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631.
Zdzislaw Wawrzak Pawel Grochulski Zdzislaw Galdecki Jane F. Griffin Phyllis D. Strong William L. Duax 《Journal of chemical crystallography》1992,22(1):65-69
The X-ray structure of 6-methyl-3,20-dioxo-4,6-pregnadien-17-yl acetate is reported. The crystals are monoclinic, space groupP21,Z=4,a=28.955(7),b=6.597(2),c=11.064(3) Å,/gb=90.80(2) °. The two crystallographically independent molecules have very similar overall geometries. The A rings have intermediate sofa-half-chair conformations and are bent relative to the steroid skeleton. The conformation of the 17-progesterone side chain is stabilized by the 17-ester substituent; the C(16)-C(17)-C(20)-O(20) torsion angle is –19.4(6) and –20.6(7)°. 相似文献
632.
In this paper we study the gap probability problem in the Gaussian unitary ensembles of \(n\) by \(n\) matrices : The probability that the interval \(J := (-a,a)\) is free of eigenvalues. In the works of Tracy and Widom, Adler and Van Moerbeke, and Forrester and Witte on this subject, it has been shown that two Painlevé type differential equations arise in this context. The first is the Jimbo–Miwa–Okomoto \(\sigma \) -form and the second is a particular Painlevé IV. Using the ladder operator technique of orthogonal polynomials we derive three quantities associated with the gap probability, denoted as \(\sigma _n(a)\) , \(R_n(a)\) and \(r_n(a)\) . We show that each one satisfies a second order Painlevé type differential equation as well as a discrete Painlevé type equation. In particular, in addition to providing an elementary derivation of the aforementioned \(\sigma \) -form and Painlevé IV we are able to show that the quantity \(r_n(a)\) satisfies a particular case of Chazy’s second degree second order differential equation. For the discrete equations we show that the quantity \(r_n(a)\) satisfies a particular form of the modified discrete Painlevé II equation obtained by Grammaticos and Ramani in the context of Backlund transformations. We also derive second order second degree difference equations for the quantities \(R_n(a)\) and \(\sigma _n(a)\) . 相似文献
633.
Rodriguez-Aristegui S Clapham KM Barrett L Cano C Desage-El Murr M Griffin RJ Hardcastle IR Payne SL Rennison T Richardson C Golding BT 《Organic & biomolecular chemistry》2011,9(17):6066-6074
Amino-substituted biphenyls were obtained by Suzuki cross-coupling of 2,6-dibromoaniline with a phenylboronic acid (substituted with Me, NO(2), OH, OMe or Cl) preferably assisted by microwave irradiation. Conversion of the amino group into a thiol preceded a base-induced intramolecular substitution, also facilitated by microwave heating, to generate the second C-S bond of the target dibenzothiophene. The 1-, 2-, 3- or 4-substituted 6-halodibenzothiophenes obtained were subjected to a palladium-mediated coupling with 2-morpholin-4-yl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4H-chromen-4-one to give the respective 6-, 7-, 8- or 9-substituted dibenzothiophen-4-ylchromenones. These compounds were evaluated as inhibitors of DNA-dependent protein kinase (DNA-PK) and compared to the parent 8-(dibenzo[b,d]thiophen-4-yl)-2-morpholin-4-yl-4H-chromen-4-one. Notably, derivatives bearing hydroxy or methoxy substituents at C-8 or C-9 retained activity, whereas substitution at C-7 lowered activity. Substitution with chloro at C-6 was not detrimental to activity, but a chloro group at C-7 or C-8 reduced potency. The data indicate permissive elaboration of hydroxyl at C-8 or C-9, enabling the possibility of improved pharmaceutical properties, whilst retaining potency against DNA-PK. 相似文献
634.
Chalmers MJ Pascal BD Willis S Zhang J Iturria SJ Dodge JA Griffin PR 《International journal of mass spectrometry》2011,302(1-3):59-68
Hydrogen/deuterium exchange (HDX) mass spectrometry has been widely applied to the characterization of protein dynamics. More recently, differential HDX has been shown to be effective for the characterization of ligand binding. Previously we have described a fully automated HDX system for use as a ligand screening platform. Here we describe and validate the required data analysis workflow to facilitate the use of HDX as a robust approach for ligand screening. Following acquisition of HDX data at a single on-exchange time point (n ≥ 3), one way analysis of variance in conjunction with the Tukey multiple comparison procedure is used to establish the significance of any measured difference. Analysis results are graphed with respect to a single peptide, ligand or group of ligands, or displayed as an overview within a heat map. For the heat map display, only Δ%D values with a Tukey-adjusted P value less than 0.05 are colored. Hierarchical clustering is used to bin compounds with highly similar HDX signatures. The workflow is evaluated with a small data set showing the ligand binding domain (LDB) of the nuclear receptor peroxisome proliferator-activated receptor gamma (PPARγ) screened against 10 functionally selective ligands. More significantly, data for the vitamin D receptor (VDR) in complex with 87 ligands are presented. To highlight the robustness and precision of our automated HDX platform we analyzed the data from 4191 replicate HDX measurements acquired over an eight month timeframe. Ninety six percent of these measurements were within 10 percent of the mean value. Work has begun to integrate these analysis and graphing components within our HDX software suite. 相似文献
635.
