Background: Dual-process models propose that recognition memory (RM) involves two processes: conscious recollection and familiarity-aware memory. Studies investigating RM in schizophrenia report a selective deficit in conscious recollection and intact levels of familiarity-driven RM for stimuli presented in the visual and olfactory domains. It has been suggested that abnormalities in conscious recollection result from a breakdown in frontal strategic memory processes involved in encoding and retrieval and executive functions linked to reality monitoring and decision making.
View Article and Find Full Text PDFUltrafast relaxation dynamics of the excited singlet (S(1)) state of Michler's ketone (MK) has been investigated in different kinds of solvents using a time-resolved absorption spectroscopic technique with 120 fs time resolution. This technique reveals that conversion of the locally excited (LE) state to the twisted intramolecular charge transfer (TICT) state because of twisting of the N,N-dimethylanilino groups with respect to the central carbonyl group is the major relaxation process responsible for the multi-exponential and probe-wavelength-dependent transient absorption dynamics of the S1 state of MK, but solvation dynamics does not have a significant role in this process. Theoretical optimization of the ground-state geometry of MK shows that the dimethylanilino groups attached to the central carbonyl group are at a dihedral angle of about 51 degrees with respect to each other because of steric interaction between the phenyl rings.
View Article and Find Full Text PDFThe effect of the microenvironment of a Nafion membrane on the excited-state proton transfer (ESPT) of 2-(2'-pyridyl)benzimidazole (2PBI) has been investigated by steady-state and time-resolved fluorescence spectroscopy. The mechanism of the ESPT is found to depend remarkably on the water content of the membrane. In the protonated form of the membrane, ESPT is found to involve the dicationic (D) form of the fluorophore, whereas in cation-exchanged membranes, it is found to involve the monocation (C).
View Article and Find Full Text PDFPhotoisomerization of 3,3'-diethyloxadicarbocyanine iodide (DODCI) has been investigated in water, 5% and 30% aqueous triblock copolymer, poly(ethylene oxide)20-poly(propylene oxide)70-poly(ethylene oxide)20 (P123) by measuring the fluorescence quantum yields and lifetimes in the temperature range 293-318 K. Reports available in literature indicate that 5% aqueous P123 exists as micellar solution, whereas 30% aqueous P123 forms gel due to micelle-micelle entanglement. This study has been undertaken to find out how the polyene photoisomerization rates are influenced in the sol and gel phases.
View Article and Find Full Text PDFThough organ transplantation has evolved in many a ways over the years, it is not without the disadvantage of causing rejections. Cyclosporin, azathioprine and corticosteroids are time tested and efficacious; however each is accompanied with its own array of disadvantages. Sirolimus is a relatively new immunosuppressant isolated from a macrolide antibiotic.
View Article and Find Full Text PDFResonance Raman (RR) and surface-enhanced resonance Raman scattering (SERRS) of 4'-(N,N'-dimethylaminostyryl)-4-propylpyridinium bromide (hemicyanine, HC dye) in acetonitrile solution and on a colloidal silver surface have been investigated. The structure of the dye in the ground (S0) and excited (S1) electronic states was optimized using density functional calculations along with the B3LYP and the configuration interaction with the singlet excitation (CIS) methods, respectively, using the 6-31G basis set. The vibrational frequencies of the molecule were computed at the optimized geometry and compared with the observed Raman bands.
View Article and Find Full Text PDFWe have investigated the structure and electronic properties of cesium clusters following all electron ab initio theoretical methods based on configuration interaction, second-order Moller-Plesset (MP2) perturbation theory, and density-functional theory. Becke's three-parameter nonlocal hybrid exchange-correlation functional (B3LYP) is found to perform best on the present systems with a split valence 3-21G basis function. We have calculated the optimized geometries of neutral and singly charged cesium clusters having up to ten atoms, their binding energy per atom, ionization potentials (IPs), and adiabatic electron affinity (EA).
