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1.
华庆新 《中国科学B辑(英文版)》1989,(8)
Resonance assignments of the ~1H spectrum of insulin are the basis on which to investi-gate its solution conformation by using NMR method. Owing to the complicated aggregationbehaviour of the molecule to give broadened n. m. r. lines, only limited resonance assignmentshave been reported. S-sulfonated A and B chains of insulin gave ~1H spectra with good reso-lutions. Based on the 500 MHz absolute 2D-COSY spectrum and 400 MHz phase sensitiveDQF-COSY, Relayed-COSY and NOESY spectra of B chain recorded in D_2O, all of thespin system identifications of the non-labile protons in the S-sulfonated B chain of insulinwere reported including the specific resonance assignments of eight residues: B_3Asn, B_9Ser,B_(16)Tyr, B_(22)Arg, B_(26)Tyr, B_(27)Thr, B_(28)Pro and B_(29)Lys. The pK values of B_(16) and B_(26) tyrosineare 10.65 and 10.60 respectively from pH titration. 相似文献
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进入21世纪以来,核磁共振技术有了飞速的发展.在硬件方面:9000 MHz核磁共振仪(900MHz,场漂移<1.5 Hz/hr)的投入使用,标志着超导核磁共振仪向大型化又迈出了重要的一步.与此同时,H/C/N超导核磁共振仪又为生物大分子的结构剖析提供了新的手段和方法.在软件方面:新的脉冲系列不断地被开发,针对某一领域的软件系统也在不断地更新.核磁共振技术发挥着重要的作用. 相似文献
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We describe three anisotropic ultrafast (UF) QUadrupolar Ordered SpectroscopY (QUOSY) 2D-NMR experiments (referred to as ADUF 2D NMR spectroscopy) designed for recording the 2H homonuclear 2D spectra of weakly aligned (deuterated) solutes in sub-second experiment times. These new ADUF 2D experiments derive from the Q-COSY, Q-resolved and Q-DQ 2D pulse sequences (J. Am. Chem. Soc. 1999 , 121, 5249) and allow the correlation between the two components of each quadrupolar doublet, and then their assignment on the basis of 2H chemical shifts. The UF 2D pulse sequences are analyzed by using the Cartesian spin-operator formalism for spin I=1 nuclei with a small quadrupolar moment. The optimal experimental/practical conditions as well as the resolution, sensitivity and quantification issues of these ADUF 2D experiments are discussed on comparison to their conventional 2D counterparts and their analytical potentialities. Illustrative ADUF 2D experiments using deuterated achiral/prochiral/chiral solutes in poly-γ-benzyl-L-glutamate based chiral liquid crystals are presented, as well as the first examples of natural abundance deuterium (ANADUF) 2D spectrum using 14.1 T magnetic field and a basic gradient unit (53 G.cm−1) in oriented solvents. 相似文献
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NMR relaxation data on disordered proteins can provide insight into both structural and dynamic properties of these molecules. Because of chemical shift degeneracy in correlation spectra, detailed site-specific analyses of side chain dynamics have not been possible. Here, we present new experiments for the measurement of side chain dynamics in methyl-containing residues in unfolded protein states. The pulse schemes are similar to recently proposed methods for measuring deuterium spin relaxation rates in (13)CH(2)D methyl groups in folded proteins.(1) However, because resolution in (1)H-(13)C correlation maps of unfolded proteins is limiting, relaxation data are recorded as a series of (1)H-(15)N spectra. The methodology is illustrated with an application to the study of side chain dynamics in delta131delta, a large disordered fragment of staphylococcal nuclease containing residues 1-3 and 13-140 of the wide-type protein. A good correlation between the order parameters of the symmetry axes of the methyl groups and the backbone (1)H-(15)N bond vectors of the same residue is observed. Simulations establish that such a correlation is only possible if the unfolded state is comprised of an ensemble of structures which are not equiprobable. A motional model, which combines wobbling-in-a-cone and Gaussian axial fluctuations, is proposed to estimate chi(1) torsion angle fluctuations, sigma(chi)()1, of Val and Thr residues on the basis of the backbone and side chain order parameters. Values of sigma(chi)()1 are approximately 10 degrees larger than what has previously been observed in folded proteins. Of interest, the value of sigma(chi)()1 for Val 104 is considerably smaller than for other Val or Thr residues, suggesting that it may be part of a hydrophobic cluster. Notably large (15)N transverse relaxation rates are observed in this region. To our knowledge, this is the first time that side chain dynamics in an unfolded state have been studied in detail by NMR. 相似文献
