Raman spectroscopic study of the hydration of short-chain poly(oxyethylene)s C <Subscript>1</Subscript>E<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C <Subscript>1</Subscript> (<Emphasis Type="Italic">n</Emphasis>=1−4)

The hypothesis that the degree of hydration of poly(oxyethylene) (POE) in aqueous solution depends on the mole ratio of water molecules to ether oxygen atoms in the molecule has been verified by studying the isotropic Raman spectra in the O−H stretching region for four short-chain POEs (C ₁E _n C ₁ withn=1−4). Excellent coincidence of the O−H stretching Raman band for all four POEs studied in the range of mole ratio H₂O/O _ether from 25 to 0.6 was observed, thus confirming the assumption stated above. A conclusion that all ether oxygen atoms in the POE molecule participate in hydrogen bonding with water molecules has been made.     

FTIR study of CO adsorption on molybdena-alumina catalysts for surface characterization

CO adsorption at low temperature has been used to probe Lewis acid sites created upon dehydroxylation of γ-Al₂O₃ and reduction of Mo/Al₂O₃ catalysts, using Fourier Transform Infrared spectroscopy (FTIR). Carbon-monoxide adsorption on γ-Al₂O₃ and Mo/Al₂O₃ catalysts dehydroxylated and reduced at different temperatures was studied at 78 K by IR spectroscopy. However, our results indicate that there is an approximately linear correlation between the increase either of dehydroxylation or the extent of reduction of the catalysts and the increasing absorbance of CO due to CO adsorption on Lewis acid sites created upon dehydroxylation of γ-Al₂O₃ and reduction of Mo/Al₂O₃.     

Effect of Poly(methacrylic acid) on the Cytokine Level in an In Vivo Tumor Model

Cancer is a leading cause of mortality globally. Despite remarkable improvements in cancer-treatment approaches, disease recurrence and progression remain major obstacles to therapy. While chemotherapy is still a first-line treatment for a variety of cancers, the focus has shifted to the development and application of new approaches to therapy. Nevertheless, the relationship between immune response, neoplastic diseases and treatment efficiency is not fully understood. Therefore, the aim of the study was to investigate the immunopharmacological effects of methacrylic acid homopolymer in an in vivo tumor model. Materials and methods: Monomeric methacrylic acid was used to synthesize polymers. Methacrylic acid was polymerized in dioxane in the presence of 4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid. To study the molecular weight characteristics of PMAA by GPC, carboxyl groups were preliminarily methylated with diazomethane. An experimental cancer model was obtained by grafting RMK1 breast cancer cells. The serum levels of IL-6, IL-10, IL-17, transforming growth factor β1 (TGF-β1), and tumor necrosis factor α (TNF-α) were measured by ELISA. Results: The effect of PMAA on the serum concentrations of several cytokines was studied upon its single administration to laboratory animals in early neoplastic process. The IL-6, IL-17 and TGF-β1 concentrations were found to change significantly and reach the level observed in intact rats. The IL-10 concentration tended to normalize. Conclusion: The positive results obtained are the basis for further studies on the effect of methacrylic-acid polymers with different molecular-weight characteristics on the neoplastic process.     

Synthesis of tetrazole containing 1,2,3-thiadiazole derivatives via U-4CR and their anti-TMV activity

A series of novel tetrazole containing 1,2,3-thiadiazole derivatives were designed and synthesized via Ugi reaction. Their structures were confirmed by melting points, IR, 1H NMR, and HRMS (ESI). Preliminary bioassay indicated that most target compounds exhibited very good direct anti-TMV activity at 100 μg/mL, which was equal to or higher than that of ribavirin. Among them, compounds 4b, 4c and 4i also showed equivalent protection effect to ribavirin in vivo at 100 μg/mL.     

Unusual stereoselectivity of methionine-γ-lyase from Citrobacterfreundii toward diastereomeric (S)-methionine S-oxide

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TG and DSC analyses of eucalyptus black liquor as alternative methods to estimate solids content

As a consequence of the continuous increase in the production rate of pulp and paper mills around the world, a great quantity of black liquor, a by-product of the wood digestion process, is produced. This by-product has a great potential as biomass, but needs to be concentrated to higher solids content to be burned as fuel in a recovery boiler. This is necessary to make the pulping process economically feasible, incinerating black liquor to produce high pressure steam, recycling inorganic chemicals to the process. The greater the solids content in black liquor, the better the combustion process in the boiler. Nevertheless, concentration of solids in black liquor above 75 mass/%, causes scaling formation on the heat transfer surfaces of evaporators and concentrators, due to the precipitation of sodium salts, reducing the overall efficiency of this equipment. The aim of this work is to evaluate the use of thermal analyses techniques, TG and DSC, as alternative methods to estimate solids content in eucalyptus black liquor samples since this information is essential to understand scaling formation process, allowing actions to reduce this industrial problem. Traditional techniques applied to determine solids content use gravimetric methods, which are simple, fine, but take a lot of time to be executed. Thermal analyses have proved to be very accurate and have the advantage to be faster than the traditional techniques. On the other hand, the cost-benefit relationship of the traditional technique is much greater and the final decision which one should be used depends on the conditions available.     

Calorimetric study of poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K

For the first time, the heat capacity $ C_{\text{p}}^{^\circ } $ of poly(2-ethylhexyl acrylate) has been studied in an adiabatic vacuum calorimeter between 7 and 350 K, the standard thermodynamic functions: heat capacity $ C_{\text{p}}^{^\circ } $ (T), enthalpy H°(T) ? H°(0), entropy S°(T) ? S°(0), Gibbs function G°(T) ? H°(0) have been calculated from T → 0 to 350 K. The energy of combustion Δ_c U of the compound under study has been measured in a calorimeter with a stationary bomb and an isothermal shell. The standard enthalpy of combustion Δ_c H° and thermodynamic parameters of formation—enthalpy Δ_f H°, entropy Δ_f S°, Gibbs function Δ_f G°—at T = 298.15 K have been calculated. The results have been used to calculate the thermodynamic characteristics of 2-ethylhexyl acrylate bulk polymerization into poly(2-ethylhexyl acrylate) over the range from T → 0 to 350 K.     

Fully Protected Glycosylated Zinc (II) Phthalocyanine Shows High Uptake and Photodynamic Cytotoxicity in MCF‐7 Cancer Cells

Phthalocyanine photosensitizers are effective in anticancer photodynamic therapy (PDT) but suffer from limited solubility, limited cellular uptake and limited selectivity for cancer cells. To improve these characteristics, we synthesized isopropylidene‐protected and partially deprotected tetra β‐glycosylated zinc (II) phthalocyanines and compared their uptake and accumulation kinetics, subcellular localization, in vitro photocytotoxicity and reactive oxygen species generation with those of disulfonated aluminum phthalocyanine. In MCF‐7 cancer cells, one of the compounds, zinc phthalocyanine {4}, demonstrated 10‐fold higher uptake, 5‐fold greater PDT‐induced cellular reactive oxygen species concentration and 2‐fold greater phototoxicity than equimolar (9 μm ) disulfonated aluminum phthalocyanine. Thus, isopropylidene‐protected β‐glycosylation of phthalocyanines provides a simple method of improving the efficacy of PDT.