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Chemical Shifts (chemical + shift)
Kinds of Chemical Shifts Terms modified by Chemical Shifts Selected AbstractsDensity-Functional Calculation of the 183W and 17O NMR Chemical Shifts for Large PolyoxotungstatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2006Jose Gracia Abstract A phosphane sulfate relativistic DFT method (ZORA)has been used to calculate the 183W and 17O NMR chemicalshifts for large polyoxotungstates, including W6O192,,CH3OTiW5O183,, W5O18WIINO3,, W10O324,, ,-,-,-XW12O40n,, ,-PW9O28Br63,, P2W18O626,, PW2O143,, and W7O246,, based on their optimized molecular structures. Despite sizeable deviations between the calculated and experimental values, the calculations correctly reproduce the trends in the change of the chemical shift for both nuclei. As expected, the diamagnetic term is almost constant throughout the whole series. The change in the chemical shifts is shown to be determined by the paramagnetic term, which depends on the electronic structure of the whole anion under study and, in particular, on the local geometry around a given tungsten atom. On the other hand, there is no correlation between the chemical shift and HOMO,LUMO gap, showing that deeper occupied levels and several unoccupied orbitals play an important role in the paramagnetic term. However, analysis of the components of the paramagnetic shielding has shown that the most significant transitions determining the change of both 183W and 17O NMR chemical shifts for anions consisting of tungsten and oxygen atoms are the occupied,occupied and not the occupied,virtual ones.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Solvent Effects on the NMR Chemical Shifts of Imidazolium-Based Ionic Liquids and Cellulose ThereinMACROMOLECULAR SYMPOSIA, Issue 2 2010Stephanie Hesse-Ertelt Abstract The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The 1H- and 13C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d6, D2O, CD3OD, and CDCl3). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %). [source] Further Conventions for NMR Shielding and Chemical Shifts (IUPAC Recommendations 2008),MAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2008Applied Chemistry Physical, Biophysical Chemistry Division, International Union of Pure Abstract IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem.73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating 13C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice. © 2008 IUPAC. Reprinted with permission from Pure Appl. Chem. 2008; 80: 59. This article can be freely downloaded from http://www.iupac.org/publications/pac/80/1/0059/ and can be copied, provided acknowledgement to IUPAC is given. [source] Direct Assessment of Electron Delocalization Using NMR Chemical Shifts,ANGEWANDTE CHEMIE, Issue 52 2009Stephan Festgenagelt: Mit dem neuen BLW-IGLO-Ansatz lassen sich die magnetischen Eigenschaften von Molekülen auswerten, in denen konjugative Wechselwirkungen ,unterdrückt" sind (rote Bindungen im Bild). Die NMR-spektroskopischen Parameter der lokalisierten Strukturen liefern ideale Referenzwerte für die Verschiebungen nichtaromatischer olefinischer Wasserstoffatome. [source] Leucine Side-Chain Conformation and Dynamics in Proteins from 13C NMR Chemical ShiftsCHEMBIOCHEM, Issue 9 2009Frans A. A. Mulder Dr. Abstract Look to the left: The carbon nucleus of a substituent in the gauche position about a subtending dihedral angle experiences an NMR chemical shift of about 5 ppm relative to the same chemical group present in the trans position. We demonstrate that this ",-gauche effect" can be utilized to determine the conformation and extent of rotameric averaging for leucine amino acid side chains in the protein calbindin D9k. The success of this approach suggests that rules can be established to define the orientation of other side chains in proteins as well, offering an easy gauge of protein side-chain flexibility, as well as avenues to advance protein structure determination by using side-chain chemical shifts. [source] ChemInform Abstract: Substituent Influences on the Stability of the Ring and Chain Tautomers in 1,3-O,N-Heterocyclic Systems: Characterization by 13C NMR Chemical Shifts, PM3 Charge Densities, and Isodesmic ReactionsCHEMINFORM, Issue 39 2001Kari Neuvonen Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Quantum Mechanical Calculations of Conformationally Relevant 1H and 13C,NMR Chemical Shifts of N-, O-, and S-Substituted Calixarene SystemsCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2007Giuseppe Bifulco Prof. Abstract QM GIAO calculations of 13C and 1H chemical shift values of the ArCH2Ar group in N-, O-, and S-substituted calixarene systems were performed with a hybrid DFT functional MPW1PW91 and 6-31G(d,p) basis set. A good reproduction of experimental data was obtained for some representative calixarenes and for a series of simplified calixarene models. This allowed the derivation of chemical shift surfaces versus , and , dihedral angles. