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Quantum Coherence (quantum + coherence)
Kinds of Quantum Coherence Selected AbstractsSulfoalkyl ether-alkyl ether cyclodextrin derivatives, their synthesis, NMR characterization, and binding of 6,-methylprednisoloneJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 11 2005Serena Tongiani Abstract The objective of this study is to see if random alkyl ethers of various sulfoalkyl ether cyclodextrins can be synthesized and characterized. The purpose of the alkylation was to test the hypothesis that an increase in the "height" of a cyclodextrins cavity would help in the binding/complexation of larger more structurally complex molecules. The synthesis of new cyclodextrin derivatives comprising a mixture of sulfoalkyl ether and alkyl ether substituents on the same cyclodextrin ring was performed in aqueous alkaline solutions using various sultones and alkylsulfates. The method presented provided an easy and efficient way to modify cyclodextrins avoiding the use of organic solvents and high quantities of alkylating agents and could be carried out in either a two step or "one pot" single step process. Purification was by neutralization followed by ultrafiltration. The derivatives were characterized by 1D, (1H and 13C), and a 2D NMR technique (HMQC, Heteronuclear Multiple Quantum Coherence). The combination of these techniques allowed an analysis of the degree of substitution and the site of substitution on the cyclodextrin (CD) nucleus. For both ,- and ,-CD, sulfoakylation was preferred on the 2,>,3,>,6 hydroxyls while alkylation was preferred 6,>,2,>,3. Due to the simultaneous presence of short alkyl ether chains and negatively charged sulfoalkyl ether chains, these mixed water-soluble cyclodextrin derivatives, especially those of ,-cyclodextrin, should be able to bind more complex drugs. The improved binding capacity of these new modified CDs with the model drug 6,-methylprednisolone is reported. © 2005 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 94:2380-2392, 2005 [source] Temperature-induced reversible conformational change in the first 100 residues of ,-synucleinPROTEIN SCIENCE, Issue 3 2006Brian C. McNulty Abstract Natively disordered proteins are a growing class of anomalies to the structure,function paradigm. The natively disordered protein ,-synuclein is the primary component of Lewy bodies, the cellular hallmark of Parkinson's disease. We noticed a dramatic difference in dilute solution 1H- 15N Heteronuclear Single Quantum Coherence (HSQC) spectra of wild-type ,-synuclein and two disease-related mutants (A30P and A53T), with spectra collected at 35°C showing fewer cross-peaks than spectra acquired at 10°C. Here, we show the change to be the result of a reversible conformational exchange linked to an increase in hydrodynamic radius and secondary structure as the temperature is raised. Combined with analytical ultracentrifugation data showing ,-synuclein to be monomeric at both temperatures, we conclude that the poor quality of the 1H- 15N HSQC spectra obtained at 35°C is due to conformational fluctuations that occur on the proton chemical shift time scale. Using a truncated variant of ,-synuclein, we show the conformational exchange occurs in the first 100 amino acids of the protein. Our data illustrate a key difference between globular and natively disordered proteins. The properties of globular proteins change little with solution conditions until they denature cooperatively, but the properties of natively disordered proteins can vary dramatically with solution conditions. [source] NMR analysis of butyl acrylate/methylmethacrylate/,-methyl styrene terpolymersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Neil T. McManus Abstract Composition analysis for butyl acrylate (BA)/ methyl methacrylate (MMA)/,-methyl styrene terpolymers was carried out by NMR spectroscopy methods. 1H-NMR was used primarily for this analysis, but because the method did not provide independent measurements for the BA and MMA fractions, the terpolymer composition analysis was open to higher than normal levels of uncertainty. Supplementary analyses were made with quantitative 13C-NMR methods to confirm the results from 1H-NMR (quantitative 13C-NMR was used to provide corroboration of selected composition analyses). To confirm spectral assignments in the 1H- and 13C-NMR spectra, heteronuclear multiple quantum coherence and J Modulated Spin Echo (JMOD) pulse sequences were used. