NMR Signals (nmr + signal)

Distribution by Scientific Domains
Distribution within Chemistry

Terms modified by NMR Signals

  • nmr signal assignment

  • Selected Abstracts

    NMR diffusion measurements under chemical exchange between sites involving a large chemical shift difference

    S. Leclerc
    Abstract This study concerns the thallium-205 cation in aqueous solution in the presence of a calixarene molecule. Although the measurement of the self-diffusion coefficient of pure thallium (without calixarene in the aqueous solution) does not pose any particular problem, major difficulties are encountered with the standard method using gradient strength increment as soon as thallium is partly complexed by calixarene. With static magnetic field gradients, the NMR signal is so weak that it prevents any reliable measurement, whereas radio frequency (rf) field gradients lead to an unrealistic value of the diffusion coefficient. This failure is explained by the fact that thallium is in fast exchange between two sites (complexed and free thallium) thus exhibiting a single NMR signal although, in the course of the experiment, two signals, with an important difference in resonance frequencies (due to the large thallium chemical shift range), are effectively involved. With the objective to understand these quite unexpected observations, the theory underlying NMR diffusion experiments is first reviewed, and criteria of fast exchange are discussed for three parameters: chemical shifts, relaxation rates, and diffusion coefficients. It turns out that off-resonance effects are responsible for unwanted defocusing due to rf pulses in the static magnetic field gradient method and for time-dependent gradients in the rf field gradient method. Concerning the latter, a remedy is proposed which consists in applying the stronger gradient and incrementing the gradient pulse durations. After correction for relaxation, the expected value of the diffusion coefficient is retrieved. © 2010 Wiley Periodicals, Inc. Concepts Magn Reson Part A 36A: 127,137, 2010. [source]

    The origins and present status of the radio wave controversy in NMR

    D.I. Hoult
    Abstract The origins, history, and present status of the controversy surrounding a quantum description of the NMR signal as being due to radio waves are traced. With the Principle of Relativity and Coulomb's Law as formal starting points and the minimum of mathematics needed for understanding, the derivation of a classical electromagnetic theory of signal reception is first given. The agreement between that classical theory and a recent NMR experiment is then presented, leading to proof that, except for the highest field imaging experiments, there is no significant contribution of radio waves to the signal. Attention is drawn to the very different properties of the near and far energy, momenta, and fields inherent in the derivation. The role of the Correspondence Principle in formulating a quantum description is then emphasized and it is shown that the standard NMR interpretation of Dicke's theory of coherent spontaneous emission,that the latter is responsible for the NMR signal,cannot be correct. Finally, the author speculates on some of the intriguing relationships found in the classical electrodynamics of NMR signal reception and attempts to relate them to a common quantum electrodynamic precept of near field interaction: that the free induction decay voltage present at the terminals of an open-circuit receiving coil is based on an exchange of virtual photons between the nuclei in a sample and the free electrons in a receiving coil. © 2009 Crown in the right of Canada. Concepts Magn Reson Part A 34A: 193,216, 2009. [source]

    Analysis of b -value calculations in diffusion weighted and diffusion tensor imaging

    Daniel Güllmar
    Abstract Diffusion weighted imaging has opened new diagnostic possibilities by using microscopic diffusion of water molecules as a means of image contrast. The directional dependence of diffusion has led to the development of diffusion tensor imaging, which allows us to characterize microscopic tissue geometry. The link between the measured NMR signal and the self-diffusion tensor is established by the so-called b matrices that depend on the gradient's direction, strength, and timing. However, in the calculation of b -matrix elements, the influence of imaging gradients on each element of the b matrix is often neglected. This may cause errors, which in turn leads to an incorrect extraction of diffusion coefficients. In cases where the imaging gradients are high (high spatial resolution), these errors may be substantial. Using a generic pulsed gradient spin-echo (PGSE) imaging sequence, the effects of neglecting the imaging gradients on the b -matrix calculation are demonstrated. By measuring an isotropic phantom with this sequence it can be analytically as well as experimentally shown that large deviations in single b -matrix elements are generated. These deviations are obtained by applying the diffusion weighting in the readout direction of the imaging dimension in combination with relatively large imaging gradients. The systematic errors can be avoided by a full b -matrix calculation considering all the gradients of the sequence or by generating cross-term free signals using the geometric average of two diffusion weighted images with opposite polarity. The importance of calculating the exact b matrices by the proposed methods is based on the fact that more precise diffusion parameters are obtained for extracting correct property maps, such as fractional anisotropy, volume ratio, or conductivity tensor maps. © 2005 Wiley Periodicals, Inc. Concepts Magn Reson Part A 25A: 53,66, 2005 [source]