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《Tetrahedron letters》1986,27(23):2613-2616
The structure of a dimeric steroid compound, isolated via basic treatment of Butenandt acid, is described. The previously known “ketone 104” is also fully analysed by means of 2D-nmr spectroscopy. 相似文献
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Crabtree KN Kauffman CA Tom BA Beçka E McGuire BA McCall BJ 《The Journal of chemical physics》2011,134(19):194311
The nuclear spin dependence of the chemical reaction H(3)(+)+ H(2) → H(2)?+ H(3)(+) has been studied in a hollow cathode plasma cell. Multipass infrared direct absorption spectroscopy has been employed to monitor the populations of several low-energy rotational levels of ortho- and para-H(3)(+) (o-H(3)(+) and p-H(3)(+)) in hydrogenic plasmas of varying para-H(2) (p-H(2)) enrichment. The ratio of the rates of the proton hop (k(H)) and hydrogen exchange (k(E)) reactions α ≡ k(H)/k(E) is inferred from the observed p-H(3)(+) fraction as a function of p-H(2) fraction using steady-state chemical models. Measurements have been performed both in uncooled (T(kin) ~ 350 K) and in liquid-nitrogen-cooled (T(kin) ~ 135 K) plasmas, marking the first time this reaction has been studied at low temperature. The value of α has been found to decrease from 1.6 ± 0.1 at 350 K to 0.5 ± 0.1 at 135 K. 相似文献
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Muon spin relaxation has been used to study the muon dynamics in the layered zirconium phosphate Zr(H(2)PO(4))(PO(4)).2H(2)O as a function of temperature. Radiofrequency decoupling was used to establish the origin of the local dipolar field as coupling with (1)H spins. Muons were trapped at two sites, one identified as HMuO and the other consistent with PO-Mu on the basis of their zero-field second moments. Although a small decrease in the local nuclear dipolar field was seen with temperature, the muons remained essentially static over the temperature range 20-300 K. 相似文献
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The chemical reaction H(3)(+) + H(2) → H(2) + H(3)(+) is the simplest bimolecular reaction involving a polyatomic, yet is complex enough that exact quantum mechanical calculations to adequately model its dynamics are still unfeasible. In particular, the branching fractions for the "identity," "proton hop," and "hydrogen exchange" reaction pathways are unknown, and to date, experimental measurements of this process have been limited. In this work, the nuclear-spin-dependent steady-state kinetics of the H(3)(+) + H(2) reaction is examined in detail, and employed to generate models of the ortho:para ratio of H(3)(+) formed in plasmas of varying ortho:para H(2) ratios. One model is based entirely on nuclear spin statistics, and is appropriate for temperatures high enough to populate a large number of H(3)(+) rotational states. Efforts are made to include the influence of three-body collisions in this model by deriving nuclear spin product branching fractions for the H(5)(+) + H(2) reaction. Another model, based on rate coefficients calculated using a microcanonical statistical approach, is appropriate for lower-temperature plasmas in which energetic considerations begin to compete with the nuclear spin branching fractions. These models serve as a theoretical framework for interpreting the results of laboratory studies on the reaction of H(3)(+) with H(2). 相似文献
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Wen-Juan Tian Hui Bai Hai-Gang Lu Yan-Bo Wu Si-Dian Li 《Journal of Cluster Science》2013,24(4):1127-1137
