Radiation induced nano-scale free volume modifications in amorphous polymeric material: a study using positron annihilation lifetime spectroscopy

Radiation exposure modifies the nano scale free volume of the polymers which has direct correlation to certain properties of polymeric materials. CR-39 (DOP) polycarbonate polymeric films were exposed to gamma radiation at different doses for the study of nano scale free volume as well as structural and optical properties. An overall increase in the number of free volume holes at all doses was observed. UV–visible studies showed an improvement in the optical properties due to decrease in direct band gap energy. X-ray diffraction spectra of the polymer samples showed the increased amorphous nature of the polymer.     

Structure of de-oxy corticosterone-21-hemisuccinate

Synthetic glucocorticoid de-oxy corticosterone-21-hemisuccinate crystallizes in the monoclinic space group C2, with a = 21.896(2), b = 7.596(3) and c = 14.291(3) Å, Z = 4. Ring A is a distorted half chair, ring B and C are in the chair configuration and ring D is in the 14-half chair configuration. The ring junctions B/C and C/D are both trans. The molecule as a whole is slightly convex towards the -side, with an angle of 18.4(2)° between the C(10)--C(19) and C(13)--C(18) vectors. In addition to packing and stacking interaction, intermolecular hydrogen bonding plays an important role in structural association. The X-ray structure determination of the title compound was undertaken to study its high binding affinity to serum protein like globulin.     

2'-deoxycytidines carrying amino and thiol functionality: synthesis and incorporation by Vent (exo-) polymerase

[reaction: see text] The synthesis of 2'-deoxycytidine nucleosides bearing amino and thiol groups appended to the 5-position of the nucleobase via a butynyl linker is described. The corresponding triphosphates were then synthesized from the nucleoside and incorporated into oligonucleotides by Vent (exo(-)) DNA polymerase. The ability of Vent (exo(-)) polymerase to amplify oligonucleotides containing these functionalized cytidine derivatives in a polymerase chain reaction (PCR) was demonstrated for the amino-functionalized derivative.     

H homonuclear dipolar decoupling at high magic-angle spinning frequencies with rotor-synchronised symmetry sequences

We demonstrate here application of symmetry-adapted sequences of the form to obtain high-resolution ¹H spectra in solid-state nuclear magnetic resonance under high-speed magic-angle spinning. Experimental results are shown for samples of alanine and glycine for spinning speeds up to 30 kHz with radio-frequency nutation rates of around 100 kHz.     

K-K electron capture from adenine and CO2 molecule by fast carbon ions using KLL-Auger electron technique

The experimental measurement of total electron transfer cross section in Bragg peak energy region is important to understand energy loss in the biomolecular system. In this study, we have measured state selective, K-K electron capture and K-ionization cross sections for adenine (C ₅H ₅N ₅) in collisions with fast (2.5–5 MeV/u) C ions. These are compared with the data for smaller gas molecule, CO ₂. These are derived from a study of the KLL-Auger electron emission yields as a function projectile charge state. The K-ionization cross-section (σ_KI) data are compared with the ECUSAR (united and separated atom [USA] approximation with energy loss [E], Coulomb deflection [C], and relativistic [R] corrections) model calculation. The measured σ_KI data and the calculations are in good agreement. The K-K transfer cross-section (σ_K−K) data are compared with the CPSSR (perturbed stationary state [PSS] with Coulomb deflection [C] and relativistic corrections [R]) calculation that underestimates the measured data for such symmetric collision system. The energy dependence of σ_K−K for adenine is found to be flat in contrast to a sharp variation predicted by the model. The K-transfer cross section is found to be substantial fraction of the K-ionization.     

DMSO–POCl3: a reagent for methylthiolation of imidazo[1,2-a]pyridines and other imidazo-fused heterocycles

A practical and metal free method for methylthiolation of imidazo[1,2-a]pyridines and other imidazo-fused heterocycles using DMSO–POCl₃ complex is reported. The reactions are carried out at room temperature that give the corresponding methylthiolated products in good to excellent yield. Further, its application to indole has been demonstrated.     

A year away to 100th year of vitamin E synthesis

Vitamin E was discovered in the year 1922 as a dietary constituent by Herbert McLean Evans and Katharine J. Scott Bishop. Next year we will be celebrating 100th year anniversary of vitamin E discovery. This minireview highlights discoveries of eight naturally available forms (tocopherols and tocotrienols) of vitamin E and their most important synthetic attempts. This minireview is dedicated to the pioneers of vitamin E for serving a crucial biomolecule to the mankind.     

Rapid self-assembly of core-shell organosilicon microcapsules within a microfluidic device

The preparation of hierarchically structured organosilicon microcapsules from commercially available starting materials is described. Using a microfluidic device, an emulsion of dichlorodiphenylsilane is formed in a continuous phase of aqueous glycerol. The silane droplets undergo hydrolysis, condensation, and crystallization within minutes to form self-assembled, core-shell microcapsules. The microparticles have been characterized with light and electron microscopy, nuclear magnetic resonance spectroscopy (NMR), diffusion-ordered NMR spectroscopy (DOSY), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and powder X-ray diffraction (XRD). The characterization data show that the microcapsule walls consist of amorphous, oligomeric poly(diphenylsiloxane) surrounded by a spiny layer of crystalline diphenylsilanediol. Glycerol is occluded within the wall material but is not covalently bound to the silicon components. Glycerol is a crucial element for producing low-dispersity microcapsules with well-ordered surface spines, as the use of methyl cellulose as viscomodifier yields amorphous surfaces.     

Determination of rare-earth elements and yttrium in silicate rocks by sequential inductively-coupled plasma emission spectrometry

An ICP—AES method for determination of rare-earth elements (REE) and yttrium at trace levels in silicate rocks is described. The method involves decomposition of the rock sample by heating with a mixture of hydrofluoric and perchloric acid, followed by precipitation of the REE and Y as oxalates, with calcium as carrier. The oxalate precipitate is ignited to the oxide, which is then dissolved in dilute nitric acid and the solution is used for ICP—AES measurements, with use of pure REE solutions as calibration standards. The method has been applied to the determination of REE in a number of standard reference materials and the results have been compared with the reported values. Three other silicate rock samples have also been analysed for REE and Y by this method.     

Effect of heating on dissociation of water vapor in high-frequency plasmas and formation of hydrogen peroxide in a cold trap downstream of the plasma

At low flow rates (0.7–2.8 mmol hr^–1) and long residence times (2.3–8.5 s) nearly 60% of the input water vapor was decomposed by a 13.56-MHz rf discharge. Downstream of the discharge a trap cooled by liquid nitrogen collected nearly constant yields of H₂O₂. The decomposition is representable by the equation 2H₂O=H₂O₂+H₂. The overall rate of decomposition was found to depend on the absorbed power density. Heating the rf plasma and its spatial afterglow from 25 to 600°C did not significantly change the percent decomposition of H₂O and the formation of H₂O₂. Above 600°C, however, a continuous decrease in H₂O₂ yield was observed with increasing temperature, and this was associated with the increasing formation of H₂O from the dissociated products such as highly excited OH radicals which otherwise produce the precursors of H₂O₂. The same heating effects were observed in the case of the spatial afterglow of a 2.45-GHz microwave cavity discharge in water vapor under essentially similar conditions. It appears that at the high temperatures the reaction OH+OHH₂O+O is favored over the reaction O+OHO₂+H. This limits the formation of O₂ and consequently decreases the H₂O₂ yield.