    Quantitative solid-state 13C NMR spectroscopy of organic matter fractions in lowland rice soils

    R. J. Smernik
    Summary Spin counting on solid-state 13C cross-polarization (CP) nuclear magnetic resonance (NMR) spectra of two humic fractions isolated from tropical lowland soils showed that only 32,81% of potential 13C NMR signal was detected. The observability of 13C NMR signal (Cobs) was higher in the mobile humic acid (MHA) than in the calcium humate (CaHA) fraction, and increased with increasing intensity of irrigated rice cropping. NMR observability appeared to be related to the nature of the organic carbon, with phenol- and methoxyl-rich samples having the higher values of Cobs. The Bloch decay (BD) technique provided more quantitatively reliable 13C NMR spectra, as evidenced by values of Cobs in the range 91,100% for seven of the eight humic fractions studied. The BD spectra contained considerably more aryl and carbonyl signal, and less O,alkyl and alkyl signal, with the greatest differences between CP and BD spectra observed for the samples with low Cobs(CP). The causes of low CP observability were investigated using the spectral editing technique RESTORE ( REstoration of Spectra via TCH and T One Rho (T1,H) Editing). Rapid T1,H relaxation was found to be primarily responsible for the under-representation of carbonyl carbon, whereas inefficient cross-polarization was primarily responsible for the under-representation of aryl carbon in CP spectra. Proton NMR relaxation rates T1H and T1,H were found to correlate with other NMR properties and also with cropping management. Non-uniform rates of T1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra. [source]

    The analysis of pH-dependent protonated conformers of 1-hydroxyethylidene-1,1-diphosphonic acid by means of FT-Raman spectroscopy, multivariate curve resolution and DFT modelling

    Werner Barnard
    Abstract 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP) solutions in the pH range 0.98,13.00 were analysed using FT-Raman spectroscopy and 31P and 23Na NMR spectroscopy. Vibrational bands for different protonated species were observed in the Raman spectra, whereas only a single NMR signal that shifted with pH was observed for all samples over the entire pH range. No significant shift in the 23Na NMR signal was observed, confirming that formation of Na+(aq) complexes did not take place; hence, no interference with the different protonated forms of HEDP occurred. Vibrational bands were assigned using density functional theory(DFT)-calculated spectra of the most likely conformers in solution. Multivariate curve resolution was performed on the Raman spectra in the region containing the PO stretching vibrations to determine the number of protonated species formed over the entire pH range. Chemometric analysis compares very favourably with the experimental species distribution diagram which was generated using the reported log KH values. Copyright © 2009 John Wiley & Sons, Ltd. [source]

    Kinetics of Demixing and Remixing Transitions in Aqueous Solutions of Poly(N -isopropylacrylamide): A Temperature-Jump 1H NMR Study

    Pavel V. Yushmanov
    Abstract Summary: The time course of the coil-to-globule collapse and intermolecular aggregation of poly(N -isopropylacrylamide) in aqueous solution upon exceeding the lower critical solution temperature (LCST) are investigated by temperature-jump 1H NMR spectroscopy. After the temperature jump, we record the time dependences of (i) the mobile fraction of the polymer chain as revealed by the intensity of the liquid-like NMR signal, (ii) the local mobility of those chains as revealed by the transverse relaxation time T2, and (iii) their self-diffusion coefficient D. The same data are also reported at their temperature-dependent long-time limits. The results suggest a sudden, faster than one second, collapse and intermolecular aggregation into globules and a slower reorganization/redistribution of the individual chains among and within the globular and mobile states. We found that all molecular changes are reversible if the temperature remains less than ca. 6,8 K above the LCST for less than a few minutes; under those conditions, experiments upon sudden temperature quench below the LCST show that the aggregates disintegrate and swell into coils in less than a few seconds. 1H NMR signal intensity of the methyl groups of 1 wt.-% PNIPAM dissolved in 0.1 M NaCl solution in D2O in a temperature-jump experiment from 300 to 312 K. The data were recorded by the 90°,,,(180°,2, -)n -detection of the CPMG pulse sequence. [source]