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated. [source] Thermal Effects and Vibrational Corrections to Transition Metal NMR Chemical ShiftsCHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2004Sonja Grigoleit Dr. Abstract Both zero-point and classical thermal effects on the chemical shift of transition metals have been calculated at appropriate levels of density functional theory for a number of complexes of titanium, vanadium, manganese and iron. The zero-point effects were computed by applying a perturbational approach, whereas classical thermal effects were probed by Car,Parrinello molecular dynamics simulations. The systematic investigation shows that both procedures lead to a deshielding of the magnetic shielding constants evaluated at the GIAO-B3,LYP level, which in general also leads to a downfield shift in the relative chemical shifts, ,. The effect is small for the titanium and vanadium complexes, where it is typically on the order of a few dozen ppm, and is larger for the manganese and iron complexes, where it can amount to several hundred ppm. Zero-point corrections are usually smaller than the classical thermal effect. The pronounced downfield shift is due to the sensitivity of the shielding of the metal centre with regard to the metal,ligand bond length, which increase upon vibrational averaging. Both applied methods improve the accuracy of the chemical shifts in some cases, but not in general. [source] 103Rh NMR Chemical Shifts in Organometallic Complexes: A Combined Experimental and Density Functional StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2004Laura Orian Dr. Abstract Experimental 103Rh NMR chemical shifts of mono- and binuclear rhodium(I) complexes containing s - or as -hydroindacenide and indacenediide bridging ligands with different ancillary ligands (1,5-cyclooctadiene, ethylene, carbonyl) are presented. A protocol, based on density functional theory calculations, was established to determine 103Rh NMR shielding constants in order to rationalise the effects of electronic and structural variations on the spectroscopic signal, and to gain insight into the efficiency of this computational method when applied to organometallic systems. Scalar and spin,orbit relativistic effects based on the ZORA (zeroth order regular approximation) level have been taken into account and discussed. A good agreement was found for model compounds over a wide range of chemical shifts of rhodium (,10,000 ppm). This allowed us to discuss the experimental and calculated ,(103Rh) in larger complexes and to relate it to their electronic structure. [source] Deciphered Chemical Shifts in Aliased Spectra Recorded with two Slightly Different Narrow Windows or Differential Chemical Shift EvolutionCHEMPHYSCHEM, Issue 12 2010Mohammadali Foroozandeh The overlap of two HSQC spectra recorded with 10 and 9.9 ppm carbon spectral windows gives rise to highly resolved signals with a pattern providing unambiguous precise and accurate chemical shifts (see picture). Alternatively, the new DENA-HSQC pulse sequence takes advantage of a differential evolution of carbon chemical shift to do the same in a single experiment. Combined with multiplicity edition, DENA-HSQC advantageously replaces commonly used 1D DEPT-135 experiments. [source] Crystal structures and spectroscopic characterization of chiral and racemic 4-phenyl-1,3-oxazolidin-2-oneCRYSTAL RESEARCH AND TECHNOLOGY, Issue 4 2004S. Kitoh Abstract Crystal structures of (R)- and (rac)-4-phenyl-1,3-oxazolidin-2-one (4-POO) have been determined by X-ray diffraction and characterized by the solid state 13C NMR and IR spectra. Molecular geometries and intermolecular interactions in (R)- and (rac)-4-POO crystals are very similar to each other; 4-POO molecules are linked via the N-H,O intermolecular hydrogen bonds to form the chained structure. Chemical shifts of the solid state 13C NMR spectra are very similar to each other, whereas the 1H spin-lattice relaxation times (T1H) value for (R)-4-POO is five times as large as that for (rac)-4-POO, reflecting the more restricted mobility of the (R)-4-POO chain. Although both crystals contain an unique molecule in the asymmetric unit, a doublet feature is observed for the C=O stretching mode in the IR spectra of (R)- and (rac)-4-POO crystals. The frequency gap of the C=O bands are correlated with the strength of the dipole-dipole interactions