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排序方式: 共有549条查询结果,搜索用时 625 毫秒
91.
Yan Zhang Phani Morisetti Jeffery Kim Lynelle Smith Hai Lin 《Theoretical chemistry accounts》2008,121(5-6):313-319
Theoretical studies are presented into the experimentally observed regioselectivity difference of testosterone hydroxylation by cytochrome P450 3A4 at the 1β, 2β, 6β, and 15β positions. Such regioselectivity is investigated by density functional theory calculations on a model system. The barrier heights of hydrogen abstraction, which are corrected by zero-point vibrational energies, are computed to be about 10.1, 13.6, 14.4, and 16.2 kcal/mol for the 6β-, 2β-, 15β-, and 1β-positions, respectively. The calculated barriers suggest the regioselectivity preference of 6β ? 2β > 15β > 1β, which is in good agreement with experimental findings. 相似文献
92.
The antifungal natural product citrafungin A was synthesized using, as key steps, an asymmetric aldol reaction of a chiral oxazolidinone, diastereoselective alkylation of a chiral 1,3-dioxolan-2-one, semihydrogenation of an enyne, and selective methyl ester deprotection. 相似文献
93.
Sai S. Patkar Yao Tang Arriana M. Bisram Tianren Zhang Jeffery G. Saven Darrin J. Pochan Kristi L. Kiick 《Angewandte Chemie (International ed. in English)》2023,62(25):e202301331
Thermoresponsive resilin-like polypeptides (RLPs) of various lengths were genetically fused to two different computationally designed coiled coil-forming peptides with distinct thermal stability, to develop new strategies to assemble coiled coil peptides via temperature-triggered phase separation of the RLP units. Their successful production in bacterial expression hosts was verified via gel electrophoresis, mass spectrometry, and amino acid analysis. Circular dichroism (CD) spectroscopy, ultraviolet-visible (UV/Vis) turbidimetry, and dynamic light scattering (DLS) measurements confirmed the stability of the coiled coils and showed that the thermosensitive phase behavior of the RLPs was preserved in the genetically fused hybrid polypeptides. Cryogenic-transmission electron microscopy and coarse-grained modeling revealed that functionalizing the coiled coils with thermoresponsive RLPs leads to their thermally triggered noncovalent assembly into nanofibrillar assemblies. 相似文献
94.
Rapid postcolumn methodology for determination of paralytic shellfish toxins in shellfish tissue 总被引:1,自引:0,他引:1
Rourke WA Murphy CJ Pitcher G van de Riet JM Burns BG Thomas KM Quilliam MA 《Journal of AOAC International》2008,91(3):589-597
A rapid liquid chromatographic (LC) method with postcolumn oxidation and fluorescence detection (excitation 330 nm, emission 390 nm) for the determination of paralytic shellfish toxins (PSTs) in shellfish tissue has been developed. Extracts prepared for mouse bioassay (MBA) were treated with trichloroacetic acid to precipitate protein, centrifuged, and pH-adjusted for LC analysis. Saxitoxin (STX), neoSTX (NEO), decarbamoylSTX (dcSTX), and the gonyautoxins, GTX1, GTX2, GTX3, GTX4, GTX5, dcGTX2, and dcGTX3, were separated on a polar-linked alkyl reversed-phase column using a step gradient elution; the N-sulfocarbamoyl GTXs, C1, C2, C3, and C4, were determined on a C-8 reversed-phase column in the isocratic mode. Relative toxicities were used to determine STX-dihydrochloride salt (diHCl) equivalents (STXeq). Calibration graphs were linear for all toxins studied with STX showing a correlation coefficient of 0.999 and linearity between 0.18 and 5.9 ng STX-diHCI injected (equivalent to 3.9-128 microg STXeq/100 g in tissue). Detection limits for individual toxins ranged from 0.07 microg STXeq/100 g for C1 and C3 to 4.1 microg STXeq/100 g for GTX1. Spike recoveries ranged from 76 to 112% in mussel tissue. The relative standard deviation (RSD) of repeated injections of GTX and STX working standard solutions was < 4%. Uncertainty of measurement at a level of 195 microg STXeq/100 g was 9%, and within-laboratory reproducibility expressed as RSD was 4.6% using the same material. Repeatability of a 65 microg STXeq/100 g sample was 3.0% RSD. Seventy-three samples were analyzed by the new postcolumn method and both AOAC Official Methods for PST determination: the MBA (y = 1.22x + 13.99, r2 = 0.86) and the precolumn LC oxidation method of Lawrence (y = 2.06x + 12.21, r2 = 0.82). 相似文献
95.