    Quantitative determination of SH groups using 19F NMR spectroscopy and disulfide of 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid

    Dmitrii I. Potapenko
    Abstract A new method of measurement of thiol concentration by 19F NMR spectroscopy is developed. The method is based on the detection of products of the exchange reaction of thiols with a newly synthesized fluorinated disulfide, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid (BSSB). A significant broadening of the 19F NMR signal of BSSB in the presence of thiols was observed and attributed to the exchange reaction between the parent disulfide and 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid. The rate constant for this reaction was found to be equal to (63 ± 11) × 103 M,1 s,1 at pH 7.0. The method was applied for the measurement of concentration of glutathione and albumin in rat blood. Copyright © 2005 John Wiley & Sons, Ltd. [source]

    A simple approach for phase-modulated single-scan 2D NMR spectroscopy

    Nikolas Salisbury Andersen
    Abstract Conventional NMR spectroscopy techniques require long acquisition times due to the recovery time between the repeated excitations necessary for each increment of the evolution times in the indirectly detected dimensions. Here we outline a pulse sequence element for gradient-assisted ultrafast multidimensional NMR spectroscopy using frequency-modulated ,chirp' pulses to generate phase-modulated magnetization in an indirectly detected spectral dimension. The potential of this sequence element is demonstrated by acquiring a correlation spectroscopy (COSY) spectrum in 96 ms. This new pulse sequence element is an extension of ultrafast spectroscopy techniques based on the generation of amplitude modulation of the NMR signal in the indirectly detected spectral dimensions. The use of phase modulation instead of amplitude modulation helps broaden the applicability and may provide an increase of sensitivity in some experiments due to the ability to distinguish between positive and negative frequency offsets relative to the carrier frequency of the sequence element. Copyright © 2005 John Wiley & Sons, Ltd. [source]

    Distinguishing multiple chemotaxis Y protein conformations with laser-polarized 129Xe NMR

    PROTEIN SCIENCE, Issue 4 2005
    Thomas J. Lowery
    Abstract The chemical shift of the 129Xe NMR signal has been shown to be extremely sensitive to the local environment around the atom and has been used to follow processes such as ligand binding by bacterial periplasmic binding proteins. Here we show that the 129Xe shift can sense more subtle changes: magnesium binding, BeF3, activation, and peptide binding by the Escherichia coli chemotaxis Y protein. 1H- 15N correlation spectroscopy and X-ray crystallography were used to identify two xenon-binding cavities in CheY that are primarily responsible for the shift changes. One site is near the active site, and the other is near the peptide binding site. [source]

    Protein dynamics of bovine dentin phosphophoryn

    K.J. Cross
    Abstract:, Bovine dentin phosphophoryn (BDP), a protein rich in aspartyl (Asp) and o -phosphoseryl [Ser(P)] residues, is synthesized by odontoblasts and believed to be involved in matrix-mediated biomineralization of dentin. The elucidation of the structure,function relationship of phosphophoryn has been a challenge because of its high-molecular weight, high negative charge, repetitive sequence, and lability. We have used the dynamic behavior of the 1H NMR signal at 600 MHz to provide insight into the molecular dynamics of phosphophoryn. Our results indicate that phosphophoryn is a molecule of uniformly high mobility, thus belonging to a recently identified class of intrinsically disordered proteins that are characterized by sequences of low complexity and rich in polar and charged residues. The significance of our results is that phosphophoryn, because of its uniform nature has the potential to be replaced by biomimetic synthetic peptide analogs that together with amorphous calcium phosphate may lead to the development of novel, nontoxic, apatite-based dental restorative materials. [source]

    Use of (S)-BINOL as NMR chiral solvating agent for the enantiodiscrimination of omeprazole and its analogs

    CHIRALITY, Issue 5 2010
    Jordi Redondo
    Abstract The application of (S)-1,1,-binaphthyl-2,2,-diol as NMR chiral solvating agent (CSA) for omeprazole, and three of its analogs (lanso-, panto-, and rabe-prazole) was investigated. The formation of diastereomeric host,guest complexes in solution between the CSA and the racemic substrates produced sufficient NMR signal splitting for the determination of enantiomeric excesses by 1H- or 19F-NMR spectroscopy. Using of hydrophobic deuterated solvents was mandatory for obtaining good enantiodiscrimination, thus suggesting the importance of intermolecular hydrogen bonds in the stabilization of the complexes. The method was applied to the fast quantification of the enantiomeric purity of in-process samples of S -omeprazole. Chirality, 2010. © 2009 Wiley-Liss, Inc. [source]

