Keggin ions as UV-switchable reducing agents in the synthesis of Au core-Ag shell nanoparticles

Keggin ion-mediated synthesis of Au core-Ag shell bimetallic nanoparticles is described. Exposure of photochemically reduced aqueous (PW12O40)3- Keggin ions to AuCl4- ions leads to the formation of stable gold nanoparticles capped by the Keggin ions. The surface-bound Keggin ions may then be activated by UV irradiation and, upon exposure to Ag+ ions, reduce the metal ions to form a silver shell around the gold core. That the capping agent not only stabilizes the metal nanoparticles but also plays the role of a switchable reducing agent is a highlight of this approach with important implications in nanomaterials synthesis and catalysis.     

Photo-induced oxidation of aqueous solution of Na2[Mo(V)2O4EDTA] in neutral KBr and K2S2O8 medium

When an aqueous solution of Na₂[Mo(V)₂O₄EDTA] (ethylene diamine tetraacetate) was photolyzed in the presence of excess KBr and K₂S₂O₈ at neutral pH, the complex was found to be oxidized due to the reactions of Br ₂ ^–. and SO ₄ ^–. , respectively. Oxidation of the complex was also observed due to the reactions of the complex with radiolytically generated Br ₂ ^–. and SO ₄ ^–. radicals. When the oxidation of the complex with SO ₄ ^–. was conducted in an unbuffered solution, a chain reaction was observed in the oxidation of the complex. The time resolved kinetics for the formation and decay of different transient intermediates and the relevant rate constants were investigated with a flash photolysis technique, and a probable mechanism for the oxidation process was given.     

Quantitative treatment of the dye partition method of analysis of surfactants and of ionic groups in high polymers

A quantitative treatment of the extraction of ionic dyes from aqueous solutions into organic solvents of low dielectric constant by surfactants or polymers with ionic groups having a charge opposite to that of the dye ion, is presented. The assumption is made that the extracted species are ion-paired in the organic phase. Based on this, a graphical extrapolation method is suggested for the quantitative estimation of ionic groups in polymers. Theoretically, the method should yield quantitative results irrespective of polymer chain length and character. This method of analysis does not require any calibration data.     

Scope of enantioselective palladium(II)-catalyzed aerobic alcohol oxidations with (-)-sparteine

Evaluation of the substrate scope for Pd(II)/ (-)-sparteine catalyzed aerobic oxidative kinetic resolution of secondary alcohols is disclosed. An improved system is found with use of tert-butyl alcohol solvent in which benzylic and aliphatic alcohols as well as alcohols containing olefins are effectively oxidatively resolved. For substrates that successfully undergo oxidative kinetic resolution, k(rel) values are generally between 10 and 20. Successful scale-up of various substrates to 10-mmol scale is described. Extension to oxidative desymmetrization of 1,3-meso-diols is successful with enantiomeric excesses ranging from 78 to 85%.     

SENSITIZER-INDUCED CONFORMATIONAL CHANGES IN LENS CRYSTALLIN—I. PHOTODYNAMIC ACTION OF METHYLENE BLUE AND N-FORMYLKYNURENINE ON BOVINE α-CRYSTALLIN

Abstract— Fluorescence and circular dichroic properties of bovine a-crystallin have been monitored to detect changes in the structural integrity of the protein following photoreactions in the presence of sensitizer, either methylene blue or N-formylkynurenine. Methylene blue-sensitized photooxidation causes a change in the tertiary structure as manifested in the near-UV CD; this is observed within 0.5 h of irradiation during which time tryptophan emission decreases rapidly. Using inhibitors specific for active species of oxygen, it has been shown that singlet oxygen predominantly causes this change but the sensitizer molecules also have some role in this process. Upon 6 h of irradiation in the presence of methylene blue under both aerobic and anaerobic conditions, the thiol groups that were in a non-polar region of the protein are exposed to polar environments. In conformity with these fluorescence results. near-UV CD (tertiary structure) suffers a drastic alteration whereas the far-UV CD (secondary structure) remains virtually unchanged. The studies with inhibitors indicate that sensitizer molecule itself is primarily responsible for this process. This major change in the conformation has been explained by suggesting that a large portion of the protein unfolds in the photosensitized reaction, thereby altering microenviron-ments, orientation, and intermolecular interactions of different amino acids. N-formylkynurenine also shows some changes in the near-UV CD, presumably, caused by H₂O₂ generated in the photosensitized reaction. But the major alteration in the microenvironments of thiol groups and in the near-UV CD, as observed in the case of methylene blue, does not occur even when the protein is irradiated for 6 h in the presence of N-formylkynurenine and air.     

