Ester derivatives of α-hydroxymethylacrylates: Itaconate isomers giving high molecular weight polymers

New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using acid chlorides (traditional solution reactions), sodium salts of acids (with phase transfer catalysis), and trifluoroacetic anhydride (trifluoroacetate). The interfacial process gave high yields of clean products under very mild conditions. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with 2,2′-azobis (isobutyronitrile) gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million [based on size-exclusion chromatography (SEC) comparison to polystyrene standards]. These high molecular weights were the result of autoacceleration in the bulk as shown by monitoring molecular weight with respect to conversion. Solution polymerization in benzene gave more typical polymer, e.g., the acetate derivative showed an SEC molecular weight of 52,000. Glass transition temperatures for the n-alkyl esters decreased from the formate (77°C) to the hexanoate (15°C); the stearate showed a side-chain melting point of 40°C but no T_g. Glass transitions were observed for the trifluoroacetate, benzoate, and adamantanoate polymers at 69, 130, and 214°C, respectively. Solution ¹³C-NMR showed evidence of tacticity information for the formate and acetate derivatives with appaent preference for syndiotactic polymer formation similar to that of methyl methacrylate. FTIR and solid-state ¹³C-NMR analysis gave spectra with functional group peaks and chemical shift values expected based on composition. The stearate monomer and polymer gave solid-state ¹³C chemical shifts of 34 and 33 ppm, respectively, for the central CH₂ units consistent with monoclinic and orthorhombic crystal packing. © 1994 John Wiley & Sons, Inc.     

Oxidation of isobutane catalyzed by vanadyl, copper and cesium substituted H3PMo12O40

Effects of Cs⁺, H⁺ and Cu²⁺ counterions in the vanadium containing heteropoly compounds Cs_xH_1-xVO[PMo₁₂O₄₀] and Cs_yH_0.5-yCu_0.25VO[PMo₁₂O₄₀] on the catalytic oxidation of isobutane and characterization by TGA, IR and ESR spectroscopies are reported. A high selectivity of 76% for methacrylic acid and methacrolein together has been obtained with Cs_0.75H_0.25VO[PMo₁₂O₄₀] catalysts at a reactivity of 5.3x10^-1 mmol/h cm³.     

Optimization of tetramethoxysilane-derived sol gel entrapment protocol stabilizes highly active chlorophyllase

Entrapment of membrane proteins is a challenging task compared to that involving soluble proteins. Chlorophyllase, a membrane protein, was successfully entrapped in tetramethoxysilane-derived sol-gel. Pre-gel sol typically consists of an aqueous suspension of chlorophyllase, precursors including tetramethoxysilane and/or methytrimethoxysilane, and sodium fluoride as catalyst. To obtain a highly active entrapped enzyme preparation, the effects of various immobilization parameters, including the chemical compositions of pre-gel sol (water/silane ratio, precursor type and proportions, enzyme loading, sodium fluoride concentration), and sol-gel process parameters (aging and drying time and approach) have been investigated. Chlorophyllase demonstrated the highest activity in gel derived from a pre-gel sol with water/silane ratio of 30 and enzyme loading of 0.257 mg_protein/g_gel, and showed moderately lower activity in organically modified sol-gel than that in hydrophilic sol-gel. The effects of water/silane ratio and precursor combinations on the activity of entrapped chlorophyllase were also studied by examining the pore morphology of gel via nitrogen adsorption-desorption. Longer aging time leads to an entrapped chlorophyllase preparation with higher activity. Chlorophyllase preparation demonstrated negligible activity after air-drying for 12 h while lyophilized chlorophyllase preparation demonstrated 8, 4 and 4 times higher activity than air-dried, vacuum-dried and solvent-dried preparations. Chlorophyllase demonstrated 30% higher activity in the improved sol-gel protocol than that from a non-optimized sol-gel protocol developed in a previous study.     

Proposed Mechanism for the Antitrypanosomal Activity of Quercetin and Myricetin Isolated from Hypericum afrum Lam.: Phytochemistry,In Vitro Testing and Modeling Studies

The in vitro activity of L. donovani (promastigotes, axenic amastigotes and intracellular amastigotes in THP1 cells) and T. brucei, from the fractions obtained from the hydroalcoholic extract of the aerial part of Hypericum afrum and the isolated compounds, has been evaluated. The chloroform, ethyl acetate and n-butanol extracts showed significant antitrypanosomal activity towards T. brucei, with IC₅₀ values of 12.35, 13.53 and 12.93 µg/mL and with IC₉₀ values of 14.94, 19.31 and 18.67 µg/mL, respectively. The phytochemical investigation of the fractions led to the isolation and identification of quercetin (1), myricitrin (2), biapigenin (3), myricetin (4), hyperoside (5), myricetin-3-O-β-d-galactopyranoside (6) and myricetin-3’-O-β-d-glucopyranoside (7). Myricetin-3’-O-β-d-glucopyranoside (7) has been isolated for the first time from this genus. The chemical structures were elucidated by using comprehensive one- and two-dimensional nuclear magnetic resonance (1D and 2D NMR) spectroscopic data, as well as high-resolution electrospray ionization mass spectrometry (HR-ESI–MS). These compounds have also been evaluated for their antiprotozoal activity. Quercetin (1) and myricetin (4) showed noteworthy activity against T. brucei, with IC₅₀ and IC₉₀ values of 7.52 and 5.71 µM, and 9.76 and 7.97 µM, respectively. The T. brucei hexokinase (TbHK1) enzyme was further explored as a potential target of quercetin and myricetin, using molecular modeling studies. This proposed mechanism assists in the exploration of new candidates for novel antitrypanosomal drugs.     