View Article and Find Full Text PDFThe work presents ab initio results on structure and electronic properties of Br2*-.nH2O(n=1-10) and Br2.nH2O(n=1-8) hydrated clusters to study the effects of an excess electron on the microhydration of the halide dimer.
View Article and Find Full Text PDFThe JAK/STAT pathway was first identified in mammals as a signaling mechanism central to hematopoiesis and has since been shown to exert a wide range of pleiotropic effects on multiple developmental processes. Its inappropriate activation is also implicated in the development of numerous human malignancies, especially those derived from hematopoietic lineages. The JAK/STAT signaling cascade has been conserved through evolution and although the pathway identified in Drosophila has been closely examined, the full complement of genes required to correctly transduce signaling in vivo remains to be identified.
View Article and Find Full Text PDFJ Colloid Interface Sci
May 2006
An end-to-end assembly of spherical Ag nanoparticles takes place in the presence of biotin to form long fiberlike microstructures. These microstructures are about 4 mum long with a thickness of 1 mum, obtained from SEM studies. TEM studies showed the presence of spherical silver nanoparticles having an average size of 20 nm.
View Article and Find Full Text PDFIn an attempt to understand the nature of interactions between organic solutes and room temperature ionic liquids, temperature-dependent rotational relaxation of two structurally similar nondipolar solutes--2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP)--has been examined in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim+][PF6(-)]). Even with the ionic liquid, where the cation and the anion are strongly associated, the solute DPP experiences specific interactions, which is evident from its reorientation times that are 50%-60% longer in relation to DMDPP. It has been noticed that the reorientation times of both the solutes are faster in [bmim+][PF6(-)] than in glycerol, which is also a strongly associated solvent and whose viscosity is similar to the ionic liquid.
View Article and Find Full Text PDFA series of metal-ligand complexes were prepared by the reaction of various metal ions, namely, Cu(II), Mn(II), or Fe(II) with phenolic derivatives of [catechol, chlorogenic acid (CGA), n-propyl gallate (nPG), 3-hydroxy anthranilic acid, resveratrol, and rutin] and characterized by UV-vis spectroscopy. The metal/ligand complexing ratio and complexation constants have been determined. The complexes were probed for their reactivity toward various free radicals (e aq-, CO2*-, and O2*-).
View Article and Find Full Text PDFNonrelativistic energy of the (2p(2))(3)P(e) state of Be(2+) has been calculated using Ritz-variational method. The trial wave function is of Hylleraas type. The upper-bound energy E=-3.
View Article and Find Full Text PDFReactions of sulfasalazine (SAZ) and its metabolites, 5-aminosalicylic acid (5-ASA) and sulfapyridine (SP), with various oxidizing and reducing free radicals (hydroxyl, haloperoxyl, one-electron oxidizing, lipid peroxyl, glutathiyl, superoxide, tryptophanyl, etc.) have been studied to understand the mechanistic aspects of its action against free radicals produced during inflammation. Nanosecond pulse radiolysis technique coupled with transient spectrophotometry has been used for in situ generation of free radicals and to follow their reaction pathways.
View Article and Find Full Text PDFRotational dynamics of two structurally similar hydrophobic solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), has been investigated in 30% wv aqueous solution of triblock copolymer, poly(ethylene oxide)(20)-poly(propylene oxide)(70)-poly(ethylene oxide)(20) as a function of temperature. This study has been undertaken in an attempt to explore how the dynamics of a solute molecule solubilized in a copolymer solution is influenced when it undergoes sol-to-gel transition. It has been observed that the anisotropy decays of both DMDPP and DPP can be described by biexponential functions in the sol as well as in the gel phase.
