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NMR Chemical Shifts (nmr + chemical_shift)
Terms modified by NMR 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] 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] 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] Density functional computations of 99Ru chemical shifts: relativistic effects, influence of the density functional, and study of solvent effects on fac,[Ru(CO)3I3],MAGNETIC RESONANCE IN CHEMISTRY, Issue 11 2006Jochen Autschbach Abstract Solvent effects on the 99Ru NMR chemical shift of the complex fac,[Ru(CO)3I3], are investigated computationally using density functional theory. Further, benchmark calculations of the 99Ru shift for a set of ten Ru complexes have been performed in order to calibrate the computational model and to determine the importance of relativistic effects on the 99Ru nuclear magnetic shielding and on the chemical shift. A computational model for fac,[Ru(CO)3I3], that includes both explicit solvent molecules and a continuum model is shown to yield the best agreement with experiment. Relativistic corrections are shown to be of minor importance for determining 99Ru chemical shifts. On the other hand, the nature of the density functional is of importance. In agreement with literature data for ligand trends of 99Ru chemical shifts, the chemical shift range for different solvents is also best reproduced by a hybrid functional. Copyright © 2006 John Wiley & Sons, Ltd. [source] Crystallographic report: Bis(triphenyltin) oxalateAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 11 2003Libasse Diop Abstract The centrosymmetric structure of bis(triphenyltin) oxalate contains essentially four-coordinated tin and monodentate carboxylate moieties despite a Mössbauer quadrupole splitting of 2.8 mm s,1 and a 119Sn NMR chemical shift of ,503 ppm. Copyright © 2003 John Wiley & Sons, Ltd. [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] Calculated on 1H and 13C NMR chemical shifts of 2,4-difluorobenzaldehyde isonicotinoylhydrazone and 2,3-dichlorobenzaldehyde isonicotinoylhydrazone with GIAO, IGAIM, and CSGT modelsCONCEPTS IN MAGNETIC RESONANCE, Issue 5 2009N. Günay Abstract The 1H and 13C NMR chemical shifts of the 2,4-difluorobenzaldehyde isonicotinoylhydrazone (I) and 2,3-dichlorobenzaldehyde isonicotinoylhydrazone (II) were determined with the help of full spectral analysis. The geometry and electronic structure of the title compounds were investigated at both the ab initio Hartree-Fock and the B3LYP levels with 6-31+G(d,p) basis set. The NMR data were calculated by means of the GIAO, CSGT, and IGAIM methods. All quantum-chemical calculations, including those of NMR data, were performed by ab initio level HF and DFT methods. Excellent agreement between the theoretical and experimental results was found for the HF level 1H and 13C chemical shifts. The parameters of molecular geometry and 1H and 13C chemical shift values of the title compounds (I, II) in the ground state have been calculated and and compared with corresponding experimental result. © 2009 Wiley Periodicals, Inc. Concepts Magn Reson Part A 34A: 297,304, 2009. [source] NMR nomenclature: Nuclear spin properties and conventions for chemical shifts (IUPAC recommendations 2001),CONCEPTS IN MAGNETIC RESONANCE, Issue 5 2002Robin K. Harris Abstract A unified scale is recommended for reporting the NMR chemical shifts of all nuclei relative to the 1H resonance of tetramethylsilane. The unified scale is designed to provide a precise ratio, ,, of the resonance frequency of a given nuclide to that of the primary reference, the 1H resonance of tetramethylsilane (TMS) in dilute solution (volume fraction, , < 1%) in chloroform. Referencing procedures are discussed, including matters of practical application of the unified scale. Special attention is paid to recommended reference samples and values of , for secondary references on the unified scale are listed, many of which are the results of new measurements. Some earlier recommendations relating to the reporting of chemical shifts are endorsed. The chemical shift, ,, is redefined to avoid previous ambiguities but to leave practical usage unchanged. Relations between the unified scale and recently published recommendations for referencing in aqueous solutions (for specific use in biochemical work) are discussed, as well as the special effects of working in the solid state with magic-angle spinning. In all, nine