between the neighboring C=O groups. © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [source] Structural elucidation by 1D and 2D NMR of three isomers of a carotenoid lysophosphocholine and its synthetic precursorsMAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2004Bente Jeanette Foss Abstract A carotenoic acid was used to obtain a long-chain unsaturated lysophosphocholine. The carotenoid lysophosphocholine was synthesized by two methods. The first method resulted in mixtures of regioisomers for each step in the synthetic route. Homo- and heteronuclear 1D and 2D NMR methods were employed to elucidate the structures of the individual isomers and their intermediates. The pure regioisomer [1-(,-apo-8, -carotenoyl)-2-lyso- glycero -3-phosphocholine] was obtained by a second method, but in low yield. The 1D 1H NMR subtraction spectrum of the mixture and the pure regioisomer was used to interpret the 1H shifts of the unsaturated acyl moieties. The 1H and 13C signals of the acyl chain show characteristic shifts depending on the positions of the choline and the acyl group attached to the glycerol backbone. Therefore, the unsaturated acyl chain signals have diagnostic values for the identification of isomers of unsaturated (lyso)phosphocholines. Chemical shifts and indirect coupling constants are reported for each of the major components of the mixtures. The methods used were 1D (1H, 13C and 31P) and 2D (H,H-COSY, HMBC, HSQC and HETCOR) NMR. Copyright © 2004 John Wiley & Sons, Ltd. [source] Metric spaces in NMR crystallographyCONCEPTS IN MAGNETIC RESONANCE, Issue 4 2009David M. Grant Abstract The anisotropic character of the chemical shift can be measured by experiments that provide shift tensor values and comparing these experimental components, obtained from microcrystalline powders, with 3D nuclear shielding tensor components, calculated with quantum chemistry, yields structural models of the analyzed molecules. The use of a metric tensor for evaluating the mean squared deviations, d2, between two or more tensors provides a statistical way to verify the molecular structure governing the theoretical shielding components. The sensitivity of the method is comparable with diffraction methods for the heavier organic atoms (i.e., C, O, N, etc.) but considerably better for the positions of H atoms. Thus, the method is especially powerful for H-bond structure, the position of water molecules in biomolecular species, and other proton important structural features, etc. Unfortunately, the traditional Cartesian tensor components appear as reducible metric representations and lack the orthogonality of irreducible icosahedral and irreducible spherical tensors, both of which are also easy to normalize. Metrics give weighting factors that carry important statistical significance in a structure determination. Details of the mathematical analysis are presented and examples given to illustrate the reason nuclear magnetic resonance are rapidly assuming an important synergistic relationship with diffraction methods (X-ray, neutron scattering, and high energy synchrotron irradiation). © 2009 Wiley Periodicals, Inc.Concepts Magn Reson Part A 34A: 217,237, 2009. [source] NMR studies of chiral organic compounds in non-isotropic phasesCONCEPTS IN MAGNETIC RESONANCE, Issue 3 2008Marek J. Potrzebowski Abstract In this article, new applications and perspectives of one- and two-dimensional NMR spectroscopy for study of chiral organic compounds in the non-isotropic phases (solid state and liquid crystals) are presented. The review is organized into five sections. In the first part, theoretical background and short introduction to solid state NMR are shown. The second part presents how NMR isotropic chemical shift can be used for distinguishing of racemates and enantiomers. In the third section, the power of the ODESSA pulse sequence for investigation of racemates, enantiomers and establishing of enantiomeric excess are discussed. The fourth part shows the application of analysis of principal elements of chemical shift tensors obtained by means of 2D NMR techniques for searching of absolute configuration and conformational changes in the solid state. The final part presents recent achievements of chiral liquid crystals NMR methodology for study of chiral compounds. © 2008 Wiley Periodicals, Inc. Concepts Magn Reson Part A 32A:201,218, 2008. [source] Alignment and structural analysis of membrane polypeptides by 15N and 31P solid-state NMR spectroscopyCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2003Burkhard Bechinger Abstract In contrast to solution NMR spectroscopy, where complete or almost complete averaging leads to isotropic values, the anisotropic