Positron annihilation measurements across the superconducting transition in Y1Ba2Cu3O7−x

Positron lifetime and Doppler broadened annihilation radiation lineshape measurements have been carried out in Y₁Ba₂Cu₃O_7−x as a function of temperature in the range of 300 K to 58 K. The positron lifetime and the peak parameter of the annihilation radiation lineshape are observed to decrease on lowering the temperature without showing any discontinuous change across the superconducting transition temperature of 90 K as determined by susceptibility measurements. The variation of positron annihilation parameters with temperature in the superconducting state is significantly larger than that in the normal state. This is qualitatively explained in terms of the dimerization of oxygen ions in the superconducting state of Y₁Ba₂Cu₃O_7−x .     

Electronic and vibrational spectra of CrO2−4 in cesium halide lattices

The electronic spectra of CrO^2?₄ ions embedded in cesium halide lattices show two well defined bands due to dipole allowed transitions along with some weak bands due to forbidden transitions. All the above bands are interpreted in terms of transitions within molecu ar orbital levels using the Ballhausen and Liehr scheme. It is observed that superposed on the electronic transitions there is a vibrational fine structure which arises due to the coupling between the electronic transitions and the totally symmetric stretching frequency of the ion. IR absorption spectrum of Analar grade CsI :CrO^2?₄ shows seven lines, whereas Specpure CsI :CrO^2?₄ shows five lines. The above spectra are interpreted on the basis of different local symmetries of CrO^2?₄ ions in the lattice.     

Improved SCF interaction energy decomposition scheme corrected for basis set superposition effect

A modified scheme for SCF interaction energy decomposition has been proposed where the nonphysical basis set superposition error (BSSE ) has been corrected by means of the counterpoise method. A new procedure to separate the exchange and induction energy terms free of nonphysical BSSE has been tested in the case of the H₂O dimer. The first order BSSE appears to be non-negligible for strong hydrogen bonded complexes. In addition the scheme allows separation of the long-controversial charge-transfer contribution within the induction term, which has been considerably overestimated in previous studies.     

Improved Utility of Photolabile Solid Phase Synthesis Supports for the Synthesis of Oligonucleotides Containing 3'-Hydroxyl Termini

Oligonucleotides are synthesized on, and cleaved from, a solid phase support (6) using the o-nitrobenzyl intramolecular photochemical redox reaction. The yields of isolated oligonucleotides relative to yields obtained using conventional hydrolytic cleavage vary between 67% and 82.5%. Synthesis of oligonucleotides using phosphoramidites that do not contain N-benzoyl protecting groups enables one to photolytically cleave the biopolymers in good yields using a commonly available UV irradiation source. Tritium labeling indicates that less than 3% thymidine.thymidine photodimers are formed during photolytic cleavage of polythymidylates from 6 using a transilluminator. No UV-induced damage is detected via HPLC analysis of enzymatically digested oligonucleotides that were obtained following photolytic cleavage from 6.     

Highly Luminescent Heterostructured Copper‐Doped Zinc Sulfide Nanocrystals for Application in Cancer Cell Labeling

The structural characteristics of the seed‐mediated synthesis of heterostructured CuS–ZnS nanocrystals (NCs) and Cu‐doped ZnS (ZnS:Cu) NCs synthesized by two different protocols are compared and analyzed. At high Cu dopant concentrations, segregated subclusters of ZnS and CuS are observed. The photoluminescence quantum yield of ZnS:Cu NCs is about 50–80 %; a value much higher than that of ZnS NCs (6 %). Finally, these NCs are coated with a thin silica shell by using (3‐mercaptopropyl)triethoxysilane in a reverse microemulsion to make them water soluble. Cytotoxicity experiments show that these silica‐coated NCs have greatly reduced toxicity on both cancerous HeLa and noncancerous Chinese hamster ovary cells. The labeling of cancerous HeLa cells is also demonstrated.     

Context-dependent photodimerization in isolated thymine-thymine steps in DNA

The effect of 280 nm irradiation on a family of synthetic DNA hairpins possessing an alkane linker connecting a six-base pair stem having a single T-T step located at different positions within the hairpin has been investigated. A single adduct assigned to the product of 2+2 dimerization is obtained except in the case of a T-T step located adjacent to the linker, in which case both 2+2 and 6-4 adducts are obtained. The efficiency of dimerization is similar for three hairpins having a T-T step located within the duplex interior. Lower efficiency is observed for a T-T step located at the open end of the hairpin and in T overhangs, whereas higher efficiency is observed for the T-T step adjacent to the linker and in a single T bulge. The context-dependence of dimerization efficiency is discussed.     

Polyesters with Aromatic Groups in the Backbone from Reactions of 3- and 4-Bromomethylbenzoic Acids with Triethylamine

Abstract

Aromatic polyesters were obtained in relatively good yields (～ 70%) from reactions of 3- and 4-bromomethylbenzoic acids with tri-ethylamine in chlorobenzene. A copolymer was prepared in 58% yield by reaction of a 1:1 mixture of the two acids under similar conditions. The polyesters were characterized by IR, ¹H- and ¹³3C-NMR spectra, x-ray powder diffraction, DSC behavior, solution viscosity, and hydrolysis to the corresponding hydroxymethylbenzoic acids. Molecular weights were determined by ¹H-NMR endgroup analysis. Possible mechanisms for the reactions are discussed.     

Synthesis of Phosphonopeptide Derivatives

In 1959, Horiguchi and Kandatsu¹ first isolated 2-aminomethylphos-phonic acid from ciliate protozoa. Since then the compound has been found in numerous other organisms² and recently it has been found in human brain³, liver, heart and skeletal muscles⁴, and in red blood cell membrane. These findings establish the biological importance of the carbon-phosphorus bond in nature. Quin² suggested that the naturally occurring aminophosphonic acids are bound to proteins and peptides.