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61.
Subhajit Bal Krishnendu Das Sahnawaz Ahmed Dibyendu Das 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(1):250-253
In living systems, dissipative processes are driven by the endergonic hydrolysis of chemical fuels such as nucleoside triphosphates. Now, through a simple model system, a transient self‐assembled state is realized by utilizing the catalytic effect of histidine on the formation and breaking of ester bonds. First, histidine facilitates the ester bond formation, which then rapidly co‐assembles to form a self‐supporting gel. An out‐of‐equilibrium state is realized owing to the cooperative catalysis by the proximal histidines in the assembled state, driving the second pathway and resulting in disassembly to sol. Cooperative effects that use the dual role of imidazoles as nucleophile and as proton donor is utilized to achieve transient assemblies. This simple system mimics the structural journey seen in microtubule formation where the substrate GTP facilitates the non‐covalent assembly and triggers a cooperative catalytic process, leading to substrate hydrolysis and subsequent disassembly. 相似文献
62.
We present exact and analytically accurate results for the problem of a flexible polymer chain in shear flow. Under such a flow the polymer tumbles, and the probability distribution of the tumbling times tau of the polymer decays exponentially as approximately exp(-alphatau/tau_{0}) (where tau_{0} is the longest relaxation time). We show that for a Rouse chain this nontrivial constant alpha can be calculated in the limit of a large Weissenberg number (high shear rate) and is in excellent agreement with our simulation result of alpha approximately 0.324. We also derive exactly the distribution functions for the length and the orientational angles of the end-to-end vector R of the polymer. 相似文献
63.
We consider heat conduction across an ordered oscillator chain with harmonic interparticle interactions and also onsite harmonic
potentials. The onsite spring constant is the same for all sites excepting the boundary sites. The chain is connected to Ohmic
heat reservoirs at different temperatures. We use an approach following from a direct solution of the Langevin equations of
motion. This works both in the classical and quantum regimes. In the classical case we obtain an exact formula for the heat
current in the limit of system size N→∞. In special cases this reduces to earlier results obtained by Rieder, Lebowitz and Lieb and by Nakazawa. We also obtain
results for the quantum mechanical case where we study the temperature dependence of the heat current. We briefly discuss
results in higher dimensions. 相似文献
64.
65.
Dibyendu Ganguli 《Journal of solid state chemistry》1979,30(3):353-356
A survey of known compounds which can assume K2NiF4-type structure at least over a certain P, T range was made. The cationic radius ratios rA/rB of this family of compounds were found to vary over a relatively narrow range of values around 2.00, in contrast to the much wider ranges known for other important A2BX4 structure groups, e.g., β-K2SO4, thenardite, olivine, etc., providing thereby a constraint on the crystal chemical variabilities in this group of compounds. Usefulness of the simple size parameter rA(IX)/rB(VI) in predicting formation of new K2NiF4-type compounds is discussed. 相似文献
66.
Dibyendu Das 《Tetrahedron letters》2007,48(32):5635-5639
The ionic liquid (IL), tetrakis (2-hydroxyethyl) ammonium triflouromethanesulfonate is rationally designed for horseradish peroxidase (HRP) on the basis of its stability and activity in the presence of an excipient, tris(hydroxymethyl)aminoethane (TRIS) in different ILs. The activity of HRP in this tailor made IL is at least 30-240-fold higher than that in conventional ILs. Also, the activity is more than 10 times greater than that in methanol, a common organic solvent used for HRP. 相似文献
67.
Sarkar J Chowdhury J Ghosh M De R Talapatra GB 《The journal of physical chemistry. B》2005,109(26):12861-12867
Surface-enhanced Raman scattering (SERS) spectra of the biologically important 2-aminobenzothiazole (2-ABT) molecule adsorbed on silver hydrosols are compared with its FTIR spectrum and normal Raman spectroscopy (NRS) spectrum in the bulk and in solution. The optimized structural parameters and the computed vibrational wavenumbers of the compound have been estimated from ab initio (Hatree-Fock) and density functional calculations. Some vibrational modes of the molecule have been reassigned. Concentration-dependent SERS spectra of the molecule reveal the existence of two types of vertically adsorbed species on colloidal silver particles, whose relative population varies with the adsorbate concentrations. The adsorption geometry and structural parameters of one type of adsorbed species are related to the NRS spectrum of the chemically prepared and theoretically modeled 2-ABT-Ag(I) coordination compound. 相似文献
68.