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2093,2098, 2007 [source] Microstructure of glycidylmethacrylate/vinyl acetate copolymers by two-dimensional nuclear magnetic resonance spectroscopyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2001A. S. Brar Abstract Glycidylmethacrylate/vinyl acetate copolymers were prepared by solution polymerization with benzene as a solvent and benzoyl peroxide as an initiator. Copolymer compositions were determined from 1H NMR spectra, and comonomer reactivity ratios were determined by the Kelen,Tudos (KT) method and the nonlinear least-squares error-in-variable method (EVM). The reactivity ratios obtained from KT and EVM were rG = 37.4 ± 12.0 and rV = 0.036 ± 0.019 and rG = 35.2 and rV = 0.03, respectively. Complete spectral assignments of 13C and 1H NMR spectra were done with the help of distortionless enhancement by polarization transfer and two-dimensional 13C,1H heteronuclear single quantum coherence and total correlation spectroscopy. The methyl, methine, and methylene carbon resonance showed both stereochemical and compositional sensitivity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4051,4060, 2001 [source] Identification of oleuropein oligomers in olive pulp and pomaceJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 10 2006Susana M Cardoso Abstract Analysis of a purified fraction from acetone extracts of olive pulp and pomace by electrospray ionisation tandem mass spectrometry (ESI-MSn) showed the presence of oleuropein oligomers, whose occurrence has not been reported previously in the literature. The main ionic species (m/z 1613) in the ESI-MS spectrum was an oleuropein trimer containing three linkages through the hydroxytyrosol backbone. In both samples, oleuropein dimers (m/z 1075), trimers comprising two hydroxytyrosol linkages (m/z 1615), tetramers (m/z 2153) and pentamers (m/z 2691) were also detected by MS. The occurrence of oleuropein oligomers was also observed by nuclear magnetic resonance (NMR). 13C, 13C distortionless enhancement by polarisation transfer DEPT 90, 13C DEPT 135, gHSQC (heteronuclear single quantum coherence) and gHMBC (heteronuclear multiple bond coherence) spectra showed all carbon and proton resonances of oleuropein with the exception of the low-mobility and asymmetric signals of the aromatic rings. Since mature olives were used in this study, it is possible that the disappearance of oleuropein that has been described to occur with the olive fruit maturation, could be associated with the formation of phenolic oligomers together with lower-molecular-weight compounds resulting from its degradation. Copyright © 2006 Society of Chemical Industry [source] Effects of decay-induced coherence and microwaveinducedcoherence on the index of refraction in a three-level , -type atomic systemLASER PHYSICS LETTERS, Issue 4 2004Wei-Hua Xu Abstract We study the dispersion-absorption properties in a three-level , -type atomic system with two closely lying lower levels. We consider two schemes: in the first, the two lower levels are coupled by decay-induced coherence, and in the second, quantum coherence is created by coupling the two lower levels to each other by a microwave field. We found that due to the decay-induced coherence or microwave-induced coherence, the dispersion-absorption properties can be controlled by the relative phase of applied fields, large index of refraction without absorption always can be obtained just by choosing proper values of the (© 2004 by ASTRO, Ltd. Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA) [source] Synthesis of rhodium(III) complexes with tris/tetrakis-benzimidazoles and benzothiazoles,quick identification of cyclometallation by nuclear magnetic resonance spectroscopyMAGNETIC RESONANCE IN CHEMISTRY, Issue 8 2009N. Chandrashekhar Abstract Reactions of rhodium(III) halides with multidentate N,S -heterocycles, (LH3) 1,3,5-tris(benzimidazolyl)benzene (L1H3; 1), 1,3,5-tris(N -methylbenzimidazolyl) benzene (L2H3; 2) and 1,3,5-tris(benzothiazolyl)benzene (L3H3; 3), in the molar ratio 1:1 in methanol,chloroform produced mononuclear cyclometallated products of the composition [RhX2(LH2)(H2O)] (X = Cl, Br, I; LH2 = L1H2, L2H2, L3H2). When the metal to ligand (1,3 or 1,2,4,5-tetrakis(benzothiazolyl)benzene [L4H2; 4]) molar ratio was 2:1, the reactions yielded binuclear complexes of the compositions [Rh2Cl5(LH2)(H2O)3] (LH2 = L1H2, L2H2, L3H2) and [Rh2X4(L4)(H2O)2] (X = Cl, Br, I). Elemental analysis, IR and 1H nuclear magnetic resonance (NMR) chemical shifts supported the binuclear nature of the complexes. Cyclometallation was detected by conventional 13C NMR spectra that showed a doublet around ,190 ppm. Cyclometallation was also detected by gradient-enhanced heteronuclear multiple bond correlation (g-HMBC) experiment that showed cross-peaks between the cyclometallated carbon and the central benzene ring protons of 1,3. Cyclometallation was substantiated by two-dimensional 1H1H correlated experiments (gradiant-correlation spectroscopy and rotating frame Overhauser effect