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51.
Biplab K. Bera Subhasis Mallick Arup Mandal Parnajyoti Karmakar Asok K. Datta Alak K. Ghosh 《Transition Metal Chemistry》2010,35(5):541-547
The kinetics of the aqua ligand substitution from hydroxopentaaquarhodium(III) ion, [Rh(H2O)5(OH)]2+, by l-Arginine has been studied spectrophotometrically as a function of Arginine concentration, and temperature, at pH 4.3. The
reaction proceeds via a rapid outer sphere association complex formation step followed by two consecutive steps. The first
of these involves ligand-assisted anation, while the second involves chelation as the second aqua ligand is displaced. The
association equilibrium constant for the outer sphere complex formation has been evaluated together with the rate constants
for the two subsequent steps. The activation parameters for both steps have been evaluated using Eyring’s equation. Thermodynamic
parameters calculated from the temperature dependence of the outer sphere association equilibrium constants are also consistent
with an associative mode of activation. The product of the reaction has been characterized by conductivity measurement and
IR spectroscopic analysis. 相似文献
52.
Haldar B Chakrabarty A Mallick A Mandal MC Das P Chattopadhyay N 《Langmuir : the ACS journal of surfaces and colloids》2006,22(8):3514-3520
Steady-state fluorescence measurements and isothermal titration calorimetric experiments have been performed to study the interaction between a telechelic polymer, pyrene-end-capped poly(ethylene oxide) (PYPY), and sodium alkyl sulfate surfactants having decyl, dodecyl, and tetradecyl hydrocarbon tails. Fluorometric results suggest polymer-surfactant interaction in the very low range of polymer concentrations. The relative variation in the excimer to monomer pyrene emission intensities with varying surfactant concentration reveals that initial addition of surfactant favors intramolecular preassociation until the surfactant molecules start binding with the ethylene oxide (EO) chain. With the growing number of surfactant aggregates along the EO chain, the association becomes hindered due to the polyelectrolyte effect. The results from microcalorimetric titrations in the low concentration range of PYPY solution (approximately 10(-6) M) with alkyl sulfates suggest two kinds of surfactant-polymer interactions, one with the polymer hydrophobic end groups and the other with the ethylene oxide backbone. The overall polymer-surfactant interaction starts at a much lower surfactant concentration for the hydrophobically modified polymers compared to that in the case of unsubstituted poly(ethylene oxide) homopolymer. From the experiments critical aggregation concentration values and the second critical concentration where free micelles start forming have been determined. An endeavor has been made to unveil the mechanism underlying the corresponding associations of the surfactants with the polymer. 相似文献
53.
Das P Mallick A Chakrabarty A Haldar B Chattopadhyay N 《The Journal of chemical physics》2006,125(4):44516
In continuation of our recent study on the steady state photophysics of a biologically active beta-carboline derivative, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), in the present article we have investigated the effect of nanocavity confinement on the excited state dynamics and rotational relaxation of the probe using picosecond time resolved fluorescence and fluorescence anisotropy techniques. The polarity dependent intramolecular charge transfer process is responsible for the remarkable sensitivity of this biological fluorophore in micellar environments. The fluorescence anisotropy decay of AODIQ incorporated inside the micelle is biexponential. The rotational motion of the probe was interpreted on the basis of a two step model consisting of a fast restricted rotation of the probe and a slow lateral diffusion of the probe in the micelle; both coupled to the overall rotation of the micelle. Experimental results reveal that micellar environment causes significant retardation of both the wobbling as well as the translational motion of the probe. 相似文献
54.
Mallick A Haldar B Maiti S Bera SC Chattopadhyay N 《The journal of physical chemistry. B》2005,109(30):14675-14682
Photophysical properties of 3-acetyl-4-oxo-6,7-dihydro-12H-indolo[2,3-a]quinolizine (AODIQ), a bioactive molecule, has been investigated in well-characterized, monodispersed biomimicking nanocavities formed by sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in heptane using steady-state and picosecond time resolved fluorescence and fluorescence anisotropy. The emission behavior of AODIQ is very much dependent upon the water/surfactant mole ratio (W), i.e., on the water pool size of the reverse micellar core. AODIQ exhibits a sharp decrease in fluorescence anisotropy with increasing W, implying that the overall motional restriction experienced by the molecule is decreased with increased hydration. Some of the depth-dependent relevant fluorescence parameters, namely, fluorescence maxima and fluorescence anisotropy (r), have been monitored for exploiting the distribution and microenvironment around the probe in the reverse micelles. Fluorescence spectral position and fluorescence quenching studies suggest that the probe does not penetrate into the reverse micellar core; rather it binds at the interfacial region. Quantitaive estimates of the micropolarity and microviscosity at the binding sites of the probe molecule have been determined as a function of W. 相似文献
55.
