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Sample records for 2-d nmr spectroscopy

  1. Ultrafast 2D NMR: an emerging tool in analytical spectroscopy.

    PubMed

    Giraudeau, Patrick; Frydman, Lucio

    2014-01-01

    Two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy is widely used in chemical and biochemical analyses. Multidimensional NMR is also witnessing increased use in quantitative and metabolic screening applications. Conventional 2D NMR experiments, however, are affected by inherently long acquisition durations, arising from their need to sample the frequencies involved along their indirect domains in an incremented, scan-by-scan nature. A decade ago, a so-called ultrafast (UF) approach was proposed, capable of delivering arbitrary 2D NMR spectra involving any kind of homo- or heteronuclear correlation, in a single scan. During the intervening years, the performance of this subsecond 2D NMR methodology has been greatly improved, and UF 2D NMR is rapidly becoming a powerful analytical tool experiencing an expanded scope of applications. This review summarizes the principles and main developments that have contributed to the success of this approach and focuses on applications that have been recently demonstrated in various areas of analytical chemistry--from the real-time monitoring of chemical and biochemical processes, to extensions in hyphenated techniques and in quantitative applications. PMID:25014342

  2. Ultrafast 2D NMR: An Emerging Tool in Analytical Spectroscopy

    NASA Astrophysics Data System (ADS)

    Giraudeau, Patrick; Frydman, Lucio

    2014-06-01

    Two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy is widely used in chemical and biochemical analyses. Multidimensional NMR is also witnessing increased use in quantitative and metabolic screening applications. Conventional 2D NMR experiments, however, are affected by inherently long acquisition durations, arising from their need to sample the frequencies involved along their indirect domains in an incremented, scan-by-scan nature. A decade ago, a so-called ultrafast (UF) approach was proposed, capable of delivering arbitrary 2D NMR spectra involving any kind of homo- or heteronuclear correlation, in a single scan. During the intervening years, the performance of this subsecond 2D NMR methodology has been greatly improved, and UF 2D NMR is rapidly becoming a powerful analytical tool experiencing an expanded scope of applications. This review summarizes the principles and main developments that have contributed to the success of this approach and focuses on applications that have been recently demonstrated in various areas of analytical chemistry—from the real-time monitoring of chemical and biochemical processes, to extensions in hyphenated techniques and in quantitative applications.

  3. NMR Analysis of Unknowns: An Introduction to 2D NMR Spectroscopy

    ERIC Educational Resources Information Center

    Alonso, David E.; Warren, Steven E.

    2005-01-01

    A study combined 1D (one-dimensional) and 2D (two-dimensional) NMR spectroscopy to solve structural organic problems of three unknowns, which include 2-, 3-, and 4-heptanone. Results showed [to the first power]H NMR and [to the thirteenth power]C NMR signal assignments for 2- and 3-heptanone were more challenging than for 4-heptanone owing to the…

  4. Fast acquisition of high-resolution 2D NMR spectroscopy in inhomogeneous magnetic fields

    NASA Astrophysics Data System (ADS)

    Lin, Liangjie; Wei, Zhiliang; Zeng, Qing; Yang, Jian; Lin, Yanqin; Chen, Zhong

    2016-05-01

    High-resolution nuclear magnetic resonance (NMR) spectroscopy plays an important role in chemical and biological analyses. In this study, we combine the J-coupling coherence transfer module with the echo-train acquisition technique for fast acquisition of high-resolution 2D NMR spectra in magnetic fields with unknown spatial variations. The proposed method shows satisfactory performance on a 5 mM ethyl 3-bromopropionate sample, under a 5-kHz (10 ppm at 11.7 T) B0 inhomogeneous field, as well as under varying degrees of pulse-flip-angle deviations. Moreover, a simulative ex situ NMR measurement is also conducted to show the effectiveness of the proposed pulse sequence.

  5. (13)C NMR assignments of regenerated cellulose from solid-state 2D NMR spectroscopy.

    PubMed

    Idström, Alexander; Schantz, Staffan; Sundberg, Johan; Chmelka, Bradley F; Gatenholm, Paul; Nordstierna, Lars

    2016-10-20

    From the assignment of the solid-state (13)C NMR signals in the C4 region, distinct types of crystalline cellulose, cellulose at crystalline surfaces, and disordered cellulose can be identified and quantified. For regenerated cellulose, complete (13)C assignments of the other carbon regions have not previously been attainable, due to signal overlap. In this study, two-dimensional (2D) NMR correlation methods were used to resolve and assign (13)C signals for all carbon atoms in regenerated cellulose. (13)C-enriched bacterial nanocellulose was biosynthesized, dissolved, and coagulated as highly crystalline cellulose II. Specifically, four distinct (13)C signals were observed corresponding to conformationally different anhydroglucose units: two signals assigned to crystalline moieties and two signals assigned to non-crystalline species. The C1, C4 and C6 regions for cellulose II were fully examined by global spectral deconvolution, which yielded qualitative trends of the relative populations of the different cellulose moieties, as a function of wetting and drying treatments. PMID:27474592

  6. Differentiation of enantiomers by 2D NMR spectroscopy at 1 T using residual dipolar couplings.

    PubMed

    Koos, Martin R M; Danieli, Ernesto; Casanova, Federico; Blümich, Bernhard; Luy, Burkhard

    2016-06-01

    Differentiating enantiomers using 2D bench-top NMR spectroscopy. Spectrometers working with permanent magnets at 1 T field strength allow the acquisition of 2D data sets. In conjunction with previously reported chiral alignment media, this setup allows the measurement of enantiomeric excess via residual dipolar couplings in stretched gelatine as a result of the reduced line width obtained by 2D J-resolved spectroscopy. PMID:25773020

  7. Stereochemistry of 16a-hydroxyfriedelin and 3-Oxo-16-methylfriedel-16-ene established by 2D NMR spectroscopy.

    PubMed

    Duarte, Lucienir Pains; Silva de Miranda, Roqueline Rodrigues; Rodrigues, Salomão Bento Vasconcelos; de Fátima Silva, Grácia Divina; Vieira Filho, Sidney Augusto; Knupp, Vagner Fernandes

    2009-01-01

    Friedelin (1), 3beta-friedelinol (2), 28-hydroxyfriedelin (3), 16alpha-hydroxyfriedelin (4), 30-hydroxyfriedelin (5) and 16alpha,28-dihydroxyfriedelin (6) were isolated through fractionation of the hexane extract obtained from branches of Salacia elliptica. After a week in CDCl(3) solution, 16alpha-hydroxyfriedelin (4) reacted turning into 3-oxo-16-methylfriedel-16-ene (7). This is the first report of a dehydration followed by a Nametkin rearrangement of a pentacyclic triterpene in CDCl(3) solution occurring in the NMR tube. These seven pentacyclic triterpenes was identified through NMR spectroscopy and the stereochemistry of compound 4 and 7 was established by 2D NMR (NOESY) spectroscopy and mass spectrometry (GC-MS). It is also the first time that all the (13)C-NMR and 2D NMR spectral data are reported for compounds 4 and 7. PMID:19214150

  8. Acid epimerization of 20-keto pregnane glycosides is determined by 2D-NMR spectroscopy.

    PubMed

    García, Víctor P

    2011-05-01

    Carbohydrates influence many essential biological events such as apoptosis, differentiation, tumor metastasis, cancer, neurobiology, immunology, development, host-pathogen interactions, diabetes, signal transduction, protein folding, and many other contexts. We now report on the structure determination of pregnane glycosides isolated from the aerial parts of Ceropegia fusca Bolle (Asclepiadaceae). The observation of cicatrizant, vulnerary and cytostatic activities in some humans and animals of Ceropegia fusca Bolle, a species endemic to the Canary Islands, encouraged us to begin a pharmacological study to determine their exact therapeutic properties. High resolution (1)H-NMR spectra of pregnane glycosides very often display well-resolved signals that can be used as starting points in several selective NMR experiments to study scalar (J coupling), and dipolar (NOE) interactions. ROESY is especially suited for molecules such that ωτ(c) ~ 1, where τ(c) are the motional correlation times and ω is the angular frequency. In these cases the NOE is nearly zero, while the rotating-frame Overhauser effect spectroscopy (ROESY) is always positive and increases monotonically for increasing values of τ(c). The ROESY shows dipolar interactions cross peaks even in medium-sized molecules which are helpful in unambiguous assignment of all the interglycosidic linkages. Selective excitation was carried out using a double pulsed-field gradient spin-echo sequence (DPFGSE) in which 180° Gaussian pulses are sandwiched between sine shaped z-gradients. Scalar interactions were studied by homonuclear DPFGSE-COSY and DPFGSE-TOCSY experiments, while DPFGSE-ROESY was used to monitor the spatial environment of the selectively excited proton. Dipolar interactions between nuclei close in space can be detected by the 1D GROESY experiment, which is a one-dimensional counterpart of the 2D ROESY method. The C-12 and C-17 configurations were determined by ROESY experiments. PMID:21431831

  9. Combined analysis of C-18 unsaturated fatty acids using natural abundance deuterium 2D NMR spectroscopy in chiral oriented solvents.

    PubMed

    Lesot, Philippe; Baillif, Vincent; Billault, Isabelle

    2008-04-15

    The quantitative determination of isotopic (2H/1H)i ratios at natural abundance using the SNIF-NMR protocol is a well-known method for understanding the enzymatic biosynthesis of metabolites. However, this approach is not always successful for analyzing large solutes and, specifically, is inadequate for prochiral molecules such as complete essential unsaturated fatty acids. To overcome these analytical limitations, we use the natural abundance deuterium 2D NMR (NAD 2D NMR) spectroscopy on solutes embedded in polypeptide chiral liquid crystals. This approach, recently explored for measuring (2H/1H)i ratios of small analytes (Lesot, P.; Aroulanda, C.; Billault, I. Anal. Chem. 2004, 76, 2827-2835), is a powerful way to separate the 2H signals of all nonequivalent enantioisotopomers on the basis both of the 2H quadrupolar interactions and of the 2H chemical shift. Two significant advances over our previous work are presented here and allow the complete isotopic analysis of four mono- and polyunsaturated fatty acid methyl esters: methyl oleate (1), methyl linoleate (2), methyl linolenate (3), and methyl vernoleate (4). The first consists of using NMR spectrometers operating at higher magnetic field strength (14.1 T) and equipped with a selective cryoprobe optimized for deuterium nuclei. The second is the development of Q-COSY Fz 2D NMR experiments able to produce phased 2H 2D maps after a double Fourier transformation. This combination of modern hardware and efficient NMR sequences provides a unique tool to analyze the (2H/1H)i ratios of large prochiral molecules (C-18) dissolved in organic solutions of poly(gamma-benzyl-L-glutamate) and requires smaller amounts of solute than previous study on fatty acids. For each compound (1-4), all 2H quadrupolar doublets visible in the 2D spectra have been assigned on the basis of 2H chemical shifts, isotopic data obtained from isotropic quantitative NAD NMR, and by an interspectral comparison of the anisotropic NAD spectra of four

  10. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    DOE PAGESBeta

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  11. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  12. 2D exchange 31P NMR spectroscopy of bacteriophage M13 and tobacco mosaic virus.

    PubMed Central

    Magusin, P C; Hemminga, M A

    1995-01-01

    Two-dimensional (2D) exchange 31P nuclear magnetic resonance spectroscopy is used to study the slow overall motion of the rod-shaped viruses M13 and tobacco mosaic virus in concentrated gels. Even for short mixing times, observed diagonal spectra differ remarkably from projection spectra and one-dimensional spectra. Our model readily explains this to be a consequence of the T2e anisotropy caused by slow overall rotation of the viruses about their length axis. 2D exchange spectra recorded for 30% (w/w) tobacco mosaic virus with mixing times < 1 s do not show any off-diagonal broadening, indicating that its overall motion occurs in the sub-Hz frequency range. In contrast, the exchange spectra obtained for 30% M13 show significant off-diagonal intensity for mixing times of 0.01 s and higher. A log-gaussian distribution around 25 Hz of overall diffusion coefficients mainly spread between 1 and 10(3) Hz faithfully reproduces the 2D exchange spectra of 30% M13 recorded at various mixing times in a consistent way. A small but notable change in diagonal spectra at increasing mixing time is not well accounted for by our model and is probably caused by 31P spin diffusion. PMID:7756532

  13. Interactions of sialic acid with phosphatidylcholine liposomes studied by 2D NMR spectroscopy.

    PubMed

    Timoszyk, Anna; Latanowicz, Lidia

    2013-01-01

    Biological membranes are complex systems which have attracted scientific interest for a long time and for various reasons. The sialic acid-liposome interactions at the molecular level depend on their hydro-lipophilic characteristics. The aim of the present study was to investigate the changes of conformation of the phospholipid (1,2-Diacyl-sn-glycero-3-phosphocholine) and sialic acid (2,8-(N-acetylneuraminic acid)) molecules and the type of interactions induced by the sialic acid molecules on membrane-like systems (liposomes) by 2D NMR (TOCSY, HETCOR, ROESY). The nature of the interaction of sialic acid with the model membrane depends on the structure of the phospholipid headgroups and the hydration of membrane. In ROESY spectra was observed the absence of dipole-dipole couplings within the choline head, between headgroups and glycerol, and between glycerol and fatty acid chains. It indicates an increase of the membrane dynamics in the presence of sialic acid. Moreover, the conformation of sialic acid molecule is changed in the presence of liposomes, which depends on stereochemistry of the chemical groups of the carbon atoms C7 and C8, and oxygen O8. The observed differences between the ROESY spectra of free and liposome bound sialic acid may be a consequence of a changed orientation of the pyranose ring from trans to gauche in the presence of liposomes. The sialic acid penetrate into the phospholipid bilayer to a sufficient depth to allow the dipole interaction. The present result that the correlation signal was found only between the methyl protons from the acetyl group of sialic acid and the methylene tail of phospholipid molecule in the ROESY spectrum indicates that the opposite end of the sialic acid molecule stays in the aqueous phase without interacting with membrane molecules. PMID:24364043

  14. Conformational studies of [Nphe5]SFTI-1 by means of 2D NMR spectroscopy in conjunction with molecular dynamics calculations

    NASA Astrophysics Data System (ADS)

    Brzozowski, K.; Stawikowski, M.; Ślusarz, R.; Sikorska, E.; Lesner, A.; Łęgowska, A.; Rolka, K.

    2015-11-01

    Trypsin inhibitor SFTI-1 is the smallest and the most potent among BBI inhibitors. It is also an interesting object for SAR studies since it is cyclic 14 amino acid molecule which additionally contains disulfide bridge. We showed that elimination of head-to-tail cycliztion did not influence its activity. Moreover peptoid monomers of Nlys and Nphe introduced in the substrate specificity P1 position of monocyclic SFTI-1 preserved trypsin and chymotripsin inhibitory activity respectively and made P1-P1‧ bond proteolytically stable. These findings motivated us to perform conformational analysis of [Nphe5]SFTI-1 by means of 2D NMR spectroscopy and molecular dynamics calculations. Obtained structure occurred to be in a good agreement with published structures for wild-type SFTI-1, its monocyclic analog with disulfide bridge only as well as one containing Nlys peptoid monomer in P1 position.

  15. GEL-STATE NMR OF BALL-MILLED WHOLE CELL WALLS IN DMSO-d6 USING 2D SOLUTION-STATE NMR SPECTROSCOPY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant cell walls were used for obtaining 2D solution-state NMR spectra without actual solubilization or structural modification. Ball-milled whole cell walls were swelled directly in the NMR tube with DMSO-d6 where they formed a gel. There are relatively few gel-state NMR studies. Most have involved...

  16. Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 2: 2D NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Deshmukh, Ashish P.; Pacheco, Carlos; Hay, Michael B.; Myneni, Satish C. B.

    2007-07-01

    Carboxyl groups are abundant in natural organic molecules (NOM) and play a major role in their reactivity. The structural environments of carboxyl groups in IHSS soil and river humic samples were investigated using 2D NMR (heteronuclear and homonuclear correlation) spectroscopy. Based on the 1H- 13C heteronuclear multiple-bond correlation (HMBC) spectroscopy results, the carboxyl environments in NOM were categorized as Type I (unsubstituted and alkyl-substituted aliphatic/alicyclic), Type II (functionalized carbon substituted), Type IIIa, b (heteroatom and olefin substituted), and Type IVa, b (5-membered heterocyclic aromatic and 6-membered aromatic). The most intense signal in the HMBC spectra comes from the Type I carboxyl groups, including the 2JCH and 3JCH couplings of unsubstituted aliphatic and alicyclic acids, though this spectral region also includes the 3JCH couplings of Type II and III structures. Type II and III carboxyls have small but detectable 2JCH correlations in all NOM samples except for the Suwannee River humic acid. Signals from carboxyls bonded to 5-membered aromatic heterocyclic fragments (Type IVa) are observed in the soil HA and Suwannee River FA, while correlations to 6-membered aromatics (Type IVb) are only observed in Suwannee River HA. In general, aromatic carboxylic acids may be present at concentrations lower than previously imagined in these samples. Vibrational spectroscopy results for these NOM samples, described in an accompanying paper [Hay M. B. and Myneni S. C. B. (2007) Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: Infrared spectroscopy. Geochim. Cosmochim. Acta (in press)], suggest that Type II and Type III carboxylic acids with α substituents (e.g., -OH, -OR, or -CO 2H) constitute the majority of carboxyl structures in all humic substances examined. Furoic and salicylic acid structures (Type IV) are also feasible fragments, albeit as minor constituents. The

  17. Two dimensional NMR spectroscopy

    SciTech Connect

    Schram, J.; Bellama, J.M.

    1988-01-01

    Two dimensional NMR represents a significant achievement in the continuing effort to increase solution in NMR spectroscopy. This book explains the fundamentals of this new technique and its analytical applications. It presents the necessary information, in pictorial form, for reading the ''2D NMR,'' and enables the practicing chemist to solve problems and run experiments on a commercial spectrometer by using the software provided by the manufacturer.

  18. Unraveling the heterogeneity in N butyl-N-methylpiperidinium trifluromethanesulfonimide ionic liquid by 1D and 2D NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tripathi, Neha; Saha, Satyen

    2014-06-01

    Room temperature ionic liquids are one of the most exciting classes of materials in the last decade. In particular piperidinium (PIP) cation based ionic liquid (IL) (such as PIP14NTf2) have found application in electrochemistry/batteries. In this Letter, 2D NMR (NOESY and HOESY) is employed for studying the interactions present between cations and anions. HOESY spectrum shows that fluorine of NTf2 unusually interacts with all proton of the cation (PIP14). Combined HOESY and NOESY indicate that NTf2 anion is distributed heterogeneously in liquid. Existence of micro heterogeneity in this important class of IL is proposed.

  19. Analytical contribution of NAD 2D-NMR spectroscopy in polypeptide mesophases to the investigation of triglycerides.

    PubMed

    Lesot, Philippe; Serhan, Zeinab; Aroulanda, Christie; Billault, Isabelle

    2012-12-01

    In this work, we report and discuss on the use and limitations of the natural abundance deuterium two-dimensional NMR spectroscopy in polypeptide chiral and achiral aligning media in the studies of homogenous triglycerides at 14.1 T. As illustrative examples, two triglycerides with short and long alkyl chains were investigated: the 1,3-di(butanoyloxy)propan-2-yl butanoate or tributyrin (TB) and the 1,3-di(tetradecanoyloxy)propan-2-yl tetradecanoate or trimyristin (TM). If both flexible compounds are theoretically of C(s) symmetry on average, according to the Altmann's definition (Proc. Roy. Soc., 1967, A298, 184.), the analysis of spectral data in terms of enantiotopic and diastereotopic discriminations shows noticeable differences related to their orientational ordering behavior inside the mesophases. Although from NMR analysis viewpoint, TB behaves as a C(s) symmetry molecule as expected, the NMR results obtained for TM suggest a behavior that could be formally predicted for a C(3v) symmetry molecule on average. This conclusion was nicely supported by the comparison with the tri-n-propylorthoformate, a real C(3v) symmetry solute on average on the NMR timescale. This difference of effective orientational behavior could originate from the difference of size and shape between lateral and central alkyl chains of the solute molecule. PMID:23280656

  20. Synthesis and Resolution of the Atropisomeric 1,1'-Bi-2-Naphthol: An Experiment in Organic Synthesis and 2-D NMR Spectroscopy

    ERIC Educational Resources Information Center

    Mak, Kendrew K. W.

    2004-01-01

    NMR spectroscopy is presented. It is seen that the experiment regarding the synthesis and resolution of 1,1'-Bi-2-naphtol presents a good experiment for teaching organic synthesis and NMR spectroscopy and provides a strategy for obtaining enantiopure compounds from achiral starting materials.

  1. 2D 31P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP7

    NASA Astrophysics Data System (ADS)

    Benndorf, Christopher; Hohmann, Andrea; Schmidt, Peer; Eckert, Hellmut; Johrendt, Dirk; Schäfer, Konrad; Pöttgen, Rainer

    2016-03-01

    Phase pure polycrystalline PbP7 was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1 mm were obtained. The assignment of the previously published 31P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency driven dipolar recoupling (RFDR) experiments. As commonly found in other solid polyphosphides there is no obvious correlation between the 31P chemical shift and structural parameters. PbP7 decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550 K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP7 as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s2 lone pairs in the electron localization function ELF.

  2. Two-dimensional NMR spectroscopy

    SciTech Connect

    Croasmun, W.R.; Carlson, R.M.K.

    1987-01-01

    Written for chemists and biochemists who are not NMR spectroscopists, but who wish to use the new techniques of two-dimensional NMR spectroscopy, this book brings together for the first time much of the practical and experimental data needed. It also serves as information source for industrial, academic, and graduate student researchers who already use NMR spectroscopy, but not yet in two dimensions. The authors describe the use of 2-D NMR in a wide variety of chemical and biochemical fields, among them peptides, steroids, oligo- and poly-saccharides, nucleic acids, natural products (including terpenoids, alkaloids, and coal-derived heterocyclics), and organic synthetic intermediates. They consider throughout the book both the advantages and limitations of using 2-D NMR.

  3. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-01

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological

  4. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-21

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D (1)H/(13)C/(1)H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond (13)C/(1)H and (13)C/(13)C chemical shift correlations, the 3D (1)H/(13)C/(1)H experiment also provides a COSY-type (1)H/(1)H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ((1)H/(1)H chemical shift correlation spectrum) at different (13)C chemical shift frequencies from the 3D (1)H/(13)C/(1)H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D (1)H/(13)C/(1)H experiment would be useful to study the structure and dynamics of

  5. Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations.

    PubMed

    Wang, Tuo; Yang, Hui; Kubicki, James D; Hong, Mei

    2016-06-13

    The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D (13)C-(13)C correlation spectra of uniformly (13)C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose (13)C chemical shifts differ significantly from the (13)C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing, and hydrogen bonding from celluloses of other organisms. 2D (13)C-(13)C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Celluloses f and g are well mixed chains on the microfibril surface, celluloses a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of

  6. In-Cell Protein Structures from 2D NMR Experiments.

    PubMed

    Müntener, Thomas; Häussinger, Daniel; Selenko, Philipp; Theillet, Francois-Xavier

    2016-07-21

    In-cell NMR spectroscopy provides atomic resolution insights into the structural properties of proteins in cells, but it is rarely used to solve entire protein structures de novo. Here, we introduce a paramagnetic lanthanide-tag to simultaneously measure protein pseudocontact shifts (PCSs) and residual dipolar couplings (RDCs) to be used as input for structure calculation routines within the Rosetta program. We employ this approach to determine the structure of the protein G B1 domain (GB1) in intact Xenopus laevis oocytes from a single set of 2D in-cell NMR experiments. Specifically, we derive well-defined GB1 ensembles from low concentration in-cell NMR samples (∼50 μM) measured at moderate magnetic field strengths (600 MHz), thus offering an easily accessible alternative for determining intracellular protein structures. PMID:27379949

  7. Study of the cyclodextrin and its complexation with 2,4-dinitrobenzoic acid through photophysical properties and 2D NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Stalin, T.; Srinivasan, K.; Sivakumar, K.

    2014-02-01

    The host-guest inclusion complex formation of 2,4-dinitrobenzoic acid (2,4-DNB) with nano-hydrophobic cavity of β-cyclodextrin (β-CD) in solution phase were studied by UV-visible spectrophotometer and electrochemical method (cyclic voltammetry, CV). The prototropic behaviors of 2,4-DNB with and without β-CD and the ground state acidity constant (pKa) of host-guest inclusion complex (2,4-DNB-β-CD) was studied. The binding constant of the inclusion complex at 303 K was calculated using Benesi-Hildebrand plot. The solid inclusion complex formation between β-CD and 2,4-DNB was confirmed by 1H NMR, 2D 1H NMR (ROESY), FT-IR, XRD and SEM analysis. A schematic representation of this inclusion process is proposed by molecular docking studies using the patch dock server.

  8. 2D NMR-spectroscopic screening reveals polyketides in ladybugs

    PubMed Central

    Deyrup, Stephen T.; Eckman, Laura E.; McCarthy, Patrick H.; Smedley, Scott R.; Meinwald, Jerrold; Schroeder, Frank C.

    2011-01-01

    Small molecules of biological origin continue to yield the most promising leads for drug design, but systematic approaches for exploring nature’s cache of structural diversity are lacking. Here, we demonstrate the use of 2D NMR spectroscopy to screen a library of biorationally selected insect metabolite samples for partial structures indicating the presence of new chemical entities. This NMR-spectroscopic survey enabled detection of novel compounds in complex metabolite mixtures without prior fractionation or isolation. Our screen led to discovery and subsequent isolation of two families of tricyclic pyrones in Delphastus catalinae, a tiny ladybird beetle that is employed commercially as a biological pest control agent. The D. catalinae pyrones are based on 23-carbon polyketide chains forming 1,11-dioxo-2,6,10-trioxaanthracene and 4,8-dioxo-1,9,13-trioxaanthracene derivatives, representing ring systems not previously found in nature. This study highlights the utility of 2D NMR-spectroscopic screening for exploring nature’s structure space and suggests that insect metabolomes remain vastly underexplored. PMID:21646540

  9. 2D NMR-spectroscopic screening reveals polyketides in ladybugs.

    PubMed

    Deyrup, Stephen T; Eckman, Laura E; McCarthy, Patrick H; Smedley, Scott R; Meinwald, Jerrold; Schroeder, Frank C

    2011-06-14

    Small molecules of biological origin continue to yield the most promising leads for drug design, but systematic approaches for exploring nature's cache of structural diversity are lacking. Here, we demonstrate the use of 2D NMR spectroscopy to screen a library of biorationally selected insect metabolite samples for partial structures indicating the presence of new chemical entities. This NMR-spectroscopic survey enabled detection of novel compounds in complex metabolite mixtures without prior fractionation or isolation. Our screen led to discovery and subsequent isolation of two families of tricyclic pyrones in Delphastus catalinae, a tiny ladybird beetle that is employed commercially as a biological pest control agent. The D. catalinae pyrones are based on 23-carbon polyketide chains forming 1,11-dioxo-2,6,10-trioxaanthracene and 4,8-dioxo-1,9,13-trioxaanthracene derivatives, representing ring systems not previously found in nature. This study highlights the utility of 2D NMR-spectroscopic screening for exploring nature's structure space and suggests that insect metabolomes remain vastly underexplored. PMID:21646540

  10. Hydrogen bonding induced distortion of CO3 units and kinetic stabilization of amorphous calcium carbonate: results from 2D (13)C NMR spectroscopy.

    PubMed

    Sen, Sabyasachi; Kaseman, Derrick C; Colas, Bruno; Jacob, Dorrit E; Clark, Simon M

    2016-07-27

    Systematic correlation in alkaline-earth carbonate compounds between the deviation of the CO3 units from the perfect D3h symmetry and their (13)C nuclear magnetic resonance (NMR) chemical shift anisotropy (CSA) parameters is established. The (13)C NMR CSA parameters of amorphous calcium carbonate (ACC) are measured using two-dimensional (13)C phase adjusted spinning sidebands (PASS) NMR spectroscopy and are analyzed on the basis of this correlation. The results indicate a distortion of the CO3 units in ACC in the form of an in-plane displacement of the C atom away from the centroid of the O3 triangle, resulting from hydrogen bonding with the surrounding H2O molecules, without significant out-of-plane displacement. Similar distortion for all C atoms in the structure of ACC suggests a uniform spatial disposition of H2O molecules around the CO3 units forming a hydrogen-bonded amorphous network. This amorphous network is stabilized against crystallization by steric frustration, while additives such as Mg presumably provide further stabilization by increasing the energy of dehydration. PMID:27276013

  11. Structural studies of an arabinan from the stems of Ephedra sinica by methylation analysis and 1D and 2D NMR spectroscopy.

    PubMed

    Xia, Yong-Gang; Liang, Jun; Yang, Bing-You; Wang, Qiu-Hong; Kuang, Hai-Xue

    2015-05-01

    Plant arabinan has important biological activity. In this study, a water-soluble arabinan (Mw∼6.15kDa) isolated from the stems of Ephedra sinica was found to consist of (1→5)-Araƒ, (1→3,5)-Araƒ, T-Araƒ, (1→3)-Araƒ and (1→2,5)-Araƒ residues at proportions of 10:2:3:2:1. A tentative structure was proposed by methylation analysis, nuclear magnetic resonance (NMR) spectroscopy ((1)H NMR, (13)C NMR, DEPT-135, (1)H-(1)H COSY, HSQC, HMBC and ROESY) and literature. The structure proposed includes a branched (1→5)-α-Araf backbone where branching occurs at the O-2 and O-3 positions of the residues with 7.7% and 15.4% of the 1,5-linked α-Araf substituted at the O-2 and O-3 positions. The presence of a branched structure was further observed by atomic force microscopy. This polymer was characterized as having a much longer linear (1→5)-α-Araf backbone as a repeating unit. In particular, the presence of α-Araf→3)-α-Araf-(1→3)-α-Araf-(1→ attached at the O-2 is a new finding. This study may facilitate a deeper understanding of structure-activity relationships of biological polysaccharides from the stems of E. sinica. PMID:25659720

  12. Intercalation complex of imidazoacridinone C-1311, a potential anticancer drug, with DNA helix d(CGATCG)2: stereostructural studies by 2D NMR spectroscopy.

    PubMed

    Laskowski, Tomasz; Czub, Jacek; Sowiński, Paweł; Mazerski, Jan

    2016-03-01

    Imidazoacridinone C-1311 (Symadex®) is a powerful antitumor agent, which successfully made its way through the Phase I clinical trials and has been recommended for Phase II few a years ago. It has been shown experimentally that during the initial stage of its action C-1311 forms a relatively stable intercalation complex with DNA, yet it has shown no base-sequence specificity while binding to DNA. In this paper, the d(CGATCG)2:C-1311 intercalation complex has been studied by means of two-dimensional NMR spectroscopy, yielding a full assignment of the resonance lines observed in (1)H NMR spectra. The observation of the intermolecular NOE contacts between C-1311 and DNA allowed locating the ligand between the guanine and adenine moieties. Formation of a symmetric complex was pointed out on the basis of the lack of a second set of the (1)H resonances. The resulting stereostructure of the complex was then improved by means of molecular dynamics, using the CHARMM force field and GROMACS software. To this end, distance restraints derived from the NOESY cross-peak volumes were applied to the atomistic model of the d(CGATCG)2:C-1311 complex. Obtained results are in full agreement with biochemical data on the mechanism of action of C-1311, in particular with the previously postulated post-intercalation enzymatic activation of the studied drug. PMID:26211888

  13. Enantiodiscrimination by NMR spectroscopy.

    PubMed

    Uccello-Barretta, Gloria; Balzano, Federica; Salvadori, Piero

    2006-01-01

    The analysis of enantiorecognition processes involves the detection of enantiomeric species as well as the study of chiral discrimination mechanisms. In both fields Nuclear Magnetic Resonance (NMR) spectroscopy plays a fundamental role, providing several tools, based on the use of suitable chiral auxiliaries, for observing distinct signals of enantiomers and for investigating the complexation phenomena involved in enantiodiscrimination processes. PMID:17100610

  14. Internal Photoemission Spectroscopy of 2-D Materials

    NASA Astrophysics Data System (ADS)

    Nguyen, Nhan; Li, Mingda; Vishwanath, Suresh; Yan, Rusen; Xiao, Shudong; Xing, Huili; Cheng, Guangjun; Hight Walker, Angela; Zhang, Qin

    Recent research has shown the great benefits of using 2-D materials in the tunnel field-effect transistor (TFET), which is considered a promising candidate for the beyond-CMOS technology. The on-state current of TFET can be enhanced by engineering the band alignment of different 2D-2D or 2D-3D heterostructures. Here we present the internal photoemission spectroscopy (IPE) approach to determine the band alignments of various 2-D materials, in particular SnSe2 and WSe2, which have been proposed for new TFET designs. The metal-oxide-2-D semiconductor test structures are fabricated and characterized by IPE, where the band offsets from the 2-D semiconductor to the oxide conduction band minimum are determined by the threshold of the cube root of IPE yields as a function of photon energy. In particular, we find that SnSe2 has a larger electron affinity than most semiconductors and can be combined with other semiconductors to form near broken-gap heterojunctions with low barrier heights which can produce a higher on-state current. The details of data analysis of IPE and the results from Raman spectroscopy and spectroscopic ellipsometry measurements will also be presented and discussed.

  15. A new inversion method for (T2, D) 2D NMR logging and fluid typing

    NASA Astrophysics Data System (ADS)

    Tan, Maojin; Zou, Youlong; Zhou, Cancan

    2013-02-01

    One-dimensional nuclear magnetic resonance (1D NMR) logging technology has some significant limitations in fluid typing. However, not only can two-dimensional nuclear magnetic resonance (2D NMR) provide some accurate porosity parameters, but it can also identify fluids more accurately than 1D NMR. In this paper, based on the relaxation mechanism of (T2, D) 2D NMR in a gradient magnetic field, a hybrid inversion method that combines least-squares-based QR decomposition (LSQR) and truncated singular value decomposition (TSVD) is examined in the 2D NMR inversion of various fluid models. The forward modeling and inversion tests are performed in detail with different acquisition parameters, such as magnetic field gradients (G) and echo spacing (TE) groups. The simulated results are discussed and described in detail, the influence of the above-mentioned observation parameters on the inversion accuracy is investigated and analyzed, and the observation parameters in multi-TE activation are optimized. Furthermore, the hybrid inversion can be applied to quantitatively determine the fluid saturation. To study the effects of noise level on the hybrid method and inversion results, the numerical simulation experiments are performed using different signal-to-noise-ratios (SNRs), and the effect of different SNRs on fluid typing using three fluid models are discussed and analyzed in detail.

  16. Isolation and characterization of a potential process related impurity of phenazopyridine HCl by preparative HPLC followed by MS-MS and 2D-NMR spectroscopy.

    PubMed

    Rao, R Nageswara; Maurya, Pawan K; Raju, A Narasa

    2009-07-12

    During the process development of phenazopyridine HCl bulk drug, a potential impurity was detected in the routine impurity profiles by HPLC. Using MS-MS and multidimensional NMR techniques, the trace level impurity was unambiguously identified to be 3-phenyl-5-phenylazo-pyridine-2,6-diamine after its isolation from phenazopyridine HCl by semi-preparative HPLC. The formation of the impurity was discussed. To our knowledge, it is a novel impurity not reported elsewhere. PMID:19376664

  17. Application of quantitative artificial neural network analysis to 2D NMR spectra of hydrocarbon mixtures.

    PubMed

    Väänänen, Taito; Koskela, Harri; Hiltunen, Yrjö; Ala-Korpela, Mika

    2002-01-01

    Understanding relationships between the structure and composition of molecular mixtures and their chemical properties is a main industrial aim. One central field of research is oil chemistry where the key question is how the molecular characteristics of composite hydrocarbon mixtures can be associated with the macroscopic properties of the oil products. Apparently these relationships are complex and often nonlinear and therefore call for advanced spectroscopic techniques. An informative and an increasingly used approach is two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy. In the case of composite hydrocarbons the application of 2D NMR methodologies in a quantitative manner pose many technical difficulties, and, in any case, the resulting spectra contain many overlapping resonances that challenge the analytical work. Here, we present a general methodology, based on quantitative artificial neural network (ANN) analysis, to resolve overlapping information in 2D NMR spectra and to simultaneously assess the relative importance of multiple spectral variables on the sample properties. The results in a set of 2D NMR spectra of oil samples illustrate, first, that use of ANN analysis for quantitative purposes is feasible also in 2D and, second, that this methodology offers an intrinsic opportunity to assess the complex and nonlinear relationships between the molecular composition and sample properties. The presented ANN methodology is not limited to the analysis of NMR spectra but can also be applied in a manner similar to other (multidimensional) spectroscopic data. PMID:12444730

  18. Characterization of Porous Medium Properties Using 2D NMR

    NASA Astrophysics Data System (ADS)

    Sun, Boqin; Dunn, Keh-Jim

    2003-03-01

    We have successfully applied the concept of 2D NMR to the characterization of properties of fluid-saturated porous medium. Using a two-windowed modified CPMG pulse sequence, we were able to explore the magnetic internal filed gradient distribution within the pore space of a fluid-saturated porous medium due to magnetic susceptibility contrast between the solid matrix and pore fluid. Similar scheme is used to identify and quantify different types of pore fluids, such as oil, water, and gas, based on the contrast in their diffusion coefficients. The magic angle spinning technique (MAS) can also be applied in the 2D NMR framework for delineating the chemical shift spectra of the pore fluids in a porous medium at different T1 or T2 relaxation times. The results can be displayed in a two-dimensional plot, with one axis being the T1 or T2 relaxation times, the other axis being the internal field gradient, diffusion coefficient, or chemical shift, and the third axis being the proton population. Our preliminary laboratory work indicates that the 2D NMR approach can be a powerful tool for the characterization of properties of fluid-saturated porous medium, such as fluid typing, oil viscosity determination, surface wettability, etc.

  19. Modern NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Jelinski, Lynn W.

    1984-01-01

    Discusses direct chemical information that can be obtained from modern nuclear magnetic resonance (NMR) methods, concentrating on the types of problems that can be solved. Shows how selected methods provide information about polymers, bipolymers, biochemistry, small organic molecules, inorganic compounds, and compounds oriented in a magnetic…

  20. Dolphin: a tool for automatic targeted metabolite profiling using 1D and 2D (1)H-NMR data.

    PubMed

    Gómez, Josep; Brezmes, Jesús; Mallol, Roger; Rodríguez, Miguel A; Vinaixa, Maria; Salek, Reza M; Correig, Xavier; Cañellas, Nicolau

    2014-12-01

    One of the main challenges in nuclear magnetic resonance (NMR) metabolomics is to obtain valuable metabolic information from large datasets of raw NMR spectra in a high throughput, automatic, and reproducible way. To date, established software packages used to match and quantify metabolites in NMR spectra remain mostly manually operated, leading to low resolution results and subject to inconsistencies not attributable to the NMR technique itself. Here, we introduce a new software package, called Dolphin, able to automatically quantify a set of target metabolites in multiple sample measurements using an approach based on 1D and 2D NMR techniques to overcome the inherent limitations of 1D (1)H-NMR spectra in metabolomics. Dolphin takes advantage of the 2D J-resolved NMR spectroscopy signal dispersion to avoid inconsistencies in signal position detection, enhancing the reliability and confidence in metabolite matching. Furthermore, in order to improve accuracy in quantification, Dolphin uses 2D NMR spectra to obtain additional information on all neighboring signals surrounding the target metabolite. We have compared the targeted profiling results of Dolphin, recorded from standard biological mixtures, with those of two well established approaches in NMR metabolomics. Overall, Dolphin produced more accurate results with the added advantage of being a fully automated and high throughput processing package. PMID:25370160

  1. "Solvent Effects" in 1H NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Cavaleiro, Jose A. S.

    1987-01-01

    Describes a simple undergraduate experiment in chemistry dealing with the "solvent effects" in nuclear magnetic resonance (NMR) spectroscopy. Stresses the importance of having students learn NMR spectroscopy as a tool in analytical chemistry. (TW)

  2. Studies of organic paint binders by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Spyros, A.; Anglos, D.

    2006-06-01

    Nuclear magnetic resonance spectroscopy is applied to the study of aged binding media used in paintings, namely linseed oil, egg tempera and an acrylic medium. High resolution 1D and 2D NMR experiments establish the state of hydrolysis and oxidation of the linseed and egg tempera binders after five years of aging, by determining several markers sensitive to the hydrolytic and oxidative processes of the binder lipid fraction. The composition of the acrylic binder co-polymer is determined by 2D NMR spectroscopy, while the identification of a surfactant, poly(ethylene glycol), found in greater amounts in aged acrylic medium, is reported. The non-destructive nature of the proposed analytical NMR methodology, and minimization of the amount of binder material needed through the use of sophisticated cryoprobes and hyphenated LC-NMR techniques, make NMR attractive for the arts analyst, in view of its rapid nature and experimental simplicity.

  3. Photocurrent spectroscopy of 2D materials

    NASA Astrophysics Data System (ADS)

    Cobden, David

    Confocal photocurrent measurements provide a powerful means of studying many aspects of the optoelectronic and electrical properties of a 2D device or material. At a diffraction-limited point they can provide a detailed absorption spectrum, and they can probe local symmetry, ultrafast relaxation rates and processes, electron-electron interaction strengths, and transport coefficients. We illustrate this with several examples, once being the photo-Nernst effect. In gapless 2D materials, such as graphene, in a perpendicular magnetic field a photocurrent antisymmetric in the field is generated near to the free edges, with opposite sign at opposite edges. Its origin is the transverse thermoelectric current associated with the laser-induced electron temperature gradient. This effect provides an unambiguous demonstration of the Shockley-Ramo nature of long-range photocurrent generation in gapless materials. It also provides a means of investigating quasiparticle properties. For example, in the case of graphene on hBN, it can be used to probe the Lifshitz transition that occurs due to the minibands formed by the Moire superlattice. We also observe and discuss photocurrent generated in other semimetallic (WTe2) and semiconducting (WSe2) monolayers. Work supported by DoE BES and NSF EFRI grants.

  4. Two-dimensional NMR spectroscopy. Applications for chemists and biochemists

    SciTech Connect

    Croasmun, W.R.; Carlson, R.M.K.

    1987-01-01

    Two-dimensional nuclear magnetic resonance spectroscopy (2-D NMR) has become a very powerful class of experiments (in the hands of an adept scientist) with broad adaptability to new situations. It is the product of a happy marriage between modern pulse FT-NMR technology, with its large memory and high-speed computers, and the physicists and chemists who love to manipulate spin systems. Basic 2-D experiments are now a standard capability of modern NMR spectrometers, and this timely book intends to make 2-D NMR users of those who are familiar with normal 1-D NMR. The 2-D NMR goal is correlation of the lines of the observed NMR spectrum with other properties of the system. This book deals with applications to high-resolution spectrum analysis, utilizing either coupling between the NMR-active nuclei or chemical exchange to perform the correlation. The coupling can be scalar (through bonds) or direct through space (within 5 A). The coupling may be homonuclear (between like nuclei) or heteronuclear.

  5. Hyperpolarized 131Xe NMR spectroscopy

    PubMed Central

    Stupic, Karl F.; Cleveland, Zackary I.; Pavlovskaya, Galina E.; Meersmann, Thomas

    2011-01-01

    Hyperpolarized (hp) 131Xe with up to 2.2% spin polarization (i.e., 5000-fold signal enhancement at 9.4 T) was obtained after separation from the rubidium vapor of the spin-exchange optical pumping (SEOP) process. The SEOP was applied for several minutes in a stopped-flow mode, and the fast, quadrupolar-driven T1 relaxation of this spin I = 3/2 noble gas isotope required a rapid subsequent rubidium removal and swift transfer into the high magnetic field region for NMR detection. Because of the xenon density dependent 131Xe quadrupolar relaxation in the gas phase, the SEOP polarization build-up exhibits an even more pronounced dependence on xenon partial pressure than that observed in 129Xe SEOP. 131Xe is the only stable noble gas isotope with a positive gyromagnetic ratio and shows therefore a different relative phase between hp signal and thermal signal compared to all other noble gases. The gas phase 131Xe NMR spectrum displays a surface and magnetic field dependent quadrupolar splitting that was found to have additional gas pressure and gas composition dependence. The splitting was reduced by the presence of water vapor that presumably influences xenon-surface interactions. The hp 131Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp 131Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I⩾1/2 nuclei is presented. PMID:21051249

  6. 1D and 2D NMR studies of isobornyl acrylate - Methyl methacrylate copolymers

    NASA Astrophysics Data System (ADS)

    Khandelwal, Deepika; Hooda, Sunita; Brar, A. S.; Shankar, Ravi

    2011-10-01

    Isobornyl acrylate - methyl methacrylate (B/M) copolymers of different compositions were synthesized by atom transfer radical polymerization (ATRP) using methyl-2-bromopropionate as an initiator and PMDETA copper complex as catalyst under nitrogen atmosphere at 70 °C. 1H NMR spectrum was used to determine the compositions of copolymer. The copolymer compositions were then used to determine the reactivity ratios of monomers. Reactivity ratios of co-monomers in B/M copolymer, determined from linear Kelen-Tudos method (KT) and non linear Error-in-Variable Method (EVM), are rB = 0.41 ± 0.11, rM = 1.11 ± 0.33 and rB = 0.52, rM = 1.31 respectively. The complete resonance assignments of 1H and 13C{ 1H} NMR spectra were carried out with the help of Distortion less Enhancement by Polarization Transfer (DEPT), two-dimensional Heteronuclear Single Quantum Coherence (HSQC). 2D HSQC assignments were further confirmed by 2D Total Correlation Spectroscopy (TOCSY). The carbonyl carbon of B and M units and methyl carbon of M unit were assigned up to triad compositional and configurational sequences whereas β-methylene carbons were assigned up to tetrad compositional and configurational sequences. Similarly the methine carbon of B unit was assigned up to pentad level. 1,3 and 1,4 bond order couplings of carbonyl carbon and quaternary carbon resonances with methine, methylene and methyl protons were studied in detail using 2D Hetero Nuclear Multiple Bond Correlation (HMBC) spectra.

  7. NMR Spectroscopy and Its Value: A Primer

    ERIC Educational Resources Information Center

    Veeraraghavan, Sudha

    2008-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is widely used by chemists. Furthermore, the use of NMR spectroscopy to solve structures of macromolecules or to examine protein-ligand interactions is popular. Yet, few students entering graduate education in biological sciences have been introduced to this method or its utility. Over the last six…

  8. Isolation and 2D NMR Studies of Alkaloids from Comptonella sessilifoliola1.

    PubMed

    Pusset, J; Lopez, J L; Pais, M; Neirabeyeh, M A; Veillon, J M

    1991-04-01

    Six known furanoquinoline alkaloids have been isolated from the wood and trunk bark of COMPTONELLA SESSILIFOLIOLA (Guillaumin) Hartley (Rutaceae). 2D NMR experiments gave the assignment of all the signals for both (1)H- and (13)C-NMR spectra. Pteleine and kokusaginine were used as models. The two-dimensional carbon-proton correlation experiments, performed for the first time on furanoquinoline alkaloids, led us to correct (13)C-NMR assignments previously described in the literature. PMID:17226139

  9. Novel stilbene-based Fischer base analog of leuco-TAM - (2E,2'Z)-{2-(4-(E)-styrylphenyl)propane-1,3-diylidene}bis(1,3,3-trimethylindoline) - derivatives: synthesis and structural consideration by 1D NMR and 2D NMR spectroscopy.

    PubMed

    Keum, Sam-Rok; Lim, Hyun-Woo

    2016-02-01

    We report the synthesis of a series of novel stilbene-based (St) Fischer base analogs of leuco-triarylmethane (LTAM) dyes by treating Fischer base with (E)-4-styrylbenzaldehyde derivatives. All St-LTAM molecules examined herein are characterized by 1D and 2D NMR. They were found to exhibit ZE configuration and isomerize to their diastereomers EE and ZZ in 2-3 h. They exhibit type I behavior of diastereomeric isomerization. PMID:26448377

  10. Application of high-performance liquid chromatography-nuclear magnetic resonance coupling to the identification of limonoids from mahogany tree (Switenia macrophylla, Meliaceae) by stopped-flow 1D and 2D NMR spectroscopy.

    PubMed

    Schefer, Alexandre B; Braumann, Ulrich; Tseng, Li-Hong; Spraul, Manfred; Soares, Marisi G; Fernandes, João B; da Silva, Maria F G F; Vieira, Paulo C; Ferreira, Antonio G

    2006-09-22

    Separation and characterization of limonoids from Switenia macrophylla (Meliaceae) by HPLC-NMR technique has been described. Analyses were carried out using reversed-phase gradient HPLC elution coupled to NMR (600 MHz) spectrometer in stopped-flow mode. Separated peaks were collected into an interface unit prior to NMR measurements, which were performed with suppression of solvent signals by shaped pulses sequences. Structure elucidation of the limonoids was attained by data obtained from 1H NMR, TOCSY, gHSQC and gHMBC spectra without conventional isolation that is usually applied in natural products studies. PMID:16904679

  11. Modern NMR spectroscopy: a guide for chemists

    SciTech Connect

    Sanders, J.K.M.; Hunter, B.K.

    1988-01-01

    The aim of the authors of Modern NMR Spectroscopy is to bridge the communication gap between the chemist and the spectroscopist. The approach is nonmathematical, descriptive, and pictorial. To illustrate the ideas introduced in the text, the authors provide original spectra obtained specially for this purpose. Examples include spectroscopy of protons, carbon, and less receptive nuclei of interest to inorganic chemists. The authors succeed in making high-resolution NMR spectroscopy comprehensible for the average student or chemist.

  12. Structural description of acid-denatured cytochrome c by hydrogen exchange and 2D NMR

    SciTech Connect

    Jeng, Meifen; Englander, S.W.; Elove, G.A.; Wand, A.J.; Roder, H. )

    1990-11-01

    Hydrogen exchange and two-dimensional nuclear magnetic resonance (2D NMR) techniques were used to characterize the structure of oxidized horse cytochrome c at acid pH and high ionic strength. Under these conditions, cytochrome c is known to assume a globular conformation (A state) with properties resembling those of the molten globule state described for other proteins. In order to measure the rate of hydrogen-deuterium exchange for individual backbone amide protons in the A state, samples of oxidized cytochrome c were incubated at 20 {degree}C in D{sub 2}O buffer for time periods ranging from 2 min to 500 h. The exchange reaction was then quenched by transferring the protein to native conditions. The extent of exchange for 44 amide protons trapped in the refolded protein was measured by 2D NMR spectroscopy. The results show that this approach can provide detailed information on H-bonded secondary and tertiary structure in partially folded equilibrium forms of a protein. All of the slowly exchanging amide protons in the three major helices of native cytochrome c are strongly protected from exchange at acid pH, indicating that the A state contains native-like elements of helical secondary structure. By contrast, a number of amide protons involved in irregular tertiary H-bonds of the native structure are only marginally protected in the A state, indicating that these H-bonds are unstable or absent. The H-exchange results suggest that the major helices of cytochrome c and their common hydrophobic domain are largely preserved in the globular acidic form while the loop region of the native structure is flexible and partly disordered.

  13. Scalable NMR spectroscopy with semiconductor chips

    PubMed Central

    Ha, Dongwan; Paulsen, Jeffrey; Sun, Nan; Song, Yi-Qiao; Ham, Donhee

    2014-01-01

    State-of-the-art NMR spectrometers using superconducting magnets have enabled, with their ultrafine spectral resolution, the determination of the structure of large molecules such as proteins, which is one of the most profound applications of modern NMR spectroscopy. Many chemical and biotechnological applications, however, involve only small-to-medium size molecules, for which the ultrafine resolution of the bulky, expensive, and high-maintenance NMR spectrometers is not required. For these applications, there is a critical need for portable, affordable, and low-maintenance NMR spectrometers to enable in-field, on-demand, or online applications (e.g., quality control, chemical reaction monitoring) and co-use of NMR with other analytical methods (e.g., chromatography, electrophoresis). As a critical step toward NMR spectrometer miniaturization, small permanent magnets with high field homogeneity have been developed. In contrast, NMR spectrometer electronics capable of modern multidimensional spectroscopy have thus far remained bulky. Complementing the magnet miniaturization, here we integrate the NMR spectrometer electronics into 4-mm2 silicon chips. Furthermore, we perform various multidimensional NMR spectroscopies by operating these spectrometer electronics chips together with a compact permanent magnet. This combination of the spectrometer-electronics-on-a-chip with a permanent magnet represents a useful step toward miniaturization of the overall NMR spectrometer into a portable platform. PMID:25092330

  14. Scalable NMR spectroscopy with semiconductor chips.

    PubMed

    Ha, Dongwan; Paulsen, Jeffrey; Sun, Nan; Song, Yi-Qiao; Ham, Donhee

    2014-08-19

    State-of-the-art NMR spectrometers using superconducting magnets have enabled, with their ultrafine spectral resolution, the determination of the structure of large molecules such as proteins, which is one of the most profound applications of modern NMR spectroscopy. Many chemical and biotechnological applications, however, involve only small-to-medium size molecules, for which the ultrafine resolution of the bulky, expensive, and high-maintenance NMR spectrometers is not required. For these applications, there is a critical need for portable, affordable, and low-maintenance NMR spectrometers to enable in-field, on-demand, or online applications (e.g., quality control, chemical reaction monitoring) and co-use of NMR with other analytical methods (e.g., chromatography, electrophoresis). As a critical step toward NMR spectrometer miniaturization, small permanent magnets with high field homogeneity have been developed. In contrast, NMR spectrometer electronics capable of modern multidimensional spectroscopy have thus far remained bulky. Complementing the magnet miniaturization, here we integrate the NMR spectrometer electronics into 4-mm(2) silicon chips. Furthermore, we perform various multidimensional NMR spectroscopies by operating these spectrometer electronics chips together with a compact permanent magnet. This combination of the spectrometer-electronics-on-a-chip with a permanent magnet represents a useful step toward miniaturization of the overall NMR spectrometer into a portable platform. PMID:25092330

  15. Quantum process tomography by 2D fluorescence spectroscopy

    SciTech Connect

    Pachón, Leonardo A.; Marcus, Andrew H.; Aspuru-Guzik, Alán

    2015-06-07

    Reconstruction of the dynamics (quantum process tomography) of the single-exciton manifold in energy transfer systems is proposed here on the basis of two-dimensional fluorescence spectroscopy (2D-FS) with phase-modulation. The quantum-process-tomography protocol introduced here benefits from, e.g., the sensitivity enhancement ascribed to 2D-FS. Although the isotropically averaged spectroscopic signals depend on the quantum yield parameter Γ of the doubly excited-exciton manifold, it is shown that the reconstruction of the dynamics is insensitive to this parameter. Applications to foundational and applied problems, as well as further extensions, are discussed.

  16. Numerical simulation of ( T 2, T 1) 2D NMR and fluid responses

    NASA Astrophysics Data System (ADS)

    Tan, Mao-Jin; Zou, You-Long; Zhang, Jin-Yan; Zhao, Xin

    2012-12-01

    One-dimensional nuclear magnetic resonance (1D NMR) logging technology is limited for fluid typing, while two-dimensional nuclear magnetic resonance (2D NMR) logging can provide more parameters including longitudinal relaxation time ( T 1) and transverse relaxation time ( T 2) relative to fluid types in porous media. Based on the 2D NMR relaxation mechanism in a gradient magnetic field, echo train simulation and 2D NMR inversion are discussed in detail. For 2D NMR inversion, a hybrid inversion method is proposed based on the damping least squares method (LSQR) and an improved truncated singular value decomposition (TSVD) algorithm. A series of spin echoes are first simulated with multiple waiting times ( T W s) in a gradient magnetic field for given fluid models and these synthesized echo trains are inverted by the hybrid method. The inversion results are consistent with given models. Moreover, the numerical simulation of various fluid models such as the gas-water, light oil-water, and vicious oil-water models were carried out with different echo spacings ( T E s) and T W s by this hybrid method. Finally, the influences of different signal-to-noise ratios (SNRs) on inversion results in various fluid models are studied. The numerical simulations show that the hybrid method and optimized observation parameters are applicable to fluid typing of gas-water and oil-water models.

  17. A Guided Inquiry Approach to NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    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.

  18. Gated cardiac NMR imaging and 2D echocardiography in the detection of intracardial neoplasm

    SciTech Connect

    Go, R.T.; O'Donnell, J.K.; Salcedo, E.E.; Feiglin, D.H.; Underwood, D.A.; MacIntyre, W.J.; Meaney, T.F.

    1985-05-01

    Noninvasive 2D echocardiography has replaced contrast angiography as the procedure of choice in the diagnosis of intracardiac neoplasm. The purpose of this study was to determine whether intracardiac neoplasm can be detected as well by gated cardiac NMR. Four patients with known intracardiac neoplasm previously diagnosed by 2D echocardiography had gated cardiac NMR imaging using a superconductive 0.6 Tesla magnet. All patients were performed using a Tl weighted spin echo pulse sequence with a TE of 30 msec and TR of one R-R interval. Two-dimensional planar single or multiple slice techniques were used. In one patient, imaging at different times along the R-R interval were performed for cine display. The results of the present study show detection of the intracardiac neoplasm in all four cases by gated cardiac NMR imaging and the results were comparable to 2D echocardiography. The former imaging technique showed superior spatial resolution. Despite its early stage of development, gated cardiac NMR imaging appears at least equal to 2D echocardiography in the detection of intracardiac neoplasm. The availability of multislice coupled with multiframe acquisition techniques now being developed will provide a cinematic display that will be more effective in the display of the tumor in motion within the cardiac chamber involved and facilitate visualization of the relationship of the tumor to adjacent cardiac structures.

  19. 2D NMR spectroscopic analyses of archangelicin from the seeds of Angelica archangelica.

    PubMed

    Muller, Melanie; Byres, Maureenx; Jaspars, Marcel; Kumarasamy, Yashodharan; Middleton, Moira; Nahar, Lutfun; Shoeb, Mohammad; Sarker, Satyajit D

    2004-12-01

    A total of six coumarins, bergapten (1), xanthotoxin (2), imperatorin (3), isoimperatorin (4), phellopterin (5) and archangelicin (6), have been isolated from an n-hexane extract of the seeds of Angelica archangelica. The results of comprehensive 2D NMR analyses of archangelicin are discussed. PMID:15634612

  20. A high-resolution 2D J-resolved NMR detection technique for metabolite analyses of biological samples

    PubMed Central

    Huang, Yuqing; Zhang, Zhiyong; Chen, Hao; Feng, Jianghua; Cai, Shuhui; Chen, Zhong

    2015-01-01

    NMR spectroscopy is a commonly used technique for metabolite analyses. Due to the observed macroscopic magnetic susceptibility in biological tissues, current NMR acquisitions in measurements of biological tissues are generally performed on tissue extracts using liquid NMR or on tissues using magic-angle spinning techniques. In this study, we propose an NMR method to achieve high-resolution J-resolved information for metabolite analyses directly from intact biological samples. A dramatic improvement in spectral resolution is evident in our contrastive demonstrations on a sample of pig brain tissue. Metabolite analyses for a postmortem fish from fresh to decayed statuses are presented to further reveal the capability of the proposed method. This method is a previously-unreported high-resolution 2D J-resolved spectroscopy for biological applications without specialised hardware requirements or complicated sample pretreatments. It provides a significant contribution to metabolite analyses of biological samples, and may be potentially applicable to in vivo samples. Furthermore, this method also can be applied to measurements of semisolid and viscous samples. PMID:25670027

  1. A high-resolution 2D J-resolved NMR detection technique for metabolite analyses of biological samples.

    PubMed

    Huang, Yuqing; Zhang, Zhiyong; Chen, Hao; Feng, Jianghua; Cai, Shuhui; Chen, Zhong

    2015-01-01

    NMR spectroscopy is a commonly used technique for metabolite analyses. Due to the observed macroscopic magnetic susceptibility in biological tissues, current NMR acquisitions in measurements of biological tissues are generally performed on tissue extracts using liquid NMR or on tissues using magic-angle spinning techniques. In this study, we propose an NMR method to achieve high-resolution J-resolved information for metabolite analyses directly from intact biological samples. A dramatic improvement in spectral resolution is evident in our contrastive demonstrations on a sample of pig brain tissue. Metabolite analyses for a postmortem fish from fresh to decayed statuses are presented to further reveal the capability of the proposed method. This method is a previously-unreported high-resolution 2D J-resolved spectroscopy for biological applications without specialised hardware requirements or complicated sample pretreatments. It provides a significant contribution to metabolite analyses of biological samples, and may be potentially applicable to in vivo samples. Furthermore, this method also can be applied to measurements of semisolid and viscous samples. PMID:25670027

  2. In situ fluid typing and quantification with 1D and 2D NMR logging.

    PubMed

    Sun, Boqin

    2007-05-01

    In situ nuclear magnetic resonance (NMR) fluid typing has recently gained momentum due to data acquisition and inversion algorithm enhancement of NMR logging tools. T(2) distributions derived from NMR logging contain information on bulk fluids and pore size distributions. However, the accuracy of fluid typing is greatly overshadowed by the overlap between T(2) peaks arising from different fluids with similar apparent T(2) relaxation times. Nevertheless, the shapes of T(2) distributions from different fluid components are often different and can be predetermined. Inversion with predetermined T(2) distributions allows us to perform fluid component decomposition to yield individual fluid volume ratios. Another effective method for in situ fluid typing is two-dimensional (2D) NMR logging, which results in proton population distribution as a function of T(2) relaxation time and fluid diffusion coefficient (or T(1) relaxation time). Since diffusion coefficients (or T(1) relaxation time) for different fluid components can be very different, it is relatively easy to separate oil (especially heavy oil) from water signal in a 2D NMR map and to perform accurate fluid typing. Combining NMR logging with resistivity and/or neutron/density logs provides a third method for in situ fluid typing. We shall describe these techniques with field examples. PMID:17466778

  3. Probing Cancer Cell Metabolism Using NMR Spectroscopy.

    PubMed

    Hollinshead, Kate E R; Williams, Debbie S; Tennant, Daniel A; Ludwig, Christian

    2016-01-01

    Altered cellular metabolism is now accepted to be at the core of many diseases including cancer. Over the past 20 years, NMR has become a core technology to study these metabolic perturbations in detail. This chapter reviews current NMR-based methods for steady-state metabolism and, in particular, the use of non-radioactive stable isotope-enriched tracers. Opportunities and challenges for each method, such as 1D (1)H NMR spectroscopy and (13)C carbon-based NMR spectroscopic methods, are discussed. Ultimately, the combination of NMR and mass spectra as orthogonal technologies are required to compensate for the drawbacks of each technique when used singly are discussed. PMID:27325263

  4. QUANTITATIVE 15N NMR SPECTROSCOPY

    EPA Science Inventory

    Line intensities in 15N NMR spectra are strongly influenced by spin-lattice and spin-spin relaxation times, relaxation mechanisms and experimental conditions. Special care has to be taken in using 15N spectra for quantitative purposes. Quantitative aspects are discussed for the 1...

  5. Broadband THz Spectroscopy of 2D Nanoscale Materials

    NASA Astrophysics Data System (ADS)

    Chen, Lu; Tripathi, Shivendra; Huang, Mengchen; Hsu, Jen-Feng; D'Urso, Brian; Lee, Hyungwoo; Eom, Chang-Beom; Irvin, Patrick; Levy, Jeremy

    Two-dimensional (2D) materials such as graphene and transition-metal dichalcogenides (TMDC) have attracted intense research interest in the past decade. Their unique electronic and optical properties offer the promise of novel optoelectronic applications in the terahertz regime. Recently, generation and detection of broadband terahertz (10 THz bandwidth) emission from 10-nm-scale LaAlO3/SrTiO3 nanostructures created by conductive atomic force microscope (c-AFM) lithography has been demonstrated . This unprecedented control of THz emission at 10 nm length scales creates a pathway toward hybrid THz functionality in 2D-material/LaAlO3/SrTiO3 heterostructures. Here we report initial efforts in THz spectroscopy of 2D nanoscale materials with resolution comparable to the dimensions of the nanowire (10 nm). Systems under investigation include graphene, single-layer molybdenum disulfide (MoS2), and tungsten diselenide (WSe2) nanoflakes. 1. Y. Ma, et al., Nano Lett. 13, 2884 (2013). We gratefully acknowledge financial support from the following agencies and grants: AFOSR (FA9550-12-1-0268 (JL, PRI), FA9550-12-1-0342 (CBE)), ONR (N00014-13-1-0806 (JL, CBE), N00014-15-1-2847 (JL)), NSF DMR-1124131 (JL, CBE) and DMR-1234096 (CBE).

  6. Optimizing water hyperpolarization and dissolution for sensitivity-enhanced 2D biomolecular NMR

    NASA Astrophysics Data System (ADS)

    Olsen, Greg; Markhasin, Evgeny; Szekely, Or; Bretschneider, Christian; Frydman, Lucio

    2016-03-01

    A recent study explored the use of hyperpolarized water, to enhance the sensitivity of nuclei in biomolecules thanks to rapid proton exchanges with labile amide backbone and sidechain groups. Further optimizations of this approach have now allowed us to achieve proton polarizations approaching 25% in the water transferred into the NMR spectrometer, effective water T1 times approaching 40 s, and a reduction in the dilution demanded for the cryogenic dissolution process. Further hardware developments have allowed us to perform these experiments, repeatedly and reliably, in 5 mm NMR tubes. All these ingredients - particularly the ⩾3000× 1H polarization enhancements over 11.7 T thermal counterparts, long T1 times and a compatibility with high-resolution biomolecular NMR setups - augur well for hyperpolarized 2D NMR studies of peptides, unfolded proteins and intrinsically disordered systems undergoing fast exchanges of their protons with the solvent. This hypothesis is here explored by detailing the provisions that lead to these significant improvements over previous reports, and demonstrating 1D coherence transfer experiments and 2D biomolecular HMQC acquisitions delivering NMR spectral enhancements of 100-500× over their optimized, thermally-polarized, counterparts.

  7. Optimizing water hyperpolarization and dissolution for sensitivity-enhanced 2D biomolecular NMR.

    PubMed

    Olsen, Greg; Markhasin, Evgeny; Szekely, Or; Bretschneider, Christian; Frydman, Lucio

    2016-03-01

    A recent study explored the use of hyperpolarized water, to enhance the sensitivity of nuclei in biomolecules thanks to rapid proton exchanges with labile amide backbone and sidechain groups. Further optimizations of this approach have now allowed us to achieve proton polarizations approaching 25% in the water transferred into the NMR spectrometer, effective water T1 times approaching 40s, and a reduction in the dilution demanded for the cryogenic dissolution process. Further hardware developments have allowed us to perform these experiments, repeatedly and reliably, in 5mm NMR tubes. All these ingredients--particularly the ⩾ 3000× (1)H polarization enhancements over 11.7T thermal counterparts, long T1 times and a compatibility with high-resolution biomolecular NMR setups - augur well for hyperpolarized 2D NMR studies of peptides, unfolded proteins and intrinsically disordered systems undergoing fast exchanges of their protons with the solvent. This hypothesis is here explored by detailing the provisions that lead to these significant improvements over previous reports, and demonstrating 1D coherence transfer experiments and 2D biomolecular HMQC acquisitions delivering NMR spectral enhancements of 100-500× over their optimized, thermally-polarized, counterparts. PMID:26920830

  8. Three-Dimensional Maximum-Quantum Correlation HMQC NMR Spectroscopy (3D MAXY-HMQC)

    NASA Astrophysics Data System (ADS)

    Liu, Maili; Mao, Xi-An; Ye, Chaohui; Nicholson, Jeremy K.; Lindon, John C.

    1997-11-01

    The extension of two-dimensional maximum-quantum correlation spectroscopy (2D MAXY NMR), which can be used to simplify complex NMR spectra, to three dimensions (3D) is described. A new pulse sequence for 3D MAXY-HMQC is presented and exemplified using the steroid drug dexamethasone. The sensitivity and coherence transfer efficiency of the MAXY NMR approach has also been assessed in relation to other HMQC- and HSQC-based 3D methods.

  9. Medical applications of NMR imaging and NMR spectroscopy with stable isotopes. Summary

    SciTech Connect

    Matwiyoff, N.A.

    1983-01-01

    The current status of NMR imaging and NMR spectroscopy are summarized. For the most part examples from the March 1983 Puerto Rico symposium are used to illustrate the utility of NMR in medicine. 18 refs., 5 figs.

  10. Epitope mapping by solution NMR spectroscopy.

    PubMed

    Bardelli, M; Livoti, E; Simonelli, L; Pedotti, M; Moraes, A; Valente, A P; Varani, L

    2015-06-01

    Antibodies play an ever more prominent role in basic research as well as in the biotechnology and pharmaceutical sectors. Characterizing their epitopes, that is, the region that they recognize on their target molecule, is useful for purposes ranging from molecular biology research to vaccine design and intellectual property protection. Solution NMR spectroscopy is ideally suited to the atomic level characterization of intermolecular interfaces and, as a consequence, to epitope discovery. Here, we illustrate how NMR epitope mapping can be used to rapidly and accurately determine protein antigen epitopes. The basic concept is that differences in the NMR signal of an antigen free or bound by an antibody will identify epitope residues. NMR epitope mapping provides more detailed information than mutagenesis or peptide mapping and can be much more rapid than X-ray crystallography. Advantages and drawbacks of this technique are discussed together with practical considerations. PMID:25726811

  11. Picoliter H-1 NMR Spectroscopy

    SciTech Connect

    Minard, Kevin R. ); Wind, Robert A. )

    2002-02-01

    A RF probe that fits inside the bore of a small gradient coil package is described for routine 1H-NMR microscopy measurements on small samples. The probe operates at 500 MHz and houses a 267-um-diameter solenoid transceiver. When used in three dimensional chemical shift imaging (3D-CSI) experiments, the measured signal-to-noise ratio (SNR) is shown to be within 20-30 percent of theoretical limits formulated by only considering the solenoid's resistive losses. This is illustrated using a 100-um-diameter globule of triacylglycerols ({approx}900mM) that may be an oocyte precursor in young Xenopus Laevis frogs, and water sample containing choline at a concentration often found in live cells ({approx}33mM). In chemical shift images generated using a few thousand scans, the choline methyl line is found to have an acceptable SNR in resolved from just 5 picoliters in the Xenopus globule. It is concluded that the probe's sensitivity is sufficient for performing 1H-NMR on picoliter-scale volumes in biological cells and tissues.