Clayton HJ Harding LP Irvine JP Jeffery JC Riis-Johannessen T Laws AP Rice CR Whitehead M 《Chemical communications (Cambridge, England)》2008,(1):108-110
The reaction of a potentially tetradentate bis(pyridyl-thiazole) ligand with acetone is allosterically activated upon complexation with Cd(II) but deactivated by reaction with Cu(I), demonstrating metal-specific allosteric controlled reactivity. 相似文献
96.
Driscoll JA Allard MM Wu L Heeg MJ da Rocha SR Verani CN 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(31):9665-9674
Herein, we describe the synthesis and characterization of a novel series of single-tail amphiphiles LPyCn (Py=pyridine, Cn=C18, C16, C14, C10) and their copper(II)-containing complexes, which are of relevance for patterned films. The N-(pyridine-2-ylmethyl)alkyl-1-amine ligands and their complexes [CuIICl2(LPyC18)] (1), [CuIICl2(LPyC16)] (2), [CuIICl2(LPyC14)] (3), [CuIIBr2(LPyC18)] (4), [CuIIBr2(LPyC16)] (5), and [CuIIBr2(LPyC10)] (6) were synthesized, isolated, and characterized by means of mass spectrometry, IR and NMR spectroscopies, and elemental analysis. Complexes 1, 2, 3, and 6 had their molecular structure solved by X-ray diffraction methods, which showed that the local geometry around the metal center is distorted square planar. With the aim of using these species as precursors for redox-responsive films, an assessment of their electrochemical properties involved cyclic voltammetry in different solvents, with different supporting electrolytes and scan rates. Density functional theory calculations of relevant species in bulk and at interfaces were used to evaluate their electronic structure and dipole moments. The morphology and order of the resulting films at the air/water interface were studied by isothermal compression and Brewster angle microscopy. Biphasic patterned Langmuir films were observed for all complexes except 3 and 6, and dependence on the chain length and the nature of the halogen coligand determine the characteristics of the isotherms and their intricate topology. Complexes 3 and 6, which have shorter chain lengths, failed to exhibit organization. These results exemplify the first comprehensive study of the behavior of single-tail metallosurfactants, which are likely to lead to high-end technological applications based on their patterned films. 相似文献
97.
Dr. Alison C. McQuilken Quang Minh Dao Dr. Allan Jay P. Cardenas Dr. Jeffery A. Bertke Prof. Dr. Stefan Grimme Prof. Dr. Timothy H. Warren 《Angewandte Chemie (International ed. in English)》2016,55(46):14335-14339
We report a new class of frustrated Lewis pairs (FLPs) by the hydroboration of bulky isocyanates iPr2ArNCO (iPr2Ar=2,6‐iPr2C6H3) and Ph2tBuArNCO (Ph2tBuAr=2,6‐Ph2‐4‐tBuC6H2) with Piers’ borane (HB(C6F5)2). While hydroboration of smaller isocyanates such as iPr2ArNCO leads to isocyanate—N/B FLP adducts, hydroboration of the bulkier Ph2tBuArNCO allows isolation of the substrate‐free aminoborane with a short, covalent N?B bond. This confused FLP reversibly binds unsaturated substrates such as isocyanates and isocyanides, suggesting the intermediacy of a “normal” FLP along the reaction pathway, supported by high‐level DFT studies and variable‐temperature NMR spectroscopy. These results underscore the possibility of FLP behavior in systems that possess no obvious frustrated Lewis acid–base interaction. 相似文献
98.
