Sound velocity in alumino-silicate liquids determined up to 2550 K from Brillouin spectroscopy: glass transition and crossover temperatures

Hypersonic longitudinal sound velocities in five silicate and alumino-silicate liquids have been measured between 293 and 2550 K by Brillouin spectroscopy. Together with previous observations for four other glasses and liquids of the system SiO₂-Al₂O₃-CaO-MgO, these results are used to discuss changes in hypersonic velocities in three adjacent temperature domains, i.e., below, in, and above the glass transformation range. The temperature dependence of Brillouin velocities is consistent with the observed variations with temperature of viscosity, density, and mean heat capacity for the same three temperature domains. These variations of physical properties of alumino-silicate liquids are qualitatively in agreement with the Inherent Structure Theory for liquids.     

A new general-purpose isothermal microcalorimeter for use at temperatures up to 200 °C

The design and some properties of a new general-purpose isothermal microcalorimeter are reported. The instrument is a twin thermopile heat conduction calorimeter, which is designed for use up to 200 °C. The calorimetric units and surrounding heat sink are suspended inside a hollow aluminium construction, which is thermostated. Above that unit a second thermostated block is positioned and the whole assembly is suspended inside a Dewar vessel. When the instrument is used at room temperature and below, the thermostated units are cooled by use of an insertion Peltier effect cooler. The instrument can be used with a wide range of different reaction vessels (diameter 14 mm). Baseline experiments have been conducted in the temperature range 15-200 °C. Typical values obtained during 10 h periods at 200 °C are ±3 and ±10 nW for the baseline drift and baseline fluctuations, respectively. The heat detection limit, determined by release of electrical energy, is about 2 μJ. Preliminary stability measurements have been conducted at 100 °C on samples of stabilised and non-stabilised polyamide film.     

Novelties of solid-liquid phase transfer catalysed synthesis of p-toluenesulfonyl fluoride from p-toluenesulfonyl chloride

Organic sulfonyl fluorides are of interest owing to their insecticidal, germicidal and enzyme inhibitory properties. In the current work, synthesis of p-toluenesufonyl fluoride was accomplished by reacting p-toluenesulfonyl chloride with solid potassium fluoride using PEG-400 as a catalyst under solid-liquid phase transfer catalysis (S-L PTC) at 30 °C. p-Toluenesulfonyl fluoride is used as peroxygen bleach activator. It also finds use in the treatment of Alzheimer's disease. The mechanism is based on homogeneous solubilization of solid. PEG forms a complex with metal cation which associates with the nucleophile and it participates in SN₂ type reactions. The reaction is intrinsically kinetically controlled. A complete theoretical analysis is done to determine both the rate constant and equilibrium constant from the same set of data. The activation energy and Gibbs free energy are also calculated.     

Dependence of the relative retention of organic compounds on the nature and pressure of the carrier gas and on the thickness of the PEG-20M film in the capillary column

The effects of the carrier gas nature and pressure on the relative retention values of organic compounds were studied using a series of capillary columns differing in the film thickness of the polar stationary phase (PEG-20M). Relative retention depends linearly on the carrier gas pressure. This dependence becomes more pronounced in the following order of carrier gases: helium < nitrogen < carbon dioxide. The limiting relative retention at a carrier gas pressure approaching zero rather than relative retention values measured experimentally (relative retention time, Kovats retention index,etc.) is an invariant characteristic of a compound subjected to chromatography. For the carrier gases studied, the limiting retention values almost does not depend on the nature of the carrier gas used. The limiting indicating the complex absorption-adsorption nature of these parameters. Dissolution of a carrier gas in the stationary liquid phase has an effect on the relative retention. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2177–2186, December, 1997.     

Facile polyethylene glycol (PEG-400) promoted synthesis of β-ketosulfones

An efficient and convenient synthesis of β-ketosulfones is described. Reaction of an α-haloketone with sodium alkyl/aryl sulphinate yields the corresponding β-ketosulfone promoted by polyethylene glycol (PEG-400) as an efficient reaction medium.     