Abstract A series of unsymmetrical dimeric mesogens was prepared, members of which were composed of a 4′-pentyloxybiphenyl-4-carboxyl core and a 4′-substituted-benzylidene-4-oxyaniline core joined via an alklyene spacer. The structural variants were cyano, nitro and trifluoromethyl. Comparison of mesophase behaviour of the unsymmetrical dimers with that of corresponding monomeric ‘halves’ and also with that of corresponding symmetrical dimers indicated a tendency for the unsymmetrical dimers to form smectic phases although not as highly ordered as those of some of the monomers corresponding to a relevant core group. 相似文献
636.
Griffin RG 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,(2):410-412
In the 1990’s we initiated development of high frequency gyrotron microwave sources with the goal of performing dynamic nuclear polarization at magnetic fields (∼5–23 T) used in contemporary NMR experiments. This article describes the motivation for these efforts and the developments that led to the operation of a gyrotron source for DNP operating at 250 GHz. We also mention results obtained with this instrument that would have been otherwise impossible absent the increased sensitivity. Finally, we describe recent efforts that have extended DNP to 460 GHz and 700 MHz 1H frequencies. 相似文献
637.
Vikram S. Bajaj Melody L. Mak-Jurkauskas Marina Belenky Judith Herzfeld Robert G. Griffin 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2010,202(1):9-13
We describe a new approach to multiple 13C–15N distance measurements in uniformly labeled solids, frequency-selective (FS) TEDOR. The method shares features with FS-REDOR and ZF- and BASE-TEDOR, which also provide quantitative 15N–13C spectral assignments and distance measurements in U-[13C,15N] samples. To demonstrate the validity of the FS-TEDOR sequence, we measured distances in [U-13C,15N]-asparagine which are in good agreement with other methods. In addition, we integrate high frequency dynamic nuclear polarization (DNP) into the experimental protocol and use FS-TEDOR to record a resolved correlation spectrum of the Arg-13Cγ–15Nε region in [U-13C,15N]-bacteriorhodopsin. We resolve six of the seven cross-peaks expected based on the primary sequence of this membrane protein. 相似文献
638.
Griffin L. Barnes Allen Y. Hong Prof. Christopher D. Vanderwal 《Angewandte Chemie (International ed. in English)》2023,62(4):e202215098
We offer a new biogenetic proposal for the origin of the complex alkaloid alstonlarsine A, through rearrangement of the Strychnos alkaloids alstolucines B and F. Further, we provide evidence of the chemical feasibility of this proposal in the facile conversion of synthetic alstolucines into alstonlarsine A through a short, efficient sequence of N-methylation, β-elimination, and a cascade 1,7-hydride shift/Mannich cyclization. We believe that this is the first biogenetic proposal involving the “tert-amino effect”, a hydride-shift-based internal redox trigger of a Mannich cyclization. A further interesting feature of the cascade is that its stereochemical outcome most likely originates in conformational preferences during the hydride shift. 相似文献
639.
Complexation between pyridines and carboxylic acids is driven by hydrogen bonding. This simple, single hydrogen bond is shown to be capable of serving concomitantly as both the agent of liquid crystallinity and as the coupling bond generating an extended linear chain structure. Three such complexes made from an aromatic diacid and three structurally different bis pyridyls were prepared. In each case the association complex self-assembles into an organized liquid crystalline phase. Discussion of this complexation as a step-growth polymerization process is presented along with an examination of the suitability of various methods for characterizing these materials. 相似文献
640.
Nuwayo Eric Munyaneza Carlos Posada Zhen Xu Vincenzo De Altin Popiolek Griffin Paddock Charles McKee Dr. Guoliang Liu 《Angewandte Chemie (International ed. in English)》2023,62(36):e202307042
Polystyrene (PS) is one of the least recycled large-volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of “degradation-upcycling” to synthesize a library of high-value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value-added chemicals. 相似文献