Km. Meenu Dibyendu S. Bag Rekha Lagarkha Radha Tomar Arvind Kumar Gupta 《Phosphorus, sulfur, and silicon and the related elements》2020,195(4):348-358
AbstractWe report the synthesis and characterization of multifunctional polysilane copolymers containing chiral and azobenzene chromophore as a pendant group. Multifunctional polymers of poly(methylphenylsilane) (PMPS) with (R)-N-(1-phenylethyl)methacrylamide (R-NPEMAM) and disperse red 1 methacrylate (DR1MA) were synthesized in a quartz tube using UV-technique. The molecular weights of such synthesized copolymers were found to be in the order of 103. The appearance of two glass transition temperatures in DSC indicated that the synthesized copolymers are block copolymers. The electronic absorbance of synthesized polymers was observed at 272?nm (π-π* transition of aromatic ring), 330?nm (σ-σ* transition of Si-Si chain of PMPS) and 475?nm (n-π* with π-π* transition due to azobenzene chromophore of DR1MA unit). The chirality of the synthesized polymer was confirmed through circular dichroism observed at 261?nm. Induced chirality appeared at 330?nm and 470?nm due to the association of the Si-Si chain of PMPS and the presence of azobenzene chromophore of the DR1MA unit respectively. The photoluminescence (PL) properties of the synthesized copolymers (SCDRDM-1B, SCDRDM-2B, and SCDRDM-3B) were observed at 307?nm and 415?nm when excited at 275?nm. The λem was also observed at 415?nm when excited by 325?nm. The multi-emission spectra appeared at 500?nm, 550 and 590?nm are presumed to be due to exciton coupling between azobenzene chromophore of DR1MA, and Si-Si σ-conjugation in association with the aromatic ring of PMPS and chiral unit R-NPEMAM block. 相似文献
69.
Self-assembly properties of a single-tailed chiral cationic surfactant, (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide (DMEB), have been studied in water. The molecular self-assemblies of the amphiphile have been characterized by surface tension, fluorescence probes, light scattering, and microscopic techniques. The results have been compared with those of dodecyltrimethylammonium bromide (DTAB) surfactant. The critical aggregation concentration of DMEB was found to be much less than that of DTAB. Surface tension and fluorescence probe studies have suggested formation of micellar structures at low temperature (<28 degrees C) and spontaneous formation of giant vesicles in water above 28 degrees C. The mean size of the aggregates has been measured by a dynamic light scattering method. The micropolarity and microviscosity of the self-assemblies were determined by fluorescence probe technique. The (1)H NMR and FTIR spectra were recorded to elucidate the role of the hydrophobic head group towards the formation of bilayer structures. The phase transition temperatures of the vesicular aggregates were determined by measurement of fluorescence anisotropy at various temperatures. 相似文献
70.
Sudip Baguli Subham Sarkar Soumajit Nath Dr. Dibyendu Mallick Dr. Debabrata Mukherjee 《Angewandte Chemie (International ed. in English)》2023,62(47):e202312858
Azomethine ylides are typically in situ generated synthons for making N-heterocycles through cycloaddition reactions. But an offbeat aspect about them is the isomeric nature of aldiminium-based azomethine ylides and (alkyl/aryl)(amino)carbenes, interconvertible by a formal 1,3-H+ transfer. Herein, two thermally robust azomethine ylides with a N-appended picolyl sidearm are isolated, which cyclize to pyaziridines at 80 °C but unprecedentedly result N−picoCAAC-CuCl (CAAC=cyclic(alkyl)(amino)carbene) complexes when heated with CuCl at merely 60 °C. The pendant Npy, as revealed by computational analysis, plays a crucial role in this unusual 1,3-H+ shift using a deprotonation-protonation sequence, as well as in placing the CuCl at the carbenic site in tandem. The softer nature of Cu(I) is also critical. Chelating CAACs are rare and one with a N-tethered additional donor is priorly unknown. Both N-picoCAAC and pyaziridine are bidentate chelators giving highly active cationic Rh(I) catalysts for hydrosilylating unactivated olefins by Et3SiH. Notably, the pyaziridine-Rh(I) is superior than the N-picoCAAC-Rh(I) catalyst. 相似文献