    On the inversion of multicomponent NMR relaxation and diffusion decays in heterogeneous systems

    Raffaele Lamanna
    Abstract The analysis of the decay of NMR signals in heterogeneous samples requires the solution of an ill-posed inverse problem to evaluate the distributions of relaxation and diffusion parameters. Laplace transform is the most widely accepted algorithm used to describe the NMR decay in heterogeneous systems. In this article we suggest that a superposition of Fredholm integrals, with different kernels, is a more suitable model for samples in which liquid and solid-like phases are both present. In addition, some algorithms for the inversion of Laplace and Fredholm inverse problems are illustrated. The quadrature methods and regularization function in connection with the use of nonlinear discretization grids are also discussed. The described inversion algorithms are tested on simulated and experimental data, and the role of noise is discussed. © 2005 Wiley Periodicals, Inc. Concepts Magn Reson Part A 26A: 78,90, 2005 [source]

    N -(Aryl)picolinamide Complexes of Ruthenium: Usual Coordination and Strategic Cyclometalation

    Sumon Nag
    Abstract Reaction of five N -(4- R -phenyl)picolinamides (R = OCH3, CH3, H, Cl, and NO2) with [Ru(PPh3)2(CO)2Cl2] in refluxing 2-methoxyethanol in the presence of a base (NEt3) affords two geometrical isomers of a group of complexes (1-R and 2-R), each of which contains an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphanes, a carbonyl, and a hydride. Similar reaction of N -(naphthyl)picolinamide with [Ru(PPh3)2(CO)2Cl2] affords an organometallic complex, 3, in which the amide ligand is coordinated to the metal center, by C,H activation of the naphthyl ring at the 8-position, as a dianionic tridentate N,N,C donor along with two triphenylphosphanes and one carbonyl. Structures of the 1-OCH3, 2-CH3, and 3 complexes have been determined by X-ray crystallography. In all the complexes the two triphenylphosphanes are trans. In the 1-R complexes the hydride is trans to the pyridine nitrogen and in the 2-R complexes it is trans to the amide-nitrogen. All the complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a RuII,RuIII oxidation within 0.71,0.93 V versus SCE. An oxidation and a reduction of the coordinated amide ligand are also observed within 1.29,1.69 V versus SCE and ,1.02 to ,1.21 V versus SCE respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

    Complexes of Bidentate Phosphane Selenide Ligands with Mesitylenetellurenyl Iodide and with Tellurium Diiodide,

    Cristian G. Hrib
    Abstract Bis(diphenylphosphanyl)methane diselenide (dppmSe2, 1) and bis(diphenylphosphanyl)ethane diselenide (dppeSe2, 2) reacted with 2 equiv. Br2 or I2 to form the insoluble solid products, dppm(SeX2)2 (X = Br, 3; X = I, 4) and dppe(SeX2)2 (X = Br, 5; X = I, 6). However, using the iodine-like electrophile mesitylenetellurenyl iodide (MesTeI, 7), fairly soluble complexes, dppmSe2[Te(I)Mes]2 (8) and dppeSe2[Te(I)Mes]2 (9), were obtained. Complexes 8 and 9 contain two T-shaped (10-Te-3) Se,Te(Mes),I moieties bridged by dppm or dppe; solid 9 exhibits intermolecular soft,soft interactions between approximately linear Se,Te,I units. In a side reaction accompanying the crystallisation of complex 8, or by the reaction of 1 with Te and I2, a chelate complex dppmSe2TeI2 (10) was formed. Fortuitously, a crystal of the related compound dppeSe2TeI2 (11) was also obtained. In 10, a square planar cis -Se2TeI2 group is part of a six-membered ring, and 11 is a coordination polymer with trans -Se2TeI2 moieties bridged by dppe. Averaged 31P- and 77Se NMR signals including 77Se,31P couplings, together with broad 125Te NMR singlets indicate phosphane selenide ligand exchange in solution, that is, the kinetically labile behaviour of complexes 8 and 9. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