spectroscopy) and 1H13C single bond correlated two-dimensional NMR experiments (gradient-enhanced heteronuclear single quantum coherence). The 1H15N g-HMBC experiment suggested the coordination of the heterocycles to the metal ion via tertiary nitrogen. Copyright © 2009 John Wiley & Sons, Ltd. [source] Complete assignments of 1H and 13C NMR spectral data for three new triterpenoid saponins from Ilex hainanensis Merr.MAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2009Xiao-Qing Chen Abstract Three new oleanane-type triterpenoid saponins, ilexhainanoside C, D and E, all with 24, 28-dioic acid groups, were isolated from the leaves of Ilex hainanensis. They were 3,-hydroxyolean-12-ene-24, 28-dioic acid-28- O -,- D -glucopyranoside(1), 3,, 19,-dihydroxyolean-12-ene-24, 28-dioic acid-28- O -,- D -glucopyranoside(2) and 3,, 29-dihydroxyolean-12-ene-24, 28-dioic acid-28- O -,- D -glucopyranoside(3). The structures of these three new compounds were elucidated and complete assignments of the 1H and 13C NMR spectroscopic data were achieved by 1D and 2D NMR experiments [heteronuclear single quantum coherence (HSQC), HMBC and rotational nuclear Overhauser effect spectroscopy (ROESY)]. Copyright © 2008 John Wiley & Sons, Ltd. [source] Characterization of nonderivatized plant cell walls using high-resolution solution-state NMR spectroscopy,MAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2008Daniel J. Yelle Abstract A recently described plant cell wall dissolution system has been modified to use perdeuterated solvents to allow direct in-NMR-tube dissolution and high-resolution solution-state NMR of the whole cell wall without derivatization. Finely ground cell wall material dissolves in a solvent system containing dimethylsulfoxide- d6 and 1-methylimidazole- d6 in a ratio of 4:1 (v/v), keeping wood component structures mainly intact in their near-native state. Two-dimensional NMR experiments, using gradient-HSQC (heteronuclear single quantum coherence) 1-bond 13C1H correlation spectroscopy, on nonderivatized cell wall material from a representative gymnosperm pinus taeda (loblolly pine), an angiosperm Populus tremuloides (quaking aspen), and a herbaceous plant Hibiscus cannabinus (kenaf) demonstrate the efficacy of the system. We describe a method to synthesize 1-methylimidazole- d6 with a high degree of perdeuteration, thus allowing cell wall dissolution and NMR characterization of nonderivatized plant cell wall structures. Copyright © 2008 John Wiley & Sons, Ltd. [source] Characterization of two series of nitrogen-containing dendrimers by natural abundance 15N NMRMAGNETIC RESONANCE IN CHEMISTRY, Issue 5 2008Rodolphe Deloncle Abstract Two series of small generation dendrimers built with phosphorus atoms at each branching point and various types of nitrogen atoms at natural abundance of 15N within the branches are characterized by a gradient enhanced GHNMQC (gradient hydrogen,nitrogen multiple quantum coherence) 1H15N NMR technique. The first series contains two types of nitrogen atoms, included in phosphorhydrazone linkages (CHNNMeP(S)), whereas the second series contains four types of nitrogen atoms included in azobenzene linkages (ArNNAr,) in addition to the phosphorhydrazone. The influence of the trans/cis isomerization of the azo bond on the 15N NMR has also been studied. Despite the low solubility of the azobenzene-containing dendrimers, which renders the detection of some signals difficult, 15N NMR appears as a very sensitive tool to detect chemical changes in the dendritic structure. Copyright © 2008 John Wiley & Sons, Ltd. [source] HSQC pulse sequences for 19FMAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2008Bruce Adams Abstract Heteronuclear single quantum coherence (HSQC) sequences using adiabatic (or composite) 180° pulses, suitable for applications requiring wide spectral widths in F2, are described. The sequences can be used with or without multiplicity editing. One variant will work even in the presence of homonuclear couplings that are equal to the heteronuclear 1-bond coupling. Copyright © 2008 John Wiley & Sons, Ltd. [source] Assignments of 1H and 13C NMR spectral data for ondansetron and its two novel metabolites, 1-hydroxy-ondansetron diastereoisomersMAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2006Mingyu Duan Abstract Assignments of 1H and 13C NMR chemical shifts were made by means of heteronuclear single quantum coherence (HSQC) and heteronuclear multiple bond correlation (HMBC) experiments for ondansetron, and by means of 1H- 1H correlation spectroscopy (1H- 1H COSY) and two-dimensional nuclear Overhauser effect spectroscopy (NOESY) experiments for two novel metabolites (M1 and M2) of ondansetron. These two metabolites were isolated for the first time from Mucor