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1.
The thermal and photochemical fragmentations of a few bisazoalkenes have been investigated. 2-Phenyl-4,5-disubstituted-1, 2,3-triazoles were obtained both in the thermolysis and photolysis of 1, 2-bisphenylazo-(4, 4′-dichloro) stilbene, 1, 2-bisphenylazo(4, 4′-dimethoxy)stilbene, 1, 2-bisphenylazocyclohexene and o-(phenylazo) phenyldiazocyanide. Both 2, 3-bisphenylazo-2-butene and 1, 2-bisphenylazoethylene failed to undergo either photolysis or thermolysis in the expected manner. However, 2, 3-bisphenylazo-2-butene underwent an acid-catalysed valence isomerisation to anhydro 1-phenylimino-2-phenyl-4, 5-dimethyl-1, 2, 3-trizolium hydroxide, which on photolysis gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. The same iminotriazolium intermediate gave a cycloadduct, 2, 6-diphenyl-3, 3a-dimethyl-4, 5-dicarbomethoxypyrazolino [2.3.c][1.2.3] triazole, on treatment with dimethyl acetylenedicarboxylate, whereas treatment with carbon disulphide gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. Both photolysis and thermolysis of C-biphenylene-Nα(4-chlorophenyl)-Nβ-cyanoazomethine imine gave 9-fluorenone-N- (4-chlorophenyl) anil. Photolysis of 1, 2-bisphenylazoacenaphthylene in methanol gave acenaphthenequinone monophenylhydrazone. 相似文献
2.
Cytochrome P-450 isozymes represent a critical component of nature’s spectrum of detoxification catalysts that could be exploited
for bioremediation. The ethanol-inducible human cytochrome P-450 2E1 serves as a model eukaryotic P-450 that complements the
bacterial P-450 cam in dehalogenation and detoxification of environmental pollutants. We explored the construction of novel
chimeric P-450s using cytochrome P-450 camC and 2E1 genes. For construction of chimera 1 (478 amino acids, 55.14 kDa), 145 amino acids from the N-terminus of P-450 2E1 protein
(493 amino acids, 56.84 kDa) were replaced with 130 amino acids from the N-terminus of P-450 camC protein (415 amino acids,
46.66 kDa). In chimera 2 (525 amino acids, 60.24 kDa) the strategy involves replacement of 28 amino acids in the C-terminus
of chimera 1 with 75 amino acids from the C-terminus of P-450 camC gene. Homology models of both the chimeric proteins were
developed using SWISS-MODEL based on the known crystal structure of cytochrome P-450 camC, BM-3, 1DT6A, and 2C17A. The models
indicated that the proposed heme-binding site was intact, which is inevitable for catalytic activity of cytochrome P-450s.
The expression of chimera 1 and 2 genes in Escherichia coli DH5α was evident from light-pink cell pellets, protein band in sodium dodecyl sulfate polyacrylamide gel electrophoresis,
and diagnostic carbon monoxide-difference spectra. Our studies show that strategies can be developed to exploit the natural
diversity of the P-450 superfamily to generate chimeric biocatalysts that would provide new templates amenable to directed
evolution. 相似文献
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4.
Jeongyun Heo Thomas A. Sobiech Hilliard L. Kutscher Lee Chaves Dinesh K. Sukumaran Shanta Karki Admire Dube Paras N. Prasad Jessica L. Reynolds 《Macromolecular bioscience》2021,21(1)
A nanoformulation composed of curdlan, a linear polysaccharide of 1,3‐β‐linked d ‐glucose units, hydrogen bonded to poly(γ ‐glutamic acid) (PGA), was developed to stimulate macrophage. Curdlan/PGA nanoparticles (C‐NP) are formulated by physically blending curdlan (0.2 mg mL?1 in 0.4 m NaOH) with PGA (0.8 mg mL?1). Forster resonance energy transfer (FRET) analysis demonstrates a heterospecies interpolymer complex formed between curdlan and PGA. The 1H‐NMR spectra display significant peak broadening as well as downfield chemical shifts of the hydroxyl proton resonances of curdlan, indicating potential intermolecular hydrogen bonding interactions. In addition, the cross peaks in 1H‐1H 2D‐NOESY suggest intermolecular associations between the OH‐2/OH‐4 hydroxyl groups of curdlan and the carboxylic‐/amide‐groups of PGA via hydrogen bonding. Intracellular uptake of C‐NP occurs over time in human monocyte‐derived macrophage (MDM). Furthermore, C‐NP nanoparticles dose‐dependently increase gene expression for TNF‐α, IL‐6, and IL‐8 at 24 h in MDM. C‐NP nanoparticles also stimulate the release of IL‐lβ, MCP‐1, TNF‐α, IL‐8, IL‐12p70, IL‐17, IL‐18, and IL‐23 from MDM. Overall, this is the first demonstration of a simplistic nanoformulation formed by hydrogen bonding between curdlan and PGA that modulates cytokine gene expression and release of cytokines from MDM. 相似文献
5.