character of nuclear interactions is apparent in solid-state NMR spectra. The orientation dependence of chemical shift and dipolar or quadrupolar interactions has been used to obtain dynamic as well as angular information from polypeptides that strongly interact with phospholipid bilayers. This article illustrates the advantageous characteristics of the anisotropic 15N or 31P chemical shift interactions that in a direct manner allow one to obtain information on the alignment of helical polypeptides or of phospholipid head groups with respect to the membrane normal. © 2003 Wiley Periodicals, Inc. Concepts Magn Reson 18A: 130,145, 2003 [source] Density-Functional Calculation of the 183W and 17O NMR Chemical Shifts for Large PolyoxotungstatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2006Jose Gracia Abstract A phosphane sulfate relativistic DFT method (ZORA)has been used to calculate the 183W and 17O NMR chemicalshifts for large polyoxotungstates, including W6O192,,CH3OTiW5O183,, W5O18WIINO3,, W10O324,, ,-,-,-XW12O40n,, ,-PW9O28Br63,, P2W18O626,, PW2O143,, and W7O246,, based on their optimized molecular structures. Despite sizeable deviations between the calculated and experimental values, the calculations correctly reproduce the trends in the change of the chemical shift for both nuclei. As expected, the diamagnetic term is almost constant throughout the whole series. The change in the chemical shifts is shown to be determined by the paramagnetic term, which depends on the electronic structure of the whole anion under study and, in particular, on the local geometry around a given tungsten atom. On the other hand, there is no correlation between the chemical shift and HOMO,LUMO gap, showing that deeper occupied levels and several unoccupied orbitals play an important role in the paramagnetic term. However, analysis of the components of the paramagnetic shielding has shown that the most significant transitions determining the change of both 183W and 17O NMR chemical shifts for anions consisting of tungsten and oxygen atoms are the occupied,occupied and not the occupied,virtual ones.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Oligonucleotide Analogues with Integrated Bases and Backbone.HELVETICA CHIMICA ACTA, Issue 12 2006Abstract The self-complementary UA and AU dinucleotide analogues 41,45, 47, 48, and 51,60 were prepared by Sonogashira coupling of 6-iodouridines with C(5,) -ethynylated adenosines and of 8-iodoadenosines with C(5,) -ethynylated uridines. The dinucleotide analogues associate in CDCl3 solution. The C(6/I) -unsubstituted AU dimers 51 and 54 prefer an anti -oriented uracilyl group and form stretched linear duplexes. The UA propargyl alcohols 41 and 43,45 possess a persistent intramolecular O(5,/I)H,,,N(3/I) H-bond and, thus, a syn -oriented adeninyl and a gt - or tg -oriented ethynyl moiety; they form corrugated linear duplexes. All other dimers form cyclic duplexes characterized by syn -oriented nucleobases. The preferred orientation of the ethynyl moiety (the C(4,),C(5,) torsion angle) defines a conformation between gg and one where the ethynyl group eclipses O(4,/I). The UA dimers 42, 47, and 48 form Watson,Crick H-bonds, the AU dimers 56 and 58,60 H-bonds of the Watson,Crick -type, the AU dimers 53 and 55 reverse- Hoogsteen, and 57Hoogsteen H-bonds. The pairing mode depends on the substituent of C(5,/I) (H, OSiiPr3; OH) and on the H-bonds of HOC(5,/I) in the AU dimers. Association constants were derived from the concentration-dependent chemical shift for HN(3) of the uracilyl moiety; they vary from 45,104,M,1 for linear duplexes to 197,2307,M,1 for cyclic duplexes. The thermodynamic parameters were determined by van't Hoff analysis of the temperature-dependence of the (concentration-dependent) chemical shift for HN(3) of the uracilyl moiety. Neglecting stacking energies, one finds an average energy of 3.5,4.0,kcal/mol per intermolecular H-bond. Base stacking is evidenced by the temperature-dependent CD spectra. The crystal structure of 54 shows two antiparallel chains of dimers connected by Watson-Crick H-bonds. The chains are bridged by a strong H-bond between the propargylic OH and OC(4) and by weak reverse A,,,A Hoogsteen H-bonds. [source] Theoretical study of NMR chemical shift induced by H/D isotope effectINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 15 2010Kimikazu Sugimori Abstract The isotope effect induced by deuterium substituted species is observed in molecular properties, such as geometry, kinetics, and electronic state, of the molecules through nuclear-electron interaction. Theoretical considerations and experimental alignments have been studied by ab initio molecular orbital, density functional