Metabolomics might help us to improve our knowledge about the biochemical mechanisms underlying labour. Urine samples (n = 59), collected from pregnant women at term of gestation before and/or after the onset of labour, were analysed by GC/MS and NMR techniques in order to identify the metabolic profile. Both GC/MS and NMR data matrices containing the identified metabolites were analysed by multivariate statistical techniques in order to characterise the discriminant variables between labour (L) and not labour (NL) status. 18 potential metabolites (11 with (1)HNMR, eight with GC-MS: glycine was relevant in both) were found discriminant in urine of women during labour. Taken together, the identified metabolites produced a composite biomarker pattern, a sort of barcode, capable of differentiating between labour and not labour conditions. Major discriminant metabolites for NMR and GC/MS analysis were: alanine, glycine, acetone, 3-hydroxybutiyric acid, 2,3,4-trihydroxybutyric acid and succinic acid, giving a urine metabolite signature on the late phase of labour. The metabolomics analysis evidenced clusters of metabolites involved in labour condition able to discriminate between urine samples collected before the onset and during labour, potentially offering the promise of a robust screening test. 82. In-cell NMR: an emerging approach for monitoring metal-related events in living cells. Li, Hongyan; Sun, Hongzhe 2014-01-01 In-cell NMR, an isotope-assisted multi-dimensional NMR technique, has been proven to be successful in the investigation of protein dynamics, folding, conformational changes induced by binding events, posttranslational modification in the complex native environments, as well as in vivo drug screening, even de novo 3D protein structure determination in living cells. This technique was initially applied to bacterial cells, and subsequently has been extended to various other cells including eukaryotic cells. In this review, we briefly summarize the methodology and application of in-cell NMR with a focus on its application in metallomics and metalloproteomics. This emerging technique is anticipated to be an excellent tool for studying metal-associated events in complex native environments of living cells. 83. Study of the cardiotoxicity of Venenum Bufonis in rats using an 1H NMR-based metabolomics approach. Ge Dong Full Text Available Venenum Bufonis, a well-known traditional Chinese medicine, has been widely used in Asia and has gained popularity in Western countries over the last decade. Venenum Bufonis has obvious side effects that have been observed in clinical settings, but few studies have reported on its cardiotoxicity. In this work, the cardiotoxicity of Venenum Bufonis was investigated using a 11H NMR-based metabolomics approach. The 1H NMR profiles of the serum, myocardial extracts and liver extracts of specificpathogen-free rats showed that Venenum Bufonis produced significant metabolic perturbations dose-dependently with a distinct time effect, peaking at 2 hr after dosing and attenuating gradually. Clinical chemistry, electrocardiographic recordings, and histopathological evaluation provided additional evidence of Venenum Bufonis-induced cardiac damage that complemented and supported the metabolomics findings. The combined results demonstrated that oxidative stress, mitochondrial dysfunction, and energy metabolism perturbations were associated with the cardiac damage that results from Venenum Bufonis. 84. Advanced control room evaluation: General approach and rationale O' Hara, J.M. (Brookhaven National Lab., Upton, NY (USA)); Wachtel, J. (Nuclear Regulatory Commission, Washington, DC (USA)) 1991-01-01 Advanced control rooms (ACRs) for future nuclear power plants (NPPs) are being designed utilizing computer-based technologies. The US Nuclear Regulatory Commission reviews the human engineering aspects of such control rooms to ensure that they are designed to good human factors engineering principles and that operator performance and reliability are appropriately supported in order to protect public health and safety. This paper describes the rationale and general approach to the development of a human factors review guideline for ACRs. The factors influencing the guideline development are discussed, including the review environment, the types of advanced technologies being addressed, the human factors issues associated with advanced technology, and the current state-of-the-art of human factors guidelines for advanced human-system interfaces (HSIs). The proposed approach to ACR review would track the design and implementation process through the application of review guidelines reflecting four review modules: planning, design process analysis, human factors engineering review, and dynamic performance evaluation. 