  12. An Introduction to Biological NMR Spectroscopy*

    PubMed Central

    Marion, Dominique

    2013-01-01

    NMR spectroscopy is a powerful tool for biologists interested in the structure, dynamics, and interactions of biological macromolecules. This review aims at presenting in an accessible manner the requirements and limitations of this technique. As an introduction, the history of NMR will highlight how the method evolved from physics to chemistry and finally to biology over several decades. We then introduce the NMR spectral parameters used in structural biology, namely the chemical shift, the J-coupling, nuclear Overhauser effects, and residual dipolar couplings. Resonance assignment, the required step for any further NMR study, bears a resemblance to jigsaw puzzle strategy. The NMR spectral parameters are then converted into angle and distances and used as input using restrained molecular dynamics to compute a bundle of structures. When interpreting a NMR-derived structure, the biologist has to judge its quality on the basis of the statistics provided. When the 3D structure is a priori known by other means, the molecular interaction with a partner can be mapped by NMR: information on the binding interface as well as on kinetic and thermodynamic constants can be gathered. NMR is suitable to monitor, over a wide range of frequencies, protein fluctuations that play a crucial role in their biological function. In the last section of this review, intrinsically disordered proteins, which have escaped the attention of classical structural biology, are discussed in the perspective of NMR, one of the rare available techniques able to describe structural ensembles. This Tutorial is part of the International Proteomics Tutorial Programme (IPTP 16 MCP). PMID:23831612

  13. Gint2D-T2 correlation NMR of porous media

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Blümich, Bernhard

    2015-03-01

    The internal magnetic field gradient induced in porous media by magnetic susceptibility differences at material interfaces impacts diffusion measurements in particular at high magnetic field and can be used to probe the pore structure. Insight about the relationship between pore space and internal gradient Gint can be obtained from 2D Laplace NMR experiments. When measuring distributions of transverse relaxation times T2 in fluid filled porous media, relaxation and diffusion in internal gradients arise simultaneously and data are often interpreted with the assumption that one or the other parameter be constant throughout the sample. To examine this assumption we measure correlations of the distributions of Gint2D and T2 by 2D Laplace NMR for three different kinds of samples, glass beads with different bead diameters saturated with water, glass beads filled with oil and water, and a wet mortar sample. For the first two samples the cases where either the internal gradient or diffusion dominates were examined separately in order to better understand the relationship between Gint and D. These results are useful for assessing the impact of internal gradients and diffusion in unknown samples, such as the mortar sample. The experiments were performed at different magnetic field strengths corresponding to 300 MHz and 700 MHz 1H Larmor frequency to identify the impact of the magnetic field on the internal gradient. Subsequently, spatially resolved Gint2D-T2 maps were obtained to study the sample heterogeneity.

  14. Gint2D-T2 correlation NMR of porous media.

    PubMed

    Zhang, Yan; Blümich, Bernhard

    2015-03-01

    The internal magnetic field gradient induced in porous media by magnetic susceptibility differences at material interfaces impacts diffusion measurements in particular at high magnetic field and can be used to probe the pore structure. Insight about the relationship between pore space and internal gradient G(int) can be obtained from 2D Laplace NMR experiments. When measuring distributions of transverse relaxation times T(2) in fluid filled porous media, relaxation and diffusion in internal gradients arise simultaneously and data are often interpreted with the assumption that one or the other parameter be constant throughout the sample. To examine this assumption we measure correlations of the distributions of G(int)(2)D and T(2) by 2D Laplace NMR for three different kinds of samples, glass beads with different bead diameters saturated with water, glass beads filled with oil and water, and a wet mortar sample. For the first two samples the cases where either the internal gradient or diffusion dominates were examined separately in order to better understand the relationship between G(int) and D. These results are useful for assessing the impact of internal gradients and diffusion in unknown samples, such as the mortar sample. The experiments were performed at different magnetic field strengths corresponding to 300 MHz and 700 MHz (1)H Larmor frequency to identify the impact of the magnetic field on the internal gradient. Subsequently, spatially resolved Gint(2)D-T(2) maps were obtained to study the sample heterogeneity. PMID:25723135

  15. Multidimensional NMR spectroscopy in a single scan.

    PubMed

    Gal, Maayan; Frydman, Lucio

    2015-11-01

    Multidimensional NMR has become one of the most widespread spectroscopic tools available to study diverse structural and functional aspects of organic and biomolecules. A main feature of multidimensional NMR is the relatively long acquisition times that these experiments demand. For decades, scientists have been working on a variety of alternatives that would enable NMR to overcome this limitation, and deliver its data in shorter acquisition times. Counting among these methodologies is the so-called ultrafast (UF) NMR approach, which in principle allows one to collect arbitrary multidimensional correlations in a single sub-second transient. By contrast to conventional acquisitions, a main feature of UF NMR is a spatiotemporal manipulation of the spins that imprints the chemical shift and/or J-coupling evolutions being sought, into a spatial pattern. Subsequent gradient-based manipulations enable the reading out of this information and its multidimensional correlation into patterns that are identical to those afforded by conventional techniques. The current review focuses on the fundamental principles of this spatiotemporal UF NMR manipulation, and on a few of the methodological extensions that this form of spectroscopy has undergone during the years. PMID:26249041

  16. Tritiation methods and tritium NMR spectroscopy

    SciTech Connect

    Jaiswal, D.K.; Morimoto, H.; Salijoughian, M.; Williams, P.G.

    1991-09-01

    We have used a simple process for the production of highly tritiated water and characterized the product species by {sup 1}H and {sup 3}H NMR spectroscopy. The water is readily manipulated and used in subsequent reactions either as T{sub 2}O, CH{sub 3}COOT or CF{sub 3}COOT. Development of tritiated diimide has progressed to the point where cis-hydrogenated products at 1-20 Ci/mmole S.A. are possible. Tri-n-butyl tin tritide has been produced at >95% tritium content and well characterized by multinuclear NMR techniques. 27 refs., 3 figs.

  17. Earle K. Plyler Prize for Molecular Spectroscopy and Dynamics Lecture: 2D IR Spectroscopy of Peptide Conformation

    NASA Astrophysics Data System (ADS)

    Tokmakoff, Andrei

    2012-02-01

    Descriptions of protein and peptide conformation are colored by the methods we use to study them. Protein x-ray and NMR structures often lead to impressions of rigid or well-defined conformations, even though these are dynamic molecules. The conformational fluctuations and disorder of proteins and peptides is more difficult to quantify. This presentation will describe an approach toward characterizing and quantifying structural heterogeneity and disorder in peptides using 2D IR spectroscopy. Using amide I vibrational spectroscopy, isotope labeling strategies, and computational modeling based on molecular dynamics simulations and Markov state models allows us to characterize distinct peptide conformers and conformational variation. The examples illustrated include the beta-hairpin tripzip2 and elastin-like peptides.

  18. Adsorption mechanism at the molecular level between polymers and uremic octapeptide by the 2D 1H NMR Technique.

    PubMed

    Li, Guohua; Li, Jihong; Wang, Wei; Yang, Mei; Zhang, Yuanwei; Sun, Pingchuan; Yuan, Zhi; He, Binglin; Yu, Yaoting

    2006-06-01

    To remove uremic octapeptide from the blood stream of uremic patients, various modified polyacylamide cross-linked absorbents were prepared. Adsorption experiments showed these absorbents have significant differences in adsorption capacity to the target peptide. In this paper, two-dimension proton nuclear magnetic resonance (2D 1H NMR) spectroscopy was used to investigate the interaction mechanism between the peptide and the adsorbents. Because of the insolubility of the absorbent, some soluble linear polymers with the same functional groups as the absorbents were employed as the model adsorbents in 2D 1H NMR. The preferred binding site for the peptide and polymers was identified to be at the C-terminal carboxyl group of the octapeptide via chemical shift perturbation effects. In this study, we found that hydrogen bonding, electrostatic, and hydrophobic interactions all play a role in the interaction force but had different contributions. Especially, the great chemical shift changes of the aromatic amino acid residues (Trp) during the interaction between butyl-modified polyacrylamide and octapeptide suggested the hydrophobic interaction, incorporated with the electrostatic force, played an important role in the binding reaction in aqueous solutions. This information not only rationally explained the results of the adsorption experiments, but also identified the effective binding site and mechanism, and shall provide a structural basis for designing better affinity-type adsorbents for the target peptide. PMID:16768402

  19. Real-time reaction monitoring by ultrafast 2D NMR on a benchtop spectrometer.

    PubMed

    Gouilleux, Boris; Charrier, Benoît; Danieli, Ernesto; Dumez, Jean-Nicolas; Akoka, Serge; Felpin, François-Xavier; Rodriguez-Zubiri, Mireia; Giraudeau, Patrick

    2015-12-01

    Reaction monitoring is widely used to follow chemical processes in a broad range of application fields. Recently, the development of robust benchtop NMR spectrometers has brought NMR under the fume hood, making it possible to monitor chemical reactions in a safe and accessible environment. However, these low-field NMR approaches suffer from limited resolution leading to strong peak overlaps, which can limit their application range. Here, we propose an approach capable of recording ultrafast 2D NMR spectra on a compact spectrometer and of following in real time reactions in the synthetic chemistry laboratory. This approach--whose potential is shown here on a Heck-Matsuda reaction--is highly versatile; the duration of the measurement can be optimized to follow reactions whose time scale ranges from between a few tens of seconds to a few hours. It makes it possible to monitor complex reactions in non-deuterated solvents, and to confirm in real time the molecular structure of the compounds involved in the reaction while giving access to relevant kinetic parameters. PMID:26501887

  20. Accelerated 2D magnetic resonance spectroscopy of single spins using matrix completion

    PubMed Central

    Scheuer, Jochen; Stark, Alexander; Kost, Matthias; Plenio, Martin B.; Naydenov, Boris; Jelezko, Fedor

    2015-01-01

    Two dimensional nuclear magnetic resonance (NMR) spectroscopy is one of the major tools for analysing the chemical structure of organic molecules and proteins. Despite its power, this technique requires long measurement times, which, particularly in the recently emerging diamond based single molecule NMR, limits its application to stable samples. Here we demonstrate a method which allows to obtain the spectrum by collecting only a small fraction of the experimental data. Our method is based on matrix completion which can recover the full spectral information from randomly sampled data points. We confirm experimentally the applicability of this technique by performing two dimensional electron spin echo envelope modulation (ESEEM) experiments on a two spin system consisting of a single nitrogen vacancy (NV) centre in diamond coupled to a single 13C nuclear spin. The signal to noise ratio of the recovered 2D spectrum is compared to the Fourier transform of randomly subsampled data, where we observe a strong suppression of the noise when the matrix completion algorithm is applied. We show that the peaks in the spectrum can be obtained with only 10% of the total number of the data points. We believe that our results reported here can find an application in all types of two dimensional spectroscopy, as long as the measured matrices have a low rank. PMID:26631593

  1. Accelerated 2D magnetic resonance spectroscopy of single spins using matrix completion

    NASA Astrophysics Data System (ADS)

    Scheuer, Jochen; Stark, Alexander; Kost, Matthias; Plenio, Martin B.; Naydenov, Boris; Jelezko, Fedor

    2015-12-01

    Two dimensional nuclear magnetic resonance (NMR) spectroscopy is one of the major tools for analysing the chemical structure of organic molecules and proteins. Despite its power, this technique requires long measurement times, which, particularly in the recently emerging diamond based single molecule NMR, limits its application to stable samples. Here we demonstrate a method which allows to obtain the spectrum by collecting only a small fraction of the experimental data. Our method is based on matrix completion which can recover the full spectral information from randomly sampled data points. We confirm experimentally the applicability of this technique by performing two dimensional electron spin echo envelope modulation (ESEEM) experiments on a two spin system consisting of a single nitrogen vacancy (NV) centre in diamond coupled to a single 13C nuclear spin. The signal to noise ratio of the recovered 2D spectrum is compared to the Fourier transform of randomly subsampled data, where we observe a strong suppression of the noise when the matrix completion algorithm is applied. We show that the peaks in the spectrum can be obtained with only 10% of the total number of the data points. We believe that our results reported here can find an application in all types of two dimensional spectroscopy, as long as the measured matrices have a low rank.

  2. Sodium ion effect on silk fibroin conformation characterized by solid-state NMR and generalized 2D NMR NMR correlation

    NASA Astrophysics Data System (ADS)

    Ruan, Qing-Xia; Zhou, Ping

    2008-07-01

    In the present work, we investigated Na + ion effect on the silk fibroin (SF) conformation. Samples are Na +-involved regenerated silk fibroin films. 13C CP-MAS NMR demonstrates that as added [Na +] increases, partial silk fibroin conformation transit from helix-form to β-form at certain Na + ion concentration which is much higher than that in Bombyx mori silkworm gland. The generalized two-dimensional NMR-NMR correlation analysis reveals that silk fibroin undergoes several intermediate states during its conformation transition process as [Na +] increase. The appearance order of the intermediates is followed as: helix and/or random coil → helix-like → β-sheet-like → β-sheet, which is the same as that produced by pH decrease from 6.8 to 4.8 in the resultant regenerated silk fibroin films. The binding sites of Na + to silk fibroin might involve the carbonyl oxygen atom of certain amino acids sequence which could promote the formation of β-sheet conformation. Since the Na +sbnd O bond is weak, the ability of Na + inducing the secondary structure transition is weaker than those of Ca 2+, Cu 2+ and even K +. It is maybe a reason why the sodium content is much lower than potassium in the silkworm gland.

  3. 2D NMR Methods for Structural Delineation of Copper(II) Complexes of Penicillin and Pilocarpine

    PubMed Central

    Gaggelli, Elena; Gaggelli, Nicola

    1994-01-01

    A method was developed for delineating the structure of paramagnetic metal complexes. The selective disappearance of cross-peaks in proton-carbon shift correlated 2D NMR maps was shown to uniquely depend upon the scalar and/or dipolar interaction between ligand nuclei and the unpaired electron(s), thus providing a means of identifying binding sites. Copper(II) was shown to form metal complexes with both Penicillin (PNC) and Pilocarpine (PLC) and the structure of the two 1:2 complexes in water solution at physiological pH were determined. PMID:18476239

  4. Dynamic UltraFast 2D EXchange SpectroscopY (UF-EXSY) of hyperpolarized substrates

    NASA Astrophysics Data System (ADS)

    Leon Swisher, Christine; Koelsch, Bertram; Sukumar, Subramianam; Sriram, Renuka; Santos, Romelyn Delos; Wang, Zhen Jane; Kurhanewicz, John; Vigneron, Daniel; Larson, Peder

    2015-08-01

    In this work, we present a new ultrafast method for acquiring dynamic 2D EXchange SpectroscopY (EXSY) within a single acquisition. This technique reconstructs two-dimensional EXSY spectra from one-dimensional spectra based on the phase accrual during echo times. The Ultrafast-EXSY acquisition overcomes long acquisition times typically needed to acquire 2D NMR data by utilizing sparsity and phase dependence to dramatically undersample in the indirect time dimension. This allows for the acquisition of the 2D spectrum within a single shot. We have validated this method in simulations and hyperpolarized enzyme assay experiments separating the dehydration of pyruvate and lactate-to-pyruvate conversion. In a renal cell carcinoma cell (RCC) line, bidirectional exchange was observed. This new technique revealed decreased conversion of lactate-to-pyruvate with high expression of monocarboxylate transporter 4 (MCT4), known to correlate with aggressive cancer phenotypes. We also showed feasibility of this technique in vivo in a RCC model where bidirectional exchange was observed for pyruvate-lactate, pyruvate-alanine, and pyruvate-hydrate and were resolved in time. Broadly, the technique is well suited to investigate the dynamics of multiple exchange pathways and applicable to hyperpolarized substrates where chemical exchange has shown great promise across a range of disciplines.

  5. Dynamic UltraFast 2D EXchange SpectroscopY (UF-EXSY) of hyperpolarized substrates

    PubMed Central

    Swisher, Christine Leon; Koelsch, Bertram; Sukumar, Subramianam; Sriram, Renuka; Santos, Romelyn Delos; Wang, Zhen Jane; Kurhanewicz, John; Vigneron, Daniel; Larson, Peder

    2015-01-01

    In this work, we present a new ultrafast method for acquiring dynamic 2D EXchange SpectroscopY (EXSY) within a single acquisition. This technique reconstructs two-dimensional EXSY spectra from one-dimensional spectra based on the phase accrual during echo times. The Ultrafast-EXSY acquisition overcomes long acquisition times typically needed to acquire 2D NMR data by utilizing sparsity and phase dependence to dramatically undersample in the indirect time dimension. This allows for the acquisition of the 2D spectrum within a single shot. We have validated this method in simulations and hyperpolarized enzyme assay experiments separating the dehydration of pyruvate and lactate-to-pyruvate conversion. In a renal cell carcinoma cell (RCC) line, bidirectional exchange was observed. This new technique revealed decreased conversion of lactate-to-pyruvate with high expression of monocarboxylate transporter 4 (MCT4), known to correlate with aggressive cancer phenotypes. We also showed feasibility of this technique in vivo in a RCC model where bidirectional exchange was observed for pyruvate–lactate, pyruvate–alanine, and pyruvate–hydrate and were resolved in time. Broadly, the technique is well suited to investigate the dynamics of multiple exchange pathways and applicable to hyperpolarized substrates where chemical exchange has shown great promise across a range of disciplines. PMID:26117655

  6. Differential Analysis of 2D NMR Spectra: New Natural Products from a Pilot-Scale Fungal Extract Library

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Using a newly developed protocol for the differential analysis of arrays of 2D NMR spectra, we were able to rapidly identify two previously unreported indole alkaloids from a library of unfractionated fungal extracts. Differential analyses of NMR spectra thus constitute an effective tool for the non...

  7. Two dimensional spectroscopy of Liquids in THz-domain: THz analogue of 2D Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Okumura, K.; Tanimura, Y.

    1998-03-01

    After the initial proposal(Y. Tanimura and S. Mukamel, J. Chem. Phys. 99, 9496 (1993)), the two dimensional Raman spectroscopy in the liquid phase has been received a considerable attention. Both experimental and theoretical activity of this field has been quite high. Since we have two controllable delay times, we can obtain more information than the lower-order experiments such as OKE. The new information includes that on heterogeneous distribution in liquids. Recently, it is found that the coupling between the modes in liquids can be investigated by the technique, both experimentally and theoretically(A. Tokmakoff, M.J. Lang, D.S. Larsen, G.R. Fleming, V. Chernyak, and S. Mukamel, Phys. Rev. Lett. (in press))^,(K. Okumura and Y. Tanimura, Chem. Phys. Lett. 278, 175 (1997)) In this talk, we will emphasize that we can perform the THz analogue of the 2D Raman spectroscopy if the THz short-pulse laser becomes available, which may not be in the far future. Theoretically, we can formulate this novel THz spectroscopy on the same footing as the 2D Raman spectroscopy. We will clarify new aspects of this technique comparing with the 2D Raman spectroscopy--- the reason it worth trying the tough experiment. See

  8. 2D NMR Barcoding and Differential Analysis of Complex Mixtures for Chemical Identification: The Actaea Triterpenes

    PubMed Central

    2015-01-01

    The interpretation of NMR spectroscopic information for structure elucidation involves decoding of complex resonance patterns that contain valuable molecular information (δ and J), which is not readily accessible otherwise. We introduce a new concept of 2D-NMR barcoding that uses clusters of fingerprint signals and their spatial relationships in the δ−δ coordinate space to facilitate the chemical identification of complex mixtures. Similar to widely used general barcoding technology, the structural information of individual compounds is encoded as a specifics pattern of their C,H correlation signals. Software-based recognition of these patterns enables the structural identification of the compounds and their discrimination in mixtures. Using the triterpenes from various Actaea (syn. Cimicifuga) species as a test case, heteronuclear multiple-bond correlation (HMBC) barcodes were generated on the basis of their structural subtypes from a statistical investigation of their δH and δC data in the literature. These reference barcodes allowed in silico identification of known triterpenes in enriched fractions obtained from an extract of A. racemosa (black cohosh). After dereplication, a differential analysis of heteronuclear single-quantum correlation (HSQC) spectra even allowed for the discovery of a new triterpene. The 2D barcoding concept has potential application in a natural product discovery project, allowing for the rapid dereplication of known compounds and as a tool in the search for structural novelty within compound classes with established barcodes. PMID:24673652

  9. 2D NMR barcoding and differential analysis of complex mixtures for chemical identification: the Actaea triterpenes.

    PubMed

    Qiu, Feng; McAlpine, James B; Lankin, David C; Burton, Ian; Karakach, Tobias; Chen, Shao-Nong; Pauli, Guido F

    2014-04-15

    The interpretation of NMR spectroscopic information for structure elucidation involves decoding of complex resonance patterns that contain valuable molecular information (δ and J), which is not readily accessible otherwise. We introduce a new concept of 2D-NMR barcoding that uses clusters of fingerprint signals and their spatial relationships in the δ-δ coordinate space to facilitate the chemical identification of complex mixtures. Similar to widely used general barcoding technology, the structural information of individual compounds is encoded as a specifics pattern of their C,H correlation signals. Software-based recognition of these patterns enables the structural identification of the compounds and their discrimination in mixtures. Using the triterpenes from various Actaea (syn. Cimicifuga) species as a test case, heteronuclear multiple-bond correlation (HMBC) barcodes were generated on the basis of their structural subtypes from a statistical investigation of their δH and δC data in the literature. These reference barcodes allowed in silico identification of known triterpenes in enriched fractions obtained from an extract of A. racemosa (black cohosh). After dereplication, a differential analysis of heteronuclear single-quantum correlation (HSQC) spectra even allowed for the discovery of a new triterpene. The 2D barcoding concept has potential application in a natural product discovery project, allowing for the rapid dereplication of known compounds and as a tool in the search for structural novelty within compound classes with established barcodes. PMID:24673652

  10. Novel 2D Triple-Resonance NMR Experiments for Sequential Resonance Assignments of Proteins

    NASA Astrophysics Data System (ADS)

    Ding, Keyang; Gronenborn, Angela M.

    2002-06-01

    We present 2D versions of the popular triple resonance HN(CO) CACB, HN(COCA)CACB, HN(CO)CAHA, and HN(COCA) CAHA experiments, commonly used for sequential resonance assignments of proteins. These experiments provide information about correlations between amino proton and nitrogen chemical shifts and the α- and β-carbon and α-proton chemical shifts within and between amino acid residues. Using these 2D spectra, sequential resonance assignments of H N, N, C α, C β, and H α nuclei are easily achieved. The resolution of these spectra is identical to the well-resolved 2D 15N- 1H HSQC and H(NCO)CA spectra, with slightly reduced sensitivity compared to their 3D and 4D versions. These types of spectra are ideally suited for exploitation in automated assignment procedures and thereby constitute a fast and efficient means for NMR structural determination of small and medium-sized proteins in solution in structural genomics programs.

  11. Protein Motions and Folding Investigated by NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Palmer, Arthur

    2002-03-01

    NMR spin relaxation spectroscopy is a powerful experimental approach for globally characterizing conformational dynamics of proteins in solution. Laboratory frame relaxation measurements are sensitive to overall rotational diffusion and internal motions on picosecond-nanosecond time scales, while rotating frame relaxation measurements are sensitive to chemical exchange processes on microsecond-millisecond time scales. The former approach is illustrated by ^15N laboratory-frame relaxation experiments as a function of temperature for the helical subdomain HP36 of the F-actin-binding headpiece domain of chicken villin. The data are analyzed using the model-free formalism to characterize order parameters and effective correlation times for intramolecular motions of individual ^15N sites. The latter approach is illustrated by ^13C Carr-Purcell-Meiboom-Gill relaxation measurements for the de novo designed α_2D protein and by ^15N rotating-frame relaxation measurements for the peripheral subunit-binding domain (PSBD) from the dihydrolopoamide acetyltransferase component of the pyruvate dehydrogenase multienzyme complex from Bacillus stearothermophilus. These experiments are used to determine the folding and unfolding kinetic rate constants for the two proteins. The results for HP36, α_2D, and PSBD illustrate the capability of current NMR methods for characterizing dynamic processes on multiple time scales in proteins.

  12. Protein Dynamics Studied with Ultrafast 2D IR Vibrational Echo Spectroscopy

    PubMed Central

    THIELGES, MEGAN C.; FAYER, MICHAEL D.

    2012-01-01

    CONSPECTUS Proteins, enzymes, and other biological molecules undergo structural dynamics as an intrinsic part of their biological functions. While many biological processes occur on the millisecond, second, and even longer time scales, the fundamental structural dynamics that eventually give rise to such processes occur on much faster time scales. Many decades ago, chemical kineticists focused on the inverse of the reaction rate constant as the important time scale for a chemical reaction. However, through transition state theory and a vast amount of experimental evidence, we now know that the key events in a chemical reaction can involve structural fluctuations that take a system of reactants to its transitions state, the crossing of a barrier, and the eventual relaxation to product states. Such dynamics occur on very fast time scales. Today researchers would like to investigate the fast structural fluctuations of biological molecules to gain an understanding of how biological processes proceed from simple structural changes in biomolecules to the final, complex biological function. The study of the fast structural dynamics of biological molecules requires experiments that operate on the appropriate time scales, and in this Account, we discuss the application of ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy to the study of dynamics. The 2D IR vibrational echo experiment is akin to 2D NMR, but it operates on time scales many orders of magnitude faster. In the experiments, a particular vibrational oscillator serves as a vibrational dynamics probe. As the structure of the protein evolves in time, the structural changes are manifested as time dependent changes in the frequency of the vibrational dynamics probe. The 2D IR vibrational echo experiments can track the vibrational frequency evolution, which we then relate to the time evolution of the protein structure. In particular, we measured protein substate interconversion for mutants of

  13. Theory for spiralling ions for 2D FT-ICR and comparison with precessing magnetization vectors in 2D NMR.

    PubMed

    Sehgal, Akansha Ashvani; Pelupessy, Philippe; Rolando, Christian; Bodenhausen, Geoffrey

    2016-04-01

    Two-dimensional (2D) Fourier transform ion cyclotron resonance (FT-ICR) offers an approach to mass spectrometry (MS) that pursuits similar objectives as MS/MS experiments. While the latter must focus on one ion species at a time, 2D FT ICR can examine all possible correlations due to ion fragmentation in a single experiment: correlations between precursors, charged and neutral fragments. We revisited the original 2D FT-ICR experiment that has hitherto fallen short of stimulating significant analytical applications, probably because it is technically demanding. These shortcomings can now be overcome by improved FT-ICR instrumentation and computer hard- and software. We seek to achieve a better understanding of the intricacies of the behavior of ions during a basic two-dimensional ICR sequence comprising three simple monochromatic pulses. Through simulations based on Lorentzian equations, we have mapped the ion trajectories for different pulse durations and phases. PMID:26974979

  14. Confirming the 3D Solution Structure of a Short Double-Stranded DNA Sequence Using NMR Spectroscopy

    ERIC Educational Resources Information Center

    Ruhayel, Rasha A.; Berners-Price, Susan J.

    2010-01-01

    2D [superscript 1]H NOESY NMR spectroscopy is routinely used to give information on the closeness of hydrogen atoms through space. This work is based on a 2D [superscript 1]H NOESY NMR spectrum of a 12 base-pair DNA duplex. This 6-h laboratory workshop aims to provide advanced-level chemistry students with a basic, yet solid, understanding of how…

  15. Chemical Shifts to Metabolic Pathways: Identifying Metabolic Pathways Directly from a Single 2D NMR Spectrum.

    PubMed

    Dubey, Abhinav; Rangarajan, Annapoorni; Pal, Debnath; Atreya, Hanudatta S

    2015-12-15

    Identifying cellular processes in terms of metabolic pathways is one of the avowed goals of metabolomics studies. Currently, this is done after relevant metabolites are identified to allow their mapping onto specific pathways. This task is daunting due to the complex nature of cellular processes and the difficulty in establishing the identity of individual metabolites. We propose here a new method: ChemSMP (Chemical Shifts to Metabolic Pathways), which facilitates rapid analysis by identifying the active metabolic pathways directly from chemical shifts obtained from a single two-dimensional (2D) [(13)C-(1)H] correlation NMR spectrum without the need for identification and assignment of individual metabolites. ChemSMP uses a novel indexing and scoring system comprised of a "uniqueness score" and a "coverage score". Our method is demonstrated on metabolic pathways data from the Small Molecule Pathway Database (SMPDB) and chemical shifts from the Human Metabolome Database (HMDB). Benchmarks show that ChemSMP has a positive prediction rate of >90% in the presence of decluttered data and can sustain the same at 60-70% even in the presence of noise, such as deletions of peaks and chemical shift deviations. The method tested on NMR data acquired for a mixture of 20 amino acids shows a success rate of 93% in correct recovery of pathways. When used on data obtained from the cell lysate of an unexplored oncogenic cell line, it revealed active metabolic pathways responsible for regulating energy homeostasis of cancer cells. Our unique tool is thus expected to significantly enhance analysis of NMR-based metabolomics data by reducing existing impediments. PMID:26556218

  16. Simulation of 2D NMR Spectra of Carbohydrates Using GODESS Software.

    PubMed

    Kapaev, Roman R; Toukach, Philip V

    2016-06-27

    Glycan Optimized Dual Empirical Spectrum Simulation (GODESS) is a web service, which has been recently shown to be one of the most accurate tools for simulation of (1)H and (13)C 1D NMR spectra of natural carbohydrates and their derivatives. The new version of GODESS supports visualization of the simulated (1)H and (13)C chemical shifts in the form of most 2D spin correlation spectra commonly used in carbohydrate research, such as (1)H-(1)H TOCSY, COSY/COSY-DQF/COSY-RCT, and (1)H-(13)C edHSQC, HSQC-COSY, HSQC-TOCSY, and HMBC. Peaks in the simulated 2D spectra are color-coded and labeled according to the signal assignment and can be exported in JCAMP-DX format. Peak widths are estimated empirically from the structural features. GODESS is available free of charge via the Internet at the platform of the Carbohydrate Structure Database project ( http://csdb.glycoscience.ru ). PMID:27227420

  17. Access to NMR Spectroscopy for Two-Year College Students: The NMR Site at Trinity University

    ERIC Educational Resources Information Center

    Mills, Nancy S.; Shanklin, Michael

    2011-01-01

    Students at two-year colleges and small four-year colleges have often obtained their exposure to NMR spectroscopy through "canned" spectra because the cost of an NMR spectrometer, particularly a high-field spectrometer, is prohibitive in these environments. This article describes the design of a NMR site at Trinity University in which spectral…

  18. Rapid characterization of molecular diffusion by NMR spectroscopy.

    PubMed

    Pudakalakatti, Shivanand M; Chandra, Kousik; Thirupathi, Ravula; Atreya, Hanudatta S

    2014-11-24

    An NMR-based approach for rapid characterization of translational diffusion of molecules has been developed. Unlike the conventional method of acquiring a series of 2D (13)C and (1)H spectra, the proposed approach involves a single 2D NMR spectrum, which can be acquired in minutes. Using this method, it was possible to detect the presence of intermediate oligomeric species of diphenylalanine in solution during the process of its self-assembly to form nanotubular structures. PMID:25331210

  19. Solution conformation of 2-aminopurine (2-AP) dinucleotide determined by ultraviolet 2D fluorescence spectroscopy (UV-2D FS)

    PubMed Central

    Widom, Julia R.; Johnson, Neil P.; von Hippel, Peter H.; Marcus, Andrew H.

    2013-01-01

    We have observed the conformation-dependent electronic coupling between the monomeric subunits of a dinucleotide of 2-aminopurine (2-AP), a fluorescent analog of the nucleic acid base adenine. This was accomplished by extending two-dimensional fluorescence spectroscopy (2D FS) – a fluorescence-detected variation of 2D electronic spectroscopy – to excite molecular transitions in the ultraviolet (UV) regime. A collinear sequence of four ultrafast laser pulses centered at 323 nm was used to resonantly excite the coupled transitions of 2-AP dinucleotide. The phases of the optical pulses were continuously swept at kilohertz frequencies, and the ensuing nonlinear fluorescence was phase-synchronously detected at 370 nm. Upon optimization of a point-dipole coupling model to our data, we found that in aqueous buffer the 2-AP dinucleotide adopts an average conformation in which the purine bases are non-helically stacked (center-to-center distance R12 = 3.5 Å ± 0.5 Å, twist angle θ12 = 5° ± 5°), which differs from the conformation of such adjacent bases in duplex DNA. These experiments establish UV-2D FS as a method for examining the local conformations of an adjacent pair of fluorescent nucleotides substituted into specific DNA or RNA constructs, which will serve as a powerful probe to interpret, in structural terms, biologically significant local conformational changes within the nucleic acid framework of protein-nucleic acid complexes. PMID:24223491

  20. Human erythrocytes analyzed by generalized 2D Raman correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Wesełucha-Birczyńska, Aleksandra; Kozicki, Mateusz; Czepiel, Jacek; Łabanowska, Maria; Nowak, Piotr; Kowalczyk, Grzegorz; Kurdziel, Magdalena; Birczyńska, Malwina; Biesiada, Grażyna; Mach, Tomasz; Garlicki, Aleksander

    2014-07-01

    The most numerous elements of the blood cells, erythrocytes, consist mainly of two components: homogeneous interior filled with hemoglobin and closure which is the cell membrane. To gain insight into their specific properties we studied the process of disintegration, considering these two constituents, and comparing the natural aging process of human healthy blood cells. MicroRaman spectra of hemoglobin within the single RBC were recorded using 514.5, and 785 nm laser lines. The generalized 2D correlation method was applied to analyze the collected spectra. The time passed from blood donation was regarded as an external perturbation. The time was no more than 40 days according to the current storage limit of blood banks, although, the average RBC life span is 120 days. An analysis of the prominent synchronous and asynchronous cross peaks allow us to get insight into the mechanism of hemoglobin decomposition. Appearing asynchronous cross-peaks point towards globin and heme separation from each other, while synchronous shows already broken globin into individual amino acids. Raman scattering analysis of hemoglobin “wrapping”, i.e. healthy erythrocyte ghosts, allows for the following peculiarity of their behavior. The increasing power of the excitation laser induced alterations in the assemblage of membrane lipids. 2D correlation maps, obtained with increasing laser power recognized as an external perturbation, allows for the consideration of alterations in the erythrocyte membrane structure and composition, which occurs first in the proteins. Cross-peaks were observed indicating an asynchronous correlation between the senescent-cell antigen (SCA) and heme or proteins vibrations. The EPR spectra of the whole blood was analyzed regarding time as an external stimulus. The 2D correlation spectra points towards participation of the selected metal ion centers in the disintegration process.

  1. Exploring RNA polymerase regulation by NMR spectroscopy

    PubMed Central

    Drögemüller, Johanna; Strauß, Martin; Schweimer, Kristian; Wöhrl, Birgitta M.; Knauer, Stefan H.; Rösch, Paul

    2015-01-01

    RNA synthesis is a central process in all organisms, with RNA polymerase (RNAP) as the key enzyme. Multisubunit RNAPs are evolutionary related and are tightly regulated by a multitude of transcription factors. Although Escherichia coli RNAP has been studied extensively, only little information is available about its dynamics and transient interactions. This information, however, are crucial for the complete understanding of transcription regulation in atomic detail. To study RNAP by NMR spectroscopy we developed a highly efficient procedure for the assembly of active RNAP from separately expressed subunits that allows specific labeling of the individual constituents. We recorded [1H,13C] correlation spectra of isoleucine, leucine, and valine methyl groups of complete RNAP and the separately labeled β’ subunit within reconstituted RNAP. We further produced all RNAP subunits individually, established experiments to determine which RNAP subunit a certain regulator binds to, and identified the β subunit to bind NusE. PMID:26043358

  2. Spatially resolved spectroscopy using tapered stripline NMR

    NASA Astrophysics Data System (ADS)

    Tijssen, Koen C. H.; Bart, Jacob; Tiggelaar, Roald M.; Janssen, J. W. G. (Hans); Kentgens, Arno P. M.; van Bentum, P. Jan M.

    2016-02-01

    Magnetic field B0 gradients are essential in modern Nuclear Magnetic Resonance spectroscopy and imaging. Although RF/B1 gradients can be used to fulfill a similar role, this is not used in common practice because of practical limitations in the design of B1 gradient coils. Here we present a new method to create B1 gradients using stripline RF coils. The conductor-width of a stripline NMR chip and the strength of its radiofrequency field are correlated, so a stripline chip can be tapered to produce any arbitrary shaped B1 field gradient. Here we show the characterization of this tapered stripline configuration and demonstrate three applications: magnetic resonance imaging on samples with nL-μL volumes, reaction monitoring of fast chemical reactions (10-2-101 s) and the compensation of B0 field gradients to obtain high-resolution spectra in inhomogeneous magnetic fields.

  3. 2D 1H and 3D 1H-15N NMR of zinc-rubredoxins: contributions of the beta-sheet to thermostability.

    PubMed Central

    Richie, K. A.; Teng, Q.; Elkin, C. J.; Kurtz, D. M.

    1996-01-01

    Based on 2D 1H-1H and 2D and 3D 1H-15N NMR spectroscopies, complete 1H NMR assignments are reported for zinc-containing Clostridium pasteurianum rubredoxin (Cp ZnRd). Complete 1H NMR assignments are also reported for a mutated Cp ZnRd, in which residues near the N-terminus, namely, Met 1, Lys 2, and Pro 15, have been changed to their counterparts, (-), Ala and Glu, respectively, in rubredoxin from the hyperthermophilic archaeon, Pyrococcus furiosus (Pf Rd). The secondary structure of both wild-type and mutated Cp ZnRds, as determined by NMR methods, is essentially the same. However, the NMR data indicate an extension of the three-stranded beta-sheet in the mutated Cp ZnRd to include the N-terminal Ala residue and Glu 15, as occurs in Pf Rd. The mutated Cp Rd also shows more intense NOE cross peaks, indicating stronger interactions between the strands of the beta-sheet and, in fact, throughout the mutated Rd. However, these stronger interactions do not lead to any significant increase in thermostability, and both the mutated and wild-type Cp Rds are much less thermostable than Pf Rd. These correlations strongly suggest that, contrary to a previous proposal [Blake PR et al., 1992, Protein Sci 1:1508-1521], the thermostabilization mechanism of Pf Rd is not dominated by a unique set of hydrogen bonds or electrostatic interactions involving the N-terminal strand of the beta-sheet. The NMR results also suggest that an overall tighter protein structure does not necessarily lead to increased thermostability. PMID:8732760

  4. Stray-light correction in 2D spectroscopy

    NASA Astrophysics Data System (ADS)

    Schlichenmaier, R.; Franz, M.

    2013-07-01

    Context. In solar physics, spectropolarimeters based on Fabry-Pérot interferometers are commonly used for high spatial resolution observations. In the data pipeline, corrections for scattered light may be performed on each narrow band image. Aims: We elaborate on the effects of stray-light corrections on Doppler maps. Methods: First, we demonstrate the basic correction effect in a simplified situation of two profiles that suffer from stray light. Then, we study the correction effects on velocity maps by transforming a Hinode SP map into a two-dimensional spectroscopic data set with i(x,y) at each wavelength point, which mimicks narrow band images. Velocity maps are inferred from line profiles of original and stray-light corrected data. Results: The correction of scattered light in narrow band images affects the inferred Doppler velocity maps: relative red shifts always become more red, and relative blue shifts become more blue. This trend is independent of whether downflows have dark or bright intensities. As a result, the effects of overcorrection produce both downflows and upflows. Conclusions: In 2D spectropolarimetry, corrections for scattered light can improve the image intensity and velocity contrast but inherently produce downflow signatures in the penumbra. Hence, such corrections are justified only if the properties of the stray light (seeing, telescope, and instrument) are well known.

  5. 2D XAFS-XEOL Spectroscopy - Some recent developments

    NASA Astrophysics Data System (ADS)

    Ward, M. J.; Smith, J. G.; Regier, T. Z.; Sham, T. K.

    2013-03-01

    The use of optical photons to measure the modulation of the absorption coefficient upon X-ray excitation, or optical XAFS, is of particular interest for application to the study of light emitting semiconducting nanomaterials due to the additional information that may be gained. The potential for site-selectivity, elemental and excitation energy specific luminescence decay channels, and surface vs. bulk effects all make the use of X-ray excited optical luminescence (XEOL) desirable as a detection method. Previous experiments have made use of a monochromator to select the optical emission wavelength used to monitor optical XAFS. This method of detection suffers from the primary limitation of only being able to monitor the optical response at one emission wavelength. By combining the high resolution soft X-ray Spherical Grating Monochromator beam-line at the Canadian Light Source with an Ocean Optics QE 65000 fast CCD spectrophotometer and custom integration software we have developed a technique for collecting 2D XAFS-XEOL spectra, in which the excitation energy is scanned and a XEOL spectra is collected for every energy value. Herein we report the development of this technique and its capabilities using the study of the luminescence emitted from single crystal zinc oxide as an example.

  6. Imaging Excited State Dynamics with 2d Electronic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Engel, Gregory S.

    2012-06-01

    Excited states in the condensed phase have extremely high chemical potentials making them highly reactive and difficult to control. Yet in biology, excited state dynamics operate with exquisite precision driving solar light harvesting in photosynthetic complexes though excitonic transport and photochemistry through non-radiative relaxation to photochemical products. Optimized by evolution, these biological systems display manifestly quantum mechanical behaviors including coherent energy transfer, steering wavepacket trajectories through conical intersections and protection of long-lived quantum coherence. To image the underlying excited state dynamics, we have developed a new spectroscopic method allowing us to capture excitonic structure in real time. Through this method and other ultrafast multidimensional spectroscopies, we have captured coherent dynamics within photosynthetic antenna complexes. The data not only reveal how biological systems operate, but these same spectral signatures can be exploited to create new spectroscopic tools to elucidate the underlying Hamiltonian. New data on the role of the protein in photosynthetic systems indicates that the chromophores mix strongly with some bath modes within the system. The implications of this mixing for excitonic transport will be discussed along with prospects for transferring underlying design principles to synthetic systems.

  7. Multiplet-separated heteronuclear two-dimensional NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Levitt, Malcolm H.; Sørensen, O. W.; Ernst, R. R.

    1983-02-01

    Techniques are described for the identification and separation of peaks of different multiplicity in heteronuclear two-dimensional NMR spectroscopy. The methods are applied to the two-dimensional 13C- 1H shift correlation spectrum of menthol.

  8. Reduced dimensionality (3,2)D NMR experiments and their automated analysis: implications to high-throughput structural studies on proteins.

    PubMed

    Reddy, Jithender G; Kumar, Dinesh; Hosur, Ramakrishna V

    2015-02-01

    Protein NMR spectroscopy has expanded dramatically over the last decade into a powerful tool for the study of their structure, dynamics, and interactions. The primary requirement for all such investigations is sequence-specific resonance assignment. The demand now is to obtain this information as rapidly as possible and in all types of protein systems, stable/unstable, soluble/insoluble, small/big, structured/unstructured, and so on. In this context, we introduce here two reduced dimensionality experiments – (3,2)D-hNCOcanH and (3,2)D-hNcoCAnH – which enhance the previously described 2D NMR-based assignment methods quite significantly. Both the experiments can be recorded in just about 2-3 h each and hence would be of immense value for high-throughput structural proteomics and drug discovery research. The applicability of the method has been demonstrated using alpha-helical bovine apo calbindin-D9k P43M mutant (75 aa) protein. Automated assignment of this data using AUTOBA has been presented, which enhances the utility of these experiments. The backbone resonance assignments so derived are utilized to estimate secondary structures and the backbone fold using Web-based algorithms. Taken together, we believe that the method and the protocol proposed here can be used for routine high-throughput structural studies of proteins. PMID:25178811

  9. Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-05-01

    Benzene carboxylic acids and benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by 1H, 13C and 15N NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations.

  10. An Integrated Laboratory Project in NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Hudson, Reggie L.; Pendley, Bradford D.

    1988-01-01

    Describes an advanced NMR project that can be done with a 60-MHz continuous-wave proton spectrometer. Points out the main purposes are to give students experience in second-order NMR analysis, the simplification of spectra by raising the frequency, and the effect of non-hydrogen nuclei on proton resonances. (MVL)

  11. Characterization of novel isobenzofuranones by DFT calculations and 2D NMR analysis.

    PubMed

    Teixeira, Milena G; Alvarenga, Elson S

    2016-08-01

    Phthalides are frequently found in naturally occurring substances and exhibit a broad spectrum of biological activities. In the search for compounds with insecticidal activity, phthalides have been used as versatile building blocks for the syntheses of novel potential agrochemicals. In our work, the Diels-Alder reaction between furan-2(5H)-one and cyclopentadiene was used successfully to obtain (3aR,4S,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aS,4R,7S,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (2) and (3aS,4S,7R,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aR,4R,7S,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (3). The endo adduct (2) was brominated to afford (3aR,4R,5R,7R,7aS,8R)-5,8-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aS,4S,5S,7S,7aR,8S)-5,8-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (4) and (3aS,4R,5R,6S,7S,7aR)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aR,4S,5S,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (5). Following the initial analysis of the NMR spectra and the proposed two novel unforeseen products, we have decided to fully analyze the classical and non-classical assay structures with the aid of computational calculations. Computation to predict the (13) C and (1) H chemical shifts for mean absolute error analyses have been carried out by gauge-including atomic orbital method at M06-2X/6-31+G(d,p) and B3LYP/6-311+G(2d,p) levels of theory for all viable conformers. Characterization of the novel unforeseen compounds (4) and (5) were not possible by employing only the experimental NMR data; however, a more conclusive structural identification was performed by comparing the experimental and theoretical (1) H and (13) C chemical shifts by mean absolute error and DP4 probability analyses. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26811211

  12. Off-resonance effects on 2D NMR nutation spectra of I = 3/2 quadrupolar nuclei in static samples.

    PubMed

    Xia, Y; Deng, F; Ye, C

    1995-12-01

    The off-resonance effects on 2D NMR nutation of I = 3/2 quadrupolar nuclei are demonstrated with perturbation theory and numerical calculation in static samples. The off-resonant (delta omega) rf field (omega 1) enlarges a nutation frequency and consequently increases the measurement range of nuclear quadrupolar interaction parameters. When omega e > omega Qmax, and arctg(omega 1/delta omega) = +/- 54.7 degrees (magic angle), the satellite lines (produced by coherence transfers) in a nutation spectrum are superimposed with the line of central transition, and hence the nutation spectrum is simplified and its sensitivity is enhanced. The nuclear quadrupolar interaction parameters of 23Na nuclei in Na omega molecular sieve are obtained using 2D NMR nutation. PMID:9053113

  13. Fragment-Based Drug Discovery Using NMR Spectroscopy

    PubMed Central

    Harner, Mary J.; Frank, Andreas O.; Fesik, Stephen W.

    2013-01-01

    Nuclear magnetic resonance (NMR) spectroscopy has evolved into a powerful tool for fragment-based drug discovery over the last two decades. While NMR has been traditionally used to elucidate the three-dimensional structures and dynamics of biomacromolecules and their interactions, it can also be a very valuable tool for the reliable identification of small molecules that bind to proteins and for hit-to-lead optimization. Here, we describe the use of NMR spectroscopy as a method for fragment-based drug discovery and how to most effectively utilize this approach for discovering novel therapeutics based on our experience. PMID:23686385

  14. Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy.

    PubMed

    Ardenkjaer-Larsen, Jan-Henrik; Boebinger, Gregory S; Comment, Arnaud; Duckett, Simon; Edison, Arthur S; Engelke, Frank; Griesinger, Christian; Griffin, Robert G; Hilty, Christian; Maeda, Hidaeki; Parigi, Giacomo; Prisner, Thomas; Ravera, Enrico; van Bentum, Jan; Vega, Shimon; Webb, Andrew; Luchinat, Claudio; Schwalbe, Harald; Frydman, Lucio

    2015-08-01

    In the Spring of 2013, NMR spectroscopists convened at the Weizmann Institute in Israel to brainstorm on approaches to improve the sensitivity of NMR experiments, particularly when applied in biomolecular settings. This multi-author interdisciplinary Review presents a state-of-the-art description of the primary approaches that were considered. Topics discussed included the future of ultrahigh-field NMR systems, emerging NMR detection technologies, new approaches to nuclear hyperpolarization, and progress in sample preparation. All of these are orthogonal efforts, whose gains could multiply and thereby enhance the sensitivity of solid- and liquid-state experiments. While substantial advances have been made in all these areas, numerous challenges remain in the quest of endowing NMR spectroscopy with the sensitivity that has characterized forms of spectroscopies based on electrical or optical measurements. These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed. PMID:26136394

  15. Radiofrequency Spectroscopy and Thermodynamics of Fermi Gases in the 2D to Quasi-2D Dimensional Crossover

    NASA Astrophysics Data System (ADS)

    Cheng, Chingyun; Kangara, Jayampathi; Arakelyan, Ilya; Thomas, John

    2016-05-01

    We tune the dimensionality of a strongly interacting degenerate 6 Li Fermi gas from 2D to quasi-2D, by adjusting the radial confinement of pancake-shaped clouds to control the radial chemical potential. In the 2D regime with weak radial confinement, the measured pair binding energies are in agreement with 2D-BCS mean field theory, which predicts dimer pairing energies in the many-body regime. In the qausi-2D regime obtained with increased radial confinement, the measured pairing energy deviates significantly from 2D-BCS theory. In contrast to the pairing energy, the measured radii of the cloud profiles are not fit by 2D-BCS theory in either the 2D or quasi-2D regimes, but are fit in both regimes by a beyond mean field polaron-model of the free energy. Supported by DOE, ARO, NSF, and AFOSR.

  16. Probing dipole-dipole interaction in a rubidium gas via double-quantum 2D spectroscopy.

    PubMed

    Gao, Feng; Cundiff, Steven T; Li, Hebin

    2016-07-01

    We have implemented double-quantum 2D spectroscopy on a rubidium vapor and shown that this technique provides sensitive and background-free detection of the dipole-dipole interaction. The 2D spectra include signals from both individual atoms and interatomic interactions, allowing quantitative studies of the interaction. A theoretical model based on the optical Bloch equations is used to reproduce the experimental spectrum and confirm the origin of double-quantum signals. PMID:27367074

  17. Study of inclusion complex between 2,6-dinitrobenzoic acid and β-cyclodextrin by 1H NMR, 2D 1H NMR (ROESY), FT-IR, XRD, SEM and photophysical methods.

    PubMed

    Srinivasan, Krishnan; Stalin, Thambusamy

    2014-09-15

    The formation of host-guest inclusion complex of 2,6-dinitrobenzoic acid (2,6-DNB) with nano-hydrophobic cavity of β-cyclodextrin (β-CD) in solution phase has been studied by UV-visible spectroscopy and electrochemical analysis (cyclic voltammetry, CV). The effect of acid-base concentrations of 2,6-DNB has been studied in presence and absence of β-CD to determination for the ground state acidity constant (pKa). The binding constant of inclusion complex at 303 K was calculated using Benesi-Hildebrand plot and thermodynamic parameter (ΔG) was also calculated. The solid inclusion complex formation between β-CD and 2,6-DNB was confirmed by 1H NMR, 2D 1H NMR (ROESY), FT-IR, XRD and SEM analysis. A schematic representation of this inclusion process was proposed by molecular docking studies using patch dock server. PMID:24769381

  18. Study of inclusion complex between 2,6-dinitrobenzoic acid and β-cyclodextrin by 1H NMR, 2D 1H NMR (ROESY), FT-IR, XRD, SEM and photophysical methods

    NASA Astrophysics Data System (ADS)

    Srinivasan, Krishnan; Stalin, Thambusamy

    2014-09-01

    The formation of host-guest inclusion complex of 2,6-dinitrobenzoic acid (2,6-DNB) with nano-hydrophobic cavity of β-cyclodextrin (β-CD) in solution phase has been studied by UV-visible spectroscopy and electrochemical analysis (cyclic voltammetry, CV). The effect of acid-base concentrations of 2,6-DNB has been studied in presence and absence of β-CD to determination for the ground state acidity constant (pKa). The binding constant of inclusion complex at 303 K was calculated using Benesi-Hildebrand plot and thermodynamic parameter (ΔG) was also calculated. The solid inclusion complex formation between β-CD and 2,6-DNB was confirmed by 1H NMR, 2D 1H NMR (ROESY), FT-IR, XRD and SEM analysis. A schematic representation of this inclusion process was proposed by molecular docking studies using patch dock server.

  19. Solid-State NMR Spectroscopy for the Physical Chemistry Laboratory

    ERIC Educational Resources Information Center

    Kinnun, Jacob J.; Leftin, Avigdor; Brown, Michael F.

    2013-01-01

    Solid-state nuclear magnetic resonance (NMR) spectroscopy finds growing application to inorganic and organic materials, biological samples, polymers, proteins, and cellular membranes. However, this technique is often neither included in laboratory curricula nor typically covered in undergraduate courses. On the other hand, spectroscopy and…

  20. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material?

    NASA Astrophysics Data System (ADS)

    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 solid-state 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, Ü., 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., Mak-Jurkauskas, M.L., Sirigiri, J.R., Herzfeld, J

  1. A modularized pulse programmer for NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Mao, Wenping; Bao, Qingjia; Yang, Liang; Chen, Yiqun; Liu, Chaoyang; Qiu, Jianqing; Ye, Chaohui

    2011-02-01

    A modularized pulse programmer for a NMR spectrometer is described. It consists of a networked PCI-104 single-board computer and a field programmable gate array (FPGA). The PCI-104 is dedicated to translate the pulse sequence elements from the host computer into 48-bit binary words and download these words to the FPGA, while the FPGA functions as a sequencer to execute these binary words. High-resolution NMR spectra obtained on a home-built spectrometer with four pulse programmers working concurrently demonstrate the effectiveness of the pulse programmer. Advantages of the module include (1) once designed it can be duplicated and used to construct a scalable NMR/MRI system with multiple transmitter and receiver channels, (2) it is a totally programmable system in which all specific applications are determined by software, and (3) it provides enough reserve for possible new pulse sequences.

  2. Simultaneous Acquisition of 2D and 3D Solid-State NMR Experiments for Sequential Assignment of Oriented Membrane Protein Samples

    PubMed Central

    Gopinath, T.; Mote, Kaustubh R; Veglia, Gianluigi

    2016-01-01

    We present a new method called DAISY (Dual Acquisition orIented ssNMR spectroScopY) for the simultaneous acquisition of 2D and 3D oriented solid-state NMR experiments for membrane proteins aligned in mechanically or magnetically lipid bilayers. DAISY utilizes dual acquisition of sine and cosine dipolar or chemical shift coherences and long living 15N longitudinal polarization to obtain two multi-dimensional spectra, simultaneously. In these new experiments, the first acquisition gives the polarization inversion spin exchange at the magic angle (PISEMA) or heteronuclear correlation (HETCOR) spectra, the second acquisition gives PISEMA-mixing or HETCOR-mixing spectra, where the mixing element enables inter-residue correlations through 15N-15N homonuclear polarization transfer. The analysis of the two 2D spectra (first and second acquisitions) enables one to distinguish 15N-15N inter-residue correlations for sequential assignment of membrane proteins. DAISY can be implemented in 3D experiments that include the polarization inversion spin exchange at magic angle via I spin coherence (PISEMAI) sequence, as we show for the simultaneous acquisition of 3D PISEMAI-HETCOR and 3D PISEMAI-HETCOR-mixing experiments. PMID:25749871

  3. Simultaneous acquisition of 2D and 3D solid-state NMR experiments for sequential assignment of oriented membrane protein samples.

    PubMed

    Gopinath, T; Mote, Kaustubh R; Veglia, Gianluigi

    2015-05-01

    We present a new method called DAISY (Dual Acquisition orIented ssNMR spectroScopY) for the simultaneous acquisition of 2D and 3D oriented solid-state NMR experiments for membrane proteins reconstituted in mechanically or magnetically aligned lipid bilayers. DAISY utilizes dual acquisition of sine and cosine dipolar or chemical shift coherences and long living (15)N longitudinal polarization to obtain two multi-dimensional spectra, simultaneously. In these new experiments, the first acquisition gives the polarization inversion spin exchange at the magic angle (PISEMA) or heteronuclear correlation (HETCOR) spectra, the second acquisition gives PISEMA-mixing or HETCOR-mixing spectra, where the mixing element enables inter-residue correlations through (15)N-(15)N homonuclear polarization transfer. The analysis of the two 2D spectra (first and second acquisitions) enables one to distinguish (15)N-(15)N inter-residue correlations for sequential assignment of membrane proteins. DAISY can be implemented in 3D experiments that include the polarization inversion spin exchange at magic angle via I spin coherence (PISEMAI) sequence, as we show for the simultaneous acquisition of 3D PISEMAI-HETCOR and 3D PISEMAI-HETCOR-mixing experiments. PMID:25749871

  4. Structural studies of pravastatin and simvastatin and their complexes with SDS micelles by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Rakhmatullin, I. Z.; Galiullina, L. F.; Klochkova, E. A.; Latfullin, I. A.; Aganov, A. V.; Klochkov, V. V.

    2016-02-01

    Conformational features of pravastatin and simvastatin molecules in solution and in their complexes with sodium dodecyl sulfate micelles (SDS) were studied by 2D NOESY NMR spectroscopy. On the basis of the nuclear magnetic resonance experiments it was established that pravastatin and simvastatin can form molecular complex with SDS micelles which were considered as the model of cell membrane. In addition, interatomic distances for studied compounds were calculated based on 2D NOESY NMR experiments. It was shown that pravastatin interacts only with a surface of model membrane. However, in contrast to pravastatin, simvastatin penetrates into the inner part of SDS micelles. Observed distinctions in the mechanisms of interaction of pravastatin and simvastatin with models of cell membranes could explain the differences in their pharmacological properties.

  5. Cell signaling, post-translational protein modifications and NMR spectroscopy

    PubMed Central

    Theillet, Francois-Xavier; Smet-Nocca, Caroline; Liokatis, Stamatios; Thongwichian, Rossukon; Kosten, Jonas; Yoon, Mi-Kyung; Kriwacki, Richard W.; Landrieu, Isabelle; Lippens, Guy

    2016-01-01

    Post-translationally modified proteins make up the majority of the proteome and establish, to a large part, the impressive level of functional diversity in higher, multi-cellular organisms. Most eukaryotic post-translational protein modifications (PTMs) denote reversible, covalent additions of small chemical entities such as phosphate-, acyl-, alkyl- and glycosyl-groups onto selected subsets of modifiable amino acids. In turn, these modifications induce highly specific changes in the chemical environments of individual protein residues, which are readily detected by high-resolution NMR spectroscopy. In the following, we provide a concise compendium of NMR characteristics of the main types of eukaryotic PTMs: serine, threonine, tyrosine and histidine phosphorylation, lysine acetylation, lysine and arginine methylation, and serine, threonine O-glycosylation. We further delineate the previously uncharacterized NMR properties of lysine propionylation, butyrylation, succinylation, malonylation and crotonylation, which, altogether, define an initial reference frame for comprehensive PTM studies by high-resolution NMR spectroscopy. PMID:23011410

  6. Membrane Protein Structure and Dynamics from NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hong, Mei; Zhang, Yuan; Hu, Fanghao

    2012-05-01

    We review the current state of membrane protein structure determination using solid-state nuclear magnetic resonance (NMR) spectroscopy. Multidimensional magic-angle-spinning correlation NMR combined with oriented-sample experiments has made it possible to measure a full panel of structural constraints of membrane proteins directly in lipid bilayers. These constraints include torsion angles, interatomic distances, oligomeric structure, protein dynamics, ligand structure and dynamics, and protein orientation and depth of insertion in the lipid bilayer. Using solid-state NMR, researchers have studied potassium channels, proton channels, Ca2+ pumps, G protein-coupled receptors, bacterial outer membrane proteins, and viral fusion proteins to elucidate their mechanisms of action. Many of these membrane proteins have also been investigated in detergent micelles using solution NMR. Comparison of the solid-state and solution NMR structures provides important insights into the effects of the solubilizing environment on membrane protein structure and dynamics.

  7. An inversion method of 2D NMR relaxation spectra in low fields based on LSQR and L-curve

    NASA Astrophysics Data System (ADS)

    Su, Guanqun; Zhou, Xiaolong; Wang, Lijia; Wang, Yuanjun; Nie, Shengdong

    2016-04-01

    The low-field nuclear magnetic resonance (NMR) inversion method based on traditional least-squares QR decomposition (LSQR) always produces some oscillating spectra. Moreover, the solution obtained by traditional LSQR algorithm often cannot reflect the true distribution of all the components. Hence, a good solution requires some manual intervention, for especially low signal-to-noise ratio (SNR) data. An approach based on the LSQR algorithm and L-curve is presented to solve this problem. The L-curve method is applied to obtain an improved initial optimal solution by balancing the residual and the complexity of the solutions instead of manually adjusting the smoothing parameters. First, the traditional LSQR algorithm is used on 2D NMR T1-T2 data to obtain its resultant spectra and corresponding residuals, whose norms are utilized to plot the L-curve. Second, the corner of the L-curve as the initial optimal solution for the non-negative constraint is located. Finally, a 2D map is corrected and calculated iteratively based on the initial optimal solution. The proposed approach is tested on both simulated and measured data. The results show that this algorithm is robust, accurate and promising for the NMR analysis.

  8. Broadband 2D Electronic Spectroscopy Reveals Coupling Between Dark 1Bu- State of Carotenoid and Qx State of Bacteriochlorophyll

    NASA Astrophysics Data System (ADS)

    Ostroumov, Evgeny E.; Jumper, Chanelle C.; Mulvaney, Rachel M.; Cogdell, Richard J.; Scholes, Gregory D.

    2013-03-01

    The study of LH2 protein of purple bacteria by broadband 2D electronic spectroscopy is presented. The dark 1Bu- carotenoid state is directly observed in 2D spectra and its role in carotenoid-bacteriochlorophyll interaction is discussed.

  9. Combining solid-state NMR spectroscopy with first-principles calculations - a guide to NMR crystallography.

    PubMed

    Ashbrook, Sharon E; McKay, David

    2016-06-01

    Recent advances in the application of first-principles calculations of NMR parameters to periodic systems have resulted in widespread interest in their use to support experimental measurement. Such calculations often play an important role in the emerging field of "NMR crystallography", where NMR spectroscopy is combined with techniques such as diffraction, to aid structure determination. Here, we discuss the current state-of-the-art for combining experiment and calculation in NMR spectroscopy, considering the basic theory behind the computational approaches and their practical application. We consider the issues associated with geometry optimisation and how the effects of temperature may be included in the calculation. The automated prediction of structural candidates and the treatment of disordered and dynamic solids are discussed. Finally, we consider the areas where further development is needed in this field and its potential future impact. PMID:27117884

  10. Quantitative structure parameters from the NMR spectroscopy of quadrupolar nuclei

    DOE PAGESBeta

    Perras, Frédéric A.

    2016-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is one of the most important characterization tools in chemistry, however, 3/4 of the NMR active nuclei are underutilized due to their quadrupolar nature. This short review centers on the development of methods that use solid-state NMR of quadrupolar nuclei for obtaining quantitative structural information. Namely, techniques using dipolar recoupling as well as the resolution afforded by double-rotation are presented for the measurement of spin–spin coupling between quadrupoles, enabling the measurement of internuclear distances and connectivities. Two-dimensional

  11. Quantitative structure parameters from the NMR spectroscopy of quadrupolar nuclei

    SciTech Connect

    Perras, Frederic A.

    2015-12-15

    Here, nuclear magnetic resonance (NMR) spectroscopy is one of the most important characterization tools in chemistry, however, 3/4 of the NMR active nuclei are underutilized due to their quadrupolar nature. This short review centers on the development of methods that use solid-state NMR of quadrupolar nuclei for obtaining quantitative structural information. Namely, techniques using dipolar recoupling as well as the resolution afforded by double-rotation are presented for the measurement of spin–spin coupling between quadrupoles, enabling the measurement of internuclear distances and connectivities.

  12. New Views of Functionally Dynamic Proteins by Solution NMR Spectroscopy.

    PubMed

    Kay, Lewis E

    2016-01-29

    In the past several decades solution NMR spectroscopy has emerged as a powerful technique for the study of the structure and dynamics of proteins, providing detailed insights into biomolecular function. Herein, I provide a summary of two important areas of application, focusing on NMR studies of (i) supramolecular systems with aggregate molecular masses in the hundreds of kilodaltons and of (ii) sparsely populated and transiently formed protein states that are thermally accessible from populated ground-state conformers. The critical role of molecular dynamics in function is emphasized, highlighting the utility of the NMR technique in providing such often elusive information. PMID:26707200

  13. Analysis of experimentally shocked minerals by NMR spectroscopy

    SciTech Connect

    Cygan, R.T.; Boslough, M.B.

    1994-10-01

    The shock-loading of natural materials by an impact or explosion can result in the formation of modified and altered phases. In order to characterize the resulting material and to evaluate the extent of shock modification, the authors have used nuclear magnetic resonance (NMR) spectroscopy to examine several experimentally shocked minerals. In three related NMR studies, they have (1) examined shocked clinoptilolite, (2) performed a preliminary analysis of shocked quartz, and (3) reproduced shocked quartz results with detailed spectral deconvolutions, and extended it with NMR analysis of shocked feldspar powders.

  14. Nanoscale NMR spectroscopy and imaging of multiple nuclear species

    NASA Astrophysics Data System (ADS)

    Devience, Stephen J.; Pham, Linh M.; Lovchinsky, Igor; Sushkov, Alexander O.; Bar-Gill, Nir; Belthangady, Chinmay; Casola, Francesco; Corbett, Madeleine; Zhang, Huiliang; Lukin, Mikhail; Park, Hongkun; Yacoby, Amir; Walsworth, Ronald L.

    2015-02-01

    Nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) provide non-invasive information about multiple nuclear species in bulk matter, with wide-ranging applications from basic physics and chemistry to biomedical imaging. However, the spatial resolution of conventional NMR and MRI is limited to several micrometres even at large magnetic fields (>1 T), which is inadequate for many frontier scientific applications such as single-molecule NMR spectroscopy and in vivo MRI of individual biological cells. A promising approach for nanoscale NMR and MRI exploits optical measurements of nitrogen-vacancy (NV) colour centres in diamond, which provide a combination of magnetic field sensitivity and nanoscale spatial resolution unmatched by any existing technology, while operating under ambient conditions in a robust, solid-state system. Recently, single, shallow NV centres were used to demonstrate NMR of nanoscale ensembles of proton spins, consisting of a statistical polarization equivalent to ˜100-1,000 spins in uniform samples covering the surface of a bulk diamond chip. Here, we realize nanoscale NMR spectroscopy and MRI of multiple nuclear species (1H, 19F, 31P) in non-uniform (spatially structured) samples under ambient conditions and at moderate magnetic fields (˜20 mT) using two complementary sensor modalities.

  15. High field and 2D-nmr studies with the aporphine alkaloid glaucine.

    PubMed

    Kerr, K M; Kook, A M; Davis, P J

    1986-01-01

    The aporphine alkaloid glaucine (1) was examined by comparison of the high field (600 MHz) 1H-nmr spectra of 1 vs. racemic 6a,7,7-trideutereoglaucine (4,5), by computer-simulated 1H-nmr spectra at 600 MHz, by using decoupled proton spectra, and two-dimensional COSY and HETCOR experiments with 1 at 500 and 360 MHz, respectively, and using high field (90 MHZ) 13C-nmr of S-(+)-glaucine (1). Emphasis was placed on the resolution of the chemical shifts and coupling constants for the H-4 alpha, H-4 beta, H-5 alpha, H-5 beta, H-6 alpha, H-7 alpha, and H-7 beta alicyclic protons of the molecule, which were previously unassigned. The complete assignment of the alicyclic protons of 1 by 1H-nmr was required for the structural elucidation of deuterated analogs of glaucine, which will be used in microbial transformation studies to determine the stereochemical course of aporphine dehydrogenation by the fungi Fusarium solani (ATCC 12823) and Aspergillus flavipes (ATCC 1030). PMID:3783155

  16. Influence of anthraquinone scaffold on E/Z isomer distribution of two thiosemicarbazone derivatives. 2D NMR and DFT studies

    NASA Astrophysics Data System (ADS)

    Marković, Violeta; Joksović, Milan D.; Marković, Svetlana; Jakovljević, Ivan

    2014-01-01

    A distribution of possible isomeric and tautomeric forms of two tautomerizable anthraquinone-thiosemicarbazones with pronounced cytotoxic potential was investigated using 2D NMR and DFT studies. Conformational analysis of the E and Z isomers of both thiosemicarbazones was performed to find out the most stable conformation for each molecule. It was found that superior stability of E-isomers results from ten-membered intramolecular hydrogen bond between thiosemicarbazone N2H and anthraquinone carbonyl group. This hydrogen bond is stronger than that between thiosemicarbazone N2H and ester oxygen, owing to the large partial negative charge on the anthraquinone oxygen.