theory, and other empirical strategies. The Born-Oppenheimer approximation with nuclear vibrational wavefunction can treat isotope effect because nuclear mass effect account for the average distance of vibrational motion. In this study, we introduce Morse anharmonic oscillator model to calculate average internuclear distance of diatomic molecules having X-H bonding and X-D bonding. Morse parameters are determined by fitting to potential energy surface of molecular orbital and/or density functional calculations, and then the average distance are obtained as the expectation value of the analytical Morse vibrational wavefunction. Nuclear magnetic resonance shielding constants of the H/D isotopomer are calculated again on the average distance by using GIAO with B3LYP and CCSD calculation. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] New insights on the bridge carbon,carbon bond in propellanes: A theoretical study based on the analysis of the electron localization functionJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 5 2007Victor Polo Abstract The nature of the bonding between bridgehead carbon atoms (Ca, Ca,) as well as the ring strain in a family of 10 propellanes formed by three-, four-, or five-member rings: [1.1.1] (I), [2.1.1] (II), [3.1.1] (III), [2.2.1] (IV), [3.2.1] (V), [2.2.2] (VI), [3.3.1] (VII), [3.2.2] (VIII), [3.3.2] (IX), and [3.3.3] (X) are studied by means of the electron localization function (ELF) at the DFT level (B3LYP/cc-pVTZ). The ELF analysis of smaller propellanes (I, II, and III) reveals the coexistence of two resonance forms: one with a nonbonding electron pair partially delocalized between Ca and Ca, atoms outside the cage (ionic) and the other with a bridge bond between the same atoms (covalent). The weights of each form are calculated according to the ELF-basin populations, yielding 94, 88, and 53% for the ionic structure of I, II, and III, respectively, while larger propellanes (IV,X) present only the covalent form. The question of the s-character of the bridge bond is addressed by dissecting the bridge-bond ELF basin into the molecular orbital contributions. Finally, ,-aromaticity associated to surface electron delocalization has been analyzed by means of nucleus-independent chemical shift (NICS) calculations. The results point out that the stability of the fused ring structure of propellanes I, II, and III, can be assigned to the remarkable ,-aromaticity of the involved three-member rings. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Toward direct determination of conformations of protein building units from multidimensional NMR experiments.JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 10 2003Abstract Knowledge of chemical shift,structure relationships could greatly facilitate the NMR chemical shift assignment and structure refinement processes that occur during peptide/protein structure determination via NMR spectroscopy. To determine whether such correlations exist for polar side chain containing amino acid residues the serine dipeptide model, For- L -Ser-NH2, was studied. Using the GIAO-RHF/6-31+G(d) and GIAO-RHF/TZ2P levels of theory the NMR chemical shifts of all hydrogen (1HN, 1H,, 1H,1, 1H,2), carbon (13C,, 13C,, 13C,) and nitrogen (15N) atoms have been computed for all 44 stable conformers of For- L -Ser-NH2. An attempt was made to establish correlation between chemical shift of each nucleus and the major conformational variables (,0, ,, ,, ,1, ,,1 and ,2). At both levels of theory a linear correlation can be observed between 1H,/,, 13C,/,, and 13C,/,. These results indicate that the backbone and side-chain structures of For- L -Ser-NH2 have a strong influence on its chemical shifts. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1157,1171, 2003 [source] Infrared and nuclear magnetic resonance properties of benzoyl derivatives of five-membered monoheterocycles and determination of aromaticity indicesJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 5 2003Kyu Ok Jeon Benzophenones, 2-benzoylthiophenes, 2-benzoylpyrroles, and 2-benzoylfurans, which have substituents at m - and p -positions of the benzoyl ring were prepared and their ir and nmr spectra were obtained in 0.1 M chloroform- d solution. The chemical shift values of each series were plotted against the Hammett substituent parameters to give good correlation, with the exception of the ortho -Hs and -Cs. The slopes as well as the differences in chemical shift gave sets of meaningful values for the indices of aromaticy. [source] Self-association of cromolyn sodium in aqueous solution characterized by nuclear magnetic resonance spectroscopyJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2004Xuan