21 refs. 85. Isotope labeling for NMR studies of macromolecular structure and interactions Wright, P.E. [Scripps Research Institute, La Jolla, CA (United States) 1994-12-01 Implementation of biosynthetic methods for uniform or specific isotope labeling of proteins, coupled with the recent development of powerful heteronuclear multidimensional NMR methods, has led to a dramatic increase in the size and complexity of macromolecular systems that are now amenable to NMR structural analysis. In recent years, a new technology has emerged that combines uniform {sup 13}C, {sup 15}N labeling with heteronuclear multidimensional NMR methods to allow NMR structural studies of systems approaching 25 to 30 kDa in molecular weight. In addition, with the introduction of specific {sup 13}C and {sup 15}N labels into ligands, meaningful NMR studies of complexes of even higher molecular weight have become feasible. These advances usher in a new era in which the earlier, rather stringent molecular weight limitations have been greatly surpassed and NMR can begin to address many central biological problems that involve macromolecular structure, dynamics, and interactions. 86. Positional enrichment by proton analysis (PEPA). A one-dimensional {sup 1}H-NMR approach for {sup 13}C stable isotope tracer studies in metabolomics Vinaixa, Maria; Yanes, Oscar [Department of Electronic Engineering-Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Rodriguez, Miguel A.; Capellades, Jordi [Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Aivio, Suvi; Stracker, Travis H. [Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (Spain); Gomez, Josep; Canyellas, Nicolau [Department of Electronic Engineering-, Universitat Rovira i Virgili, Tarragona (Spain) 2017-03-20 A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of {sup 13}C-satellite peaks using 1D-{sup 1}H-NMR spectra. In comparison with {sup 13}C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of {sup 13}C positions in labeled metabolites and the

quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of {sup 1}H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.) 87. New approach for understanding experimental NMR relaxivity properties of magnetic nanoparticles: focus on cobalt ferrite. Rollet, Anne-Laure; Neveu, Sophie; Porion, Patrice; Dupuis, Vincent; Cherrak, Nadine; Levitz, Pierre 2016-12-07 Relaxivities r1 and r2 of cobalt ferrite magnetic nanoparticles (MNPs) have been investigated in the aim of improving the models of NMR relaxation induced by magnetic nanoparticles. On one hand a large set of relaxivity data has been collected for cobalt ferrite MNP dispersions. On the other hand the relaxivity has been calculated for dispersions of cobalt ferrite MNPs with size ranging from 5 to 13 nm, without using any fitting procedure. The model is based on the magnetic dipolar interaction between the magnetic moments of the MNPs and the (1)H nuclei. It takes into account both the longitudinal and transversal contributions of the magnetic moments of MNPs leading to three contributions in the relaxation equations. The comparison of the experimental and theoretical data shows a good agreement of the NMR profiles as well as the temperature dependence. 88. Advanced approaches to failure mode and effect analysis (FMEA applications D. Vykydal 2015-10-01 Full Text Available The present paper explores advanced approaches to the FMEA method (Failure Mode and Effect Analysis which take into account the costs associated with occurrence of failures during the manufacture of a product. Different approaches are demonstrated using an example FMEA application to production of drawn wire. Their purpose is to determine risk levels, while taking account of the above-mentioned costs. Finally, the resulting priority levels are compared for developing actions mitigating the risks. 