  17. High-resolution heteronuclear multi-dimensional NMR spectroscopy in magnetic fields with unknown spatial variations

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyong; Huang, Yuqing; Smith, Pieter E. S.; Wang, Kaiyu; Cai, Shuhui; Chen, Zhong

    2014-05-01

    Heteronuclear NMR spectroscopy is an extremely powerful tool for determining the structures of organic molecules and is of particular significance in the structural analysis of proteins. In order to leverage the method’s potential for structural investigations, obtaining high-resolution NMR spectra is essential and this is generally accomplished by using very homogeneous magnetic fields. However, there are several situations where magnetic field distortions and thus line broadening is unavoidable, for example, the samples under investigation may be inherently heterogeneous, and the magnet’s homogeneity may be poor. This line broadening can hinder resonance assignment or even render it impossible. We put forth a new class of pulse sequences for obtaining high-resolution heteronuclear spectra in magnetic fields with unknown spatial variations based on distant dipolar field modulations. This strategy’s capabilities are demonstrated with the acquisition of high-resolution 2D gHSQC and gHMBC spectra. These sequences’ performances are evaluated on the basis of their sensitivities and acquisition efficiencies. Moreover, we show that by encoding and decoding NMR observables spatially, as is done in ultrafast NMR, an extra dimension containing J-coupling information can be obtained without increasing the time necessary to acquire a heteronuclear correlation spectrum. Since the new sequences relax magnetic field homogeneity constraints imposed upon high-resolution NMR, they may be applied in portable NMR sensors and studies of heterogeneous chemical and biological materials.

  18. CHARACTERIZATION OF METABOLITES IN SMALL FISH BIOFLUIDS AND TISSUES BY NMR SPECTROSCOPY

    EPA Science Inventory

    Nuclear magnetic resonance (NMR) spectroscopy has been utilized for assessing ecotoxicity in small fish models by means of metabolomics. Two fundamental challenges of NMR-based metabolomics are the detection limit and characterization of metabolites (or NMR resonance assignments...

  19. Protein folding on the ribosome studied using NMR spectroscopy

    PubMed Central

    Waudby, Christopher A.; Launay, Hélène; Cabrita, Lisa D.; Christodoulou, John

    2013-01-01

    NMR spectroscopy is a powerful tool for the investigation of protein folding and misfolding, providing a characterization of molecular structure, dynamics and exchange processes, across a very wide range of timescales and with near atomic resolution. In recent years NMR methods have also been developed to study protein folding as it might occur within the cell, in a de novo manner, by observing the folding of nascent polypeptides in the process of emerging from the ribosome during synthesis. Despite the 2.3 MDa molecular weight of the bacterial 70S ribosome, many nascent polypeptides, and some ribosomal proteins, have sufficient local flexibility that sharp resonances may be observed in solution-state NMR spectra. In providing information on dynamic regions of the structure, NMR spectroscopy is therefore highly complementary to alternative methods such as X-ray crystallography and cryo-electron microscopy, which have successfully characterized the rigid core of the ribosome particle. However, the low working concentrations and limited sample stability associated with ribosome–nascent chain complexes means that such studies still present significant technical challenges to the NMR spectroscopist. This review will discuss the progress that has been made in this area, surveying all NMR studies that have been published to date, and with a particular focus on strategies for improving experimental sensitivity. PMID:24083462

  20. Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy

    PubMed Central

    Xiong, Wei; Laaser, Jennifer E.; Mehlenbacher, Randy D.; Zanni, Martin T.

    2011-01-01

    In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple “atop” configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces. PMID:22143772

  1. High-resolution NMR spectroscopy under the fume hood.

    PubMed

    Küster, Simon K; Danieli, Ernesto; Blümich, Bernhard; Casanova, Federico

    2011-08-01

    This work reports the possibility to acquire high-resolution (1)H NMR spectra with a fist-sized NMR magnet directly installed under the fume hood. The small NMR sensor based on permanent magnets was used to monitor the trimerization of propionaldehyde catalyzed by indium trichloride in real time by continuously circulating the reaction mixture through the magnet bore in a closed loop with the help of a peristaltic pump. Thanks to the chemical selectivity of NMR spectroscopy the progress of the reaction can be monitored on-line by determining the concentrations of both reactant and product from the area under their respective lines in the NMR spectra as a function of time. This in situ measurement demonstrates that NMR probes can be used in chemistry laboratories, e.g. for reaction optimization, or installed at specific points of interest along industrial process lines. Therefore, it will open the door for the implementation of feedback control based on spectroscopic NMR data. PMID:21698335

  2. Structural dynamics inside a functionalized metal–organic framework probed by ultrafast 2D IR spectroscopy

    PubMed Central

    Nishida, Jun; Tamimi, Amr; Fei, Honghan; Pullen, Sonja; Ott, Sascha; Cohen, Seth M.; Fayer, Michael D.

    2014-01-01

    The structural elasticity of metal–organic frameworks (MOFs) is a key property for their functionality. Here, we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants of 7 and 670 ps with no solvent. Filling the MOF pores with dimethylformamide (DMF) slows the structural fluctuations by reducing the ability of the MOF to undergo deformations, and the dynamics of the DMF molecules are also greatly restricted. Methodology advances were required to remove the severe light scattering caused by the macroscopic-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Förster vibrational excitation transfer. PMID:25512539

  3. Hydrogen Bond Migration between Molecular Sites Observed with Ultrafast 2D IR Chemical Exchange Spectroscopy

    PubMed Central

    Rosenfeld, Daniel E.; Kwak, Kyungwon; Gengeliczki, Zsolt

    2010-01-01

    Hydrogen bonded complexes between phenol and phenylacetylene are studied using ultrafast two-dimensional infrared (2D IR) chemical exchange spectroscopy. Phenylacetylene has two possible π hydrogen bonding acceptor sites (phenyl or acetylene) that compete for hydrogen bond donors in solution at room temperature. The OD stretch frequency of deuterated phenol is sensitive to which acceptor site it is bound. The appearance of off-diagonal peaks between the two vibrational frequencies in the 2D IR spectrum reports on the exchange process between the two competitive hydrogen bonding sites of phenol-phenylacetylene complexes in the neat phenylacetylene solvent. The chemical exchange process occurs in ∼5 ps, and is assigned to direct hydrogen bond migration along the phenylacetylene molecule. Other non-migration mechanisms are ruled out by performing 2D IR experiments on phenol dissolved in the phenylacetylene/carbon tetrachloride mixed solvent. The observation of direct hydrogen bond migration can have implications for macromolecular systems. PMID:20121275

  4. A salt-bridge structure in solution revealed by 2D-IR spectroscopy.

    PubMed

    Huerta-Viga, Adriana; Domingos, Sérgio R; Amirjalayer, Saeed; Woutersen, Sander

    2014-08-14

    Salt bridges are important interactions for the stability of protein conformations, but up to now it has been difficult to determine salt-bridge geometries in solution. Here we characterize the spatial structure of a salt bridge between guanidinium (Gdm(+)) and acetate (Ac(-)) using two-dimensional vibrational (2D-IR) spectroscopy. We find that as a result of salt bridge formation there is a significant change in the infrared response of Gdm(+) and Ac(-), and cross peaks between them appear in the 2D-IR spectrum. From the 2D-IR spectrum we determine the relative orientation of the transition-dipole moments of the vibrational modes of Gdm(+) and Ac(-), as well as the coupling between them. PMID:24676430

  5. Computer-assisted assignment of 2D 1H NMR spectra of proteins: basic algorithms and application to phoratoxin B.

    PubMed

    Kleywegt, G J; Boelens, R; Cox, M; Llinás, M; Kaptein, R

    1991-05-01

    A suite of computer programs (CLAIRE) is described which can be of assistance in the process of assigning 2D 1H NMR spectra of proteins. The programs embody a software implementation of the sequential assignment approach first developed by Wüthrich and co-workers (K. Wüthrich, G. Wider, G. Wagner and W. Braun (1982) J. Mol. Biol. 155, 311). After data-abstraction (peakpicking), the software can be used to detect patterns (spin systems), to find cross peaks between patterns in 2D NOE data sets and to generate assignments that are consistent with all available data and which satisfy a number of constraints imposed by the user. An interactive graphics program called CONPAT is used to control the entire assignment process as well as to provide the essential feedback from the experimental NMR spectra. The algorithms are described in detail and the approach is demonstrated on a set of spectra from the mistletoe protein phoratoxin B, a homolog of crambin. The results obtained compare well with those reported earlier based entirely on a manual assignment process. PMID:1841687

  6. Solvation and crystal effects in bilirubin studied by NMR spectroscopy and density functional theory.

    PubMed

    Rohmer, Thierry; Matysik, Jörg; Mark, Franz

    2011-10-27

    The open-chain tetrapyrrole compound bilirubin was investigated in chloroform and dimethyl sulfoxide solutions by liquid-state NMR and as solid by (1)H, (13)C, and (15)N magic-angle spinning (MAS) solid-state NMR spectroscopy. Density functional theory (DFT) calculations were performed to interpret the data, using the B3LYP exchange-correlation functional to optimize geometries and to compute NMR chemical shieldings by the gauge-including atomic orbital method. The dependence of geometries and chemical shieldings on the size of the basis sets was investigated for the reference molecules tetramethylsilane, NH(3), and H(2)O, and for bilirubin as a monomer and in clusters consisting of up to six molecules. In order to assess the intrinsic errors of the B3LYP approximation in calculating NMR shieldings, complete basis set estimates were obtained for the nuclear shielding values of the reference molecules. The experimental liquid-state NMR data of bilirubin are well reproduced by a monomeric bilirubin molecule using the 6-311+G(2d,p) basis set for geometry optimization and for calculating chemical shieldings. To simulate the bilirubin crystal, a hexameric model was required. It was constructed from geometry-optimized monomers using information from the X-ray structure of bilirubin to fix the monomeric entities in space and refined by partial optimization. Combining experimental (1)H-(13)C and (1)H-(15)N NMR correlation spectroscopy and density functional theory, almost complete sets of (1)H, (13)C, and (15)N chemical shift assignments were obtained for both liquid and solid states. It is shown that monomeric bilirubin in chloroform solution is formed by 3-vinyl anti conformers, while bilirubin crystals are formed by 3-vinyl syn conformers. This conformational change leads to characteristic differences between the liquid- and solid-state NMR resonances. PMID:21846145

  7. Ultrafast double-quantum NMR spectroscopy with optimized sensitivity for the analysis of mixtures.

    PubMed

    Rouger, Laetitia; Gouilleux, Boris; Pourchet-Gellez, Mariane; Dumez, Jean-Nicolas; Giraudeau, Patrick

    2016-03-01

    Ultrafast (UF) 2D NMR enables the acquisition of 2D spectra within a single-scan. This methodology has become a powerful analytical tool, used in a large array of applications. However, UF NMR spectroscopy still suffers from the need to compromise between sensitivity, spectral width and resolution. With the commonly used UF-COSY pulse sequence, resolution issues are compounded by the presence of strong auto-correlation signals, particularly in the case of samples with high dynamic ranges. The recently proposed concept of UF Double Quantum Spectroscopy (DQS) allows a better peak separation as it provides a lower spectral peak density. This paper presents the detailed investigation of this new NMR tool in an analytical chemistry context. Theoretical calculations and numerical simulations are used to characterize the modulation of peak intensities as a function of pulse-sequence parameters, and thus enable a significant enhancement of the sensitivity. The analytical comparison of UF-COSY and UF-DQS shows similar performances, however the ultrafast implementation of the DQS approach is found to have some sensitivity advantages over its conventional counterpart. The analytical performance of the pulse sequence is illustrated by the quantification of taurine in complex mixtures (homemade and commercial energy drinks). The results demonstrate the high potential of this experiment, which forms a valuable alternative to UF-COSY spectra when the latter are characterized by strong overlaps and high dynamic ranges. PMID:26865359

  8. MULTIVARIATE CURVE RESOLUTION OF NMR SPECTROSCOPY METABONOMIC DATA

    EPA Science Inventory

    Sandia National Laboratories is working with the EPA to evaluate and develop mathematical tools for analysis of the collected NMR spectroscopy data. Initially, we have focused on the use of Multivariate Curve Resolution (MCR) also known as molecular factor analysis (MFA), a tech...

  9. Drug solubilization mechanism of α-glucosyl stevia by NMR spectroscopy.

    PubMed

    Zhang, Junying; Higashi, Kenjirou; Ueda, Keisuke; Kadota, Kazunori; Tozuka, Yuichi; Limwikrant, Waree; Yamamoto, Keiji; Moribe, Kunikazu

    2014-04-25

    We investigated the drug solubilization mechanism of α-glucosyl stevia (Stevia-G) which was synthesized from stevia (rebaudioside-A) by transglycosylation. (1)H and (13)C NMR peaks of Stevia-G in water were assigned by two-dimensional (2D) NMR experiments including (1)H-(1)H correlation, (1)H-(13)C heteronuclear multiple bond correlation, and (1)H-(13)C heteronuclear multiple quantum coherence spectroscopies. The (1)H and (13)C peaks clearly showed the incorporation of two glucose units into rebaudioside-A to produce Stevia-G, supported by steviol glycoside and glucosyl residue assays. The concentration-dependent chemical shifts of Stevia-G protons correlated well with a mass-action law model, indicating the self-association of Stevia-G molecules in water. The critical micelle concentration (CMC) was 12.0 mg/mL at 37°C. The aggregation number was 2 below the CMC and 12 above the CMC. Dynamic light scattering and 2D (1)H-(1)H nuclear Overhauser effect spectroscopy (NOESY) NMR experiments demonstrated that Stevia-G self-associated into micelles of a few nanometers in size with a core-shell structure, containing a kaurane diterpenoid-based hydrophobic core and a glucose-based shell. 2D (1)H-(1)H NOESY NMR measurements also revealed that a poorly water-soluble drug, naringenin, was incorporated into the hydrophobic core of the Stevia-G micelle. The Stevia-G self-assembly behavior and micellar drug inclusion capacity can achieve significant enhancement in drug solubility. PMID:24508331

  10. Transient 2D IR spectroscopy of charge injection in dye-sensitized nanocrystalline thin films.

    PubMed

    Xiong, Wei; Laaser, Jennifer E; Paoprasert, Peerasak; Franking, Ryan A; Hamers, Robert J; Gopalan, Padma; Zanni, Martin T

    2009-12-23

    We use nonlinear 2D IR spectroscopy to study TiO(2) nanocrystalline thin films sensitized with a Re dye. We find that the free electron signal, which often obscures the vibrational features in the transient absorption spectrum, is not observed in the 2D IR spectra. Its absence allows the vibrational features of the dye to be much better resolved than with the typical IR absorption probe. We observe multiple absorption bands but no cross peaks in the 2D IR spectra, which indicates that the dyes have at least three conformations. Furthermore, by using a pulse sequence in which we initiate electron transfer in the middle of the infrared pulse train, we are able to assign the excited state features by correlating them to the ground state vibrational modes and determine that the three conformations have different time scales and cross sections for electron injection. 2D IR spectroscopy is proving to be very useful in disentangling overlapping structural distributions in biological and chemical physics processes. These experiments demonstrate that nonlinear infrared probes are also a powerful new tool for studying charge transfer at interfaces. PMID:19947603

  11. Isolation, LC-MS/MS and 2D-NMR characterization of alkaline degradants of tenofovir disoproxil fumarate.

    PubMed

    Anandgaonkar, Vaibhav; Gupta, Abhishek; Kona, Srinivas; Talluri, M V N Kumar

    2015-03-25

    The present work describes the preparative isolation and characterization of two alkaline degradation products of tenofovir disoproxil fumarate (TDF). Tenofovir disoproxil is a prodrug of tenofovir (antiviral agent) and co-crystal form of this prodrug with fumaric acid is tenofovir disoproxil fumarate. The drug is subjected to alkaline degradation with 0.1N sodium hydroxide for 2 min at room temperature. The two degradants were detected by high performance liquid chromatography (HPLC) at relative retention of 0.26 and 0.73 with respect to the drug. HPLC method involves gradient elution on Kromasil Eternity column (150 mm × 2.1 mm, 2.5 μm) using ammonium acetate (10mM) - acetonitrile as mobile phase at flow rate of 0.3 mL/min and UV detection at 260 nm. Two degradation products were isolated by preparative HPLC and further characterized by LC-MS, (1)H NMR, (13)C NMR and 2D-NMR. On the basis of this spectral data, the structure of two DPs are confirmed as methyl hydrogen ({[1-(6-amino-9H-purin-9-yl)propan-2-yl]oxy}methyl)phosphonate for DP-I and dimethyl ({[1-(6-amino-9H-purin-9-yl)propan-2-yl]oxy}methyl)phosphonate for DP-II. PMID:25594895

  12. Cannibalism Affects Core Metabolic Processes in Helicoverpa armigera Larvae-A 2D NMR Metabolomics Study.

    PubMed

    Vergara, Fredd; Shino, Amiu; Kikuchi, Jun

    2016-01-01

    Cannibalism is known in many insect species, yet its impact on insect metabolism has not been investigated in detail. This study assessed the effects of cannibalism on the metabolism of fourth-instar larvae of the non-predatory insect Helicoverpa armigera (Lepidotera: Noctuidea). Two groups of larvae were analyzed: one group fed with fourth-instar larvae of H. armigera (cannibal), the other group fed with an artificial plant diet. Water-soluble small organic compounds present in the larvae were analyzed using two-dimensional nuclear magnetic resonance (NMR) and principal component analysis (PCA). Cannibalism negatively affected larval growth. PCA of NMR spectra showed that the metabolic profiles of cannibal and herbivore larvae were statistically different with monomeric sugars, fatty acid- and amino acid-related metabolites as the most variable compounds. Quantitation of ¹H-(13)C HSQC (Heteronuclear Single Quantum Coherence) signals revealed that the concentrations of glucose, glucono-1,5-lactone, glycerol phosphate, glutamine, glycine, leucine, isoleucine, lysine, ornithine, proline, threonine and valine were higher in the herbivore larvae. PMID:27598144

  13. 2D fluorescence spectroscopy for monitoring ion-exchange membrane based technologies - Reverse electrodialysis (RED).

    PubMed

    Pawlowski, Sylwin; Galinha, Claudia F; Crespo, João G; Velizarov, Svetlozar

    2016-01-01

    Reverse electrodialysis (RED) is one of the emerging, membrane-based technologies for harvesting salinity gradient energy. In RED process, fouling is an undesirable operation constraint since it leads to a decrease of the obtainable net power density due to increasing stack electric resistance and pressure drop. Therefore, early fouling detection is one of the main challenges for successful RED technology implementation. In the present study, two-dimensional (2D) fluorescence spectroscopy was used, for the first time, as a tool for fouling monitoring in RED. Fluorescence excitation-emission matrices (EEMs) of ion-exchange membrane surfaces and of natural aqueous streams were acquired during one month of a RED stack operation. Fouling evolvement on the ion-exchange membrane surfaces was successfully followed by 2D fluorescence spectroscopy and quantified using principal components analysis (PCA). Additionally, the efficiency of cleaning strategy was assessed by measuring the membrane fluorescence emission intensity before and after cleaning. The anion-exchange membrane (AEM) surface in contact with river water showed to be significantly affected due to fouling by humic compounds, which were found to cross through the membrane from the lower salinity (river water) to higher salinity (sea water) stream. The results obtained show that the combined approach of using 2D fluorescence spectroscopy and PCA has a high potential for studying fouling development and membrane cleaning efficiency in ion exchange membrane processes. PMID:26497936

  14. Residue-Specific Structural Kinetics of Proteins through the Union of Isotope Labeling, Mid-IR Pulse Shaping, and Coherent 2D IR Spectroscopy

    PubMed Central

    Middleton, Chris T.; Woys, Ann Marie; Mukherjee, Sudipta S.; Zanni, Martin T.

    2010-01-01

    We describe a methodology for studying protein kinetics using a rapid-scan technology for collecting 2D IR spectra. In conjunction with isotope labeling, 2D IR spectroscopy is able to probe the secondary structure and environment of individual residues in polypeptides and proteins. It is particularly useful for membrane and aggregate proteins. Our rapid-scan technology relies on a mid-IR pulse shaper that computer generates the pulse shapes, much like in an NMR spectrometer. With this device, data collection is faster, easier, and more accurate. We describe our 2D IR spectrometer, as well as protocols for 13C=18O isotope labeling, and then illustrate the technique with an application to the aggregation of the human islet amyloid polypeptide form type 2 diabetes. PMID:20472067

  15. GFT projection NMR spectroscopy for proteins in the solid state

    PubMed Central

    Franks, W. Trent; Atreya, Hanudatta S.; Szyperski, Thomas

    2011-01-01

    Recording of four-dimensional (4D) spectra for proteins in the solid state has opened new avenues to obtain virtually complete resonance assignments and three-dimensional (3D) structures of proteins. As in solution state NMR, the sampling of three indirect dimensions leads per se to long minimal measurement time. Furthermore, artifact suppression in solid state NMR relies primarily on radio-frequency pulse phase cycling. For an n-step phase cycle, the minimal measurement times of both 3D and 4D spectra are increased n times. To tackle the associated ‘sampling problem’ and to avoid sampling limited data acquisition, solid state G-Matrix Fourier Transform (SS GFT) projection NMR is introduced to rapidly acquire 3D and 4D spectral information. Specifically, (4,3)D (HA)CANCOCX and (3,2)D (HACA)NCOCX were implemented and recorded for the 6 kDa protein GB1 within about 10% of the time required for acquiring the conventional congeners with the same maximal evolution times and spectral widths in the indirect dimensions. Spectral analysis was complemented by comparative analysis of expected spectral congestion in conventional and GFT NMR experiments, demonstrating that high spectral resolution of the GFT NMR experiments enables one to efficiently obtain nearly complete resonance assignments even for large proteins. PMID:21052779

  16. HyperSPASM NMR: A new approach to single-shot 2D correlations on DNP-enhanced samples

    NASA Astrophysics Data System (ADS)

    Donovan, Kevin J.; Frydman, Lucio

    2012-12-01

    Dissolution DNP experiments are limited to a single or at most a few scans, before the non-Boltzmann magnetization has been consumed. This makes it impractical to record 2D NMR data by conventional, t1-incremented schemes. Here a new approach termed HyperSPASM to establish 2D heteronuclear correlations in a single scan is reported, aimed at dealing with this kind of challenge. The HyperSPASM experiment relies on imposing an amplitude-modulation of the data by a single Δt1 indirect-domain evolution time, and subsequently monitoring the imparted encoding on separate echo and anti-echo pathway signals within a single continuous acquisition. This is implemented via the use of alternating, switching, coherence selection gradients. As a result of these manipulations the phase imparted by a heteronucleus over its indirect domain evolution can be accurately extracted, and 2D data unambiguously reconstructed with a single-shot excitation. The nature of this sequence makes the resulting experiment particularly well suited for collecting indirectly-detected HSQC data on hyperpolarized samples. The potential of the ensuing HyperSPASM method is exemplified with natural-abundance hyperpolarized correlations on model systems.

  17. Recovering Invisible Signals by Two-Field NMR Spectroscopy.

    PubMed

    Cousin, Samuel F; Kadeřávek, Pavel; Haddou, Baptiste; Charlier, Cyril; Marquardsen, Thorsten; Tyburn, Jean-Max; Bovier, Pierre-Alain; Engelke, Frank; Maas, Werner; Bodenhausen, Geoffrey; Pelupessy, Philippe; Ferrage, Fabien

    2016-08-16

    Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two-field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low-field dimension. Two-field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields. PMID:27417269

  18. Structure elucidation of organic compounds from natural sources using 1D and 2D NMR techniques

    NASA Astrophysics Data System (ADS)

    Topcu, Gulacti; Ulubelen, Ayhan

    2007-05-01

    In our continuing studies on Lamiaceae family plants including Salvia, Teucrium, Ajuga, Sideritis, Nepeta and Lavandula growing in Anatolia, many terpenoids, consisting of over 50 distinct triterpenoids and steroids, and over 200 diterpenoids, several sesterterpenoids and sesquiterpenoids along with many flavonoids and other phenolic compounds have been isolated. For Salvia species abietanes, for Teucrium and Ajuga species neo-clerodanes for Sideritis species ent-kaurane diterpenes are characteristic while nepetalactones are specific for Nepeta species. In this review article, only some interesting and different type of skeleton having constituents, namely rearranged, nor- or rare diterpenes, isolated from these species will be presented. For structure elucidation of these natural diterpenoids intensive one- and two-dimensional NMR techniques ( 1H, 13C, APT, DEPT, NOE/NOESY, 1H- 1H COSY, HETCOR, COLOC, HMQC/HSQC, HMBC, SINEPT) were used besides mass and some other spectroscopic methods.

  19. Analysis and aging of unsaturated polyester resins in contemporary art installations by NMR spectroscopy.

    PubMed

    Stamatakis, Georgios; Knuutinen, Ulla; Laitinen, Kai; Spyros, Apostolos

    2010-12-01

    Two original art installations constructed from unsaturated polyester resins (UPR) and four different reference UPR products (before and after UVB aging) were analyzed by high-resolution 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. Breaking strain studies were also conducted for the four UPR model products before and after different aging procedures (moisture, UVB exposure, melt/freeze). NMR analysis of the chemical composition of the UPR resin extracts showed they contain several low MW organic compounds and oligomers rich in polar -OH groups that play a significant role in the degradation behavior of the composite UPR materials. Statistical analysis of the NMR compositional data showed that styrene and benzaldehyde contents can be used to differentiate between fresh and aged UPR samples. The phthalate and propylene glycol unit speciation (esterified, primary or secondary -OH) of the extracts provided evidence that UPR resin C was used in the construction of the two art installations, and direct comparison of (1)H and (13)C NMR spectra verified this compositional similarity. UPR resin C was shown by both NMR and breaking strain studies to be the reference UPR most susceptible to degradation by different aging procedures, a characteristic attributed to the lower styrene content of resin C. PMID:20922516

  20. Silver-109 NMR spectroscopy of inorganic solids.

    PubMed

    Penner, Glenn H; Li, Wenli

    2004-09-01

    In this study the (109)Ag NMR spectra of the following solid inorganic silver-containing compounds were investigated: AgNO(3), AgNO(2), Ag(2)SO(4), Ag(2)SO(3), AgCO(3), Ag(3)PO(4), AgCl, AgBr, AgI, AgSO(3)CH(3), silver p-toluenesulfonate, NaAg(CN)(2), KAg(CN)(2), K(3)Ag(CN)(4), Me(4)NAgCl(2), silver diethylthiocarbamate, silver lactate, silver acetate, silver citrate, and bis[(N,N(1)-di-tert-butylformamidinato)silver(I)]. The magic angle spinning (MAS) spectra of all compounds were obtained. In some cases, when protons were available, the (1)H to (109)Ag cross-polarization (CP) technique was used to enhance the signal and shorten the experimental relaxation delay. It was possible to obtain slow MAS (or CP/MAS) or nonspinning spectra for 10 samples, allowing the determination of the principal components of the (109)Ag chemical shift (CS) tensors. The isotropic chemical shifts and the CS tensors are discussed in light of the available crystal structures. The need for an accepted standard for referencing (109)Ag chemical shifts and the use of AgSO(3)CH(3) as a CP setup sample are also discussed. PMID:15332810

  1. Evaluation of 2D spatially selective MR spectroscopy using parallel excitation at 7 T

    PubMed Central

    Haas, Martin; Darji, Niravkumar; Speck, Oliver

    2015-01-01

    Background In this work, two-dimensional (2D) spatially selective magnetic resonance spectroscopy (MRS) was evaluated in both phantom and human brain using 8-channel parallel excitation (pTX) at 7 T and compared to standard STEAM. Materials and methods A 2D spiral excitation k-space trajectory was segmented into multiple individual segments to increase the bandwidth. pTX was used to decrease the number of segments by accelerating the trajectory. Different radio frequency (RF) shim settings were used for refocusing, water suppression and fat saturation pulses. Results Phantom experiments demonstrate that, although segmented 2D excitation provided excellent spatial selectivity and spectral quality, STEAM outperformed it in terms of outer volume suppression with 0.6% RMSD compared to 1.7%, 2.5%, 3.9% and 5.5% RMSDs for acceleration factors of R=1, 2, 3 and 4, respectively. Seven major metabolites [choline (Cho), creatine (Cr), phosphocreatine (PCr), glutamate (Glu), glutamine (Gln), glutathione (GSH) and N-acetylaspartate (NAA)] were detected with sufficient accuracy [Cramér-Rao lower bounds (CRLBs) <20%] from the in vivo spectra of both methods. Conservative RF power limits resulted in reduced SNR for 2D selective MR spectra (SNR 131 and 82 for R=1 and 2, respectively) compared to the reference STEAM spectrum (SNR 199). Conclusions Single voxel spectra acquired using 2D selective MRS with and without pTX showed very good agreement with the reference STEAM spectrum. Efficient SAR management of the 2D selective MRS sequence would potentially improve the SNR of spectra. PMID:26029637

  2. Dye aggregation identified by vibrational coupling using 2D IR spectroscopy

    SciTech Connect

    Oudenhoven, Tracey A.; Laaser, Jennifer E.; Zanni, Martin T.; Joo, Yongho; Gopalan, Padma

    2015-06-07

    We report that a model dye, Re(CO){sub 3}(bypy)CO{sub 2}H, aggregates into clusters on TiO{sub 2} nanoparticles regardless of our preparation conditions. Using two-dimensional infrared (2D IR) spectroscopy, we have identified characteristic frequencies of monomers, dimers, and trimers. A comparison of 2D IR spectra in solution versus those deposited on TiO{sub 2} shows that the propensity to dimerize in solution leads to higher dimer formation on TiO{sub 2}, but that dimers are formed even if there are only monomers in solution. Aggregates cannot be washed off with standard protocols and are present even at submonolayer coverages. We observe cross peaks between aggregates of different sizes, primarily dimers and trimers, indicating that clusters consist of microdomains in close proximity. 2D IR spectroscopy is used to draw these conclusions from measurements of vibrational couplings, but if molecules are close enough to be vibrationally coupled, then they are also likely to be electronically coupled, which could alter charge transfer.

  3. Folding of a heterogeneous β-hairpin peptide from temperature-jump 2D IR spectroscopy

    PubMed Central

    Jones, Kevin C.; Peng, Chunte Sam; Tokmakoff, Andrei

    2013-01-01

    We provide a time- and structure-resolved characterization of the folding of the heterogeneous β-hairpin peptide Tryptophan Zipper 2 (Trpzip2) using 2D IR spectroscopy. The amide I′ vibrations of three Trpzip2 isotopologues are used as a local probe of the midstrand contacts, β-turn, and overall β-sheet content. Our experiments distinguish between a folded state with a type I′ β-turn and a misfolded state with a bulged turn, providing evidence for distinct conformations of the peptide backbone. Transient 2D IR spectroscopy at 45 °C following a laser temperature jump tracks the nanosecond and microsecond kinetics of unfolding and the exchange between conformers. Hydrogen bonds to the peptide backbone are loosened rapidly compared with the 5-ns temperature jump. Subsequently, all relaxation kinetics are characterized by an observed 1.2 ± 0.2-μs exponential. Our time-dependent 2D IR spectra are explained in terms of folding of either native or nonnative contacts from a common compact disordered state. Conversion from the disordered state to the folded state is consistent with a zip-out folding mechanism. PMID:23382249

  4. Mobile sensor for high resolution NMR spectroscopy and imaging

    NASA Astrophysics Data System (ADS)

    Danieli, Ernesto; Mauler, Jörg; Perlo, Juan; Blümich, Bernhard; Casanova, Federico

    2009-05-01

    In this work we describe the construction of a mobile NMR tomograph with a highly homogeneous magnetic field. Fast MRI techniques as well as NMR spectroscopy measurements were carried out. The magnet is based on a Halbach array built from identical permanent magnet blocks generating a magnetic field of 0.22 T. To shim the field inhomogeneities inherent to magnet arrays constructed from these materials, a shim strategy based on the use of movable magnet blocks is employed. With this approach a reduction of the line-width from ˜20 kHz to less than 0.1 kHz was achieved, that is by more than two orders of magnitude, in a volume of 21 cm 3. Implementing a RARE sequence, 3D images of different objects placed in this volume were obtained in short experimental times. Moreover, by reducing the sample size to 1 cm 3, sub ppm resolution is obtained in 1H NMR spectra.

  5. RNA structure determination by solid-state NMR spectroscopy

    PubMed Central

    Marchanka, Alexander; Simon, Bernd; Althoff-Ospelt, Gerhard; Carlomagno, Teresa

    2015-01-01

    Knowledge of the RNA three-dimensional structure, either in isolation or as part of RNP complexes, is fundamental to understand the mechanism of numerous cellular processes. Because of its flexibility, RNA represents a challenge for crystallization, while the large size of cellular complexes brings solution-state NMR to its limits. Here, we demonstrate an alternative approach on the basis of solid-state NMR spectroscopy. We develop a suite of experiments and RNA labeling schemes and demonstrate for the first time that ssNMR can yield a RNA structure at high-resolution. This methodology allows structural analysis of segmentally labelled RNA stretches in high-molecular weight cellular machines—independent of their ability to crystallize— and opens the way to mechanistic studies of currently difficult-to-access RNA-protein assemblies. PMID:25960310

  6. Quantitating Metabolites in Protein Precipitated Serum Using NMR Spectroscopy

    PubMed Central

    2015-01-01

    Quantitative NMR-based metabolite profiling is challenged by the deleterious effects of abundant proteins in the intact blood plasma/serum, which underscores the need for alternative approaches. Protein removal by ultrafiltration using low molecular weight cutoff filters thus represents an important step. However, protein precipitation, an alternative and simple approach for protein removal, lacks detailed quantitative assessment for use in NMR based metabolomics. In this study, we have comprehensively evaluated the performance of protein precipitation using methanol, acetonitrile, perchloric acid, and trichloroacetic acid and ultrafiltration approaches using 1D and 2D NMR, based on the identification and absolute quantitation of 44 human blood metabolites, including a few identified for the first time in the NMR spectra of human serum. We also investigated the use of a “smart isotope tag,” 15N-cholamine for further resolution enhancement, which resulted in the detection of a number of additional metabolites. 1H NMR of both protein precipitated and ultrafiltered serum detected all 44 metabolites with comparable reproducibility (average CV, 3.7% for precipitation; 3.6% for filtration). However, nearly half of the quantified metabolites in ultrafiltered serum exhibited 10–74% lower concentrations; specifically, tryptophan, benzoate, and 2-oxoisocaproate showed much lower concentrations compared to protein precipitated serum. These results indicate that protein precipitation using methanol offers a reliable approach for routine NMR-based metabolomics of human blood serum/plasma and should be considered as an alternative to ultrafiltration. Importantly, protein precipitation, which is commonly used by mass spectrometry (MS), promises avenues for direct comparison and correlation of metabolite data obtained from the two analytical platforms to exploit their combined strength in the metabolomics of blood. PMID:24796490

  7. Water dynamics in salt solutions studied with ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy.

    PubMed

    Fayer, Michael D; Moilanen, David E; Wong, Daryl; Rosenfeld, Daniel E; Fenn, Emily E; Park, Sungnam

    2009-09-15

    Water is ubiquitous in nature, but it exists as pure water infrequently. From the ocean to biology, water molecules interact with a wide variety of dissolved species. Many of these species are charged. In the ocean, water interacts with dissolved salts. In biological systems, water interacts with dissolved salts as well as charged amino acids, the zwitterionic head groups of membranes, and other biological groups that carry charges. Water plays a central role in a vast number of chemical processes because of its dynamic hydrogen-bond network. A water molecule can form up to four hydrogen bonds in an approximately tetrahedral arrangement. These hydrogen bonds are continually being broken, and new bonds are being formed on a picosecond time scale. The ability of the hydrogen-bond network of water to rapidly reconfigure enables water to accommodate and facilitate chemical processes. Therefore, the influence of charged species on water hydrogen-bond dynamics is important. Recent advances in ultrafast coherent infrared spectroscopy have greatly expanded our understanding of water dynamics. Two-dimensional infrared (2D IR) vibrational echo spectroscopy is providing new observables that yield direct information on the fast dynamics of molecules in their ground electronic state under thermal equilibrium conditions. The 2D IR vibrational echoes are akin to 2D nuclear magnetic resonance (NMR) but operate on time scales that are many orders of magnitude shorter. In a 2D IR vibrational echo experiment (see the Conspectus figure), three IR pulses are tuned to the vibrational frequency of interest, which in this case is the frequency of the hydroxyl stretching mode of water. The first two pulses "label" the initial molecular structures by their vibrational frequencies. The system evolves between pulses two and three, and the third pulse stimulates the emission of the vibrational echo pulse, which is the signal. The vibrational echo pulse is heterodyne, detected by combining it

  8. 103Rh NMR spectroscopy and its application to rhodium chemistry.

    PubMed

    Ernsting, Jan Meine; Gaemers, Sander; Elsevier, Cornelis J

    2004-09-01

    Rhodium is used for a number of large processes that rely on homogeneous rhodium-catalyzed reactions, for instance rhodium-catalyzed hydroformylation of alkenes, carbonylation of methanol to acetic acid and hydrodesulfurization of thiophene derivatives (in crude oil). Many laboratory applications in organometallic chemistry and catalysis involve organorhodium chemistry and a wealth of rhodium coordination compounds is known. For these and other areas, 103Rh NMR spectroscopy appears to be a very useful analytical tool. In this review, most of the literature concerning 103Rh NMR spectroscopy published from 1989 up to and including 2003 has been covered. After an introduction to several experimental methods for the detection of the insensitive 103Rh nucleus, a discussion of factors affecting the transition metal chemical shift is given. Computational aspects and calculations of chemical shifts are also briefly addressed. Next, the application of 103Rh NMR in coordination and organometallic chemistry is elaborated in more detail by highlighting recent developments in measurement and interpretation of 103Rh NMR data, in relation to rhodium-assisted reactions and homogeneous catalysis. The dependence of the 103Rh chemical shift on the ligands at rhodium in the first coordination sphere, on the complex geometry, oxidation state, temperature, solvent and concentration is treated. Several classes of compounds and special cases such as chiral rhodium compounds are reviewed. Finally, a section on scalar coupling to rhodium is provided. PMID:15307053

  9. Molecular structure by two-dimensional NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Freeman, R.

    Two examples are presented of the use of two-dimensional NMR spectroscopy to solve molecular structure problems. The first is called correlation spectroscopy (COSY) and it allows us to disentangle a complex network of spin-spin couplings. By dispersing the NMR information in two frequency dimensions, it facilitates the analysis of very complex spectra of organic and biochemical molecules, normally too crowded to be tractable. The second application exploits the special properties of multiple-quantum coherence to explore the molecular framework one CC linkage at a time. The natural product panamine is used as a test example; with some supplementary evidence, the structure of this six-ringed heterocyclic molecule is elucidated from the double-quantum filtered two-dimensional spectrum.

  10. Single-sided sensor for high-resolution NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Perlo, J.; Casanova, F.; Blümich, B.

    2006-06-01

    The unavoidable spatial inhomogeneity of the static magnetic field generated by open sensors has precluded their use for high-resolution NMR spectroscopy. In fact, this application was deemed impossible because these field variations are usually orders of magnitude larger than those created by the microscopic structure of the molecules to be detected. Recently, chemical shift resolved NMR spectra were observed for the first time outside a portable single-sided magnet by implementing a method that exploits inhomogeneities in the rf field designed to reproduce variations of the static magnetic field [J. Perlo, V. Demas, F. Casanova, C.A. Meriles, J. Reimer, A. Pines, B. Blümich, High-resolution spectroscopy with a portable single-sided sensor, Science 308 (2005) 1279]. In this communication, we describe in detail the magnet system built from permanent magnets as well as the rf coil geometry used to compensate the static field variations.

  11. Proton-detected 2D radio frequency driven recoupling solid-state NMR studies on micelle-associated cytochrome-b5

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Vivekanandan, Subramanian; Yamamoto, Kazutoshi; Im, Sangchoul; Waskell, Lucy; Ramamoorthy, Ayyalusamy

    2014-05-01

    Solid-state NMR spectroscopy is increasingly used in the high-resolution structural studies of membrane-associated proteins and peptides. Most such studies necessitate isotopically labeled (13C, 15N and 2H) proteins/peptides, which is a limiting factor for some of the exciting membrane-bound proteins and aggregating peptides. In this study, we report the use of a proton-based slow magic angle spinning (MAS) solid-state NMR experiment that exploits the unaveraged 1H-1H dipolar couplings from a membrane-bound protein. We have shown that the difference in the buildup rates of cross-peak intensities against the mixing time - obtained from 2D 1H-1H radio frequency-driven recoupling (RFDR) and nuclear Overhauser effect spectroscopy (NOESY) experiments on a 16.7-kDa micelle-associated full-length rabbit cytochrome-b5 (cytb5) - can provide insights into protein dynamics and could be useful to measure 1H-1H dipolar couplings. The experimental buildup curves compare well with theoretical simulations and are used to extract relaxation parameters. Our results show that due to fast exchange of amide protons with water in the soluble heme-containing domain of cyb5, coherent 1H-1H dipolar interactions are averaged out for these protons while alpha and side chain protons show residual dipolar couplings that can be obtained from 1H-1H RFDR experiments. The appearance of resonances with distinct chemical shift values in 1H-1H RFDR spectra enabled the identification of residues (mostly from the transmembrane region) of cytb5 that interact with micelles.

  12. Proton-Detected 2D Radio Frequency Driven Recoupling Solid-state NMR Studies on Micelle-associated Cytochrome-b5

    PubMed Central

    Pandey, Manoj Kumar; Vivekanandan, Subramanian; Yamamoto, Kazutoshi; Im, Sangchoul; Waskell, Lucy; Ramamoorthy, Ayyalusamy

    2014-01-01

    Solid-state NMR spectroscopy is increasingly used in the high-resolution structural studies of membrane-associated proteins and peptides. Most such studies necessitate isotopically labeled (13C, 15N and 2H) proteins/peptides, which is a limiting factor for some of the exciting membrane-bound proteins and aggregating peptides. In this study, we report the use of a proton-based slow magic angle spinning (MAS) solid-state NMR experiment that exploits the unaveraged 1H-1H dipolar couplings from a membrane-bound protein. We have shown that the difference in the buildup rates of cross peak intensities against the mixing time - obtained from 2D 1H-1H radio frequency-driven recoupling (RFDR) and nuclear Overhauser effect spectroscopy (NOESY) experiments on a 16.7-kDa micelle-associated full-length rabbit cytochrome-b5 (cytb5) - can provide insights into protein dynamics and could be useful to measure 1H-1H dipolar couplings. The experimental buildup curves compare well with theoretical simulations and are used to extract relaxation parameters. Our results show that due to fast exchange of amide protons with water in the soluble heme-containing domain of cyb5, coherent 1H-1H dipolar interactions are averaged out for these protons while alpha and side chain protons show residual dipolar couplings that can be obtained from 1H-1H RFDR experiments. The appearance of resonances with distinct chemical shift values in 1H-1H RFDR spectra enabled the identification of residues (mostly from the transmembrane region) of cytb5 that interact with micelles. PMID:24657390

  13. Ultra-wideline solid-state NMR spectroscopy.

    PubMed

    Schurko, Robert W

    2013-09-17

    large spectral breadths. We have suggested the term ultra-wideline NMR (UWNMR) spectroscopy to describe this set of methodologies. This Account describes recent developments in pulse sequences and strategies for the efficient acquisition of UWNMR spectra. After an introduction to anisotropically broadened NMR patterns, we give a brief history of methods used to acquire UWNMR spectra. We then discuss new acquisition methodologies, including the acquisition of CPMG echo trains and the application of pulses capable of broadband excitation and refocusing. Finally, we present several applications of UWNMR methods that use these broadband pulses. PMID:23745683

  14. Dihydrofolate reductase: Sequential resonance assignments using 2D and 3D NMR and secondary structure determination in solution

    SciTech Connect

    Carr, M.D.; Birdsall, B.; Jimenez-Barbero, J.; Polshakov, V.I.; McCormick, J.E.; Feeney, J.; Frenkiel, T.A.; Bauer, C.J. ); Roberts, G.C.K. )

    1991-06-25

    Three-dimensional (3D) heteronuclear NMR techniques have been used to make sequential {sup 1}H and {sup 15}H resonance assignments for most of the residues of Lactobacillus casei dihydrofolate reductase (DHFR), a monomeric protein of molecular mass 18,300 Da. A uniformly {sup 15}N-labeled sample of the protein was prepared and its complex with methotrexate (MTX) studied by 3D {sup 15}N/{sup 1}H nuclear Overhauserheteronuclear multiple quantum coherence (NOESY-HMQC), Harmann-Hahn-heteronuclear multiple quantum coherence (HOHAHA-HMQC), and HMQC-NOESY-HMQC experiments. These experiments overcame most of the spectral overlap problems caused by chemical shift degeneracies in 2D spectra and allowed the {sup 1}H-{sup 1}H through-space and through-bond connectivities to be identified unambiguously, leading to the resonance assignments. The novel HMQC-NOESY-HMQC experiment allows NOE cross peaks to be detected between NH protons even when their {sup 1}H chemical shifts are degenerate as long as the amide {sup 15}N chemical shifts are nondegenerate. The 3D experiments, in combination with conventional 2D NOESY, COSY, and HOHAHA experiments on unlabelled and selectively deuterated DHFR, provide backbone assignments for 146 of the 162 residues and side-chain assignments for 104 residues of the protein. Data from the NOE-based experiments and identification of the slowly exchanging amide protons provide detailed information about the secondary structure of the binary complex of the protein with methotrexate.

  15. NMR spectroscopy to follow reaction progress in ionic liquids.

    PubMed

    Butler, Bradley J; Thomas, Donald S; Hook, James M; Harper, Jason B

    2016-06-01

    In order to understand reaction outcomes in ionic liquids, it is crucial to be able to follow the progress of these reactions. This review highlights the advantages of NMR spectroscopy over other analytical techniques in following reaction progress in ionic liquids, particularly addressing the practical aspects of the methodology and highlighting the range of processes that can be readily followed. Copyright © 2014 John Wiley & Sons, Ltd. PMID:25287592

  16. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    SciTech Connect

    Not Available

    1990-02-02

    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens.

  17. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    SciTech Connect

    Not Available

    1990-02-02

    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not? by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens.

  18. HIFI-C: a robust and fast method for determining NMR couplings from adaptive 3D to 2D projections.

    PubMed

    Cornilescu, Gabriel; Bahrami, Arash; Tonelli, Marco; Markley, John L; Eghbalnia, Hamid R

    2007-08-01

    We describe a novel method for the robust, rapid, and reliable determination of J couplings in multi-dimensional NMR coupling data, including small couplings from larger proteins. The method, "High-resolution Iterative Frequency Identification of Couplings" (HIFI-C) is an extension of the adaptive and intelligent data collection approach introduced earlier in HIFI-NMR. HIFI-C collects one or more optimally tilted two-dimensional (2D) planes of a 3D experiment, identifies peaks, and determines couplings with high resolution and precision. The HIFI-C approach, demonstrated here for the 3D quantitative J method, offers vital features that advance the goal of rapid and robust collection of NMR coupling data. (1) Tilted plane residual dipolar couplings (RDC) data are collected adaptively in order to offer an intelligent trade off between data collection time and accuracy. (2) Data from independent planes can provide a statistical measure of reliability for each measured coupling. (3) Fast data collection enables measurements in cases where sample stability is a limiting factor (for example in the presence of an orienting medium required for residual dipolar coupling measurements). (4) For samples that are stable, or in experiments involving relatively stronger couplings, robust data collection enables more reliable determinations of couplings in shorter time, particularly for larger biomolecules. As a proof of principle, we have applied the HIFI-C approach to the 3D quantitative J experiment to determine N-C' RDC values for three proteins ranging from 56 to 159 residues (including a homodimer with 111 residues in each subunit). A number of factors influence the robustness and speed of data collection. These factors include the size of the protein, the experimental set up, and the coupling being measured, among others. To exhibit a lower bound on robustness and the potential for time saving, the measurement of dipolar couplings for the N-C' vector represents a realistic

  19. Probing Intermolecular Interactions in Polycyclic Aromatic Hydrocarbons with 2D IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Krummel, Amber

    2014-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment and impact geochemical processes that are critical to sustainable energy resources. For example, asphaltenes exist naturally in geologic formations and their aggregates heavily impact the petroleum economy. Unfortunately, the chemical dynamics that drive asphaltene nanoaggregation processes are still poorly understood. Solvent dynamics and intermolecular interactions such as π-stacking interactions play integral roles in asphaltene nanoaggregation. Linear and nonlinear vibrational spectroscopy including two-dimensional infrared spectroscopy (2DIR), are well suited to explore these fundamental interactions. Teasing apart the vibrational characteristics in PAHs that model asphaltenic compounds represents an important step towards utilizing 2D IR spectroscopy to understand the intermolecular interactions that are prevalent in asphaltene nanoaggregation. A solar dye, N,N'-Dioctyl-3,4,9,10-perylenedicarboximide, is used in this work to model aphaltenes. Carbonyl and ring vibrations are used to probe the nanoaggregates of the model compounds. However, the characteristics of these normal modes change as a function of the size of the conjugated ring system. Thus, in order to fully understand the nature of these normal modes, we include a systematic study of a series of quinones. Our investigation employs a combination of 2DIR spectroscopy and electronic structure calculations to explore vibrational coupling in quinones and PAHs. We compare the calculated vibrational characteristics to those extracted from 2DIR spectra. ATK acknowledges the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  20. Water of Hydration Dynamics in Minerals Gypsum and Bassanite: Ultrafast 2D IR Spectroscopy of Rocks.

    PubMed

    Yan, Chang; Nishida, Jun; Yuan, Rongfeng; Fayer, Michael D

    2016-08-01

    Water of hydration plays an important role in minerals, determining their crystal structures and physical properties. Here ultrafast nonlinear infrared (IR) techniques, two-dimensional infrared (2D IR) and polarization selective pump-probe (PSPP) spectroscopies, were used to measure the dynamics and disorder of water of hydration in two minerals, gypsum (CaSO4·2H2O) and bassanite (CaSO4·0.5H2O). 2D IR spectra revealed that water arrangement in freshly precipitated gypsum contained a small amount of inhomogeneity. Following annealing at 348 K, water molecules became highly ordered; the 2D IR spectrum became homogeneously broadened (motional narrowed). PSPP measurements observed only inertial orientational relaxation. In contrast, water in bassanite's tubular channels is dynamically disordered. 2D IR spectra showed a significant amount of inhomogeneous broadening caused by a range of water configurations. At 298 K, water dynamics cause spectral diffusion that sampled a portion of the inhomogeneous line width on the time scale of ∼30 ps, while the rest of inhomogeneity is static on the time scale of the measurements. At higher temperature, the dynamics become faster. Spectral diffusion accelerates, and a portion of the lower temperature spectral diffusion became motionally narrowed. At sufficiently high temperature, all of the dynamics that produced spectral diffusion at lower temperatures became motionally narrowed, and only homogeneous broadening and static inhomogeneity were observed. Water angular motions in bassanite exhibit temperature-dependent diffusive orientational relaxation in a restricted cone of angles. The experiments were made possible by eliminating the vast amount of scattered light produced by the granulated powder samples using phase cycling methods. PMID:27385320

  1. Advancements in waste water characterization through NMR spectroscopy: review.

    PubMed

    Alves Filho, Elenilson G; Alexandre e Silva, Lorena M; Ferreira, Antonio G

    2015-09-01

    There are numerous organic pollutants that lead to several types of ecosystem damage and threaten human health. Wastewater treatment plants are responsible for the removal of natural and anthropogenic pollutants from the sewage, and because of this function, they play an important role in the protection of human health and the environment. Nuclear magnetic resonance (NMR) has proven to be a valuable analytical tool as a result of its versatility in characterizing both overall chemical composition as well as individual species in a wide range of mixtures. In addition, NMR can provide physical information (rigidity, dynamics, etc.) as well as permit in depth quantification. Hyphenation with other techniques such as liquid chromatography, solid phase extraction and mass spectrometry creates unprecedented capabilities for the identification of novel and unknown chemical species. Thus, NMR is widely used in the study of different components of wastewater, such as complex organic matter (fulvic and humic acids), sludge and wastewater. This review article summarizes the NMR spectroscopy methods applied in studies of organic pollutants from wastewater to provide an exhaustive review of the literature as well as a guide for readers interested in this topic. PMID:25280056

  2. Proton zero-quantum 2D NMR of 2-propenenitrile aligned by an electric field. Determination of the 2H and 14N quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Ruessink, B. H.; De Kanter, F. J. J.; MaClean, C.

    Zero-quantum NMR, selectively detected by 2D NMR, is applied to observe small 1H- 1H dipolar couplings in a polar liquid partially oriented by a strong electric field. The normal (single-quantum) 1H spectrum is severely broadened, which prevents the observation of small couplings. The results from the zero-quantum proton spectrum are used to calculate the 2H and 14N quadrupole coupling constants of 2-deutero-2-propenenitrile from the 2H and 14N NMR spectra.

  3. NMR spectroscopy of proteins encapsulated in a positively charged surfactant.

    PubMed

    Lefebvre, Brian G; Liu, Weixia; Peterson, Ronald W; Valentine, Kathleen G; Wand, A Joshua

    2005-07-01

    Traditionally, large proteins, aggregation-prone proteins, and membrane proteins have been difficult to examine by modern multinuclear and multidimensional solution NMR spectroscopy. A major limitation presented by these protein systems is that their slow molecular reorientation compromises many aspects of the more powerful solution NMR methods. Several approaches have emerged to deal with the various spectroscopic difficulties arising from slow molecular reorientation. One of these takes the approach of actively seeking to increase the effective rate of molecular reorientation by encapsulating the protein of interest within the protective shell of a reverse micelle and dissolving the resulting particle in a low viscosity fluid. Since the encapsulation is largely driven by electrostatic interactions, the preparation of samples of acidic proteins suitable for NMR spectroscopy has been problematic owing to the paucity of suitable cationic surfactants. Here, it is shown that the cationic surfactant CTAB may be used to prepare samples of encapsulated anionic proteins dissolved in low viscosity solvents. In a more subtle application, it is further shown that this surfactant can be employed to encapsulate a highly basic protein, which is completely denatured upon encapsulation using an anionic surfactant. PMID:15949753

  4. Solid-State NMR Spectroscopy of Protein Complexes

    PubMed Central

    Sun, Shangjin; Han, Yun; Paramasivam, Sivakumar; Yan, Si; Siglin, Amanda E.; Williams, John C.; Byeon, In-Ja L.; Ahn, Jinwoo; Gronenborn, Angela M.; Polenova, Tatyana

    2016-01-01

    Protein-protein interactions are vital for many biological processes. These interactions often result in the formation of protein assemblies that are large in size, insoluble and difficult to crystallize, and therefore are challenging to study by structure biology techniques, such as single crystal X-ray diffraction and solution NMR spectroscopy. Solid-state NMR (SSNMR) spectroscopy is emerging as a promising technique for studies of such protein assemblies because it is not limited by molecular size, solubility or lack of long-range order. In the past several years, we have applied magic angle spinning SSNMR based methods to study several protein complexes. In this chapter, we discuss the general solid-state NMR methodologies employed for structural and dynamics analyses of protein complexes with specific examples from our work on thioredoxin reassemblies, HIV-1 capsid protein assemblies and microtubule-associated protein assemblies. We present protocols for sample preparation and characterization, pulse sequences, SSNMR spectra collection and data analysis. PMID:22167681

  5. Large structure rearrangement of colicin ia channel domain after membrane binding from 2D 13C spin diffusion NMR.

    PubMed

    Luo, Wenbin; Yao, Xiaolan; Hong, Mei

    2005-05-01

    One of the main mechanisms of membrane protein folding is by spontaneous insertion into the lipid bilayer from the aqueous environment. The bacterial toxin, colicin Ia, is one such protein. To shed light on the conformational changes involved in this dramatic transfer from the polar to the hydrophobic milieu, we carried out 2D magic-angle spinning (13)C NMR experiments on the water-soluble and membrane-bound states of the channel-forming domain of colicin Ia. Proton-driven (13)C spin diffusion spectra of selectively (13)C-labeled protein show unequivocal attenuation of cross-peaks after membrane binding. This attenuation can be assigned to distance increases but not reduction of the diffusion coefficient. Analysis of the statistics of the interhelical and intrahelical (13)C-(13)C distances in the soluble protein structure indicates that the observed cross-peak reduction is well correlated with a high percentage of short interhelical contacts in the soluble protein. This suggests that colicin Ia channel domain becomes open and extended upon membrane binding, thus lengthening interhelical distances. In comparison, cross-peaks with similar intensities between the two states are dominated by intrahelical contacts in the soluble state. This suggests that the membrane-bound structure of colicin Ia channel domain may be described as a "molten globule", in which the helical secondary structure is retained while the tertiary structure is unfolded. This study demonstrates that (13)C spin diffusion NMR is a valuable tool for obtaining qualitative long-range distance constraints on membrane protein folding. PMID:15853348

  6. Simulation of selective pulse techniques for localized NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Garwood, Michael; Schleich, Thomas; Robin Bendall, M.

    The results of a computer simulation investigation delineating the limits of resolution, sensitivity, and accuracy of the depth- resolved suface-coil spectroscopy (DRESS), volume-selective excitation (VSE), and image-selected in vivo spectroscopy (ISIS) methods for achieving spatially localized NMR spectroscopy are presented. A computer program, which numerically solves the Bloch equations for variable input parameters, is used to simulate the spatial localization afforded by each technique. Because the numerical solution of the Bloch equations describes the behavior of the bulk magnetization with great precision, the simulations provide an objective and realistic means of evaluating the performance of the individual localization schemes and reveal nuances and limitations not discussed in the original experimental papers. The results of this computer simulation study should encourage the optimization of localization methodology for use in specific applications.

  7. Perspectives on DNP-enhanced NMR spectroscopy in solutions

    NASA Astrophysics Data System (ADS)

    van Bentum, Jan; van Meerten, Bas; Sharma, Manvendra; Kentgens, Arno

    2016-03-01

    More than 60 years after the seminal work of Albert Overhauser on dynamic nuclear polarization by dynamic cross relaxation of coupled electron-nuclear spin systems, the quest for sensitivity enhancement in NMR spectroscopy is as pressing as ever. In this contribution we will review the status and perspectives for dynamic nuclear polarization in the liquid state. An appealing approach seems to be the use of supercritical solvents that may allow an extension of the Overhauser mechanism towards common high magnetic fields. A complementary approach is the use of solid state DNP on frozen solutions, followed by a rapid dissolution or in-situ melting step and NMR detection with substantially enhanced polarization levels in the liquid state. We will review recent developments in the field and discuss perspectives for the near future.

  8. Perspectives on DNP-enhanced NMR spectroscopy in solutions.

    PubMed

    van Bentum, Jan; van Meerten, Bas; Sharma, Manvendra; Kentgens, Arno

    2016-03-01

    More than 60 years after the seminal work of Albert Overhauser on dynamic nuclear polarization by dynamic cross relaxation of coupled electron-nuclear spin systems, the quest for sensitivity enhancement in NMR spectroscopy is as pressing as ever. In this contribution we will review the status and perspectives for dynamic nuclear polarization in the liquid state. An appealing approach seems to be the use of supercritical solvents that may allow an extension of the Overhauser mechanism towards common high magnetic fields. A complementary approach is the use of solid state DNP on frozen solutions, followed by a rapid dissolution or in-situ melting step and NMR detection with substantially enhanced polarization levels in the liquid state. We will review recent developments in the field and discuss perspectives for the near future. PMID:26920831

  9. Recombinant Kinase Production and Fragment Screening by NMR Spectroscopy.

    PubMed

    Han, Byeonggu; Ahn, Hee-Chul

    2016-01-01

    During the past decade fragment-based drug discovery (FBDD) has rapidly evolved and several drugs or drug candidates developed by FBDD approach are clinically in use or in clinical trials. For example, vemurafenib, a V600E mutated BRAF inhibitor, was developed by utilizing FBDD approach and approved by FDA in 2011. In FBDD, screening of fragments is the starting step for identification of hits and lead generation. Fragment screening usually relies on biophysical techniques by which the protein-bound small molecules can be detected. NMR spectroscopy has been extensively used to study the molecular interaction between the protein and the ligand, and has many advantages in fragment screening over other biophysical techniques. This chapter describes the practical aspects of fragment screening by saturation transfer difference NMR. PMID:26501900

  10. Maximum entropy signal processing in practical NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sibisi, Sibusiso; Skilling, John; Brereton, Richard G.; Laue, Ernest D.; Staunton, James

    1984-10-01

    NMR spectroscopy is intrinsically insensitive, a frequently serious limitation especially in biochemical applications where sample size is limited and compounds may be too insoluble or unstable for data to be accumulated over long periods. Fourier transform (FT) NMR was developed by Ernst1 to speed up the accumulation of useful data, dramatically improving the quality of spectra obtained in a given observing time by recording the free induction decay (FID) data directly in time, at the cost of requiring numerical processing. Ernst also proposed that more information could be obtained from the spectrum if the FID was multiplied by a suitable apodizing function before being Fourier transformed. For example (see ref. 2), an increase in sensitivity can result from the use of a matched filter1, whereas an increase in resolution can be achieved by the use of gaussian multiplication1,3, application of sine bells4-8 or convolution difference9. These methods are now used routinely in NMR data processing. The maximum entropy method (MEM)10 is theoretically capable of achieving simultaneous enhancement in both respects11, and this has been borne out in practice in other fields where it has been applied. However, this technique requires relatively heavy computation. We describe here the first practical application of MEM to NMR, and we analyse 13C and 1H NMR spectra of 2-vinyl pyridine. Compared with conventional spectra, MEM gives considerable suppression of noise, accompanied by significant resolution enhancement. Multiplets in the 1H spectra are resolved better leading to improved visual clarity.

  11. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoaceticum metabolic profiles

    SciTech Connect

    Xue, Junfeng; Isern, Nancy G.; Ewing, R James; Liyu, Andrey V.; Sears, Jesse A.; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R.; Ahring, Birgitte K.; Majors, Paul D.

    2014-06-20

    An in-situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch-growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution, high sensitivity NMR (HR-NMR) spectroscopy. In-situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at an NMR frequency of 500 MHz, and aliquots of the bioreactor contents were taken for 600 MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in-situ NMR bioreactor facilitated monitoring of the fermentation process in real time, enabling identification of intermediate and end-point metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with the HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  12. Analysis of amorphous solid dispersions using 2D solid-state NMR and (1)H T(1) relaxation measurements.

    PubMed

    Pham, Tran N; Watson, Simon A; Edwards, Andrew J; Chavda, Manisha; Clawson, Jacalyn S; Strohmeier, Mark; Vogt, Frederick G

    2010-10-01

    Solid-state NMR (SSNMR) can provide detailed structural information about amorphous solid dispersions of pharmaceutical small molecules. In this study, the ability of SSNMR experiments based on dipolar correlation, spin diffusion, and relaxation measurements to characterize the structure of solid dispersions is explored. Observation of spin diffusion effects using the 2D (1)H-(13)C cross-polarization heteronuclear correlation (CP-HETCOR) experiment is shown to be a useful probe of association between the amorphous drug and polymer that is capable of directly proving glass solution formation. Dispersions of acetaminophen and indomethacin in different polymers are examined using this approach, as well as (1)H double-quantum correlation experiments to probe additional structural features. (1)H-(19)F CP-HETCOR serves a similar role for fluorinated drug molecules such as diflunisal in dispersions, providing a rapid means to prove the formation of a glass solution. Phase separation is detected using (13)C, (19)F, and (23)Na-detected (1)H T(1) experiments in crystalline and amorphous solid dispersions that contain small domains. (1)H T(1) measurements of amorphous nanosuspensions of trehalose and dextran illustrate the ability of SSNMR to detect domain size effects in dispersions that are not glass solutions via spin diffusion effects. Two previously unreported amorphous solid dispersions involving up to three components and containing voriconazole and telithromycin are analyzed using these experiments to demonstrate the general applicability of the approach. PMID:20681586

  13. An omics approach to rational feed: Enhancing growth in CHO cultures with NMR metabolomics and 2D-DIGE proteomics.

    PubMed

    Blondeel, Eric J M; Ho, Raymond; Schulze, Steffen; Sokolenko, Stanislav; Guillemette, Simon R; Slivac, Igor; Durocher, Yves; Guillemette, J Guy; McConkey, Brendan J; Chang, David; Aucoin, Marc G

    2016-09-20

    Expression of recombinant proteins exerts stress on cell culture systems, affecting the expression of endogenous proteins, and contributing to the depletion of nutrients and accumulation of waste metabolites. In this work, 2D-DIGE proteomics was employed to analyze differential expression of proteins following stable transfection of a Chinese Hamster Ovary (CHO) cell line to constitutively express a heavy-chain monoclonal antibody. Thirty-four proteins of significant differential expression were identified and cross-referenced with cellular functions and metabolic pathways to identify points of cell stress. Subsequently, 1D-(1)H NMR metabolomics experiments analyzed cultures to observe nutrient depletion and waste metabolite accumulations to further examine these cell stresses and pathways. From among fifty metabolites tracked in time-course, eight were observed to be completely depleted from the production media, including: glucose, glutamine, proline, serine, cystine, asparagine, choline, and hypoxanthine, while twenty-three excreted metabolites were also observed to accumulate. The differentially expressed proteins, as well as the nutrient depletion and accumulation of these metabolites corresponded with upregulated pathways and cell systems related to anaplerotic TCA-replenishment, NADH/NADPH replenishment, tetrahydrofolate cycle C1 cofactor conversions, limitations to lipid synthesis, and redox modulation. A nutrient cocktail was assembled to improve the growth medium and alleviate these cell stresses to achieve a ∼75% improvement to peak cell densities. PMID:27496566

  14. Automated structure verification based on a combination of 1D (1)H NMR and 2D (1)H - (13)C HSQC spectra.

    PubMed

    Golotvin, Sergey S; Vodopianov, Eugene; Pol, Rostislav; Lefebvre, Brent A; Williams, Antony J; Rutkowske, Randy D; Spitzer, Timothy D

    2007-10-01

    A method for structure validation based on the simultaneous analysis of a 1D (1)H NMR and 2D (1)H - (13)C single-bond correlation spectrum such as HSQC or HMQC is presented here. When compared with the validation of a structure by a 1D (1)H NMR spectrum alone, the advantage of including a 2D HSQC spectrum in structure validation is that it adds not only the information of (13)C shifts, but also which proton shifts they are directly coupled to, and an indication of which methylene protons are diastereotopic. The lack of corresponding peaks in the 2D spectrum that appear in the 1D (1)H spectrum, also gives a clear picture of which protons are attached to heteroatoms. For all these benefits, combined NMR verification was expected and found by all metrics to be superior to validation by 1D (1)H NMR alone. Using multiple real-life data sets of chemical structures and the corresponding 1D and 2D data, it was possible to unambiguously identify at least 90% of the correct structures. As part of this test, challenging incorrect structures, mostly regioisomers, were also matched with each spectrum set. For these incorrect structures, the false positive rate was observed as low as 6%. PMID:17694570

  15. A new approach to the optimisation of non-uniform sampling schedules for use in the rapid acquisition of 2D NMR spectra of small molecules.

    PubMed

    Sidebottom, Philip J

    2016-08-01

    Non-uniform sampling allows the routine, rapid acquisition of 2D NMR data. When the number of points in the NUS schedule is low, the quality of the data obtained is very dependent of the schedule used. A simple proceedure for finding optimium schedules has been developed and is demonstrated for the multiplicity edited HSQC experiment. PMID:27160788

  16. Interactions in two-component liposomes studied by 2D correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Murawska, Agnieszka; Cieślik-Boczula, Katarzyna; Czarnik-Matusewicz, Bogusława

    2010-06-01

    The effect of dipping amphiphilic ICPANs (1-Alkylaminium, N-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]ethyl]-N,N-dimethyl-, bromide) homologues, characterized by varying alkyl chain length ( n = 8, 10, 12, and 16), into large multilamellar vesicles (MLVs) of dipalmitoylphosphatidylcholine (DPPC) was studied. Attenuated total reflectance infrared (ATR-IR) spectroscopy combined with 31P-NMR enabled observing a cut-off effect for the longest homologue. By employing two-dimensional correlation spectroscopy (2DCOS) for monitoring spectral changes induced by the heating process, detailed information about structural changes was obtained. They confirmed the substantial reorganization in the structure of the interfacial region in the ICPAN-C16/DPPC vesicles compared with the shorter homologues, where mainly the alkyl chains experience significant trans-to-gauche reorganization. Absorbance changes around 1400 cm -1 assigned to the symmetric deformation mode δsym ( +N(CH 3) 3) are a good marker of changes in vesicle shape and are sensitive to the percentage of DPPC molecules directly interacting with the surface of the ATR crystal. This study clearly demonstrates the potential of 2DCOS in investigating interactions in two-component liposomes.

  17. 2D-Spectroscopy of Two SBS Galaxies with Star Formation Regions

    NASA Astrophysics Data System (ADS)

    Hakopian, Susanna

    2007-08-01

    About 500 SBS-galaxies in the selected fields were classified using a scheme, adapted to slit spectroscopic data obtained for them. Continuing the investigation of these objects as the members of subclasses of objects with nuclear and starforming activity, we are using 2D - spectroscopy, allowing to extend in understanding of the details of morphology, dynamic and kinematic processes and physical nature, by which the differences and similarities in subclasses are caused. This work presents a detailed study of two starforming galaxies in different stages of activity, both consisting of HII-regions, SBS 1202+583 and SBS 1533+574. Observations have been carried out with multipupil spectrographs VAGR at 2.6m and MPFS at 6m telescopes.