new recommendations relating to chemical shifts are made. Standardized nuclear spin data are also presented in tabular form for the stable (and some unstable) isotopes of all elements with non-zero quantum numbers. The information given includes quantum numbers, isotopic abundances, magnetic moments, magnetogyric ratios and receptivities, together with quadrupole moments and linewidth factors (where appropriate). © 2001 IUPAC. Concepts Magn Reson 14:326,346, 2002 [source] Synthesis, Characterization, and Protonation Reactions of Ar-BIAN and Ar-BICAT Diimine Platinum Diphenyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2010Jerome Parmene Abstract PtII diphenyl complexes (N,N)PtPh2 [N,N = diimines Ar,N=C(An)C=N,Ar with Ar = substituted aryl groups] have been prepared and characterized by 1H, 13C, and 195Pt NMR spectroscopy. The 195Pt NMR spectroscopic data establish the electronic influence exerted by substituents at the backbone of the diimine ligand system to the metal center. When compared to diimines Ar,N=CMe,CMe=N,Ar, the electron-withdrawing ability of the Ar-BIAN ligand and the electron-donating ability of the O,O-heterocyclic Ar-BICAT systems are demonstrated. Trends in 195Pt NMR chemical shifts suggest that electronic tuning of the metal center is better achieved through variations of the diimine backbone substituents rather than variation of the substituents at the N-Aryl groups. Protonation of (N,N)PtPh2 in dichloromethane/acetonitrile at ,78 °C furnishes the corresponding PtIV hydrides (N,N)PtPh2H(NCMe)+. The PtIV hydrides liberate benzene with the formation of (N,N)PtPh(NCMe)+ when the temperature is raised. A second protonation and rapid benzene elimination produces the dicationic PtII species (N,N)Pt(NCMe)22+ at approximately 50 °C. Protonation of (N,N)PtPh2 in the absence of acetonitrile results in the clean formation of (N,N)PtPh(,2 -C6H6)+ at temperatures that depend on the steric hindrance provided by the alkyl substituents at the diimine N-aryl groups. These findings support the notion that the metal is the kinetically preferred site of protonation. The results qualitatively agree with a recent mechanistic study of protonation-induced reactions of (diimine)PtPh2 complexes that bear simple methyl substituents at the diimine backbone. Several compounds have been crystallographically characterized. All complexes have the expected square planar environment at the metal. Modest variations in the metric parameters suggest that the Ar-BICAT system has a weaker trans influence than the Ar-BIAN and Ar-DAB systems. [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] J -Based Analysis and DFT,NMR Assignments of Natural Complex Molecules: Application to 3,,7-Dihydroxy-5,6-epoxycholestanesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2008Jesús Javier Poza Abstract In order to reproduce the stereochemical dispositions of the epoxy and hydroxy functionalities, four 3,,7-hydroxy-5,6-epoxycholestanes were easily prepared from cholesterol, and their NMR spectroscopic data were experimentally obtained from 1D and 2D NMR experiments. An exhaustive QM- J -based analysis was then performed to replicate the experimental H,H and C,H coupling constants as well as the 13C NMR chemical shifts. The B3LYP GIAO methodology with the 6-311-G(d,p) basis set was chosen and showed that the data obtained from rings A and B were sufficient to calculate the correct stereochemistry of the 5,6-epoxy and 7-hydroxy groups. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis and Reactivity of 23 - tert -Butyl- and 23 -Phenyltetraarylazuliporphyrins: an Analysis of the Effect of Bulky Substituents on Oxidative Ring Contractions to Benzocarbaporphyrins,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2007Jessica A. El-Beck Abstract 6- tert -Butyl- and 6-phenylazulene reacted with pyrrole and benzaldehyde in a molar ratio of 1:3:4 in the presence of BF3·Et2O in chloroform, followed by oxidation with DDQ, to give 23 -substituted tetraphenylazuliporphyrins in 15,20,% yield. Slightly higher yields of the related meso -tetrakis(4-chlorophenyl)azuliporphyrins were obtained using 4-chlorobenzaldehyde. The presence of an electron-donating tert -butyl substituent increased the diatropic character of the azuliporphyrin system as determined by the proton NMR chemical shifts for the internal CH resonance, while intermediary results were noted for 23 -phenylazuliporphyrins. Addition of TFA afforded dications with increased