89. NMR-based metabolomics approach to study the toxicity of lambda-cyhalothrin to goldfish (Carassius auratus) Li, Minghui [State Key Laboratory of Natural Medicines, Department of Natural Medicinal Chemistry, China Pharmaceutical University, 24 Tong Jia Xiang, Nanjing 210009 (China); Wang, Junsong, E-mail: [email protected] [Center for Molecular Metabolism, School of Environmental and Biological Engineering, Nanjing University of Science and Technology, 200 Xiao Ling Wei Street, Nanjing 210094 (China); Lu, Zhaoguang; Wei, Dandan; Yang, Minghua [State Key Laboratory of Natural Medicines, Department of Natural Medicinal Chemistry, China Pharmaceutical University, 24 Tong Jia Xiang, Nanjing 210009 (China); Kong, Lingyi, E-mail: [email protected] [State Key Laboratory of Natural Medicines, Department of Natural Medicinal Chemistry, China Pharmaceutical University, 24 Tong Jia Xiang, Nanjing 210009 (China) 2014-01-15 Highlights: •A goldfish model was established to investigate the toxicity of lambda-cyhalothrin (LCT) exposure on multiple organs. •NMR based metabolomics approach were firstly used to provide a global view of the toxicity of LCT. •LCT induced neurotransmitters and osmoregulatory imbalances, oxidative stress, energy and amino acid metabolic disorders. •Glutamate–glutamine–GABA axis as a potential target for LCT toxicity was first found. -- Abstract: In this study, a {sup 1}H nuclear magnetic resonance (NMR) based metabolomics approach was applied to investigate the toxicity of lambda-cyhalothrin (LCT) in goldfish (Carassius auratus). LCT showed tissue-specific damage to gill, heart, liver and kidney tissues of goldfish. NMR profiling combined with statistical methods such as orthogonal partial least squares discriminant analysis (OPLS-DA) and two-dimensional statistical total correlation spectroscopy (2D-STOCSY) was developed to discern metabolite changes occurring after one week LCT exposure in brain, heart and kidney tissues of goldfish. LCT exposure influenced levels of many metabolites (e.g., leucine, isoleucine and valine in brain and kidney; lactate in brain, heart and kidney; alanine in brain and kidney; choline in brain, heart and kidney; taurine in brain, heart and kidney; N-acetylaspartate in brain; myo-inositol in brain; phosphocreatine in brain and heart; 2-oxoglutarate in brain; cisaconitate in brain, and etc.), and broke the balance of neurotransmitters and osmoregulators, evoked oxidative stress, disturbed metabolisms of energy and amino acids. The implication of glutamate–glutamine–gamma-aminobutyric axis in LCT induced toxicity was demonstrated for the first time. Our findings demonstrated the applicability and potential of metabolomics approach for the elucidation of toxicological effects of pesticides and the underlying mechanisms, and the discovery of biomarkers for pesticide pollution in aquatic environment. 90. Adapting advanced engineering design approaches to building design. Potential benefits Böhms, M. 2006-01-01 A number of industries continuously progress advancing their design approaches based on the changing market constraints. Examples such as car, ship and airplane manufacturing industries utilize process setups and techniques, that differ significantly from the processes and techniques used by the tra 91. Exploring Advanced Piano Students' Approaches to Sight-Reading Zhukov, Katie 2014-01-01 The ability to read music fluently is fundamental for undergraduate music study yet the training of sight-reading is often neglected. This study compares approaches to sight-reading and accompanying by students with extensive sight-reading experience to those with limited experience, and evaluates the importance of this skill to advanced pianists… 92. Adapting advanced engineering design approaches to building design. Potential benefits Böhms, M. 2006-01-01 A number of industries continuously progress advancing their design approaches based on the changing market constraints. Examples such as car, ship and airplane manufacturing industries utilize process setups and techniques, that differ significantly from the processes and techniques used by the 93. Advanced language modeling approaches, case study: Expert search Hiemstra, Djoerd 2008-01-01 This tutorial gives a clear and detailed overview of advanced language modeling approaches and tools, including the use of document