View Article and Find Full Text PDFPhotoinduced electron transfer (ET) between coumarin dyes and aromatic amine has been investigated in two cationic micelles, namely, cetyltrimethyl ammonium bromide (CTAB) and dodecyltrimethyl ammonium bromide (DTAB), and the results have been compared with those observed earlier in sodium dodecyl sulphate (SDS) and triton-X-100 (TX-100) micelles for similar donor-acceptor pairs. Due to a reasonably high effective concentration of the amines in the micellar Stern layer, the steady-state fluorescence results show significant static quenching. In the time-resolved (TR) measurements with subnanosecond time resolution, contribution from static quenching is avoided.
View Article and Find Full Text PDFThis paper presents a model for the efficient and accurate simulations of laminar diffusion-based complex electrokinetic passive micromixers by representing them as a system of mixing elements of relatively simple geometry. Parameterized and analytical models for such elements are obtained, which hold for general sample concentration profiles and arbitrary flow ratios at the element inlet. A lumped-parameter and system-level model is constructed for a complex micromixer, in which the constituent mixing elements are represented by element models, in such a way that an appropriate set of parameters are continuous at the interface between each pair of adjacent elements.
View Article and Find Full Text PDFA density-functional theory is presented to study the structure of polymers, having attractive interactions, confined between attractive surfaces. The theory treats the ideal-gas free-energy functional exactly and uses weighted density approximation for the hard-chain contribution to the excess free-energy functional. The bulk interactions of freely jointed hard spheres are obtained from generalized Flory equation of state and the attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure.
View Article and Find Full Text PDFA simple dual vessel in situ analyte distillation (IAD) system has been developed for suppressed ion chromatographic determination of chloride and fluoride ions in complex matrices. In IAD system, water vapours generated from the outer vessel reacts with sulfuric acid generating heat, thus favouring the quantitative distillation of chloride and fluoride within 30 min on water bath temperature (approximately 80 degrees C). The distilled analytes, as their respective acids in water, were directly injected into an ion-chromatograph.
View Article and Find Full Text PDFPolygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed.
View Article and Find Full Text PDFWe have cloned and expressed the 43 kDa N-terminal domain of Leishmania donovani topoisomerase II. This protein has an intrinsic ATPase activity and obeys Michaelis-Menten kinetics. Cross-linking studies indicate that the N-terminal domain exists as a dimer both in the presence and absence of nucleotides.
View Article and Find Full Text PDFEngagement of the receptor for advanced glycation end products (RAGE) by its signal transduction ligands is implicated in the development and progression of atherosclerosis. TNFalpha, a proinflammatory cytokine, is a potent inducer of RAGE expression in endothelial cells. In the present study, we demonstrate that reactive oxygen species (ROS) generated by TNFalpha stimulated human umbilical vein endothelial cells (HUVECs) induce RAGE expression.
View Article and Find Full Text PDFCardiovascular diseases (CVD) are the most significant cause of death in postmenopausal women. The loss of estrogen biosynthesis with advanced age is suggested as one of the major causes of higher CVD in postmenopausal women. While some studies show beneficial effects of estrogen therapy (ET)/hormonal replacement therapy (HRT) in the cardiovascular system of healthy postmenopausal women, similar studies in diabetic counterparts contradict these findings.
View Article and Find Full Text PDFEstrogens are known to induce the expression of the receptor for advanced glycation end products (RAGE). In the current investigation, we examined the effect of three estrogens with different potency for specific estrogen receptors (ER) on RAGE expression in human microvascular endothelial cells (HMEC-1). Of the three estrogens tested, ethinyl estradiol (EE), an estrogen receptor alpha (ERalpha) agonist, was the strongest inducer of RAGE expression in HMEC-1.
View Article and Find Full Text PDFPhotoinduced electron transfer (ET) reactions between anthraquinone derivatives and aromatic amines have been investigated in sodium dodecyl sulphate (SDS) micellar solutions. Significant static quenching of the quinone fluorescence due to high amine concentration in the micellar phase has been observed in steady-state measurements. The bimolecular rate constants for the dynamic quenching in the present systems k(q) (TR), as estimated from the time-resolved measurements, have been correlated with the free energy changes DeltaG(0) for the ET reactions.
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