aromatic ring currents, but electron-donating substituents (tBu,>,Ph) again produced a larger upfield shift for the internal CH signal due to stabilization of the tropylium character that is required so that the system can attain carbaporphyrin-type aromaticity. The substituted azuliporphyrins reacted with nickel(II) acetate or palladium(II) acetate to give the corresponding organometallic derivatives. In addition, oxidations with tBuOOH and KOH afforded benzocarbaporphyrin products in approximately 50,% yield. The presence of tert -butyl or phenyl substituents did not block these oxidative ring contraction processes, and the rate of reaction was slightly increased compared to 23 -unsubstituted azuliporphyrins. The major products were 22 - tert -butyl or phenyl-substituted benzocarbaporphyrins and minor products with an additional formyl substituent were also isolated. These products are consistent with an initial nucleophilic addition occurring at the position adjacent to the R group on the azulene ring. Detailed mechanisms are proposed to explain these observations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A Haigh,Mallion-Based Approach for the Evaluation of the Intensity Factors of Aromatic RingsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2006Cristiano Zonta Abstract A novel method for the determination of intensity factors of benzenoid systems based on the Haigh,Mallion (HM) theory has been developed. In this paper, the magnetic anisotropy generated by the ring-current effect in polycondensed arenes has been quantitatively calculated as nuclear independent chemical shieldings (NICSs) in a three-dimensional grid of points using the B3LYP/6-31G(d) method implemented in the Gaussian 98 program. The fitting of the calculated values to the HM model gives intensity factors for each ring. A comparison of the obtained values with Schleyer's NICS0 is given. The obtained intensity factors may find application in software using 1H NMR chemical shifts for structure determination.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Isolation and Structure Determination of Aplidinones A,C from the Mediterranean Ascidian Aplidium conicum: A Successful Regiochemistry Assignment by Quantum Mechanical 13C NMR Chemical Shift CalculationsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2005Anna Aiello Abstract A chemical investigation of a Mediterranean ascidian, Aplidium conicum, has resulted in the isolation of the new metabolites aplidinone A (1), B (2), and C (3). The structures of aplidinones A,C were determined by interpretation of spectroscopic data, whereas the regiochemistry was determined by the comparison of experimental 13C NMR chemical shifts with those predicted by GIAO shielding calculations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis of Pyrazolyl-2-pyrazolines by Treatment of 3-(3-Aryl-3-oxopropenyl)chromen-4-ones with Hydrazine and Their Oxidation to Bis(pyrazoles)EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 22 2004Albert Lévai Abstract The synthesis of several 1-acetyl-3-aryl-5-[3-(2-hydroxyphenyl)pyrazol-4-yl]-2-pyrazolines 3a,3h has been accomplished by treatment of the 3-(3-aryl-3-oxopropenyl)chromen-4-ones 1a,h with hydrazine hydrate in hot acetic acid. The 1-acetyl-3-aryl-5-(3-chromonyl)-2-pyrazolines 2a,2f were also obtained as by-products. Oxidation of the 1-acetyl-4-pyrazolyl-2-pyrazolines 3a,3f with DDQ gave the 3(5)-aryl-5(3)-[3-(2-hydroxyphenyl)pyrazol-4-yl]pyrazoles 5a,5f. The oxidation of the 2-pyrazoline rings was accompanied by N -deacylation. The reaction mechanisms of both transformations are discussed, the first one being supported by experimental results. The structures of all new derivatives were established by NMR and the evidence of prototropic tautomerism is carefully discussed. Theoretical calculations of energies and of the 1H and 13C NMR chemical shifts of the possible tautomeric forms of 5(3)-[3-(2-hydroxyphenyl)pyrazol-4-yl]-3(5)-(4-methoxyphenyl)pyrazole (5c), by B3LYP and GIAO, showed that compounds of this type probably exist as mixtures of two tautomers. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Properties of 2,2,2-Trifluoroethanol/Water Mixtures: Acidity, Basicity, and DipolarityHELVETICA CHIMICA ACTA, Issue 2 2005Paz Sevilla, Sierra In this report, we focus our attention on the characterization of 2,2,2-trifluoroethanol(TFE)/H2O mixtures and describe their intrinsic parameters; i.e., solvent acidity (SA), solvent basicity (SB), and solvent dipolarity/polarizability (SPP), by the probe/homomorph-couple method for a range of mixtures from 0,100% (v/v) TFE. Variation of these parameters is not linear and has a singular and unpredictable behavior depending on the precise composition of the mixture. Based on these parameters, we describe the TFE-induced changes in some physical properties; i.e., viscosity (,), partial molar volume (V,), density (,), dielectric constant (,), vapor pressure (pv), and spectroscopic properties; i.e., NMR chemical shifts (,(1H)) of TFE Me group for all molar fractions studied. In addition, by means of CD studies, we report that formation of the secondary structure, as percentage of helical content, ,, of a polypeptide, poly(L -lysine), in several TFE/H2O mixtures is adequately described by these mixture parameters. SA, SB, and SPP of TFE/H2O mixtures provide an excellent tool for the interpretation of formation and stability of intramolecular H-bonds, and, thus, of secondary structures in polypeptides. [source] Combined 13C NMR and DFT/GIAO studies of the polyketides Aurasperone A and Fonsecinone AINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2008Sergio de Lazaro Abstract Structural characterization by NMR spectroscopy and DFT calculations was performed for two dimeric naphtho-,-pyrones, the polyketides Aurasperone A and Fonsecinone A. Experimental data (13C NMR chemical shifts and interatomic geometries) were found to be in reasonable agreement with theoretical ones, obtained at B3LYP level for three different basis sets (6-31G/6-31G(d)/6-31G(d,p)). Additionally, the dipolar moments calculation allowed explaining the different solubility for these molecules. The 13C NMR theoretical chemical shifts were calculated with the GIAO method and the solvent effects were taken into account by means of the PCM approximation. In this work, the DFT/GIAO methodology shows to be a reliable tool in the assignment of experimental NMR chemical shifts of similar molecules. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [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] 1H and 13C NMR conformational study of 2-(benzotriazol-1-yl)-substituted tetrahydrofuransJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2003Alan 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] Synthesis and stability study of dental monomers containing methacrylamidoethyl phosphonic acidsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2007Xiaoming Xu Abstract Three new dental monomers containing methacrylamidoethyl phosphonic acids were synthesized. The structures of the synthesized monomers were determined with electrospray mass spectrometry (ESMS), Fourier transform infrared, and NMR. The hydrolytic stabilities of the synthesized monomers and a commercial monomer, 2-methacryloyloxyethyl phosphoric acid (MEP; used as a control), were studied with flow injection (FI)/ESMS, 1H NMR, and 31P NMR analysis of a CD3OD/D2O (4:1 v/v) solution of each monomer before and after storage at 60 °C for 2 months. The 1H NMR and 31P NMR chemical shifts of the monomers 2-methacrylamidoethylphosphonic acid (I) and N,N,-[4,4,-(propane-2,2-diyl)-bis(phenoxy-2-hydroxypropyl)]-bis(2-methacrylamidoethylphosphonic acid) (II) showed little change after storage at 60 °C for 2 months, but those of MEP changed significantly. FI/ESMS also showed that MEP was nearly completely decomposed, whereas monomers I and II remained largely intact. MEP could react with H2ZrF6 to form ternary zirconium fluoride complexes that were partially soluble in methanol, but all the monomers containing phosphonic acids formed precipitates. This study demonstrates that ESMS is a more sensitive and effective method than NMR for studying the hydrolytic stability or degradation of dental monomers. The new monomers containing methacrylamidoethyl phosphonic acids have higher hydrolytic stability than methacrylate phosphate monomers and may be used in dental bonding agents and other dental materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 99,110, 2007 [source] 13Carbon nuclear magnetic resonance of ethylene,propylene,1-decene terpolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2003Fernanda F. Nunes Escher Abstract Many studies have been reported on the 13C NMR characterization of ethylene,,-olefin copolymers, but only a few have been reported on terpolymers. The incorporation of an ,-olefin into the polyethylene chain changes the structure