    Reaction of 1,3,5-Triazacyclohexanes with TiCl4: Formation of Cationic Complexes

    Randolf D. Köhn
    Abstract N -substituted 1,3,5-triazacyclohexanes [R3TAC; R = cyclohexyl, p -fluorobenzyl or Ph(CH2)n (n = 1, 2, 3)] react with excess TiCl4 to give the corresponding cationic ,3 complexes [(R3TAC)TiCl3][Ti2Cl9]. Attempts to prepare complexes with titanium-free anions at lower Ti:R3TAC ratio or with added Me3SiOTf lead to the same cations with [Ti2Cl10]2, and [Ti2Cl8(OTf)], anions. Five complexes as well as (p -fluorobenzyl)3TAC have been characterised by X-ray crystallography. The ring C,H bonds engage in hydrogen bonding interactions in the crystals and strongly solvent and anion dependent 1H NMR signals are detected in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

    Pyrazolate-Based Dinucleating Ligands in L2M2 Scaffolds: Effects of Bulky Substituents and Coligands on Structures and M···H,C Interactions

    Jens C. Röder
    Abstract A series of nickel(II) and palladium(II) complexes [L2M2]2+ have been prepared and structurally characterized, where L is a pyrazolate ligand with bulky 2,6-dimethyl- or 2,6-di(isopropyl)anilinomethyl side arms. Coordinating counter anions such as chloride can bind to axial sites of the dinickel species in a solvent-dependent process, giving rise to five-coordinate high-spin metal ions. In the case of weakly coordinating anions, the metal ions are found in roughly square-planar environments, and the structures are governed by the tendency of the bulky aryl groups to avoid each other, which forces the methyl or isopropyl substituents in the aryl 2- and 6-positions to approach the metal ions from the axial directions. This leads to drastic low-field shifts of the respective 1H NMR signals, e.g. , = 7.86 ppm for the isopropyl ,CH which comes in close proximity to the low-spin nickel(II) center. The relevance of such low-field NMR resonances of protons close to the axial sites of d8 metal ions for possible three-center four-electron M···H,C hydrogen bonds involving the filled d orbital of the metal ion is discussed. In the present case, attractive M···H interactions are assumed to be of no major significance. This was corroborated by the structure of a further [L2Ni2]2+ type complex where the anilinomethyl side arms bear only a single 2-isopropyl group, which was found rotated away from the metal. Additional spectroscopic and electrochemical properties of the various complexes are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

    NMR Quantification of Tautomeric Populations in Biogenic Purine Bases

    Abstract Purine bases such as purine, adenine, hypoxanthine, and mercaptopurine are known to exist in several tautomeric forms. Characterization of their tautomeric equilibria is important not only for predicting the regioselectivity of their N -alkylation reactions, but also for gaining knowledge of the patterns with which these compounds of significant biological activity form hydrogen bonds with their biological targets. The tautomeric equilibria of purine and some purine derivatives in methanol and N,N -dimethylformamide solutions were investigated by low-temperature 1H and 13C NMR spectroscopy. The N(7)H and N(9)H tautomeric forms were quantified by integrating the individual 1H NMR signals at low temperatures. The Gibbs free energy differences were calculated and the effects of substitution on the N(7)H/N(9)H ratio discussed. A previously published theoretically predicted mechanism of the tautomeric exchange is compared with our measurements in deuteriated solvents. The influence of concentration on the temperature of coalescence indicates that supramolecular clusters play a significant role in this proton transfer process. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

    1,3-Diethynylallenes: Stable Monomers, Length-Defined Oligomers, Asymmetric Synthesis, and Optical Resolution

    Matthijs K. J. ter Wiel
    Abstract A series of differently substituted 1,3-diethynylallenes (DEAs) have been synthesized, confirming that the previously introduced construction protocols tolerate a variety of functional groups. The new DEAs bear at least one polar group to facilitate enantiomer separations on chiral stationary phases and to allow further functionalization. They are thermally and environmentally stable compounds since bulky substituents next to the cumulene moiety suppress the tendency to undergo [2+2] cyclodimerization. A series of length-defined oligomers were obtained as mixtures of stereoisomers by oxidative coupling of a monomeric DEA under Glaser,Hay conditions. The electronic absorption data indicate a lack of extended ,-electron conjugation across the oligomeric backbone due to the orthogonality of the allenic ,-systems. Remarkably, even complex mixtures of stereoisomers only yield one single set of NMR signals, which underlines the low stereodifferentiation in acyclic allenoacetylenic structures. Optical resolution of DEAs represents an amazing challenge, and preliminary results on the analytical level are reported. Asymmetric synthesis by Pd-mediated SN2,-type cross-coupling of an alkyne to an optically pure bispropargylic precursor opens another promising route to optically active allenes with stereoselectivities currently reaching up to 78,% ee. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