priors, translation models, relevance models, parsimonious models and expectation maximization training. Expert search will be used as a case study to explain the 94. (1)H NMR based metabolomics approach to study the toxic effects of herbicide butachlor on goldfish (Carassius auratus). Xu, Hua-Dong; Wang, Jun-Song; Li, Ming-Hui; Liu, Yan; Chen, Ting; Jia, Ai-Qun 2015-02-01 Butachlor, one of the most widely used herbicides in agriculture, has been reported with high ecotoxicity to aquatic plants and animals. In this study, a (1)H NMR based metabolomics approach combined with histopathological examination and biochemical assays was applied to comprehensively investigate the toxic effects of butachlor on four important organs (gill, brain, liver and kidney) of goldfish (Carassius auratus) for the first time. After 10 days' butachlor exposure at two dosages of 3.2 and 0.64 μmol/L, fish tissues (gill, brain, liver and kidney) and serum were collected. Histopathological inspection revealed severe impairment of gill filaments and obvious cellular edema in livers and kidneys. The increase of glutathione peroxidase (GSH-Px) activity in gill and methane dicarboxylic aldehyde (MDA) level in four tissues reflected the disturbance of antioxidative system in the intoxicated goldfish. Serum lactate dehydrogenase (LDH) activity and creatinine (CRE) level were increased in butachlor exposure groups, suggesting liver and kidney injuries induced by butachlor. Orthogonal signal correction partial least-squares discriminant analysis (OSC-PLS-DA) of NMR profiles disclosed metabolic changes that were related to the toxic effects of butachlor including oxidative stress, disorder of energy metabolism and amino acids metabolism, and disturbance of neurotransmitter balance in butachlor exposed goldfish. This integrated metabolomics approach provided a molecular basis underlying the toxicity of butachlor and demonstrated that metabolomics was a powerful and highly effective approach to elucidate the toxicity and underlying mechanisms of herbicides and pesticides, applicable for their risk assessment. 95. Petroacoustic Modelling of Heterolithic Sandstone Reservoirs: A Novel Approach to Gassmann Modelling Incorporating Sedimentological Constraints and NMR Porosity data Matthews, S.; Lovell, M.; Davies, S. J.; Pritchard, T.; Sirju, C.; Abdelkarim, A. 2012-12-01 includes a capillary bound water porosity component, is used. The novel approach attempts to better address this assumption through incorporation of NMR porosity data which distinguishes between bound water and free (movable) fluid components of porosity. The simplistic approach to heterolithic sandstone sedimentology, with poor linkage between petrophysical and sedimentological analyses and ignorance of model caveats, compounds petroacoustic modelling issues. This research uses a single well dataset comprising a log suite including NMR and OBMI data, together with extensive core data including core-NMR, SEM images and detailed sedimentological analysis. Integration of log and core data enables better insight to the key sedimentological properties influencing reservoir elastic properties. This approach improves understanding of key sedimentological properties affecting acoustic propagation in heterolithic sandstones and in turn provides better models for describing these important reservoirs. This contributes to enhanced seismic data interpretation of reservoir properties, including fluid saturations, during exploration and development phases. 96. Advanced Safeguards Approaches for New TRU Fuel Fabrication Facilities Durst, Philip C.; Ehinger, Michael H.; Boyer, Brian; Therios, Ike; Bean, Robert; Dougan, A.; Tolk, K. 2007-12-15 This second report in a series of three reviews possible safeguards approaches for the new transuranic (TRU) fuel fabrication processes to be deployed at AFCF – specifically, the ceramic TRU (MOX) fuel fabrication line and the metallic (pyroprocessing) line. The most common TRU fuel has been fuel composed of mixed plutonium and uranium dioxide, referred to as “MOXâ€. However, under the Advanced Fuel Cycle projects custom-made fuels with higher contents of neptunium, americium, and curium may also be produced to evaluate if these “minor actinides†can be effectively burned and transmuted through irradiation in the ABR. A third