Chiral discrimination in stearoyl amine glycerol monolayers

Chiral discrimination in Langmuir monolayers of amphiphilic 1-stearylamine-glycerol is studied using the hybrid quantum mechanical/molecular mechanical method. Using the experimental information about the lattice structure [D. Vollhardt, U. Gehlert, J. Phys. Chem. B. 2002, 106, 4419], the intermolecular interaction profiles for enantiomeric and racemic pair are studied as a function of mutual tilt and azimuth for different values of intermolecular separation. The present study reveals that, at shorter separation, the interaction profile of the racemic pair has deeper minima than the enantiomeric pair, whereas at larger separation the minimum of the enantiomeric pair is deeper. Thus, the theoretical studies reveal an interesting crossover from heterochiral preference to homochiral preference in 1-stearylamine-glycerol monolayers, with the increase in the intermolecular separation corresponding to a larger area per molecule in the monolayer. This predicts that, with gradual compression, the interactions between racemic pair dominate the experimental features, whereas, under nonequilibrium conditions at the beginning of the formation of the condensed phase, the experimental characteristics of homochirality are observable. The study conclusively shows that the chiral structure of the molecule and the lattice packing drive the chiral preference at the mesoscopic level.     

Role of dipolar interaction in the mesoscopic domains of phospholipid monolayers: dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylethanolamine

The role of dipolar interactions in determining the lipid domain shapes at the air-water interface with a change in the chemical structure of the head groups of lipids is theoretically studied. The phospholipids considered are dipalmitoylphosphatidylcholine (D,L-DPPC) and dipalmitoylphosphatidylethanolamine (DPPE). Despite closely similar chemical structures, the domains of the two lipids are strikingly different. The DPPC domains exhibit elongated arms, while the DPPE domains are nearly round-shaped. To compare the dipolar repulsions in the domains of the two phospholipids, different energy-minimized conformers of DPPC and DPPE are studied using the semiempirical quantum chemical method (PM3). It is found that the dipole moment of DPPC is significantly larger than that of DPPE. The in-plane and out-of-plane components of the dipole moments are calculated using grazing incidence X-ray diffraction data at different surface pressure values, as used in the experiment. The result indicates that the magnitude of the dipolar interaction is significantly larger in DPPC than that in DPPE over the surface pressure range considered. The enhanced dipolar repulsion corroborates well with the difference in the domain shapes in the two phospholipid monolayers. The larger dipolar repulsion in DPPC leads to development of elongated domain arms, while relatively less dipolar repulsion allows a closed shape of the condensed-phase DPPE domains.     

Preparation of size-controlled, highly populated, stable, and nearly monodispersed Ag nanoparticles in an organic medium from a simple interfacial redox process using a conducting polymer

The reducing property of an organically soluble conducting polymer (poly(o-methoxyaniline), POMA) is used to prepare monodisperse, size-controlled, highly populated, and highly stable silver nanoparticles in an organic medium through an interfacial redox process with an aqueous AgNO3 solution. The transition of emeraldine base (EB) to the pernigraniline base (PB) form of POMA occurs during nanoparticle formation, and the nitrogen atoms of POMA(PB) stabilize Ag nanoparticles by coordination to the adsorbed Ag(+) on the nanoparticle surface. The conductivity of the nanocomposite is on the order of 10(-11) S/cm, indicating that no doping of POMA occurs under the preparation conditions. The nanoparticles are free of excess oxidant and external stabilizer particles. The POMA (EB) concentration tailors the size of nanoparticles, and at its higher concentration (0.01% POMA with 0.01 N AgNO3), very dense Ag nanoparticles (6 x 10(15) particles/m(2)) of almost uniform size and shape are produced. The rate constant and Avrami exponent values of the nanoparticle formation are measured from the time-dependent UV-vis spectra using the Avrami equation. The Avrami exponent (n) values are close to 1, indicating 2D athermal nucleation with the circular shape of the nuclei having diffusion-controlled growth. The rate constant values are almost independent of AgNO3 concentration but are strongly dependent on POMA concentration. The higher rate constant with increasing POMA(EB) concentration has been attributed for the lowering of nanoparticle size due to increased nucleation density.     

An equilibrium study on the distribution of structural defects between the lamellar and amorphous portions of poly(vinylidene fluoride) and (vinylidene fluoride‐tetra fluoro ethylene) copolymer crystals

Samples of poly(vinylidene fluoride) (PVF₂) and (vinylidene fluoride‐tetra fluoroethylene) (VF₂‐VF₄) copolymer were etched with a chromium‐based etching reagent. The etching rate was lower for the VF₂‐VF₄ copolymer samples than for the PVF₂ samples. The melting point and enthalpy of fusion increased with increased etching time of the etched specimen. This was also true for the melt‐quenched (etched) samples, whose values were always lower than those obtained from the direct run of the etched samples. The scanning electron micrographs of specimens etched for 24 h indicated that only the amorphous portion was etched without affecting the crystalline lamella. The sequence distribution of the PVF₂ and VF₂‐VF₄ copolymer crystals were determined by ¹⁹F NMR measurements of the samples and their etched species. The observed probabilities (P_obs), calculated from the integrated area of the NMR peaks, indicated that the crystalline lamella had a more oriented chain structure than that of the amorphous overlayer portion. The head‐to‐head defects calculated from the aforementioned sequence analysis indicated a greater propensity in the amorphous portion than in the crystalline lamella. The equilibrium constant (K) for the distribution of defects between the lamella and amorphous portion of the crystal varied from 0.7 to 0.9. It was higher at a higher quenching rate of the crystallization, and in the isothermal crystallization, it also had a substantially high value, indicating the equilibrium inclusion of defects in the crystal. The distribution constant increased with an increase in the defect content in the chain and decreased with an increase in the defect size. The sequence distribution data, analyzed through a suitable melting‐point depression equation, indicated a defect energy of 2.25 kcal/mol for the α‐phase PVF₂ crystals and 0.68 kcal/mol for the β‐phase VF₂‐VF₄ copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 297–308, 2000     