    Effect of residual vanadyl ions on the spectroscopic analysis of humic acids: a multivariate approach

    E. H. Novotny
    Summary In a study of the vanadyl (VO2+)-humic acids system, the residual vanadyl ion suppressed fluorescence and specific electron paramagnetic resonance (EPR) and NMR signals. In the case of NMR, the proton rotating frame relaxation times (T1,H) indicate that this suppression is due to an inefficient H-C cross polarization, which is a consequence of a shortening of T1,H. Principal components analysis (PCA) facilitated the isolation of the effect of the VO2+ ion and indicated that the organic free radical signal was due to at least two paramagnetic centres and that the VO2+ ion preferentially suppressed the species whose electronic density is delocalized over O atoms (greater g -factor). Additionally, the newly obtained variables (principal components , PC) indicated that, as the result of the more intense tillage a relative increase occurred in the accumulation of: (i) recalcitrant structures; (ii) lignin and long-chain alkyl structures; and (iii) organic free radicals with smaller g -factors. [source]

    Comparison of DNA Complex Formation Behaviour for Two Closely Related Lexitropsin Analogues


    Abstract Two closely related lexitropsin analogues that differ only in the form of the ,headgroup' functionality (CHO (for 1) vs. Ac (for 2)) have been studied in their DNA-binding capacity for the sequence d(GCATATATGC) using 1H-NMR spectroscopy. DNA-Complex formation for the CHO derivative was apparent from the observation of new NMR signals on titration of DNA with ligand. Detailed investigation and assignment of the data for a ligand/DNA-duplex ratio of 2,:,1 clearly delineated the structure as one associated with the ,minor groove' class of DNA complexes. The structure of the complex was determined on the basis of the acquired NMR data. Features characteristic of typical 2,:,1 minor-groove complexes were apparent. In a similar experimental approach, the Ac analogue ligand,DNA binding response was investigated. Despite the close similarity in chemical structure to the CHO case, the Ac analogue was found to produce NMR data of a much poorer quality. This was attributed to more rapid on/off chemical exchange equilibrium between ligand and DNA. From close analysis and comparison of the NMR data for the ,Ac' and ,CHO' headgroup ligand,DNA complexes, it was possible to ascertain that the same type of complex formed in each case but with different relative binding constants. Consideration of the nature and form of these complexes has been made with reference to a previously determined structure from our laboratory for the related lexitropsin analogue thiazotropsin A. [source]

    NMR Conformational Analysis and Theoretical Calculations for 2-Aryl- 1,3-dihydroxy-4,4,5,5-tetramethylimidazolidines

    Conformational studies of 1,3-dihydroxy-4,4,5,5-tetramethyl-2-(pyridin-1-yl)imidazolidine (1a) and 1,3-dihydroxy-4,4,5,5-tetramethyl-2-(pyridin-3-yl)imidazolidine (1b), carried out by using 1D 1H- and 13C-NMR and 2D HMQC, HMBC, and NOESY experiments and with the aid of theoretical calculations, indicate that the OH groups are trans to the pyridinyl substituent. Because the two 1H-NMR signals of the Me groups are distinguishable and do not change between 290 and 380,K, it is proposed that 1a and 1b have each only one conformation in this temperature range. This behavior was not found with 1,3-dihydroxy-4,4,5,5-tetramethyl-2-(pyridin-2-yl)imidazolidine (1c) because its Me 1H-NMR signals cross over at 300,K. Hence, more than one conformation must be present, beyond those produced by simple inversions. Theoretical calculations including temperature and solvent effects were performed to provide further information on the conformational analysis and to help to assign the NMR data. The combination of NMR measurements and quantum-chemical calculations is shown to be a very promising strategy for conformational analysis studies in solution. [source]

    Synthesis and structure of some imines containing furoxan ring derived from isosafrole

