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991.
The authors have investigated the interactions of the reaction centers, participating in the charge transfer reaction within the DNA molecule with the phosphate backbones and the solvent molecules, and have estimated the contribution of these interactions into the charge migration in DNA. They have determined the unequal shift of the energy surfaces of the initial and final transition states of the transfer reaction along the energy axis and the dependence of the magnitude of the energy shift on the nature of the reaction centers and the surrounding environment. The nonuniform distribution of the negative charge in the DNA phosphate backbones results in an increase of the positive shift of the energy surface of the DNA base pairs in the center of the structure, where the maximum density of the negative charge is concentrated. Localization of the positive charge on the guanine and the adenine in the DNA base pairs in the oxidized state results in a dependence of the free energy of reaction in the solvent on the pair sequences and their arrangement in the DNA chain. As an example, for the G-C/A-T configuration the positive charges are localized on the same strand that results in a decrease of the free energy of reaction in the solvent for charge migration from G-C to A-T pair by 0.125 eV. 相似文献
992.
The correlation between statistical properties of the energy landscape and the number of accessible configurational states, as measured by the exponential of the excess entropy (e(Se)), are studied in the case of a simple Lennard-Jones-type liquid in the neighborhood of the thermodynamic freezing transition. The excess entropy Se is defined as the difference between the entropy of the liquid and that of the ideal gas under identical temperature and pressure conditions and is estimated using the pair correlation contribution, S2. Landscape properties associated with three categories of configurations are considered: instantaneous configurations, inherent saddles, and inherent minima. Landscape properties studied include the energy and the key parameters of the Hessian eigenvalue distribution as well as the mean distances between instantaneous configurations and the corresponding inherent saddles and minima. The signatures of the thermodynamic freezing transition are clearest in the case of inherent structure properties which show, as a function of e(S2), a pronounced change in slope in the vicinity of the solid-liquid coexistence. The mean distance between instantaneous and saddle configurations also shows a similar change in slope when the system crosses from the stable to the supercooled regime. In the case of inherent saddles, the minimum eigenvalue acts as a similar indicator of the thermodynamic freezing transition but the average and maximum eigenvalues do not carry similar signatures. In the case of instantaneous configurations, a weak indicator of the thermodynamic freezing transition is seen in the behavior of the fraction of negative curvature directions as a function of the exponential of the excess entropy. 相似文献
993.
Basu Ray G Chakraborty I Ghosh S Moulik SP 《Journal of colloid and interface science》2007,307(2):543-553
Self-aggregation of mixed binary nonionic and ionic surfactants comprising N-methyl-N-decanoyl glucamide (MEGA 10) and alkyltrimethylammonium bromides (C(12)-, C(14)-, and C(16)TAB) has been investigated in detail by different physical methods. The counter-ion binding, aggregation number, and polarity of the mixed micelles have been determined. The results have been analyzed in the light of the theories of Rubingh and Maeda. The thermodynamic parameters of the micellization process have been evaluated and discussed. The interfacial adsorptions of the mixed amphiphiles including their surface excesses and head-group areas have also been evaluated. Based on the head-group areas, the overall shapes of the mixed micelles have been predicted from the estimation of the amphiphile packing parameters. 相似文献
994.
Chakraborty P Fasfous II Murimboh J Chakrabarti CL 《Analytical and bioanalytical chemistry》2007,388(2):463-474
There is a growing awareness of the importance of quantitative determinations of speciation parameters of the trace metals Cu, Zn, Cd and Pb in aqueous samples containing chemically heterogeneous humic substances, especially when they are present together, interacting with one another and competing for specific binding sites of the humic substances. Such determinations require fundamental knowledge and understanding of these complex interactions, gained through basic laboratory-based studies of well-characterized humic substances in model solutions. Since the chemical heterogeneity of humic substances plays an important role in the thermodynamics (stability) and kinetics (lability) of trace metal competition for humic substances, a metal speciation technique such as pseudopolarography that can reveal the special, distinctive nature of metal complexation is required, and it was therefore used in this study. A comparison of the heterogeneity parameters (Gamma) for Zn(II), Cd(II), Pb(II) and Cu(II) complexes in model solutions of Suwannee River fulvic acid (SRFA) shows that GammaCd>GammaZn>GammaPb>GammaCu, suggesting that SRFA behaves as a relatively homogeneous complexant for Zn(II) and Cd(II), whereas it behaves as a relatively heterogeneous complexant for Pb(II) and an even more heterogeneous complexant for Cu(II) under the experimental conditions used. The order of values of log K* (from the differential equilibrium function, DEF) for the trace metals at pH 5.0 follow the sequence: log K*Cu>log K*Pb>log K*Zn>log K*Cd. These results are in good agreement with the literature values. The results of this work suggest the possibility of simultaneously determining several metals in a sample in a single experiment, and hence in a shorter time than required for multiple experiments. 相似文献
995.