circinelloides. Copyright © 2006 John Wiley & Sons, Ltd. [source] Brain GABA editing by localized in vivo1H magnetic resonance spectroscopyNMR IN BIOMEDICINE, Issue 2 2004G. Bielicki Abstract Editing of GABA by 1H MRS in a specific brain area is a unique tool for in vivo non-invasive investigation of neurotransmission disorders. Selective GABA detection is achieved using sequences based on double quantum coherence (DQC). Our pulse sequence makes accurate measurements without artefacts due to spatial localization. The sequence was tested on a phantom solution. The effect of vigabatrin, a specific inhibitor of GABA transaminase, was measured in rat brain and GABA detection was performed in vivo in monkey brain using this procedure. Rats were spilt into two groups. In the control group, the rats had access to water and, in the other group (vigabatrin, VGB, rats), animals were allowed free access to drinking water containing vigabatrin. After 3 weeks of treatment, rats were anesthetized for in vivo NMR spectroscopy investigation. At the end of the experiment, brains were quickly removed, freeze-clamped and extracted with 4% perchloric acid. One part of the acid extract was used for GABA concentrations assessment by ion exchange chromatography with ninhydrin detection. The second was used for high-resolution NMR analysis. By chromatography measurements, the GABA concentration was 1.23±0.06,,mol/g for controls, while for vigabatrin-treated rats the GABA concentration was 4.89±1.60,,mol/g. The NMR in vivo results were closely correlated with the NMR ex vivo (r=0.99, p<0.01) and chromatography results (r=0.98, p<0.01). The correlation between ex vivo results and chromatography results was also high (r=0.99, p<0.001). This pulse sequence performed GABA editing from a 376,,l voxel located on the right basal ganglia area in a non-human primate brain. This in vivo GABA editing scheme can thus be proposed for accurate measurement of brain GABA concentrations. Copyright © 2004 John Wiley & Sons, Ltd. [source] All three Ca2+ -binding loops of photoproteins bind calcium ions: The crystal structures of calcium-loaded apo-aequorin and apo-obelinPROTEIN SCIENCE, Issue 3 2005Lu Deng HLH, helix,loop,helix; HSQC, heteronuclear single quantum coherence; RMSD, root mean square deviation; SAD, single wavelength anomalous dispersion Abstract The crystal structures of calcium-loaded apoaequorin and apo-obelin have been determined at resolutions 1.7 Å and 2.2 Å, respectively. A calcium ion is observed in each of the three EF-hand loops that have the canonical calcium-binding sequence, and each is coordinated in the characteristic pentagonal bipyramidal configuration. The calcium-loaded apo-proteins retain the same compact scaffold and overall fold as the unreacted photoproteins containing the bound substrate, 2-hydroperoxycoelenterazine, and also the same as the Ca2+ -discharged obelin bound with the product, coelenteramide. Nevertheless, there are easily discerned shifts in both helix and loop regions, and the shifts are not the same between the two proteins. It is suggested that these subtle shifts are the basis of the ability of these photoproteins to sense Ca2+ concentration transients and to produce their bioluminescence response on the millisecond timescale. A mechanism of intrastructural transmission of the calcium signal is proposed. [source] Highly efficient square wave distant dipolar field and its application for in vivo MRIMAGNETIC RESONANCE IN MEDICINE, Issue 4 2010Congbo Cai Abstract Intermolecular multiple quantum coherences generated by distant dipolar field (DDF) have some attractive properties, but the intrinsic weak signal intensity prevents their widespread applications. Recently, Branca et al. (J Chem Phys 2008;129:054502) suggested that square wave DDF was more efficient than conventional sinusoidal DDF because it could simultaneously produce intermolecular multiple quantum coherences signal with various major orders. In this article, instead of a series of adiabatic inversion pulses proposed previously, a more efficient composite adiabatic inversion pulse was applied to create square wave DDF. The square wave DDF was applied to in vivo MRI for the first time, and the corresponding simulations were performed. Both experimental and simulated results show that square wave DDF with composite adiabatic inversion pulse improves over the original Z-modulation enhanced to binary for self-refocused acquisition implementation and can enhance the signal intensity to about 2-fold of that from conventional correlation spectroscopy (COSY) revamped with asymmetric Z-gradient echo detection sequence for in vivo MRI, close to the theoretical prediction. Magn Reson Med, 2010. © 2010 Wiley-Liss, Inc. [source] | ||||||||||||||||