and final report in this series will evaluate and review the advanced safeguards approach options for the ABR. In reviewing and developing the advanced safeguards approach for the new TRU fuel fabrication processes envisioned for AFCF, the existing international (IAEA) safeguards approach at the Plutonium Fuel Production Facility (PFPF) and the conceptual approach planned for the new J-MOX facility in Japan have been considered as a starting point of reference. The pyro-metallurgical reprocessing and fuel fabrication process at EBR-II near Idaho Falls also provided insight for safeguarding the additional metallic pyroprocessing fuel fabrication line planned for AFCF. 97. A Global Approach to Accurate and Automatic Quantitative Analysis of NMR Spectra by Complex Least-Squares Curve Fitting Martin, Y. L. The performance of quantitative analysis of 1D NMR spectra depends greatly on the choice of the NMR signal model. Complex least-squares analysis is well suited for optimizing the quantitative determination of spectra containing a limited number of signals (20). From a general point of view it is concluded, on the basis of mathematical considerations and numerical simulations, that, in the absence of truncation of the free-induction decay, complex least-squares curve fitting either in the time or in the frequency domain and linearprediction methods are in fact nearly equivalent and give identical results. However, in the situation considered, complex least-squares analysis in the frequency domain is more flexible since it enables the quality of convergence to be appraised at every resonance position. An efficient data-processing strategy has been developed which makes use of an approximate conjugate-gradient algorithm. All spectral parameters (frequency, damping factors, amplitudes, phases, initial delay associated with intensity, and phase parameters of a baseline correction) are simultaneously managed in an integrated approach which is fully automatable. The behavior of the error as a function of the signal-to-noise ratio is theoretically estimated, and the influence of apodization is discussed. The least-squares curve fitting is theoretically proved to be the most accurate approach for quantitative analysis of 1D NMR data acquired with reasonable signal-to-noise ratio. The method enables complex spectral residuals to be sorted out. These residuals, which can be cumulated thanks to the possibility of correcting for frequency shifts and phase errors, extract systematic components, such as isotopic satellite lines, and characterize the shape and the intensity of the spectral distortion with respect to the Lorentzian model. This distortion is shown to be nearly independent of the chemical species, of the nature of the molecular site, and of the type of nucleus, but 98. (1)H NMR-based metabolomic approach for understanding the fermentation behaviors of wine yeast strains. Son, Hong-Seok; Hwang, Geum-Sook; Kim, Ki Myong; Kim, Eun-Young; van den Berg, Frans; Park, Won-Mok; Lee, Cherl-Ho; Hong, Young-Shick 2009-02-01 (1)H NMR spectroscopy coupled with multivariate statistical analysis was used for the first time to investigate metabolic changes in musts during alcoholic fermentation and wines during aging. Three Saccharomyces cerevisiae yeast strains (RC-212, KIV-1116, and KUBY-501) were also evaluated for their impacts on the metabolic changes in must and wine. Pattern recognition (PR) methods, including PCA, PLS-DA, and OPLS-DA scores plots, showed clear differences for metabolites among musts or wines for each fermentation stage up to 6 months. Metabolites responsible for the differentiation were identified as valine, 2,3-butanediol (2,3-BD), pyruvate, succinate, proline, citrate, glycerol, malate, tartarate, glucose, N-methylnicotinic acid (NMNA), and polyphenol compounds. PCA scores plots showed continuous movements away from days 1 to 8 in all musts for all yeast strains, indicating continuous and active fermentation. During alcoholic fermentation, the highest levels of 2,3-BD, succinate, and glycerol were found in musts with the KIV-1116 strain, which showed the fastest fermentation or highest fermentative activity of the three strains, whereas the KUBY-501 strain showed the slowest fermentative activity. This study highlights the applicability of NMR-based metabolomics for monitoring wine fermentation and evaluating the fermentative characteristics of yeast strains. 