Brajagopal Samanta Joy Chakraborty R.K. Bhubon Singh Manas K. Saha Stuart R. Batten Paul Jensen M. Salah El. Fallah Samiran Mitra 《Polyhedron》2007
Two new cyano bridged Cu–Co and Cu–Fe trinuclear bimetallic assemblies, [(CuL)[Co(CN)6](CuL)]ClO4 · 3.5H2O (1) and [(CuL)[Fe(CN)6](CuL)] · 13H2O (2) where [L = (3E,5E)-N1,N4-bis((pyridin-2-yl)methylene)butane-1,4-diamine] have been prepared using cyanometallates as anion precursors and characterised by elemental analyses, spectroscopic studies, single crystal X-ray diffraction and cryomagnetic susceptibility measurements. Magneto-structural correlations have been drawn from cryomagnetic susceptibility measurements over a wide temperature range (2–300 K) under 0.5 T magnetic fields. Weak antiferromagnetic interactions with J = −0.81 and −0.73 cm−1 are found for 1 and 2, respectively, showing a very weak coupling, as expected from the diamagnetic long chain –NC–Co–CN–CN– and –NC–Fe–CN–CN– bridges revealed from the single crystal X-ray diffraction studies. 相似文献
996.
In this paper, a generalized surface-kinetics based model is developed to analytically investigate the influences of the substrate types and the buffer compositions on the macromolecular transport and hybridization in microfluidic channels, under electrokinetic influences. For specific illustration, three typical microchannel substrates, namely silanized glass, polycarbonate and PDMS, are considered, in order to obtain analytical expressions for their zeta potentials as a function of the buffer pH and the substrate compositions. The expressions for the zeta potential are subsequently employed to derive the respective velocity distributions, under the application of electric fields of identical strengths in all cases. It is also taken into consideration that the charged macromolecules introduced into these channels are subjected to electrophoretic influences on account of the applied electric fields. Closed form expressions are derived to predict the transport behaviour of the macromolecules and their subsequent hybridization characteristics. From the analysis presented, it is shown that the modification of the channel surface with silane-treatment becomes useful for enhancing the macromolecular transport and surface hybridization, only if the buffer pH permits a large surface charge density. The analytical solutions are also compared with full-scale numerical solutions of the coupled problem of fluid dynamic and macromolecular transport in presence of the pertinent surface reactions, in order to justify the effectiveness of closed-form expressions derived in this study. 相似文献
997.
Mitra D Chakraborty I Bhattacharya SC Moulik SP 《Langmuir : the ACS journal of surfaces and colloids》2007,23(6):3049-3061
The adsorption and solution behaviors of symmetrical tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides (TMAB, TEAB, TPAB, and TBAB, respectively) were studied at the air/water interface and in the bulk aqueous environments. Their salts were prepared by reacting tetraalkylammonium bromide (TAAB) with sodium dodecyl sulfate (SDS) in a solution from which the products of the higher two homologues (tetrapropylammonium dodecyl sulfate (TPADS) and tetrabutylammonium dodecyl sulfate (TBADS)) could only be isolated as solids and for which detailed characterization has been performed. The interfacial behaviors of 1:1 molar mixtures of TAAB and SDS and the prepared TPADS and TBADS were examined. Micellization of the 1:1 mixtures along with the isolated species were studied in the presence and absence of NaBr salt. The energetics of the micellization process and the counterion binding of the micelles were evaluated. The interaction of the TAABs with SDS micelles was examined, and the results were evaluated in terms of single- and two-site binding interaction models. Of the formed tetraalkylammonium dodecyl sulfates (TAADSs), only TBADS evidenced clouding, which was investigated in detail along with 1:1 molar mixtures of TBAB and SDS in aqueous solution in the presence of additives such as NaBr, SDS, and TBAB. The solution behaviors of the TAADS and the clouding of TBADS have been rationalized in terms of a mixed micellar model. 相似文献
998.