Studies on Azolylacetonitriles: The Reactivity of Thiazole-2-yl,Thiadiazol-2-yl Acetonitriles Toward Electrophilic Reagents

5-Acetyl-2-cyanomethyl-4-methylthiazole, 2-aminothiazole, and 5-N-benzoylamino-1,3,4-thiadiazole-2-yl-acetonitrile react with acetone, and malononitrile derivatives in the presence of sulfur to yield the corresponding thiophene derivatives. Also, 4-furylmethylene-2-phenyl-2-oxazolin-5-ones react with thiophenol, and/or thionaphthol to give the thiolester derivatives in one-pot synthesis. The structures of the products were based on IR, 1 H NMR, and elemental analysis.     

Exact Spin Coherent State Path Integral for a Damped Two-Level Atom in an Electromagnetic Wave

The spin coherent state path integral describing the dynamics of a two-level system interacting with electromagnetic wave of circular polarization is considered. The propagator is first written in the standard form by replacing the spin by a unit vector aligned along the polar and azimuthal directions. Then it is determined exactly using a simple transformations. Thus, the exact energy spectra with corresponding wave functions are deduced.     

Study of pure and semileptonic decays of Ds meson within R-parity violating supersymmetric model

We present the comaprative study of semileptonic and leptonic decays of Ds, D±and D0meson（D →M l＋-αl-β, D → l＋αlβ, D → l＋αvα;α,β=e,μ） within the framework of R-parity violating the（ Rp） Minimal Supersymmetric Standard Model（MSSM）. The comparison shows that combination and product couplings,（λβiα λ＊ ij qor λβqkλ＊αj k）contribution to the branching fractions of the said processes（under consideration） is consistent with or comparable to the experimental measurements in most of the cases. However, some cases exist where these contributions are highly suppressed. We identify such cases in our analysis and single out the important ones suitable for exploring in the future and current experiments.     

Multifunctional mesoporous silica nanoparticles in poly(ethylene‐co‐vinyl acetate) for transparent heat retention films

Transparent inorganic‐polymer nanocomposite films are of tremendous current interest inemerging solar coverings including photovoltaic encapsulants and commercial greenhouse plastics, but suffer from significant radiative heat loss. This work provides a new and simple approach for controlling this heat loss by using mesoporous silica/quantum dot nanoparticles in poly(ethylene‐co‐vinyl acetate) (EVA) films. Mesoporous silica shells were grown on CdS‐ZnS quantum dot (QDs) cores using a reverse microemulsion technique, controlling the shell thickness. These mesoporous silica nanoparticles (MSNs) were then melt‐mixed with EVA pellets using a mini twin‐screw extruder and pressed into thin films of concentration variable controlled thickness. The results demonstrate that the experimental MSNs showed improved infrared and thermal wavebands retention in the EVA transparent films compared to commercial silica additives, even at lower concentrations. It was also found MSNs enhanced the quantum yield and photostability of the QDs, providing high visible light transmission and blocking of UV transmission of interest for next generation solar coatings. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 851–859     

Nanostructured Lipid Carriers (NLC) for Biologically Active Green Tea and Fennel Natural Oils Delivery: Larvicidal and Adulticidal Activities against Culex pipiens

(1) Background: The control of mosquitoes with essential oils is a growing demand. (2) Methods: This study evaluated the novel larvicidal and adulticidal activity of fennel and green tea oils and their nanostructured lipid carriers (NLC) against Culex pipiens (C. pipiens) in the laboratory, field conditions and evaluated their effect against non-target organisms. SLN type II nanoformulations were synthesized and characterized using dynamic light scattering (DLS), zeta potential and transmission electron microscope. (3) Results: The synthesized NLCs showed spherical shaped, homogenous, narrow, and monomodal particle size distribution. The mortality percent (MO%) post-treatment (PT) with 2000 ppm for 24 h with fennel oil and NLC fennel (NLC-F) reached 85% (LC₅₀ = 643.81 ppm) and 100% (LC₅₀ = 251.71), whereas MO% for green tea oil and NLC green tea (NLC-GT) were 80% (LC₅₀ = 746.52 ppm) and 100% (LC₅₀ = 278.63 ppm), respectively. Field trial data showed that the larval reduction percent of fennel oil and NLC-F reached 89.8% and 97.4%, 24 h PT and the reduction percent of green tea oil and NLC-GT reached 89% and 93%, 24 h PT with persistence reached 8 and 7 days, for NLC-F and NLC-GT, respectively. The adulticidal effects showed that NLC-F and NLC-GT (100% mortality) were more effective than fennel and green tea oils (90.0% and 83.33%), with 24 h PT, respectively. Moreover, their reduction of adult density after spraying with LC₉₅ X2 for 15 min, with fennel oil, NLC-F, and green tea oil, NLC-GT were 83.6%, 100%, 79.1%, and 100%, respectively, with persistence (>50%) lasting for three days. The predation rate of the mosquitofish, Gambusia affinis, and the bug, Sphaerodema urinator, was not affected in both oil and its NLC, while the predation rate of the beetle, Cybister tripunctatus increased (66% and 68.3%) by green tea oil and NLC-GT, respectively. (4) Conclusions: NLCs nanoformulation encapsulated essential oils was prepared successfully with unique properties of size, morphology, and stability. In vitro larvicidal and adulticidal effects against C. pipiens supported with field evaluations have been performed using essential oils and their nanoformulations. The biological evaluation of nanoformulations manifested potential results toward both larvicidal and adulticidal compared to the essential oils themselves, especially NLC encapsulated fennel oil which had promising larvicidal and adulticidal activity.