99. A Systematic Approach to Sensitivity Analysis of Fault Tolerant Systems in NMR Architecture Kourosh Aslansefat 2015-01-01 Full Text Available A fault tree illustrates the ways through which a system fails. It states different ways in which combination of faulty components result in an undesired event in the system. Being used in phases such as designing and exploiting industrial systems, and the designers able to evaluate the dependability attributes such as reliability, MTTF and sensitivity. In addition, in the mentioned ability, the fault tree is a systematic method for finding systems bottlenecks and weakness point. In spite of its extensive use in evaluating the reliability of systems, fault tree is rarely used in calculating sensitivity. In the last decade, few researches has been conducted in this field, however these methods are not applicable to large scale systems and are not systematic. This paper provides a systematic method for evaluating system sensitivity through fault tree. Then, it introduces sensitivity of NMR architecture as one of the common structures of fault tolerance which is used for enhancing systems’ reliability, safety and availability in industry. This article presents a comprehensive and parameterized formula for NMR structure's sensitivity. The presented method can be a great help for designing and exploiting reliable systems engineers in systematic and instant calculation of sensitivity by means of fault tree. 100. A robust approach to correct for pronounced errors in temperature measurements by controlling radiation damping feedback fields in solution NMR. Wolahan, Stephanie M; Li, Zhao; Hsu, Chao-Hsiung; Huang, Shing-Jong; Clubb, Robert; Hwang, Lian-Pin; Lin, Yung-Ya 2014-11-01 Accurate temperature measurement is a requisite for obtaining reliable thermodynamic and kinetic information in all NMR experiments. A widely used method to calibrate sample temperature depends on a secondary standard with temperature-dependent chemical shifts to report the true sample temperature, such as the hydroxyl proton in neat methanol or neat ethylene glycol. The temperature-dependent chemical shift of the hydroxyl protons arises from the sensitivity of the hydrogen-bond network to small changes in temperature. The frequency separation between the alkyl and the hydroxyl protons are then converted to sample temperature. Temperature measurements by this method, however, have been reported to be inconsistent and incorrect in modern NMR, particularly for spectrometers equipped with cryogenically-cooled probes. Such errors make it difficult or even impossible to study chemical exchange and molecular dynamics or to compare data acquired on different instruments, as is frequently done in biomolecular NMR. In this work, we identify the physical origins for such errors to be unequal amount of dynamical frequency shifts on the alkyl and the hydroxyl protons induced by strong radiation damping (RD) feedback fields. Common methods used to circumvent RD may not suppress such errors. A simple, easy-to-implement solution was demonstrated that neutralizes the RD effect on the frequency separation by a "selective crushing recovery" pulse sequence to equalize the transverse magnetization of both spin species. Experiments using cryoprobes at 500 MHz and 800 MHz demonstrated that this approach can effectively reduce the errors in temperature measurements from about ±4.0 K to within ±0.4 K in general. « 3 4 5 6 7 » « 4 5 6 7 8 » 101. NMR ANALYSIS OF MALE FATHEAD MINNOW URINARY METABOLITES: A POTENTIAL APPROACH FOR STUDYING IMPACTS OF CHEMICAL EXPOSURES The potential for profiling endogenous metabolites in urine from male fathead minnows (Pimephales promelas) to assess chemical exposures was explored using nuclear magnetic resonance (NMR) spectroscopy. Both one dimensional (1D) and two dimensional (2D) NMR spectroscopy w... 102. Deterministic and risk-informed approaches for safety analysis of advanced reactors: Part I, deterministic approaches Ahn, Sang Kyu [Korea Institute of Nuclear Safety, 19 Kusong-dong, Yuseong-gu, Daejeon 305-338 (Korea, Republic of); Kim, Inn Seock, E-mail: [email protected] [ISSA Technology, 21318 Seneca Crossing Drive, Germantown, MD 20876 (United States); Oh, Kyu