Visible radiation effects on flavocytochrome b2 in dilute aqueous solution: a steady-state and laser flash photolysis study

Irradiation of flavocytochrome b2 by visible radiation at 450 nm in dilute aqueous solution is found to have a devastating effect not only on its activity but also on the important flavin mononucleotide (FMN) constituents. The active site and the substrate binding site are also found to be largely modified on exposure to visible radiation. This has a telling effect on the constituent aromatic amino acids, tryptophan and tyrosine, and therefore justifies the role of FMN as a very potent photosensitizer. Partial unfolding of the irradiated enzyme molecule is also observed. Damage is much greater in deaerated conditions, which indicates that molecular oxygen plays a protecting role in this particular system. The inactivation is mediated through rapid electron transfer from tryptophan and tyrosine to excited flavin, forming flavin semiquinone and tryptophanyl and tyrosinyl radicals, which in turn cause permanent damage at the molecular level.     

Borate ester plasticizer for PEO-based solid polymer electrolytes

Lithium rechargeable batteries featuring solvent-free highly conductive solid polymer electrolytes (SPEs) will make a dramatic impact on the electric and hybrid-electric vehicles (EV/HEV) industry by eliminating hazards related to the use of liquid electrolytes. In this paper, we report the synthesis and characterization of a star-shaped borate ester plasticizer, which was then incorporated into the poly(ethylene oxide) polymer matrix in different proportions. Significant improvement was observed in conductivity, with the best value of 9.1 × 10⁻⁵ S/cm at 30 °C. These borate ester plasticized SPEs also exhibited excellent thermal and electrochemical stabilities.     

A Carbohydrate-based Synthetic Approach to Diverse Structurally and Stereochemically Complex Chiral Polyheterocycles

Chiral polyheterocycles are one of the most frequently encountered scaffolds in natural products and in current drugs repertoire. A carbohydrate-based diversity oriented synthetic (DOS) approach has been employed for gaining access to many structurally diverse and stereochemically complex rigid polyheterocyclic molecules with multiple chiral hydroxyl groups to enhance aqueous solubility. Inexpensive chiral pool of D-Glucose has been judiciously exploited to get access of complex chiral polyheterocyclic structures using inexpensive, common achiral reagents and domino-Knoevenagel hetero-Diels-Alder (DKHDA) reaction as one of the key synthetic tools. Stereochemistry of newly generated stereocenters of polycyclic structures are unambiguously determined through NMR and X-ray crystallographic study. A chemoinformatic comparison (PCA and PMI) with 40 branded blockbuster drugs showed that newly generated polyheterocycles have good three-dimensional scaffold diversity and most of these pass the Lipinski filter of drug-likeness.     

Bio-inspired Underwater Super-Oil-Wettability for Controlling Platelet Adhesion

Control promotion and prevention of platelet adhesion are important for various biomedical applications. In the past, surface topography and chemical modifications have been commonly utilized for tailoring the promotion and prevention of platelet adhesion. Recently, lotus-leaf-inspired superhydrophobicity has appeared as an efficient avenue to prevent platelet adhesion. However, such extreme water repellent interfaces fail to perform upon prolonged and continuous exposure to aqueous phase. In this communication, the strategic use of a catalyst-free 1,4-conjugate addition reaction between amine and acrylate allowed us to investigate the impact of two distinct underwater oil-wettability on platelet adhesion activity. While underwater superoleophobicity inhibited platelet-adhesion, a highly aggregated fibrous network of adhered platelets was observed on underwater superoleophilic coating. Further, this biocompatible and haemocompatible underwater superoleophobic multilayer coating was deposited on a commercially available catheter tube to examine its potential towards the prevention of platelet attachment.