l-Glutamine amidohydrolase (l-glutaminase, EC 3.5.1.2) is a therapeutically and industrially important enzyme. Because it is a potent antileukemic agent
and a flavor-enhancing agent used in the food industry, many researchers have focused their attention on l-glutaminase. In this article, we report the continuous production of extracellular l-glutaminase by the marine fungus Beauveria bassiana BTMF S-10 in a packed-bed reactor. Parameters influencing bead production and performance under batch mode were optimized
in the order-support (Na-alginate) concentration, concentration of CaCl2 for bead preparation, curing time of beads, spore inoculum concentration, activation time, initial pH of enzyme production
medium, temperature of incubation, and retention time. Parameters optimized under batch mode for l-glutaminase production were incorporated into the continuous production studies. Beads with 12×108 spores/g of beads were activated in a solution of 1% glutamine in seawater for 15 h, and the activated beads were packed
into a packed-bed reactor. Enzyme production medium (pH 9.0) was pumped through the bed, and the effluent was collected from
the top of the column. The effect of flow rate of the medium, substrate concentration, aeration, and bed height on continuous
production of l-glutaminase was studied. Production was monitored for 5 h in each case, and the volumetric productivity was calculated. Under
the optimized conditions for continuous production, the reactor gave a volumetric productivity of 4.048 U/(mL·h), which indicates
that continuous production of the enzyme by Ca-alginate-immobilized spores is well suited for B. bassiana and results in a higher yield of enzyme within a shorter time. The results indicate the scope of utilizing immobilized B. bassiana for continuous commercial production of l-glutaminase. 相似文献
6.
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8.
Sathish K. Sukumaran Gary S. Grest Kurt Kremer Ralf Everaers 《Journal of polymer science. Part A, Polymer chemistry》2005,43(8):917-933
Similar to entangled ropes, polymer chains cannot slide through each other. These topological constraints, the so-called entanglements, dominate the viscoelastic behavior of high-molecular-weight polymeric liquids. Tube models of polymer dynamics and rheology are based on the idea that entanglements confine a chain to small fluctuations around a primitive path which follows the coarse-grained chain contour. To establish the microscopic foundation for these highly successful phenomenological models, we have recently introduced a method for identifying the primitive path mesh that characterizes the microscopic topological state of computer-generated conformations of long-chain polymer melts and solutions. Here we give a more detailed account of the algorithm and discuss several key aspects of the analysis that are pertinent for its successful use in analyzing the topology of the polymer configurations. We also present a slight modification of the algorithm that preserves the previously neglected self-entanglements and allows us to distinguish between local self-knots and entanglements between distant sections of the same chain. Our results indicate that the latter make a negligible contribution to the tube and that the contour length between local self-knots, Nlk is significantly larger than the entanglement length Ne. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 917–933, 2005 相似文献
9.
Babu SS Saeki A Seki S Möhwald H Nakanishi T 《Physical chemistry chemical physics : PCCP》2011,13(11):4830-4834
The coassembly of C(60) derivatives through arene-perfluoroarene interactions has been used for the first time to develop millimeter-sized flat crystalline sheets. Time-resolved microwave conductivity (TRMC) measurements exhibited anisotropic features with over double the charge carrier mobility in the direction parallel to the plane of the crystal than perpendicular to the plane. This study demonstrates a strategy to obtain large-sized 2-dimensional architectures of C(60) with anisotropic optoelectronic functions. 相似文献
10.
Goudappagouda Ananthakrishnan Manthanath Vivek Chandrakant Wakchaure Kayaramkodath Chandran Ranjeesh Tamal Das Kumar Vanka Takashi Nakanishi Sukumaran Santhosh Babu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(8):2306-2310
Organic phosphors have been widely explored with an understanding that crystalline molecular ordering is a requisite for enhanced intersystem crossing. In this context, we explored the room‐temperature phosphorescence features of a solvent‐free organic liquid phosphor in air. While alkyl chain substitution varied the physical states of the bromonaphthalimides, the phosphorescence remained unaltered for the solvent‐free liquid in air. As the first report, a solvent‐free liquid of a long swallow‐tailed bromonaphthalimide exhibits room‐temperature phosphorescence in air. Doping of the phosphor with carbonyl guests resulted in enhanced phosphorescence, and hence a large‐area paintable phosphorescent liquid composite with improved lifetime and quantum yield was developed. 相似文献