Myung [Korea Institute of Nuclear Safety, 19 Kusong-dong, Yuseong-gu, Daejeon 305-338 (Korea, Republic of) 2010-05-15 The objective of this paper and a companion paper in this issue (part II, risk-informed approaches) is to derive technical insights from a critical review of deterministic and riskinformed safety analysis approaches that have been applied to develop licensing requirements for water-cooled reactors, or proposed for safety verification of the advanced reactor design. To this end, a review was made of a number of safety analysis approaches including those specified in regulatory guides and industry standards, as well as novel methodologies proposed for licensing of advanced reactors. This paper and the companion paper present the review insights on the deterministic and risk-informed safety analysis approaches, respectively. These insights could be used in making a safety case or developing a new licensing review infrastructure for advanced reactors including Generation IV reactors. 103. Relationships between 1H NMR Relaxation Data and Some Technological Parameters of Meat: A Chemometric Approach Brown, Robert J. S.; Capozzi, Francesco; Cavani, Claudio; Cremonini, Mauro A.; Petracci, Massimiliano; Placucci, Giuseppe 2000-11-01 In this paper chemometrics (ANOVA and PCR) is used to measure unbiased correlations between NMR spin-echo decays of pork M. Longissimus dorsi obtained through CarrPurcell-Meiboom-Gill (CPMG) experiments at low frequency (20 MHz) and the values of 14 technological parameters commonly used to assess pork meat quality. On the basis of the ANOVA results, it is also found that the CPMG decays of meat cannot be best interpreted with a "discrete" model (i.e., by expanding the decays in a series of a discrete number of exponential components, each with a different transverse relaxation time), but rather with a "continuous" model, by which a continuous distribution of T2's is allowed. The latter model also agrees with literature histological results. 104. Relationships between (1)H NMR relaxation data and some technological parameters of meat: a chemometric approach. Brown, R J; Capozzi, F; Cavani, C; Cremonini, M A; Petracci, M; Placucci, G 2000-11-01 In this paper chemometrics (ANOVA and PCR) is used to measure unbiased correlations between NMR spin-echo decays of pork M. Longissimus dorsi obtained through CarrPurcell-Meiboom-Gill (CPMG) experiments at low frequency (20 MHz) and the values of 14 technological parameters commonly used to assess pork meat quality. On the basis of the ANOVA results, it is also found that the CPMG decays of meat cannot be best interpreted with a "discrete" model (i.e., by expanding the decays in a series of a discrete number of exponential components, each with a different transverse relaxation time), but rather with a "continuous" model, by which a continuous distribution of T(2)'s is allowed. The latter model also agrees with literature histological results. Copyright 2000 Academic Press. 105. Probing into the Interaction of Nicotine and Bovine Submaxillary Mucin: NMR, Fluorescence, and FTIR Approaches Xiaoxiang Liao 2016-01-01 Full Text Available Nicotine, the important component of cigarette products, may have an impact on the oral environment after inhalation. The research of interaction between nicotine and bovine submaxillary mucin (BSM contributes to understand the binding mechanism of nicotine and BSM, and the effects of nicotine on the structure and function of the mucin. NMR data demonstrated that the interaction between nicotine and BSM did exist, and it was pyrrolidyl ring of nicotine playing the major role in the binding. The quenching mechanisms of nicotine and BSM in different pH were different: for acidic environment, the quenching was dynamic; while it became static in the alkaline circumstance. Synchronous fluorescence spectra indicated that nicotine had effect on the microenvironment of the Trp rather than Tyr residue. Meanwhile, the impact of nicotine on the conformation of BSM was also confirmed by 3D fluorescence and FTIR spectra. 106. Structural features of a bituminous coal and their changes during low-temperature oxidation and loss of volatiles investigated by advanced solid-state NMR spectroscopy Mao, J.