Dr. Subrata Kundu Prof. Dr. S. Chantal E. Stieber Dr. Maryline G. Ferrier Dr. Stosh A. Kozimor Dr. Jeffery A. Bertke Prof. Dr. Timothy H. Warren 《Angewandte Chemie (International ed. in English)》2016,55(35):10321-10325
Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox‐active nitric oxide derivative. Capture of nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [iPr2NNF6]Ni results in reduction of the PhNO ligand to a (PhNO)./? species coordinated to a square planar NiII center in [iPr2NNF6]Ni(η2‐ONPh). Ligand centered reduction leads to the (PhNO)2? moiety bound to NiII supported by XAS studies. Systematic investigation of structure–reactivity patterns of (PhNO)./? and (PhNO)2? ligands reveals parallels with superoxo (O2)./? and peroxo (O2)2? ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand. 相似文献
99.
Benzimidazole- and benzothiazole-quinones: excellent substrates for NAD(P)H:quinone oxidoreductase 1
Newsome JJ Colucci MA Hassani M Beall HD Moody CJ 《Organic & biomolecular chemistry》2007,5(22):3665-3673
A series of benzimidazole- and benzothiazole-quinones has been synthesized. The ability of these heterocyclic quinones to act as substrates for recombinant human NAD(P)H:quinone oxidoreductase (NQO1), a two-electron reductase upregulated in tumour cells, was determined. Overall, the quinones were excellent substrates for NQO1. 相似文献
100.
Evan-Salem T Frish L van Leeuwen FW Reinhoudt DN Verboom W Kaucher MS Davis JT Cohen Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(7):1969-1977
Cation-templated self-assembly of the lipophilic isoguanosine (isoG 1) with different monovalent cations (M(+)=Li(+), Na(+), K(+), NH(4) (+), and Cs(+)) was studied in solvents of different polarity by using diffusion NMR spectroscopy. Previous studies that did not use diffusion NMR techniques concluded that isoG 1 forms both pentamers (isoG 1)(5)M(+) and decamers (isoG 1)(10)M(+) in the presence of alkali-metal cations. The present diffusion NMR studies demonstrate, however, that isoG 1 does not form (isoG 1)(5)M(+) pentamers. In fact, the diffusion NMR data indicates that both doubly charged decamers of formula (isoG 1)(10)2 M(+) and singly charged decamers, (isoG 1)(10)M(+), are formed with lithium, sodium, potassium, and ammonium tetraphenylborate salts (LiB(Ph)(4), KB(Ph)(4), NaB(Ph)(4) and NH(4)B(Ph)(4)), depending on the isoG 1:salt stoichiometry of the solution. In the presence of CsB(Ph)(4), isoG 1 affords only the singly charged decamers (isoG 1)(10)Cs(+). By monitoring the diffusion coefficient of the B(Ph)(4) (-) ion in the different mixtures of solvents, we also concluded that the anion is more strongly associated to the doubly charged decamers (isoG 1)(10)2 M(+) than to the singly charged decamers (isoG 1)(10)M(+). The (isoG 1)(10)2 M(+) species can, however, exist in solution without the mediation of the anion. This last conclusion was supported by the finding that the doubly charged decamers (isoG 1)(10)2 M(+) also prevail in 1:1 CD(3)CN:CDCl(3), a solvent mixture in which the B(Ph)(4) (-) ion does not interact significantly with the self-assembled complex. These diffusion measurements, which have provided new and improved structural information about these decameric isoG 1 assemblies, demonstrate the utility of combining diffusion NMR techniques with conventional NMR methods in seeking to characterize labile, multicomponent, supramolecular systems in solution, especially those with high symmetry. 相似文献