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41.
We present a novel pulse sequence, SESAME-HSQC, for the simultaneous measurement of several NH and CH scalar and residual dipolar couplings in double labeled proteins. The proposed Spin-statE Selective All Multiplicity Edited (SESAME)-HSQC combines gradient selected and sensitivity enhanced (15)N- and constant-time (13)C-HSQC experiments with the recently introduced spin-state selective method (Nolis et al., J. Magn. Reson. 180 (2006) 39-50) for measuring couplings simultaneously at amide and aliphatic regions. Excellent resolution and high sensitivity is warranted by removing all coupling interactions during the indirectly detected t(1) period, and by employing pulsed field gradients for coherence selection and utilizing coherence order selective spin-state selection. The scalar and residual dipolar couplings can be readily measured from a two-dimensional (15)N/(13)C-HSQC spectrum without additional spectral crowding. SESAME-HSQC can be used for epitope mapping by observing chemical shift changes in both amide and aliphatic regions. Simultaneously, potential conversion in protein conformation can be probed by analyzing changes in residual dipolar couplings induced by ligand binding. The pulse sequence is experimentally verified with a sample of (15)N/(13)C enriched human ubiquitin. The internuclear vector directions determined from the residual dipolar couplings are found to be in excellent correlation with those predicted from ubiquitin's refined solution structure. 相似文献
42.
Pd(PPh3)4 catalyzed Suzuki-Miyaura cross-coupling reactions of 4-tosyloxycoumarins or 4-tosyloxyquinolin-2(1H)-one with various potassium aryl trifluoroborates afforded the corresponding 4-substituted coumarins or 4-substituted quinolin-2(1H)-ones in good to excellent yield. 相似文献
43.
Dr. Davy Sinnaeve Dr. Mohammadali Foroozandeh Dr. Mathias Nilsson Prof. Dr. Gareth A. Morris 《Angewandte Chemie (International ed. in English)》2016,55(3):1090-1093
Couplings between protons, whether scalar or dipolar, provide a wealth of structural information. Unfortunately, the high number of 1H‐1H couplings gives rise to complex multiplets and severe overlap in crowded spectra, greatly complicating their measurement. Many different methods exist for disentangling couplings, but none approaches optimum resolution. Here, we present a general new 2D J‐resolved method, PSYCHEDELIC, in which all homonuclear couplings are suppressed in F2, and only the couplings to chosen spins appear, as simple doublets, in F1. This approaches the theoretical limit for resolving 1H‐1H couplings, with close to natural linewidths and with only chemical shifts in F2. With the same high sensitivity and spectral purity as the parent PSYCHE pure shift experiment, PSYCHEDELIC offers a robust method for chemists seeking to exploit couplings for structural, conformational, or stereochemical analyses. 相似文献
44.
Nessan J. Kerrigan 《Tetrahedron letters》2004,45(49):9087-9090
The samarium(II) iodide-mediated coupling of ketones with β-alkoxyacrylates gives β-hydroxy-γ-butyrolactones in moderate yield. The process has been applied to the asymmetric synthesis of an antifungal, γ-butyrolactone natural product. 相似文献
45.
Keyang Ding Angela M. Gronenborn 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,167(2):554-258
Sensitivity-enhanced 2D IPAP experiments using the accordion principle for measuring one-bond 13C'-13Calpha and 1Halpha-13Calpha dipolar couplings in proteins are presented. The resolution of the resulting spectra is identical to that of the decoupled HSQC spectra and the sensitivity of the corresponding 1D acquisitions are only slightly lower than those obtained with 3D HNCO and 3D HN(COCA)HA pulse sequences due to an additional delay 2Delta. For cases of limited resolution in the 2D 15N-1HN HSQC spectrum the current pulse sequences can easily be modified into 3D versions by introducing a poorly digitized third dimension, if so desired. The experiments described here are a valuable addition to the suites available for determination of residual dipolar couplings in biological systems. 相似文献
46.
Niemitz M Laatikainen R Chen SN Kleps R Kozikowski AP Pauli GF 《Magnetic resonance in chemistry : MRC》2007,45(10):878-882
Complete analysis of the (1)H NMR spectrum of huperzine A, 1-amino-13-ethylidene-11-methyl-6-aza-tricyclo[7.3.1.0(2, 7)]trideca-2(7),3,10-trien-5-one, a Lycopodium alkaloid and anti-Alzheimer drug lead containing an ABCD(E)(MN)(OP)X(3)Y(3)-type system of 15 nonexchangeable proton spins, is reported for the first time, and earlier assignments are corrected. The complete (1)H parameter set of 11 chemical shifts clarifies the diastereotopism of both methylene groups, and provides a total of 38 observed H,H-couplings including 31 long-range ((4-6)J) connectivities. The NMR data is consistent with the comparatively rigid alicyclic backbone predicted by molecular mechanics calculations, and forms the basis for (1)H NMR fingerprint analysis for the purpose of dereplication, purity analysis, and elucidation of structural analogs. 相似文献
47.
48.
The (1)H and (13)C NMR spectra of two stereoisomeric bis-Tr?ger's bases and four stereoisomeric tris-Tr?ger's bases asymmetrically substituted on the external aromatic rings were recorded and the corresponding signals assigned. The relative configuration of the stereogenic units has been unequivocally determined on the basis of homoallylic couplings and NOE experiments. 相似文献
49.
在高极化多自旋液体样品中,同时存在着分子间偶极(D)耦合和分子内标量(J)耦合,它们的共同作用产生了一些原来观测不到的分子间多量子相干信号。而且,信号的裂分模式与只存在J耦合的多自旋体系中观测到的多量子相干信号的裂分模式不同。本文从理论和实验上研究了这些禁阻的共振峰及其独特的裂分模式。为了比较验证,我们以I2S3+X自旋体系为例,结合使用选择和非选择性的射频脉冲序列来获得分子间双量子相干信号的五种裂分模式。进而归纳出对IpSq+Xk (p, q, k = 1, 2, 3,…)自旋体系普适的裂分模式规则。并指出,它们中如(1:0:-1)的裂分模式会放大J耦合裂分,使得J耦合常数的测量更精确,特别在J耦合常数很小或不均匀场中的J耦合常数的测量中具有诱人的应用前景。结果表明理论预测,计算机模拟和实验观测结果三者吻合的很好。 相似文献
50.
Banci L Bertini I Felli IC Sarrou J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,172(2):191-200
CH(alpha) residual dipolar couplings (Deltardc's) were measured for the oxidized cytochrome b562 from Escherichia coli as a result of its partial self-orientation in high magnetic fields due to the anisotropy of the overall magnetic susceptibility tensor. Both the low spin iron (III) heme and the four-helix bundle fold contribute to the magnetic anisotropy tensor. CH(alpha) Deltardc's, which span a larger range than the analogous NH values (already available in the literature) sample large space variations at variance with NH Deltardc's, which are largely isooriented within alpha helices. The whole structure is now significantly refined with the chemical shift index and CH(alpha) Deltardc's. The latter are particularly useful also in defining the molecular magnetic anisotropy parameters. It is shown here that the backbone folding can be conveniently and accurately determined using backbone restraints only, which include NOEs, hydrogen bonds, residual dipolar couplings, pseudocontact shifts, and chemical shift index. All these restraints are easily and quickly determined from the backbone assignment. The calculated backbone structure is comparable to that obtained by using also side chain restraint. Furthermore, the structure obtained with backbone only restraints is, in its whole, very similar to that obtained with the complete set of restraints. The paramagnetism based restraints are shown to be absolutely relevant, especially for Deltardc's. 相似文献