-D.; Schimmelmann, A.; Mastalerz, Maria; Hatcher, P.G.; Li, Y. 2010-01-01 Quantitative and advanced 13C solid-state NMR techniques were employed to investigate (i) the chemical structure of a high volatile bituminous coal, as well as (ii) chemical structural changes of this coal after evacuation of adsorbed gases, (iii) during oxidative air exposure at room temperature, and (iv) after oxidative heating in air at 75 ??C. The solidstate NMR techniques employed in this study included quantitative direct polarization/magic angle spinning (DP/MAS) at a high spinning speed of 14 kHz, cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH, CH2, and CHn selection, 13C chemical shift anisotropy (CSA) filtering, two-dimensional (2D) 1H-13C heteronuclear correlation NMR (HETCOR), and 2D HETCOR with 1H spin diffusion. With spectral editing techniques, we identified methyl CCH 3, rigid and mobile methylene CCH2C, methine CCH, quaternary Cq, aromatic CH, aromatic carbons bonded to alkyls, small-sized condensed aromatic moieties, and aromatic C-O groups. With direct polarization combined with spectral-editing techniques, we quantified 11 different types of functional groups. 1H-13C 2D HETCOR NMR experiments indicated spatial proximity of aromatic and alkyl moieties in cross-linked structures. The proton spin diffusion experiments indicated that the magnetization was not equilibrated at a 1H spin diffusion time of 5 ms. Therefore, the heterogeneity in spatial distribution of different functional groups should be above 2 nm. Recoupled C-H long-range dipolar dephasing showed that the fraction of large charcoal-like clusters of polycondensed aromatic rings was relatively small. The exposure of this coal to atmospheric oxygen at room temperature for 6 months did not result in obvious chemical structural changes of the coal, whereas heating at 75 ??C in air for 10 days led to oxidation of coal and generated some COO groups. Evacuation removed most volatiles and caused a significant reduction in aliphatic signals in its DP 107. Benzocaine complexation with p-sulfonic acid calix[n]arene: experimental ((1) H-NMR) and theoretical approaches. Arantes, Lucas M; Varejão, Eduardo V V; Pelizzaro-Rocha, Karin J; Cereda, CÃntia M S; de Paula, Eneida; Lourenço, Maicon P; Duarte, Hélio A; Fernandes, Sergio A 2014-05-01 The aim of this work was to study the interaction between the local anesthetic benzocaine and p-sulfonic acid calix[n]arenes using NMR and theoretical calculations and to assess the effects of complexation on cytotoxicity of benzocaine. The architectures of the complexes were proposed according to (1) H NMR data (Job plot, binding constants, and ROESY) indicating details on the insertion of benzocaine in the cavity of the calix[n]arenes. The proposed inclusion compounds were optimized using the PM3 semiempirical method, and the electronic plus nuclear repulsion energy contributions were performed at the DFT level using the PBE exchange/correlation functional and the 6-311G(d) basis set. The remarkable agreement between experimental and theoretical approaches adds support to their use in the structural characterization of the inclusion complexes. In vitro cytotoxic tests showed that complexation intensifies the intrinsic toxicity of benzocaine, possibly by increasing the water solubility of the anesthetic and favoring its partitioning inside of biomembranes. 108. A systematic approach to obtain validated partial least square models for predicting lipoprotein subclasses from serum NMR spectra. Mihaleva, Velitchka V; van Schalkwijk, Daniël B; de Graaf, Albert A; van Duynhoven, John; van Dorsten, Ferdinand A; Vervoort, Jacques; Smilde, Age; Westerhuis, Johan A; Jacobs, Doris M 2014-01-07 A systematic approach is described for building validated PLS models that predict cholesterol and triglyceride concentrations in lipoprotein subclasses in fasting serum from a normolipidemic, healthy population. The PLS models were built on diffusion-edited (1)H NMR spectra and calibrated on HPLC-derived lipoprotein subclasses. The PLS models were validated using an independent test set. In addition to total VLDL, LDL, and HDL lipoproteins, statistically significant PLS models were obtained for 13 subclasses, including 5 VLDLs (particle size 64-31.3 nm), 4 LDLs (particle size 28.6-20.7 nm) and 4 HDLs (particle size 13.5-9.8 nm). The best models were obtained for triglycerides in VLDL (0.82 < Q(2)