pH‐Dependent Nitrotyrosine Formation in Ribonuclease A is Enhanced in the Presence of Polyethylene Glycol (PEG)

Protein nitration can occur as a result of peroxynitrite‐mediated oxidative stress. Excess production of peroxynitrite (PN) within the cellular medium can cause oxidative damage to biomolecules. The in vitro nitration of Ribonuclease A (RNase A) results in nitrotyrosine (NT) formation with a strong dependence on the pH of the medium. In order to mimic the cellular environment in this study, PN‐mediated RNase A nitration has been carried out in a crowded medium. The degree of nitration is higher at pH 7.4 (physiological pH) compared to pH 6.0 (tumor cell pH). The extent of nitration increases significantly when PN is added to RNase A in the presence of crowding agents PEG 400 and PEG 6000. PEG has been found to stabilize PN over a prolonged period, thereby increasing the degree of nitration. NT formation in RNase A also results in a significant loss in enzymatic activity.     

Current gain and external quantum efficiency modeling of GeSn based direct bandgap multiple quantum well heterojunction phototransistor

This paper aims to provide the performance characteristics of proposed, strain balanced direct band gap multiple quantum wells (MQWs) hetero phototransistor (HPT) made of SiGeSn/GeSn alloys grown on Si substrate which is compatible with recent CMOS fabrication technology. This also presents a comprehensive comparison of this proposed structure with the existing HPT structure made of indirect gap Ge/SiGe MQWs. Alloys of Ge and Sn grown on Si platform shows about tenfold increase in absorption over Ge at C and L-bands due to direct nature of band gap in GeSn. Initial work begins the solution of continuity equation to solve the different terminal current densities and optical gain of the multiple quantum well structure. Main analysis was concentrated on finding the external quantum efficiency depending on the doping variations of emitter and base, base width etc. Finally the photocurrent density variations are estimated for the structure and compared with existing indirect band gap HPT. The calculated values for direct band gap GeSn HPT device are found to be comparable with those for indirect band gap SiGe device to flourish as a potential candidate of photo detectors for the present day telecommunication network.     

Cobalt-thioalkylazoimidazole complexes: Structures, spectra and redox properties

1-Alkyl-2-{(o-thioalkyl)phenylazo}imidazole (SRaaiNR^/, 1) reacts with Co(ClO₄)₂·6H₂O to form [Co(SRaaiNR^/)₂](ClO₄)₂ (2). The single crystal X-ray structure of one of the complexes of 2 shows a tridentate chelation N(imidazole), N(azo), S(thioether) system. In the structure one of ClO₄⁻ anions shows disorder and forms an (imidazole)C–H···O(ClO₃) interaction leading to a 1-D chain. Co(OAc)₂.4H₂O and SRaaiNR^/ react in the presence of NH₄SCN (1:1:2 mole ratio) in methanol and the complex [Co(SRaaiNR^/)₂(SCN)₂] (3) has been separated. The single crystal X-ray structure determination has established the structure of the complexes in which the ligand SRaaiNR^/ acts in a bidentate N(imidazole), N(azo) chelation mode. A cyclic voltammogram shows a Co(III)/Co(II) oxidative response at 0.6–0.8 V and azo reductions. DFT computation using optimized geometry support the electronic spectral and redox properties of the complexes.     

Dinucleosides with non-natural backbones: a new class of ribonuclease A and angiogenin inhibitors

Ribonuclease?A (RNase A) serves as a convenient model enzyme in the identification and development of inhibitors of proteins that are members of the ribonuclease superfamily. This is principally because the biological activity of these proteins, such as angiogenin, is linked to their catalytic ribonucleolytic activity. In an attempt to inhibit the biological activity of angiogenin, which involves new blood vessel formation, we employed different dinucleosides with varied non-natural backbones. These compounds were synthesized by coupling aminonucleosides with dicarboxylic acids and amino- and carboxynucleosides with an amino acid. These molecules show competitive inhibition with inhibition constant (K(i)) values of (59±3) and (155±5) μM for RNase A. The compounds were also found to inhibit angiogenin in a competitive fashion with corresponding K(i) values in the micromolar range. The presence of an additional polar group attached to the backbone of dinucleosides was found to be responsible for the tight binding with both proteins. The specificity of different ribonucleolytic subsites were found to be altered because of the incorporation of a non-natural backbone in between the two nucleosidic moieties. In spite of the replacement of the phosphate group by non-natural linkers, these molecules were found to selectively interact with the ribonucleolytic site residues of angiogenin, whereas the cell binding site and nuclear translocation site residues remain unperturbed. Docked conformations of the synthesized compounds with RNase A and angiogenin suggest a binding preference for the thymine-adenine pair over the thymine-thymine pair.