  18. TOCCATA: a customized carbon total correlation spectroscopy NMR metabolomics database.

    PubMed

    Bingol, Kerem; Zhang, Fengli; Bruschweiler-Li, Lei; Brüschweiler, Rafael

    2012-11-01

    A customized metabolomics NMR database, TOCCATA, is introduced, which uses (13)C chemical shift information for the reliable identification of metabolites, their spin systems, and isomeric states. TOCCATA, whose information was derived from the BMRB and HMDB databases and the literature, currently contains 463 compounds and 801 spin systems, and it can be used through a publicly accessible web server. TOCCATA allows the identification of metabolites in the submillimolar concentration range from (13)C-(13)C total correlation spectroscopy experiments of complex mixtures, which is demonstrated for an Escherichia coli cell lysate, a carbohydrate mixture, and an amino acid mixture, all of which were uniformly (13)C-labeled. PMID:23016498

  19. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoacetica metabolic profiles.

    PubMed

    Xue, Junfeng; Isern, Nancy G; Ewing, R James; Liyu, Andrei V; Sears, Jesse A; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R; Ahring, Birgitte K; Majors, Paul D

    2014-10-01

    An in situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution NMR (HR-NMR) spectroscopy. In situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at 500 MHz, and aliquots of the bioreactor contents were taken for 600-MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol, and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in situ NMR bioreactor facilitated monitoring of the fermentation process, enabling identification of intermediate and endpoint metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts. PMID:24946863

  20. Zwitterionic phosphorylated quinines as chiral solvating agents for NMR spectroscopy.

    PubMed

    Rudzińska-Szostak, Ewa; Górecki, Łukasz; Berlicki, Łukasz; Ślepokura, Katarzyna; Mucha, Artur

    2015-10-01

    Because of their unique 3D arrangement, naturally occurring Cinchona alkaloids and their synthetic derivatives have found wide-ranging applications in chiral recognition. Recently, we determined the enantioselective properties of C-9-phosphate mixed triesters of quinine as versatile chiral solvating agents in nuclear magnetic resonance (NMR) spectroscopy. In the current study, we introduce new zwitterionic members of this class of molecules containing a negatively charged phosphate moiety (i.e., ethyl, n-butyl and phenyl hydrogen quininyl phosphate). An efficient approach for synthesizing these compounds is elaborated, and full characterization, including conformational and autoaggregation phenomena studies, was performed. Therefore, their ability to induce NMR anisochrony of selected enantiomeric substrates (i.e., primarily N-DNB-protected amino acids and their methyl esters) was analyzed compared to uncharged diphenyl quininyl phosphate and its positively charged quaternary ammonium hydrochloride salt. In addition, (1) H and (13) C NMR experiments revealed their enantiodiscrimination potential toward novel analytes, such as secondary amines and nonprotected amino acids. PMID:26415853

  1. 13C NMR spectroscopy applications to brain energy metabolism

    PubMed Central

    Rodrigues, Tiago B.; Valette, Julien; Bouzier-Sore, Anne-Karine

    2013-01-01

    13C nuclear magnetic resonance (NMR) spectroscopy is the method of choice for studying brain metabolism. Indeed, the most convincing data obtained to decipher metabolic exchanges between neurons and astrocytes have been obtained using this technique, thus illustrating its power. It may be difficult for non-specialists, however, to grasp thefull implication of data presented in articles written by spectroscopists. The aim of the review is, therefore, to provide a fundamental understanding of this topic to facilitate the non-specialists in their reading of this literature. In the first part of this review, we present the metabolic fate of 13C-labeled substrates in the brain in a detailed way, including an overview of some general neurochemical principles. We also address and compare the various spectroscopic strategies that can be used to study brain metabolism. Then, we provide an overview of the 13C NMR experiments performed to analyze both intracellular and intercellular metabolic fluxes. More particularly, the role of lactate as a potential energy substrate for neurons is discussed in the light of 13C NMR data. Finally, new perspectives and applications offered by 13C hyperpolarization are described. PMID:24367329

  2. Novel monosaccharide fermentation products in Caldicellulosiruptor saccharolyticus identified using NMR spectroscopy

    SciTech Connect

    Isern, Nancy G.; Xue, Junfeng; Rao, Jaya V.; Cort, John R.; Ahring, Birgitte K.

    2013-04-03

    Profiles of metabolites produced by the thermophilic obligately anaerobic cellulose-degrading Gram-positive bacterium Caldicellulosiruptor saccharolyticus DSM 8903 strain following growth on different monosaccharides (D-glucose, D-mannose, L-arabinose, D-arabinose, D-xylose, L-fucose, and D-fucose) as carbon sources revealed several unexpected fermentation products, suggesting novel metabolic capacities and unexplored metabolic pathways in this organism. Both 1H and 13C nuclear magnetic resonance (NMR) spectroscopy were used to determine intracellular and extracellular metabolite profiles. Metabolite profiles were determined from 1-D 1H NMR spectra by curve fitting against spectral libraries provided in Chenomx software. To reduce uncertainties due to unassigned, overlapping, or poorly-resolved peaks, metabolite identifications were confirmed with 2-D homonuclear and heteronuclear NMR experiments. In addition to expected metabolites such as acetate, lactate, glycerol, and ethanol, several novel fermentation products were identified: ethylene glycol (from growth on D-arabinose, though not L-arabinose), acetoin and 2,3-butanediol (from D-glucose and L-arabinose), and hydroxyacetone (from D-mannose and L-arabinose). Production of ethylene glycol from D-arabinose was particularly notable, with around 10% of the substrate carbon converted into this uncommon fermentation product. The novel products have not previously been reported to be produced by C. saccharolyticus, nor would they be easily predicted from the current genome annotation, and show new potentials for using this strain for production of bioproducts.

  3. Structure of Colloidal Quantum Dots from Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy.

    PubMed

    Piveteau, Laura; Ong, Ta-Chung; Rossini, Aaron J; Emsley, Lyndon; Copéret, Christophe; Kovalenko, Maksym V

    2015-11-01

    Understanding the chemistry of colloidal quantum dots (QDs) is primarily hampered by the lack of analytical methods to selectively and discriminately probe the QD core, QD surface and capping ligands. Here, we present a general concept for studying a broad range of QDs such as CdSe, CdTe, InP, PbSe, PbTe, CsPbBr3, etc., capped with both organic and inorganic surface capping ligands, through dynamic nuclear polarization (DNP) surface enhanced NMR spectroscopy. DNP can enhance NMR signals by factors of 10-100, thereby reducing the measurement times by 2-4 orders of magnitude. 1D DNP enhanced spectra acquired in this way are shown to clearly distinguish QD surface atoms from those of the QD core, and environmental effects such as oxidation. Furthermore, 2D NMR correlation experiments, which were previously inconceivable for QD surfaces, are demonstrated to be readily performed with DNP and provide the bonding motifs between the QD surfaces and the capping ligands. PMID:26473384

  4. Report on neptunium speciation by NMR and optical spectroscopies

    SciTech Connect

    Tait, C.D.; Palmer, P.D.; Ekberg, S.A.; Clark, D.L.

    1995-11-01

    Hydrolysis and carbonate complexation reactions were examined for NpO{sub 2}{sup 2+} and NpO{sub 2}{sup +} ions by a variety of techniques including potentiometric titration, UV-Vis-NIR and NMR spectroscopy. The equilibrium constant for the reaction 3NpO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} + 3H{sup +} {rightleftharpoons} (NpO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} + 3HCO{sub 3}{sup {minus}} was determined to be logK = 19.7 ({plus_minus} 0.8) (I = 2.5 m). {sup 17}O NMR spectroscopy of NpO{sub 2}{sup n+} ions (n = 1,2) reveals a readily observable {sup 17}O resonance for n = 2, but not for n = 1. The first hydrolysis constant for NpO{sub 2}{sup +} was studied as a function of temperature, and the functional form for the temperature-dependent equilibrium constant for the reaction written as NpO{sub 2}{sup +} + H{sub 2}O {rightleftharpoons} NpO{sub 2}OH + H{sup +} was found to be logK = 2.28 {minus} 3780/T, where T is in {degree}K. Finally, the temperature dependence of neptunium(V) carbonate complexation constants was studied. For the first carbonate complexation constant, the appropriate functional form was found to be log{beta}{sub 01} = 1.47 + 786/T.

  5. Spectroscopic characterization of the 1-substituted 3,3-diphenyl-4-(2'-hydroxyphenyl)azetidin-2-ones: Application of 13C NMR, 1H- 13C COSY NMR and mass spectroscopy

    NASA Astrophysics Data System (ADS)

    Singh, Girija S.; Pheko, Tshepo

    2008-08-01

    The article deals with spectroscopic characterization of azetidin-2-ones. The presence of substituents like hydroxyl, fluoro, methoxy and benzhydryl, etc., on the azetidin-2-one ring significantly affects the IR absorption and 13C NMR frequencies of the carbonyl group present in these compounds. The presence of an ester carbonyl group or too many methine protons in the molecule has been observed to limit the scope of IR and 1H NMR spectroscopy in unambiguous assignment of the structure. The application of 13C NMR, 2D NMR ( 1H- 13C COSY) and mass spectroscopy in characterization of complex azetidin-2-ones is discussed. An application of the latter two techniques is described in deciding unequivocally between an azetidin-2-one ring and chroman-2-one ring structure for the product obtained by treatment of the 1-substituted 3,3-diphenyl-4-[2'-( O-diphenylacyl)hydroxyphenyl]-2-azetidinones with ethanolic sodium hydroxide at room temperature.

  6. Understanding J-Modulation during Spatial Encoding for Sensitivity-Optimized Ultrafast NMR Spectroscopy.

    PubMed

    Gouilleux, Boris; Rouger, Laetitia; Charrier, Benoît; Kuprov, Ilya; Akoka, Serge; Dumez, Jean-Nicolas; Giraudeau, Patrick

    2015-10-01

    Ultrafast (UF) NMR spectroscopy is an approach that yields 2D spectra in a single scan. This methodology has become a powerful analytical tool that is used in a large array of applications. However, UF NMR spectroscopy still suffers from an intrinsic low sensitivity, and from the need to compromise between sensitivity, spectral width, and resolution. In particular, the modulation of signal intensities by the spin-spin J-coupling interaction (J-modulation) impacts significantly on the intensities of the spectral peaks. This effect can lead to large sensitivity losses and even to missing spectral peaks, depending on the nature of the spin system. Herein, a general simulation package (Spinach) is used to describe J-modulation effects in UF experiments. The results from simulations match with experimental data and the results of product operator calculations. Several methods are proposed to optimize the sensitivity in UF COSY spectra. The potential and drawbacks of the different strategies are also discussed. These approaches provide a way to adjust the sensitivity of UF experiments for a large range of applications. PMID:26401975

  7. Dynamics-based selective 2D (1)H/(1)H chemical shift correlation spectroscopy under ultrafast MAS conditions.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of (1)H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of (1)H/(1)H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials. PMID:26026440

  8. In vivo two-dimensional NMR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Kraft, Robert A.

    1999-10-01

    The poor resolution of in-vivo one- dimensional nuclear magnetic resonance spectroscopy (NMR) has limited its clinical potential. Currently, only the large singlet methyl resonances arising from N-acetyl aspartate (NAA), choline, and creatine are quantitated in a clinical setting. Other metabolites such as myo- inositol, glutamine, glutamate, lactate, and γ- amino butyric acid (GABA) are of clinical interest but quantitation is difficult due to the overlapping resonances and limited spectral resolution. To improve the spectral resolution and distinguish between overlapping resonances, a series of two- dimensional chemical shift correlation spectroscopy experiments were developed for a 1.5 Tesla clinical imaging magnet. Two-dimensional methods are attractive for in vivo spectroscopy due to their ability to unravel overlapping resonances with the second dimension, simplifying the interpretation and quantitation of low field NMR spectra. Two-dimensional experiments acquired with mix-mode line shape negate the advantages of the second dimension. For this reason, a new experiment, REVOLT, was developed to achieve absorptive mode line shape in both dimensions. Absorptive mode experiments were compared to mixed mode experiments with respect to sensitivity, resolution, and water suppression. Detailed theoretical and experimental calculations of the optimum spin lock and radio frequency power deposition were performed. Two-dimensional spectra were acquired from human bone marrow and human brain tissue. The human brain tissue spectra clearly reveal correlations among the coupled spins of NAA, glutamine, glutamate, lactate, GABA, aspartate and myo-inositol obtained from a single experiment of 23 minutes from a volume of 59 mL. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253-1690.)

  9. Theory of mirrored time domain sampling for NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Ghosh, Arindam; Wu, Yibing; He, Yunfen; Szyperski, Thomas

    2011-12-01

    enables one to accurately measure secondary phase shifts and amplitude imbalances. Application to constant time 2D [ 13C, 1H]-HSQC spectra recorded for a protein sample with canonical MHS/HS schemes showed that accurate CAM data acquisition can be readily implemented on modern spectrometers for experiments based on through-bond polarization transfer. Fourth, when moderate variations of secondary phase shifts with primary phase shift and/or sampling directionality are encountered, generalized theory allowed comparison of the robustness of different MHS/HS schemes for CAM data acquisition, and thus to identify the scheme best suited to suppress dispersive peak components and quadrature image peaks. Moreover, it is shown that for spectra acquired with several indirect evolution periods, the best suited scheme can be identified independently for each of the periods.

  10. Theory of mirrored time domain sampling for NMR spectroscopy.

    PubMed

    Ghosh, Arindam; Wu, Yibing; He, Yunfen; Szyperski, Thomas

    2011-12-01

    one to accurately measure secondary phase shifts and amplitude imbalances. Application to constant time 2D [13C, 1H]-HSQC spectra recorded for a protein sample with canonical MHS/HS schemes showed that accurate CAM data acquisition can be readily implemented on modern spectrometers for experiments based on through-bond polarization transfer. Fourth, when moderate variations of secondary phase shifts with primary phase shift and/or sampling directionality are encountered, generalized theory allowed comparison of the robustness of different MHS/HS schemes for CAM data acquisition, and thus to identify the scheme best suited to suppress dispersive peak components and quadrature image peaks. Moreover, it is shown that for spectra acquired with several indirect evolution periods, the best suited scheme can be identified independently for each of the periods. PMID:21974999

  11. Spatial structure of fibrinopeptide B in water solution with DPC micelles by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Blokhin, Dmitriy S.; Fayzullina, Adeliya R.; Filippov, Andrei V.; Karataeva, Farida Kh.; Klochkov, Vladimir V.

    2015-12-01

    Fibrinopeptide B (GluFib) is one of the factors of thrombosis. Normal blood protein soluble, fibrinogen (fibrinopeptide A and fibrinopeptide B), is transformed into the insoluble, fibrin, which in the form of filaments adheres to the vessel wall at the site of injury, forming a grid. However, the spatial structure of this peptide has not been established till now. In this article, GluFib peptide is investigated together with dodecylphosphocholine (DPC) micelles which were used for mimicking the environment of peptide in blood vessels. The spatial structure was obtained by applying 1D and 2D 1H-1H NMR spectroscopy (TOCSY, NOESY). It was shown that the fibrinopeptide B does not have a secondary structure but we can distinguish the fragment Gly 9 - Arg 14 with a good convergence (the backbone RMSD for the Gly9 - Arg14 is 0.18 ± 0.08 Å).

  12. Dynamic nuclear polarization-enhanced 13C NMR spectroscopy of static biological solids

    PubMed Central

    Potapov, Alexey; Yau, Wai-Ming; Tycko, Robert

    2013-01-01

    We explore the possibility of using dynamic nuclear polarization (DNP) to enhance signals in structural studies of biological solids by solid state NMR without sample spinning. Specifically, we use 2D 13C-13C exchange spectroscopy to probe the peptide backbone torsion angles (ϕ,ψ) in a series of selectively 13C-labeled 40-residue β-amyloid (Aβ1–40) samples, in both fibrillar and non-fibrillar states. Experiments are carried out at 9.39 T and 8 K, using a static double-resonance NMR probe and low-power microwave irradiation at 264 GHz. In frozen solutions of Aβ1–40 fibrils doped with DOTOPA-TEMPO, we observe DNP signal enhancement factors of 16–21. We show that the orientation- and frequency-dependent spin polarization exchange between sequential backbone carbonyl 13C labels can be simulated accurately using a simple expression for the exchange rate, after experimentally determined homogeneous 13C lineshapes are incorporated in the simulations. The experimental 2D 13C-13C exchange spectra place constraints on the ϕ and ψ angles between the two carbonyl labels. Although the data are not sufficient to determine ϕ and ψ uniquely, the data do provide non-trivial constraints that could be included in structure calculations. With DNP at low temperatures, 2D 13C-13C exchange spectra can be obtained from a 3.5 mg sample of Aβ1–40 fibrils in 4 hr or less, despite the broad 13C chemical shift anisotropy line shapes that are observed in static samples. PMID:23562665

  13. Dynamic nuclear polarization-enhanced 13C NMR spectroscopy of static biological solids

    NASA Astrophysics Data System (ADS)

    Potapov, Alexey; Yau, Wai-Ming; Tycko, Robert

    2013-06-01

    We explore the possibility of using dynamic nuclear polarization (DNP) to enhance signals in structural studies of biological solids by solid state NMR without sample spinning. Specifically, we use 2D 13C-13C exchange spectroscopy to probe the peptide backbone torsion angles (ϕ, ψ) in a series of selectively 13C-labeled 40-residue β-amyloid (Aβ1-40) samples, in both fibrillar and non-fibrillar states. Experiments are carried out at 9.39 T and 8 K, using a static double-resonance NMR probe and low-power microwave irradiation at 264 GHz. In frozen solutions of Aβ1-40 fibrils doped with DOTOPA-TEMPO, we observe DNP signal enhancement factors of 16-21. We show that the orientation- and frequency-dependent spin polarization exchange between sequential backbone carbonyl 13C labels can be simulated accurately using a simple expression for the exchange rate, after experimentally determined homogeneous 13C lineshapes are incorporated in the simulations. The experimental 2D 13C-13C exchange spectra place constraints on the ϕ and ψ angles between the two carbonyl labels. Although the data are not sufficient to determine ϕ and ψ uniquely, the data do provide non-trivial constraints that could be included in structure calculations. With DNP at low temperatures, 2D 13C-13C exchange spectra can be obtained from a 3.5 mg sample of Aβ1-40 fibrils in 4 h or less, despite the broad 13C chemical shift anisotropy line shapes that are observed in static samples.

  14. An Oil Spill in a Tube: An Accessible Approach for Teaching Environmental NMR Spectroscopy

    ERIC Educational Resources Information Center

    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…

  15. Multiplicative or t1 Noise in NMR Spectroscopy

    SciTech Connect

    Granwehr, Josef

    2005-01-25

    The signal in an NMR experiment is highly sensitive to fluctuations of the environment of the sample. If, for example, the static magnetic field B{sub 0}, the amplitude and phase of radio frequency (rf) pulses, or the resonant frequency of the detection circuit are not perfectly stable and reproducible, the magnetic moment of the spins is altered and becomes a noisy quantity itself. This kind of noise not only depends on the presence of a signal, it is in fact proportional to it. Since all the spins at a particular location in a sample experience the same environment at any given time, this noise primarily affects the reproducibility of an experiment, which is mainly of importance in the indirect dimensions of a multidimensional experiment, when intense lines are suppressed with a phase cycle, or for difference spectroscopy techniques. Equivalently, experiments which are known to be problematic with regard to their reproducibility, like flow experiments or experiments with a mobile target, tend to be affected stronger by multiplicative noise. In this article it is demonstrated how multiplicative noise can be identified and characterized using very simple, repetitive experiments. An error estimation approach is developed to give an intuitive, yet quantitative understanding of its properties. The consequences for multidimensional NMR experiments are outlined, implications for data analysis are shown, and strategies for the optimization of experiments are summarized.

  16. Saturation in Deuteron Hadamard NMR Spectroscopy of Solids

    NASA Astrophysics Data System (ADS)

    Greferath, M.; Blumich, B.; Griffith, W. M.; Hoatson, G. L.

    Hadamard NMR was investigated for wide-line solid-state deuteron spectroscopy by numerical simulations and experiments on hexamethylbenzene. Similar signal-to-noise ratios were obtained at large filter bandwidths (500 kHz) by both the quadrupolar echo and the Hadamard methods, although the excitation power differs by up to four orders in magnitude. Increasing the excitation power leads to systematic, noise-like features in Hadamard spectra. In contrast to phase modulation, simulations indicate that for amplitude modulation of the pseudorandom excitation, the pulse sequence burns a saturation hole into the lineshape at the carrier frequency. Violation of the cyclicity requirement by introduction of a recycle delay between successive Hadamard scans results in a high-frequency noise contribution. Finite pulse widths are shown not to cause significant spectral distortions.

  17. Elucidating structural characteristics of biomass using solution-state 2 D NMR with a mixture of deuterated dimethylsulfoxide and hexamethylphosphoramide

    DOE PAGESBeta

    Pu, Yunqiao; Ragauskas, Arthur J.; Yoo, Chang Geun; Li, Mi

    2016-04-26

    In recent developments of NMR methods for characterization of lignocellulosic biomass allow improved understanding of plant cell-wall structures with minimal deconstruction and modification of biomass. This study introduces a new NMR solvent system composed of dimethylsulfoxide (DMSO-d6) and hexamethylphosphoramide (HMPA-d18). HMPA as a co-solvent enhanced swelling and mobility of the biomass samples; thereby it allowed enhancing signals of NMR spectra. Moreover, the structural information of biomass was successfully analyzed by the proposed NMR solvent system (DMSO-d6/HMPA-d18; 4:1, v/v) with different biomass. The proposed bi-solvent system does not require derivatization or isolation of biomass, facilitating a facile sample preparation and involvingmore » with no signals overlapping with biomass peaks. Furthermore, it also allows analyzing biomass with a room-temperature NMR probe instead of cryo-probes, which are traditionally used for enhancing signal intensities.« less

  18. Quality assessment of fluoxetine and fluvoxamine pharmaceutical formulations purchased in different countries or via the Internet by 19F and 2D DOSY 1H NMR.

    PubMed

    Trefi, Saleh; Gilard, Véronique; Balayssac, Stéphane; Malet-Martino, Myriam; Martino, Robert

    2008-03-13

    A simple and selective (19)F NMR method has been validated for the quantitation of fluoxetine (FLX) and fluvoxamine (FLV) in methanol solutions and in human plasma and urine. The regression equations for FLX and FLV showed a good linearity in the range of 1.4-620 microg mL(-1) (3.3 x 10(-6)-1.8 x 10(-3) mol L(-1)) with a limit of detection of approximately 0.5 microg mL(-1) (1.3 x 10(-6) mol L(-1)) and a limit of quantification of approximately 2 microg mL(-1) (4.6 x 10(-6) mol L(-1)). The precision of the assay depends on the concentrations and is comprised between 1.5 and 9.5% for a range of concentrations between 1.2 x 10(-3) and 3.2 x 10(-6) mol L(-1). The accuracy evaluated through recovery studies ranged from approximately 96 to 103% in methanol solutions and in urine, and from approximately 93 to 104% in plasma, with standard deviations <7.5%. The low sensitivity of the method precludes its use for the assay of these antidepressants in biofluids at least at therapeutic doses as the ranges of FLX and FLV plasma levels are 0.15-0.5 microg mL(-1) and 0.15-0.25 microg mL(-1), respectively. The method was applied successfully to the determination of FLX and FLV contents in pharmaceutical samples (brand-named and generic) purchased in several countries or via the Internet. All the commercial formulations contain the active ingredient in the range 94-103% of stated concentration. A "signature" of the formulations (solid and liquid) was obtained with 2D Diffusion-Ordered SpectroscopY (DOSY) (1)H NMR which allowed the characterisation of the active ingredient and excipients present in the formulations studied. Finally, the DOSY separation of FLX and FLV whose molecular weights are very close was obtained by using beta-cyclodextrin as host-guest complexing agent. PMID:18206329

  19. 33S NMR spectroscopy 3. Substituent effects on 33S NMR parameters in 2-substituted ethanesulfonates.

    PubMed

    Musio, Roberta; Sciacovelli, Oronzo

    2006-08-01

    33S NMR parameters (chemical shifts and linewidths) in 2-substituted sodium ethanesulfonates, XCH2CH2SO3Na (X = H, CH3, OH, SH, NH2, Cl, Br, NH3+) depend upon the electronic properties of substituents. To explain experimental results and obtain additional information on the origin of the observed substituent effect (SE), sulfur isotropic absolute shielding constants have been calculated at DFT level of theory (B3LYP/6-311++G(2d,p)) by gauge-including atomic orbitals (GIAO) method. Data have been interpreted with the aid of natural bond orbital (NBO) method and natural chemical shielding (NCS) analysis. It has been demonstrated that in the class of compounds considered the diamagnetic contribution to sulfur-shielding constant is constant and the observed upfield shift of 33S resonance induced by electron-withdrawing substituents (reverse chemical shift effect) can be related to variations of the paramagnetic contribution. Substituents with different electronic properties cause variations in the polarization of S-C and S-O bonds of the -C-SO3- moiety thus determining changes of the electron density at sulfur nucleus and consequently the expansion or contraction of 3p sulfur orbitals. Also oxygen lone-pairs and sulfur core 2p electrons can play an active role in determining the paramagnetic contribution to sulfur shielding. With regard to linewidth variations, they can be ascribed primarily to changes in the nuclear quadrupole coupling constant values. B3LYP/6-311++G(2d,p) method allows obtaining a good reproducibility of SE on the electric field gradient (EFG) at sulfur, although its values tend to be underestimated significantly. Moreover, 17O shielding constants have been calculated. PMID:16741982

  20. Experimental implementations of 2D IR spectroscopy through a horizontal pulse shaper design and a focal plane array detector.

    PubMed

    Ghosh, Ayanjeet; Serrano, Arnaldo L; Oudenhoven, Tracey A; Ostrander, Joshua S; Eklund, Elliot C; Blair, Alexander F; Zanni, Martin T

    2016-02-01

    Aided by advances in optical engineering, two-dimensional infrared spectroscopy (2D IR) has developed into a promising method for probing structural dynamics in biophysics and material science. We report two new advances for 2D IR spectrometers. First, we report a fully reflective and totally horizontal pulse shaper, which significantly simplifies alignment. Second, we demonstrate the applicability of mid-IR focal plane arrays (FPAs) as suitable detectors in 2D IR experiments. FPAs have more pixels than conventional linear arrays and can be used to multiplex optical detection. We simultaneously measure the spectra of a reference beam, which improves the signal-to-noise by a factor of 4; and two additional beams that are orthogonally polarized probe pulses for 2D IR anisotropy experiments. PMID:26907414

  1. Characterization of pyrogenic organic matter by 2-dimenstional HETeronucleus CORelation solid-state 13C NMR (HETCOR) spectroscopy

    NASA Astrophysics Data System (ADS)

    Knicker, Heike

    2016-04-01

    During the last years, increasing evidences are provided that the common view of charcoal as a polyaromatic network is too much simplified. Experiments with model compounds indicated that it represents a heterogeneous mixture of thermally altered biomacromolecules with N, O and likely also S substitutions as common features. If produced from a N-rich feedstock, the so called black nitrogen (BN) has to be considered as an integral part of the aromatic charcoal network. In order to study this network one-dimensional (1D) solid-state nuclear magnetic resonance (NMR) spectroscopy is often applied. However, this technique suffers from broad resonance lines and low resolution. Applying 2D techniques can help but until recently, this was unfeasible for natural organic matter (NOM) due to sensitivity problems and the high complexity of the material. On the other hand, during the last decade, the development of stronger magnetic field instruments and advanced pulse sequences has put them into reach for NOM research. Although 2D NMR spectroscopy has many different applications, all pulse sequences are based on the introduction of a preparation time during which the magnetization of a spin system is adjusted into a state appropriate to whatever properties are to be detected in the indirect dimension. Then, the spins are allowed to evolve with the given conditions and after their additional manipulation during a mixing period the modulated magnetization is detected. Assembling several 1D spectra with incrementing evolution time creates a data set which is two-dimensional in time (t1, t2). Fourier transformation of both dimensions leads to a 2D contour plot correlating the interactions detected in the indirect dimension t1 with the signals detected in the direct dimension t2. The so called solid-state heteronuclear correlation (HETCOR) NMR spectroscopy represents a 2D technique allows the determination which protons are interacting with which carbons. In the present work this

  2. Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

    SciTech Connect

    Mao, Kanmi

    2011-01-01

    The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-γ nuclei (e.g., 13C and 15N) via the sensitive high-{gamma} nuclei (e.g., 1H and 19F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for 1H-1H homonuclear decoupling. Also presented is a simple new strategy for optimization of 1H-1H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in 1H detected 2D 1H{l_brace}13C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional 13C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in addition to through-space correlation. To further benefit the sensitivity of the INEPT transfer in rigid solids, the combined rotation and multiple-pulse spectroscopy (CRAMPS) was implemented for homonuclear 1H decoupling under fast MAS (Chapter 3). Several decoupling schemes (PMLG5m$\\bar{x}$, PMLG5mm$\\bar{x}$x and SAM3) were analyzed to maximize the performance of through-bond transfer based

  3. NMR Investigations of Nitrophorin 2 Belt Side Chain Effects on Heme Orientation and Seating of Native N-terminus NP2 and NP2(D1A)

    PubMed Central

    Muthu, Dhanasekaran; Shokhireva, Tatiana K.; Garrett, Sarah A.; Goren, Allena M.; Zhang, Hongjun

    2014-01-01

    Nitrophorin 2, one of the four NO–storing and –releasing proteins found in the saliva of the blood-sucking bug Rhodnius prolixus, has a more ruffled heme and a high preference for a particular heme orientation (B), compared to those of NP1 and NP4, which show no preference (A:B ~ 1:1), suggesting that it fits more tightly in the β-barrel protein. In this work we have prepared a series of “Belt” mutants of NP2(D1A) and (ΔM0)NP2 aimed at reducing the size of aromatic or other residues that surround the heme, and investigated them as the high-spin aqua and low-spin N-methylimidazole (NMeIm) complexes. The “Belt” mutants included Y38A, Y38F, F42A, F66A, Y85A, Y85F, Y104A, I120T and a triple mutant of NP2(D1A), the F42L,L106F,I120T mutant. Although I120 has been mainly considered to be a distal pocket residue, the CδH3 of I120 lies directly above the heme 3-methyl, at 2.67 Å, of heme orientation B, or 2-vinyl of A, and it thus plays a role as a “Belt” mutant, a role that turns out to be extremely important in creating the strong favoring of the B heme orientation (A:B = 1:14) for NP2(D1A) or 1:12 for (ΔM0)NP2. The results show that the 1D 1H NMR spectra of the high-spin forms are quite sensitive to changes in the shape of the heme binding cavity. The single mutation I120T eliminates the favorability of the B heme orientation by producing a heme A:B orientation of 1:1, while the single mutation F42A reverses the heme orientation from A:B = 1:14 seen for NP2(D1A) to 10:1 for NP2(D1A,F42A). The most extreme ratio was found for the triple mutant of NP2(D1A), NP2(D1A,F42L,L105F,I120T), in which A:B ~25:1, a ΔG change of about −3.5 kcal/mol or −14.1 kJ/mol with respect to NP2(D1A). The seating of the heme is modified as well in that mutant and several others, by rotations of the heme by up to 4° from the seating observed in NP2(D1A), in order to relieve steric interactions between a vinyl β-carbon and a protein side chain, or to fill a cavity

  4. Two-dimensional NMR spectroscopy strongly enhances soil organic matter composition analysis

    NASA Astrophysics Data System (ADS)

    Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Hedenström, Mattias; Schleucher, Jürgen

    2016-04-01

    Soil organic matter (SOM) is the largest terrestrial carbon pool and strongly affects soil properties. With climate change, understanding SOM processes and turnover and how they could be affected by increasing temperatures becomes critical. This is particularly key for organic soils as they represent a huge carbon pool in very sensitive ecosystems, like boreal ecosystems and peatlands. Nevertheless, characterization of SOM molecular composition, which is essential to elucidate soil carbon processes, is not easily achieved, and further advancements in that area are greatly needed. Solid-state one-dimensional (1D) 13C nuclear magnetic resonance (NMR) spectroscopy is often used to characterize its molecular composition, but only provides data on a few major functional groups, which regroup many different molecular fragments. For instance, in the carbohydrates region, signals of all monosaccharides present in many different polymers overlap. This overlap thwarts attempts to identify molecular moieties, resulting in insufficient information to characterize SOM composition. Here we show that two-dimensional (2D) liquid-state 1H-13C NMR spectra provided much richer data on the composition of boreal plant litter and organic surface soil. The 2D spectra indeed resolved overlaps observed in 1D 13C spectra and displayed signals from hundreds of identifiable molecular groups. For example, in the aromatics region, signals from individual lignin units could be recognized. It was hence possible to follow the fate of specific structural moieties in soils. We observed differences between litter and soil samples, and were able to relate them to the decomposition of identifiable moieties. Sample preparation and data acquisition were both simple and fast. Further, using multivariate data analysis, we aimed at linking the detailed chemical fingerprints of SOM to turnover rates in a soil incubation experiment. With the multivariate models, we were able to identify specific molecular

  5. Quantitative high-resolution on-line NMR spectroscopy in reaction and process monitoring.

    PubMed

    Maiwald, Michael; Fischer, Holger H; Kim, Young-Kyu; Albert, Klaus; Hasse, Hans

    2004-02-01

    On-line nuclear magnetic resonance spectroscopy (on-line NMR) is a powerful technique for reaction and process monitoring. Different set-ups for direct coupling of reaction and separation equipment with on-line NMR spectroscopy are described. NMR spectroscopy can be used to obtain both qualitative and quantitative information from complex reacting multicomponent mixtures for equilibrium or reaction kinetic studies. Commercial NMR probes can be used at pressures up to 35 MPa and temperatures up to 400 K. Applications are presented for studies of equilibria and kinetics of complex formaldehyde-containing mixtures as well as homogeneously and heterogeneously catalyzed esterification kinetics. Direct coupling of a thin-film evaporator is described as an example for the benefits of on-line NMR spectroscopy in process monitoring. PMID:14729025

  6. Detection of Taurine in Biological Tissues by 33S NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Musio, Roberta; Sciacovelli, Oronzo

    2001-12-01

    The potential of 33S NMR spectroscopy for biochemical investigations on taurine (2-aminoethanesulfonic acid) is explored. It is demonstrated that 33S NMR spectroscopy allows the selective and unequivocal identification of taurine in biological samples. 33S NMR spectra of homogenated and intact tissues are reported for the first time, together with the spectrum of a living mollusc. Emphasis is placed on the importance of choosing appropriate signal processing methods to improve the quality of the 33S NMR spectra of biological tissues.

  7. Nuclear Magnetic Resonance (NMR) Spectroscopy For Metabolic Profiling of Medicinal Plants and Their Products.

    PubMed

    Kumar, Dinesh

    2016-09-01

    NMR spectroscopy has multidisciplinary applications, including excellent impact in metabolomics. The analytical capacity of NMR spectroscopy provides information for easy qualitative and quantitative assessment of both endogenous and exogenous metabolites present in biological samples. The complexity of a particular metabolite and its contribution in a biological system are critically important for understanding the functional state that governs the organism's phenotypes. This review covers historical aspects of developments in the NMR field, its applications in chemical profiling, metabolomics, and quality control of plants and their derived medicines, foods, and other products. The bottlenecks of NMR in metabolic profiling are also discussed, keeping in view the future scope and further technological interventions. PMID:26575437

  8. Applications of Diffusion Ordered Spectroscopy (DOSY-NMR)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Diffusion-ordered NMR (DOSY-NMR) is a powerful, but under-utilized, technique for the investigation of mixtures based on translational diffusion rates. DOSY spectra allow for determination by NMR of components that may differ in molecular weight, geometry or complexation. Typical applications coul...

  9. Applications of 2D IR spectroscopy to peptides, proteins, and hydrogen-bond dynamics

    PubMed Central

    Kim, Yung Sam; Hochstrasser, Robin M.

    2010-01-01

    Following a survey of 2D IR principles this Feature Article describes recent experiments on the hydrogen-bond dynamics of small ions, amide-I modes, nitrile probes, peptides, reverse transcriptase inhibitors, and amyloid fibrils. PMID:19351162

  10. Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Gopinath, T.; Veglia, Gianluigi

    2013-05-01

    We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils.

  11. Homo- and heteronuclear 2D NMR approaches to analyse a mixture of deuterated unlike/like stereoisomers using weakly ordering chiral liquid crystals

    NASA Astrophysics Data System (ADS)

    Ben Ali, Karim; Lafon, Olivier; Zimmermann, Herbert; Guittet, Eric; Lesot, Philippe

    2007-08-01

    We describe several homo- and heteronuclear 2D NMR strategies dedicated to the analysis of anisotropic 2H spectra of a mixture of dideuterated unlike/like stereoisomers with two remote stereogenic centers, using weakly orienting chiral liquid crystals. To this end, we propose various 2D correlation experiments, denoted "D(H) nD" or "D(H) nC" (with n = 1, 2), that involve two heteronuclear polarization transfers of INEPT-type with one or two proton relays. The analytical expressions of correlation signals for four pulse sequences reported here were calculated using the product-operators formalism for spin I = 1 and S = 1/2. The features and advantages of each scheme are presented and discussed. The efficiency of these 2D sequences is illustrated using various deuterated model molecules, dissolved in organic solutions of polypeptides made of poly- γ-benzyl- L-glutamate (PBLG) or poly- ɛ-carbobenzyloxy- L-lysine (PCBLL) and NMR numerical simulations.

  12. Coherence selection in double CP MAS NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, Jen-Hsien; Chou, Fang-Chieh; Tzou, Der-Lii M.

    2008-11-01

    Applications of double cross-polarization (CP) magic-angle spinning (MAS) NMR spectroscopy, via 1H/ 15N and then 15N/ 13C coherence transfers, for 13C coherence selection are demonstrated on a 15N/ 13C-labeled N-acetyl-glucosamine (GlcNAc) compound. The 15N/ 13C coherence transfer is very sensitive to the settings of the experimental parameters. To resolve explicitly these parameter dependences, we have systematically monitored the 13C{ 15N/ 1H} signal as a function of the rf field strength and the MAS frequency. The data reveal that the zero-quantum coherence transfer, with which the 13C effective rf field is larger than that of the 15N by the spinning frequency, would give better signal sensitivity. We demonstrate in one- and two-dimensional double CP experiments that spectral editing can be achieved by tailoring the experimental parameters, such as the rf field strengths and/or the MAS frequency.

  13. Broadband 7-fs diffractive-optic-based 2D electronic spectroscopy using hollow-core fiber compression.

    PubMed

    Ma, Xiaonan; Dostál, Jakub; Brixner, Tobias

    2016-09-01

    We demonstrate noncollinear coherent two-dimensional (2D) electronic spectroscopy for which broadband pulses are generated in an argon-filled hollow-core fiber pumped by a 1-kHz Ti:Sapphire laser. Compression is achieved to 7 fs duration (TG-FROG) using dispersive mirrors. The hollow fiber provides a clean spatial profile and smooth spectral shape in the 500-700 nm region. The diffractive-optic-based design of the 2D spectrometer avoids directional filtering distortions and temporal broadening from time smearing. For demonstration we record data of cresyl-violet perchlorate in ethanol and use phasing to obtain broadband absorptive 2D spectra. The resulting quantum beating as a function of population time is consistent with literature data. PMID:27607681

  14. Development of a micro flow-through cell for high field NMR spectroscopy.

    SciTech Connect

    Alam, Todd Michael; McIntyre, Sarah K.

    2011-05-01

    A highly transportable micro flow-through detection cell for nuclear magnetic resonance (NMR) spectroscopy has been designed, fabricated and tested. This flow-through cell allows for the direct coupling between liquid chromatography (LC) and gel permeation chromatography (GPC) resulting in the possibility of hyphenated LC-NMR and GPC-NMR. The advantage of the present flow cell design is that it is independent and unconnected to the detection probe electronics, is compatible with existing commercial high resolution NMR probes, and as such can be easily implemented at any NMR facility. Two different volumes were fabricated corresponding to between {approx}3.8 and 10 {micro}L detection volume. Examples of the performance of the cell on different NMR instruments, and using different NMR detection probes were demonstrated.

  15. Distinctive features of complexation of anthracycline antibiotic daunomycin with deoxyhexanucleotide d(GCATGC) in aqueous solution: 1D- and 2D-NMR analysis

    NASA Astrophysics Data System (ADS)

    Pahomov, Valery I.; Rogova, Olga V.; Volynkin, Vladimir S.; Veselkov, Kyrill A.; Hernandez Santiago, Adrian A.; Semanin, Alexander V.; Djimant, Leonid N.; Veselkov, Alexei N.

    2004-07-01

    Complexation of anthracycline antibiotic daunomycin (DAU) with self-complementary deoxyhexanucleotide d(GCATGC) in aqueous solution has been investigated by one-dimensional and two-dimensional homonuclear 'H NMR spectroscopy (TOCSY and NOESY) and heteronuclear 'H-31P NMR spectroscopy (HMBC). Quantitative determination of parameters of oligonucleotide self-association and its complexation with DAU was based on the analysis of the dependences of proton chemical shifts on concentration and temperature. Experimental results were analysed in terms of the equilibrium reaction constants, limiting proton chemical shifts and thermodynamical parameters (enthalpies AN, entropies AS) of the formation of hexamer duplex and different drug-DNA complexes. The most favourable structures of the single-stranded form of d(GCATGC) and the intercalated DAU-hexamer complex have been determined using X-PLOR software taking into consideration both intra- and intermolecular NOE contacts.

  16. Investigation on the conformations of AOT in water-in-oil microemulsions using 2D-ATR-FTIR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Lai, Zuliang; Wu, Peiyi

    2008-07-01

    The carbonyl groups of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in the water-in-oil (W/O) microemulsions of AOT/tetrachloromethane/water were investigated by using two-dimensional attenuated total reflection Fourier transform infrared (2D-ATR-FTIR) correlation spectroscopy under a perturbation of temperature. The results of a traditional curve fitting method were compared with the 2D correlation spectra results. The peaks at 1718 and 1736 cm -1 were assigned to different carbonyl groups in trans conformation and gauche conformation of AOT molecules, respectively. With the increase of temperature, the trans conformation increased quickly at the lower temperature below 35 °C and decreased slowly at the higher temperature. The special phenomenon owed to the composition and decomposition of the hydrogen bonding between water of the inner polar core and carbonyl groups of AOT molecules. Two new peaks at 1707 and 1747 cm -1 in the 2D correlation spectra implied the process of the transition of AOT molecule conformation and the deviation of correlation coefficients of curve fitting method. 2D-ATR-FTIR correlation spectroscopy exhibited the superiority over the traditional curve fitting method.

  17. Simple fully reflective method of scatter reduction in 2D-IR spectroscopy.

    PubMed

    Spector, Ivan C; Olson, Courtney M; Huber, Christopher J; Massari, Aaron M

    2015-04-15

    A fully reflective two-dimensional IR (2D-IR) setup is described that enables efficient cancellation of scattered light from multiple pulses in the phase-matched direction. The local oscillator pulse and the pulse that stimulates the vibrational echo signal are synchronously modulated (or fibrillated) in time maintaining their phase relationships with the echo wavepacket. The modification is cost-effective and can be easily implemented on existing 2D-IR instruments, and it avoids the addition of dispersive elements into the beam paths. The fibrillation results in a decrease of waiting-time resolution of only tens of femtoseconds and has no impact on the spectral lineshape, making it a general improvement for 2D-IR spectrometers even for weakly or non-scattering samples. PMID:25872090

  18. Measurement of Solution Viscosity via Diffusion-Ordered NMR Spectroscopy (DOSY)

    ERIC Educational Resources Information Center

    Li, Weibin; Kagan, Gerald; Hopson, Russell; Williard, Paul G.

    2011-01-01

    Increasingly, the undergraduate chemistry curriculum includes nuclear magnetic resonance (NMR) spectroscopy. Advanced NMR techniques are often taught including two-dimensional gradient-based experiments. An investigation of intermolecular forces including viscosity, by a variety of methods, is often integrated in the undergraduate physical and…

  19. Functional group analysis in coal by sup 31 P NMR spectroscopy

    SciTech Connect

    Verkade, J.G.

    1989-05-01

    The purpose of this research is to determine the labile-hydrogen functional group composition of coal and coal-derived materials by the nmr spectroscopy of their derivatives made with reagents containing the nmr-active nuclei {sup 31}P, {sup 119}Sn, or {sup 205}Tl. 7 refs.

  20. Mobility and Diffusion-Ordered Two-Dimensional NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Morris, Kevin Freeman

    Mobility and diffusion-ordered two-dimensional nuclear magnetic resonance spectroscopy experiments have been developed for the analysis of mixtures. In the mobility -ordered experiments, the full range of positive and negative electrophoretic mobilities is displayed in one dimension and chemical shifts are displayed in the other. A concentric cylindrical tube electrophoresis chamber was designed to reduce the effective pathlength for current and to provide unidirectional flow for ions of interest. Techniques based upon the reverse precession method were also implemented to recover the signs of the mobilities and improved resolution in the mobility dimension was obtained by replacing Fourier transformation of truncated data sets with a linear prediction analysis. In the diffusion-ordered two-dimensional NMR experiments, the conventional chemical shift spectrum is resolved in one dimension and spectra of diffusion rates or molecular radii are resolved in the other. Diffusion dependent pulsed field gradient NMR data sets were inverted by means of the computer programs SPLMOD or DISCRETE, when discrete diffusion coefficients were present, and CONTIN when continuous distributions were present. Since the inversion is ill -conditioned, it was necessary to introduce additional information to limit the range of the solutions. In addition to prior knowledge of the decay kernels and non-negativity of amplitudes and damping constants, a set of rejection criteria was constructed for the discrete analysis case that took into account physical limits on diffusion coefficients, experimentally accessible values, and variations in effective decay kernels resulting from instrumental non-linearities. Examples of analyses of simulated data and experimental data for mixtures are presented as well as two-dimensional spectra generated by CONTIN for polydisperse polymer samples. Also, resolution in the diffusion dimension was increased by performing experiments on hydrophobic molecules in

  1. Contribution of NAD 2D-NMR in liquid crystals to the determination of hydrogen isotope profile of methyl groups in miliacin

    NASA Astrophysics Data System (ADS)

    Berdagué, Philippe; Lesot, Philippe; Jacob, Jérémy; Terwilliger, Valery J.; Le Milbeau, Claude

    2016-01-01

    The hydrogen isotopic composition (δD or (D/H) value) of molecular biomarkers preserved in sedimentary archives is increasingly used to provide clues about the evolution of past climatic conditions. The rationale is that intact biomarkers retain isotopic information related to the climatic conditions that prevailed at the time of their synthesis. Some of these biomarkers may be degraded during diagenesis, however. The extent to which these degradations alter the original δD value of the source biomarker is presently debated and the capacity to resolve this question by determination of compound-specific δD values alone is limited. The "bulk" or "global" δD value of any molecule is in fact a composite of δD values at each site within this molecule (δDi or (D/H)i with i = number of hydrogen/deuterium atoms in the considered molecule). Determination of this site-specific δDi value in biomarkers could not only yield outstanding paleoenvironmental information but also help forecast the impacts of diagenesis and define essential steps in biosynthetic pathways. This task is analytically challenging. Here, we examined the capabilities of natural abundance deuterium 2D-NMR (NAD 2D-NMR) using homopolypeptide liquid crystals as an NMR solvent to: (i) analyze the NAD spectra of biomakers; (ii) determine the site-specific distribution of hydrogen in the nine methyl groups (δDMei with i = 23-31) of miliacin, a pentacyclic triterpene of the amyrin family and key biomarker for broomcorn millet in sedimentary archives. Relative (D/H)Mei values were established by anisotropic NAD 2D-NMR. Then absolute δDMei values were obtained by determining δDMei value of the methoxy group of miliacin using two independent approaches: isotropic NAD NMR (SNIF-NMR™) and GC-irMS. The resulting isotope profile for miliacin shows, for the first time, large variations in δDMei values that can directly be explained by biosynthetic processes. This approach has also the potential to permit

  2. NMR profiling of biomolecules at natural abundance using 2D 1H-15N and 1H-13C multiplicity-separated (MS) HSQC spectra

    NASA Astrophysics Data System (ADS)

    Chen, Kang; Freedberg, Darón I.; Keire, David A.

    2015-02-01

    2D NMR 1H-X (X = 15N or 13C) HSQC spectra contain cross-peaks for all XHn moieties. Multiplicity-edited1H-13C HSQC pulse sequences generate opposite signs between peaks of CH2 and CH/CH3 at a cost of lower signal-to-noise due to the 13C T2 relaxation during an additional 1/1JCH period. Such CHn-editing experiments are useful in assignment of chemical shifts and have been successfully applied to small molecules and small proteins (e.g. ubiquitin) dissolved in deuterated solvents where, generally, peak overlap is minimal. By contrast, for larger biomolecules, peak overlap in 2D HSQC spectra is unavoidable and peaks with opposite phases cancel each other out in the edited spectra. However, there is an increasing need for using NMR to profile biomolecules at natural abundance dissolved in water (e.g., protein therapeutics) where NMR experiments beyond 2D are impractical. Therefore, the existing 2D multiplicity-edited HSQC methods must be improved to acquire data on nuclei other than 13C (i.e.15N), to resolve more peaks, to reduce T2 losses and to accommodate water suppression approaches. To meet these needs, a multiplicity-separated1H-X HSQC (MS-HSQC) experiment was developed and tested on 500 and 700 MHz NMR spectrometers equipped with room temperature probes using RNase A (14 kDa) and retroviral capsid (26 kDa) proteins dissolved in 95% H2O/5% D2O. In this pulse sequence, the 1/1JXH editing-period is incorporated into the semi-constant time (semi-CT) X resonance chemical shift evolution period, which increases sensitivity, and importantly, the sum and the difference of the interleaved 1JXH-active and the 1JXH-inactive HSQC experiments yield two separate spectra for XH2 and XH/XH3. Furthermore we demonstrate improved water suppression using triple xyz-gradients instead of the more widely used z-gradient only water-suppression approach.

  3. Metabolic Study of Breast MCF-7 Tumor Spheroids after Gamma Irradiation by 1H NMR Spectroscopy and Microimaging

    PubMed Central

    Palma, Alessandra; Grande, Sveva; Luciani, Anna Maria; Mlynárik, Vladimír; Guidoni, Laura; Viti, Vincenza; Rosi, Antonella

    2016-01-01

    Multicellular tumor spheroids are an important model system to investigate the response of tumor cells to radio- and chemotherapy. They share more properties with the original tumor than cells cultured as 2D monolayers do, which helps distinguish the intrinsic properties of monolayer cells from those induced during cell aggregation in 3D spheroids. The paper investigates some metabolic aspects of small tumor spheroids of breast cancer and their originating MCF-7 cells, grown as monolayer, by means of high–resolution (HR) 1H NMR spectroscopy and MR microimaging before and after gamma irradiation. The spectra of spheroids were characterized by higher intensity of mobile lipids, mostly neutral lipids, and glutamine (Gln) signals with respect to their monolayer cells counterpart, mainly owing to the lower oxygen supply in spheroids. Morphological changes of small spheroids after gamma-ray irradiation, such as loss of their regular shape, were observed by MR microimaging. Lipid signal intensity increased after irradiation, as evidenced in both MR localized spectra of the single spheroid and in HR NMR spectra of spheroid suspensions. Furthermore, the intense Gln signal from spectra of irradiated spheroids remained unchanged, while the low Gln signal observed in monolayer cells increased after irradiation. Similar results were observed in cells grown in hypoxic conditions. The different behavior of Gln in 2D monolayers and in 3D spheroids supports the hypothesis that a lower oxygen supply induces both an upregulation of Gln synthetase and a downregulation of glutaminases with the consequent increase in Gln content, as already observed under hypoxic conditions. The data herein indicate that 1H NMR spectroscopy can be a useful tool for monitoring cell response to different constraints. The use of spheroid suspensions seems to be a feasible alternative to localized spectroscopy since similar effects were found after radiation treatment. PMID:27200293

  4. Observation of kinetic networks of hydrogen-bond exchange using 2D IR echo spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Yung Sam; Hochstrasser, Robin M.

    The ultrafast H-bond motion in acetonitrile/methanol and of methanol and water around a dicarbonyl (piperidone) dominates the mechanism of vibrational coherence transfer in linear and 2D IR echo spectra. Multiple state coherence transfer and energy transfer are seen at and between the two carbonyl groups of the piperidone in both water and methanol.

  5. 2D-Raman-THz spectroscopy: A sensitive test of polarizable water models

    NASA Astrophysics Data System (ADS)

    Hamm, Peter

    2014-11-01

    In a recent paper, the experimental 2D-Raman-THz response of liquid water at ambient conditions has been presented [J. Savolainen, S. Ahmed, and P. Hamm, Proc. Natl. Acad. Sci. U. S. A. 110, 20402 (2013)]. Here, all-atom molecular dynamics simulations are performed with the goal to reproduce the experimental results. To that end, the molecular response functions are calculated in a first step, and are then convoluted with the laser pulses in order to enable a direct comparison with the experimental results. The molecular dynamics simulation are performed with several different water models: TIP4P/2005, SWM4-NDP, and TL4P. As polarizability is essential to describe the 2D-Raman-THz response, the TIP4P/2005 water molecules are amended with either an isotropic or a anisotropic polarizability a posteriori after the molecular dynamics simulation. In contrast, SWM4-NDP and TL4P are intrinsically polarizable, and hence the 2D-Raman-THz response can be calculated in a self-consistent way, using the same force field as during the molecular dynamics simulation. It is found that the 2D-Raman-THz response depends extremely sensitively on details of the water model, and in particular on details of the description of polarizability. Despite the limited time resolution of the experiment, it could easily distinguish between various water models. Albeit not perfect, the overall best agreement with the experimental data is obtained for the TL4P water model.

  6. 2D-Raman-THz spectroscopy: A sensitive test of polarizable water models

    SciTech Connect

    Hamm, Peter

    2014-11-14

    In a recent paper, the experimental 2D-Raman-THz response of liquid water at ambient conditions has been presented [J. Savolainen, S. Ahmed, and P. Hamm, Proc. Natl. Acad. Sci. U. S. A. 110, 20402 (2013)]. Here, all-atom molecular dynamics simulations are performed with the goal to reproduce the experimental results. To that end, the molecular response functions are calculated in a first step, and are then convoluted with the laser pulses in order to enable a direct comparison with the experimental results. The molecular dynamics simulation are performed with several different water models: TIP4P/2005, SWM4-NDP, and TL4P. As polarizability is essential to describe the 2D-Raman-THz response, the TIP4P/2005 water molecules are amended with either an isotropic or a anisotropic polarizability a posteriori after the molecular dynamics simulation. In contrast, SWM4-NDP and TL4P are intrinsically polarizable, and hence the 2D-Raman-THz response can be calculated in a self-consistent way, using the same force field as during the molecular dynamics simulation. It is found that the 2D-Raman-THz response depends extremely sensitively on details of the water model, and in particular on details of the description of polarizability. Despite the limited time resolution of the experiment, it could easily distinguish between various water models. Albeit not perfect, the overall best agreement with the experimental data is obtained for the TL4P water model.

  7. Structural and conformational study of the aluminum-thymulin complex using 1-D and 2-D NMR techniques

    SciTech Connect

    Laussac, J.P.; Lefrancier, P.; Dardenne, M.; Bach, J.F.; Marraud, M.; Cung, M.T.

    1988-11-16

    The interaction between aluminum and thymulin, a linear nonapeptide of thymic origin isolated from serum, was investigated by means of one- and two-dimensional NMR experiments. These experiments were performed in dimethyl-d/sub 6/ sulfoxide solution at different metal:peptide ratios. The results lead the following conclusions: (i) the Al(III) complexation corresponds to a fast exchange on the NMR time scale; (ii) the evolution of /sup 1/H and /sup 13/C NMR chemical shifts indicates the existence of one type of complex with a 1:2 stoichiometry, associating two peptide molecules and one Al(III) ion; (iii) analysis of the spectra suggests that Al(III) has a specific binding site involving the Asn/sup 9/COO/sup /minus// terminal group and the hydroxyl group of the Ser/sup 4/ residue; (iv) from the NOESY data a conformation has been proposed and compared to the biologically active Zn(II)-thymulin complex. 23 refs., 6 figs., 1 tab.

  8. Identification and quantification of major steviol glycosides in Stevia rebaudiana purified extracts by 1H NMR spectroscopy.

    PubMed

    Pieri, Valerio; Belancic, Andrea; Morales, Susana; Stuppner, Hermann

    2011-05-11

    The use of (1)H NMR spectroscopy for the characterization of Stevia rebaudiana extracts is presented. The developed method allows qualitative and quantitative determination of the major steviol glycosides in purified extracts and fractions obtained from various stages of the purification process. Moreover, it proved to be a powerful tool to differentiate between glycosides which are naturally occurring in the stevia plant and artifacts formed in the course of the manufacturing process. Identification of steviol glycosides was achieved by the use of 2D NMR techniques, whereas quantification is based on qHNMR using anthracene as internal standard. The solvent mixture pyridine-d(5)-DMSO-d(6) (6:1) enabled satisfactory separation of the signals to be integrated. Validation of the method was performed in terms of specificity, precision, accuracy, linearity, robustness, and stability. Quantitative results were compared to those obtained with the JECFA HPLC-UV method and were found to be in reasonable agreement. NMR analysis does not rely on the use of reference compounds and enables significantly faster analysis compared to HPLC-UV. Thus, NMR represents a feasible alternative to HPLC-based methods for the quality control of Stevia rebaudiana extracts. PMID:21417451

  9. Characterization and quantification of microstructures of a fluorinated terpolymer by both homonuclear and heteronuclear two-dimensional NMR spectroscopy.

    PubMed

    Ok, Salim

    2015-02-01

    Fluoropolymers are usually insoluble in organic solvents. Insolubility of fluoropolymers limits basic characterization such as microstructural investigations. In the family of fluoropolymers, terpolymer of tetrafluorethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF), named THV is one of the newest members. There are nine grades of THV available. Among the nine grades, THV-221 G is an ideal model polymer for basic characterization purposes. THV-221 G is soluble in solvents such as acetone and ethyl acetate. In the current report, both homonuclear and heteronuclear 2D NMR experiments were employed in solution on THV-221 G. The homonuclear gradient correlation spectroscopy NMR measurement revealed that THV has two adjacent TFE units in addition to TFE-HFP sequence orders. The fraction of the microstructures is quantified by the analysis of 1D solution (19)F NMR spectrum. Further, the gradient heteronuclear single quantum coherence experiment helped with the clarification of chemical environments of the units TFE, HFP, and VDF. The 1D solution (13)C NMR spectrum was helpful in clarifying sequence assignments of VDF. It is concluded that THV is a random polymer with a limited fraction of TFE-TFE and TFE-HFP sequence orders in addition to head-to-tail polymerization of VDF unit. PMID:25327292

  10. Functional groups identified by solid state 13C NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Animal manure is generally high in organic matter intensity so it is well suitable for 13C nuclear magnetic resonance (NMR) analysis. Solid-state 13C NMR techniques used in characterizing organic matter and its components include, but are not limited to, cross-polarization /magic angle spinning (CP...

  11. Characterization of protein hydration by solution NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Wand, Joshua

    A comprehensive understanding of the interactions between protein molecules and hydration water remains elusive. Solution nuclear magnetic resonance (NMR) spectroscopy has been proposed as a means to characterize these interactions but is plagued with artifacts when employed in bulk aqueous solution. Encapsulation of proteins in reverse micelles prepared in short chain alkane solvents can overcome these technical limitations. Application of this approach has revealed that the interaction of water with the surface of protein molecules is quite heterogeneous with some regions of the protein having long-lived interactions while other regions show relatively transient hydration. Results from several proteins will be presented including ubiquitin, staphylococcal nuclease, interleukin 1beta, hen egg white lysozyme (HEWL) and T4 lysozyme. Ubiquitin and interleukin 1beta are signaling proteins and interact with other proteins through formation of dry protein-protein interfaces. Interestingly, the protein surfaces of the free proteins show relatively slowed (restricted) motion at the surface, which is indicative of low residual entropy. Other regions of the protein surface have relatively high mobility water. These results are consistent with the idea that proteins have evolved to maximize the hydrophobic effect in optimization of binding with protein partners. As predicted by simulation and theory, we find that hydration of internal hydrophobic cavities of interleukin 1beta and T4 lysozyme is highly disfavored. In contrast, the hydrophilic polar cavity of HEWL is occupied by water. Initial structural correlations suggest that hydration of alpha helical structure is characterized by relatively mobile water while those of beta strands and loops are more ordered and slowed. These and other results from this set of proteins reveals that the dynamical and structural character of hydration of proteins is heterogeneous and complex. Supported by the National Science Foundation.

  12. In vivo 1D and 2D correlation MR spectroscopy of the soleus muscle at 7T

    NASA Astrophysics Data System (ADS)

    Ramadan, Saadallah; Ratai, Eva-Maria; Wald, Lawrence L.; Mountford, Carolyn E.

    2010-05-01

    AimThis study aims to (1) undertake and analyse 1D and 2D MR correlation spectroscopy from human soleus muscle in vivo at 7T, and (2) determine T1 and T2 relaxation time constants at 7T field strength due to their importance in sequence design and spectral quantitation. MethodSix healthy, male volunteers were consented and scanned on a 7T whole-body scanner (Siemens AG, Erlangen, Germany). Experiments were undertaken using a 28 cm diameter detunable birdcage coil for signal excitation and an 8.5 cm diameter surface coil for signal reception. The relaxation time constants, T1 and T2 were recorded using a STEAM sequence, using the 'progressive saturation' method for the T1 and multiple echo times for T2. The 2D L-Correlated SpectroscopY (L-COSY) method was employed with 64 increments (0.4 ms increment size) and eight averages per scan, with a total time of 17 min. ResultsT1 and T2 values for the metabolites of interest were determined. The L-COSY spectra obtained from the soleus muscle provided information on lipid content and chemical structure not available, in vivo, at lower field strengths. All molecular fragments within multiple lipid compartments were chemically shifted by 0.20-0.26 ppm at this field strength. 1D and 2D L-COSY spectra were assigned and proton connectivities were confirmed with the 2D method. ConclusionIn vivo 1D and 2D spectroscopic examination of muscle can be successfully recorded at 7T and is now available to assess lipid alterations as well as other metabolites present with disease. T1 and T2 values were also determined in soleus muscle of male healthy volunteers.

  13. Recovering the Fermi surface with 2D-ACAR spectroscopy in samples with defects

    NASA Astrophysics Data System (ADS)

    Dugdale, S. B.; Laverock, J.

    2014-04-01

    When two-dimensional angular correlation of positron annihilation radiation (2D-ACAR) experiments are performed in metals containing defects, conventional analysis in which the measured momentum distribution is folded back into the first Brillouin zone is rendered ineffective due to the contribution from positrons annihilating from the defect. However, by working with the radial anisotropy of the spectrum, it is shown that an image of the Fermi surface can be recovered since the defect contribution is essentially isotropic.

  14. Interrogating Fiber Formation Kinetics with Automated 2D-IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Strasfeld, David B.; Ling, Yun L.; Shim, Sang-Hee; Zanni, Martin T.

    A new method for collecting 2D-IR spectra that utilizes both a pump-probe beam geometry and a mid-IR pulse shaper is used to gain a fuller understanding of fiber formation in the human islet amyloid polypeptide (hIAPP). We extract structural kinetics in order to better understand aggregation in hIAPP, the protein component of the amyloid fibers found to inhibit insulin production in type II diabetes patients.

  15. [Non-invasive analysis of proteins in living cells using NMR spectroscopy].

    PubMed

    Tochio, Hidehito; Murayama, Shuhei; Inomata, Kohsuke; Morimoto, Daichi; Ohno, Ayako; Shirakawa, Masahiro

    2015-01-01

    NMR spectroscopy enables structural analyses of proteins and has been widely used in the structural biology field in recent decades. NMR spectroscopy can be applied to proteins inside living cells, allowing characterization of their structures and dynamics in intracellular environments. The simplest "in-cell NMR" approach employs bacterial cells; in this approach, live Escherichia coli cells overexpressing a specific protein are subjected to NMR. The cells are grown in an NMR active isotope-enriched medium to ensure that the overexpressed proteins are labeled with the stable isotopes. Thus the obtained NMR spectra, which are derived from labeled proteins, contain atomic-level information about the structure and dynamics of the proteins. Recent progress enables us to work with higher eukaryotic cells such as HeLa and HEK293 cells, for which a number of techniques have been developed to achieve isotope labeling of the specific target protein. In this review, we describe successful use of electroporation for in-cell NMR. In addition, (19)F-NMR to characterize protein-ligand interactions in cells is presented. Because (19)F nuclei rarely exist in natural cells, when (19)F-labeled proteins are delivered into cells and (19)F-NMR signals are observed, one can safely ascertain that these signals originate from the delivered proteins and not other molecules. PMID:25759048

  16. Two-dimensional NMR spectroscopy links structural moieties of soil organic matter to the temperature sensitivity of its decomposition

    NASA Astrophysics Data System (ADS)

    Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Schleucher, Jürgen

    2015-04-01

    Soil organic matter (SOM) represents a huge carbon pool, specifically in boreal ecosystems. Warming-induced release of large amounts of CO2 from the soil carbon pool might become a significant exacerbating feedback to global warming, if decomposition rates of boreal soils were more sensitive to increased temperatures. Despite a large number of studies dedicated to the topic, it has proven difficult to elucidate how the organo-chemical composition of SOM influences its decomposition, or its quality as a substrate for microbial metabolism. A great part of this challenge results from our inability to achieve a detailed characterization of the complex composition of SOM on the level of molecular structural moieties. 13C nuclear magnetic resonance (NMR) spectroscopy is a common tool to characterize SOM. However, SOM is a very complex mixture and the chemical shift regions distinguished in the 13C NMR spectra often represent many different molecular fragments. For example, in the carbohydrates region, signals of all monosaccharides present in many different polymers overlap. This overlap thwarts attempts to identify molecular moieties, resulting in insufficient information to characterize SOM composition. We applied two-dimensional (2D) NMR to characterize SOM with highly increased resolution. We directly dissolved finely ground litters and forest floors'fibric and humic horizons'of both coniferous and deciduous boreal forests in dimethyl sulfoxide and analyzed the resulting solution with a 2D 1H-13C NMR experiment. In the 2D planes of these spectra, signals of CH groups can be resolved based on their 13C and 1H chemical shifts, hence the resolving power and information content of these NMR spectra is hugely increased. The 2D spectra indeed resolved overlaps observed in 1D 13C spectra, so that hundreds of distinct CH groups could be observed and many molecular fragments could be identified. For instance, in the aromatics region, signals from individual lignin units could

  17. A new sequence for shaped voxel spectroscopy in the human brain using 2D spatially selective excitation and parallel transmission.

    PubMed

    Waxmann, Patrick; Mekle, Ralf; Schubert, Florian; Brühl, Rüdiger; Kuehne, Andre; Lindel, Tomasz D; Seifert, Frank; Speck, Oliver; Ittermann, Bernd

    2016-08-01

    Spatially selective excitation in two dimensions (2D-SSE) utilizing parallel transmission was applied as a means to acquire signal from voxels adapted to the anatomy of interest for in vivo (1) H MR spectroscopy. A novel method to select spectroscopy voxels with arbitrary shapes in two dimensions was investigated. An on-off scheme with an adiabatic slice selective inversion pulse preceding a 2D-SSE pulse together with a segmented inward spiral excitation k-space trajectory enabled rapid free induction decay acquisitions. Performance of the sequence was evaluated in simulations, phantom experiments, and in vivo measurements at 3 T. High spatial fidelity of the excitation profile was achieved for different target shapes and with little off-resonance deterioration. Metabolite concentrations in human brain determined with the new sequence were quantified with Cramér-Rao lower bounds less than 20%. They were in the physiological range and did not deviate systematically from results acquired with a conventional SPECIAL sequence. In conclusion, a new approach for shaped voxel MRS in the human brain is presented, which complements existing sequences. Simulations show that 2D-SSE pulses yield reduced chemical shift artifact when compared with conventional localization methods. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27254102

  18. Spin-coated and PECVD low dielectric constant porous organosilicate films studied by 1D and 2D solid-state NMR.

    PubMed

    Gerbaud, Guillaume; Hediger, Sabine; Bardet, Michel; Favennec, Laurent; Zenasni, Aziz; Beynet, Julien; Gourhant, Olivier; Jousseaume, Vincent

    2009-11-14

    In the research field of the sub-65 nm semiconductor industry, organosilicate SiOCH films with low dielectric constant (k < 2.4) need to be developed in order to improve the performance of integrated circuits [International Roadmap for Semiconductors (ITRS), San Jose, CA, 2004]. One way to produce SiOCH films of low dielectric constant is to introduce pores into the film. This is usually obtained in two steps. Firstly, co-deposition of a matrix precursor, with a sacrificial organic porogen, either by plasma enhanced chemical vapor deposition (PECVD) or spin-coating. Secondly, application of a specific thermal treatment to remove the porogen and create the porosity. This last step can be improved by adding to the thermal process a super-critical CO(2) treatment, an UV irradiation or an electronic bombardment (e-beam). In this study, the two deposition processes as well as the various treatments applied to eliminate the porogens were evaluated and compared using high-resolution solid-state NMR. For this purpose, hybrid (containing porogens) and porous films were extensively characterized on the basis of their (1)H, (13)C and (29)Si high-resolution NMR spectra. Information was obtained concerning the crosslinking of the Si skeleton. Spectral features could be correlated to the processes used. Isotropic chemical shift analyses and 2D correlation NMR experiments were used to show the existence and nature of the interactions between the matrix precursor and the organic porogen. PMID:19851550

  19. Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d6/pyridine-d5†

    PubMed Central

    Ralph, John

    2014-01-01

    NMR fingerprinting of the components of finely divided plant cell walls swelled in DMSO has been recently described. Cell wall gels, produced directly in the NMR tube with perdeutero-dimethylsulfoxide, allowed the acquisition of well resolved/dispersed 2D 13C–1H correlated solution-state NMR spectra of the entire array of wall polymers, without the need for component fractionation. That is, without actual solubilization, and without apparent structural modification beyond that inflicted by the ball milling and ultrasonication steps, satisfactorily interpretable spectra can be acquired that reveal compositional and structural details regarding the polysaccharide and lignin components in the wall. Here, the profiling method has been improved by using a mixture of perdeuterated DMSO and pyridine (4:1, v/v). Adding pyridine provided not only easier sample handling because of the better mobility compared to the DMSO-d6-only system but also considerably elevated intensities and improved resolution of the NMR spectra due to the enhanced swelling of the cell walls. This modification therefore provides a more rapid method for comparative structural evaluation of plant cell walls than is currently available. We examined loblolly pine (Pinus taeda, a gymnosperm), aspen (Populus tremuloides, an angiosperm), kenaf (Hibiscus cannabinus, an herbaceous plant), and corn (Zea mays L., a grass, i.e., from the Poaceae family). In principle, lignin composition (notably, the syringyl : guaiacyl : p-hydroxyphenyl ratio) can be quantified without the need for lignin isolation. Correlations for p-coumarate units in the corn sample are readily seen, and a variety of the ferulate correlations are also well resolved; ferulates are important components responsible for cell wall cross-linking in grasses. Polysaccharide anomeric correlations were tentatively assigned for each plant sample based on standard samples and various literature data. With the new potential for chemometric analysis

  20. Perspectives of solution NMR spectroscopy for structural and functional studies of integral membrane proteins

    NASA Astrophysics Data System (ADS)

    Reckel, Sina; Hiller, Sebastian

    2013-04-01

    This article discusses future perspectives of solution NMR spectroscopy to study structures and functions of integral membrane proteins at atomic resolution, based on a review of recent progress in this area. Several selected examples of structure determinations, as well as functional studies of integral membrane proteins are highlighted. We expect NMR spectroscopy to make future key scientific contributions to understanding membrane protein function, in particular for large membrane protein systems with known three-dimensional structure. Such situations can benefit from the fact that functional NMR studies have substantially less limitations by molecular size than a full de novo structure determination. Therefore, the general potential for NMR spectroscopy to solve biologic key questions associated with integral membrane proteins is very promising.