    Nguyen Huu Dinh
    A series of 14 imines containing furoxan and benzene rings has been prepared starting from isosafrole. The structure of reported compounds have been confirmed by elemental analysis, EI MS, UV, IR, and NMR spectroscopy. It is shown that, on treatment with Na2S2O4, the nitro group on the benzene ring was reduced to amino group, but the N,O group of the furoxan ring was not. The 1H- and 13C NMR signals are assigned based on their spin-spin splitting patterns, in some cases, NOESY and HMBC spectra are used. The NOESY spectra indicate that for reported imines, the benzene and the furoxan rings could not be co-planar; the imine group has E -configuration. [source]

    Fingerprinting Analysis of Rhizoma Chuanxiong of Commercial Types using 1H Nuclear Magnetic Resonance Spectroscopy and High Performance Liquid Chromatography Method

    Hai-Lin Qin
    Abstract The 1H nuclear magnetic resonance (1H NMR) fingerprints of fractionated non-polar extracts (control substance for a plant drug (CSPD) A) from Rhizoma chuanxiong, the rhizomes of Ligusticum chuanxiong Hort., of seven specimens from different sources were measured on Fourier Transform (FT)-NMR spectrometer and assigned by comparing them with the 1H NMR spectra of the isolated pure compounds. The 1H NMR fingerprints showed exclusively characteristic resonance signals of the major special constituents of the plant. Although the differences in the relative intensity of the 1H NMR signals due to a discrepancy in the ratio of the major constituents among these samples could be confirmed by high performance liquid chromatography analysis, the general features of the 1H NMR fingerprint established for an authentic sample of the rhizomes of L. chuanxiong exhibited exclusive data from those special compounds and can be used for authenticating L. Chuanxiong species. [source]

    1H and 13C NMR conformational study of 2-(benzotriazol-1-yl)-substituted tetrahydrofurans

    Alan R. Katritzky
    Abstract Assignments of the proton and carbon NMR signals for 2-(benzotriazol-1-yl)tetrahydrofurans 1,6 are based on 1H,1H COSY, NOESY, 1H,13C heteronuclear HETCOR, 1H,13C heteronuclear long-range HETCOR-LR and nuclear Overhauser enhancement experiments, and supported by selective spin decoupling experiments. The electronic and steric effects of the 2-benzotriazolyl substituent on the 1H and 13C NMR chemical shifts are evaluated and discussed. Conformational isomers cis and trans are distinguished by the magnitude of the J(H,2,H,3) coupling constant, by one-bond 1J(C,2, H,2) coupling constants and by 13C chemical shifts of the C-2 anomeric carbon. The benzotriazol-1-yl group prefers the pseudo-axial orientation in each of 1,6. The stereochemistry and conformation of 6 are rigorously demonstrated by an x-ray structure. Copyright © 2003 John Wiley & Sons, Ltd. [source]

    Characterization of Phase Separation and Thermal History Effects in Magnesium Silicate Glass Fibers by Nuclear Magnetic Resonance Spectroscopy

    Jonathan F. Stebbins
    Liquid,liquid immiscibility, leading to the separation of silica-rich and silica-poor domains, is a common phenomenon in binary silicate glasses, but can be difficult to detect and characterize when rapid cooling results in nano-scale domain dimensions. 29Si nuclear magnetic resonance (NMR) spectroscopy can be very useful for detecting such phase separation, because the exclusion of paramagnetic impurity ions from the silica-rich regions can greatly slow their spin-lattice relaxation rates. Properly designed experiments can therefore largely isolate the NMR signals from high-silica and low-silica domains, and thus provide information about their proportions, compositions, and short- to intermediate-range structures. We demonstrate this approach here for fiber glasses that are predominantly magnesium, or calcium-magnesium silicates, with minor contents of alumina. For bulk compositions within the known region of stable liquid immiscibility, phase separation occurs even when extremely rapid cooling yields fibers less than 1 ,m in mean diameter. Slower cooling increases the extent of separation, while the addition of small amounts of alumina reduces it. [source]

    Investigation of the correlations between 19F and 1H NMR signals for various mono- and di-substituted octafluoro[2.2]paracyclophanes

