Effect of iodine sorption on the free volume of polycarbonate

 The effect of iodine sorption on the free volume of polycarbonate is investigated by Positron Annihilation Lifetime method. The observed results are interpreted in terms of the Charge Transfer Complex formation and precipitation of iodine at the initial and final stages of sorption, respectively. At higher levels of sorption, changes in the second lifetime and its intensity seem to suggest a conformational transformation, probably due to the net change in the amorphous-crystalline boundary regions of the polymer matrix. The free volume cavities have been predominantly occupied by I^- ₃ species and the diffusion process obeys Fick’s law. An exponential type correlation has been observed between fractional free volume and the diffusion coefficient. Received: 13 June 1996/Accepted: 20 September 1996     

A Miura of the Painlevé I Equation and Its Discrete Analogs

We present Miura transformations for the continuous and several discrete Painlev\'e I equations. In the case of the continuous P_I, we use the Hamiltonian formulation of the Painlev\'e equations and show that there exists a Miura transformation between P_I and the binomial, second degree, equation of Cosgrove SD_V. In the case of the discrete P_I's we obtain two different kinds of Miuras. One kind relates a d-P_I to some other d-P_I while the other leads to discrete four-point equations which are the discrete analogs of the derivative of Cosgrove's equation SD_V.     

Contiguity relations for linearisable systems of Gambier type

We introduce the Schlesinger transformations for the Gambier, linearisable, equation and by combining the former construct the contiguity relations of the solutions of the latter. We extend the approach to the discrete domain obtaining thus the Schlesinger transformations and the contiguity relations of the solutions of the Gambier mapping. In all cases the resulting contiguity relation is a linearisable equation, involving free functions, and which can be related to the generic Gambier mapping.     

Reactive blends derived from modified soybean oil and silicone

Reactive blends prepared from methoxysilane terminated silicone polymers and silylated soybean oil are described and characterized. Although simple mixing of soy and silicones results in gross phase separation, homogeneous polymeric products are obtained by introducing reactive sites. These products can be used as protective coatings, additives to adhesives and new sealants. Exposure of the mixtures to moisture leads to hydrolysis of the methoxysilanes and subsequent condensation of the resulting silanols that yields stable siloxane linkages between the two immiscible phases. FTIR, TGA, and swell‐gel analyses indicate effective formation of these siloxane crosslinks. Reactive blends containing less than 20% silylated oil appeared completely transparent but increasing the soy content decreased the optical transparency. SEM micrographs reveal the silicone polymer as the continuous phase with individual spherical silylated soy oil particles distributed in it. The properties of these reactive blends vary from high elongation elastomers to high modulus resins depending on the composition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3086–3093     

An Improved Procedure for Hydrosilation of α,β-Unsaturated Esters and an Extension to Conjugated Diene Esters

Treatment of α,β-unsaturated esters with triethylsilane in benzene in the presence of a catalytic amount of tris(triphenylphosphine)rhodium chloride at room temperature followed by chromatography on silica gel gave rise to the corresponding saturated esters. Under similar conditions, fully conjugated diene esters were reduced to the dihydrolevel to give β,γ- or γ,δ-unsaturated esters depending upon the substitution pattern of the starting substrate.     

Serendipitous discovery of light-induced (<Emphasis Type="Italic">In Situ</Emphasis>) formation of an Azo-bridged dimeric sulfonated naphthol as a potent PTP1B inhibitor

Background

Protein tyrosine phosphatases (PTPs) like dual specificity phosphatase 5 (DUSP5) and protein tyrosine phosphatase 1B (PTP1B) are drug targets for diseases that include cancer, diabetes, and vascular disorders such as hemangiomas. The PTPs are also known to be notoriously difficult targets for designing inihibitors that become viable drug leads. Therefore, the pipeline for approved drugs in this class is minimal. Furthermore, drug screening for targets like PTPs often produce false positive and false negative results.

Results

Studies presented herein provide important insights into: (a) how to detect such artifacts, (b) the importance of compound re-synthesis and verification, and (c) how in situ chemical reactivity of compounds, when diagnosed and characterized, can actually lead to serendipitous discovery of valuable new lead molecules. Initial docking of compounds from the National Cancer Institute (NCI), followed by experimental testing in enzyme inhibition assays, identified an inhibitor of DUSP5. Subsequent control experiments revealed that this compound demonstrated time-dependent inhibition, and also a time-dependent change in color of the inhibitor that correlated with potency of inhibition. In addition, the compound activity varied depending on vendor source. We hypothesized, and then confirmed by synthesis of the compound, that the actual inhibitor of DUSP5 was a dimeric form of the original inhibitor compound, formed upon exposure to light and oxygen. This compound has an IC₅₀ of 36 μM for DUSP5, and is a competitive inhibitor. Testing against PTP1B, for selectivity, demonstrated the dimeric compound was actually a more potent inhibitor of PTP1B, with an IC₅₀ of 2.1 μM. The compound, an azo-bridged dimer of sulfonated naphthol rings, resembles previously reported PTP inhibitors, but with 18-fold selectivity for PTP1B versus DUSP5.

Conclusion

We report the identification of a potent PTP1B inhibitor that was initially identified in a screen for DUSP5, implying common mechanism of inhibitory action for these scaffolds.

     

Perturbation solution for secondary bifurcation in the quadratically-damped Mathieu equation

This paper concerns the quadratically-damped Mathieu equation:

     

An easily accessible Re-based catalyst for the selective conversion of methanol: evidence for an unprecedented active site structure through combined operando techniques

Heterogeneous Re/SiO(2) catalysts prepared using a one pot sol-gel synthesis were found to display high activity in the direct, selective methanol conversion to methylal, which is correlated to an unprecedented rhenium oxide structure.     

A study of the discrete Pv equation: Miura transformations and particular solutions

We derive the form of the Miura transformation of the discrete P_v equation and show that it is indeed an auto-Bäcklund transformation, i.e. it relates the discrete P_v to itself. Using this auto-Bäcklund, we obtain the Schlesinger transformations of discrete P_v which relate the solution for one set of the parameters of the equation to that of another set of neighbouring parameters. Finally, we obtain particular solutions of the discrete P_v (i.e. solutions that exist only for some specific values of the parameters). These solutions are of two types: solutions involving the confluent hypergeometric function (on codimension-one submanifold of parameters) and rational solutions (on codimension-two submanifold of parameters).