  1. Hartmann-Hahn 2D-map to optimize the RAMP-CPMAS NMR experiment for pharmaceutical materials.

    PubMed

    Suzuki, Kazuko; Martineau, Charlotte; Fink, Gerhard; Steuernagel, Stefan; Taulelle, Francis

    2012-02-01

    Cross polarization-magic angle spinning (CPMAS) is the most used experiment for solid-state NMR measurements in the pharmaceutical industry, with the well-known variant RAMP-CPMAS its dominant implementation. The experimental work presented in this contribution focuses on the entangled effects of the main parameters of such an experiment. The shape of the RAMP-CP pulse has been considered as well as the contact time duration, and a particular attention also has been devoted to the radio-frequency (RF) field inhomogeneity. (13)C CPMAS NMR spectra have been recorded with a systematic variation of (13)C and (1)H constant radiofrequency field pair values and represented as a Hartmann-Hahn matching two-dimensional map. Such a map yields a rational overview of the intricate optimal conditions necessary to achieve an efficient CP magnetization transfer. The map also highlights the effects of sweeping the RF by the RAMP-CP pulse on the number of Hartmann-Hahn matches crossed and how RF field inhomogeneity helps in increasing the CP efficiency by using a larger fraction of the sample. In the light of the results, strategies for optimal RAMP-CPMAS measurements are suggested, which lead to a much higher efficiency than constant amplitude CP experiment. PMID:22367881

  2. NMR Stark Spectroscopy: New Methods to Calibrate NMR Sensitivity to Electric Fields

    NASA Astrophysics Data System (ADS)

    Tarasek, Matthew R.

    The influence of electrostatics on NMR parameters is well accepted. Thus, NMR is a promising route to probe electrical features within molecules and materials. However, applications of NMR Stark effects (E-field induced changes in spin energy levels) have been elusive. I have developed new approaches to resolve NMR Stark effects from an applied E field. This calibrates nuclear probes whose spectral response might later be used to evaluate internal E fields that are critical to function, such as those due to local charge distributions or sample structure. I will present two novel experimental approaches for direct calibration of NMR quadrupolar Stark effects (QSEs). In the first, steady-state (few-second) excitation by an E field at twice the NMR frequency (2ω 0) is used to saturate spin magnetization. The extent of saturation vs. E-field amplitude calibrates the QSE response rate, while measurements vs sample orientation determine tensorial character. The second method instead synchronizes short (few µs) pulses of the 2ω0 E field with a multiple-pulse NMR sequence. This, “POWER” (Perturbations Observed With Enhanced Resolution) approach enables more accurate measure of small QSEs (i.e. few Hz spectral changes). A 2nd key advantage is the ability to define tensorial response without reorienting the sample, but instead varying the phase of the 2ω0 field. I will describe these experiments and my home-built NMR “Stark probe”, employed on a conventional wide-bore solid-state NMR system. Results with GaAs demonstrate each method, while extensions to a wider array of molecular and material systems may now be possible using these methods.

  3. Characterization of the isomeric configuration and impurities of (Z)-endoxifen by 2D NMR, high resolution LC⬜MS, and quantitative HPLC analysis.

    PubMed

    Elkins, Phyllis; Coleman, Donna; Burgess, Jason; Gardner, Michael; Hines, John; Scott, Brendan; Kroenke, Michelle; Larson, Jami; Lightner, Melissa; Turner, Gregory; White, Jonathan; Liu, Paul

    2014-01-01

    (Z)-Endoxifen (4-hydroxy-N-desmethyltamoxifen), an active metabolite generated via actions of CYP3A4/5 and CYP2D6, is a more potent selective estrogen receptor modulator (SERM) than tamoxifen. In the MCF-7 human mammary tumor xenograft model with female athymic mice, (Z)-endoxifen, at an oral dose of 4⬜8 mg/kg, significantly inhibits tumor growth. (Z)-Endoxifen's potential as an alternative therapeutic agent independent of CYP2D6 activities, which can vary widely in ER+ breast cancer patients, is being actively evaluated. This paper describes confirmation of the configuration of the active (Z)-isomer through 2D NMR experiments, including NOE (ROESY) to establish spatial proton⬜proton correlations, and identification of the major impurity as the (E)-isomer in endoxifen drug substance by HPLC/HRMS (HPLC/MS-TOF). Stability of NMR solutions was confirmed by HPLC/UV analysis. For pre-clinical studies, a reverse-phase HPLC⬜UV method, with methanol/water mobile phases containing 10 mM ammonium formate at pH 4.3, was developed and validated for the accurate quantitation and impurity profiling of drug substance and drug product. Validation included demonstration of linearity, method precision, accuracy, and specificity in the presence of impurities, excipients (for the drug product), and degradation products. Ruggedness and reproducibility of the method were confirmed by collaborative studies between two independent laboratories. The method is being applied for quality control of the API and oral drug product. Kinetic parameters of Z- to E-isomerization were also delineated in drug substance and in aqueous formulation, showing conversion at temperatures above 25 °C. PMID:24055701

  4. NMR Spectroscopy for Thin Films by Magnetic Resonance Force Microscopy

    PubMed Central

    Won, Soonho; Saun, Seung-Bo; Lee, Soonchil; Lee, SangGap; Kim, Kiwoong; Han, Yunseok

    2013-01-01

    Nuclear magnetic resonance (NMR) is a fundamental research tool that is widely used in many fields. Despite its powerful applications, unfortunately the low sensitivity of conventional NMR makes it difficult to study thin film or nano-sized samples. In this work, we report the first NMR spectrum obtained from general thin films by using magnetic resonance force microscopy (MRFM). To minimize the amount of imaging information inevitably mixed into the signal when a gradient field is used, we adopted a large magnet with a flat end with a diameter of 336 μm that generates a homogeneous field on the sample plane and a field gradient in a direction perpendicular to the plane. Cyclic adiabatic inversion was used in conjunction with periodic phase inversion of the frequency shift to maximize the SNR. In this way, we obtained the 19F NMR spectrum for a 34 nm-thick CaF2 thin film. PMID:24217000

  5. Applications of high resolution /sup 3/H NMR spectroscopy

    SciTech Connect

    Williams, P.G.

    1987-10-01

    The advantages of tritium as an NMR nucleus are pointed out. Examples of its use are given, including labelled toluene, hydrogenation of ..beta..-methylstyrene, and maltose and its binding proteins. 7 refs., 2 figs. (DLC)

  6. Removal of t1 noise from metabolomic 2D 1H- 13C HSQC NMR spectra by Correlated Trace Denoising

    NASA Astrophysics Data System (ADS)

    Poulding, Simon; Charlton, Adrian J.; Donarski, James; Wilson, Julie C.

    2007-12-01

    The presence of t1 noise artefacts in 2D phase-cycled Heteronuclear Single Quantum Coherence (HSQC) spectra constrains the use of this experiment despite its superior sensitivity. This paper proposes a new processing algorithm, working in the frequency-domain, for reducing t1 noise. The algorithm has been developed for use in contexts, such as metabolomic studies, where existing denoising techniques cannot always be applied. Two test cases are presented that show the algorithm to be effective in improving the SNR of peaks embedded within t1 noise by a factor of more than 2, while retaining the intensity and shape of genuine peaks.

  7. XAFS data acquisition with 2D-detectors: Transmission mode XAFS and grazing incidence EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Lützenkirchen-Hecht, D.; Gasse, J.-C.; Bögel, R.; Wagner, R.; Frahm, R.

    2016-05-01

    XAFS-experiments in transmission and reflection modes have been performed using a Pilatus 100K pixel detector. Transmission mode XAFS spectra from a Co metal foil and Co3O4 were recorded to evaluate the data quality offered by this 2D-detector. Furthermore, the pixel detector was also used to measure reflection mode grazing incidence EXAFS data. Using different regions of interest in the collected scattering patterns, we will show that the diffuse scattering can be separated for the different contributing surfaces and interfaces, allowing simultaneous investigations of surfaces and buried interfaces within multi-layered samples.

  8. Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kramer, Patrick L.; Nishida, Jun; Giammanco, Chiara H.; Tamimi, Amr; Fayer, Michael D.

    2015-05-01

    In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, , than in the standard all parallel configuration, , in which all four pulses have the same polarization. The 2D IR experiment with polarizations ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system.

  9. Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy.

    PubMed

    Kramer, Patrick L; Nishida, Jun; Giammanco, Chiara H; Tamimi, Amr; Fayer, Michael D

    2015-05-14

    In nearly all applications of ultrafast multidimensional infrared spectroscopy, the spectral degrees of freedom (e.g., transition frequency) and the orientation of the transition dipole are assumed to be decoupled. We present experimental results which confirm that frequency fluctuations can be caused by rotational motion and observed under appropriate conditions. A theory of the frequency-frequency correlation function (FFCF) observable under various polarization conditions is introduced, and model calculations are found to reproduce the qualitative trends in FFCF rates. The FFCF determined with polarization-selective two-dimensional infrared (2D IR) spectroscopy is a direct reporter of the frequency-rotational coupling. For the solute methanol in a room temperature ionic liquid, the FFCF of the hydroxyl (O-D) stretch decays due to spectral diffusion with different rates depending on the polarization of the excitation pulses. The 2D IR vibrational echo pulse sequence consists of three excitation pulses that generate the vibrational echo, a fourth pulse. A faster FFCF decay is observed when the first two excitation pulses are polarized perpendicular to the third pulse and the echo, 〈XXY Y〉, than in the standard all parallel configuration, 〈XXXX〉, in which all four pulses have the same polarization. The 2D IR experiment with polarizations 〈XY XY〉 ("polarization grating" configuration) gives a FFCF that decays even more slowly than in the 〈XXXX〉 configuration. Polarization-selective 2D IR spectra of bulk water do not exhibit polarization-dependent FFCF decays; spectral diffusion is effectively decoupled from reorientation in the water system. PMID:25978898

  10. Improving the resolution in proton-detected through-space heteronuclear multiple quantum correlation NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Shen, Ming; Trébosc, J.; Lafon, O.; Pourpoint, F.; Hu, Bingwen; Chen, Qun; Amoureux, J.-P.

    2014-08-01

    Connectivities and proximities between protons and low-gamma nuclei can be probed in solid-state NMR spectroscopy using two-dimensional (2D) proton-detected heteronuclear correlation, through Heteronuclear Multiple Quantum Correlation (HMQC) pulse sequence. The indirect detection via protons dramatically enhances the sensitivity. However, the spectra are often broadened along the indirect F1 dimension by the decay of heteronuclear multiple-quantum coherences under the strong 1H-1H dipolar couplings. This work presents a systematic comparison of the performances of various decoupling schemes during the indirect t1 evolution period of dipolar-mediated HMQC (D-HMQC) experiment. We demonstrate that 1H-1H dipolar decoupling sequences during t1, such as symmetry-based schemes, phase-modulated Lee-Goldburg (PMLG) and Decoupling Using Mind-Boggling Optimization (DUMBO), provide better resolution than continuous wave 1H irradiation. We also report that high resolution requires the preservation of 1H isotropic chemical shifts during the decoupling sequences. When observing indirectly broad spectra presenting numerous spinning sidebands, the D-HMQC sequence must be fully rotor-synchronized owing to the rotor-synchronized indirect sampling and dipolar recoupling sequence employed. In this case, we propose a solution to reduce artefact sidebands caused by the modulation of window delays before and after the decoupling application during the t1 period. Moreover, we show that 1H-1H dipolar decoupling sequence using Smooth Amplitude Modulation (SAM) minimizes the t1-noise. The performances of the various decoupling schemes are assessed via numerical simulations and compared to 2D 1H-{13C} D-HMQC experiments on [U-13C]-L-histidineṡHClṡH2O at various magnetic fields and Magic Angle spinning (MAS) frequencies. Great resolution and sensitivity enhancements resulting from decoupling during t1 period enable the detection of heteronuclear correlation between aliphatic protons and

  11. 13C and 1H chemical shift assignments and conformation confirmation of trimedlure-Y via 2-D NMR

    NASA Astrophysics Data System (ADS)

    Warthen, J. D.; Waters, R. M.; McGovern, T. P.

    The conformation of 1,1-dimethylethyl 5-chloro- cis-2-methylcyclohexane-1-carboxylate (trimedlure-Y) was confirmed as 1,2,5 equatorial, axial, equatorial via 13C, 1H, APT, CSCM and COSY NMR analyses. The carbon and proton nuclei in trimedlure-Y and the previously unassigned eight cyclohexyl protons (1.50-2.60 ppm) in 1,1-dimethylethyl 5-chloro- trans-2-methylcyclohexane-1-carboxylate (trimedlure-B 1; 1,2,5 equatorial, equatorial, equatorial) were also characterized by these methods. The effects of the 2-CH 3 in the axial or equatorial conformation upon the chemical shifts of the other nuclei in the molecule are discussed.

  12. Functional genomics by NMR spectroscopy. Phenylacetate catabolism in Escherichia coli.

    PubMed

    Ismail, Wael; El-Said Mohamed, Magdy; Wanner, Barry L; Datsenko, Kirill A; Eisenreich, Wolfgang; Rohdich, Felix; Bacher, Adelbert; Fuchs, Georg

    2003-07-01

    Aerobic metabolism of phenylalanine in most bacteria proceeds via oxidation to phenylacetate. Surprisingly, the further metabolism of phenylacetate has not been elucidated, even in well studied bacteria such as Escherichia coli. The only committed step is the conversion of phenylacetate into phenylacetyl-CoA. The paa operon of E. coli encodes 14 polypeptides involved in the catabolism of phenylacetate. We have found that E. coli K12 mutants with a deletion of the paaF, paaG, paaH, paaJ or paaZ gene are unable to grow with phenylacetate as carbon source. Incubation of a paaG mutant with [U-13C8]phenylacetate yielded ring-1,2-dihydroxy-1,2-dihydrophenylacetyl lactone as shown by NMR spectroscopy. Incubation of the paaF and paaH mutants with phenylacetate yielded delta3-dehydroadipate and 3-hydroxyadipate, respectively. The origin of the carbon atoms of these C6 compounds from the aromatic ring was shown using [ring-13C6]phenylacetate. The paaG and paaZ mutants also converted phenylacetate into ortho-hydroxyphenylacetate, which was previously identified as a dead end product of phenylacetate catabolism. These data, in conjunction with protein sequence data, suggest a novel catabolic pathway via CoA thioesters. According to this, phenylacetyl-CoA is attacked by a ring-oxygenase/reductase (PaaABCDE proteins), generating a hydroxylated and reduced derivative of phenylacetyl-CoA, which is not re-oxidized to a dihydroxylated aromatic intermediate, as in other known aromatic pathways. Rather, it is proposed that this nonaromatic intermediate CoA ester is further metabolized in a complex reaction sequence comprising enoyl-CoA isomerization/hydration, nonoxygenolytic ring opening, and dehydrogenation catalyzed by the PaaG and PaaZ proteins. The subsequent beta-oxidation-type degradation of the resulting CoA dicarboxylate via beta-ketoadipyl-CoA to succinyl-CoA and acetyl-CoA appears to be catalyzed by the PaaJ, PaaF and PaaH proteins. PMID:12846838

  13. Application of NMR Spectroscopy in the Assessment of Radiation Dose in Human Primary Cells.

    PubMed

    Kang, Chang-Mo; Seong Hyeon, Jin; Ra Kim, So; Kyeong Lee, Eun; Jin Yun, Hyun; Young Kim, Sun; Kee Chae, Young

    2015-11-01

    We employed the primary cell model system as a first step toward establishing a method to assess the influence of ionizing radiation by using a combination of common and abundant metabolites. We applied X-ray irradiation amounts of 0, 1, and 5 Gy to the cells that were harvested 24, 48, or 72 h later, and profiled metabolites by 2D-NMR spectroscopy to sort out candidate molecules that could be used to distinguish the samples under different irradiation conditions. We traced metabolites stemming from the input ¹³C-glucose, identified twelve of them from the cell extracts, and applied statistical analysis to find out that all the metabolites, including glycine, alanine, and gluatamic acid, increased upon irradiation. The combinatorial use of the selected metabolites showed promising results where the product of signal intensities of alanine and lactate could differentiate samples according to the dose of X-ray irradiation. We hope that this work can form a base for treating radiation-poisoned patients in the future. PMID:26567947

  14. Determination of Dihydrobenzoacridinone Structures by NMR, IR, and UV Spectroscopy and Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Kozlov, N. G.; Zhiharko, Yu. D.; Skakovsky, E. D.; Baranovsky, A. V.; Ogorodnikova, M. M.; Basalaeva, L. I.

    2016-01-01

    Condensation of 2-naphthylamine, aromatic aldehydes, and dimedone was found to produce 9,10-dihydrobenzo[a] acridin-11-one derivatives according to PMR, 13C NMR, and IR spectroscopy and mass spectrometry. Correlation spectroscopy showed that the carbonyl in the synthesized dihydrobenzoacridinone derivatives was located on C11.

  15. Establishing resolution-improved NMR spectroscopy in high magnetic fields with unknown spatiotemporal variations.

    PubMed

    Zhang, Zhiyong; Smith, Pieter E S; Cai, Shuhui; Zheng, Zhenyao; Lin, Yulan; Chen, Zhong

    2015-12-28

    A half-century quest for higher magnetic fields has been an integral part of the progress undergone in the Nuclear Magnetic Resonance (NMR) study of materials' structure and dynamics. Because 2D NMR relies on systematic changes in coherences' phases as a function of an encoding time varied over a series of independent experiments, it generally cannot be applied in temporally unstable fields. This precludes most NMR methods from being used to characterize samples situated in hybrid or resistive magnets that are capable of achieving extremely high magnetic field strength. Recently, "ultrafast" NMR has been developed into an effective and widely applicable methodology enabling the acquisition of a multidimensional NMR spectrum in a single scan; it can therefore be used to partially mitigate the effects of temporally varying magnetic fields. Nevertheless, the strong interference of fluctuating fields with the spatial encoding of ultrafast NMR still severely restricts measurement sensitivity and resolution. Here, we introduce a strategy for obtaining high resolution NMR spectra that exploits the immunity of intermolecular zero-quantum coherences (iZQCs) to field instabilities and inhomogeneities. The spatial encoding of iZQCs is combined with a J-modulated detection scheme that removes the influence of arbitrary field inhomogeneities during acquisition. This new method can acquire high-resolution one-dimensional NMR spectra in large inhomogeneous and fluctuating fields, and it is tested with fields experimentally modeled to mimic those of resistive and resistive-superconducting hybrid magnets. PMID:26723664

  16. Establishing resolution-improved NMR spectroscopy in high magnetic fields with unknown spatiotemporal variations

    SciTech Connect

    Zhang, Zhiyong; Cai, Shuhui; Zheng, Zhenyao; Lin, Yulan E-mail: lylfj2005@xmu.edu.cn; Chen, Zhong E-mail: lylfj2005@xmu.edu.cn; Smith, Pieter E. S.

    2015-12-28

    A half-century quest for higher magnetic fields has been an integral part of the progress undergone in the Nuclear Magnetic Resonance (NMR) study of materials’ structure and dynamics. Because 2D NMR relies on systematic changes in coherences’ phases as a function of an encoding time varied over a series of independent experiments, it generally cannot be applied in temporally unstable fields. This precludes most NMR methods from being used to characterize samples situated in hybrid or resistive magnets that are capable of achieving extremely high magnetic field strength. Recently, “ultrafast” NMR has been developed into an effective and widely applicable methodology enabling the acquisition of a multidimensional NMR spectrum in a single scan; it can therefore be used to partially mitigate the effects of temporally varying magnetic fields. Nevertheless, the strong interference of fluctuating fields with the spatial encoding of ultrafast NMR still severely restricts measurement sensitivity and resolution. Here, we introduce a strategy for obtaining high resolution NMR spectra that exploits the immunity of intermolecular zero-quantum coherences (iZQCs) to field instabilities and inhomogeneities. The spatial encoding of iZQCs is combined with a J-modulated detection scheme that removes the influence of arbitrary field inhomogeneities during acquisition. This new method can acquire high-resolution one-dimensional NMR spectra in large inhomogeneous and fluctuating fields, and it is tested with fields experimentally modeled to mimic those of resistive and resistive-superconducting hybrid magnets.

  17. Establishing resolution-improved NMR spectroscopy in high magnetic fields with unknown spatiotemporal variations

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyong; Smith, Pieter E. S.; Cai, Shuhui; Zheng, Zhenyao; Lin, Yulan; Chen, Zhong

    2015-12-01

    A half-century quest for higher magnetic fields has been an integral part of the progress undergone in the Nuclear Magnetic Resonance (NMR) study of materials' structure and dynamics. Because 2D NMR relies on systematic changes in coherences' phases as a function of an encoding time varied over a series of independent experiments, it generally cannot be applied in temporally unstable fields. This precludes most NMR methods from being used to characterize samples situated in hybrid or resistive magnets that are capable of achieving extremely high magnetic field strength. Recently, "ultrafast" NMR has been developed into an effective and widely applicable methodology enabling the acquisition of a multidimensional NMR spectrum in a single scan; it can therefore be used to partially mitigate the effects of temporally varying magnetic fields. Nevertheless, the strong interference of fluctuating fields with the spatial encoding of ultrafast NMR still severely restricts measurement sensitivity and resolution. Here, we introduce a strategy for obtaining high resolution NMR spectra that exploits the immunity of intermolecular zero-quantum coherences (iZQCs) to field instabilities and inhomogeneities. The spatial encoding of iZQCs is combined with a J-modulated detection scheme that removes the influence of arbitrary field inhomogeneities during acquisition. This new method can acquire high-resolution one-dimensional NMR spectra in large inhomogeneous and fluctuating fields, and it is tested with fields experimentally modeled to mimic those of resistive and resistive-superconducting hybrid magnets.

  18. [Analysis of streamer properties and emission spectroscopy of 2-D OH distribution of pulsed corona discharge].

    PubMed

    Zhao, Lei; Gao, Xiang; Luo, Zhong-Yang; Xuan, Jian-Yong; Jiang, Jian-Ping; Cen, Ke-Fa

    2011-11-01

    Streamer plays a key role in the process of OH radical generation. The propagation of primary and secondary streamers of positive wire-plate pulsed corona discharge was observed using a short gate ICCD in air environment. The influence of the applied voltage on the properties was investigated. It was shown that the primary streamer propagation velocity, electric coverage and length of secondary streamer increased significantly with increasing the applied voltage. Then 2-D OH distribution was investigated by the emission spectrum. With the analysis of the OH emission spectra, the distribution of OH radicals showed a trend of decreasing from the wire electrode to its circumambience. Compared with the streamer propagation trace, the authors found that OH radical distribution and streamer are in the same area. Both OH radical concentration and the intensity of streamer decreased when far away from the wire electrode. PMID:22242481

  19. 2D spectroscopy of galaxies with star formation regions. Study of SBS 1533+574

    NASA Astrophysics Data System (ADS)

    Hakopian, S. A.; Balayan, S. K.; Dodonov, S. N.; Movsessian, T. A.

    2006-10-01

    A preliminary analysis is given of 2D spectroscopic data on the galaxy SBS 1533+574(AB) obtained using the multipupil spectrographs on the 2.6-m telescope at the BAO (VAGR) and the 6-m telescope at the SAO (MPFS). The two components of the galaxy are star formation regions in different stages. The component SBS 1533+574B is known to be a BCDG. The plots of the intensity distribution of the radiation in the recombination lines of hydrogen and the forbidden lines of gases with a low degree of ionization obtained here make it possible to compare the basic characteristics of the HII-zones and the surrounding shell. The velocity distribution over the field of the galaxy is indicative of a common rotation of the system and of an intrinsic rotation of the components which is more distinct for component B.

  20. Communication: two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): simultaneous planar imaging and multiplex spectroscopy in a single laser shot.

    PubMed

    Bohlin, Alexis; Kliewer, Christopher J

    2013-06-14

    Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15,000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm(2). PMID:23781772

  1. Communication: Two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): Simultaneous planar imaging and multiplex spectroscopy in a single laser shot

    NASA Astrophysics Data System (ADS)

    Bohlin, Alexis; Kliewer, Christopher J.

    2013-06-01

    Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15 000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm2.

  2. Communication: Two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): Simultaneous planar imaging and multiplex spectroscopy in a single laser shot

    SciTech Connect

    Bohlin, Alexis; Kliewer, Christopher J.

    2013-01-01

    Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15, 000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm2.

  3. Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes.

    PubMed

    Arges, Christopher G; Ramani, Vijay

    2013-02-12

    Anion exchange membranes (AEMs) find widespread applications as an electrolyte and/or electrode binder in fuel cells, electrodialysis stacks, flow and metal-air batteries, and electrolyzers. AEMs exhibit poor stability in alkaline media; their degradation is induced by the hydroxide ion, a potent nucleophile. We have used 2D NMR techniques to investigate polymer backbone stability (as opposed to cation stability) of the AEM in alkaline media. We report the mechanism behind a peculiar, often-observed phenomenon, wherein a demonstrably stable polysulfone backbone degrades rapidly in alkaline solutions upon derivatization with alkaline stable fixed cation groups. Using COSY and heteronuclear multiple quantum correlation spectroscopy (2D NMR), we unequivocally demonstrate that the added cation group triggers degradation of the polymer backbone in alkaline via quaternary carbon hydrolysis and ether hydrolysis, leading to rapid failure. This finding challenges the existing perception that having a stable cation moiety is sufficient to yield a stable AEM and emphasizes the importance of the often ignored issue of backbone stability. PMID:23335629

  4. Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes

    PubMed Central

    Arges, Christopher G.; Ramani, Vijay

    2013-01-01

    Anion exchange membranes (AEMs) find widespread applications as an electrolyte and/or electrode binder in fuel cells, electrodialysis stacks, flow and metal-air batteries, and electrolyzers. AEMs exhibit poor stability in alkaline media; their degradation is induced by the hydroxide ion, a potent nucleophile. We have used 2D NMR techniques to investigate polymer backbone stability (as opposed to cation stability) of the AEM in alkaline media. We report the mechanism behind a peculiar, often-observed phenomenon, wherein a demonstrably stable polysulfone backbone degrades rapidly in alkaline solutions upon derivatization with alkaline stable fixed cation groups. Using COSY and heteronuclear multiple quantum correlation spectroscopy (2D NMR), we unequivocally demonstrate that the added cation group triggers degradation of the polymer backbone in alkaline via quaternary carbon hydrolysis and ether hydrolysis, leading to rapid failure. This finding challenges the existing perception that having a stable cation moiety is sufficient to yield a stable AEM and emphasizes the importance of the often ignored issue of backbone stability. PMID:23335629

  5. Conformational solution studies of neuropeptide gamma using CD and NMR spectroscopy.

    PubMed

    Rodziewicz-Motowidło, Sylwia; Brzozowskl, Krzysztof; Legowska, Anna; Liwo, Adam; Silbering, Jerzy; Smoluch, Marek; Rolka, Krzysztof

    2002-05-01

    Neuropeptide gamma is one of the largest members of the tachykinin family of peptides, exhibiting strong agonistic activity towards the NK-2 tachykinin receptor. This peptide was synthesized by the solid-phase method using the Fmoc chemistry. Circular-dichroism spectroscopy (CD) investigations of this peptide were performed in phosphate buffer, in the presence of sodium dodecylsulphate (SDS) micelles and trifluoroethanol (TFE) solutions and in DMSO-d6 using the 2D NMR technique in conjunction with two different theoretical approaches. The first assumes multiconformational equilibrium of the peptide studied characterized by the values of statistical weights of low-energy conformations. These calculations were performed using three different force fields ECEPP/3, AMBER4.1 and CHARMM (implemented in the X-PLOR program). The second method incorporates interproton distance and dihedral angle constraints into the starting conformation using the Simulated Annealing algorithm (X-PLOR program). The CD experiments revealed that although the peptide studied is flexible in polar solvents, a tendency to adopt a helical structure was observed in the hydrophobic environment. The NMR data (NOE effects) indicate a helical or reverse structure in the Ile7-His12 fragment of the peptide studied in DMSO-d6 solution. The results obtained cannot be interpreted in terms of a single conformation. Most of the conformations obtained with the ECEPP/3 force field possess a high content of a helical structure. None of the conformers, obtained with the AMBER4.1 and CHARMM force fields, can be considered as the dominant one. In all conformations several beta-turns were detected and in some cases gamma-turns were also found. But in fact, it is rather difficult to select the position of the secondary element(s) present in the structure of NPgamma in solution. All conformers calculated with the X-PLOR program (with using NMR derived distance and torsion angle constraints) are stabilized by several

  6. Ligand screening by saturation-transfer difference (STD) NMR spectroscopy.

    SciTech Connect

    Krishnan, V V

    2005-04-26

    NMR based methods to screen for high-affinity ligands have become an indispensable tool for designing rationalized drugs, as these offer a combination of good experimental design of the screening process and data interpretation methods, which together provide unprecedented information on the complex nature of protein-ligand interactions. These methods rely on measuring direct changes in the spectral parameters, that are often simpler than the complex experimental procedures used to study structure and dynamics of proteins. The goal of this review article is to provide the basic details of NMR based ligand-screening methods, with particular focus on the saturation transfer difference (STD) experiment. In addition, we provide an overview of other NMR experimental methods and a practical guide on how to go about designing and implementing them.

  7. Assessing the fate and transformation of plant residues in the terrestrial environment using HR-MAS NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kelleher, Brian P.; Simpson, Myrna J.; Simpson, Andre J.

    2006-08-01

    Plant litter decomposition plays a fundamental role in carbon and nitrogen cycles, provides key nutrients to the soil environment and represents a potentially large positive feedback to atmospheric CO 2. However, the full details of decomposition pathways and products are unknown. Here we present the first application of HR-MAS NMR spectroscopy on 13C and 15N labeled plant materials, and apply this approach in a preliminary study to monitor the environmental degradation of the pine and wheatgrass residues over time. In HR-MAS, is it possible to acquire very high resolution NMR data of plant biomass, and apply the vast array of multidimensional experiments available in conventional solution-state NMR. High levels of isotopic enrichment combined with HR-MAS significantly enhance the detection limits, and provide a wealth of information that is unattainable by any other method. Diffusion edited HR-MAS NMR data reveal the rapid loss of carbohydrate structures, while two-dimensional (2-D) HR-MAS NMR spectra demonstrate the relatively fast loss of both hydrolysable and condensed tannin structures from all plant tissues studied. Aromatic (partially lignin) and aliphatic components (waxes, cuticles) tend to persist, along with a small fraction of carbohydrate, and become highly functionalized over time. While one-dimensional (1-D) 13C HR-MAS NMR spectra of fresh plant tissue reflect compositional differences between pine and grass, these differences become negligible after decomposition suggesting that recalcitrant carbon may be similar despite the plant source. Two-dimensional 1H- 15N HR-MAS NMR analysis of the pine residue suggests that nitrogen from specific peptides is either selectively preserved or used for the synthesis of what appears to be novel structures. The amount of relevant data generated from plant components in situ using HR-MAS NMR is highly encouraging, and demonstrates that complete assignment will yield unprecedented structural knowledge of plant cell

  8. Localized double-quantum-filtered 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Thomas, M. A.; Hetherington, H. P.; Meyerhoff, D. J.; Twieg, D. B.

    The image-guided in vivo spectroscopic (ISIS) pulse sequence has been combined with a double-quantum-filter scheme in order to obtain localized and water-suppressed 1H NMR spectra of J-coupled metabolites. The coherence-transfer efficiency associated with the DQ filter for AX and A 3X spin systems is described. Phantom results of carnosine, alanine, and ethanol in aqueous solution are presented. For comparison, the 1H NMR spectrum of alanine in aqueous solution with the binomial (1331, 2662) spin-echo sequence is also shown.

  9. Forensic examination of electrical tapes using high resolution magic angle spinning ¹H NMR spectroscopy.

    PubMed

    Schoenberger, Torsten; Simmross, Ulrich; Poppe, Christian

    2016-01-01

    The application of high resolution magic angle spinning (HR-MAS) (1)H NMR spectroscopy is ideally suited for the differentiation of plastics. In addition to the actual material composition, the different types of polymer architectures and tacticity provide characteristic signals in the fingerprint of the (1)H NMR spectra. The method facilitates forensic comparison, as even small amounts of insoluble but swellable plastic particles are utilized. The performance of HR-MAS NMR can be verified against other methods that were recently addressed in various articles about forensic tape comparison. In this study samples of the 90 electrical tapes already referenced by the FBI laboratory were used. The discrimination power of HR-MAS is demonstrated by the fact that more tape groups can be distinguished by NMR spectroscopy than by using the combined evaluation of several commonly used analytical techniques. An additional advantage of this robust and quick method is the very simple sample preparation. PMID:26558760

  10. High-Resolution 3D Structure Determination of Kaliotoxin by Solid-State NMR Spectroscopy

    PubMed Central

    Korukottu, Jegannath; Schneider, Robert; Vijayan, Vinesh; Lange, Adam; Pongs, Olaf; Becker, Stefan; Baldus, Marc; Zweckstetter, Markus

    2008-01-01

    High-resolution solid-state NMR spectroscopy can provide structural information of proteins that cannot be studied by X-ray crystallography or solution NMR spectroscopy. Here we demonstrate that it is possible to determine a protein structure by solid-state NMR to a resolution comparable to that by solution NMR. Using an iterative assignment and structure calculation protocol, a large number of distance restraints was extracted from 1H/1H mixing experiments recorded on a single uniformly labeled sample under magic angle spinning conditions. The calculated structure has a coordinate precision of 0.6 Å and 1.3 Å for the backbone and side chain heavy atoms, respectively, and deviates from the structure observed in solution. The approach is expected to be applicable to larger systems enabling the determination of high-resolution structures of amyloid or membrane proteins. PMID:18523586

  11. Synthesis of new thiazolo-celecoxib analogues as dual cyclooxygenase-2/15-lipoxygenase inhibitors: Determination of regio-specific different pyrazole cyclization by 2D NMR.

    PubMed

    Abdelall, Eman K A; Kamel, Gehan M

    2016-08-01

    Two new series of 1,5-diaryl pyrazoles (5a, 5b, 7a, 7b and 10) and 1,5-diaryl pyrazoline (12a and 12b) were prepared as both Cyclooxygenase-2 and 15-lipoxygenase inhibitors. Carrageenan-induced rat paw edema, ulcer index and anti-COX-1/COX-2 and 15-LOX inhibition assays were also included. Cyclization of different pyrazoles was discussed using 2D NMR such as HSQC, HMBC and NOSEY determinations. Compound 5a is more effective with ED50 = 0.98 and 3.98 μM against COX-2 and 15-lipoxygenase respectively, than the references celecoxib (1.54 μM) and meclofenamate sodium (5.64 μM). PMID:27131067

  12. Carbon-proton scalar couplings in RNA. 3D heteronuclear and 2D isotope-edited NMR of a [sup 13]C-labeled extra-stable hairpin

    SciTech Connect

    Hines, J.V.; Landry, S.M.; Varani, G.; Tinoco, I. Jr. Lawrence Berkeley Lab., CA )

    1994-06-29

    Long range carbon-proton scalar couplings were measured for an RNA hairpin of 12 nucleotides using 3D and [sup 13]C-edited 2D NMR. The large one-bond carbon-proton scalar couplings ([sup 1]J[sub CH]) and small n-bond couplings ([sup 1]J[sub CH]) produce ECOSY type cross-peaks, thus facilitating the determination of the sign and magnitude of the smaller [sup 2]J[sub CH] or [sup 3]J[sub CH]. The UUCGRNA hairpin (5[prime]-rGGACUUCGGUCC-3[prime]), whose structure has been determined by our laboratory, was uniformly [sup 13]C-labeled at 30% isotopic enrichment. The observed [sup 1]J[sub CH] couplings were then correlated to the known structure. The signs of [sup 2]J[sub C4[prime]H5[prime

  13. NMR spectroscopy of experimentally shocked single crystal quartz: A reexamination of the NMR shock barometer

    NASA Technical Reports Server (NTRS)

    Fiske, P. S.; Gratz, A. J.; Nellis, W. J.

    1993-01-01

    Cygan and others report a broadening of the Si-29 nuclear magnetic resonance (NMR) peak for synthetic quartz powders with increasing shock pressure which they propose as a shock wave barometer for natural systems. These results are expanded by studying single crystal quartz shocked to 12 and 33 GPa using the 6.5 m two-stage light-gas gun at Lawrence Livermore National Laboratories. Our NMR results differ substantially from those of Cygan and others and suggest that the proposed shock wave barometer may require refinement. The difference in results between this study and that of Cygan and others is most likely caused by different starting materials (single crystal vs. powder) and different shock loading histories. NMR results from single crystal studies may be more applicable to natural systems.

  14. Deconvolution of 2D coincident Doppler broadening spectroscopy using the Richardson Lucy algorithm

    NASA Astrophysics Data System (ADS)

    Zhang, J. D.; Zhou, T. J.; Cheung, C. K.; Beling, C. D.; Fung, S.; Ng, M. K.

    2006-05-01

    Coincident Doppler Broadening Spectroscopy (CDBS) measurements are popular in positron solid-state studies of materials. By utilizing the instrumental resolution function obtained from a gamma line close in energy to the 511 keV annihilation line, it is possible to significantly enhance the quality of the CDBS spectra using deconvolution algorithms. In this paper, we compare two algorithms, namely the Non-Negativity Least Squares (NNLS) regularized method and the Richardson-Lucy (RL) algorithm. The latter, which is based on the method of maximum likelihood, is found to give superior results to the regularized least-squares algorithm and with significantly less computer processing time.

  15. Direct MD Simulations of Terahertz Absorption and 2D Spectroscopy Applied to Explosive Crystals.

    PubMed

    Katz, G; Zybin, S; Goddard, W A; Zeiri, Y; Kosloff, R

    2014-03-01

    A direct molecular dynamics simulation of the THz spectrum of a molecular crystal is presented. A time-dependent electric field is added to a molecular dynamics simulation of a crystal slab. The absorption spectrum is composed from the energy dissipated calculated from a series of applied pulses characterized by a carrier frequency. The spectrum of crystalline cyclotrimethylenetrinitramine (RDX) and triacetone triperoxide (TATP) were simulated with the ReaxFF force field. The proposed direct method avoids the linear response and harmonic approximations. A multidimensional extension of the spectroscopy is suggested and simulated based on the nonlinear response to a single polarized pulse of radiation in the perpendicular polarization direction. PMID:26274066

  16. Traceability of Italian garlic (Allium sativum L.) by means of HRMAS-NMR spectroscopy and multivariate data analysis.

    PubMed

    Ritota, Mena; Casciani, Lorena; Han, Bei-Zhong; Cozzolino, Sara; Leita, Liviana; Sequi, Paolo; Valentini, Massimiliano

    2012-11-15

    (1)H High Resolution Magic Angle Spinning-Nuclear Magnetic Resonance (HRMAS-NMR) spectroscopy was used to analyse garlic (Allium sativum L.) belonging to red and white varieties and collected in different Italian regions, in order to address the traceability issue. 1D and 2D NMR spectra, performed directly on untreated small pieces of garlic, so without any sample manipulation, allowed the assignment of several compounds: organic acids, sugars, fatty acids, amino acids and the nutritionally important fructo-oligosaccharides and allyl-organosulphur compounds. Application of Partial Least Squares projections to latent structures-Discrimination Analysis provided an excellent model for the discrimination of both the variety and, most important, the place origin, allowing the identification of the metabolites contributing to such classifications. The presence of organosulphurs, allicin and some allyl-organosulphurs found by HRMAS-NMR, was confirmed also by SPME-GC-MS; 11 molecules were identified, containing from one up to three sulphur atoms and with and without allyl moieties. PMID:22868146

  17. Macromolecular NMR spectroscopy for the non-spectroscopist: beyond macromolecular solution structure determination.

    PubMed

    Bieri, Michael; Kwan, Ann H; Mobli, Mehdi; King, Glenn F; Mackay, Joel P; Gooley, Paul R

    2011-03-01

    A strength of NMR spectroscopy is its ability to monitor, on an atomic level, molecular changes and interactions. In this review, which is intended for non-spectroscopist, we describe major uses of NMR in protein science beyond solution structure determination. After first touching on how NMR can be used to quickly determine whether a mutation induces structural perturbations in a protein, we describe the unparalleled ability of NMR to monitor binding interactions over a wide range of affinities, molecular masses and solution conditions. We discuss the use of NMR to measure the dynamics of proteins at the atomic level and over a wide range of timescales. Finally, we outline new and expanding areas such as macromolecular structure determination in multicomponent systems, as well as in the solid state and in vivo. PMID:21214861

  18. The novel acid degradation products of losartan: Isolation and characterization using Q-TOF, 2D-NMR and FTIR.

    PubMed

    Kumar Pandey, Avadhesh; Rapolu, Ravi; Raju, Ch Krishnam; Sasalamari, Gururaj; Kumar Goud, Sanath; Awasthi, Atul; Navalgund, Sameer G; Surendranath, Koduru V

    2016-02-20

    Forced degradation of losartan potassium in acidic condition resulted into three potential unknown impurities. These unknown degradation products marked as LD-I, LD-II and LD-III were analyzed using a new reverse-phase high performance liquid chromatography (HPLC), eluting at 3.63, 3.73 and 3.91 relative retention times with respect to losartan potassium (LOS) peak. All three were isolated from reaction mass using preparative HPLC and their structures were elucidated using LC-MS/MS, multidimensional NMR and FTIR spectroscopic techniques, as 5(2),11(2)-dibutyl-5(4),11(4)-dichloro-1(1)H,5(1)H,7(1)H,11(1)H-1(5,1),7(1,5)-ditetrazola-5,11(1,5)-diimidazola-2,8(1,2),3,9(1,4)-tetrabenzenacyclododecaphane,(Z)-5(2),11(2)-dibutyl-5(4),11(4)-dichloro-1(1)H,5(1)H,7(2)H,11(1)H-1(5,1),7(2,5)-ditetrazola-5,11(1,5)-diimidazola-2,8(1,2),3,9(1,4)-tetrabenzenacyclododecaphane, and 5(2),11(2)-dibutyl-5(4),11(4)-dichloro-1(2)H,5(1)H,7(2)H,11(1)H-1(5,2),7(2,5)-ditetrazola-5,11(1,5)-diimidazola-2,8(1,2),3,9(1,4)-tetrabenzenacyclododecaphane, respectively. To best of our knowledge, all three degradation products are novel impurities which are not discussed at any form of publication yet. PMID:26704631

  19. Computational Amide I 2D IR Spectroscopy as a Probe of Protein Structure and Dynamics.

    PubMed

    Reppert, Mike; Tokmakoff, Andrei

    2016-05-27

    Two-dimensional infrared spectroscopy of amide I vibrations is increasingly being used to study the structure and dynamics of proteins and peptides. Amide I, a primarily carbonyl stretching vibration of the protein backbone, provides information on secondary structures as a result of vibrational couplings and on hydrogen-bonding contacts when isotope labeling is used to isolate specific sites. In parallel with experiments, computational models of amide I spectra that use atomistic structures from molecular dynamics simulations have evolved to calculate experimental spectra. Mixed quantum-classical models use spectroscopic maps to translate the structural information into a quantum-mechanical Hamiltonian for the spectroscopically observed vibrations. This allows one to model the spectroscopy of large proteins, disordered states, and protein conformational dynamics. With improvements in amide I models, quantitative modeling of time-dependent structural ensembles and of direct feedback between experiments and simulations is possible. We review the advances in developing these models, their theoretical basis, and current and future applications. PMID:27023758

  20. Computational Amide I 2D IR Spectroscopy as a Probe of Protein Structure and Dynamics

    NASA Astrophysics Data System (ADS)

    Reppert, Mike; Tokmakoff, Andrei

    2016-05-01

    Two-dimensional infrared spectroscopy of amide I vibrations is increasingly being used to study the structure and dynamics of proteins and peptides. Amide I, a primarily carbonyl stretching vibration of the protein backbone, provides information on secondary structures as a result of vibrational couplings and on hydrogen-bonding contacts when isotope labeling is used to isolate specific sites. In parallel with experiments, computational models of amide I spectra that use atomistic structures from molecular dynamics simulations have evolved to calculate experimental spectra. Mixed quantum-classical models use spectroscopic maps to translate the structural information into a quantum-mechanical Hamiltonian for the spectroscopically observed vibrations. This allows one to model the spectroscopy of large proteins, disordered states, and protein conformational dynamics. With improvements in amide I models, quantitative modeling of time-dependent structural ensembles and of direct feedback between experiments and simulations is possible. We review the advances in developing these models, their theoretical basis, and current and future applications.

  1. NMR spectroscopy and perfusion of mammalian cells using surface microprobes.

    PubMed

    Ehrmann, Klaus; Pataky, Kristopher; Stettler, Matthieu; Wurm, Florian Maria; Brugger, Jürgen; Besse, Pierre-André; Popovic, Radivoje

    2007-03-01

    NMR spectra of mammalian cells are taken using surface microprobes that are based on microfabricated planar coils. The surface microprobe resembles a miniaturized Petri dish commonly used in biological research. The diameter of the planar coils is 1 mm. Chinese Hamster Ovaries are immobilized in a uniform layer on the microprobe surface or patterned by an ink-jet printer in the centre of the microcoil, where the rf-field of the planar microcoil is most uniform. The acquired NMR spectra show the prevalent metabolites found in mammalian cells. The volumes of the detected samples range from 25 nL to 1 nL (or 50,000 to 1800 cells). With an extended set-up that provides fluid inlets and outlets to the microprobe, the cells can be perfused within the NMR-magnet while constantly taking NMR spectra. Perfusion of the cells opens the way to increased cell viability for long acquisitions or to analysis of the cells' response to environmental change. PMID:17330170

  2. Guanidinoacetate methyltransferase (GAMT) deficiency diagnosed by proton NMR spectroscopy of body fluids.

    PubMed

    Engelke, Udo F H; Tassini, Maria; Hayek, Joseph; de Vries, Maaike; Bilos, Appie; Vivi, Antonio; Valensin, Gianni; Buoni, Sabrina; Zannolli, Raffaella; Brussel, Wim; Kremer, Berry; Salomons, Gajja S; Veendrick-Meekes, Monique J B M; Kluijtmans, Leo A J; Morava, Eva; Wevers, Ron A

    2009-06-01

    In patients with guanidinoacetate methyltransferase (GAMT) deficiency several parameters may point towards the diagnosis of GAMT deficiency. These include the low levels of creatine and creatinine in urine, the high concentration of guanidinoacetic acid (GAA) in urine and the low levels of creatine and creatinine in the cerebrospinal fluid (CSF). In this study, body fluids from 10 GAMT deficient patients were analysed using (1)H NMR spectroscopy. The urine 1D (1)H NMR spectra of all the patients showed a doublet resonance at 3.98 ppm (pH 2.50) derived from GAA present in high concentration. For this compound, a good recovery and good correlation was found between an LC-MS/MS method and (1)H NMR spectroscopy. In CSF NMR spectra of these patients, the singlet resonances of creatine and creatinine (3.05 and 3.13 ppm, respectively) were absent (normally always present in (1)H NMR spectra of CSF). Due to overlap by other resonances, the doublet of GAA could not be observed. Our data demonstrate that (1)H NMR spectroscopy of urine and CSF can be used to diagnose patients with GAMT deficiency. PMID:19288536

  3. Rapid identification of Pterocarpus santalinus and Dalbergia louvelii by FTIR and 2D correlation IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Fang-Da; Xu, Chang-Hua; Li, Ming-Yu; Huang, An-Min; Sun, Su-Qin

    2014-07-01

    Since Pterocarpus santalinus and Dalbergia louvelii, which are of precious Rosewood, are very similar in their appearance and anatomy characteristics, cheaper Hongmu D. louvelii is often illegally used to impersonate valuable P. santalinus, especially in Chinese furniture manufacture. In order to develop a rapid and effective method for easy confused wood furniture differentiation, we applied tri-step identification method, i.e., conventional infrared spectroscopy (FT-IR), second derivative infrared (SD-IR) spectroscopy and two-dimensional correlation infrared (2DCOS-IR) spectroscopy to investigate P. santalinus and D. louvelii furniture. According to FT-IR and SD-IR spectra, it has been found two unconditional stable difference at 848 cm-1 and 700 cm-1 and relative stable differences at 1735 cm-1, 1623 cm-1, 1614 cm-1, 1602 cm-1, 1509 cm-1, 1456 cm-1, 1200 cm-1, 1158 cm-1, 1055 cm-1, 1034 cm-1 and 895 cm-1 between D. louvelii and P. santalinus IR spectra. The stable discrepancy indicates that the category of extractives is different between the two species. Besides, the relative stable differences imply that the content of holocellulose in P. santalinus is more than that of D. louvelii, whereas the quantity of extractives in D. louvelii is higher. Furthermore, evident differences have been observed in their 2DCOS-IR spectra of 1550-1415 cm-1 and 1325-1030 cm-1. P. santalinus has two strong auto-peaks at 1459 cm-1 and 1467 cm-1, three mid-strong auto-peaks at 1518 cm-1, 1089 cm-1 and 1100 cm-1 and five weak auto-peaks at 1432 cm-1, 1437 cm-1, 1046 cm-1, 1056 cm-1 and 1307 cm-1 while D. louvelii has four strong auto-peaks at 1465 cm-1, 1523 cm-1, 1084 cm-1 and 1100 cm-1, four mid-strong auto-peaks at 1430 cm-1, 1499 cm-1, 1505 cm-1 and 1056 cm-1 and two auto-peaks at 1540 cm-1 and 1284 cm-1. This study has proved that FT-IR integrated with 2DCOS-IR could be applicable for precious wood furniture authentication in a direct, rapid and holistic manner.

  4. Energy flow between spectral components in 2D Broadband Stimulated Raman Spectroscopy

    PubMed Central

    Batignani, G.; Fumero, G.; Mukamel, S.; Scopigno, T.

    2015-01-01

    We introduce a general theoretical description of non resonant impulsive Femtosecond Stimulated Raman Spectroscopy in a multimode harmonic model. In this technique an ultrashort actinic pulse creates coherences of low frequency modes and is followed by a pair of a narrowband Raman and broadband probe pulse. Using Closed-Time-Path-Loop (CTPL) diagrams, the response on both the red and the blue sides of the broadband pulse with respect to the narrowband Raman pulse is calculated, the process couples high and low frequency modes which share the same ground state. The transmitted intensity oscillates between the red and the blue side, while the total number of photons is conserved. The total energy of the probe signal is periodically modulated in time by the coherence created in the low frequency modes. PMID:25802897

  5. Performance improvements in temperature reconstructions of 2-D tunable diode laser absorption spectroscopy (TDLAS)

    NASA Astrophysics Data System (ADS)

    Choi, Doo-Won; Jeon, Min-Gyu; Cho, Gyeong-Rae; Kamimoto, Takahiro; Deguchi, Yoshihiro; Doh, Deog-Hee

    2016-02-01

    Performance improvement was attained in data reconstructions of 2-dimensional tunable diode laser absorption spectroscopy (TDLAS). Multiplicative Algebraic Reconstruction Technique (MART) algorithm was adopted for data reconstruction. The data obtained in an experiment for the measurement of temperature and concentration fields of gas flows were used. The measurement theory is based upon the Beer-Lambert law, and the measurement system consists of a tunable laser, collimators, detectors, and an analyzer. Methane was used as a fuel for combustion with air in the Bunsen-type burner. The data used for the reconstruction are from the optical signals of 8-laser beams passed on a cross-section of the methane flame. The performances of MART algorithm in data reconstruction were validated and compared with those obtained by Algebraic Reconstruction Technique (ART) algorithm.

  6. 2D turbulence imaging in DIII-D via beam emission spectroscopy

    SciTech Connect

    Fenzi, C.; Fonck, R. J.; Jakubowski, M.; Mc Kee, G. R.

    2001-01-01

    Two-dimensional measurements of density fluctuations have been performed in DIII-D using the beam emission spectroscopy diagnostic. The 32 spatial channels are arranged to image a 5x6cm{sup 2} (radialxpoloidal) region in the plasma cross section, at a nominal 1 cm spatial resolution and separation. The typical decorrelation time, poloidal and radial correlation lengths, as well as a time-averaged flow field plot are obtained from spatial and temporal correlation analyses. A biorthogonal decomposition algorithm is applied to expand the data set into a set of modes that are orthogonal in time and in space, thus providing a simultaneous analysis of the space and time dependencies of fluctuation data.

  7. 2D-IR spectroscopy of hydrogen-bond-mediated vibrational excitation transfer.

    PubMed

    Chuntonov, Lev

    2016-05-18

    Vibrational excitation transfer along the hydrogen-bond-mediated pathways in the complex of methyl acetate (MA) and 4-cyanophenol (4CP) was studied by dual-frequency femtosecond two-dimensional infrared spectroscopy. We excited the energy-donating ester carbonyl stretching vibrational mode and followed the transfer to the energy-accepting benzene ring and cyano stretching vibrations. The complexes with no, one, and two hydrogen-bonded 4CP molecules were studied. Vibrational relaxation of the carbonyl mode is more efficient in both hydrogen-bonded complexes as compared with free MA molecules. The inter-molecular transport in a hydrogen-bonded complex involving a single 4CP molecule is slower than that in a complex with two 4CP molecules. In the former, vibrational relaxation leads to local heating, as shown by the spectroscopy of the carbonyl mode, whereas the local heating is suppressed in the latter because the excitation redistribution is more efficient. At early times, the transfer to the benzene ring is governed by its direct coupling with the energy-donating carbonyl mode, whereas at later times intermediate states are involved. The transfer to a more distant site of the cyano group in 4CP involves intermediate states at all times, since no direct coupling between the energy-donating and accepting modes was observed. We anticipate that our findings will be of importance for spectroscopic studies of bio-molecular structures and dynamics, and inter- and intra-molecular signaling pathways, and for developing molecular networking applications. PMID:27145861

  8. Two-dimensional NMR spectroscopy as a tool to link soil organic matter composition to ecosystem processes

    NASA Astrophysics Data System (ADS)

    Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Schleucher, Jürgen

    2014-05-01

    Environmental factors (e.g. temperature and moisture) and the size and composition of soil microbial populations are often considered the main drivers of soil organic matter (SOM) mineralization. Less consideration is given to the role of SOM as a substrate for microbial metabolism and the importance of the organo-chemical composition of SOM on decomposition. In addition, a fraction of the SOM is often considered as recalcitrant to mineralization leading to accumulation of SOM. However, recently the concept of intrinsic recalcitrance of SOM to mineralization has been questioned. The challenge in investigating the role of SOM composition on its mineralization to a large extent stems from the difficulties in obtaining high resolution characterization of a very complex matrix. 13C nuclear magnetic resonance (NMR) spectroscopy is a widely used tool to characterize SOM. However, SOM is a very complex mixture and in the resulting 13C NMR spectra, the identified functional groups may represent different molecular fragments that appear in the same spectral region leading to broad peaks. These overlaps defy attempts to identify molecular moieties, and this makes it impossible to derive information at a resolution needed for evaluating e.g. recalcitrance of SOM. Here we applied a method, developed in wood science for the pulp paper industry, to achieve a better characterization of SOM. We directly dissolved finely ground organic layers of boreal forest floors-litters, fibric and humic horizons of both coniferous and broadleaved stands-in dimethyl sulfoxide and analyzed the resulting solution with a two-dimensional (2D) 1H-13C NMR experiment. We will discuss methodological aspects related to the ability to identify and quantify individual molecular moieties in SOM. We will demonstrate how the spectra resolve signals of CH groups in a 2D plane determined by the 13C and 1H chemical shifts, thereby vastly increasing the resolving power and information content of NMR spectra. The

  9. Photoisomerization and structural dynamics of two nitrosylruthenium complexes: a joint study by NMR and nonlinear IR spectroscopies.

    PubMed

    Wang, Jianru; Yang, Fan; Zhao, Yan; Yu, Pengyun; Qiao, Xiaoyan; Wang, Jianping; Wang, Hongfei

    2014-11-21

    In this work, the photoisomerization and structural dynamics of two isomeric nitrosylruthenium(ii) complexes [Ru(OAc)(2cqn)2NO] (H2cqn = 2-chloro-8-quinolinol) in CDCl3 and DMSO are examined using NMR and IR spectroscopic methods. The two N atoms in the 2cqn ligand are in trans position in the synthesized cis-1 isomer, while they are in cis position in the cis-2 isomer. Kinetics monitored by NMR spectroscopy shows that the rate constant of photoisomerization from cis-2 to cis-1 isomer depends on the wavelength of irradiation and solvent polarity; it proceeds faster on irradiating near the absorption peak in the UV-Vis region, and also in more polar solvents (DMSO). Density functional theory computation indicates that the peculiarity of [Ru(ii)-NO(+)] group affects the structure and reactivity of the nitrosylruthenium complexes. Using the nitrosyl stretching (νNO) to be vibrational probe, the structural dynamics and structural distributions of the cis-1 and cis-2 isomers are examined by steady-state linear infrared and ultrafast two-dimensional infrared (2D IR) spectroscopies. The structural and photochemical aspects of the observed spectroscopic parameters are discussed in terms of solute-solvent interactions for the two nitrosylruthenium complexes. PMID:25285659

  10. Conformational analysis of oxidized peptide fragments of the C-terminal redox center in thioredoxin reductases by NMR spectroscopy.

    PubMed

    Ruggles, Erik L; Deker, P Bruce; Hondal, Robert J

    2014-05-01

    Vicinal disulfide rings (VDRs) occur when a disulfide bond forms between adjacent cysteine residues in a protein and results in a rare eight-membered ring structure. This eight-membered ring has been found to exist in four major conformations in solution, divided between cis and trans conformers. Some selenoenzymes use a special type of VDR in which selenium replaces sulfur, generating a vicinal selenosulfide ring (VSeSR). Here, we provide evidence that this substitution reduces ring strain, resulting in a strong preference for the trans conformation relative to cis in a VSeSR (cis:trans - 9:91). This was determined by using the 'γ-gauche effect', which makes use of both (1) H-NMR and two-dimensional (2D) NMR techniques for determining the amide bond conformeric ratio. The presence of selenium in a VSeSR also lowers the dihedral strain energy (DSE) of the selenosulfide bond relative to the disulfide bond of VDRs. While cis amide geometry decreases strain on the amide bond, it increases strain on the scissile disulfide bond of the VDR found in thioredoxin reductase from Drosophila melanogaster (DmTR). We hypothesize that the cis conformation of the VDR is the catalytically competent conformer for thiol/disulfide exchange. This hypothesis was investigated by computing the DSE of VDR and VSeSR conformers, the structure of which was determined by 2D NMR spectroscopy and energy minimization. The computed values of the VDR from DmTR are 16.5 kJ/mol DSE and 14.3 kJ/mol for the C+ and T- conformers, respectively, supporting the hypothesis that the enzyme uses the C+ conformer for thiol/disulfide exchange. PMID:24599608

  11. DSP-based on-line NMR spectroscopy using an anti-Hebbian learning algorithm

    SciTech Connect

    Razazian, K.; Dieckman, S.L.; Raptis, A.C.; Bobis, J.P. |

    1995-07-01

    This paper describes a nuclear magnetic resonance (NMR) system that uses an adaptive algorithm to carry out real-time NMR spectroscopy. The system employs a digital signal processor (DSP) chip to regulate the transmitted and received signal together with spectral analysis of the received signal to determine free induction decay (FID). To implement such a signal-processing routine for detection of the desired signal, an adaptive line enhancer filter that uses an anti-Hebbian learning algorithm is applied to the FID spectra. The results indicate that the adaptive filter can be a reliable technique for on-line spectroscopy study.

  12. Structural Disorder of Folded Proteins: Isotope-Edited 2D IR Spectroscopy and Markov State Modeling

    PubMed Central

    Baiz, Carlos R.; Tokmakoff, Andrei

    2015-01-01

    The conformational heterogeneity of the N-terminal domain of the ribosomal protein L9 (NTL91-39) in its folded state is investigated using isotope-edited two-dimensional infrared spectroscopy. Backbone carbonyls are isotope-labeled (13C=18O) at five selected positions (V3, V9, V9G13, G16, and G24) to provide a set of localized spectroscopic probes of the structure and solvent exposure at these positions. Structural interpretation of the amide I line shapes is enabled by spectral simulations carried out on structures extracted from a recent Markov state model. The V3 label spectrum indicates that the β-sheet contacts between strands I and II are well folded with minimal disorder. The V9 and V9G13 label spectra, which directly probe the hydrogen-bond contacts across the β-turn, show significant disorder, indicating that molecular dynamics simulations tend to overstabilize ideally folded β-turn structures in NTL91-39. In addition, G24-label spectra provide evidence for a partially disordered α-helix backbone that participates in hydrogen bonding with the surrounding water. PMID:25863066

  13. Positron spectroscopy of 2D materials using an advanced high intensity positron beam

    NASA Astrophysics Data System (ADS)

    McDonald, A.; Chirayath, V.; Lim, Z.; Gladen, R.; Chrysler, M.; Fairchild, A.; Koymen, A.; Weiss, A.

    An advanced high intensity variable energy positron beam(~1eV to 20keV) has been designed, tested and utilized for the first coincidence Doppler broadening (CDB) measurements on 6-8 layers graphene on polycrystalline Cu sample. The system is capable of simultaneous Positron annihilation induced Auger electron Spectroscopy (PAES) and CDB measurements giving it unparalleled sensitivity to chemical structure at external surfaces, interfaces and internal pore surfaces. The system has a 3m flight path up to a micro channel plate (MCP) for the Auger electrons emitted from the sample. This gives a superior energy resolution for PAES. A solid rare gas(Neon) moderator was used for the generation of the monoenergetic positron beam. The positrons were successfully transported to the sample chamber using axial magnetic field generated with a series of Helmholtz coils. We will discuss the PAES and coincidence Doppler broadening measurements on graphene -Cu sample and present an analysis of the gamma spectra which indicates that a fraction of the positrons implanted at energies 7-60eV can become trapped at the graphene/metal interface. This work was supported by NSF Grant No. DMR 1508719 and DMR 1338130.

  14. The performance of 2D array detectors for light sheet based fluorescence correlation spectroscopy.

    PubMed

    Singh, Anand Pratap; Krieger, Jan Wolfgang; Buchholz, Jan; Charbon, Edoardo; Langowski, Jörg; Wohland, Thorsten

    2013-04-01

    Single plane illumination microscopy based fluorescence correlation spectroscopy (SPIM-FCS) is a new method for imaging FCS in 3D samples, providing diffusion coefficients, transport, flow velocities and concentrations in an imaging mode. SPIM-FCS records correlation functions over a whole plane in a sample, which requires array detectors for recording the fluorescence signal. Several types of image sensors are suitable for FCS. They differ in properties such as effective area per pixel, quantum efficiency, noise level and read-out speed. Here we compare the performance of several low light array detectors based on three different technologies: (1) Single-photon avalanche diode (SPAD) arrays, (2) passive-pixel electron multiplying charge coupled device (EMCCD) and (3) active-pixel scientific-grade complementary metal oxide semiconductor cameras (sCMOS). We discuss the influence of the detector characteristics on the effective FCS observation volume, and demonstrate that light sheet based SPIM-FCS provides absolute diffusion coefficients. This is verified by parallel measurements with confocal FCS, single particle tracking (SPT), and the determination of concentration gradients in space and time. While EMCCD cameras have a temporal resolution in the millisecond range, sCMOS cameras and SPAD arrays can extend the time resolution of SPIM-FCS down to 10 μs or lower. PMID:23571955

  15. Rapid identification of osmolytes in tropical microalgae and cyanobacteria by (1)H HR-MAS NMR spectroscopy.

    PubMed

    Zea Obando, Claudia; Linossier, Isabelle; Kervarec, Nelly; Zubia, Mayalen; Turquet, Jean; Faÿ, Fabienne; Rehel, Karine

    2016-06-01

    In this study, we report the chemical characterization of 47 tropical microalgae and cyanobacteria by HR-MAS. The generated data confirm the interest of HR-MAS as a rapid screening technique with the major advantage of its easiness. The sample is used as powder of freeze-dried microalgae without any extraction process before acquisition. The spectral fingerprints of strains are then tested as variables for a chemotaxonomy study to discriminate cyanobacteria and dinoflagellates. The individual factor map generated by PCA analysis succeeds in separating the two groups, essentially thanks to the presence of specific carbohydrates. Furthermore, more resolved signals enable to identify many osmolytes. More precisely the characteristics δ of 2-O-alpha-D-glucosylglycerol (GG) are observed in all 21 h-MAS spectra of tropical cyanobacteria. After specific extraction, complementary analysis by 1D and 2D-NMR spectroscopies validates the identification of this osmolyte. PMID:27130130

  16. Genetic algorithm optimized triply compensated pulses in NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Manu, V. S.; Veglia, Gianluigi

    2015-11-01

    Sensitivity and resolution in NMR experiments are affected by magnetic field inhomogeneities (of both external and RF), errors in pulse calibration, and offset effects due to finite length of RF pulses. To remedy these problems, built-in compensation mechanisms for these experimental imperfections are often necessary. Here, we propose a new family of phase-modulated constant-amplitude broadband pulses with high compensation for RF inhomogeneity and heteronuclear coupling evolution. These pulses were optimized using a genetic algorithm (GA), which consists in a global optimization method inspired by Nature's evolutionary processes. The newly designed π and π / 2 pulses belong to the 'type A' (or general rotors) symmetric composite pulses. These GA-optimized pulses are relatively short compared to other general rotors and can be used for excitation and inversion, as well as refocusing pulses in spin-echo experiments. The performance of the GA-optimized pulses was assessed in Magic Angle Spinning (MAS) solid-state NMR experiments using a crystalline U-13C, 15N NAVL peptide as well as U-13C, 15N microcrystalline ubiquitin. GA optimization of NMR pulse sequences opens a window for improving current experiments and designing new robust pulse sequences.