    Alex J. Roche
    Abstract A selection of mono- and pseudo ortho di-substituted octafluoro[2.2]paracyclophane derivatives were analyzed using 19F- 1H HOESY, 1H COSY and 19F COSY techniques. This resulted in the unambiguous assignment of the 19F and 1H NMR resonances, and also revealed interesting solvent effects and noteworthy coupling patterns for various JHH, JHF, and JFF interactions, including observable through bond 7JFF and 8JFF couplings. For the four mono-substituted derivatives, the assignments were achieved through the combination of 19F- 1H HOESY, 1H COSY and 19F COSY techniques. The C2 symmetry of the six pseudo ortho di-substituted derivatives that were examined produced simplified spectra, and careful inspection of the characteristic 1H coupling patterns led to the assignment of 1H signals. Therefore only 19F- 1H HOESY experiments were required to complete the assignments for those molecules. Refinements and alternative strategies for previous protocols are presented for the molecules that were less responsive to nuclear Overhauser effect (nOe) experiments. Copyright © 2009 John Wiley & Sons, Ltd. [source]

    Parahydrogen induced polarization of barbituric acid derivatives: 1H hyperpolarization studies

    Meike Roth
    Abstract Homogeneous hydrogenation of barbituric acid derivatives with parahydrogen yields a substantial increase of the 1H NMR signals of the reaction products. These physiologically relevant compounds were hydrogenated at both ambient and elevated temperatures and pressures using a standard cationic rhodium catalyst. The resulting nonthermal nuclear spin polarization (hyperpolarization) is limited by the spin,lattice relaxation time T1 of the corresponding nuclei in the products, being shorter than the time constant of the hydrogenation. The signal-to-noise ratio of the NMR spectra could be further increased upon signal averaging the antiphase PHIP signals of 25 successive scans following 30° pulse experiments and a delay of 10 s. Copyright © 2008 John Wiley & Sons, Ltd. [source]

    Studying porous materials with krypton-83 NMR spectroscopy

    Zackary I. Cleveland
    Abstract This report is the first review of 83Kr nuclear magnetic resonance as a new and promising technique for exploring the surfaces of solid materials. In contrast to the spin I = 1/2 nucleus of 129Xe, 83Kr has a nuclear spin of I = 9/2 and therefore possesses a nuclear electric quadrupole moment. Interactions of the quadrupole moment with the electronic environment are modulated by surface adsorption processes and therefore affect the 83Kr relaxation rate and spectral lineshape. These effects are much more sensitive probes for surfaces than the 129Xe chemical shielding and provide unique insights into macroporous materials in which the 129Xe chemical shift is typically of little diagnostic value. The first part of this report reviews the effect of quadrupolar interactions on the 83Kr linewidth in zeolites and also the 83Kr chemical shift behavior that is distinct from that of its 129Xe cousin in some of these materials. The second part reviews hyperpolarized (hp) 83Kr NMR spectroscopy of macroporous materials in which the longitudinal relaxation is typically too slow to allow sufficient averaging of thermally polarized 83Kr NMR signals. The quadrupolar-driven T1 relaxation times of hp 83Kr in these materials are sensitive to surface chemistry, surface-to-volume ratios, coadsorption of other species on surfaces, and surface temperature. Thus, 83Kr T1 relaxation can provide information about surfaces and chemical processes in macroscopic pores and can generate surface-sensitive contrast in hp 83Kr MRI. Copyright © 2007 John Wiley & Sons, Ltd. [source]

    NMR assignments of a di-pentacyclo-undecane cyclic ether

    Hendrik G. Kruger
    Abstract The X-ray structure of a di-pentacyclo-undecane cyclic ether was recently reported. As part of a programme to use NMR spectroscopy for the structure elucidation of cage compounds, the complete NMR assignments of the cyclic ether was attempted. Major overlap of proton and carbon signals of the two cages is observed. It was required to elucidate the fragment analogues that represent similar structural features of the cyclic ether in order to get an approximate but reasonable insight into the complex overlapping signals. Normal 2D NMR techniques were utilized to assign the various NMR signals. Copyright © 2006 John Wiley & Sons, Ltd. [source]

    29Si NMR in LC,NMR analysis of silicones

    Vratislav Blechta
    Abstract It is demonstrated using a practical example that indirect detection of 29Si NMR signals is sufficiently sensitive in LC,NMR stop-flow arrangement to analyze mixtures of siloxane polymers. New cryogenic probes with better signal-to-noise ratio will turn this version of LC,NMR into a routine method for analysis of siloxane polymers. Copyright © 2005 John Wiley & Sons, Ltd. [source]