The most stable mono-layer boron sheets were predicted to have both the isolated hexagonal hole and the twin-hexagonal hole. Previous investigations indicate that planar B18H n q (n = 3–6, q = n ? 4) are the building blocks of boron sheets with isolated hexagonal holes. Extensive DFT investigations performed in this work show that D 2h B26H8, D 2h B26H8 2+, and C 2 B26H6, may serve as the building blocks of boron sheets with twin-hexagonal holes. These bicyclic clusters possess planar or quasi-planar geometries at B3LYP/6-311+G(d,p) level, with 16, 14, and 14 delocalized π electrons, respectively. Detailed analyses indicate that they are overall aromatic in nature, with the formation of islands of both σ and π aromaticity. They are analogous to D 2h C16H14 and D 2h C16H14 2+ in π bonding patterns, respectively, but fundamentally different from the latter in σ-bonding. Remarkably, all of them appear to be energetically the lowest-lying isomers obtained, which are promising targets for future gas phase syntheses. These hydroboron clusters, together with B18H n q clusters, establish the molecular basis for modeling the short-range structures, nucleation, and growth processes of monolayer boron sheets. The results obtained in this work enrich the chemistry of boron hydride clusters and expand the analogy relationship between hydroborons and hydrocarbons. 相似文献
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Comerford DW Cheesman A Carpenter TP Davies DM Fox NA Sage RS Smith JA Ashfold MN Mankelevich YA 《The journal of physical chemistry. A》2006,110(9):2868-2875
Experimental and modeling studies of the gas-phase chemistry occurring in dilute, hot filament (HF) activated B2H6/H2 and B2H6/CH4/H2 gas mixtures are reported. Spatially resolved relative number densities of B (and H) atoms have been measured by resonance enhanced multiphoton ionization methods, as a function of process conditions (e.g. the HF material and its temperature, the B2H6/H2 mixing ratio, and the presence (or not) of added CH4). Three-dimensional modeling of the H/B chemistry prevailing in such HF activated gas mixtures using a simplified representation of the gas phase chemistry succeeds in reproducing all of the experimentally observed trends, and in illustrating the key role of the "H-shifting" reactions BHx + H <= => BHx-1 + H2 (x = 1-3) in enabling rapid interconversion between the various BHx (x = 0-3) species. CH4 addition, at partial pressures appropriate for growth of boron-doped diamond by chemical vapor deposition methods, leads to approximately 30% reduction in the measured B atom signal near the HF. The modeling suggests that this is mainly due to concomitant H atom depletion near the HF, but it also allows us a first assessment of the possible contributions from B/C coupling reactions upon CH4 addition to HF activated B2H6/H2 gas mixtures. 相似文献
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《International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry》1988,31(4):615-617
The accumulation of radiation-induced defects and of H-atoms on γ-irradiation of a B2O3 + H2O system, at 77K, at different concentrations of water molecules have been investigated by ESR. The radiation-chemical yields of paramagnetic centres and of H-atoms have been determined from appropriate kinetic curves. It has been established that increasing the concentration of water molecules in the system results in a lowering of the yield of paramagnetic centres and an increase in the H-atom concentration. On the basis of the results obtained a mechanism has been suggested for heterogeneous radiation processes in this system at 77 K. 相似文献
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Jiang Jiang Yu Hua Mei Long Gen Zhu Wen Ji Wang 《中国化学快报》2007,18(5):557-560
The electrospray ionization mass spectrometry and tandem mass spectrometry investigation showed that the binding sites of Zn^2+ with oxidized insulin B chain are His 5, His 10, and Arg 22, which lead to the selective cleavages of the peptide bonds at Ash 3- Gin 4, His 5-Leu 6, Gly 8-Ser 9, and Glu 21-Arg 22 of oxidized insulin B chain. 相似文献
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Tian SX 《The journal of physical chemistry. A》2005,109(29):6580-6586
Isoelectronic molecules regarding B6H10, 2-CB5H9, 2,3-C2B4H8, 2,3,4-C3B3H7, and 2,3,4,5-C4B2H6 are studied by the density functional B3LYP/6-311G(d,p) method and the electron propagator theory in the partial third-order quasiparticale approximation, as well as the extrapolated calculation with the coupled-cluster CCSD(T) theory. The calculated ionization potentials are in good agreement with the experimental data from photoelectron spectroscopy. Valence structures are characterized with natural orbital bond (NBO) theory, exhibiting the multiple three-center two-electron bonds B-H-B, B-B-B, C-B-B, B-C-B, and C-B-C, and chemical bond rearrangements in the cations. 相似文献