EPR and optical studies on binary mixed alkali-alkaline earth oxide borate glasses doped with Cu<Superscript>2+</Superscript> ions

Mixed alkali alkaline earth oxide borate glasses of the composition (25 – x)Li₂O–xK₂O–12.5BaO–12.5MgO–49B₂O₃–1CuO (x = 0, 5, 10, 15 and 20 mol %) were prepared by the melt quenching technique. The X-ray diffractograms of all the glass samples were recorded at room temperature. Peak free X-ray spectra revealed the amorphous nature of all the prepared glasses. Modulated differential scanning calorimetry (MDSC) was used to determine the glass-transition temperature (T _g ). The probable mixed alkali effect was investigated using experimental techniques like density, molar volume, MDSC, electron paramagnetic resonance (EPR), and optical absorption studies. From the EPR spectra the spin-Hamiltonian parameters were evaluated. The spin-Hamiltonian parameter values indicated that the ground state of \(C{u^{2 + }}is{\kern 1pt} {d_{{x^2} - {y^2}}}\) orbital (²B_1g) and the site symmetry around Cu² is tetragonally distorted octahedral. The variation of g _|| and A _|| as a function of Li₂O content was found to be nonlinear. A broad optical absorption band was observed in all the glasses containing Cu² ions corresponding to ²B_1g → ²B_2g transition. From the optical absorption studies the values of the optical band gap (E _opt) for indirect, direct transitions and Urbarch energy (ΔE) have been evaluated. By co-relating the EPR and optical absorption data, bonding parameters α², β² and β ₁ ² were evaluated.     

Impact of Phosphorothioate Chirality on Double-Stranded siRNAs: A Systematic Evaluation of Stereopure siRNA Designs

Oligonucleotides are important therapeutic approaches, as evidenced by recent clinical successes with antisense oligonucleotides (ASOs) and double-stranded short interfering RNAs (siRNAs). Phosphorothioate (PS) modifications are a standard feature in the current generation of oligonucleotide therapeutics, but generate isomeric mixtures, leading to 2ⁿ isomers. All currently marketed therapeutic oligonucleotides (ASOs and siRNAs) are complex isomeric mixtures. Recent chemical methodologies for stereopure PS insertions have resulted in preliminary rules for ASOs, with multiple stereopure ASOs moving into clinical development. Although siRNAs have comparatively fewer PSs, the field has yet to embrace the idea of stereopure siRNAs. Herein, it has been investigated whether the individual isomers contribute equally to the in vivo activity of a representative siRNA. The results of a systematic evaluation of stereopure PS incorporation into antithrombin-3 (AT3) siRNA are reported and demonstrate that individual PS isomers dramatically affect in vivo activity. A standard siRNA design with six PS insertions was investigated and it was found that only about 10 % of the 64 possible isomers were as efficacious as the stereorandom control. Based on this data, it can be concluded that G1R stereochemistry is critical, G2R is important, G21S is preferable, and G22 and P1/P2 tolerate both isomers. Surprisingly, the disproportionate loss of efficacy for most isomers does not translate into significant gain for the productive isomers, and thus, warrants further mechanistic studies.     

A study on tribological behaviours of ZDDP in polymer thickened lubricating greases

Zinc Dialkyl Dithiophosphate (ZDDP) is a well‐known multifunctional additive for soap based lubricating greases. Polymers are being studied for their performance as lubricating grease thickeners and rheology modifiers. In this work the tribological study of ZDDP was carried out in polypropylene (PP), maleated polypropylene (mPP) and linear low density polyethylene (PE) thickened lubricating greases. Performance of lithium grease was taken as a reference. The tribological properties were evaluated using a four ball tester for EP properties and Optimol SRV‐III machine for coefficient of friction. The mechanism of action of ZDDP in polymer greases was established through analysis of the worn surface of steel balls with scanning electron microscope (SEM) and energy dispersive x‐ray spectroscopy (EDAX). The results show that the performance of ZDDP depends on the thickener system. The antiwear and EP property exhibited by ZDDP varies from polymer to polymer. Poor performance was observed with PP type thickener whereas performance in PE and lithium grease was comparable. Copyright © 2015 John Wiley & Sons, Ltd.     

Mixture of safflower oil and synthetic ester as a base stock for biodegradable lubricants

Biodegradable industrial lubricant applications are gaining popularity with growing environmental concern and stringent government regulations. Plant oils are major base stocks for eco‐friendly green lubricants. However, because of their poor oxidation stability, their applications are restricted to limited usages. Improvements of these plant oils can be made either by addition of functional additives or by chemical/genetic modifications. This paper evaluates the synergistic approach of phenolic and aminic antioxidants in safflower oil. Further, to enhance the oxidation properties of the plant oil, we incorporated and studied synthetic esters (SEs) for thermo‐oxidative stability by using rotating pressure vessel oxidation test and differential scanning calorimeter. The combination of phenolic and aminic antioxidants at a 2 : 1 ratio exhibited the best synergistic effect, when incorporated into a combination of plant oil and SE. In addition to thermo‐oxidative properties, the tribological properties of neat base stocks were also studied. A substitute of mineral oil‐based lubricants can be formulated cost effectively by using an appropriate mixture of plant oil and SE. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of metallic thiophosphates on dropping point and penetration properties of some greases

Thiophosphates of zinc and molybdenum have been used in lubricant formulations to impart extreme pressure and anti-wear properties for some time. Zinc dialkyldithiophosphate has found favour in greases as a multifunctional - antioxidant, extreme pressure and antiwear - additive.     

Identification of a Tricyclic PIII Chiral Auxiliary for Solid-Supported Synthesis of Stereopure Phosphorothioate-Containing Oligonucleotides

Since the recognition of oligonucleotides as a therapeutic modality, significant work has been devoted to improving therapeutic properties, including nuclease stability. Phosphorothioate (PS) modifications of phosphodiesters are one of the most explored chemical modification and integral to currently approved oligonucleotide therapeutics, including antisense oligonucleotides (ASOs) and short interfering RNAs (siRNAs). Insertion of sulfur into the phosphate bridge in an n-mer leads to 2ⁿ isomeric mixtures of PSs, with different nuclease stability and protein-binding properties. Efforts to create stereopure PS-containing oligonucleotides has spurred interest in identifying new synthetic methods. Herein, work on a novel and practical tricyclic P^III chiral auxiliary and its application in solid-supported synthesis of stereopure PS-containing oligonucleotides is reported.