and, consequently, the properties of the polymer obtained. Looking for new products, we obtained a series of ethylene,propylene,1-decene terpolymers with the metallocenic system rac -ethylene bisindenyl zirconium dichloride/methylaluminoxane. We performed a complete 13C NMR characterization of these terpolymers qualitatively and quantitatively. Here we present a detailed study of the 13C NMR chemical shifts, triad sequence distributions, monomer average sequence lengths, and reactivity ratios for these terpolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2531,2541, 2003 [source] Influence of Structure on Polymerization Rates and Ca-Binding of Phosphorus-Containing 1,6-DienesMACROMOLECULAR REACTION ENGINEERING, Issue 5 2007Aylin Ziylan Albayrak Abstract Photo- and thermal-polymerizations of 4-diethoxyphosphoryl-2,4,6-tris(ethoxycarbonyl)-1,6-heptadiene, 4,4-bis(diethoxyphosphoryl)-2,6-bis(t -butoxycarbonyl)-1,6-heptadiene and 4-diethoxyphosphoryl-4-ethoxycarbonyl-2,6-bis(t -butoxycarbonyl)-1,6-heptadiene monomers and their phosphonic and carboxylic acid derivatives were investigated to understand the effect of the cyclic monomer structure on their polymerization reactivity. A strong effect of the substituents at positions 2, 4 and 6 of the monomers on polymerization rate was observed. The polymerizability of the monomers was successfully correlated with the 13C NMR chemical shifts of the vinyl carbons. Conversion values were consistent with the Tg being a measure of the flexibility of a monomer. The monomers containing phosphonic acid groups were soluble in water and ethanol. The acidic nature of the aqueous solutions of these monomers is expected to give them etching properties, important for dental applications. The interaction of the acid monomers with hydroxyapatite was investigated using 13C NMR technique. [source] Hydrogen bonds and local symmetry in the crystal structure of gibbsiteMAGNETIC RESONANCE IN CHEMISTRY, Issue 11 2010Anastasia Vyalikh Abstract First-principles quantum mechanical calculations of NMR chemical shifts and quadrupolar parameters have been carried out to assign the 27Al MAS NMR resonances in gibbsite. The 27Al NMR spectrum shows two signals for octahedral aluminum revealing two aluminum sites coordinated by six hydroxyl groups each, although the crystallographic positions of the two Al sites show little difference. The presence of two distinguished 27Al NMR resonances characterized by rather similar chemical shifts but quadrupolar coupling constants differing by roughly a factor of two is explained by different character of the hydrogen bonds, in which the hydroxyls forming the corresponding octahedron around each aluminum site, are involved. The Al-I site characterized by a CQ = 4.6 MHz is surrounded by OHgroups participating in four intralayer and two interlayer hydrogen bonds, while the Al-II site with the smaller quadrupolar constant (2.2 MHz) is coordinated by hydroxides, of which two point toward the intralayer cavities and four OH-bonds are aligned toward the interlayer gallery. In high-resolution solid-state 1H CRAMPS (combination of rotation and multiple-pulse spectroscopy) four signals with an intensity ratio of 1:2:2:1 are resolved which allow to distinguish six nonequivalent hydrogen sites reported in the gibbsite crystal structure and to ascribe them to two types of structural OH groups associated with intralayer and interlayer hydrogen bonds. This study can be applied to characterize the gibbsite-like layer,intergallery interactions associated with hydrogen bonding in the more complex systems, such as synthetic aluminum layered double hydroxides. Copyright © 2010 John Wiley & Sons, Ltd. [source] Transition metal NMR chemical shifts and polarizability effect in organometallic complexesMAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2009Alexey N. Egorochkin Abstract The literature data on substituent influence on the 51V, 55Mn, 57Fe, 59Co, 61Ni, 95Mo, 103Rh, 183W, 187Os and 195Pt NMR chemical shifts (,) and on J (M, P; M = Mn, Fe, Mo, Rh, W, Os) coupling constants have been analyzed for 30 series of the organometallic complexes. It has been established for the first time that the , and J values depend on the inductive, resonance and polarizability effects of substituents. The polarizability effect is caused by the partial charge on the central M atom. The contribution of this effect ranges from 3 to 86%. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||