  17. Computational Analysis of Solvent Effects in NMR Spectroscopy.

    PubMed

    Dračínský, Martin; Bouř, Petr

    2010-01-12

    Solvent modeling became a standard part of first principles computations of molecular properties. However, a universal solvent approach is particularly difficult for the nuclear magnetic resonance (NMR) shielding and spin-spin coupling constants that in part result from collective delocalized properties of the solute and the environment. In this work, bulk and specific solvent effects are discussed on experimental and theoretical model systems comprising solvated alanine zwitterion and chloroform molecules. Density functional theory computations performed on larger clusters indicate that standard dielectric continuum solvent models may not be sufficiently accurate. In some cases, more reasonable NMR parameters were obtained by approximation of the solvent with partial atomic charges. Combined cluster/continuum models yielded the most reasonable values of the spectroscopic parameters, provided that they are dynamically averaged. The roles of solvent polarizability, solvent shell structure, and bulk permeability were investigated. NMR shielding values caused by the macroscopic solvent magnetizability exhibited the slowest convergence with respect to the cluster size. For practical computations, however, inclusion of the first solvation sphere provided satisfactory corrections of the vacuum values. The simulations of chloroform chemical shifts and CH J-coupling constants were found to be very sensitive to the molecular dynamics model used to generate the cluster geometries. The results show that computationally efficient solvent modeling is possible and can reveal fine details of molecular structure, solvation, and dynamics. PMID:26614339

  18. Genetic algorithm optimized triply compensated pulses in NMR spectroscopy.

    PubMed

    Manu, V S; Veglia, Gianluigi

    2015-11-01

    Sensitivity and resolution in NMR experiments are affected by magnetic field inhomogeneities (of both external and RF), errors in pulse calibration, and offset effects due to finite length of RF pulses. To remedy these problems, built-in compensation mechanisms for these experimental imperfections are often necessary. Here, we propose a new family of phase-modulated constant-amplitude broadband pulses with high compensation for RF inhomogeneity and heteronuclear coupling evolution. These pulses were optimized using a genetic algorithm (GA), which consists in a global optimization method inspired by Nature's evolutionary processes. The newly designed π and π/2 pulses belong to the 'type A' (or general rotors) symmetric composite pulses. These GA-optimized pulses are relatively short compared to other general rotors and can be used for excitation and inversion, as well as refocusing pulses in spin-echo experiments. The performance of the GA-optimized pulses was assessed in Magic Angle Spinning (MAS) solid-state NMR experiments using a crystalline U-(13)C, (15)N NAVL peptide as well as U-(13)C, (15)N microcrystalline ubiquitin. GA optimization of NMR pulse sequences opens a window for improving current experiments and designing new robust pulse sequences. PMID:26473327

  19. Discovering [superscript 13]C NMR, [superscript 1]H NMR, and IR Spectroscopy in the General Chemistry Laboratory through a Sequence of Guided-Inquiry Exercises

    ERIC Educational Resources Information Center

    Iler, H. Darrell; Justice, David; Brauer, Shari; Landis, Amanda

    2012-01-01

    This sequence of three guided-inquiry labs is designed for a second-semester general chemistry course and challenges students to discover basic theoretical principles associated with [superscript 13]C NMR, [superscript 1]H NMR, and IR spectroscopy. Students learn to identify and explain basic concepts of magnetic resonance and vibrational…

  20. Probing structure and dynamics of bulk and confined crude oils by multiscale NMR spectroscopy, diffusometry, and relaxometry.

    PubMed

    Korb, Jean-Pierre; Louis-Joseph, Alain; Benamsili, Lyès

    2013-06-13

    We propose using a set of noninvasive multiscale NMR techniques for probing the structure and dynamics of bulk and confined crude oils with and without asphaltene. High-field 1D (1)H and (13)C NMR spectroscopies evidence the proton species and the amount of asphaltene and give an average chain length for the hydrocarbon aliphatic chains. Two-dimensional (1)H diffusion-ordered NMR spectroscopy (DOSY) spectra allow us to identify two populations of hydrocarbons characterized by two distributions of translational diffusion coefficients in the presence of asphaltene and a single one without asphaltene. A detailed analysis of the distributions of longitudinal, T1, relaxation times measured at different magnetic fields is proposed in terms of highly skewed bimodal (or monomodal) log-normal distributions, confirming the two environments in the presence of asphaltene and a single one without asphaltene. We show that these distributions are similar to the gas and gel permeation chromatography distributions, thus showing a connection of the hydrocarbon dynamics with their chain lengths. The remarkable observed features of the nuclear magnetic relaxation dispersion (NMRD) profiles of <1/T1> for bulk and confined crude oils with and without asphaltene are interpreted with an original relaxation model of intermittent surface dynamics of proton species at the proximity of asphaltene nanoaggregates and bulk dynamics in between clusters of these nanoaggregates. This allows us to probe the 2D translational diffusion correlation time and the time of residence of hydrocarbons in the proximity of the asphaltene nanoaggregates. Provided that the diffusion of the hydrocarbons close to the asphaltene nanoaggregates is three times smaller than the bulk diffusion, as the DOSY experiments show, this time of residence gives an average radius of exploration for the 2D hydrocarbon diffusion, r2D ≈ 3.9 nm, of the same order of magnitude as the aggregate sizes found by J. Eyssautier with SAXS

  1. Probing oxidative degradation in polymers using {sup 17}O NMR spectroscopy

    SciTech Connect

    Alam, T.M.; Click, C.A.; Assink, R.A.

    1997-09-01

    Understanding the mechanism of oxidative degradation remains an important goal in being able to predict the aging process in polymer materials. Nuclear magnetic resonance (NMR) spectroscopy has previously been utilized to investigate polymer degradation, including both proton ({sup 1}H) and carbon ({sup 13}C) studies. These previous NMR studies, as well as other spectroscopic investigations, are complicated by the almost overwhelming signal arising from the native undegraded polymer. This makes the identification and quantification of degradation species at small concentrations difficult. In this note we discuss recent investigation into the use of oxygen ({sup 17}O) NMR spectroscopy to probe the oxidative degradation process in polymers at a molecular level. Due to the low natural abundance (0.037%) and a nuclear spin of I=5/2 possessing an appreciable quadrupolar moment, the use of {sup 17}O NMR in polymer investigations has been limited. By utilizing synthetically enriched oxygen gas during the accelerated aging process, both the difficulties of low natural abundance and background interference signals are eliminated. For enriched samples {sup 17}O NMR spectra now provide a unique probe since all of the observed NMR resonances are the direct result of oxidative degradation.

  2. Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring

    NASA Astrophysics Data System (ADS)

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

    2014-12-01

    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in

  3. Simultaneous (19)F-(1)H medium resolution NMR spectroscopy for online reaction monitoring.

    PubMed

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

    2014-10-18

    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02mm) was used as a flow cell in combination with a 5mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a (1)H Larmor frequency of 43.32MHz and 40.68MHz for (19)F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating (19)F and (1)H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02mm was characterised regarding the limit of detection (LOQ ((1)H)=0.335molL(-1) and LOQ ((19)F)=0.130molL(-1) for trifluoroethanol

  4. Total assignment and structure in solution of tetrandrine by NMR spectroscopy and molecular modelling

    NASA Astrophysics Data System (ADS)

    Thevand, André; Stanculescu, Ioana; Mandravel, Cristina; Woisel, Patrice; Surpateanu, Gheorghe

    2004-07-01

    High-resolution 1- and 2D NMR spectra of tetrandrine and molecular modelling were employed to characterise its structure in solution. Complete and unambiguous assignment of all proton and carbon resonance signals is reported. Scalar couplings were determined from dihedral angles with the Karplus equation. Inter-proton distances were evaluated from NOE correlation peaks. Comparison of simulated and X-ray conformations of tetrandrine reveals only small differences.

  5. Citron and lemon under the lens of HR-MAS NMR spectroscopy.

    PubMed

    Mucci, Adele; Parenti, Francesca; Righi, Valeria; Schenetti, Luisa

    2013-12-01

    High Resolution Magic Angle Spinning (HR-MAS) is an NMR technique that can be applied to semi-solid samples. Flavedo, albedo, pulp, seeds, and oil gland content of lemon and citron were studied through HR-MAS NMR spectroscopy, which was used directly on intact tissue specimens without any physicochemical manipulation. HR-MAS NMR proved to be a very suitable technique for detecting terpenes, sugars, organic acids, aminoacids and osmolites. It is valuable in observing changes in sugars, principal organic acids (mainly citric and malic) and ethanol contents of pulp specimens and this strongly point to its use to follow fruit ripening, or commercial assessment of fruit maturity. HR-MAS NMR was also used to derive the molar percentage of fatty acid components of lipids in seeds, which can change depending on the Citrus species and varieties. Finally, this technique was employed to elucidate the metabolic profile of mold flavedo. PMID:23871074

  6. Structural studies of PCU-hydrazones: NMR spectroscopy, X-ray diffractions, and DFT calculations

    NASA Astrophysics Data System (ADS)

    Veljković, Jelena; Šekutor, Marina; Molčanov, Krešimir; Lo, Rabindranath; Ganguly, Bishwajit; Mlinarić-Majerski, Kata

    2011-06-01

    In this article we present a detailed structural investigation for the configurational isomers of PCU-hydrazones. The structural characterization of these hydrazones was performed using NMR spectroscopy, X-ray diffraction analysis and theoretical calculations. The single crystal X-ray structures of PCU-hydrazones 6B and 6C have been solved and used to conclusively confirm the characterization obtained via NMR spectra of a particular isomer. Nuclear magnetic shielding values calculated for 6A-C using DFT calculations were correlated with the experimentally determined chemical shifts. The computed results were found to be in good agreement with the observed 13C NMR values. The computed NMR results helped to ascertain the isomers of PCU-hydrazones 4A-C.

  7. Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

    SciTech Connect

    Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy

    2015-10-14

    Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110–120 kHz), {sup 1}H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong {sup 1}H–{sup 1}H homonuclear dipolar couplings and narrow {sup 1}H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) {sup 1}H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about {sup 1}H–{sup 1}H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic

  8. Automated sample preparation station for studying self-diffusion in porous solids with NMR spectroscopy

    SciTech Connect

    Hedin, Niklas; DeMartin, Gregory J.; Reyes, Sebastian C.

    2006-03-15

    In studies of gas diffusion in porous solids with nuclear magnetic resonance (NMR) spectroscopy the sample preparation procedure becomes very important. An apparatus is presented here that pretreats the sample ex situ and accurately sets the desired pressure and temperature within the NMR tube prior to its introduction in the spectrometer. The gas manifold that supplies the NMR tube is also connected to a microbalance containing another portion of the same sample, which is kept at the same temperature as the sample in the NMR tube. This arrangement permits the simultaneous measurement of the adsorption loading on the sample, which is required for the interpretation of the NMR diffusion experiments. Furthermore, to ensure a good seal of the NMR tube, a hybrid valve design composed of titanium, a Teflon registered seat, and Kalrez registered O-rings is utilized. A computer controlled algorithm ensures the accuracy and reproducibility of all the procedures, enabling the NMR diffusion experiments to be performed at well controlled conditions of pressure, temperature, and amount of gas adsorbed on the porous sample.

  9. Characterization of proteins by in-cell NMR spectroscopy in cultured mammalian cells.

    PubMed

    Barbieri, Letizia; Luchinat, Enrico; Banci, Lucia

    2016-06-01

    In-cell NMR spectroscopy is a unique tool for characterizing biological macromolecules in their physiological environment at atomic resolution. Recent progress in NMR instruments and sample preparation methods allows functional processes, such as metal uptake, disulfide-bond formation and protein folding, to be analyzed by NMR in living, cultured human cells. This protocol describes the necessary steps to overexpress one or more proteins of interest inside human embryonic kidney 293T (HEK293T) cells, and it explains how to set up in-cell NMR experiments. The cDNA is transiently transfected as a complex with a cationic polymer (DNA:PEI (polyethylenimine)), and protein expression is carried on for 2-3 d, after which the NMR sample is prepared. (1)H and (1)H-(15)N correlation NMR experiments (for example, using band-selective optimized flip-angle short-transient heteronuclear multiple quantum coherence (SOFAST-HMQC)) can be carried out in <2 h, ensuring cell viability. Uniform (15)N labeling and amino-acid-specific (e.g., cysteine, methionine) labeling schemes are possible. The entire procedure takes 4 d from cell culture seeding to NMR data collection. PMID:27196722

  10. Structure determination of helical filaments by solid-state NMR spectroscopy

    PubMed Central

    Ahmed, Mumdooh; Spehr, Johannes; König, Renate; Lünsdorf, Heinrich; Rand, Ulfert; Lührs, Thorsten; Ritter, Christiane

    2016-01-01

    The controlled formation of filamentous protein complexes plays a crucial role in many biological systems and represents an emerging paradigm in signal transduction. The mitochondrial antiviral signaling protein (MAVS) is a central signal transduction hub in innate immunity that is activated by a receptor-induced conversion into helical superstructures (filaments) assembled from its globular caspase activation and recruitment domain. Solid-state NMR (ssNMR) spectroscopy has become one of the most powerful techniques for atomic resolution structures of protein fibrils. However, for helical filaments, the determination of the correct symmetry parameters has remained a significant hurdle for any structural technique and could thus far not be precisely derived from ssNMR data. Here, we solved the atomic resolution structure of helical MAVSCARD filaments exclusively from ssNMR data. We present a generally applicable approach that systematically explores the helical symmetry space by efficient modeling of the helical structure restrained by interprotomer ssNMR distance restraints. Together with classical automated NMR structure calculation, this allowed us to faithfully determine the symmetry that defines the entire assembly. To validate our structure, we probed the protomer arrangement by solvent paramagnetic resonance enhancement, analysis of chemical shift differences relative to the solution NMR structure of the monomer, and mutagenesis. We provide detailed information on the atomic contacts that determine filament stability and describe mechanistic details on the formation of signaling-competent MAVS filaments from inactive monomers. PMID:26733681

  11. NMR doesn't lie or how solid-state NMR spectroscopy contributed to a better understanding of the nature and function of soil organic matter (Philippe Duchaufour Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Knicker, Heike

    2016-04-01

    for organo-mineral interactions. Since decent solid-state NMR spectra cannot be obtained from graphenic components, the successful acquisition of solid-state 13C and 15N NMR spectra of charcoals challenged the well accepted model of their chemical nature. Application of advanced 2D NMR approaches confirmed the new view of charcoal as a heterogeneous material, the composition of which depends upon the feedstock and charring condition. The respective consequences of this alternative for the understanding of C sequestration are still matter of ongoing debates. Although the sensitivity of 15N for NMR spectroscopy is 50 times lower than that of 13C, first solid-state 15N NMR spectra of soils with natural 15N abundance were already published in the 1990's. They clearly identified peptide-like structures as the main organic N form in unburnt soils. However, in spite of their high contribution to SOM, the role of peptides in soils is far from understood. Considering the new technological developments in the field of NMR spectroscopy, this technique will certainly not stop to contribute to unexpected results.

  12. NMR difference spectroscopy with a dual saddle-coil difference probe.

    PubMed

    Macnaughtan, Megan A; Smith, Aaron P; Goldsbrough, Peter B; Santini, Robert E; Raftery, Daniel

    2004-03-01

    A new difference probe for nuclear magnetic resonance (NMR) spectroscopy is presented. The difference probe uses two saddle-shaped coils to excite and detect two samples simultaneously. The samples are held in a specially modified 3-mm NMR tube with an Ultem plastic disk to separate the samples. The probe's resonant circuit contains two crossed diodes that passively switch the relative phase of each coil during the NMR experiment. The result is a difference spectrum from the two samples. The degree of cancellation of common signals was determined to be approximately 90%, and the application of the probe to relaxation-edited difference spectroscopy for identifying protein-ligand interactions was demonstrated using glutathione and glutathione S-transferase binding protein. PMID:15214412

  13. Chiral Recognition Studies of α-(Nonafluoro-tert-butoxy)carboxylic Acids by NMR Spectroscopy.

    PubMed

    Nemes, Anikó; Csóka, Tamás; Béni, Szabolcs; Farkas, Viktor; Rábai, József; Szabó, Dénes

    2015-06-19

    Three chiral α-(nonafluoro-tert-butoxy)carboxylic acids (R)-1, (RS)-2, (R)-3 were synthesized to examine their application as chiral solvating agents with amines. As a model compound, first (S)- and/or (RS)-α-phenylethylamine was used, and their diastereomeric salts were investigated by (1)H and (19)F NMR and ECD spectroscopy. The NMR spectroscopic studies were carried out at room temperature using the slightly polar CDCl3 and apolar C6D6 as solvents in 5 mM and 54 mM concentrations. The difference of the chemical shifts (Δδ) in the diastereomeric complexes is comparable with other, well-known chiral derivatizing and solvating agents (e.g., Mosher's acid, Pirkle's alcohol). Diastereomeric salts of racemic acids (RS)-1 and (RS)-2 with biologically active amines (1R,2S)-ephedrine and (S)-dapoxetine were also investigated by (19)F NMR spectroscopy. PMID:26024423

  14. Surface Binding of TOTAPOL Assists Structural Investigations of Amyloid Fibrils by Dynamic Nuclear Polarization NMR Spectroscopy.

    PubMed

    Nagaraj, Madhu; Franks, Trent W; Saeidpour, Siavash; Schubeis, Tobias; Oschkinat, Hartmut; Ritter, Christiane; van Rossum, Barth-Jan

    2016-07-15

    Dynamic nuclear polarization (DNP) NMR can enhance sensitivity but often comes at the price of a substantial loss of resolution. Two major factors affect spectral quality: low-temperature heterogeneous line broadening and paramagnetic relaxation enhancement (PRE) effects. Investigations by NMR spectroscopy, isothermal titration calorimetry (ITC), and EPR revealed a new substantial affinity of TOTAPOL to amyloid surfaces, very similar to that shown by the fluorescent dye thioflavin-T (ThT). As a consequence, DNP spectra with remarkably good resolution and still reasonable enhancement could be obtained at very low TOTAPOL concentrations, typically 400 times lower than commonly employed. These spectra yielded several long-range constraints that were difficult to obtain without DNP. Our findings open up new strategies for structural studies with DNP NMR spectroscopy on amyloids that can bind the biradical with affinity similar to that shown towards ThT. PMID:27147408

  15. Rapid discrimination of extracts of Chinese propolis and poplar buds by FT-IR and 2D IR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Yan-Wen; Sun, Su-Qin; Zhao, Jing; Li, Yi; Zhou, Qun

    2008-07-01

    The extract of Chinese propolis (ECP) has recently been adulterated with that of poplar buds (EPB), because most of ECP is derived from the poplar plant, and ECP and EPB have almost identical chemical compositions. It is very difficult to differentiate them by using the chromatographic methods such as high performance liquid chromatography (HPLC) and gas chromatography (GC). Therefore, how to effectively discriminate these two mixtures is a problem to be solved urgently. In this paper, a rapid method for discriminating ECP and EPB was established by the Fourier transform infrared (FT-IR) spectra combined with the two-dimensional infrared correlation (2D IR) analysis. Forty-three ECP and five EPB samples collected from different areas of China were analyzed by the FT-IR spectroscopy. All the ECP and EPB samples tested show similar IR spectral profiles. The significant differences between ECP and EPB appear in the region of 3000-2800 cm -1 of the spectra. Based on such differences, the two species were successfully classified with the soft independent modeling of class analogy (SIMCA) pattern recognition technique. Furthermore, these differences were well validated by a series of temperature-dependent dynamic FT-IR spectra and the corresponding 2D IR plots. The results indicate that the differences in these two natural products are caused by the amounts of long-chain alkyl compounds (including long-chain alkanes, long-chain alkyl esters and long chain alkyl alcohols) in them, rather than the flavonoid compounds, generally recognized as the bioactive substances of propolis. There are much more long-chain alkyl compounds in ECP than those in EPB, and the carbon atoms of the compounds in ECP remain in an order Z-shaped array, but those in EPB are disorder. It suggests that FT-IR and 2D IR spectroscopy can provide a valuable method for the rapid differentiation of similar natural products, ECP and EPB. The IR spectra could directly reflect the integrated chemical

  16. Water Behavior in Bacterial Spores by Deuterium NMR Spectroscopy

    PubMed Central

    2015-01-01

    Dormant bacterial spores are able to survive long periods of time without nutrients, withstand harsh environmental conditions, and germinate into metabolically active bacteria when conditions are favorable. Numerous factors influence this hardiness, including the spore structure and the presence of compounds to protect DNA from damage. It is known that the water content of the spore core plays a role in resistance to degradation, but the exact state of water inside the core is a subject of discussion. Two main theories present themselves: either the water in the spore core is mostly immobile and the core and its components are in a glassy state, or the core is a gel with mobile water around components which themselves have limited mobility. Using deuterium solid-state NMR experiments, we examine the nature of the water in the spore core. Our data show the presence of unbound water, bound water, and deuterated biomolecules that also contain labile deuterons. Deuterium–hydrogen exchange experiments show that most of these deuterons are inaccessible by external water. We believe that these unreachable deuterons are in a chemical bonding state that prevents exchange. Variable-temperature NMR results suggest that the spore core is more rigid than would be expected for a gel-like state. However, our rigid core interpretation may only apply to dried spores whereas a gel core may exist in aqueous suspension. Nonetheless, the gel core, if present, is inaccessible to external water. PMID:24950158

  17. Characterization of animal manure using advanced solid-state C-13 NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Knowledge of chemical structure of animal manure is necessary for its effective utilization. However, characterization of animal manure is challenging since it is a complex mixture and partially soluble. Solid-state C-13 NMR (nuclear magnetic resonance) spectroscopy is regarded as the best tool to i...

  18. USING HIGH-RESOLUTION SOLUTION-STATE NMR SPECTROSCOPY TO INVESTIGATE PMDI REACTIONS WITH WOOD

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Solution-state NMR spectroscopy provides a powerful tool for understanding the formation of chemical bonds between wood components and adhesives. Finely ground cell wall (CW) material fully dissolves in a solvent system containing dimethylsulfoxide (DMSO-d6) and N-methyl¬imidazole (NMI-d6), keeping ...

  19. NMR imaging and spectroscopy of the mammalian central nervous system after heavy ion radiation

    SciTech Connect

    Richards, T.

    1984-09-01

    NMR imaging, NMR spectroscopic, and histopathologic techniques were used to study the proton relaxation time and related biochemical changes in the central nervous system after helium beam in vivo irradiation of the rodent brain. The spectroscopic observations reported in this dissertation were made possible by development of methods for measuring the NMR parameters of the rodent brain in vivo and in vitro. The methods include (1) depth selective spectroscopy using an optimization of rf pulse energy based on a priori knowledge of N-acetyl aspartate and lipid spectra of the normal brain, (2) phase-encoded proton spectroscopy of the living rodent using a surface coil, and (3) dual aqueous and organic tissue extraction technique for spectroscopy. Radiation induced increases were observed in lipid and p-choline peaks of the proton spectrum, in vivo. Proton NMR spectroscopy measurements on brain extracts (aqueous and organic solvents) were made to observe chemical changes that could not be seen in vivo. Radiation-induced changes were observed in lactate, GABA, glutamate, and p-choline peak areas of the aqueous fraction spectra. In the organic fraction, decreases were observed in peak area ratios of the terminal-methyl peaks, the N-methyl groups of choline, and at a peak at 2.84 ppM (phosphatidyl ethanolamine and phosphatidyl serine resonances) relative to TMS. With histology and Evans blue injections, blood-brain barrier alternations were seen as early as 4 days after irradiation. 83 references, 53 figures.

  20. Introducing High School Students to NMR Spectroscopy through Percent Composition Determination Using Low-Field Spectrometers

    ERIC Educational Resources Information Center

    Bonjour, Jessica L.; Pitzer, Joy M.; Frost, John A.

    2015-01-01

    Mole to gram conversions, density, and percent composition are fundamental concepts in first year chemistry at the high school or undergraduate level; however, students often find it difficult to engage with these concepts. We present a simple laboratory experiment utilizing portable nuclear magnetic resonance spectroscopy (NMR) to determine the…

  1. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.

    2012-01-01

    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  2. High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound

    ERIC Educational Resources Information Center

    Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.

    2014-01-01

    High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

  3. NMR Spectroscopy of Aqueous Extracts of Fenugreek ( Trigonella foenum- graecum L.)

    NASA Astrophysics Data System (ADS)

    Skakovskii, E. D.; Tychinskaya, L. Yu.; Matveichuk, S. V.; Karankevich, E. G.; Agabalaeva, E. D.; Reshetnikov, V. N.

    2014-09-01

    The amino-acid and monosaccharide compositions of aqueous extracts of fenugreek herb were determined using PMR and 13C NMR spectroscopy. The content of identified extract constituents was >70 mol%, of which the dominant amino acid was 4-hydroxyisoleucine (26.5 mol%); the major carbohydrate, glucose (10.1 mol%).

  4. In situ measurement of molecular diffusion during catalytic reaction by pulsed-field gradient NMR spectroscopy

    SciTech Connect

    Hong, Y.; Kaerger, J.; Hunger, B. ); Feoktistova, N.N.; Zhdanov, S.P. )

    1992-09-01

    Pulsed-field gradient (PFG) NMR spectroscopy is applied to study the intracrystalline diffusivity of the reactant and product molecules during the conversion of cyclopropane to propene in Zeolite X. The diffusivities are found to be large enough that any influence of intracrystalline diffusion on the overall reaction in flow reactors may be excluded.

  5. Characterization of various fast pyrolysis bio-oils by NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    NMR spectroscopy, including 1H, 13 C and DEPT spectra were used to characterize fast pyrolysis oil from numerous energy crops and other agricultural feedstocks. The bio-oils studied were produced from swithchgrass, alfalfa stems, corn stover, guayule (whole plant and latex extracted bagasse) and ch...

  6. Structural modifications of Tilia cordata wood during heat treatment investigated by FT-IR and 2D IR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Popescu, Maria-Cristina; Froidevaux, Julien; Navi, Parviz; Popescu, Carmen-Mihaela

    2013-02-01

    It is known that heat treatment of wood combined with a low percent of relative humidity causes transformations in the chemical composition of it. The modifications and/or degradation of wood components occur by hydrolysis, oxidation, and decarboxylation reactions. The aim of this study was to give better insights on wood chemical modifications during wood heat treatment under low temperature at about 140 °C and 10% percentage of relative humidity, by infrared, principal component analysis and two dimensional infrared correlation spectroscopy. For this purpose, hardwood samples of lime (Tilia cordata) were investigated and analysed. The infrared spectra of treated samples were compared with the reference ones, the most important differences being observed in the "fingerprint" region. Due to the complexity of this region, which have contributions from all the wood constituents the chemical changes during hydro-thermal treatment were examined in detail using principal component analysis and 2D IR correlation spectroscopy. By hydro-thermal treatment of wood results the formation of acetic acid, which catalyse the hydrolysis reactions of hemicelluloses and amorphous cellulose. The cleavage of the β-O-4 linkages and splitting of the aliphatic methoxyl chains from the aromatic lignin ring was also observed. For the first treatment interval, a higher extent of carbohydrates degradation was observed, then an increase of the extent of the lignin degradation also took place.

  7. NMR spectroscopy in studies of light-induced structural changes in mammalian rhodopsin: applicability of solution (19)F NMR.

    PubMed

    Klein-Seetharaman, J; Getmanova, E V; Loewen, M C; Reeves, P J; Khorana, H G

    1999-11-23

    We report high resolution solution (19)F NMR spectra of fluorine-labeled rhodopsin mutants in detergent micelles. Single cysteine substitution mutants in the cytoplasmic face of rhodopsin were labeled by attachment of the trifluoroethylthio (TET), CF(3)-CH(2)-S, group through a disulfide linkage. TET-labeled cysteine mutants at amino acid positions 67, 140, 245, 248, 311, and 316 in rhodopsin were thus prepared. Purified mutant rhodopsins (6-10 mg), in dodecylmaltoside, were analyzed at 20 degrees C by solution (19)F NMR spectroscopy. The spectra recorded in the dark showed the following chemical shifts relative to trifluoroacetate: Cys-67, 9.8 ppm; Cys-140, 10.6 ppm; Cys-245, 9.9 ppm; Cys-248, 9.5 ppm; Cys-311, 9.9 ppm; and Cys-316, 10.0 ppm. Thus, all mutants showed chemical shifts downfield that of free TET (6.5 ppm). On illumination to form metarhodopsin II, upfield changes in chemical shift were observed for (19)F labels at positions 67 (-0.2 ppm) and 140 (-0.4 ppm) and downfield changes for positions 248 (+0.1 ppm) and 316 (+0.1 ppm) whereas little or no change was observed at positions 311 and 245. On decay of metarhodopsin II, the chemical shifts reverted largely to those originally observed in the dark. The results demonstrate the applicability of solution (19)F NMR spectroscopy to studies of the tertiary structures in the cytoplasmic face of intact rhodopsin in the dark and on light activation. PMID:10570143

  8. Spectrally edited 2D 13Csbnd 13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials

    NASA Astrophysics Data System (ADS)

    Johnson, Robert L.; Anderson, Jason M.; Shanks, Brent H.; Fang, Xiaowen; Hong, Mei; Schmidt-Rohr, Klaus

    2013-09-01

    Two robust combinations of spectral editing techniques with 2D 13Csbnd 13C NMR have been developed for characterizing the aromatic components of 13C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by 13C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, Csbnd H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and Cdbnd O carbons

  9. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

    PubMed Central

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  10. New methods and applications in solid-state NMR spectroscopy of quadrupolar nuclei.

    PubMed

    Ashbrook, Sharon E; Sneddon, Scott

    2014-11-01

    Solid-state nuclear magnetic resonance (NMR) spectroscopy has long been established as offering unique atomic-scale and element-specific insight into the structure, disorder, and dynamics of materials. NMR spectra of quadrupolar nuclei (I > (1)/2) are often perceived as being challenging to acquire and to interpret because of the presence of anisotropic broadening arising from the interaction of the electric field gradient and the nuclear electric quadrupole moment, which broadens the spectral lines, often over several megahertz. Despite the vast amount of information contained in the spectral line shapes, the problems with sensitivity and resolution have, until very recently, limited the application of NMR spectroscopy of quadrupolar nuclei in the solid state. In this Perspective, we provide a brief overview of the quadrupolar interaction, describe some of the basic experimental approaches used for acquiring high-resolution NMR spectra, and discuss the information that these spectra can provide. We then describe some interesting recent examples to showcase some of the more exciting and challenging new applications of NMR spectra of quadrupolar nuclei in the fields of energy materials, microporous materials, Earth sciences, and biomaterials. Finally, we consider the possible directions that this highly informative technique may take in the future. PMID:25296129

  11. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy.

    PubMed

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (¹H, (13)C, and (31)P) and two-dimensional (¹H-(13)C and ¹H-(31)P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. ¹H, (13)C, and (31)P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the ¹H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative ¹H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the ¹H-(31)P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  12. Stable isotope-enhanced two- and three-dimensional diffusion ordered 13C-NMR spectroscopy (SIE-DOSY 13C-NMR)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stable Isotope-Enhanced Diffusion Ordered (SIE-DOSY) 13C-NMR has been applied to 13C-enriched carbohydrates and has been used to determine diffusion coefficients for pentose and hexose monosaccharides, a disaccharide and a trisaccharide. These 2D spectra were obtained with as little as 8 min of acq...

  13. Studying Protein-Protein Binding through T-Jump Induced Dissociation: Transient 2D IR Spectroscopy of Insulin Dimer.

    PubMed

    Zhang, Xin-Xing; Jones, Kevin C; Fitzpatrick, Ann; Peng, Chunte Sam; Feng, Chi-Jui; Baiz, Carlos R; Tokmakoff, Andrei

    2016-06-16

    Insulin homodimer associates through the coupled folding and binding of two partially disordered monomers. We aim to understand this dynamics by observing insulin dimer dissociation initiated with a nanosecond temperature jump using transient two-dimensional infrared spectroscopy (2D IR) of amide I vibrations. With the help of equilibrium FTIR and 2D IR spectra, and through a systematic study of the dependence of dissociation kinetics on temperature and insulin concentration, we are able to decompose and analyze the spectral evolution associated with different secondary structures. We find that the dissociation under all conditions is characterized by two processes whose influence on the kinetics varies with temperature: the unfolding of the β sheet at the dimer interface observed as exponential kinetics between 250 and 1000 μs and nonexponential kinetics between 5 and 150 μs that we attribute to monomer disordering. Microscopic reversibility arguments lead us to conclude that dimer association requires significant conformational changes within the monomer in concert with the folding of the interfacial β sheet. While our data indicates a more complex kinetics, we apply a two-state model to the β-sheet unfolding kinetics to extract thermodynamic parameters and kinetic rate constants. The association rate constant, ka (23 °C) = 8.8 × 10(5) M(-1) s(-1) (pH 0, 20% EtOD), is approximately 3 orders of magnitude slower than the calculated diffusion limited association rate, which is explained by the significant destabilizing effect of ethanol on the dimer state and the highly positive charge of the monomers at this pH. PMID:27203447

  14. Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

    SciTech Connect

    Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang; Akhtar, Parveen; Garab, Győző; Lambrev, Petar H.

    2015-06-07

    The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysis of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.

  15. Dynamics-based selective 2D {sup 1}H/{sup 1}H chemical shift correlation spectroscopy under ultrafast MAS conditions

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of {sup 1}H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of {sup 1}H/{sup 1}H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  16. Changes in Lignin and Polysaccharide Components in 13 Cultivars of Rice Straw following Dilute Acid Pretreatment as Studied by Solution-State 2D 1H-13C NMR

    PubMed Central

    Teramura, Hiroshi; Sasaki, Kengo; Oshima, Tomoko; Aikawa, Shimpei; Matsuda, Fumio; Okamoto, Mami; Shirai, Tomokazu; Kawaguchi, Hideo; Ogino, Chiaki; Yamasaki, Masanori; Kikuchi, Jun; Kondo, Akihiko

    2015-01-01

    A renewable raw material, rice straw is pretreated for biorefinery usage. Solution-state two-dimensional (2D) 1H-13 C hetero-nuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy, was used to analyze 13 cultivars of rice straw before and after dilute acid pretreatment, to characterize general changes in the lignin and polysaccharide components. Intensities of most (15 of 16) peaks related to lignin aromatic regions, such as p-coumarate, guaiacyl, syringyl, p-hydroxyphenyl, and cinnamyl alcohol, and methoxyl, increased or remained unchanged after pretreatment. In contrast, intensities of most (11 of 13) peaks related to lignin aliphatic linkages or ferulate decreased. Decreased heterogeneity in the intensities of three peaks related to cellulose components in acid-insoluble residues resulted in similar glucose yield (0.45–0.59 g/g-dry biomass). Starch-derived components showed positive correlations (r = 0.71 to 0.96) with glucose, 5-hydroxymethylfurfural (5-HMF), and formate concentrations in the liquid hydrolysates, and negative correlations (r = –0.95 to –0.97) with xylose concentration and acid-insoluble residue yield. These results showed the fate of lignin and polysaccharide components by pretreatment, suggesting that lignin aromatic regions and cellulose components were retained in the acid insoluble residues and starch-derived components were transformed into glucose, 5-HMF, and formate in the liquid hydrolysate. PMID:26083431

  17. NMR/MS Translator for the Enhanced Simultaneous Analysis of Metabolomics Mixtures by NMR Spectroscopy and Mass Spectrometry: Application to Human Urine.

    PubMed

    Bingol, Kerem; Brüschweiler, Rafael

    2015-06-01

    A novel metabolite identification strategy is presented for the combined NMR/MS analysis of complex metabolite mixtures. The approach first identifies metabolite candidates from 1D or 2D NMR spectra by NMR database query, which is followed by the determination of the masses (m/z) of their possible ions, adducts, fragments, and characteristic isotope distributions. The expected m/z ratios are then compared with the MS(1) spectrum for the direct assignment of those signals of the mass spectrum that contain information about the same metabolites as the NMR spectra. In this way, the mass spectrum can be assigned with very high confidence, and it provides at the same time validation of the NMR-derived metabolites. The method was first demonstrated on a model mixture, and it was then applied to human urine collected from a pool of healthy individuals. A number of metabolites could be detected that had not been reported previously, further extending the list of known urine metabolites. The new analysis approach, which is termed NMR/MS Translator, is fully automated and takes only a few seconds on a computer workstation. NMR/MS Translator synergistically uses the power of NMR and MS, enhancing the accuracy and efficiency of the identification of those metabolites compiled in databases. PMID:25881480

  18. Binding of Sulfonamide Antibiotics to CTABr Micelles Characterized Using (1)H NMR Spectroscopy.

    PubMed

    Sarker, Ashish K; Cashin, Patrick J; Balakrishnan, Vimal K; Exall, Kirsten; Buncel, Erwin; Brown, R Stephen

    2016-08-01

    Interactions of nine sulfonamide antibiotics (sulfadoxine, sulfathiazole, sulfamethoxazole, sulfamerazine, sulfadiazine, sulfamethazine, sulfacetamide, sulfaguanidine, and sulfanilamide) with cetyltrimethylamonium bromide (CTABr) micelles were examined using (1)H NMR spectroscopy. Seven of the nine provided a significant change in the (1)H NMR chemical shift such that the magnitude and direction (upfield vs downfield) of the chemical shift could be used to propose a locus and orientation of the sulfonamide within the micelle structure. The magnitude of the chemical shift was used to estimate the binding constant for seven sulfonamides with CTABr micelles, providing values and an overall pattern consistent with previous studies of these sulfonamides. PMID:27391918

  19. Synthesis and Proton NMR Spectroscopy of Intra-Vesicular Gamma-Aminobutyric Acid (GABA)*

    PubMed Central

    Wang, Luke Y.-J.; Tong, Rong; Kohane, Daniel S.

    2014-01-01

    We report the synthesis of vesicles containing gamma-aminobutyric acid (GABA), and their proton nuclear magnetic resonance (1H NMR) spectra. These vesicles were constructed to more closely mimic the intracellular environment wherein GABA exists. For this study, these GABA-containing vesicles were examined under 1H NMR as a potential platform for future studies on the differences between aqueous phantoms, ex vivo brain extracts, and in vivo magnetic resonance spectroscopy results. We found that intra-vesicular GABA faithfully yielded the chemical shifts and J-coupling constants of free aqueous GABA, alongside the chemical shift signals of the vesicle wall. PMID:24109882

  20. High frequency volume coils for clinical NMR imaging and spectroscopy.

    PubMed

    Vaughan, J T; Hetherington, H P; Otu, J O; Pan, J W; Pohost, G M

    1994-08-01

    A tuned transmission line resonator has been developed in theory and in practical design for the clinical NMR volume coil application at 4.1 tesla. The distributed circuit transmission line resonator was designed for high frequency, large conductive volume applications where conventional lumped element coil designs perform less efficiently. The resonator design has made use of a resonant coaxial cavity, which could be variably tuned to the Larmor frequency of interest by tunable transmission line elements. Large head- and body-sized volumes, high efficiencies, and broad tuning ranges have been shown to be characteristic of the transmission line resonator to frequencies of 500 MHz. The B1 homogeneity of the resonator has been demonstrated to be a function of the electromagnetic properties of the load itself. By numerically solving Maxwell's equations for the fully time-dependent B1 field, coil homogeneity was predicted with finite-element models of anatomic structure, and inhomogeneities corrected for. A how-to exposition of coil design and construction has been included. Simple methods of quadrature driving and double tuning the transmission line resonator have also been presented. Human head images obtained with a tuned transmission line resonator at 175 MHz have clearly demonstrated uncompromised high field advantages of signal-to-noise and spatial resolution. PMID:7968443

  1. Broadband "Infinite-Speed" Magic-Angle Spinning NMR Spectroscopy

    SciTech Connect

    Hu, Yan-Yan; Levin, E.M; Schmidt-Rohr, Klaus

    2009-06-02

    High-resolution magic-angle spinning NMR of high-Z spin- 1/2 nuclei such as {sup 125}Te, {sup 207}Pb, {sup 119}Sn, {sup 113}Cd, and {sup 195}Pt is often hampered by large (>1000 ppm) chemical-shift anisotropies, which result in strong spinning sidebands that can obscure the centerbands of interest. In various tellurides with applications as thermoelectrics and as phase-change materials for data storage, even 22-kHz magic-angle spinning cannot resolve the center- and sidebands broadened by chemical-shift dispersion, which precludes peak identification or quantification. For sideband suppression over the necessary wide spectral range (up to 200 kHz), radio frequency pulse sequences with few, short pulses are required. We have identified Gan's two-dimensional magic-angle-turning (MAT) experiment with five 90{sup o} pulses as a promising broadband technique for obtaining spectra without sidebands. We have adapted it to broad spectra and fast magic-angle spinning by accounting for long pulses (comparable to the dwell time in t{sub 1}) and short rotation periods. Spectral distortions are small and residual sidebands negligible even for spectra with signals covering a range of 1.5 {gamma}B{sub 1}, due to a favorable disposition of the narrow ranges containing the signals of interest in the spectral plane. The method is demonstrated on various technologically interesting tellurides with spectra spanning up to 170 kHz, at 22 kHz MAS.

  2. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, N.

    1996-10-17

    Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory information, the literature review, general conclusions, and four appendices. An additional four chapters and one appendix have been processed separately for inclusion on the data base.

  3. Deuterium NMR spectroscopy of biosynthetically deuterated mammalian tissues

    SciTech Connect

    Curatolo, W.; Jungalwala, F.B.; Sears, B.; Tuck, L.; Neuringer, L.J.

    1985-07-30

    The choline-containing phospholipids of mammalian membranes have been biosynthetically deuterated by raising rats on a diet supplemented with (HOCH2CH2N(CD3)3) Cl or (HOCD2CH2N(CH3)3) Cl . Deuterium NMR spectra have been obtained from excised deuterated brain, sciatic nerve, heart, and lung, from isolated brain myelin and brain microsomes, and from aqueous dispersions of lipid extracts. Measurements of residual quadrupole splittings for excised deuterated neural tissues demonstrate that the orientational order of the choline head group is similar to that observed in model membranes. The spin-lattice relaxation time of the choline head group in deuterated neural tissue is indistinguishable from that observed in model membranes. These results support the proposal that the conformation and motional dynamics of the choline head groups of the bulk choline-containing lipids of neural tissue are similar to those in model membranes. Spectra of biosynthetically deuterated brain myelin and brain microsomes exhibit similar quadrupole splittings. Since these membranes have significantly different protein contents, these results indicate that no strong polar interactions exist between membrane proteins and the choline head groups of choline-containing membrane lipids. Spectra of intact deuterated heart and lung exhibit broad lines and a range of quadrupole splittings.

  4. Fractional deuteration applied to biomolecular solid-state NMR spectroscopy.

    PubMed

    Nand, Deepak; Cukkemane, Abhishek; Becker, Stefan; Baldus, Marc

    2012-02-01

    Solid-state Nuclear Magnetic Resonance can provide detailed insight into structural and dynamical aspects of complex biomolecules. With increasing molecular size, advanced approaches for spectral simplification and the detection of medium to long-range contacts become of critical relevance. We have analyzed the protonation pattern of a membrane-embedded ion channel that was obtained from bacterial expression using protonated precursors and D(2)O medium. We find an overall reduction of 50% in protein protonation. High levels of deuteration at H(α) and H(β) positions reduce spectral congestion in ((1)H,(13)C,(15)N) correlation experiments and generate a transfer profile in longitudinal mixing schemes that can be tuned to specific resonance frequencies. At the same time, residual protons are predominantly found at amino-acid side-chain positions enhancing the prospects for obtaining side-chain resonance assignments and for detecting medium to long-range contacts. Fractional deuteration thus provides a powerful means to aid the structural analysis of complex biomolecules by solid-state NMR. PMID:22105305

  5. Highly-accelerated quantitative 2D and 3D localized spectroscopy with linear algebraic modeling (SLAM) and sensitivity encoding

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Gabr, Refaat E.; Zhou, Jinyuan; Weiss, Robert G.; Bottomley, Paul A.

    2013-12-01

    Noninvasive magnetic resonance spectroscopy (MRS) with chemical shift imaging (CSI) provides valuable metabolic information for research and clinical studies, but is often limited by long scan times. Recently, spectroscopy with linear algebraic modeling (SLAM) was shown to provide compartment-averaged spectra resolved in one spatial dimension with many-fold reductions in scan-time. This was achieved using a small subset of the CSI phase-encoding steps from central image k-space that maximized the signal-to-noise ratio. Here, SLAM is extended to two- and three-dimensions (2D, 3D). In addition, SLAM is combined with sensitivity-encoded (SENSE) parallel imaging techniques, enabling the replacement of even more CSI phase-encoding steps to further accelerate scan-speed. A modified SLAM reconstruction algorithm is introduced that significantly reduces the effects of signal nonuniformity within compartments. Finally, main-field inhomogeneity corrections are provided, analogous to CSI. These methods are all tested on brain proton MRS data from a total of 24 patients with brain tumors, and in a human cardiac phosphorus 3D SLAM study at 3T. Acceleration factors of up to 120-fold versus CSI are demonstrated, including speed-up factors of 5-fold relative to already-accelerated SENSE CSI. Brain metabolites are quantified in SLAM and SENSE SLAM spectra and found to be indistinguishable from CSI measures from the same compartments. The modified reconstruction algorithm demonstrated immunity to maladjusted segmentation and errors from signal heterogeneity in brain data. In conclusion, SLAM demonstrates the potential to supplant CSI in studies requiring compartment-average spectra or large volume coverage, by dramatically reducing scan-time while providing essentially the same quantitative results.

  6. [Identification and analysis of genuine and false Flos Rosae Rugosae by FTIR and 2D correlation IR spectroscopy].

    PubMed

    Cai, Fang; Sun, Su-qin; Yan, Wen-rong; Niu, Shi-jie; Li, Xian-en

    2009-09-01

    The genuine and false Flos Rosae Rugosae (Flos Rosae Chinensis and Flos Rosa multiflora) were examined in terms of their differences by using Fourier transform infrared spectroscopy (FTIR) combined with two-dimensional (2D) correlation IR spectroscopy. The three species were shown very similar in FTIR spectra. The peak of 1318 cm(-1) of genuine Flos Rosae Rugosae is not obvious but this peak could be found sharp in Flos Rosae Chinensis and Flos Rosa multiflora. Generally, the second derivative IR spectrum can clearly enhance the spectral resolution. Flos Rosae Rugosae and Flos rosae Chinensis have aromatic compounds distinct fingerprint characteristics at 1 617 and 1 618 cm(-1), respectively. Nevertheless, FlosRosa multiflora has the peak at 1612 cm(-1). There is a discrepancy of 5 to 6 cm(-1). FlosRosa multiflora has glucide's distinct fingerprint characteristics at 1 044 cm(-1), but Flos Rosae Rugosae and Flos Rosae Chinensis don't. The second derivative infrared spectra indicated different fingerprint characteristics. Three of them showed aromatic compounds with autopeaks at 1620, 1560 and 1460 cm(-1). Flos Rosae Chinensis and Flos Rosa multiflora have the shoulder peak at 1660 cm(-1). In the range of 850-1250 cm(-1), three of them are distinct different, Flos Rosae Rugosae has the strongest autopeak, Flos Rosae Chinensis has the feeble autopeak and Flos Rosa multiflora has no autopeak at 1050 cm(-1). In third-step identification, the different contents of aromatic compounds and glucide in Flos Rosae Rugosae, Flos Rosae Chinensis and Flos Rosa multiflora were revealed. It is proved that the method is fast and effective for distinguishing and analyzing genuine Flos Rosae Rugosae and false Flos Rosae Rugosae (Flos Rosae Chinensis and Flos Rosa multiflora). PMID:19950645

  7. Highly-accelerated quantitative 2D and 3D localized spectroscopy with linear algebraic modeling (SLAM) and sensitivity encoding

    PubMed Central

    Zhang, Yi; Gabr, Refaat E.; Zhou, Jinyuan; Weiss, Robert G.; Bottomley, Paul A.

    2013-01-01

    Noninvasive magnetic resonance spectroscopy (MRS) with chemical shift imaging (CSI) provides valuable metabolic information for research and clinical studies, but is often limited by long scan times. Recently, spectroscopy with linear algebraic modeling (SLAM) was shown to provide compartment-averaged spectra resolved in one spatial dimension with many-fold reductions in scan-time. This was achieved using a small subset of the CSI phase-encoding steps from central image k-space that maximized the signal-to-noise ratio. Here, SLAM is extended to two- and three-dimensions (2D, 3D). In addition, SLAM is combined with sensitivity-encoded (SENSE) parallel imaging techniques, enabling the replacement of even more CSI phase-encoding steps to further accelerate scan-speed. A modified SLAM reconstruction algorithm is introduced that significantly reduces the effects of signal nonuniformity within compartments. Finally, main-field inhomogeneity corrections are provided, analogous to CSI. These methods are all tested on brain proton MRS data from a total of 24 patients with brain tumors, and in a human cardiac phosphorus 3D SLAM study at 3T. Acceleration factors of up to 120-fold versus CSI are demonstrated, including speed-up factors of 5-fold relative to already-accelerated SENSE CSI. Brain metabolites are quantified in SLAM and SENSE SLAM spectra and found to be indistinguishable from CSI measures from the same compartments. The modified reconstruction algorithm demonstrated immunity to maladjusted segmentation and errors from signal heterogeneity in brain data. In conclusion, SLAM demonstrates the potential to supplant CSI in studies requiring compartment-average spectra or large volume coverage, by dramatically reducing scan-time while providing essentially the same quantitative results. PMID:24188921

  8. Bis(pentamethylcyclopentadienyl)ytterbium: An investigation of weak interactions in solution using multinuclear NMR spectroscopy

    SciTech Connect

    Schwartz, D.J.

    1995-07-01

    NMR spectroscopy is ideal for studying weak interactions (formation enthalpy {le}20 kcal/mol) in solution. The metallocene bis(pentamethylcyclopentadienyl)ytterbium, Cp*{sub 2}Yb, is ideal for this purpose. cis-P{sub 2}PtH{sub 2}complexes (P = phosphine) were used to produce slow-exchange Cp*{sub 2}YbL adducts for NMR study. Reversible formation of (P{sub 2}PtH){sub 2} complexes from cis-P{sub 2}PtH{sub 2} complexes were also studied, followed by interactions of Cp*{sub 2}Yb with phosphines, R{sub 3}PX complexes. A NMR study was done on the interactions of Cp*{sub 2}Yb with H{sub 2}, CH{sub 4}, Xe, CO, silanes, stannanes, C{sub 6}H{sub 6}, and toluene.

  9. Target-based whole-cell screening by ¹H NMR spectroscopy.

    PubMed

    Ma, Junhe; Cao, Qing; McLeod, Sarah M; Ferguson, Keith; Gao, Ning; Breeze, Alexander L; Hu, Jun

    2015-04-13

    An NMR-based approach marries the two traditional screening technologies (phenotypic and target-based screening) to find compounds inhibiting a specific enzymatic reaction in bacterial cells. Building on a previous study in which it was demonstrated that hydrolytic decomposition of meropenem in living Escherichia coli cells carrying New Delhi metallo-β-lactamase subclass 1 (NDM-1) can be monitored in real time by NMR spectroscopy, we designed a cell-based NMR screening platform. A strong NDM-1 inhibitor was identified with cellular IC50 of 0.51 μM, which is over 300-fold more potent than captopril, a known NDM-1 inhibitor. This new screening approach has great potential to be applied to targets in other cell types, such as mammalian cells, and to targets that are only stable or functionally competent in the cellular environment. PMID:25693499

  10. Structures of larger proteins in solution: Three- and four-dimensional heteronuclear NMR spectroscopy

    SciTech Connect

    Gronenborn, A.M.; Clore, G.M.

    1994-12-01

    Complete understanding of a protein`s function and mechanism of action can only be achieved with a knowledge of its three-dimensional structure at atomic resolution. At present, there are two methods available for determining such structures. The first method, which has been established for many years, is x-ray diffraction of protein single crystals. The second method has blossomed only in the last 5 years and is based on the application of nuclear magnetic resonance (NMR) spectroscopy to proteins in solution. This review paper describes three- and four-dimensional NMR methods applied to protein structure determination and was adapted from Clore and Gronenborn. The review focuses on the underlying principals and practice of multidimensional NMR and the structural information obtained.

  11. Metabolomic differentiation of Cannabis sativa cultivars using 1H NMR spectroscopy and principal component analysis.

    PubMed

    Choi, Young Hae; Kim, Hye Kyong; Hazekamp, Arno; Erkelens, Cornelis; Lefeber, Alfons W M; Verpoorte, Robert

    2004-06-01

    The metabolomic analysis of 12 Cannabis sativa cultivars was carried out by 1H NMR spectroscopy and multivariate analysis techniques. Principal component analysis (PCA) of the 1H NMR spectra showed a clear discrimination between those samples by principal component 1 (PC1) and principal component 3 (PC3) in cannabinoid fraction. The loading plot of PC value obtained from all 1)H NMR signals shows that Delta9-tetrahydrocannabinolic acid (THCA) and cannabidiolic acid (CBDA) are important metabolites to differentiate the cultivars from each other. The discrimination of the cultivars could also be obtained from a water extract containing carbohydrates and amino acids. The level of sucrose, glucose, asparagine, and glutamic acid are found to be major discriminating metabolites of these cultivars. This method allows an efficient differentiation between cannabis cultivars without any prepurification steps. PMID:15217272

  12. In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells.

    PubMed

    Blanc, Frédéric; Leskes, Michal; Grey, Clare P

    2013-09-17

    Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help

  13. Pulsed Field Gradient NMR with Sigmoid Shape Gradient Sampling To Produce More Detailed Diffusion Ordered Spectroscopy Maps of Real Complex Mixtures: Examples with Medicine Analysis.

    PubMed

    Pagès, Guilhem; Bonny, Alice; Gilard, Véronique; Malet-Martino, Myriam

    2016-03-15

    NMR diffusion measurements are based on signal attenuation. In the case of complex mixtures for which some molecules are diffusing quickly while others are significantly slower, it is challenging to obtain a diffusion ordered spectroscopy (DOSY)-type 2D map giving reliable information on all molecules. In this paper, we propose a new gradient sampling approach based on a sigmoid shape allowing the acquisition of a significant number of points for both the fast and slow diffusing molecules. We applied this new gradient sampling strategy to deformulate two medicines whose composition was known (Esomeprazole) or unknown (Mebendazole). PFG NMR associated with a sigmoid gradient ramp is an exciting strategy to study drugs as a whole, i.e., the active ingredient(s) and excipients. PMID:26905176

  14. HRMAS-NMR spectroscopy and multivariate analysis meat characterisation.

    PubMed

    Ritota, Mena; Casciani, Lorena; Failla, Sebastiana; Valentini, Massimiliano

    2012-12-01

    ¹H-High resolution magic angle spinning-nuclear magnetic resonance spectroscopy was employed to gain the metabolic profile of longissimus dorsi and semitendinosus muscles of four different breeds: Chianina, Holstein Friesian, Maremmana and Buffalo. Principal component analysis, partial least squares projection to latent structure - discriminant analysis and orthogonal partial least squares projection to latent structure - discriminant analysis were used to build models capable of discriminating the muscle type according to the breed. Data analysis led to an excellent classification for Buffalo and Chianina, while for Holstein Friesian the separation was lower. In the case of Maremmana the use of intelligent bucketing was necessary due to some resonances shifting allowed improvement of the discrimination ability. Finally, by using the Variable Importance in Projection values the metabolites relevant for the classification were identified. PMID:22819725

  15. Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

    USGS Publications Warehouse

    Cao, Xiaoyan; Aiken, George R.; Spencer, Robert G. M.; Butler, Kenna; Mao, Jingdong; Schmidt-Rohr, Klaus

    2016-01-01

    Seasonal (spring freshet, summer–autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV–visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64–74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63–77%) and TPIA (54–78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OCnp, OCnpO and Cq, 13–17% of HPOA and 15–20% of TPIA) and isolated O–CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (∼5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C–O and O–C–O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

  16. Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

    NASA Astrophysics Data System (ADS)

    Cao, Xiaoyan; Aiken, George R.; Spencer, Robert G. M.; Butler, Kenna; Mao, Jingdong; Schmidt-Rohr, Klaus

    2016-05-01

    Seasonal (spring freshet, summer-autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV-visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64-74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63-77%) and TPIA (54-78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OCnp, OCnpO and Cq, 13-17% of HPOA and 15-20% of TPIA) and isolated O-CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (∼5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C-O and O-C-O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

  17. Metabolic flux and metabolic network analysis of Penicillium chrysogenum using 2D [13C, 1H] COSY NMR measurements and cumulative bondomer simulation.

    PubMed

    van Winden, Wouter A; van Gulik, Walter M; Schipper, Dick; Verheijen, Peter J T; Krabben, Preben; Vinke, Jacobus L; Heijnen, Joseph J

    2003-07-01

    At present two alternative methods are available for analyzing the fluxes in a metabolic network: (1) combining measurements of net conversion rates with a set of metabolite balances including the cofactor balances, or (2) leaving out the cofactor balances and fitting the resulting free fluxes to measured (13)C-labeling data. In this study these two approaches are applied to the fluxes in the glycolysis and pentose phosphate pathway of Penicillium chrysogenum growing on either ammonia or nitrate as the nitrogen source, which is expected to give different pentose phosphate pathway fluxes. The presented flux analyses are based on extensive sets of 2D [(13)C, (1)H] COSY data. A new concept is applied for simulation of this type of (13)C-labeling data: cumulative bondomer modeling. The outcomes of the (13)C-labeling based flux analysis substantially differ from those of the pure metabolite balancing approach. The fluxes that are determined using (13)C-labeling data are shown to be highly dependent on the chosen metabolic network. Extending the traditional nonoxidative pentose phosphate pathway with additional transketolase and transaldolase reactions, extending the glycolysis with a fructose 6-phosphate aldolase/dihydroxyacetone kinase reaction sequence or adding a phosphoenolpyruvate carboxykinase reaction to the model considerably improves the fit of the measured and the simulated NMR data. The results obtained using the extended version of the nonoxidative pentose phosphate pathway model show that the transketolase and transaldolase reactions need not be assumed reversible to get a good fit of the (13)C-labeling data. Strict statistical testing of the outcomes of (13)C-labeling based flux analysis using realistic measurement errors is demonstrated to be of prime importance for verifying the assumed metabolic model. PMID:12740935

  18. Investigating brain metabolism at high fields using localized 13C NMR spectroscopy without 1H decoupling.

    PubMed

    Deelchand, Dinesh Kumar; Uğurbil, Kâmil; Henry, Pierre-Gilles

    2006-02-01

    Most in vivo 13C NMR spectroscopy studies in the brain have been performed using 1H decoupling during acquisition. Decoupling imposes significant constraints on the experimental setup (particularly for human studies at high magnetic field) in order to stay within safety limits for power deposition. We show here that incorporation of the 13C label from 13C-labeled glucose into brain amino acids can be monitored accurately using localized 13C NMR spectroscopy without the application of 1H decoupling. Using LCModel quantification with prior knowledge of one-bond and multiple-bond J(CH) coupling constants, the uncertainty on metabolites concentrations was only 35% to 91% higher (depending on the carbon resonance of interest) in undecoupled spectra compared to decoupled spectra in the rat brain at 9.4 Tesla. Although less sensitive, 13C NMR without decoupling dramatically reduces experimental constraints on coil setup and pulse sequence design required to keep power deposition within safety guidelines. This opens the prospect of safely measuring 13C NMR spectra in humans at varied brain locations (not only the occipital lobe) and at very high magnetic fields above 4 Tesla. PMID:16345037

  19. Characterisation of oxygen permeation into a microfluidic device for cell culture by in situ NMR spectroscopy.

    PubMed

    Yilmaz, Ali; Utz, Marcel

    2016-05-24

    A compact microfluidic device for perfusion culture of mammalian cells under in situ metabolomic observation by NMR spectroscopy is presented. The chip is made from poly(methyl methacrylate) (PMMA), and uses a poly(dimethyl siloxane) (PDMS) membrane to allow gas exchange. It is integrated with a generic micro-NMR detector developed recently by our group [J. Magn. Reson., 2016, 262, 73-80]. While PMMA is an excellent material in the context of NMR, PDMS is known to produce strong background signals. To mitigate this, the device keeps the PDMS away from the detection area. The oxygen permeation into the device is quantified using a flow chemistry approach. A solution of glucose is mixed on the chip with a solution of glucose oxidase, before flowing through the gas exchanger. The resulting concentration of gluconate is measured by (1)H NMR spectroscopy as a function of flow rate. An oxygen equilibration rate constant of 2.4 s(-1) is found for the device, which is easily sufficient to maintain normoxic conditions in a cell culture at low perfusion flow rates. PMID:27149932

  20. Differentiating and characterizing geminal silanols in silicas by (29)Si NMR spectroscopy.

    PubMed

    Murray, David K

    2010-12-01

    Single and geminal hydroxyl species in silicas have been characterized using solid-state (29)Si NMR spectroscopy. Differentiating hydroxyl types is important in understanding their roles in chemical toxicity mechanisms for inhaled crystalline silicas responsible for silicosis. (1)H-(29)Si cross polarization NMR spectroscopy has been employed to obtain (29)Si NMR chemical shift data and signal accrual and relaxation characteristics. Spectral deconvolution is used to examine relative single and geminal hydroxyl resonance areas for a series of representative silicas and silica gels. Silicon-containing materials examined include 1878a quartz, and 1879a cristobalite from the National Institute for Science and Technology, kaolin, and several widely used respirable silicas and silica gels. Geminal hydroxyls were observed in every case, with relative resonance areas accounting for 21-65% of total hydroxyl signals. Factors affecting relative areas measured as a function of contact time, relaxation, and surface area are discussed. Subsequent (29)Si and (31)P NMR studies of a silica coated with various sodium hydrogen phosphates show preferential single silanol-phosphate interaction for basic phosphates, and oligomerization products for acidic phosphates. Geminal hydroxyl resonance areas displayed significant error (4-17%) for low surface area silicas, limiting this method to studies exhibiting major changes in chemical or spectroscopic properties. PMID:20825948

  1. Uncovering Intramolecular π-Type Hydrogen Bonds in Solution by NMR Spectroscopy and DFT Calculations.

    PubMed

    Mastrorilli, Piero; Gallo, Vito; Todisco, Stefano; Latronico, Mario; Saielli, Giacomo

    2016-06-01

    Reaction between the phosphinito bridged diplatinum species [(PHCy2 )Pt(μ-PCy2 ){κ(2) P,O-μ-P(O)Cy2 }Pt(PHCy2 )](Pt-Pt) (1), and (trimethylsilyl)acetylene at 273 K affords the σ-acetylide complex [(PHCy2 )(η(1) -Me3 SiC≡C)Pt(μ-PCy2 )Pt(PHCy2 ){κP-P(OH)Cy2 }](Pt-Pt) (2) featuring an intramolecular π-type hydrogen bond. Scalar and dipolar couplings involving the POH proton were detected by 2D NMR experiments. Relativistic DFT calculations of the geometry, relative energy, and NMR properties of model systems of 2 confirmed the structural assignment and allowed the energy of the π-type hydrogen bond to be estimated (ca. 22 kJ mol(-1) ). PMID:27097847

  2. Solution State Structure Determination of Silicate Oligomers by 29Si NMR Spectroscopy and Molecular Modeling

    SciTech Connect

    Cho, Herman M.; Felmy, Andrew R.; Craciun, Raluca; Keenum, Johnathan P.; Shah, Neil K.; Dixon, David A.

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by 29Si NMR homonuclear correlation experiments of 29Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the 29Si–29Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated crosspeaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stability of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  3. Solution state structure determination of silicate oligomers by 29SI NMR spectroscopy and molecular modeling.

    PubMed

    Cho, Herman; Felmy, Andrew R; Craciun, Raluca; Keenum, J Patrick; Shah, Neil; Dixon, David A

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by (29)Si NMR homonuclear correlation experiments of (29)Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the (29)Si-(29)Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated cross-peaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stabilities of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations. PMID:16478188

  4. Structural characterization of selenosubtilisin by sup 77 Se-NMR spectroscopy

    SciTech Connect

    House, K.L.; Dunlap, R.B.; Odom, J.D.; Wu, Z.P.; Hilvert. D. Research Inst. of Scripps Clinic, La Jolla, CA )

    1991-03-15

    Selenosubtilisin is an artificial enzyme containing an active site selenocysteine residue. In this environment the selenium atom is a valuable probe of structure-function relationships and also confers novel redox and hydrolytic properties to the original protease template. The authors have used {sup 77}Se NMR spectroscopy to characterize different oxidation states of {sup 77}Se isotopically enriched selenosubtilisin. The oxidized form of the enzyme exhibits a {sup 77}Se resonance at 1,189 ppm. This is in good agreement with the {sup 77}Se chemical shifts for model seleninic acids, confirming that the prosthetic group is in the seleninic acid oxidation state. On treatment of the oxidized enzyme with three equivalents of 3-carboxy-4-nitrobenzenethiol at pH 5.0, they observe the enzyme bound selenenyl sulfide at 388.5 ppm. This work demonstrates the utility of {sup 77}Se NMR spectroscopy for examining structure-function relationships of selenium containing proteins.

  5. Monitoring the Electrochemical Processes in the Lithium-Air Battery by Solid State NMR Spectroscopy.

    PubMed

    Leskes, Michal; Moore, Amy J; Goward, Gillian R; Grey, Clare P

    2013-12-27

    A multi-nuclear solid-state NMR approach is employed to investigate the lithium-air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by (17)O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. (13)C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium-oxygen battery. PMID:24489976

  6. Monitoring the Electrochemical Processes in the Lithium–Air Battery by Solid State NMR Spectroscopy

    PubMed Central

    2013-01-01

    A multi-nuclear solid-state NMR approach is employed to investigate the lithium–air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium–oxygen battery. PMID:24489976

  7. 31P NMR 2D Mapping of Creatine Kinase Forward Flux Rate in Hearts with Postinfarction Left Ventricular Remodeling in Response to Cell Therapy.

    PubMed

    Gao, Ling; Cui, Weina; Zhang, Pengyuan; Jang, Albert; Zhu, Wuqiang; Zhang, Jianyi

    2016-01-01

    Utilizing a fast 31P magnetic resonance spectroscopy (MRS) 2-dimensional chemical shift imaging (2D-CSI) method, this study examined the heterogeneity of creatine kinase (CK) forward flux rate of hearts with postinfarction left ventricular (LV) remodeling. Immunosuppressed Yorkshire pigs were assigned to 4 groups: 1) A sham-operated normal group (SHAM, n = 6); 2) A 60 minutes distal left anterior descending coronary artery ligation and reperfusion (MI, n = 6); 3) Open patch group; ligation injury plus open fibrin patch over the site of injury (Patch, n = 6); and 4) Cell group, hiPSCs-cardiomyocytes, -endothelial cells, and -smooth muscle cells (2 million, each) were injected into the injured myocardium pass through a fibrin patch (Cell+Patch, n = 5). At 4 weeks, the creatine phosphate (PCr)/ATP ratio, CK forward flux rate (Flux PCr→ATP), and k constant of CK forward flux rate (kPCr→ATP) were severely decreased at border zone myocardium (BZ) adjacent to MI. Cell treatment results in significantly increase of PCr/ATP ratio and improve the value of kPCr→ATP and Flux PCr→ATP in BZ myocardium. Moreover, the BZ myocardial CK total activity and protein expression of CK mitochondria isozyme and CK myocardial isozyme were significantly reduced, but recovered in response to cell treatment. Thus, cell therapy results in improvement of BZ bioenergetic abnormality in hearts with postinfarction LV remodeling, which is accompanied by significantly improvements in BZ CK activity and CK isozyme expression. The fast 2D 31P MR CSI mapping can reliably measure the heterogeneity of bioenergetics in hearts with post infarction LV remodeling. PMID:27606901

  8. Solid-state proton multiple-quantum NMR spectroscopy with fast magic angle spinning

    NASA Astrophysics Data System (ADS)

    Geen, Helen; Titman, Jeremy J.; Gottwald, Johannes; Spiess, Hans W.

    1994-09-01

    The feasibility of multiple-quantum NMR spectroscopy with high resolution for protons in solids is explored. A new multiple-quantum excitation sequence suitable for use with fast magic angle spinning is described, and its performance is compared to that of both static and slow-spinning multiple-quantum methods. Modified sequences with scale the rate of development of the multiple-quantum coherences are also demonstrated, and two-dimensional double-quantum spectra of adamantane and polycarbonate are presented.

  9. Gyrotron FU CW VII for 300 MHz and 600 MHz DNP-NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Idehara, Toshitaka; Kosuga, Kosuke; Agusu, La; Ogawa, Isamu; Takahashi, Hiroki; Smith, Mark E.; Dupree, Ray

    2010-07-01

    Gyrotron FU CW VII, one of the FU CW Series Gyrotrons, has been designed, constructed and completed operational tests successfully in the Research Center for Development of Far Infrared Region, University of Fukui (FIR FU). The gyrotron operates at around 200 GHz for the fundamental cyclotron resonances and at around 400 GHz for the second harmonics. These radiation frequencies will be applied to 300 MHz and 600 MHz DNP enhanced NMR spectroscopy.

  10. 1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems

    NASA Astrophysics Data System (ADS)

    Berns, Anne E.; Conte, Pellegrino

    2010-05-01

    Cross polarization (CP) magic angle spinning (MAS) 13C-NMR spectroscopy is a solid state NMR technique widely used to study chemical composition of organic materials with low or no solubility in the common deuterated solvents used to run liquid state NMR experiments. Based on the magnetization transfer from abundant nuclei (with spin of 1 -2) having a high gyromagnetic ratio (γ), such as protons, to the less abundant 13C nuclei with low γ values, 13C-CPMAS NMR spectroscopy is often applied in environmental chemistry to obtain quantitative information on the chemical composition of natural organic matter (NOM) (Conte et al., 2004), although its quantitative assessment is still matter of heavy debates. Many authors (Baldock et al., 1997; Conte et al., 1997, 2002; Dria et al., 2002; Kiem et al., 2000; Kögel-Knabner, 2000; Preston, 2001), reported that the application of appropriate instrument setup as well as the use of special pulse sequences and correct spectra elaboration may provide signal intensities that are directly proportional to the amount of nuclei creating a NMR signal. However, many other papers dealt with the quantitative unsuitability of 13C-CPMAS NMR spectroscopy. Among those, Mao et al. (2000), Smernik and Oades (2000 a,b), and Preston (2001) reported that cross-polarized NMR techniques may fail in a complete excitation of the 13C nuclei. In fact, the amount of observable carbons via 13C-CPMAS NMR spectroscopy appeared, in many cases, lower than that measured by a direct observation of the 13C nuclei. As a consequence, cross-polarized NMR techniques may provide spectra where signal distribution may not be representative of the quantitative distribution of the different natural organic matter components. Cross-polarization is obtained after application of an initial 90° x pulse on protons and a further spin lock pulse (along the y axis) having a fixed length (contact time) for both nuclei (1H and 13C) once the Hartmann-Hahn condition is matched

  11. Single-shot diffusion trace (1)H NMR spectroscopy.

    PubMed

    de Graaf, R A; Braun, K P; Nicolay, K

    2001-05-01

    Ignoring diffusion anisotropy can severely hamper the quantitative determination of water and metabolite diffusion in complex tissues. The measurement of the trace of the diffusion tensor provides unambiguous and rotationally invariant ADC values, but usually requires three separate experiments. A single-shot technique developed earlier, originally designed for diffusion trace MR imaging (Mori and van Zijl, Magn Reson Med 1995;33:41-52), was improved and adapted for diffusion trace MR spectroscopy. A double spin-echo pulse sequence was incorporated with four pairs of bipolar gradients with specific predetermined relative signs in each of the three orthogonal directions. The combination of gradient directions leads to cancellation of all off-diagonal tensor elements while constructively adding the diagonal elements. Furthermore, the pulse scheme provides complete compensation for cross-terms between static magnetic field gradients and the applied diffusion gradients, while simultaneously avoiding cross-terms with localization gradients. The sequence was tested at 4.7 T in vivo on rat brain for MRI and on rat skeletal muscle and brain for MRS. It is shown that the average ADC as determined from the measurement of the ADCs in the three orthogonal directions is in close agreement with the ADC obtained along the trace of the diffusion tensor in a single acquisition, for both water and metabolite diffusion. The large differences in water and metabolite diffusion coefficients as measured in the individual orthogonal directions illustrate the need for diffusion trace measurements when accurate and rotationally invariant diffusion quantitation is required. The pulse scheme presented here may be applied for such purposes in MRS and MRI studies. PMID:11323799

  12. Methodology of 1H NMR Spectroscopy of the Human Brain at Very High Magnetic Fields

    PubMed Central

    Tkáč, I.; Gruetter, R.