Charles Turquand d’Auzay Nilanjan Chakraborty 《Proceedings of the Combustion Institute》2021,38(2):2775-2782
The localised forced ignition and the early stages of the subsequent flame propagation in a planar turbulent methane/air jet in ambient air have been simulated using Direct Numerical Simulation (DNS) and a two-step chemical mechanism. Sixteen identical energy depositions events were simulated for four independent flow realisations at four different locations. The successful ignition and subsequent flame propagation have been found to be well correlated to the mean mixture fraction and flammability factor values of the energy deposition location. Furthermore, similarly to what has been observed in experiments, the early stages of flame development from the ignition kernel involved initial downstream convection of the kernel, followed by simultaneous radial expansion and downstream propagation and finally the upstream propagation of the flame base indicating the onset of flame stabilisation. The mixture composition and the scalar dissipation rate (SDR) values in the immediate vicinity of the ignitor have been identified to play key roles in determining the outcome of the external energy deposition, while the development of an edge flame structure propagating along the stoichiometric mixture fraction iso-surface was found to be necessary but not sufficient for the flame to propagate upstream. It has also been found that in the case of successful self-sustained burning, the edge flame was developing in low SDR regions, and that the most probable edge flame speed remains close to the theoretical laminar value irrespective of the flame development history. Finally, the mean flame speed of the edge flame elements propagating towards the nozzle exit has been found to be considerably greater than the unstrained laminar burning velocity. Thus, the edge flame, depending on its orientation with respect to the flow, is able to propagate upstream and initiate the onset of flame stabilisation. 相似文献
999.
Raju Pandey Ashim Kumar Biswas Ujjal Chakraborty 《International Journal of Communication Systems》2024,37(9):e5764
This article investigates the mutual coupling reduction of a compact two elements wearable ultra-wideband (UWB) multiple-input multiple-output (MIMO) antenna. The ground plane of the proposed wearable MIMO antenna structure consists of three connected square ring-shaped stubs and two rectangular slots of narrow height. These ground stubs and slots minimize the mutual coupling effect between antennas and provide high isolation. The suggested MIMO antenna functions from the 1.87 to 13.82 GHz frequency spectrum covering WLAN (2.4–2.484 GHz), UWB (3.1–10.6 GHz), and X band (8–12 GHz) with 152.32% fractional bandwidth. It sustains port isolation above 27 dB throughout the 2 to 13.82 GHz frequency band. Inside the whole working frequency band, the suggested antenna offers a tiny envelope correlation coefficient (ECC < 0.098), greater diversity gain (DG > 9.93 dB), minimum channel capacity loss (CCL < 0.32 bits/s/Hz), and slight magnitude variation in mean effective gain of antenna ports (< 0.1 dB). The recommended antenna yields a SAR level below the designated threshold (<1.6 W/kg), affirming its suitability for body-worn applications. The designed MIMO antenna structure has an overall volume of 32 × 48 × 1.5 mm3. 相似文献
1000.
Shyamapada Shit Joy Chakraborty Anamika Das Glenn P. A. Yap M. S. El. Fallah Samiran Mitra 《Structural chemistry》2007,18(3):317-323
A one-dimensional (1-D) copper(II) coordination polymer [Cu(maleate)(2,2′-bipyridyl)]
n
·2H2O has been synthesised. Single crystal X-ray diffraction study reveals that maleate ion bridges two adjacent copper(II) centres
along the chain in a syn–anti fashion. A complete cryomagnetic investigation of the title complex correlates well with the distorted square pyramidal geometry
of the central copper(II) ion and bridging nature of the maleate. A τ value of 0.26 indicates the distortion towards tbp coordination allowing the magnetic orbital to acquire some character leading to a weak antiferromagnetic interaction having J = −0.26 cm−1. The complex has also been firmly established from several other instrumental techniques like Fourier transform infrared
(FT-IR) and EPR spectroscopies. 相似文献