K. Mallick 《Physica A》2007,384(1):64-68
We study the long time behaviour of a nonlinear oscillator subject to a random multiplicative noise with a spectral density (or power-spectrum) that decays as a power law at high frequencies. When the dissipation is negligible, physical observables, such as the amplitude, the velocity and the energy of the oscillator grow as power-laws with time. We calculate the associated scaling exponents and we show that their values depend on the asymptotic behaviour of the external potential and on the high frequencies of the noise. Our results are generalized to include dissipative effects and additive noise. 相似文献
56.
We present an analytical study of a nonlinear oscillator subject to an additive Ornstein–Uhlenbeck noise. Known results are mainly perturbative and are restricted to the large dissipation limit (obtained by neglecting the inertial term) or to a quasi-white noise (i.e., a noise with vanishingly small correlation time). Here, in contrast, we study the small dissipation case (we retain the inertial term) and consider a noise with finite correlation time. Our analysis is non perturbative and based on a recursive adiabatic elimination scheme a reduced effective Langevin dynamics for the slow action variable is obtained after averaging out the fast angular variable. In the conservative case, we show that the physical observables grow algebraically with time and calculate the associated anomalous scaling exponents and generalized diffusion constants. In the case of small dissipation, we derive an analytic expression of the stationary probability distribution function (PDF) which differs from the canonical Boltzmann–Gibbs distribution. Our results are in excellent agreement with numerical simulations. 相似文献
57.
Induced Correspondence of a Local π‐Aromatic Sextet in Heteroannulenes: Synthesis and Characterization 下载免费PDF全文
Abhijit Mallick Juwon Oh Prof. Dr. Dongho Kim Masatoshi Ishida Prof. Dr. Hiroyuki Furuta Prof. Dr. Harapriya Rath 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5504-5508
Acid‐catalyzed [3+3] condensation reactions of two hitherto unknown tripyrrane moieties with pentafluorobenzaldehyde has led to the formation of new generation heteroannulene (4.1.4.1) and mutant heteroannulene (1.1.1.1.1.1). Inclusion of local π‐aromatic sextets, namely the N‐methyl pyrrole rings through β,β‐linkages and α,β‐linkages, has led to the isolation of first ever heteroannulenes cross‐conjugated at four points and two points respectively within the macrocycles. 相似文献
58.
Polymer‐supported palladium was synthesized by applying a single‐step wet chemical synthesis route and the resultant composite material was characterized by means of various techniques. Infrared and UV–visible spectra provided information on the chemical structure of the polymer. Microscopy techniques showed the general morphology of the polymer. The oxidation state of palladium was determined using the X‐ray photoelectron spectroscopy method. The synthesized material was applied as a heterogeneous catalyst for the Heck coupling reaction and also as an electrocatalyst for the oxidation of cysteine. 相似文献
59.
60.
Subhasis Mallick Biplab K. Bera Parnajyoti Karmakar Subala Mondal Arup Mandal Alak K. Ghosh 《Journal of solution chemistry》2011,40(3):532-544
The interaction of di-μ-hydroxobis(bipyridyl)dipalladium(II) with the selected bio-relevant ligands: thioglycolic acid (HL1), glutathione(HL2) and DL-penicillamine(HL3) has been studied spectrophotometrically in aqueous medium as a function of complex and ligand concentrations, pH, and temperature
at constant ionic strength. Two consecutive reaction steps are observed: the first step is dependent on the incoming ligand
concentration and the second step which is independent, is assigned to ring closure. The activation parameters, conductivity
data and IR data obtained also support the proposed mechanism. 相似文献