    2009-01-01

    An ultrashort-echo-time stimulated echo-acquisition mode (STEAM) pulse sequence with interleaved outer volume suppression and VAPOR (variable power and optimized relaxation delays) water suppression was redesigned and optimized for human applications at 4 and 7 T, taking into account the specific requirements for spectroscopy at high magnetic fields and limitations of currently available hardware. In combination with automatic shimming, automated parameter adjustments and data processing, this method provided a user-friendly tool for routine 1H nuclear magnetic resonance (NMR) spectroscopy of the human brain at very high magnetic fields. Effects of first- and second-order shimming, single-scan averaging, frequency and phase corrections, and eddy currents were described. LCModel analysis of an in vivo 1H NMR spectrum measured from the human brain at 7 T allowed reliable quantification of more than fifteen metabolites noninvasively, illustrating the potential of high-field NMR spectroscopy. Examples of spectroscopic studies performed at 4 and 7 T demonstrated the high reproducibility of acquired spectra quality. PMID:20179773

  13. INVESTIGATION INTO HOW WOOD CELL WALLS INTERACT WITH SYNTHETIC ADHESIVES USING HIGH-RESOLUTION SOLUTION-STATE NMR SPECTROSCOPY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    With the continued growth of the wood adhesive industry and the need to create durable and environmentally friendly adhesive systems, it is still unclear whether covalent bonds contribute to wood adhesive bond strength. In order to investigate this question, solid-state NMR spectroscopy (NMR) has be...

  14. Magic Angle Spinning NMR Spectroscopy: A Versatile Technique for Structural and Dynamic Analysis of Solid-Phase Systems

    PubMed Central

    Polenova, Tatyana; Gupta, Rupal; Goldbourt, Amir

    2016-01-01

    Magic Angle Spinning (MAS) NMR spectroscopy is a powerful method for analysis of a broad range of systems, including inorganic materials, pharmaceuticals, and biomacromolecules. The recent developments in MAS NMR instrumentation and methodologies opened new vistas to atomic-level characterization of a plethora of chemical environments previously inaccessible to analysis, with unprecedented sensitivity and resolution. PMID:25794311

  15. Mixed micelles of Triton X-100, sodium dodecyl dioxyethylene sulfate, and synperonic l61 investigated by NOESY and diffusion ordered NMR spectroscopy.

    PubMed

    Denkova, Pavletta S; Van Lokeren, Luk; Willem, Rudolph

    2009-05-14

    Mixed micelles formed from nonionic surfactant Triton X-100 (TX100), anionic surfactant sodium dodecyl dioxyethylene sulfate (SDP2S), and triblock copolymer Synperonic L61 (SL61) were investigated by 1H NMR spectroscopy. The size and shape of the aggregates were determined by diffusion ordered NMR spectroscopy (DOSY), while 2D nuclear Overhauser enhanced spectroscopy (NOESY) NMR was used to study the mutual spatial arrangement of the surfactant molecules in the aggregated state. An average micellar hydrodynamic radius of 3.6 nm, slightly increasing upon increasing TX100 molar fraction, was found for the mixed systems without additives. Addition of SL61 to the mixed micellar systems results in a slight increase of micellar radii. In the presence of AlCl3, an increase of TX100/SDP2S micellar sizes from 4 to 10 nm was found when increasing the SDP2S molar fraction. The mixed TX100/SDP2S micelles in the presence of both AlCl3 and polymer SL61 are almost spherical, with a radius of 4.5 nm. 2D NOESY data reveal that, as the individual TX100 micelles, mixed TX100/SDP2S and TX100/SDP2S/SL61/AlCl3 micelles also have a multilayer structure, with partially overlapping internal and external layers of TX100 molecules. In these mixed micelles, the SDP2S molecules are located at the level of the external layer of TX100 molecules, whereas the SL61 polymer is partially incorporated inside of the micellar core. PMID:19385612

  16. Two-dimensional sum-frequency generation (2D SFG) spectroscopy: Summary of principles and its application to amyloid fiber monolayers

    PubMed Central

    Ghosh, Ayanjeet; Ho, Jia-Jung; Serrano, Arnaldo L.; Skoff, David R.; Zhang, Tianqi; Zanni, Martin T.

    2015-01-01

    By adding a mid-infrared pulse shaper to a sum-frequency generation (SFG) spectrometer, we have built a 2D SFG spectrometer capable of measuring spectra analogous to 2D IR spectra but with monolayer sensitivity and SFG selection rules. In this paper, we describe the experimental apparatus and provide an introduction to 2D SFG spectroscopy to help the reader interpret 2D SFG spectra. The main aim of this manuscript is to report 2D SFG spectra of the amyloid forming peptide FGAIL. FGAIL is a critical segment of the human islet amyloid polypeptide (hIAPP or amylin) that aggregates in people with type 2 diabetes. FGAIL is catalyzed into amyloid fibers by many types of surfaces. Here, we study the structure of FGAIL upon deposition onto a gold surface covered with a self-assembled monolayer of methyl 4-mercaptobenzoate (MMB) that produces an ester coating. FGAIL deposited on bare gold does not form ordered layers. The measured 2D SFG spectrum is consistent with amyloid fiber formation, exhibiting both the parallel (a+) and perpendicular (a−) symmetry modes associated with amyloid β-sheets. Cross peaks are observed between the ester stretches of the coating and the FGAIL peptides. Simulations are presented for two possible structures of FGAIL amyloid β-sheets that illustrates the sensitivity of the 2D SFG spectra to structure and orientation. These results provide some of the first molecular insights into surface catalyzed amyloid fiber structure. PMID:25611039

  17. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory

    ERIC Educational Resources Information Center

    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…

  18. Identifying metabolites related to nitrogen mineralisation using 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    . T McDonald, Noeleen; Graham, Stewart; Watson, Catherine; Gordon, Alan; Lalor, Stan; Laughlin, Ronnie; Elliott, Chris; . P Wall, David

    2015-04-01

    Exploring new analysis techniques to enhance our knowledge of the various metabolites within our soil systems is imperative. Principally, this knowledge would allow us to link key metabolites with functional influences on critical nutrient processes, such as the nitrogen (N) mineralisation in soils. Currently there are few studies that utilize proton nuclear magnetic resonance spectroscopy (1H NMR) to characterize multiple metabolites within a soil sample. The aim of this research study was to examine the effectiveness of 1H NMR for isolating multiple metabolites that are related to the mineralizable N (MN) capacity across a range of 35 Irish grassland soils. Soils were measured for MN using the standard seven day anaerobic incubation (AI-7). Additionally, soils were also analysed for a range of physio-chemical properties [e.g. total N, total C, mineral N, texture and soil organic matter (SOM)]. Proton NMR analysis was carried on these soils by extracting with 40% methanol:water, lyophilizing and reconstituting in deuterium oxide and recording the NMR spectra on a 400MHz Bruker AVANCE III spectrometer. Once the NMR data were spectrally processed and analysed using multivariate statistical analysis, seven metabolites were identified as having significant relationships with MN (glucose, trimethylamine, glutamic acid, serine, aspartic acid, 4-aminohippuirc acid and citric acid). Following quantification, glucose was shown to explain the largest percentage variability in MN (72%). These outcomes suggest that sources of labile carbon are essential in regulating N mineralisation and the capacity of plant available N derived from SOM-N pools in these soils. Although, smaller in concentration, the amino acids; 4-aminohippuirc acid, glutamic acid and serine also significantly (P<0.05) explained 43%, 27% and 19% of the variability in MN, respectively. This novel study highlights the effectiveness of using 1H NMR as a practical approach to profile multiple metabolites in

  19. Insights into the molecular basis of action of the AT1 antagonist losartan using a combined NMR spectroscopy and computational approach.

    PubMed

    Zervou, Maria; Cournia, Zoe; Potamitis, Constantinos; Patargias, George; Durdagi, Serdar; Grdadolnik, Simona Golic; Mavromoustakos, Thomas

    2014-03-01

    The drug:membrane interactions for the antihypertensive AT1 antagonist losartan, the prototype of the sartans class, are studied herein using an integrated approach. The pharmacophore arrangement of the drug was revealed by rotating frame nuclear Overhauser effect spectroscopy (2D ROESY) NMR spectroscopy in three different environments, namely water, dimethyl sulfoxide (DMSO), and sodium dodecyl sulfate (SDS) micellar solutions mimicking conditions of biological transport fluids and membrane lipid bilayers. Drug association with micelles was monitored by diffusion ordered spectroscopy (2D DOSY) and drug:micelle intermolecular interactions were characterized by ROESY spectroscopy. The localisation of the drug in the micellar environment was investigated by introducing 5-doxyl and 16-doxyl stearic acids. The use of spin labels confirmed that losartan resides close to the micelle:water interface with the hydroxymethyl group and the tetrazole heterocyclic aromatic ring facing the polar surface with the potential to interact with SDS charged polar head groups in order to increase amphiphilic interactions. The spontaneous insertion, the diffusion pathway and the conformational features of losartan were monitored by Molecular Dynamics (MD) simulations in a modeled SDS micellar aggregate environment and a long exploratory MD run (580ns) in a phospholipid dipalmitoylphosphatidylcholine (DPPC) bilayer with the AT1 receptor embedded. MD simulations were in excellent agreement with experimental results and further revealed the molecular basis of losartan:membrane interactions in atomic-level detail. This applied integrated approach aims to explore the role of membranes in losartan's pathway towards the AT1 receptor. PMID:24374319

  20. Study on antibacterial alginate-stabilized copper nanoparticles by FT-IR and 2D-IR correlation spectroscopy

    PubMed Central

    Díaz-Visurraga, Judith; Daza, Carla; Pozo, Claudio; Becerra, Abraham; von Plessing, Carlos; García, Apolinaria

    2012-01-01

    Background The objective of this study was to clarify the intermolecular interaction between antibacterial copper nanoparticles (Cu NPs) and sodium alginate (NaAlg) by Fourier transform infrared spectroscopy (FT-IR) and to process the spectra applying two-dimensional infrared (2D-IR) correlation analysis. To our knowledge, the addition of NaAlg as a stabilizer of copper nanoparticles has not been previously reported. It is expected that the obtained results will provide valuable additional information on: (1) the influence of reducing agent ratio on the formation of copper nanoparticles in order to design functional nanomaterials with increased antibacterial activity, and (2) structural changes related to the incorporation of Cu NPs into the polymer matrix. Methods Cu NPs were prepared by microwave heating using ascorbic acid as reducing agent and NaAlg as stabilizing agent. The characterization of synthesized Cu NPs by ultraviolet visible spectroscopy, transmission electron microscopy (TEM), electron diffraction analysis, X-ray diffraction (XRD), and semiquantitative analysis of the weight percentage composition indicated that the average particle sizes of Cu NPs are about 3–10 nm, they are spherical in shape, and consist of zerovalent Cu and Cu2O. Also, crystallite size and relative particle size of stabilized Cu NPs were calculated by XRD using Scherrer’s formula and FT from the X-ray diffraction data. Thermogravimetric analysis, differential thermal analysis, differential scanning calorimetry (DSC), FT-IR, second-derivative spectra, and 2D-IR correlation analysis were applied to studying the stabilization mechanism of Cu NPs by NaAlg molecules. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of stabilized Cu NPs against five bacterial strains (Staphylococccus aureus ATCC 6538P, Escherichia coli ATCC 25922 and O157: H7, and Salmonella enterica serovar Typhimurium ATCC 13311 and 14028) were evaluated with macrodilution

  1. Distinguishing Phosphate Structural Defects From Inclusions in Calcite and Aragonite by NMR Spectroscopy (Invited)

    NASA Astrophysics Data System (ADS)

    Phillips, B. L.; Mason, H. E.

    2010-12-01

    Variations in the concentration of minor and trace elements are being studied extensively for potential use as proxies to infer environmental conditions at the time of mineral deposition. Such proxies rely fundamentally on a relationship between the activities in the solution and in the solid that would seem to be simple only in the case that the species substitutes into the mineral structure. Other incorporation mechanisms are possible, including inclusions (both mineral and fluid) and occlusion of surface adsorbate complexes, that might be sensitive to other factors, such as crystallization kinetics, and difficult to distinguish analytically. For example, it is known from mineral adsorption studies that surface precipitates can be nanoscopic, and might not be apparent at resolutions typical of microchemical analysis. Techniques by which a structural relationship between the substituting element and the host mineral structure are needed to provide a sound basis for geochemical proxies. NMR spectroscopy offers methods for probing such spatial relationship. We are using solid-state NMR spectroscopy to investigate phosphate incorporation in calcium carbonate minerals, including calcite speleothems and coral skeletal aragonite, at concentrations of the order 100 μg P g -1. In 31P NMR spectra of most samples, narrow peaks arising from crystalline inclusions can be resolved, including apatite in coral aragonite and an unidentified phase in calcite. All samples studied yield also a broad 31P signal, centered near chemical shifts of +3 to +4 ppm, that could be assigned to phosphate defects in the host mineral and from which the fraction of P occurring in the carbonate mineral structure can be determined. To test this assignment we applied rotational-echo double-resonance (REDOR) NMR techniques that probe the molecular-scale proximity of carbonate groups to the phosphate responsible for the broad 31P peak. This method measures dipole-dipole coupling between 31P of

  2. NMR spectroscopy as a tool to close the gap on metabolite characterization under MIST.

    PubMed

    Caceres-Cortes, Janet; Reily, Michael D

    2010-07-01

    Withdrawals from the market due to unforeseen adverse events have triggered changes in the way therapeutics are discovered and developed. This has resulted in an emphasis on truly understanding the efficacy and toxicity profile of new chemical entities (NCE) and the contributions of their metabolites to on-target pharmacology and off-target receptor-mediated toxicology. Members of the pharmaceutical industry, scientific community and regulatory agencies have held dialogues with respect to metabolites in safety testing (MIST); and both the US FDA and International Conference on Harmonisation have issued guidances with respect to when and how to characterize metabolites for human safety testing. This review provides a brief overview of NMR spectroscopy as applied to the structure elucidation and quantification of drug metabolites within the drug discovery and development process. It covers advances in this technique, including cryogenic cooling of detection circuitry for enhanced sensitivity, hyphenated LC-NMR techniques, improved dynamic range through new solvent-suppression pulse sequences and quantitation. These applications add to the already diverse NMR toolkit and further anchor NMR as a technique that is directly applicable to meeting the requirements of MIST guidelines. PMID:21083239

  3. Survey and qualification of internal standards for quantification by 1H NMR spectroscopy.

    PubMed

    Rundlöf, Torgny; Mathiasson, Marie; Bekiroglu, Somer; Hakkarainen, Birgit; Bowden, Tim; Arvidsson, Torbjörn

    2010-09-01

    In quantitative NMR (qNMR) selection of an appropriate internal standard proves to be crucial. In this study, 25 candidate compounds considered to be potent internal standards were investigated with respect to the ability of providing unique signal chemical shifts, purity, solubility, and ease of use. The (1)H chemical shift (delta) values, assignments, multiplicities and number of protons (for each signal), appropriateness (as to be used as internal standards) in four different deuterated solvents (D(2)O, DMSO-d(6), CD(3)OD, CDCl(3)) were studied. Taking into account the properties of these 25 internal standards, the most versatile eight compounds (2,4,6-triiodophenol, 1,3,5-trichloro-2-nitrobenzene, 3,4,5-trichloropyridine, dimethyl terephthalate, 1,4-dinitrobenzene, 2,3,5-triiodobenzoic acid, maleic acid and fumaric acid) were qualified using both differential scanning calorimetry (DSC) and NMR spectroscopy employing highly pure acetanilide as the reference standard. The data from these two methods were compared as well as utilized in the quality assessment of the compounds as internal standards. Finally, the selected internal standards were tested and evaluated in a real case of quantitative NMR analysis of a paracetamol pharmaceutical product. PMID:20207092

  4. Natural abundance 17O DNP two-dimensional and surface-enhanced NMR spectroscopy

    DOE PAGESBeta

    Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek

    2015-06-22

    Due to its extremely low natural abundance and quadrupolar nature, the 17O nuclide is very rarely used for spectroscopic investigation of solids by NMR without isotope enrichment. Additionally, the applicability of dynamic nuclear polarization (DNP), which leads to sensitivity enhancements of 2 orders of magnitude, to 17O is wrought with challenges due to the lack of spin diffusion and low polarization transfer efficiency from 1H. Here, we demonstrate new DNP-based measurements that extend 17O solid-state NMR beyond its current capabilities. The use of the PRESTO technique instead of conventional 1H–17O cross-polarization greatly improves the sensitivity and enables the facile measurementmore » of undistorted line shapes and two-dimensional 1H–17O HETCOR NMR spectra as well as accurate internuclear distance measurements at natural abundance. This was applied for distinguishing hydrogen-bonded and lone 17O sites on the surface of silica gel; the one-dimensional spectrum of which could not be used to extract such detail. As a result, this greatly enhanced sensitivity has enabled, for the first time, the detection of surface hydroxyl sites on mesoporous silica at natural abundance, thereby extending the concept of DNP surface-enhanced NMR spectroscopy to the 17O nuclide.« less

  5. Structure-Correlation NMR Spectroscopy for Macromolecules Using Repeated Bidirectional Photoisomerization of Azobenzene.

    PubMed

    Nagashima, Toshio; Ueda, Keisuke; Nishimura, Chiaki; Yamazaki, Toshio

    2015-11-17

    Control over macromolecular structure offers bright potentials for manipulation of macromolecular functions. We here present structure-correlation NMR spectroscopy to analyze the correlation between polymorphic macromolecular structures driven by photoisomerization of azobenzene. The structural conversion of azobenzene was induced within the mixing time of a NOESY experiment using a colored light source, and the reverse structural conversion was induced during the relaxation delay using a light source of another color. The correlation spectrum between trans- and cis-azobenzene was then obtained. To maximize the efficiency of the bidirectional photoisomerization of azobenzene-containing macromolecules, we developed a novel light-irradiation NMR sample tube and method for irradiating target molecules in an NMR radio frequency (rf) coil. When this sample tube was used for photoisomerization of an azobenzene derivative at a concentration of 0.2 mM, data collection with reasonable sensitivity applicable to macromolecules was achieved. We performed isomerization of an azobenzene-cross-linked peptide within the mixing time of a NOESY experiment that produced cross-peaks between helix and random-coil forms of the peptide. Thus, these results indicate that macromolecular structure manipulation can be incorporated into an NMR pulse sequence using an azobenzene derivative and irradiation with light of two types of wavelengths, providing a new method for structural analysis of metastable states of macromolecules. PMID:26479462

  6. Use of diffusion-ordered NMR spectroscopy and HPLC-UV-SPE-NMR to identify undeclared synthetic drugs in medicines illegally sold as phytotherapies.

    PubMed

    Silva, Lorena M A; Filho, Elenilson G A; Thomasi, Sérgio S; Silva, Bianca F; Ferreira, Antonio G; Venâncio, Tiago

    2013-09-01

    The informal (and/or illegal) e-commerce of pharmaceutical formulations causes problems that governmental health agencies find hard to control, one of which concerns formulas sold as natural products. The purpose of this work was to explore the advantages and limitations of DOSY and HPLC-UV-SPE-NMR. These techniques were used to identify the components of a formula illegally marketed in Brazil as an herbal medicine possessing anti-inflammatory and analgesic properties. DOSY was able to detect the major components present at higher concentrations. Complete characterization was achieved using HPLC-UV-SPE-NMR, and 1D and 2D NMR analyses enabled the identification of known synthetic drugs. These were ranitidine and a mixture of orphenadrine citrate, piroxicam, and dexamethasone, which are co-formulated in a remedy called Rheumazim that is used to relieve severe pain, but it is prohibited in Brazil because of a lack of sufficient pharmacokinetic and pharmacodynamic information. PMID:23818305

  7. pKa determination by ¹H NMR spectroscopy - an old methodology revisited.

    PubMed

    Bezençon, Jacqueline; Wittwer, Matthias B; Cutting, Brian; Smieško, Martin; Wagner, Bjoern; Kansy, Manfred; Ernst, Beat

    2014-05-01

    pKa values of acids and protonated bases have an essential impact on organic synthesis, medicinal chemistry, and material and food sciences. In drug discovery and development, they are of utmost importance for the prediction of pharmacokinetic and pharmacodynamic properties. To date, various methods for the determination of pKa values are available, including UV-spectroscopic, potentiometric, and capillary electrophoretic techniques. An additional option is provided by nuclear magnetic resonance (NMR) spectroscopy. The underlying principle is the alteration of chemical shifts of NMR-active nuclei (e.g., (13)C and (1)H) depending on the protonation state of adjacent acidic or basic sites. When these chemical shifts are plotted against the pH, the inflection point of the resulting sigmoidal curve defines the pKa value. Although pKa determinations by (1)H NMR spectroscopy are reported for numerous cases, the potential of this approach is not yet fully evaluated. We therefore revisited this method with a diverse set of test compounds covering a broad range of pKa values (pKa 0.9-13.8) and made a comparison with four commonly used approaches. The methodology revealed excellent correlations (R(2)=0.99 and 0.97) with electropotentiometric and UV spectroscopic methods. Moreover, the comparison with in silico results (Epik and Marvin) also showed high correlations (R(2)=0.92 and 0.94), further confirming the reliability and utility of this approach. PMID:24462329

  8. Qualitative and Quantitative Control of Carbonated Cola Beverages Using 1H NMR Spectroscopy

    PubMed Central

    2012-01-01

    1H Nuclear magnetic resonance (NMR) spectroscopy (400 MHz) was used in the context of food surveillance to develop a reliable analytical tool to differentiate brands of cola beverages and to quantify selected constituents of the soft drinks. The preparation of the samples required only degassing and addition of 0.1% of TSP in D2O for locking and referencing followed by adjustment of pH to 4.5. The NMR spectra obtained can be considered as “fingerprints” and were analyzed by principal component analysis (PCA). Clusters from colas of the same brand were observed, and significant differences between premium and discount brands were found. The quantification of caffeine, acesulfame-K, aspartame, cyclamate, benzoate, hydroxymethylfurfural (HMF), sulfite ammonia caramel (E 150D), and vanillin was simultaneously possible using external calibration curves and applying TSP as internal standard. Limits of detection for caffeine, aspartame, acesulfame-K, and benzoate were 1.7, 3.5, 0.8, and 1.0 mg/L, respectively. Hence, NMR spectroscopy combined with chemometrics is an efficient tool for simultaneous identification of soft drinks and quantification of selected constituents. PMID:22356160

  9. 51V solid-state magic angle spinning NMR spectroscopy of vanadium chloroperoxidase.

    PubMed

    Pooransingh-Margolis, Neela; Renirie, Rokus; Hasan, Zulfiqar; Wever, Ron; Vega, Alexander J; Polenova, Tatyana

    2006-04-19

    We report 51V solid-state NMR spectroscopy of the 67.5-kDa vanadium chloroperoxidase, at 14.1 T. We demonstrate that, despite the low concentration of vanadium sites in the protein (one per molecule, 1 mumol of vanadium spins in the entire sample), the spinning sideband manifold spanning the central and the satellite transitions is readily detectable. The quadrupolar and chemical shift anisotropy tensors have been determined by numerical simulations of the spinning sideband envelopes and the line shapes of the individual spinning sidebands corresponding to the central transition. The observed quadrupolar coupling constant C(Q) of 10.5 +/- 1.5 MHz and chemical shift anisotropy delta(sigma) of -520 +/- 13 ppm are sensitive reporters of the geometric and electronic structure of the vanadium center. Density functional theory calculations of the NMR spectroscopic observables for an extensive series of active site models indicate that the vanadate cofactor is most likely anionic with one axial hydroxo- group and an equatorial plane consisting of one hydroxo- and two oxo- groups. The work reported in this manuscript is the first example of 51V solid-state NMR spectroscopy applied to probe the vanadium center in a protein directly. This approach yields the detailed coordination environment of the metal unavailable from other experimental measurements and is expected to be generally applicable for studies of diamagnetic vanadium sites in metalloproteins. PMID:16608356

  10. NMR Spectroscopy of Human Eye Tissues: A New Insight into Ocular Biochemistry

    PubMed Central

    Kryczka, Tomasz; Wylęgała, Edward; Dobrowolski, Dariusz; Midelfart, Anna

    2014-01-01

    Background. The human eye is a complex organ whose anatomy and functions has been described very well to date. Unfortunately, the knowledge of the biochemistry and metabolic properties of eye tissues varies. Our objective was to reveal the biochemical differences between main tissue components of human eyes. Methods. Corneas, irises, ciliary bodies, lenses, and retinas were obtained from cadaver globes 0-1/2 hours postmortem of 6 male donors (age: 44–61 years). The metabolic profile of tissues was investigated with HR MAS 1H NMR spectroscopy. Results. A total of 29 metabolites were assigned in the NMR spectra of the eye tissues. Significant differences between tissues were revealed in contents of the most distant eye-tissues, while irises and ciliary bodies showed minimal biochemical differences. ATP, acetate, choline, glutamate, lactate, myoinositol, and taurine were identified as the primary biochemical compounds responsible for differentiation of the eye tissues. Conclusions. In this study we showed for the first time the results of the analysis of the main human eye tissues with NMR spectroscopy. The biochemical contents of the selected tissues seemed to correspond to their primary anatomical and functional attributes, the way of the delivery of the nutrients, and the location of the tissues in the eye. PMID:25525621

  11. Qualitative and quantitative control of carbonated cola beverages using ¹H NMR spectroscopy.

    PubMed

    Maes, Pauline; Monakhova, Yulia B; Kuballa, Thomas; Reusch, Helmut; Lachenmeier, Dirk W

    2012-03-21

    ¹H Nuclear magnetic resonance (NMR) spectroscopy (400 MHz) was used in the context of food surveillance to develop a reliable analytical tool to differentiate brands of cola beverages and to quantify selected constituents of the soft drinks. The preparation of the samples required only degassing and addition of 0.1% of TSP in D₂O for locking and referencing followed by adjustment of pH to 4.5. The NMR spectra obtained can be considered as "fingerprints" and were analyzed by principal component analysis (PCA). Clusters from colas of the same brand were observed, and significant differences between premium and discount brands were found. The quantification of caffeine, acesulfame-K, aspartame, cyclamate, benzoate, hydroxymethylfurfural (HMF), sulfite ammonia caramel (E 150D), and vanillin was simultaneously possible using external calibration curves and applying TSP as internal standard. Limits of detection for caffeine, aspartame, acesulfame-K, and benzoate were 1.7, 3.5, 0.8, and 1.0 mg/L, respectively. Hence, NMR spectroscopy combined with chemometrics is an efficient tool for simultaneous identification of soft drinks and quantification of selected constituents. PMID:22356160

  12. Mapping Inhibitor Binding Modes on an Active Cysteine Protease via NMR Spectroscopy

    PubMed Central

    Lee, Gregory M.; Balouch, Eaman; Goetz, David H.; Lazic, Ana; McKerrow, James H.; Craik, Charles S.

    2013-01-01

    Cruzain is a member of the papain/cathepsin-L family of cysteine proteases, and the major cysteine protease of the protozoan Trypanosoma cruzi, the causative agent of Chagas’ disease. We report an auto-induction methodology that provides soluble-cruzain at high yields (> 30 mg per liter in minimal media). These increased yields provide sufficient quantities of active enzyme for use in NMR-based ligand mapping. Using CD and NMR spectroscopy, we also examined the solution-state structural dynamics of the enzyme in complex with a covalently bound vinyl sulfone inhibitor (K777). We report the backbone amide and side chain carbon chemical shift assignments of cruzain in complex with K777. These resonance assignments were used to identify and map residues located in the substrate binding pocket, including the catalytic Cys25 and His162. Selective 15N-Cys, 15N-His, and 13C-Met labeling was performed to quickly assess cruzain-ligand interactions for a set of eight low molecular weight compounds exhibiting micromolar binding or inhibition. Chemical shift perturbation mapping verifies that six of the eight compounds bind to cruzain at the active site. Three different binding modes were delineated for the compounds, namely covalent, non-covalent, and non-interacting. These results provide examples of how NMR spectroscopy can be used to screen compounds for fast evaluation of enzyme-inhibitor interactions in order to facilitate lead compound identification and subsequent structural studies. PMID:23181936

  13. Determination of the biogenic secondary organic aerosol fraction in the boreal forest by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Finessi, E.; Decesari, S.; Paglione, M.; Giulianelli, L.; Carbone, C.; Gilardoni, S.; Fuzzi, S.; Saarikoski, S.; Raatikainen, T.; Hillamo, R.; Allan, J.; Mentel, Th. F.; Tiitta, P.; Laaksonen, A.; Petäjä, T.; Kulmala, M.; Worsnop, D. R.; Facchini, M. C.

    2012-01-01

    The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM1) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from laboratory experiments of terpenes photo-oxidation. The second NMR

  14. Determination of neo- and D-chiro-inositol hexakisphosphate in soils by solution 31P NMR spectroscopy.

    PubMed

    Turner, Benjamin L; Cheesman, Alexander W; Godage, H Yasmin; Riley, Andrew M; Potter, Barry V L

    2012-05-01

    The inositol phosphates are an abundant but poorly understood group of organic phosphorus compounds found widely in the environment. Four stereoisomers of inositol hexakisphosphate (IP(6)) occur, although for three of these (scyllo, neo, and D-chiro) the origins, dynamics, and biological function remain unknown, due in large part to analytical limitations in their measurement in environmental samples. We synthesized authentic neo- and D-chiro-IP(6) and used them to identify signals from these compounds in three soils from the Falkland Islands. Both compounds resisted hypobromite oxidation and gave quantifiable (31)P NMR signals at δ = 6.67 ppm (equatorial phosphate groups of the 4-equatorial/2-axial conformer of neo-IP(6)) and δ = 6.48 ppm (equatorial phosphate groups of the 2-equatorial/4-axial conformer of D-chiro-IP(6)) in soil extracts. Inositol hexakisphosphate accounted for 46-54% of the soil organic phosphorus, of which the four stereoisomers constituted, on average, 55.9% (myo), 32.8% (scyllo), 6.1% (neo), and 5.2% (D-chiro). Reappraisal of the literature based on the new signal assignments revealed that neo- and D-chiro-IP(6) occur widely in both terrestrial and aquatic ecosystems. These results confirm that the inositol phosphates can constitute a considerable fraction of the organic phosphorus in soils and reveal the prevalence of neo- and D-chiro-IP(6) in the environment. The hypobromite oxidation and solution (31)P NMR spectroscopy procedure allows the simultaneous quantification of all four IP(6) stereoisomers in environmental samples and provides a platform for research into the origins and ecological significance of these enigmatic compounds. PMID:22489788

  15. NMR spectroscopy of hyperpolarized ^129Xe at high fields: Maintaining spin polarization after optical pumping.

    NASA Astrophysics Data System (ADS)

    Patton, Brian; Kuzma, Nicholas N.; Lisitza, Natalia V.; Happer, William

    2003-05-01

    Spin-polarized ^129Xe has become an invaluable tool in nuclear magnetic resonance research, with applications ranging from medical imaging to high-resolution spectroscopy. High-field NMR studies using hyperpolarized xenon as a spectroscopic probe benefit from the high signal-to-noise ratios and large chemical shifts typical of optically-pumped noble gases. The experimental sensitivity is ultimately determined by the absolute polarization of the xenon in the sample, which can be substantially decreased during purification and transfer. NMR of xenon at high fields (9.4 Tesla) will be discussed, and potential mechanisms of spin relaxation during the distillation, storage(N. N. Kuzma, B. Patton, K. Raman, and W. Happer, Phys. Rev. Lett. 88), 147602 (2002)., and delivery of hyperpolarized xenon will be analyzed.

  16. An instrument control and data analysis program for NMR imaging and spectroscopy

    SciTech Connect

    Roos, M.S.; Mushlin, R.A.; Veklerov, E.; Port, J.D.; Ladd, C.; Harrison, C.G.

    1988-01-01

    We describe a software environment created to support real-time instrument control and signal acquisition as well as array-processor based signal and image processing in up to five dimensions. The environment is configured for NMR imaging and in vivo spectroscopy. It is designed to provide flexible tools for implementing novel NMR experiments in the research laboratory. Data acquisition and processing operations are programmed in macros which are loaded in assembled from to minimize instruction overhead. Data arrays are dynamically allocated for efficient use of memory and can be mapped directly into disk files. The command set includes primitives for real-time control of data acquisition, scalar arithmetic, string manipulation, branching, a file system and vector operations carried out by an array processor. 6 figs.

  17. Uncovering the triggers for GPCR activation using solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kimata, Naoki; Reeves, Philip J.; Smith, Steven O.

    2015-04-01

    G protein-coupled receptors (GPCRs) span cell membranes with seven transmembrane helices and respond to a diverse array of extracellular signals. Crystal structures of GPCRs have provided key insights into the architecture of these receptors and the role of conserved residues. However, the question of how ligand binding induces the conformational changes that are essential for activation remains largely unanswered. Since the extracellular sequences and structures of GPCRs are not conserved between receptor subfamilies, it is likely that the initial molecular triggers for activation vary depending on the specific type of ligand and receptor. In this article, we describe NMR studies on the rhodopsin subfamily of GPCRs and propose a mechanism for how retinal isomerization switches the receptor to the active conformation. These results suggest a general approach for determining the triggers for activation in other GPCR subfamilies using NMR spectroscopy.

  18. Isotope-Filtered 4D NMR Spectroscopy for Structure Determination of Humic Substances**

    PubMed Central

    Bell, Nicholle G A; Michalchuk, Adam A L; Blackburn, John W T; Graham, Margaret C; Uhrín, Dušan

    2015-01-01

    Humic substances, the main component of soil organic matter, could form an integral part of green and sustainable solutions to the soil fertility problem. However, their global-scale application is hindered from both scientific and regulatory perspectives by the lack of understanding of the molecular make-up of these chromatographically inseparable mixtures containing thousands of molecules. Here we show how multidimensional NMR spectroscopy of isotopically tagged molecules enables structure characterization of humic compounds. We illustrate this approach by identifying major substitution patterns of phenolic aromatic moieties of a peat soil fulvic acid, an operational fraction of humic substances. Our methodology represents a paradigm shift in the use of NMR active tags in structure determination of small molecules in complex mixtures. Unlike previous tagging methodologies that focused on the signals of the tags, we utilize tags to directly probe the identity of the molecules they are attached to. PMID:26036217

  19. (1)H NMR spectroscopy in the diagnosis of Pseudomonas aeruginosa-induced urinary tract infection.

    PubMed

    Gupta, Ashish; Dwivedi, Mayank; Nagana Gowda, G A; Ayyagari, Archana; Mahdi, A A; Bhandari, M; Khetrapal, C L

    2005-08-01

    The utility of (1)H NMR spectroscopy is suggested and demonstrated for the diagnosis of Pseudomonas aeruginosa in urinary tract infection (UTI). The specific property of P. aeruginosa of metabolizing nicotinic acid to 6-hydroxynicotinic acid (6-OHNA) is exploited. The quantity of 6-OHNA produced correlates well with the viable bacterial count. Other common bacteria causing UTI such as Escherichia coli, Klebsiella pneumonia, Enterobacter aerogenes, Acinetobacter baumanii, Proteus mirabilis, Citrobacter frundii, Enterococcus faecalis, Streptococcus gp B and Staphylococcus aureus do not metabolize nicotinic acid under similar conditions. The method provides a single-step documentation of P. aeruginosa qualitatively as well as quantitatively. The NMR method is demonstrated on urine samples from 30 patients with UTI caused by P. aeruginosa. PMID:15759292

  20. Determination of iodine value of lubricating oils by nuclear magnetic resonance (NMR) spectroscopy

    SciTech Connect

    Sarpal, A.S.; Kapur, G.S.; Mukherjee, S.

    1995-03-01

    A direct, quick and non-destructive method for estimating the iodine value of fats, fatty oils and their blends in mineral oils has been developed based on {sup 1}H and {sup 13}C-NMR spectroscopy. The method involves the determination of unsaturation content of the samples by {sup 1}H and {sup 13}C-NMR spectroscopic techniques. The iodine value of the sample is directly proportional to the unsaturated proton or carbon content. The value of the proportionality constant is independent of the nature of the fats and their blends in mineral oils for the limited samples studied. The iodine value determined by this method also includes the contribution from additives containing unsaturation. Saturated ingredients in the sample do not contribute to the iodine value as is the case with the standard IP-84 method. 5 refs., 3 figs., 4 tabs.

  1. N-15 NMR Spectroscopy as a Method for Comparing the Rates of Imidization of Several Diamines

    NASA Technical Reports Server (NTRS)

    Johnson, J. Christopher; Kuczmarski, Maria A.

    2006-01-01

    The relative rates of the conversion of amide-acid to imide was measured for a series or aromatic diamines that have been identified as potential replacements for 4,4'-methylene dianiline (MDA) in high-temperature polyimides and polymer composites. These rates were compared with the N-15 NMR resonances of the unreacted amines. The initial rates of imidization track with the difference in chemical shift between the amine nitrogens in MDA and those in the subject diamines. This comparison demonstrated that N-15 NMR spectroscopy is appropriate for the rapid screening of candidate diamines to determine their reactivity relative to MDA, and can serve to provide guidance to the process of creating the time-temperature profiles used in processing these materials into polymer matrix composites.

  2. Natural abundance high-resolution solid state 2 H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Aliev, Abil E.; Harris, Kenneth D. M.; Apperley, David C.

    1994-08-01

    We report for the first time an approach for natural abundance solid state 2 H NMR spectroscopy involving magic angle sample spinning (MAS), high-power 1 H decoupling (HPPD) and 1 H- 2 H cross polarization (CP). Taking tetrakis(trimethylsilyl)silane (TTMSS), adamantane, 1-chloroadamantane, hexamethylbenzene (HMB), 2,2-dimethyl-1,3-propanediol (DMPD) and 2-hydroxymethyl-2-methyl-1,3-propanediol (HMPD) as examples, it has been shown that the combination of HPPD and MAS can be applied readily to study rotator phase solids, allowing isotropic peaks arising from chemically inequivalent 2 H nuclei to be resolved. For natural abundance samples of TTMSS and chloroadamantane, it has been shown that 2 H CP/HPPD/MAS NMR experiments, involving polarization transfer from 1 H to 2 H, may provide considerable sensitivity enhancement in comparison with single pulse experiments.

  3. Natural abundance high-resolution solid state 2 H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Aliev, Abil E.; Harris, Kenneth D. M.; Apperley, David C.

    1994-08-01

    We report for the first time an approach for natural abundance solid state 2H NMR spectroscopy involving magic angle sample spinning (MAS), high-power 1H decoupling (HPPD) and 1H- 2H cross polarization (CP). Taking tetrakis(trimethylsilyl)silane (TTMSS), adamantane, 1-chloroadamantane, hexamethylbenzene (HMB), 2,2-dimethyl-1,3-propanediol (DMPD) and 2-hydroxymethyl-2-methyl-1,3-propanediol (HMPD) as examples, it has been shown that the combination of HPPD and MAS can be applied readily to study rotator phase solids, allowing isotropic peaks arising from chemically inequivalent 2H nuclei to be resolved. For natural abundance samples of TTMSS and chloroadamantane, it has been shown that 2H CP/HPPD/MAS NMR experiments, involving polarization transfer from 1H to 2H, may provide considerable sensitivity enhancement in comparison with single pulse experiments.

  4. 2H-DNP-enhanced 2H–13C solid-state NMR correlation spectroscopy

    PubMed Central

    Maly, Thorsten; Andreas, Loren B.; Smith, Albert A.

    2015-01-01

    Perdeuteration of biological macromolecules for magic angle spinning solid-state NMR spectroscopy can yield high-resolution 2H–13C correlation spectra and the method is therefore of great interest for the structural biology community. Here we demonstrate that the combination of sample deuteration and dynamic nuclear polarization yields resolved 2H–13C correlation spectra with a signal enhancement of ε ≥ 700 compared to a spectrum recorded with microwaves off and otherwise identical conditions. To our knowledge, this is the first time that 2H-DNP has been employed to enhance MAS-NMR spectra of a biologically relevant system. The DNP process is studied using several polarizing agents and the technique is applied to obtain 2H–13C correlation spectra of U-[2H, 13C] proline. PMID:20458422

  5. Detoxification of organophosphorus pesticides and nerve agents through RSDL: efficacy evaluation by (31)P NMR spectroscopy.

    PubMed

    Elsinghorst, Paul W; Worek, Franz; Koller, Marianne

    2015-03-01

    Intoxication by organophosphorus compounds, especially by pesticides, poses a considerable risk to the affected individual. Countermeasures involve both medical intervention by means of antidotes as well as external decontamination to reduce the risk of dermal absorption. One of the few decontamination options available is Reactive Skin Decontamination Lotion (RSDL), which was originally developed for military use. Here, we present a (31)P NMR spectroscopy based methodology to evaluate the detoxification efficacy of RSDL with respect to a series of organophosphorus pesticides and nerve agents. Kinetic analysis of the obtained NMR data provided degradation half-lives proving that RSDL is also reasonably effective against organophosphorus pesticides. Unexpected observations of different RSDL degradation patterns are presented in view of its reported oximate-catalyzed mechanism of action. PMID:25597861

  6. Mapping hypoxia-induced bioenergetic rearrangements and metabolic signaling by 18O-assisted 31P NMR and 1H NMR spectroscopy.

    PubMed

    Pucar, Darko; Dzeja, Petras P; Bast, Peter; Gumina, Richard J; Drahl, Carmen; Lim, Lynette; Juranic, Nenad; Macura, Slobodan; Terzic, Andre

    2004-01-01

    Brief hypoxia or ischemia perturbs energy metabolism inducing paradoxically a stress-tolerant state, yet metabolic signals that trigger cytoprotection remain poorly understood. To evaluate bioenergetic rearrangements, control and hypoxic hearts were analyzed with 18O-assisted 31P NMR and 1H NMR spectroscopy. The 18O-induced isotope shift in the 31P NMR spectrum of CrP, betaADP and betaATP was used to quantify phosphotransfer fluxes through creatine kinase and adenylate kinase. This analysis was supplemented with determination of energetically relevant metabolites in the phosphomonoester (PME) region of 31P NMR spectra, and in both aromatic and aliphatic regions of 1H NMR spectra. In control conditions, creatine kinase was the major phosphotransfer pathway processing high-energy phosphoryls between sites of ATP consumption and ATP production. In hypoxia, creatine kinase flux was dramatically reduced with a compensatory increase in adenylate kinase flux, which supported heart energetics by regenerating and transferring beta- and gamma-phosphoryls of ATP. Activation of adenylate kinase led to a build-up of AMP, IMP and adenosine, molecules involved in cardioprotective signaling. 31P and 1H NMR spectral analysis further revealed NADH and H+ scavenging by alpha-glycerophosphate dehydrogenase (alphaGPDH) and lactate dehydrogenase contributing to maintained glycolysis under hypoxia. Hypoxia-induced accumulation of alpha-glycerophosphate and nucleoside 5'-monophosphates, through alphaGPDH and adenylate kinase reactions, respectively, was mapped within the increased PME signal in the 31P NMR spectrum. Thus, 18O-assisted 31P NMR combined with 1H NMR provide a powerful approach in capturing rearrangements in cardiac bioenergetics, and associated metabolic signaling that underlie the cardiac adaptive response to stress. PMID:14977188

  7. Structural characterization of chemical warfare agent degradation products in decontamination solutions with proton band-selective (1)H-(31)P NMR spectroscopy.

    PubMed

    Koskela, Harri; Hakala, Ullastiina; Vanninen, Paula

    2010-06-15

    Decontamination solutions, which are usually composed of strong alkaline chemicals, are used for efficient detoxification of chemical warfare agents (CWAs). The analysis of CWA degradation products directly in decontamination solutions is challenging due to the nature of the matrix. Furthermore, occasionally an unforeseen degradation pathway can result in degradation products which could be eluded to in standard analyses. Here, we present the results of the application of proton band-selective (1)H-(31)P NMR spectroscopy, i.e., band-selective 1D (1)H-(31)P heteronuclear single quantum coherence (HSQC) and band-selective 2D (1)H-(31)P HSQC-total correlation spectroscopy (TOCSY), for ester side chain characterization of organophosphorus nerve agent degradation products in decontamination solutions. The viability of the approach is demonstrated with a test mixture of typical degradation products of nerve agents sarin, soman, and VX. The proton band-selective (1)H-(31)P NMR spectroscopy is also applied in characterization of unusual degradation products of VX in GDS 2000 solution. PMID:20507069

  8. Microfabricated Inserts for Magic Angle Coil Spinning (MACS) Wireless NMR Spectroscopy

    PubMed Central

    Badilita, Vlad; Fassbender, Birgit; Kratt, Kai; Wong, Alan; Bonhomme, Christian; Sakellariou, Dimitris; Korvink, Jan G.; Wallrabe, Ulrike

    2012-01-01

    This article describes the development and testing of the first automatically microfabricated probes to be used in conjunction with the magic angle coil spinning (MACS) NMR technique. NMR spectroscopy is a versatile technique for a large range of applications, but its intrinsically low sensitivity poses significant difficulties in analyzing mass- and volume-limited samples. The combination of microfabrication technology and MACS addresses several well-known NMR issues in a concerted manner for the first time: (i) reproducible wafer-scale fabrication of the first-in-kind on-chip LC microresonator for inductive coupling of the NMR signal and reliable exploitation of MACS capabilities; (ii) improving the sensitivity and the spectral resolution by simultaneous spinning the detection microcoil together with the sample at the “magic angle” of 54.74° with respect to the direction of the magnetic field (magic angle spinning – MAS), accompanied by the wireless signal transmission between the microcoil and the primary circuit of the NMR spectrometer; (iii) given the high spinning rates (tens of kHz) involved in the MAS methodology, the microfabricated inserts exhibit a clear kinematic advantage over their previously demonstrated counterparts due to the inherent capability to produce small radius cylindrical geometries, thus tremendously reducing the mechanical stress and tearing forces on the sample. In order to demonstrate the versatility of the microfabrication technology, we have designed MACS probes for various Larmor frequencies (194, 500 and 700 MHz) testing several samples such as water, Drosophila pupae, adamantane solid and LiCl at different magic angle spinning speeds. PMID:22936994

  9. Solid-state Ru-99 NMR spectroscopy: a useful tool for characterizing prototypal diamagnetic ruthenium compounds.

    PubMed

    Ooms, Kristopher J; Wasylishen, Roderick E

    2004-09-01

    The feasibility of (99)Ru NMR spectroscopy as a tool to characterize solid compounds is demonstrated. Results of the first solid-state (99)Ru NMR investigation of diamagnetic compounds are presented for Ru(NH(3))(6)Cl(2), K(4)Ru(CN)(6). xH(2)O (x = 0, 3), LaKRu(CN)(6), and Ru(3)(CO)(12). The sensitivity of the ruthenium magnetic shielding tensor to subtle changes in the local structure about the ruthenium nucleus is highlighted by comparing the (99)Ru isotropic chemical shift of Ru(NH(3))(6)Cl(2) in aqueous solutions and in the solid state. The narrow isotropic (99)Ru NMR peak observed for solid Ru(NH(3))(6)Cl(2) indicates that this compound is an ideal secondary reference sample for solid-state (99)Ru NMR studies. The isotropic (99)Ru chemical shift, (99)Ru nuclear quadrupolar coupling constant, C(Q), and quadrupolar asymmetry parameter of K(4)Ru(CN)(6). xH(2)O (x = 0, 3) are shown to be sensitive to x. For Ru(3)(CO)(12), the magnetic shielding tensors of each of the three nonequivalent Ru nuclei have spans of 1300-1400 ppm, and the (99)Ru C(Q) values are also similar, 1.36-1.85 MHz, and are surprisingly small given that (99)Ru has a moderate nuclear quadrupole moment. Information about the relative orientation of the Ru magnetic shielding and electric field gradient tensors has been determined for Ru(3)(CO)(12) from experimental (99)Ru NMR spectra as well as quantum chemical calculations. PMID:15339183

  10. Microfabricated inserts for magic angle coil spinning (MACS) wireless NMR spectroscopy.

    PubMed

    Badilita, Vlad; Fassbender, Birgit; Kratt, Kai; Wong, Alan; Bonhomme, Christian; Sakellariou, Dimitris; Korvink, Jan G; Wallrabe, Ulrike

    2012-01-01

    This article describes the development and testing of the first automatically microfabricated probes to be used in conjunction with the magic angle coil spinning (MACS) NMR technique. NMR spectroscopy is a versatile technique for a large range of applications, but its intrinsically low sensitivity poses significant difficulties in analyzing mass- and volume-limited samples. The combination of microfabrication technology and MACS addresses several well-known NMR issues in a concerted manner for the first time: (i) reproducible wafer-scale fabrication of the first-in-kind on-chip LC microresonator for inductive coupling of the NMR signal and reliable exploitation of MACS capabilities; (ii) improving the sensitivity and the spectral resolution by simultaneous spinning the detection microcoil together with the sample at the "magic angle" of 54.74° with respect to the direction of the magnetic field (magic angle spinning - MAS), accompanied by the wireless signal transmission between the microcoil and the primary circuit of the NMR spectrometer; (iii) given the high spinning rates (tens of kHz) involved in the MAS methodology, the microfabricated inserts exhibit a clear kinematic advantage over their previously demonstrated counterparts due to the inherent capability to produce small radius cylindrical geometries, thus tremendously reducing the mechanical stress and tearing forces on the sample. In order to demonstrate the versatility of the microfabrication technology, we have designed MACS probes for various Larmor frequencies (194, 500 and 700 MHz) testing several samples such as water, Drosophila pupae, adamantane solid and LiCl at different magic angle spinning speeds. PMID:22936994

  11. Recent Progresses in Studying Helix-Helix Interactions in Proteins by Incorporating the Wenxiang Diagram into the NMR Spectroscopy.

    PubMed

    Zhou, Guo-Ping; Chen, Dong; Liao, Siming; Huang, Ri-Bo

    2016-01-01

    All residues in an alpha helix can be characterized and dispositioned on a 2D the wenxiang diagram, which possesses the following features: (1) the relative locations of the amino acids in the α-helix can be clearly displayed regardless how long it is; (2) direction of an alphahelix can be indicated; and (3) more information regarding each of the constituent amino acid residues in an alpha helix. Owing to its intuitionism and easy visibility, wenxiang diagrams have had an immense influence on our understanding of protein structure, protein-protein interactions, and the effect of helical structural stability on protein conformational transitions. In this review, we summarize two recent applications of wenxiang diagrams incorporating NMR spectroscopy in the researches of the coiled-coil protein interactions related to the regulation of contraction or relaxation states of vascular smooth muscle cells, and the effects of α-helical stability on the protein misfolding in prion disease, in hopes that the gained valuable information through these studies can stimulate more and more widely applications of wenxiang diagrams in structural biology. PMID:26286215

  12. Discrimination of adulterated milk based on two-dimensional correlation spectroscopy (2D-COS) combined with kernel orthogonal projection to latent structure (K-OPLS).

    PubMed

    Yang, Renjie; Liu, Rong; Xu, Kexin; Yang, Yanrong

    2013-12-01

    A new method for discrimination analysis of adulterated milk and pure milk is proposed by combining two-dimensional correlation spectroscopy (2D-COS) with kernel orthogonal projection to latent structure (K-OPLS). Three adulteration types of milk with urea, melamine, and glucose were prepared, respectively. The synchronous 2D spectra of adulterated milk and pure milk samples were calculated. Based on the characteristics of 2D correlation spectra of adulterated milk and pure milk, a discriminant model of urea-tainted milk, melamine-tainted milk, glucose-tainted milk, and pure milk was built by K-OPLS. The classification accuracy rates of unknown samples were 85.7, 92.3, 100, and 87.5%, respectively. The results show that this method has great potential in the rapid discrimination analysis of adulterated milk and pure milk. PMID:24359648

  13. Correlating high-resolution magic angle spinning NMR spectroscopy and gene analysis in osteoarthritic cartilage.

    PubMed

    Tufts, Lauren; Shet Vishnudas, Keerthi; Fu, Eunice; Kurhanewicz, John; Ries, Michael; Alliston, Tamara; Li, Xiaojuan

    2015-05-01

    Osteoarthritis (OA) is a common multifactorial and heterogeneous degenerative joint disease, and biochemical changes in cartilage matrix occur during the early stages of OA before morphological changes occur. Thus, it is desired to measure regional biochemical changes in the joint. High-resolution magic angle spinning (HRMAS) NMR spectroscopy is a powerful method of observing cartilaginous biochemical changes ex vivo, including the concentrations of alanine and N-acetyl, which are markers of collagen and total proteoglycan content, respectively. Previous studies have observed significant changes in chondrocyte metabolism of OA cartilage via the altered gene expression profiles of ACAN, COL2A1 and MMP13, which encode aggrecan, type II collagen and matrix metalloproteinase 13 (a protein crucial in the degradation of type II collagen), respectively. Employing HRMAS, this study aimed to elucidate potential relationships between N-acetyl and/or alanine and ACAN, COL2A1 and/or MMP13 expression profiles in OA cartilage. Thirty samples from the condyles of five subjects undergoing total knee arthroplasty to treat OA were collected. HRMAS spectra were obtained at 11.7 T for each sample. RNA was subsequently extracted to determine gene expression profiles. A significant negative correlation between N-acetyl metabolite and ACAN gene expression levels was observed; this provides further evidence of N-acetyl as a biomarker of cartilage degeneration. The alanine doublet was distinguished in the spectra of 15 of the 30 specimens of this study. Alanine can only be detected with HRMAS NMR spectroscopy when the collagen framework has been degraded such that alanine is sufficiently mobile to form a distinguished peak in the spectrum. Thus, HRMAS NMR spectroscopy may provide unique localized measurements of collagenous degeneration in OA cartilage. The identification of imaging markers that could provide a link between OA pathology and chondrocyte metabolism will facilitate the

  14. Heteronuclear dipolar couplings, total spin coherence, and bilinear rotations in NMR spectroscopy

    SciTech Connect

    Garbow, J.R.

    1983-07-01

    In Chapter 1 a variety of different introductory topics are presented. The potential complexity of the nuclear magnetic resonsnace (NMR) spectra of molecules dissolved in liquid crystal solvents serves to motivate the development of multiple quantum (MQ) spectroscopy. The basics of MQ NMR are reviewed in Chapter 2. An experimental search procedure for the optimization of MQ pulse sequences is introduced. Chapter 3 discusses the application of MQ NMR techniques to the measurement of dipolar couplings in heteronuclear spin systems. The advantages of MQ methods in such systems are developed and experimental results for partially oriented (1-/sup 13/C) benzene are presented. Several pulse sequences are introduced which employ a two-step excitation of heteronuclear MQ coherence. A new multiple pulse method, involving the simultaneous irradiation of both rare and abundant spin species, is described. The problem of the broadening of MQ transitions due to magnetic field inhomogeneity is considered in Chapter 4. The method of total spin coherence transfer echo spectroscopy (TSCTES) is presented, with experimets on partially oriented acetaldehyde serving to demonstrate this new technique. TSCTES results in MQ spectra which are sensitive to all chemical shifts and spin-spin couplings and which are free of inhomogeneous broadening. In Chapter 5 the spectroscopy of spin systems of several protons and a /sup 13/C nucleus in the isotropic phase is discussed. The usefulness of the heteronuclear bilinear rotation as a calculational tool is illustrated. Compensated bilinear ..pi.. rotations, which are relatively insensitive to timing parameter missets, are presented. A new technique for homonuclear proton decoupling, Bilinear Rotation Decoupling, is described and its success in weakly coupled systems is demonstrated.

  15. The structure of salt bridges between Arg+ and Glu- in peptides investigated with 2D-IR spectroscopy: Evidence for two distinct hydrogen-bond geometries

    NASA Astrophysics Data System (ADS)

    Huerta-Viga, Adriana; Amirjalayer, Saeed; Domingos, Sérgio R.; Meuzelaar, Heleen; Rupenyan, Alisa; Woutersen, Sander

    2015-06-01

    Salt bridges play an important role in protein folding and in supramolecular chemistry, but they are difficult to detect and characterize in solution. Here, we investigate salt bridges between glutamate (Glu-) and arginine (Arg+) using two-dimensional infrared (2D-IR) spectroscopy. The 2D-IR spectrum of a salt-bridged dimer shows cross peaks between the vibrational modes of Glu- and Arg+, which provide a sensitive structural probe of Glu-⋯Arg+ salt bridges. We use this probe to investigate a β-turn locked by a salt bridge, an α-helical peptide whose structure is stabilized by salt bridges, and a coiled coil that is stabilized by intra- and intermolecular salt bridges. We detect a bidentate salt bridge in the β-turn, a monodentate one in the α-helical peptide, and both salt-bridge geometries in the coiled coil. To our knowledge, this is the first time 2D-IR has been used to probe tertiary side chain interactions in peptides, and our results show that 2D-IR spectroscopy is a powerful method for investigating salt bridges in solution.

  16. High-resolution magic-angle-spinning NMR spectroscopy of intact tissue.

    PubMed

    Giskeødegård, Guro F; Cao, Maria D; Bathen, Tone F

    2015-01-01

    High-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy is a nondestructive technique that is used to obtain the metabolite profile of a tissue sample. This method requires minimal sample preparation. However, it is important to handle the sample with care and keep it frozen during preparation to minimize degradation. Here, we describe a typical protocol for HR-MAS analysis of intact tissue. We also include examples of typical pulse sequence programs and quantification methods that are used today. PMID:25677145

  17. Electromagnetic susceptibility anisotropy and its importance for paramagnetic NMR and optical spectroscopy in lanthanide coordination chemistry.

    PubMed

    Blackburn, Octavia A; Edkins, Robert M; Faulkner, Stephen; Kenwright, Alan M; Parker, David; Rogers, Nicola J; Shuvaev, Sergey

    2016-04-19

    The importance of the directional dependence of magnetic susceptibility in magnetic resonance and of electric susceptibility in the optical spectroscopy of lanthanide coordination complexes is assessed. A body of more reliable shift, relaxation and optical emission data is emerging for well-defined isostructural series of complexes, allowing detailed comparative analyses to be undertaken. Such work is highlighting the limitations of the current NMR shift and relaxation theories, as well as emphasising the absence of a compelling theoretical framework to explain optical emission phenomena. PMID:26898996

  18. Application of nmr spectroscopy to determine the thermodynamic characteristics of water bound to OX-50 nanosilica

    NASA Astrophysics Data System (ADS)

    Turov, V. V.; Gun'ko, V. M.; Gaishun, V. E.; Kosenok, Ya. A.; Golovan, A. P.

    2010-09-01

    We have used low-temperature 1H NMR spectroscopy to determine the thermodynamic characteristics of water bound to OX-50 nanosilica (SBET ≈ 50 m2/g) in different media: aqueous, air, chloroform medium, and gaseous methane. We demonstrate the difference between the hydration parameters of silica OX-50 on going from an aqueous suspension to a hydrated powder. We present the water cluster size distributions in the studied systems, calculated from the Gibbs-Thomson equation. We found that the average water cluster size in suspension is considerably larger than the cluster sizes in hydrated powders.

  19. Silica sol assisted chromatographic NMR spectroscopy for resolution of trans- and cis-isomers.

    PubMed

    Yang, Ying; Wu, Rui; Huang, Shaohua; Bai, Zhengwu

    2016-04-01

    Chromatographic NMR spectroscopy can separate the mixtures of species with significantly different molecular size, but generally fails for isomeric species. Herein, we reported the resolution of trans- and cis-isomers and their structural analogue, which are different in molecular shapes, but similar in mass, were greatly enhanced in the presence of silica sol. The mixtures of maleic acid, fumaric acid and succinic acid, and the mixtures of trans- and cis-1,2-cyclohexanedicarboxylic acids, were distinguished by virtue of their different degrees of interaction with silica sol. Moreover, we found mixed solvents could improve the spectral resolution of DOSY spectra of mixtures. PMID:26942864

  20. Silica sol assisted chromatographic NMR spectroscopy for resolution of trans- and cis-isomers

    NASA Astrophysics Data System (ADS)

    Yang, Ying; Wu, Rui; Huang, Shaohua; Bai, Zhengwu

    2016-04-01

    Chromatographic NMR spectroscopy can separate the mixtures of species with significantly different molecular size, but generally fails for isomeric species. Herein, we reported the resolution of trans- and cis-isomers and their structural analogue, which are different in molecular shapes, but similar in mass, were greatly enhanced in the presence of silica sol. The mixtures of maleic acid, fumaric acid and succinic acid, and the mixtures of trans- and cis-1,2-cyclohexanedicarboxylic acids, were distinguished by virtue of their different degrees of interaction with silica sol. Moreover, we found mixed solvents could improve the spectral resolution of DOSY spectra of mixtures.

  1. Probing the Pu4 + magnetic moment in PuF4 with 19F NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Capan, Cigdem; Dempsey, Richard J.; Sinkov, Sergey; McNamara, Bruce K.; Cho, Herman

    2016-06-01

    The magnetic fields produced by Pu4 + centers have been measured by 19F NMR spectroscopy to elucidate the Pu-F electronic interactions in polycrystalline PuF4. Spectra acquired at applied fields of 2.35 and 7.05 T reveal a linear scaling of the 19F line shape. A model is presented that treats the line broadening and shifts as due to dipolar fields produced by Pu valence electrons in localized noninteracting orbitals. Alternative explanations for the observed line shape involving covalent Pu-F bonding, superexchange interactions, and electronic configurations with enhanced magnetic moments are considered.

  2. Impact of Hydrophilic Surfaces on Interfacial Water Dynamics Probed with NMR Spectroscopy

    PubMed Central

    Yoo, Hyok; Paranji, Rajan

    2011-01-01

    In suspensions of Nafion beads and of cationic gel beads, NMR spectroscopy showed two water–proton resonances, one representing intimate water layers next to the polymer surface, the other corresponding to water lying beyond. Both resonances show notably shorter spin–lattice relaxation times (T1) and smaller self-diffusion coefficients (D) indicating slower dynamics than bulk water. These findings confirm the existence of highly restricted water layers adsorbed onto hydrophilic surfaces and dynamically stable water beyond the first hydration layers. Thus, aqueous regions on the order of micrometers are dynamically different from bulk water. PMID:22003430

  3. Application of 13C NMR spectroscopy to paratope mapping for larger antigen-Fab complexes.

    PubMed

    Kim, H; Kato, K; Yamato, S; Igarashi, T; Matsunaga, C; Ohtsuka, H; Higuchi, A; Nomura, N; Noguchi, H; Arata, Y

    1994-06-13

    For the purpose of engineering the antibody combining site, mapping residues that are involved in antigen binding provide us with valuable information. By use of 13C NMR spectroscopy with selectively 13C-labeled Fv fragments, we have established a general strategy to identify the residues that are perturbed upon binding of small antigen (hapten) molecules [(1990) Biochemistry 30, 6604-6610]. In the present paper, we demonstrate that this strategy can be extended to molecular structural analyses of the complexes of an Fab fragment and a larger antigen molecule such as Pseudomonas aeruginosa exotoxin A with a molecular mass of 67 kDa. PMID:8013642

  4. Novel surfactant mixtures for NMR spectroscopy of encapsulated proteins dissolved in low-viscosity fluids

    PubMed Central

    Peterson, Ronald W.; Pometun, Maxim S.; Shi, Zhengshuang; Wand, A. Joshua

    2005-01-01

    NMR spectroscopy of encapsulated proteins dissolved in low-viscosity fluids is emerging as a tool for biophysical studies of proteins in atomic detail in a variety of otherwise inaccessible contexts. The central element of the approach is the encapsulation of the protein of interest within the aqueous core of a reverse micelle with high structural fidelity. The process of encapsulation is highly dependent upon the nature of the surfactant(s) employed. Here we describe novel mixtures of surfactants that are capable of successfully encapsulating a range of types of proteins under a variety of conditions. PMID:16199658

  5. Dynamic processes and chemical composition of Lepidium sativum seeds determined by means of field-cycling NMR relaxometry and NMR spectroscopy.

    PubMed

    Rachocki, A; Latanowicz, L; Tritt-Goc, J

    2012-12-01

    Proton nuclear magnetic resonance (NMR) techniques, such as field-cycling relaxometry, wide-line NMR spectroscopy, and magic angle spinning NMR spectroscopy, were applied to study the seeds of cress, Lepidium sativum. Field-cycling NMR relaxometry was used for the first time to investigate the properties of the whole molecular system of dry cress seeds. This method not only allowed the dynamics to be studied, but was also successful in the differentiation among the solid (i.e., carbohydrates, proteins, or fats forming a solid form of lipids) and liquid-like (oil compounds) components of the seeds. The (1)H NMR relaxation dispersion of oils was interpreted as a superposition of intramolecular and intermolecular contributions. The intramolecular part was described in terms of a Lorentzian spectral density function, whereas a log-Gaussian distribution of correlation times was applied for the intermolecular dipole-dipole contribution. The models applied led to very good agreement with the experimental data and demonstrate that the contribution of the intermolecular relaxation to the overall relaxation should not be disregarded, especially at low frequencies. A power-law frequency dependence of the proton relaxation dispersion was used for the interpretation of the solid components. From the analysis of the (1)H wide-line NMR spectra of the liquid-like component of hydrated cress seeds, we can conclude that the contribution of oil protons should always be taken into account when evaluating the spin-lattice relaxation times values or measuring the moisture and oil content. The application of (1)H magic angle spinning NMR significantly improves resolution in the liquid-like spectrum of seeds and allows the determination of the chemical composition of cress seeds. PMID:23001307

  6. Measured branching ratios for O II2D and 2P transitions in the wavelength range 530 to 800 A. [airglow spectroscopy

    NASA Technical Reports Server (NTRS)

    Morrison, D.; Cunningham, A. J.; Christensen, A. B.

    1981-01-01

    Branching ratios for four sets of extreme ultraviolet transitions terminating on the 2D0 and 2P0 metastable levels of ionized oxygen have been measured. The emissions were excited in both an open window hollow cathode and a capillary discharge lamp, and the branching ratios were derived from the observed intensity ratios of the multiplet pairs. The results are in good agreement with theoretical values and compare favorably, within experimental uncertainties, with line ratios obtained by EUV spectroscopy of the airglow.

  7. Probabilistic Interaction Network of Evidence Algorithm and its Application to Complete Labeling of Peak Lists from Protein NMR Spectroscopy

    PubMed Central

    Bahrami, Arash; Assadi, Amir H.; Markley, John L.; Eghbalnia, Hamid R.

    2009-01-01

    The process of assigning a finite set of tags or labels to a collection of observations, subject to side conditions, is notable for its computational complexity. This labeling paradigm is of theoretical and practical relevance to a wide range of biological applications, including the analysis of data from DNA microarrays, metabolomics experiments, and biomolecular nuclear magnetic resonance (NMR) spectroscopy. We present a novel algorithm, called Probabilistic Interaction Network of Evidence (PINE), that achieves robust, unsupervised probabilistic labeling of data. The computational core of PINE uses estimates of evidence derived from empirical distributions of previously observed data, along with consistency measures, to drive a fictitious system M with Hamiltonian H to a quasi-stationary state that produces probabilistic label assignments for relevant subsets of the data. We demonstrate the successful application of PINE to a key task in protein NMR spectroscopy: that of converting peak lists extracted from various NMR experiments into assignments associated with probabilities for their correctness. This application, called PINE-NMR, is available from a freely accessible computer server (http://pine.nmrfam.wisc.edu). The PINE-NMR server accepts as input the sequence of the protein plus user-specified combinations of data corresponding to an extensive list of NMR experiments; it provides as output a probabilistic assignment of NMR signals (chemical shifts) to sequence-specific backbone and aliphatic side chain atoms plus a probabilistic determination of the protein secondary structure. PINE-NMR can accommodate prior information about assignments or stable isotope labeling schemes. As part of the analysis, PINE-NMR identifies, verifies, and rectifies problems related to chemical shift referencing or erroneous input data. PINE-NMR achieves robust and consistent results that have been shown to be effective in subsequent steps of NMR structure determination. PMID

  8. Moving NMR

    NASA Astrophysics Data System (ADS)

    Blümich, Bernhard; Casanova, Federico; Danieli, Ernesto; Gong, Qingxia; Greferath, Marcus; Haber, Agnes; Kolz, Jürgen; Perlo, Juan

    2008-12-01

    Initiated by the use of NMR for well logging, portable NMR instruments are being developed for a variety of novel applications in materials testing and process analysis and control. Open sensors enable non-destructive testing of large objects, and small, cup-size magnets become available for high throughput analysis by NMR relaxation and spectroscopy. Some recent developments of mobile NMR are reviewed which delineate the direction into which portable NMR is moving.