Ding Abstract The major objective of this study was to investigate and characterize the solution properties of cromolyn sodium (in D2O or D2O/H2O phosphate buffer at pH 7.5) using nuclear magnetic resonance (NMR) spectroscopy. The self-association of cromolyn molecules was examined primarily via one-dimensional 1H and 13C, and two-dimensional homonuclear NOESY NMR. Significant spectral shifts were observed for a majority of cromolyn 1H and 13C resonances, and are attributed to inter-molecular ring-stacking association accompanied by intra-molecular conformational changes. The critical self-association concentration was determined to be 10 mg/mL at pH 7.5 and 25°C by measuring the chemical shift of a specific cromolyn 1H resonance. The observed magnitude and sign changes of NOESY correlations indicate the formation of cromolyn aggregates with restricted molecular mobility. Mesomorphic liquid crystal formation is suggested by uniformly pronounced line broadening in concentrated cromolyn solutions; the transition concentration was approximately 60 mg/mL at 25°C, which is consistent with literature findings based on other techniques. A stronger tendency toward association was observed at lower temperature but aggregation appeared to be independent of pH. Lastly, it was concluded that self-association of cromolyn is promoted by the presence of monovalent cations as a result of reduced electrostatic repulsive forces. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93:1351,1358, 2004 [source] Impact of ketone and amino on the inner shell of guanineJOURNAL OF SYNCHROTRON RADIATION, Issue 4 2009Quan Zhu Removal of the functional groups of guanine, i.e. ketone and amino, one by one produces model molecules of hypoxanthine, 2-aminopurine and unsubstituted purine. The impact of the ketone and amino moieties on guanine is revealed using their atomic-site-based inner-shell electronic properties and spectra. A density functional theory based model has been employed to study the model molecules. Electronic properties, such as Hirshfeld charges and inner-shell chemical shift, are found to be both site-dependent and moiety-dependent. The site-based inner-shell chemical shift of the species exhibits a simple linear correlation, although certain similarities among the model molecules regroup the species into two pairs of purine and 2-aminopurine, as well as hypoxanthine and guanine. [source] Methylation of Chitosan with Iodomethane: Effect of Reaction Conditions on Chemoselectivity and Degree of SubstitutionMACROMOLECULAR BIOSCIENCE, Issue 10 2003Elisabete Curti Abstract N,N,N -trimethylchitosan (TMC) was prepared by reacting purified chitosan with iodomethane, in the presence of sodium hydroxide, water and sodium iodide, at room temperature. The reaction medium was N -methyl-2-pyrrolidone. Different samples of TMC were obtained by adding to the reaction medium a fixed volume (5.5 mL) of aqueous NaOH solutions at different concentrations (15, 20, 30 and 40 wt.-%) and carrying out the reactions for 9 or 24 h. The features observed in the 1H and 13C NMR spectra of these chitosan derivatives, in respect of the chemical shift, number and relative intensity of the signals, depended strongly on the excess of NaOH and H3CI added to the reaction medium, but when the lowest excess was employed, the characteristics of the derivative were not affected by the reaction time to the same extent. The average degree of quaternization of these N -methylated derivatives of chitosan ranged from 10.5% to 44.8%, according to the reaction conditions. Increasing the excess of NaOH, in reactions carried out for 9 h, resulted in TMC samples with progressively higher content of trimethylated sites however, the reaction yields were correspondingly lower and O -alkylation was favored in these cases. 1H NMR spectrum of sample [AX]24h dissolved in D2O (Cp,=,10 g/L). [source] Compensating for variation in 1JCH coupling constants in HSQC spectra acquired on small organic moleculesMAGNETIC RESONANCE IN CHEMISTRY, Issue 11 2010Peter W. A. Howe Abstract The HSQC sequence provides a sensitive way of determining the 13C chemical shift of protonated carbons. It uses INEPT elements for magnetization transfer, which can only be optimized for one value of 1JCH, but small organic molecules contain a wide range of 1JCH values. One popular method of compensating for 1JCH variation is to incorporate adiabatic pulses into the INEPT elements. This article shows that this method fails for a significant subset of functional groups. It also shows that the effects of this failure can be reduced by avoiding refocusing delays and by using a J -compensated excitation element. Copyright © 2010 John Wiley & Sons, Ltd. [source] The development of an NMR chemical shift prediction application with the accuracy necessary to grade proton NMR spectra for identityMAGNETIC RESONANCE IN CHEMISTRY, Issue 12 2009Stephen G. Spanton Abstract We have developed an NMR chemical shift prediction system that enables high throughput automatic grading of NMR spectra. In support of high throughput synthetic efforts for our drug discovery program, a rapid and accurate analysis for identity was needed. The system was designed and implemented to take advantage of the NMR assignments that had been tabulated on internally generated research compounds. The system has been operational for four years and has been used in conjunction with an internally written grading program to successfully analyze several hundred thousand samples based only on their 1D 1H spectrum. A focused test of the system's accuracy on 1006 molecules demonstrated the ability to estimate the proton chemical shift with an average error of +/,0.16 ppm. This level of chemical shift accuracy allows for reliable structure confirmation by automated analysis using only proton NMR. Copyright © 2009 John Wiley & Sons, Ltd. [source] Theoretical investigation on multinuclear NMR chemical shifts of some tris(trifluoromethyl)boron complexesMAGNETIC RESONANCE IN CHEMISTRY, Issue 8 2009Jun Zhang Abstract Tris(trifluoromethyl)boron complexes have unusual properties and may find applications in many fields of chemistry, biology, and physics. To gain insight into their NMR properties, the isotropic 11B, 13C, and 19F NMR chemical shifts of a series of tris(trifluoromethyl)boron complexes were systematically studied using the gauge-included atomic orbitals (GIAO) method at the levels of B3LYP/6-31 + G(d,p)//B3LYP/6-31G* and B3LYP/6-311 + G(d,p)//B3LYP/6-311 + G(d,p). Solvent effects were taken into account by polarizable continuum models (PCM). The calculated results were compared with the experimental values. The reason that the structurally inequivalent fluorine atoms in a specific species give a same chemical shift in experimental measurements is attributed to the fast rotation of CF3 group around the BC(F3) bond because of the low energy barrier. The calculated 11B, 13C(F3), and 19F chemical shifts are in good agreement with the experimental measurements, while the deviations of calculated 13C(X, X = O, N) chemical shifts are slightly large. For the latter, the average absolute deviations of the results from B3LYP/6-311 + G(d,p)//B3LYP/6-311 + G(d,p) are smaller than those from B3LYP/6-31 + G(d,p)//B3LYP/6-31G*, and the inclusion of PCM reduces the deviation values. The calculated 19F and 11B chemical shieldings of (CF3)3BCO are greatly dependent on the optimized structures, while the influence of structural parameters on the calculated 13C chemical shieldings is minor. Copyright © 2009 John Wiley & Sons, Ltd. [source] Further Conventions for NMR Shielding and Chemical Shifts (IUPAC Recommendations 2008),MAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2008Applied Chemistry Physical, Biophysical Chemistry Division, International Union of Pure Abstract IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem.73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating 13C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice. © 2008 IUPAC. Reprinted with permission from Pure Appl. Chem. 2008; 80: 59. This article can be freely downloaded from http://www.iupac.org/publications/pac/80/1/0059/ and can be copied, provided acknowledgement to IUPAC is given. [source] Studying porous materials with krypton-83 NMR spectroscopyMAGNETIC RESONANCE IN CHEMISTRY, Issue S1 2007Zackary 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] Selective excitation of overlapping multiplets; the application of doubly selective and chemical shift filter experiments to complex NMR spectraMAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2007Sara J. Duncan Abstract Standard 1D TOCSY and NOE experiments have limitations where signals are severely overlapped. Here, two recently published selective excitation methods are evaluated, the first of which uses a chemical shift selective filter to select a single resonance based on its chemical shift, and the second of which is a doubly selective experiment comprising a 1D TOCSY preparation step and subsequent 1D NOE. We also demonstrate the improvement in spectral quality obtained by the use of the zero quantum filter, which is incorporated into both of these experiments. The application of these different methods of selectively exciting overlapped multiplets, to different types of samples is considered. Copyright © 2007 John Wiley & Sons, Ltd. [source] | |||||||||||||||||||||||||||||||||||||