  9. Correlating nuclear frequencies by two-dimensional ELDOR-detected NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kaminker, Ilia; Wilson, Tiffany D.; Savelieff, Masha G.; Hovav, Yonatan; Zimmermann, Herbert; Lu, Yi; Goldfarb, Daniella

    2014-03-01

    ELDOR (Electron Double Resonance)-detected NMR (EDNMR) is a pulse EPR experiment that is used to measure the transition frequencies of nuclear spins coupled to electron spins. These frequencies are further used to determine hyperfine and quadrupolar couplings, which are signatures of the electronic and spatial structures of paramagnetic centers. In recent years, EDNMR has been shown to be particularly useful at high fields/high frequencies, such as W-band (∼95 GHz, ∼3.5 T), for low γ quadrupolar nuclei. Although at high fields the nuclear Larmor frequencies are usually well resolved, the limited resolution of EDNMR still remains a major concern. In this work we introduce a two dimensional, triple resonance, correlation experiment based on the EDNMR pulse sequence, which we term 2D-EDNMR. This experiment allows circumventing the resolution limitation by spreading the signals in two dimensions and the observed correlations help in the assignment of the signals. First we demonstrate the utility of the 2D-EDNMR experiment on a nitroxide spin label, where we observe correlations between 14N nuclear frequencies. Negative cross-peaks appear between lines belonging to different MS electron spin manifolds. We resolved two independent correlation patterns for nuclear frequencies arising from the EPR transitions corresponding to the 14N mI = 0 and mI = -1 nuclear spin states, which severely overlap in the one dimensional EDNMR spectrum. The observed correlations could be accounted for by considering changes in the populations of energy levels that S = 1/2, I = 1 spin systems undergo during the pulse sequence. In addition to these negative cross-peaks, positive cross-peaks appear as well. We present a theoretical model based on the Liouville equation and use it to calculate the time evolution of populations of the various energy levels during the 2D-EDNMR experiment and generated simulated 2D-EDMR spectra. These calculations show that the positive cross-peaks appear due

  10. Correlating nuclear frequencies by two-dimensional ELDOR-detected NMR spectroscopy.

    PubMed

    Kaminker, Ilia; Wilson, Tiffany D; Savelieff, Masha G; Hovav, Yonatan; Zimmermann, Herbert; Lu, Yi; Goldfarb, Daniella

    2014-03-01

    ELDOR (Electron Double Resonance)-detected NMR (EDNMR) is a pulse EPR experiment that is used to measure the transition frequencies of nuclear spins coupled to electron spins. These frequencies are further used to determine hyperfine and quadrupolar couplings, which are signatures of the electronic and spatial structures of paramagnetic centers. In recent years, EDNMR has been shown to be particularly useful at high fields/high frequencies, such as W-band (∼95 GHz, ∼3.5 T), for low γ quadrupolar nuclei. Although at high fields the nuclear Larmor frequencies are usually well resolved, the limited resolution of EDNMR still remains a major concern. In this work we introduce a two dimensional, triple resonance, correlation experiment based on the EDNMR pulse sequence, which we term 2D-EDNMR. This experiment allows circumventing the resolution limitation by spreading the signals in two dimensions and the observed correlations help in the assignment of the signals. First we demonstrate the utility of the 2D-EDNMR experiment on a nitroxide spin label, where we observe correlations between (14)N nuclear frequencies. Negative cross-peaks appear between lines belonging to different MS electron spin manifolds. We resolved two independent correlation patterns for nuclear frequencies arising from the EPR transitions corresponding to the (14)N mI=0 and mI=-1 nuclear spin states, which severely overlap in the one dimensional EDNMR spectrum. The observed correlations could be accounted for by considering changes in the populations of energy levels that S=1/2, I=1 spin systems undergo during the pulse sequence. In addition to these negative cross-peaks, positive cross-peaks appear as well. We present a theoretical model based on the Liouville equation and use it to calculate the time evolution of populations of the various energy levels during the 2D-EDNMR experiment and generated simulated 2D-EDMR spectra. These calculations show that the positive cross-peaks appear due to

  11. Advanced Structural Determination of Diterpene Esters Using Molecular Modeling and NMR Spectroscopy.

    PubMed

    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. PMID:26431312

  12. Oil droplet size determination in complex flavor delivery systems by diffusion NMR spectroscopy.

    PubMed

    Fieber, Wolfgang; Hafner, Valeria; Normand, Valéry

    2011-04-15

    Droplet size distribution of flavor oils in two different solid flavor delivery systems were determined with pulsed field gradient NMR spectroscopy: yeast encapsulation system, a spray dried flavor encapsulation system based on empty yeast cells, and glassy encapsulation system, an extruded solid water soluble carbohydrate delivery system. The oil droplet sizes are limited by the yeast cell walls in the yeast encapsulation system and the size distribution is unimodal according to images from transmission electron microscopy. The droplet size determination with diffusion NMR is based on the Murday and Cotts theory of restricted diffusion of liquids in geometrical confinements. Good fits of the diffusion data could be obtained by applying a unimodal, log-normal size distribution model and average droplet sizes of about 2 μm were found that correspond approximately to the inner diameter of the yeast cells. Scanning electron microscopy images showed a multimodal droplet size distribution in the glassy extruded delivery systems. To fit the NMR data a bimodal log-normal distribution function with five independent fitting parameters was implemented that yielded consistent and robust results. The two size populations were found in the micron and sub-micron range, respectively. The method was sufficiently accurate to depict variation of droplet size distributions in glassy encapsulation systems of different formulation. PMID:21316700

  13. Methylation patterns of aquatic humic substances determined by 13C NMR spectroscopy

    USGS Publications Warehouse

    Thorn, K.A.; Steelink, C.; Wershaw, R. L.

    1987-01-01

    13C NMR spectroscopy is used to examine the hydroxyl group functionality of a series of humic and fulvic acids from different aquatic environments. Samples first are methylated with 13C-labeled diazomethane. The NMR spectra of the diazomethylated samples allow one to distinguish between methyl esters of carboxylic acids, methyl ethers of phenolic hydroxyls, and methyl ethers of phenolic hydroxyls adjacent to two substituents. Samples are then permethylated with 13C-labeled methyl iodide/NaH. 13C NMR spectra of permethylated samples show that a significant fraction of the hydroxyl groups is not methylated with diazomethane alone. In these spectra methyl ethers of carbohydrate and aliphatic hydroxyls overlap with methyl ethers of phenolic hydroxyls. Side reactions of the methyltion procedure including carbon methylation in the CH3I/NaH procedure, are also examined. Humic and fulvic acids from bog, swamp, groundwater, and lake waters showssome differences in their distribution of hydroxyl groups, mainly in the concentrations of phenolic hydroxyls, which may be attributed to their different biogeochemical origins. ?? 1987.

  14. Rapid Etiological Classification of Meningitis by NMR Spectroscopy Based on Metabolite Profiles and Host Response

    PubMed Central

    Himmelreich, Uwe; Malik, Richard; Kühn, Till; Daniel, Heide-Marie; Somorjai, Ray L.; Dolenko, Brion; Sorrell, Tania C.

    2009-01-01

    Bacterial meningitis is an acute disease with high mortality that is reduced by early treatment. Identification of the causative microorganism by culture is sensitive but slow. Large volumes of cerebrospinal fluid (CSF) are required to maximise sensitivity and establish a provisional diagnosis. We have utilised nuclear magnetic resonance (NMR) spectroscopy to rapidly characterise the biochemical profile of CSF from normal rats and animals with pneumococcal or cryptococcal meningitis. Use of a miniaturised capillary NMR system overcame limitations caused by small CSF volumes and low metabolite concentrations. The analysis of the complex NMR spectroscopic data by a supervised statistical classification strategy included major, minor and unidentified metabolites. Reproducible spectral profiles were generated within less than three minutes, and revealed differences in the relative amounts of glucose, lactate, citrate, amino acid residues, acetate and polyols in the three groups. Contributions from microbial metabolism and inflammatory cells were evident. The computerised statistical classification strategy is based on both major metabolites and minor, partially unidentified metabolites. This data analysis proved highly specific for diagnosis (100% specificity in the final validation set), provided those with visible blood contamination were excluded from analysis; 6–8% of samples were classified as indeterminate. This proof of principle study suggests that a rapid etiologic diagnosis of meningitis is possible without prior culture. The method can be fully automated and avoids delays due to processing and selective identification of specific pathogens that are inherent in DNA-based techniques. PMID:19390697

  15. Determination of rank and kerogen type by high resolution NMR spectroscopy

    SciTech Connect

    Dickinson, W.W.; Collen, J.D. ); Newman, R.H. )

    1990-06-01

    Nuclear magnetic resonance (NMR) spectroscopy is a nondestructive technique for measuring the chemical and structural properties of organic matter. Although used in organic geochemistry for the past 14 years, the technique has continually undergone refinement. Initially, only the aromatic and aliphatic signal areas of the carbon NMR spectrum could be measured. Carboxylic groups as well as oxygen-substituted groups on aromatic and aliphatic carbon can now be qualitatively measured. The authors have examined coal and shale samples of various ranks from the Williston and San Juan basins, USA, and the Taranaki and Great South basins, New Zealand. Kerogen type can be distinguished on a plot of aromaticity versus the methylene to methyl ratio. For type III kerogens, vitrinite reflectance correlates very well with the percent of oxygen substitution on aromatic carbon and aromaticity. These parameters are excellent indicators of rank because they reflect the decrease in oxygen content and the increase in aromatic carbon as organic matter matures. Although the initial cost of NMR equipment is high, the vast amount of chemical information on kerogen that may be obtained from a small sample and very little laboratory preparation make it a valuable tool for petroleum geochemistry.

  16. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    SciTech Connect

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.

    1999-07-20

    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  17. Biological effects and physical safety aspects of NMR imaging and in vivo spectroscopy

    SciTech Connect

    Tenforde, T.S.; Budinger, T.F.

    1985-08-01

    An assessment is made of the biological effects and physical hazards of static and time-varying fields associated with the NMR devices that are being used for clinical imaging and in vivo spectroscopy. A summary is given of the current state of knowledge concerning the mechanisms of interaction and the bioeffects of these fields. Additional topics that are discussed include: (1) physical effects on pacemakers and metallic implants such as aneurysm clips, (2) human health studies related to the effects of exposure to nonionizing electromagnetic radiation, and (3) extant guidelines for limiting exposure of patients and medical personnel to the fields produced by NMR devices. On the basis of information available at the present time, it is concluded that the fields associated with the current generation of NMR devices do not pose a significant health risk in themselves. However, rigorous guidelines must be followed to avoid the physical interaction of these fields with metallic implants and medical electronic devices. 476 refs., 5 figs., 2 tabs.

  18. Quality assessment and authentication of virgin olive oil by NMR spectroscopy: a critical review.

    PubMed

    Dais, Photis; Hatzakis, Emmanuel

    2013-02-26

    Nuclear Magnetic Resonance (NMR) Spectroscopy has been extensively used for the analysis of olive oil and it has been established as a valuable tool for its quality assessment and authenticity. To date, a large number of research and review articles have been published with regards to the analysis of olive oil reflecting the potential of the NMR technique in these studies. In this critical review, we cover recent results in the field and discuss deficiencies and precautions of the three NMR techniques ((1)H, (13)C, (31)P) used for the analysis of olive oil. The two methodological approaches of metabonomics, metabolic profiling and metabolic fingerprinting, and the statistical methods applied for the classification of olive oils will be discussed in critical way. Some useful information about sample preparation, the required instrumentation for an effective analysis, the experimental conditions and data processing for obtaining high quality spectra will be presented as well. Finally, a constructive criticism will be exercised on the present methodologies used for the quality control and authentication of olive oil. PMID:23410622

  19. Functional group analysis in coal and on coal surfaces by NMR spectroscopy

    SciTech Connect

    Verkade, J.G.

    1990-01-01

    An accurate knowledge of the oxygen-bearing labile hydrogen functional groups (e.g., carboxylic acids, phenols and alcohols) in coal is required for today's increasingly sophisticated coal cleaning and beneficiation processes. Phospholanes (compounds having the general structure -POCH{sub 2}CH{sub 2}O (1)) are being investigated as reagents for the tagging of liable hydrogen functional groups in coal materials with the NMR-active {sup 31}P nucleus. Of twelve such reagents investigated so far, 2 (2-chloro-1,3-dioxaphospholane, ClPOCH{sub 2}CH{sub 2}O) and 8 (2-chloro-1,3-dithiaphospholane, ClPSCH{sub 2}CH{sub 2}S) have been found to be useful in identifying and quantitating, by {sup 31}P NMR spectroscopy, labile hydrogen functional groups in an Illinois No. 6 coal condensate. Reagent 2 has also been used to quantitate moisture in pyridine extracts of Argonne Premium Coal Samples. Preliminary {sup 119}Sn NMR spectroscopic results on model compounds with the new reagent CF{sub 3}C(O)NHSnMe{sub 3} (N-trimethylstannyltrifluoroacetamide, 14) suggest that labile hydrogen functional groups in coal materials may be more precisely identified with 14 than with phospholanes. 14 refs., 2 figs., 2 tabs.

  20. 60 MHz (1)H NMR spectroscopy for the analysis of edible oils.

    PubMed

    Parker, T; Limer, E; Watson, A D; Defernez, M; Williamson, D; Kemsley, E Kate

    2014-05-01

    We report the first results from a new 60 MHz (1)H nuclear magnetic resonance (NMR) bench-top spectrometer, Pulsar, in a study simulating the adulteration of olive oil with hazelnut oil. There were qualitative differences between spectra from the two oil types. A single internal ratio of two isolated groups of peaks could detect hazelnut oil in olive oil at the level of ∼13%w/w, whereas a whole-spectrum chemometric approach brought the limit of detection down to 11.2%w/w for a set of independent test samples. The Pulsar's performance was compared to that of Fourier transform infrared (FTIR) spectroscopy. The Pulsar delivered comparable sensitivity and improved specificity, making it a superior screening tool. We also mapped NMR onto FTIR spectra using a correlation-matrix approach. Interpretation of this heat-map combined with the established annotations of the NMR spectra suggested a hitherto undocumented feature in the IR spectrum at ∼1130 cm(-1), attributable to a double-bond vibration. PMID:24850979

  1. Interaction of the replication terminator protein of Bacillus subtilis with DNA probed by NMR spectroscopy

    SciTech Connect

    Hastings, Adam F.; Otting, Gottfried; Folmer, Rutger H.A.; Duggin, Iain G.; Wake, R. Gerry; Wilce, Matthew C.J.; Wilce, Jacqueline A. . E-mail: Jackie.Wilce@med.monash.edu.au

    2005-09-23

    Termination of DNA replication in Bacillus subtilis involves the polar arrest of replication forks by a specific complex formed between the dimeric 29 kDa replication terminator protein (RTP) and DNA terminator sites. We have used NMR spectroscopy to probe the changes in {sup 1}H-{sup 15}N correlation spectra of a {sup 15}N-labelled RTP.C110S mutant upon the addition of a 21 base pair symmetrical DNA binding site. Assignment of the {sup 1}H-{sup 15}N correlations was achieved using a suite of triple resonance NMR experiments with {sup 15}N,{sup 13}C,70% {sup 2}H enriched protein recorded at 800 MHz and using TROSY pulse sequences. Perturbations to {sup 1}H-{sup 15}N spectra revealed that the N-termini, {alpha}3-helices and several loops are affected by the binding interaction. An analysis of this data in light of the crystallographically determined apo- and DNA-bound forms of RTP.C110S revealed that the NMR spectral perturbations correlate more closely to protein structural changes upon complex formation rather than to interactions at the protein-DNA interface.

  2. Implementation and characterization of flow injection in dissolution dynamic nuclear polarization NMR spectroscopy.

    PubMed

    Chen, Hsueh-Ying; Hilty, Christian

    2015-08-24

    The use of dissolution dynamic nuclear polarization (D-DNP) offers substantially increased signals in liquid-state NMR spectroscopy. A challenge in realizing this potential lies in the transfer of the hyperpolarized sample to the NMR detector without loss of hyperpolarization. Here, the use of a flow injection method using high-pressure liquid leads to improved performance compared to the more common gas-driven injection, by suppressing residual fluid motions during the NMR experiment while still achieving a short injection time. Apparent diffusion coefficients are determined from pulsed field gradient echo measurements, and are shown to fall below 1.5 times the value of a static sample within 0.8 s. Due to the single-scan nature of D-DNP, pulsed field gradients are often the only choice for coherence selection or encoding, but their application requires stationary fluid. Sample delivery driven by a high-pressure liquid will improve the applicability of these types of D-DNP advanced experiments. PMID:26139513

  3. Characterisation of the conformational preference and dynamics of the intrinsically disordered N-terminal region of Beclin 1 by NMR spectroscopy.

    PubMed

    Yao, Shenggen; Lee, Erinna F; Pettikiriarachchi, Anne; Evangelista, Marco; Keizer, David W; Fairlie, W Douglas

    2016-09-01

    Beclin 1 is a 450 amino acid protein that plays critical roles in the early stages of autophagosome formation. We recently reported the successful expression, purification and structural characterisation of the entire N-terminal region of Beclin 1 (residues 1-150), including its backbone NMR chemical shift assignments. Based on assigned backbone NMR chemical shifts, it has been established that the N-terminal region of Beclin 1 (1-150), including the BH3 domain (112-123), is intrinsically disordered in the absence of its interaction partners. Here, a detailed study of its conformational preference and backbone dynamics obtained from an analysis of its secondary structure populations using the δ2D method, and the measurements of effective hydrodynamic radius as well as (1)H temperature coefficients, (1)H solvent exchange rates, and (15)N relaxation parameters of backbone amides using NMR spectroscopy is reported. These data provide further evidence for the intrinsically disordered nature of the N-terminal region of Beclin 1 and support the view that the helical conformation adopted by the Beclin 1 BH3 domain upon interaction with binding partners such as BCL-2 pro-survival proteins is likely induced rather than pre-existing. PMID:27288992

  4. Measurement and assignment of long-range C-H dipolar couplings in liquid crystals by two-dimensional NMR spectroscopy

    SciTech Connect

    Hong, M.; Pines, A. |; Caldarelli, S.

    1996-08-29

    We describe multidimensional NMR techniques to measure and assign {sup 13}C-{sup 1}H dipolar couplings in nematic liquid crystals with high resolution. In particular, dipolar couplings between aromatic and aliphatic sites are extracted, providing valuable information on the structural correlations between these two components of thermotropic liquid crystal molecules. The NMR techniques are demonstrated on 4-pentyl-4`-biphenylcarbonitrile (5CB), a well-characterized room-temperature nematic liquid crystal. Proton-detected local-field NMR spectroscopy is employed to obtain highly resolved C-H dipolar couplings that are separated according to the chemical shifts of the carbon sites. Each {sup 13}C cross section in the 2D spectra exhibits several doublet splittings, with the largest one resulting from the directly bonded C-H coupling. The smaller splittings originate from the long-range C-H dipolar couplings and can be assigned qualitatively by a chemical shift heteronuclear correlation (HETCOR) experiment. The HETCOR experiment incorporates a mixing period for proton spin diffusion to occur, so that maximal polarization transfer can be achieved between the unbonded {sup 13}C and {sup 1}H nuclei. To assign the long-range C-H couplings quantitatively. we combined these two techniques into a novel reduced-3D experiment, in which the {sup 1}H chemical shift-displaced C-H dipolar couplings are correlated with the {sup 13}C chemical shifts. 34 refs., 6 figs., 2 tabs.

  5. Characterization of noninnocent metal complexes using solid-state NMR spectroscopy: o-dioxolene vanadium complexes.

    PubMed

    Chatterjee, Pabitra B; Goncharov-Zapata, Olga; Quinn, Laurence L; Hou, Guangjin; Hamaed, Hiyam; Schurko, Robert W; Polenova, Tatyana; Crans, Debbie C

    2011-10-17

    (51)V solid-state NMR (SSNMR) studies of a series of noninnocent vanadium(V) catechol complexes have been conducted to evaluate the possibility that (51)V NMR observables, quadrupolar and chemical shift anisotropies, and electronic structures of such compounds can be used to characterize these compounds. The vanadium(V) catechol complexes described in these studies have relatively small quadrupolar coupling constants, which cover a surprisingly small range from 3.4 to 4.2 MHz. On the other hand, isotropic (51)V NMR chemical shifts cover a wide range from -200 to 400 ppm in solution and from -219 to 530 ppm in the solid state. A linear correlation of (51)V NMR isotropic solution and solid-state chemical shifts of complexes containing noninnocent ligands is observed. These experimental results provide the information needed for the application of (51)V SSNMR spectroscopy in characterizing the electronic properties of a wide variety of vanadium-containing systems and, in particular, those containing noninnocent ligands and that have chemical shifts outside the populated range of -300 to -700 ppm. The studies presented in this report demonstrate that the small quadrupolar couplings covering a narrow range of values reflect the symmetric electronic charge distribution, which is also similar across these complexes. These quadrupolar interaction parameters alone are not sufficient to capture the rich electronic structure of these complexes. In contrast, the chemical shift anisotropy tensor elements accessible from (51)V SSNMR experiments are a highly sensitive probe of subtle differences in electronic distribution and orbital occupancy in these compounds. Quantum chemical (density functional theory) calculations of NMR parameters for [VO(hshed)(Cat)] yield a (51)V chemical shift anisotropy tensor in reasonable agreement with the experimental results, but surprisingly the calculated quadrupolar coupling constant is significantly greater than the experimental value. The

  6. Electrostatic influence on rotational mobilities of sol-gel-encapsulated solutes by NMR and EPR spectroscopies.

    PubMed

    Wheeler, Korin E; Lees, Nicholas S; Gurbiel, Ryszard J; Hatch, Shelby L; Nocek, Judith M; Hoffman, Brian M

    2004-10-20

    The rotational mobilities of small solute molecules encapsulated in tetramethyl orthosilicate (TMOS) sol-gels have been investigated by EPR spectroscopy of encapsulated nitroxide probes and by high-resolution NMR spectroscopic measurements of transferred NOE's (trNOE's), of T(1)'s, and of T(1)'s in the rotating frame (T(1)rho). The two spectroscopic methods are sensitive to motions on different time scales and hence, are nicely complementary. Suites of neutral, positively, and negatively charged nitroxide probes (EPR) and of simple diamagnetic small molecules (NMR) were selected to disclose influences of electrostatic interactions with the sol-gel walls and to probe the presence of multiple populations of molecules in distinct regions of the sol-gel pores. For neutral and negatively charged solute probes, both techniques disclose a single population with a significantly increased average rotational correlation time, which we interpret at least in part as resulting from exchange between free-volume and transiently immobilized surface populations. The electrostatic attraction between cationic probes and the negatively charged sol-gel walls causes the positively charged probes to be more effectively immobilized and/or causes a greater percentage of probes to undergo this transient immobilization. The EPR spectra directly disclose a population of cationic probes which are immobilized on the X-band EPR time scale: tau(c) greater than or approximately equal 10(-7) s. However, NMR measurements of trNOE's and of T(1)rho demonstrate that this population does exchange with the free-volume probes on the slower time scale of NMR. This approach is equally applicable to the study of solutes within other types of confined spaces, as well. PMID:15479102

  7. Noninvasive quantitation of phosphorus metabolites in human tissue by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Roth, K.; Hubesch, B.; Meyerhoff, D. J.; Naruse, S.; Gober, J. R.; Lawry, T. J.; Boska, M. D.; Matson, G. B.; Weiner, M. W.

    Quantitation of metabolite concentrations by NMR spectroscopy is complicated by the need to determine the volume from which signals are detected, and by the need to obtain the relative sensitivity of detection within this volume. The use of coils with inhomogeneous B1 fields further complicates these problems. In order to quantify metabolite concentrations using 31P NMR spectroscopy, an external reference of hexamethyl phosphoroustriamide was used. Studies were performed on phantoms, using either a surface coil or a Helmholtz head coil to confirm the accuracy of both the ISIS volume selection technique and the use of an external reference. The limitations of this method are related to contamination and signal loss inherent in the ISIS technique and difficulties with integration of broad overlapping peaks. The method was applied to seven normal human subjects. The integrals for metabolite signals in normal brain and calf muscle were determined by using NMRI software. The T1 values of the signals of all phosphorus metabolites in the selected volume were measured in order to correct for saturation effects. The concentrations for PCr, P i, and ATP were 4.9, 2.0, and 2.5 m M in brain and 36.5, 5.7, and 7.3 m M in muscle. These results are in good agreement with those reported for animals, demonstrating the validity of this quantitation technique.

  8. Labeling strategy and signal broadening mechanism of Protein NMR spectroscopy in Xenopus laevis oocytes.

    PubMed

    Ye, Yansheng; Liu, Xiaoli; Chen, Yanhua; Xu, Guohua; Wu, Qiong; Zhang, Zeting; Yao, Chendie; Liu, Maili; Li, Conggang

    2015-06-01

    We used Xenopus laevis oocytes, a paradigm for a variety of biological studies, as a eukaryotic model system for in-cell protein NMR spectroscopy. The small globular protein GB1 was one of the first studied in Xenopus oocytes, but there have been few reports since then of high-resolution spectra in oocytes. The scarcity of data is at least partly due to the lack of good labeling strategies and the paucity of information on resonance broadening mechanisms. Here, we systematically evaluate isotope enrichment and labeling methods in oocytes injected with five different proteins with molecular masses of 6 to 54 kDa. (19) F labeling is more promising than (15) N, (13) C, and (2) H enrichment. We also used (19) F NMR spectroscopy to quantify the contribution of viscosity, weak interactions, and sample inhomogeneity to resonance broadening in cells. We found that the viscosity in oocytes is only about 1.2 times that of water, and that inhomogeneous broadening is a major factor in determining line width in these cells. PMID:25965532

  9. Secondary structure determination of human. beta. -endorphin by /sup 1/H NMR spectroscopy

    SciTech Connect

    Lichtarge, O.; Jardetzky, O.; Li, C.H.

    1987-09-08

    The /sup 1/H NMR spectra of human ..beta..-endorphin indicate that the peptide exists in random-coil form in aqueous solution but becomes helical in mixed solvent. Thermal denaturation NMR experiments show that in water there is no transition between 24 and 75/sup 0/C, while a slow noncooperative thermal unfolding is observed in a 60% methanol-40% water mixed solvent in the same temperature range. These findings are consistent with circular dichroism studies by other workers concluding that ..beta..-endorphin is a random coil in water but that it forms 50% ..cap alpha..-helix or more in mixed solvents. The peptide in the mixed water-methanol solvent was further studied by correlated spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments. These allow a complete set of assignments to be made and establish two distinct stretches over which the solvent induces formation of ..cap alpha..-helices: the first occurs between Tyr-1 and Thr-12 and the second between Leu-14 and extending to Lys-28. There is evidence that the latter is capped by a turn occurring between Lys-28 and Glu-31. These helices form at the enkephalin receptor binding site, which is at the amino terminus, and at the morphine receptor binding site, located at the carboxyl terminus. The findings suggest that these two receptors may specifically recognize ..cap alpha..-helices.

  10. Phosphorus Speciation of Sequential Extracts of Organic Amendments using NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Akinremi, O.

    2009-04-01

    O.O. 1Akinremi Babasola Ajiboye and Donald N. Flaten 1Department of Soil Science, University of Manitoba, Winnipeg, R3T 2NT, Canada We carried out this study in order to determine the forms of phosphorus in various organic amendments using state-of-the art spectroscopic technique. Anaerobically digested biosolids (BIO), hog (HOG), dairy (DAIRY), beef (BEEF) and poultry (POULTRY) manures were subjected to sequential extraction. The extracts were analyzed by solution 31P nuclear magnetic resonance (NMR) spectroscopy. Most of the total P analysed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) in the sequential extracts of organic amendments were orthophosphate, except POULTRY, which was dominated by organic P. The labile P fraction in all the organic amendments, excluding POULTRY, was mainly orthophosphate P from readily soluble calcium and some aluminum phosphates. In the poultry litter, however, Ca phytate was the main P species controlling P solubility. Such knowledge of the differences in the chemical forms of phosphorus in organic amendments are essential for proper management of these amendments for agro-environmental purposes Key words: organic amendments, solution NMR, sequential fractionation, labile phosphorus

  11. Characterization of prednisolone in controlled porosity osmotic pump pellets using solid-state NMR spectroscopy.

    PubMed

    Sotthivirat, S; Lubach, J W; Haslam, J L; Munson, E J; Stella, V J

    2007-05-01

    The overall objective of this study was to demonstrate the influence of formulation and processing variables on the physical state of prednisolone (PDL) in formulations consisting of PDL, microcrystalline cellulose (MCC), and sulfobutylether-beta-cyclodextrin (CD). PDL was used as a model drug in controlled porosity osmotic pump pellet (CP-OPP) formulations, and was characterized using solid-state NMR spectroscopy and other complimentary analytical techniques. Dosage forms and the solid-state properties of drugs and excipients in a formulation may be influenced by the processing conditions used. Several processing parameters, such as amount of water used in wet granulation and subsequent drying conditions, were found to affect the solid-state transformation of PDL. In addition, the presence of excipients in the CP-OPP was observed to decrease the degree of PDL crystallinity, presumably by creating an inclusion complex with the CD. A hydrated form of PDL was created when PDL was ground with water alone; however, this form was not observed in formulated products. Solid-state NMR spectroscopy was shown to be a powerful technique for the analysis of drug formulations and investigations of the effects of processing conditions. PMID:17455361

  12. Broad identification of bacterial type in urinary tract infection using (1)h NMR spectroscopy.

    PubMed

    Gupta, Ashish; Dwivedi, Mayank; Mahdi, Abbas Ali; Khetrapal, Chunni Lal; Bhandari, Mahendra

    2012-03-01

    To address the shortcomings of urine culture for the rapid identification of urinary tract infection (UTI), we applied (1)H-nuclear magnetic resonance (NMR) spectroscopy as a surrogate method for fast screening of microorganisms. Study includes 682 urine samples from suspected UTI patients, 50 healthy volunteers, and commercially available standard strains of gram negative bacilli (GNB) (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumonia, Enterobacter, Acinetobacter, Proteus mirabilis, Citrobacter frundii) and gram positive cocci (GPC) (Enterococcus faecalis, Streptococcus group B, Staphylococcus saprophyticus). Acetate, lactate, ethanol, succinate, creatinine, trimethylamine (TMA), citrate, trimethylamin-N-oxide, glycine, urea, and hippurate were measured by (1)H NMR spectroscopy. All urine specimens were evaluated with culture method. Multivariate discriminant function analysis (DFA) reveals that acetate, lactate, succinate, and formate were able to differentiate, with high accuracy (99.5%), healthy controls from UTI patients. This statistical analysis was also able to classify GNB to GPC infected urine samples with high accuracy (96%). This technique appears to be a promising, rapid, and noninvasive approach to probing GNB and GPC infected urine specimens with its distinguishing metabolic profile. The determination of infection will be very important for rapidly and efficiently measuring the efficacy of a tailored treatment, leading to prompt and appropriate care of UTI patients. PMID:22292465

  13. The Development of 460 GHz gyrotrons for 700 MHz DNP-NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Idehara, T.; Tatematsu, Y.; Yamaguchi, Y.; Khutoryan, E. M.; Kuleshov, A. N.; Ueda, K.; Matsuki, Y.; Fujiwara, T.

    2015-07-01

    Two demountable gyrotrons with internal mode converters were developded as sub-THz radiation sources for 700 MHz DNP (Dynamic Nuclear Polarization) enhanced NMR spectroscopy. Experimental study on the DNP-NMR spectroscopy will be carried out in Osaka University, Institute for Protein Research, as a collaboration with FIR UF. Both gyrotrons operate near 460 GHz and the output CW power measured at the end of transmission system made by circular waveguides is typically 20 to 30 watts. One of them named Gyrotron FU CW GVI (we are using "Gyrotron FU CW GO-1" as an official name in Osaka University) is designed to have a special function of high speed frequency modulation δ f within 100 MHz band. This will expand excitable band width of ESR and increase the number of electron spins contributing to DNP. The other gyrotron, Gyrotron FU CW GVIA ("Gyrotron FU CW GO-II") has a function of frequency tunability Δ f in the range of wider than 1.5 GHz, which is achieved in steady state by changing magnetic field intensity. This function should be used for adjusting the output frequency at the optimal value to achieve the highest enhancement factor of DNP.

  14. Determination of RNA polymerase binding surfaces of transcription factors by NMR spectroscopy

    PubMed Central

    Drögemüller, Johanna; Strauß, Martin; Schweimer, Kristian; Jurk, Marcel; Rösch, Paul; Knauer, Stefan H.

    2015-01-01

    In bacteria, RNA polymerase (RNAP), the central enzyme of transcription, is regulated by N-utilization substance (Nus) transcription factors. Several of these factors interact directly, and only transiently, with RNAP to modulate its function. As details of these interactions are largely unknown, we probed the RNAP binding surfaces of Escherichia coli (E. coli) Nus factors by nuclear magnetic resonance (NMR) spectroscopy. Perdeuterated factors with [1H,13C]-labeled methyl groups of Val, Leu, and Ile residues were titrated with protonated RNAP. After verification of this approach with the N-terminal domain (NTD) of NusG and RNAP we determined the RNAP binding site of NusE. It overlaps with the NusE interaction surface for the NusG C-terminal domain, indicating that RNAP and NusG compete for NusE and suggesting possible roles for the NusE:RNAP interaction, e.g. in antitermination and direct transcription:translation coupling. We solved the solution structure of NusA-NTD by NMR spectroscopy, identified its RNAP binding site with the same approach we used for NusG-NTD, and here present a detailed model of the NusA-NTD:RNAP:RNA complex. PMID:26560741

  15. Flexible Stoichiometry and Asymmetry of the PIDDosome Core Complex by Heteronuclear NMR Spectroscopy and Mass Spectrometry

    PubMed Central

    Nematollahi, Lily A.; Garza-Garcia, Acely; Bechara, Chérine; Esposito, Diego; Morgner, Nina; Robinson, Carol V.; Driscoll, Paul C.

    2015-01-01

    Homotypic death domain (DD)–DD interactions are important in the assembly of oligomeric signaling complexes such as the PIDDosome that acts as a platform for activation of caspase-2-dependent apoptotic signaling. The structure of the PIDDosome core complex exhibits an asymmetric three-layered arrangement containing five PIDD-DDs in one layer, five RAIDD-DDs in a second layer and an additional two RAIDD-DDs. We addressed complex formation between PIDD-DD and RAIDD-DD in solution using heteronuclear nuclear magnetic resonance (NMR) spectroscopy, nanoflow electrospray ionization mass spectrometry and size-exclusion chromatography with multi-angle light scattering. The DDs assemble into complexes displaying molecular masses in the range 130–158 kDa and RAIDD-DD:PIDD-DD stoichiometries of 5:5, 6:5 and 7:5. These data suggest that the crystal structure is representative of only the heaviest species in solution and that two RAIDD-DDs are loosely attached to the 5:5 core. Two-dimensional 1H,15N-NMR experiments exhibited signal loss upon complexation consistent with the formation of high-molecular-weight species. 13C-Methyl-transverse relaxation optimized spectroscopy measurements of the PIDDosome core exhibit signs of differential line broadening, cross-peak splitting and chemical shift heterogeneity that reflect the presence of non-equivalent sites at interfaces within an asymmetric complex. Experiments using a mutant RAIDD-DD that forms a monodisperse 5:5 complex with PIDD-DD show that the spectroscopic signature derives from the quasi- but non-exact equivalent environments of each DD. Since this characteristic was previously demonstrated for the complex between the DDs of CD95 and FADD, the NMR data for this system are consistent with the formation of a structure homologous to the PIDDosome core. PMID:25528640

  16. Flexible stoichiometry and asymmetry of the PIDDosome core complex by heteronuclear NMR spectroscopy and mass spectrometry.

    PubMed

    Nematollahi, Lily A; Garza-Garcia, Acely; Bechara, Chérine; Esposito, Diego; Morgner, Nina; Robinson, Carol V; Driscoll, Paul C

    2015-02-27

    Homotypic death domain (DD)-DD interactions are important in the assembly of oligomeric signaling complexes such as the PIDDosome that acts as a platform for activation of caspase-2-dependent apoptotic signaling. The structure of the PIDDosome core complex exhibits an asymmetric three-layered arrangement containing five PIDD-DDs in one layer, five RAIDD-DDs in a second layer and an additional two RAIDD-DDs. We addressed complex formation between PIDD-DD and RAIDD-DD in solution using heteronuclear nuclear magnetic resonance (NMR) spectroscopy, nanoflow electrospray ionization mass spectrometry and size-exclusion chromatography with multi-angle light scattering. The DDs assemble into complexes displaying molecular masses in the range 130-158kDa and RAIDD-DD:PIDD-DD stoichiometries of 5:5, 6:5 and 7:5. These data suggest that the crystal structure is representative of only the heaviest species in solution and that two RAIDD-DDs are loosely attached to the 5:5 core. Two-dimensional (1)H,(15)N-NMR experiments exhibited signal loss upon complexation consistent with the formation of high-molecular-weight species. (13)C-Methyl-transverse relaxation optimized spectroscopy measurements of the PIDDosome core exhibit signs of differential line broadening, cross-peak splitting and chemical shift heterogeneity that reflect the presence of non-equivalent sites at interfaces within an asymmetric complex. Experiments using a mutant RAIDD-DD that forms a monodisperse 5:5 complex with PIDD-DD show that the spectroscopic signature derives from the quasi- but non-exact equivalent environments of each DD. Since this characteristic was previously demonstrated for the complex between the DDs of CD95 and FADD, the NMR data for this system are consistent with the formation of a structure homologous to the PIDDosome core. PMID:25528640

  17. Dissolution DNP-NMR spectroscopy using galvinoxyl as a polarizing agent

    NASA Astrophysics Data System (ADS)

    Lumata, Lloyd L.; Merritt, Matthew E.; Malloy, Craig R.; Sherry, A. Dean; van Tol, Johan; Song, Likai; Kovacs, Zoltan

    2013-02-01

    The goal of this work was to test feasibility of using galvinoxyl (2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy) as a polarizing agent for dissolution dynamic nuclear polarization (DNP) NMR spectroscopy. We have found that galvinoxyl is reasonably soluble in ethyl acetate, chloroform, or acetone and the solutions formed good glasses when mixed together or with other solvents such as dimethyl sulfoxide. W-band electron spin resonance (ESR) measurements revealed that galvinoxyl has an ESR linewidth D intermediate between that of carbon-centered free radical trityl OX063 and the nitroxide-based 4-oxo-TEMPO, thus the DNP with galvinoxyl for nuclei with low gyromagnetic ratio γ such as 13C and 15N is expected to proceed predominantly via the thermal mixing process. The optimum radical concentration that would afford the highest 13C nuclear polarization (approximately 6% for [1-13C]ethyl acetate) at 3.35 T and 1.4 K was found to be around 40 mM. After dissolution, large liquid-state NMR enhancements were achieved for a number of 13C and 15N compounds with long spin-lattice relaxation time T1. In addition, the hydrophobic galvinoxyl free radical can be easily filtered out from the dissolution liquid when water is used as the solvent. These results indicate that galvinoxyl can be considered as an easily available free radical polarizing agent for routine dissolution DNP-NMR spectroscopy.

  18. Reexamination of C-NMR13 in (TMTTF)2AsF6 : Comparison with infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Hirose, Shinji; Kawamoto, Atsushi; Matsunaga, Noriaki; Nomura, Kazushige; Yamamoto, Kaoru; Yakushi, Kyuya

    2010-05-01

    The charge order (CO) state can be observed by microprobe measurements such as nuclear magnetic resonance (NMR) and infrared spectroscopy. We used the infrared spectroscopy to examine (TMTTF)2AsF6 and confirmed the CO transition seen in previous C13 -NMR studies. However we found the degree of charge disproportionation, Δρ=0.16 , to be smaller than that obtained from the analysis of T1 in C13 -NMR and the redistribution of charge density below spin Peierls transition predicted by C13 -NMR was not observed at low temperature. We estimated the degree of spin disproportionation to be 0.11 from the analysis of the NMR shift in previous NMR studies. This small disproportionation does not require the redistribution of charge density at low temperature. The different behaviors of T1 at charge-rich and charge-poor molecular sites observed by C13 -NMR can be examined by the contribution of the commensurate antiferromagnetic fluctuation with 4kF .

  19. The application of HPLC and microprobe NMR spectroscopy in the identification of metabolites in complex biological matrices.

    PubMed

    Miao, Zhaoxia; Jin, Mengxia; Liu, Xia; Guo, Wei; Jin, Xiangju; Liu, Hongyue; Wang, Yinghong

    2015-05-01

    Nuclear magnetic resonance (NMR)-based metabolomics can be used directly to identify a variety of metabolites in biological fluids and tissues. Metabolite analysis is an important part of life science and metabolomics research. However, the identification of some metabolites using NMR spectroscopy remains a big challenge owing to low abundance or signal overlap. It is important to develop a method to measure these compounds accurately. Two-dimensional NMR spectroscopy, metabolite prediction software packages, and spike-in experiments with authentic standards are often used to solve these problems, but they are costly and time-consuming. In this study, methods were developed to identify metabolites in complex biological mixtures using both high-performance liquid chromatography (HPLC) and off-line microprobe NMR spectroscopy. With use of these methods, 83 and 73 metabolites were identified in Sprague Dawley rat urine and feces, respectively. Among them, 40 and 45 metabolites, respectively, could not be identified with traditional NMR methods. Our research revealed that the combination of HPLC and NMR techniques could significantly improve the accuracy of trace and overlapped metabolite identification, while offering an effective and convenient approach to identify potential biomarkers in complex biological systems. PMID:25814271

  20. 2D IR spectroscopy at 100 kHz utilizing a Mid-IR OPCPA laser source.

    PubMed

    Luther, Bradley M; Tracy, Kathryn M; Gerrity, Michael; Brown, Susannah; Krummel, Amber T

    2016-02-22

    We present a 100 kHz 2D IR spectrometer. The system utilizes a ytterbium all normal dispersion fiber oscillator as a common source for the pump and seed beams of a MgO:PPLN OPCPA. The 1030 nm OPCPA pump is generated by amplification of the oscillator in cryocooled Yb:YAG amplifiers, while the 1.68 μm seed is generated in a OPO pumped by the oscillator. The OPCPA outputs are used in a ZGP DFG stage to generate 4.65 μm pulses. A mid-IR pulse shaper delivers pulse pairs to a 2D IR spectrometer allowing for data collection at 100 kHz. PMID:26907062

  1. Terahertz Spectroscopy of the Bending Vibrations of Acetylene 12C2H2 and 12C2D2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, B.; Pearson, J.

    2009-12-01

    Several fundamental interstellar molecules, e.g., C2H2, CH4 and C3, are completely symmetric molecules and feature no permanent dipole moment and no pure rotation spectrum. As a result they have only previously been observed in the infrared. However, directly observing them with the rest of the molecular column especially when the source is spatially resolved would be very valuable in understanding chemical evolution. Vibrational difference bands provide a means to detect symmetric molecules with microwave precision using terahertz techniques. Herschel, SOFIA and ALMA have the potential to identify a number of vibrational difference bands of light symmetric species. This paper reports laboratory results on 12C2H2 and 12C2D2. Symmetric acetylene isotopologues have two bending modes, the trans bending and the cis bending. Their difference bands are allowed and occur in the microwave, terahertz, and far-infrared wavelengths, with band origins at 3500 GHz for 12C2H2 and 900 GHz for 12C2D2. Twenty 12C2H2 P branch high-J transitions and two hundred and fifty-one 12C2D2 P Q and R branch transitions have been measured in the 0.2 - 1.6 THz region with precision of 50 to 100 kHz. These lines were modeled together with prior data on the pure bending levels. Significantly improved molecular parameters were obtained for 12C2H2 and 12C2D2 with the combined data set, and new frequency and intensity predictions were made to support astrophysics applications. The research was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration. S. Y. was supported by an appointment to the NASA Postdoctoral Program, administrated by Oak Ridge Associated Universities through a contract with NASA.

  2. Four divalent transition metal carboxyarylphosphonate compounds: Hydrothermal synthesis, structural chemistry and generalized 2D FTIR correlation spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Lei, Ran; Chai, Xiaochuan; Mei, Hongxin; Zhang, Hanhui; Chen, Yiping; Sun, Yanqiong

    2010-07-01

    Four divalent transition metal carboxyarylphosphonates, [Ni(4,4'-bipy)H 2L 1(HL 1) 2(H 2O) 2]·2H 2O 1, [Ni 2(4,4'-bipy)(L 2)(OH)(H 2O) 2]·3H 2O 2, Mn(phen) 2(H 2L 1) 23 and Mn(phen)(HL 2) 4 (H 3L 1= p-H 2O 3PCH 2-C 6H 4-COOH, H 3L 2= m-H 2O 3PCH 2-C 6H 4-COOH, 4,4'-bipy=4,4'-bipyridine, phen=1,10-phenanthroline) were synthesized under hydrothermal conditions. 1 features 1D linear chains built from Ni(II) ions bridging 4,4'-bipy. In 2, neighboring Ni 4 cluster units are connected by pairs of H 3L 2 ligands to form 1D double-crankshaft chains, which are interconnected by pairs of 4,4'-bipy into 2D sheets. 3 exhibits 2D supramolecular layers via the R 22(8) ringed hydrogen bonding units. 4 has 1D ladderlike chains, in which the 4-membered rings are cross-linked by the organic moieties of the H 3L 2 ligands. Additionally, 2D FTIR correlation analysis is applied with thermal and magnetic perturbation to clarify the structural changes of functional groups from H 3L 1 and H 3L 2 ligands in the compounds more efficiently.

  3. Discrimination of Basal Cell Carcinoma from Normal Skin Tissue Using High-Resolution Magic Angle Spinning 1H NMR Spectroscopy

    PubMed Central

    Mun, Je-Ho; Lee, Heonho; Yoon, Dahye; Kim, Byung-Soo; Kim, Moon-Bum; Kim, Shukmann

    2016-01-01

    High-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy is a useful tool for investigating the metabolism of various cancers. Basal cell carcinoma (BCC) is the most common skin cancer. However, to our knowledge, data on metabolic profiling of BCC have not been reported in the literature. The objective of the present study was to investigate the metabolic profiling of cutaneous BCC using HR-MAS 1H NMR spectroscopy. HR-MAS 1H NMR spectroscopy was used to analyze the metabolite profile and metabolite intensity of histopathologically confirmed BCC tissues and normal skin tissue (NST) samples. The metabolic intensity normalized to the total spectral intensities in BCC and NST was compared, and multivariate analysis was performed with orthogonal partial least-squares discriminant analysis (OPLS-DA). P values < 0.05 were considered statistically significant. Univariate analysis revealed 9 metabolites that showed statistically significant difference between BCC and NST. In multivariate analysis, the OPLS-DA models built with the HR-MAS NMR metabolic profiles revealed a clear separation of BCC from NST. The receiver operating characteristic curve generated from the results revealed an excellent discrimination of BCC from NST with an area under the curve (AUC) value of 0.961. The present study demonstrated that the metabolite profile and metabolite intensity differ between BCC and NST, and that HR-MAS 1H NMR spectroscopy can be a valuable tool in the diagnosis of BCC. PMID:26934749

  4. The contribution of solid-state NMR spectroscopy to understanding biomineralization: Atomic and molecular structure of bone

    NASA Astrophysics Data System (ADS)

    Duer, Melinda J.

    2015-04-01

    Solid-state NMR spectroscopy has had a major impact on our understanding of the structure of mineralized tissues, in particular bone. Bone exemplifies the organic-inorganic composite structure inherent in mineralized tissues. The organic component of the extracellular matrix in bone is primarily composed of ordered fibrils of collagen triple-helical molecules, in which the inorganic component, calcium phosphate particles, composed of stacks of mineral platelets, are arranged around the fibrils. This perspective argues that key factors in our current structural model of bone mineral have come about through NMR spectroscopy and have yielded the primary information on how the mineral particles interface and bind with the underlying organic matrix. The structure of collagen within the organic matrix of bone or any other structural tissue has yet to be determined, but here too, this perspective shows there has been real progress made through application of solid-state NMR spectroscopy in conjunction with other techniques. In particular, NMR spectroscopy has highlighted the fact that even within these structural proteins, there is considerable dynamics, which suggests that one should be cautious when using inherently static structural models, such as those arising from X-ray diffraction analyses, to gain insight into molecular roles. It is clear that the NMR approach is still in its infancy in this area, and that we can expect many more developments in the future, particularly in understanding the molecular mechanisms of bone diseases and ageing.

  5. Pulsed Field Gradient Selection in Two-Dimensional Magic Angle Spinning NMR Spectroscopy of Dipolar Solids

    NASA Astrophysics Data System (ADS)

    Fritzhanns, Tilo; Hafner, Siegfried; Demco, Dan E.; Spiess, Hans W.; Laukien, Frank H.

    1998-10-01

    The utility of gradient selection in MAS spectroscopy of dipolar solids is explored in two examples. In the first, rotor-synchronized gradients of appropriate strength and duration are applied to select1H double-quantum coherences. The resulting DQ MAS spectrum of adamantane is compared with that acquired by the corresponding phase-cycling technique. As a second example, a1H 2D exchange MAS experiment is performed on an elastomer sample. In this experiment, a gradient is applied to remove undesired coherences that would otherwise distort the spectrum for short mixing times. The diagonal-peak intensities in the resulting spectrum show a linear decrease with increasing mixing time indicating cross-relaxation by slow chain motions as the relevant process. Both types of experiments demonstrate the potential of gradient-selection techniques for MAS spectroscopy of dipolar solids.

  6. No-D NMR (no-deuterium proton NMR) spectroscopy: a simple yet powerful method for analyzing reaction and reagent solutions.

    PubMed

    Hoye, Thomas R; Eklov, Brian M; Ryba, Troy D; Voloshin, Mikhail; Yao, Letitia J

    2004-03-18

    [reaction: see text] The title technique is a convenient and powerful method for directly monitoring or assaying any reaction mixture or reagent solution. Examples of some common processes (Fischer esterification, lithiation, butyllithium/THF compatibility, olefin metathesis, and a quantification assay), each interrogated in its native solvent, are presented. The spectral data are easy to acquire, and the information content makes a compelling case for routine use of No-D NMR spectroscopy. PMID:15012073

  7. Characterization of reactive intermediates by multinuclear diffusion-ordered NMR spectroscopy (DOSY).

    PubMed

    Li, Deyu; Keresztes, Ivan; Hopson, Russell; Williard, Paul G

    2009-02-17

    Nuclear magnetic resonance (NMR) is the most powerful and widely utilized technique for determining molecular structure. Although traditional NMR data analysis involves the correlation of chemical shift, coupling constant, and NOE interactions to specific structural features, a largely overlooked method introduced more than 40 years ago, pulsed gradient spin-echo (PGSE), measures diffusion coefficients of molecules in solution, thus providing their relative particle sizes. In the early 1990s, the PGSE sequence was incorporated into a two-dimensional experiment, dubbed diffusion-ordered NMR spectroscopy (DOSY), in which one dimension represents chemical shift data while the second dimension resolves species by their diffusion properties. This combination provides a powerful tool for identifying individual species in a multicomponent solution, earning the nickname "chromatography by NMR". In this Account, we describe our efforts to utilize DOSY techniques to characterize organometallic reactive intermediates in solution in order to correlate structural data to solid-state crystal structures determined by X-ray diffraction and to discover the role of aggregate formation and solvation states in reaction mechanisms. In 2000, we reported our initial efforts to employ DOSY techniques in the characterization of reactive intermediates such as organolithium aggregates. Since then, we have explored DOSY experiments with various nuclei beyond (1)H, including (6)Li, (7)Li, (11)B, (13)C, and (29)Si. Additionally, we proposed a diffusion coefficient-formula weight relationship to determine formula weight, aggregation number, and solvation state of reactive intermediates. We also introduced an internal reference system to correlate the diffusion properties of unknown reactive intermediates with known inert molecular standards, such as aromatic compounds, terminal olefins, cycloolefins, and tetraalkylsilanes. Furthermore, we utilized DOSY to interpret the role of aggregation number

  8. Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations.

    PubMed

    Yan, Chang; Yuan, Rongfeng; Pfalzgraff, William C; Nishida, Jun; Wang, Lu; Markland, Thomas E; Fayer, Michael D

    2016-05-01

    Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments. PMID:27044113

  9. Four divalent transition metal carboxyarylphosphonate compounds: Hydrothermal synthesis, structural chemistry and generalized 2D FTIR correlation spectroscopy studies

    SciTech Connect

    Lei Ran; Chai Xiaochuan; Mei Hongxin; Zhang Hanhui; Chen Yiping; Sun Yanqiong

    2010-07-15

    Four divalent transition metal carboxyarylphosphonates, [Ni(4,4'-bipy)H{sub 2}L{sup 1}(HL{sup 1}){sub 2}(H{sub 2}O){sub 2}].2H{sub 2}O 1, [Ni{sub 2}(4,4'-bipy)(L{sup 2})(OH)(H{sub 2}O){sub 2}].3H{sub 2}O 2, Mn(phen){sub 2}(H{sub 2}L{sup 1}){sub 2}3 and Mn(phen)(HL{sup 2}) 4 (H{sub 3}L{sup 1}=p-H{sub 2}O{sub 3}PCH{sub 2}-C{sub 6}H{sub 4}-COOH, H{sub 3}L{sup 2}=m-H{sub 2}O{sub 3}PCH{sub 2}-C{sub 6}H{sub 4}-COOH, 4,4'-bipy=4,4'-bipyridine, phen=1,10-phenanthroline) were synthesized under hydrothermal conditions. 1 features 1D linear chains built from Ni(II) ions bridging 4,4'-bipy. In 2, neighboring Ni{sub 4} cluster units are connected by pairs of H{sub 3}L{sup 2} ligands to form 1D double-crankshaft chains, which are interconnected by pairs of 4,4'-bipy into 2D sheets. 3 exhibits 2D supramolecular layers via the R{sub 2}{sup 2}(8) ringed hydrogen bonding units. 4 has 1D ladderlike chains, in which the 4-membered rings are cross-linked by the organic moieties of the H{sub 3}L{sup 2} ligands. Additionally, 2D FTIR correlation analysis is applied with thermal and magnetic perturbation to clarify the structural changes of functional groups from H{sub 3}L{sup 1} and H{sub 3}L{sup 2} ligands in the compounds more efficiently. - Graphical abstract: A series of divalent transition metal carboxyarylphosphonate compounds were synthesized under hydrothermal conditions. The figure displays 2D sheet structure with large windows in compound 2.

  10. Structure and Metabolic-Flow Analysis of Molecular Complexity in a (13) C-Labeled Tree by 2D and 3D NMR.

    PubMed

    Komatsu, Takanori; Ohishi, Risa; Shino, Amiu; Kikuchi, Jun

    2016-05-10

    Improved signal identification for biological small molecules (BSMs) in a mixture was demonstrated by using multidimensional NMR on samples from (13) C-enriched Rhododendron japonicum (59.5 atom%) cultivated in air containing (13) C-labeled carbon dioxide for 14 weeks. The resonance assignment of 386 carbon atoms and 380 hydrogen atoms in the mixture was achieved. 42 BSMs, including eight that were unlisted in the spectral databases, were identified. Comparisons between the experimental values and the (13) C chemical shift values calculated by density functional theory supported the identifications of unlisted BSMs. Tracing the (13) C/(12) C ratio by multidimensional NMR spectra revealed faster and slower turnover ratios of BSMs involved in central metabolism and those categorized as secondary metabolites, respectively. The identification of BSMs and subsequent flow analysis provided insight into the metabolic systems of the plant. PMID:27060701

  11. Two-dimensional correlation spectroscopy (2D-COS) variable selection for near-infrared microscopy discrimination of meat and bone meal in compound feed.

    PubMed

    Lü, Chengxu; Chen, Longjian; Yang, Zengling; Liu, Xian; Han, Lujia

    2014-01-01

    This article presents a novel method for combining auto-peak and cross-peak information for sensitive variable selection in synchronous two-dimensional correlation spectroscopy (2D-COS). This variable selection method is then applied to the case of near-infrared (NIR) microscopy discrimination of meat and bone meal (MBM). This is of important practical value because MBM is currently banned in ruminate animal compound feed. For the 2D-COS analysis, a set of NIR spectroscopy data of compound feed samples (adulterated with varying concentrations of MBM) was pretreated using standard normal variate and detrending (SNVD) and then mapped to the 2D-COS synchronous matrix. For the auto-peak analysis, 12 main sensitive variables were identified at 6852, 6388, 6320, 5788, 5600, 5244, 4900, 4768, 4572, 4336, 4256, and 4192 cm(-1). All these variables were assigned their specific spectral structure and chemical component. For the cross-peak analysis, these variables were divided into two groups, each group containing the six sensitive variables. This grouping resulted in a correlation between the spectral variables that was in accordance with the chemical-component content of the MBM and compound feed. These sensitive variables were then used to build a NIR microscopy discrimination model, which yielded a 97% correct classification. Moreover, this method detected the presence of MBM when its concentration was less than 1% in an adulterated compound feed sample. The concentration-dependent 2D-COS-based variable selection method developed in this study has the unique advantages of (1) introducing an interpretive aspect into variable selection, (2) substantially reducing the complexity of the computations, (3) enabling the transferability of the results to discriminant analysis, and (4) enabling the efficient compression of spectral data. PMID:25061786

  12. 2D IR Spectroscopy using Four-Wave Mixing, Pulse Shaping, and IR Upconversion: A Quantitative Comparison

    PubMed Central

    Rock, William; Li, Yun-Liang; Pagano, Philip; Cheatum, Christopher M.

    2013-01-01

    Recent technological advances have led to major changes in the apparatuses used to collect 2D IR spectra. Pulse shaping offers several advantages including rapid data collection, inherent phase stability, and phase cycling capabilities. Visible array detection via upconversion allows the use of visible detectors that are cheaper, faster, more sensitive, and less noisy than IR detectors. However, despite these advantages, many researchers are reluctant to implement these technologies. Here we present a quantitative study of the S/N of 2D IR spectra collected with a traditional four-wave mixing (FWM) apparatus, with a pulse shaping apparatus, and with visible detection via upconversion to address the question of whether or not weak chromophores at low concentrations are still accessible with such an apparatus. We find that the enhanced averaging capability of the pulse shaping apparatus enables the detection of small signals that would be challenging to measure even with the traditional FWM apparatus, and we demonstrate this ability on a sample of cyanylated dihydrofolate reductase (DHFR). PMID:23687988

  13. Terahertz Spectroscopy and Global Analysis of the Bending Vibrations of ^{12}C_2H_2 and ^{12}C_2D_2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, Brian J.; Pearson, John C.; Pickett, Herbert M.; Lattanzi, Valerio; Walters, Adam

    2009-06-01

    Symmetric molecules have no permanent dipole moment and are undetectable by rotational spectroscopy. Their interstellar observations have previously been limited to mid-infrared vibration-rotation spectroscopy. Although relatively weak, vibrational difference bands provide a means for detection of non polar molecules by terahertz techniques with microwave precision. Herschel, SOFIA, and ALMA have the potential to identify a number of difference bands of light symmetric species, e.g., C_2H_2, CH_4 and C_3. This paper reports the results of the laboratory study on ^{12}C_2H_2 and ^{12}C_2D_2. The symmetric isotopomers of acetylene have two bending modes, the trans bending ν_4 (^1{π}_g), and the cis bending ν_5 (^1{π}_u). For ^{12}C_2H_2, the two bending modes occur at 612 and 729 cm^{-1}, respectively. For ^{12}C_2D_2, the two bending modes occur at 511 and 538 cm^{-1}. The ν_5-ν_4 difference bands are allowed and occur in the microwave, terahertz, and far-infrared wavelengths, with band origins at 117 cm^{-1} (3500 GHz) for ^{12}C_2H_2 and 27 cm^{-1} (900 GHz) for ^{12}C_2D_2. Two hundred and fifty-one ^{12}C_2D_2 transitions, which are from ν_5-ν_4, (ν_5+ν_4)-2ν_4 and 2ν_5-(ν_5+ν_4) bands, have been measured in the 0.2-1.6 THz region, and 202 of them were observed for the first time. The precision of these measurements is estimated to be from 50 kHz to 100 kHz. A multistate analysis was carried out for the bending vibrational modes ν_4 and ν_5 of ^{12}C_2D_2, which includes the lines observed in this work and prior microwave, far-infrared and infrared data on the pure bending levels. Significantly improved molecular parameters were obtained for ^{12}C_2D_2 by adding the new measurements to the old data set which had only 10 lines with microwave measurement precision. The experiments on ^{12}C_2H_2 are in progress and ten P branch lines have been observed. We will present the ^{12}C_2H_2 results to date.

  14. In vivo 31P-NMR spectroscopy of right ventricle in pigs.

    PubMed

    Schwartz, G G; Steinman, S K; Weiner, M W; Matson, G B

    1992-06-01

    The energy metabolism of the right ventricle (RV) in vivo has been largely unexplored. The goal of this study was to develop and implement techniques for in vivo 31P nuclear magnetic resonance (NMR) spectroscopy of the RV free wall. A two-turn, crossover-design elliptical surface coil was constructed to provide high sensitivity across the thin RV wall but minimal sensitivity in the blood-filled RV cavity. In 36 open-chest, anesthetized pigs, 31P spectroscopy of the RV free wall was performed with this coil at a field strength of 2 Tesla. Spectra were obtained from 800 acquisitions in 24 min with an average signal-to-noise ratio of 13.2 for phosphocreatine (PCr). The PCr-to-ATP (PCr/ATP) ratio of porcine RV was 1.42 +/- 0.05 (mean +/- SE), uncorrected for saturation at a repetition time of 1.8 s. With the use of literature values of the time constant of longitudinal relaxation (T1) to correct for partial saturation, the RV PCr/ATP was estimated to lie between 1.7 and 2.3. Decreased RV PCr/ATP was observed during RV ischemia and pressure overload. Thus in vivo 31P spectroscopy of the RV is readily accomplished with an appropriate surface coil and can provide new information about RV energy metabolism. PMID:1621852

  15. Organic solute changes with acidification in Lake Skjervatjern as shown by 1H-NMR spectroscopy

    USGS Publications Warehouse

    Malcolm, R.L.; Hayes, T.

    1994-01-01

    1H-NMR spectroscopy has been found to be a useful tool to establish possible real differences and trends between all natural organic solute fractions (fulvic acids, humic acids, and XAD-4 acids) after acid-rain additions to the Lake Skjervatjern watershed. The proton NMR technique used in this study determined the spectral distribution of nonexchangeable protons among four peaks (aliphatic protons; aliphatic protons on carbon ?? or attached to electronegative groups; protons on carbons attached to O or N heteroatoms; and aromatic protons). Differences of 10% or more in the respective peak areas were considered to represent a real difference. After one year of acidification, fulvic acids decreased 13% (relative) in Peak 3 protons on carbon attached to N and O heteratoms and exhibited a decrease in aromatic protons between 27% and 31%. Humic acids also exhibited an 11% relative decrease in aromatic protons as a result of acidification. After one year of acidification, real changes were shown in three of the four proton assignments in XAD-4 acids. Peak 1 aliphatic protons increased by 14% (relative), Peak 3 protons on carbons attached to O and N heteroatoms decreased by 13% (relative), and aromatic protons (Peak 4) decreased by 35% (relative). Upon acidification, there was a trend in all solutes for aromatic protons to decrease and aliphatic protons to increase. The natural variation in organic solutes as shown in the Control Side B of the lake from 1990 to 1991 is perhaps a small limitation to the same data interpretations of acid rain changes at the Lake Skjervatjern site, but the proton NMR technique shows great promise as an independent scientific tool to detect and support other chemical techniques in establishing organic solute changes with different treatments (i.e., additions of acid rain).

  16. Polarization shaping in the mid-IR and polarization-based balanced heterodyne detection with application to 2D IR spectroscopy

    PubMed Central

    Middleton, Chris T.; Strasfeld, David B.; Zanni, Martin T.

    2010-01-01

    We demonstrate amplitude, phase and polarization shaping of femtosecond mid-IR pulses using a germanium acousto-optical modulator by independently shaping the frequency-dependent amplitudes and phases of two orthogonally polarized pulses which are then collinearly overlapped using a wire-grid polarizer. We use a feedback loop to set and stabilize the relative phase of the orthogonal pulses. We have also used a wire-grid polarizer to implement polarization-based balanced heterodyne detection for improved signal-to-noise of 2D IR spectra collected in a pump-probe geometry. Applications include coherent control of molecular vibrations and improvements in multidimensional IR spectroscopy. PMID:19687931

  17. Multinuclear NMR spectroscopy for differentiation of molecular configurations and solvent properties between acetone and dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Wen, Yuan-Chun; Kuo, Hsiao-Ching; Jia, Hsi-Wei

    2016-04-01

    The differences in molecular configuration and solvent properties between acetone and dimethyl sulfoxide (DMSO) were investigated using the developed technique of 1H, 13C, 17O, and 1H self-diffusion liquid state nuclear magnetic resonance (NMR) spectroscopy. Acetone and DMSO samples in the forms of pure solution, ionic salt-added solution were used to deduce their active sites, relative dipole moments, dielectric constants, and charge separations. The NMR results suggest that acetone is a trigonal planar molecule with a polarized carbonyl double bond, whereas DMSO is a trigonal pyramidal-like molecule with a highly polarized S-O single bond. Both molecules use their oxygen atoms as the active sites to interact other molecules. These different molecular models explain the differences their physical and chemical properties between the two molecules and explain why DMSO is classified as an aprotic but highly dipolar solvent. The results are also in agreement with data obtained using X-ray diffraction, neutron diffraction, and theoretical calculations.

  18. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy.

    PubMed

    Jakes, W; Gerdova, A; Defernez, M; Watson, A D; McCallum, C; Limer, E; Colquhoun, I J; Williamson, D C; Kemsley, E K

    2015-05-15

    This work reports a candidate screening protocol to distinguish beef from horse meat based upon comparison of triglyceride signatures obtained by 60 MHz (1)H NMR spectroscopy. Using a simple chloroform-based extraction, we obtained classic low-field triglyceride spectra from typically a 10 min acquisition time. Peak integration was sufficient to differentiate samples of fresh beef (76 extractions) and horse (62 extractions) using Naïve Bayes classification. Principal component analysis gave a two-dimensional "authentic" beef region (p=0.001) against which further spectra could be compared. This model was challenged using a subset of 23 freeze-thawed training samples. The outcomes indicated that storing samples by freezing does not adversely affect the analysis. Of a further collection of extractions from previously unseen samples, 90/91 beef spectra were classified as authentic, and 16/16 horse spectra as non-authentic. We conclude that 60 MHz (1)H NMR represents a feasible high-throughput approach for screening raw meat. PMID:25577043

  19. Characterization of alkyl carbon in forest soils by CPMAS 13C NMR spectroscopy and dipolar dephasing

    USGS Publications Warehouse

    Kogel-Knabner, I.; Hatcher, P.G.

    1989-01-01

    Samples obtained from forest soils at different stages of decomposition were treated sequentially with chloroform/methanol (extraction of lipids), sulfuric acid (hydrolysis), and sodium chlorite (delignification) to enrich them in refractory alkyl carbon. As revealed by NMR spectroscopy, this treatment yielded residues with high contents of alkyl carbon. In the NMR spectra of residues obtained from litter samples, resonances for carbohydrates are also present, indicating that these carbohydrates are tightly bound to the alkyl carbon structures. During decomposition in the soils this resistant carbohydrate fraction is lost almost completely. In the litter samples the alkyl carbon shows a dipolar dephasing behavior indicative of two structural components, a rigid and a more mobile component. As depth and decomposition increase, only the rigid component is observed. This fact could be due to selective degradation of the mobile component or to changes in molecular mobility during decomposition, e.g., because of an increase in cross linking or contact with the mineral matter of the soil.

  20. The Interaction between tRNALys3 and the Primer Activation Signal Deciphered by NMR Spectroscopy

    PubMed Central

    Brachet, Franck; Tisne, Carine

    2013-01-01

    The initiation of reverse transcription of the human immunodeficiency virus type 1 (HIV-1) requires the opening of the three-dimensional structure of the primer tRNALys3 for its annealing to the viral RNA at the primer binding site (PBS). Despite the fact that the result of this rearrangement is thermodynamically more stable, there is a high-energy barrier that requires the chaperoning activity of the viral nucleocapsid protein. In addition to the nucleotide complementarity to the PBS, several regions of tRNALys3 have been described as interacting with the viral genomic RNA. Among these sequences, a sequence of the viral genome called PAS for “primer activation signal” was proposed to interact with the T-arm of tRNALys3, this interaction stimulating the initiation of reverse transcription. In this report, we investigate the formation of this additional interaction with NMR spectroscopy, using a simple system composed of the primer tRNALys3, the 18 nucleotides of the PBS, the PAS (8 nucleotides) encompassed or not in a hairpin structure, and the nucleocapsid protein. Our NMR study provides molecular evidence of the existence of this interaction and highlights the role of the nucleocapsid protein in promoting this additional RNA-RNA annealing. This study presents the first direct observation at a single base-pair resolution of the PAS/anti-PAS association, which has been proposed to be involved in the chronological regulation of the reverse transcription. PMID:23762248