Glycosidases of turnip leaf tissues

Four myrosinase (β-thioglucosidase EC. 3.2.3.1) and seven disaccharase (β-fructofuranosidase, EC. 3.2.1.26) isoenzymes were isolated from turnip leaves. The most active enzymes were isolated in pure form. Myrosinase and disaccharase mol wt was 62.0 × 10³ and 69.5 × 10³ dalton, respectively, on the basis of gel filtration on Sephadex G-200. Myrosinase pH profile showed high activity between pH 5 and 7 with the optimum at pH 5.5. The purified enzyme was heat-stable for 60 min at 30°C with only loss of 24% of activity. Its activity is strongly inhibited (100%) by Pb²⁺, Ba²⁺, Cu²⁺ and Ca²⁺ ions, and activated (70%) by EDTA at 0.04M. The pure enzyme failed to hydrolyze amylose, glycogen, lactose, maltose, and sucrose. TheK _m andV _max values of myrosinase using sinigrin as specific substrate was 0.045 mM and 2.5 U, respectively. The maximal activity of disaccharase enzyme was obtained at pH 4–5 and 35–37°C. The enzyme was heat-stable at 30°C for 30 min with only 10% loss of its activity. Its activity is strongly activated (70–240%) by Ca²⁺, Ba²⁺, Cu²⁺, and EDTA at 0.01M. The enzyme activity is specific to the disaccharide sucrose and failed to hydrolyze other disaccharides (maltose and lactose). TheK _m andV _max of disaccharase were 0.123 mM and 3.33 U, respectively.     

A critical reappraisal of recent communications on the hydrodynamic characterization of silica (aerosil) hydrosols

Different results from recent communications on the hydrodynamic characterization of ultrasonicated silica (®Aerosil) hydrosols led to a critical reappraisal of the data.It can be concluded that the degree of dispersion achievable in pyrogenic (Aerosil) hydrosols by ultrasonication is highly sensitive to the detailed parameters of the dispersion process. Characterization in terms ofabsolute numbers of a limiting particle morphology, corresponding to minima of aggregate size, porosity and number of primary particles in the aggregate is not possible.The most straightforward approach for hydrodynamic characterization seems to be a combination of sedimentation and diffusion data.Other approaches using a combination of sedimentation and viscosity data underestimate the particle dimensions. Moreover, they are quite arbitrary since the final result depends upon the proper choice between several equations for fitting the viscosity concentration dependence; the most rigorous approach seems to be an extended Einstein equation which has recently been adapted to particle aggregates.     

PEG-400 mediated an efficient eco-friendly synthesis of new isoxazolyl pyrido[2,3-d]pyrimidines and their anti-inflammatory and analgesic activity

Abstract

Polyethylene glycol-400 (PEG-400) has been developed as an efficient and eco-friendly reaction medium for the synthesis of new isoxazolyl pyrido[2,3-d]pyrimidine derivatives 11 from isoxazolyl cyanoacetamide synthon 7. Compound 7 was employed with various aromatic aldehydes 8 and malononitrile 9 in the presence of triethylamine (Et₃N) to afford the corresponding (E)-6-amino-1-(3-methyl-5-styrylisoxazol-4-yl)-2-oxo-4-phenyl-1,2-dihydro- pyridine-3,5-dicarbonitrile 10 at room temperature by using PEG-400 as a solvent medium as well as catalyst. The intermediate 10 on treatment with thiourea in the presence of PEG-400 at 90?°C to give the target compounds isoxazolyl pyrido[2,3-d]pyrimidines 11 in good to excellent yields. The newly synthesized compounds 10 and 11 were characterized by IR, ¹H NMR, ¹³C NMR, and HRMS analysis. The target compounds 11a-x was screened for their anti-inflammatory and analgesic activities. Among the tested compounds, the compounds 11s, 11t, 11u, 11v, 11w, and 11x showed significant anti-inflammatory and potent analgesic activities as that of reference drugs. The advantages of this protocol are operational simplicity, catalyst free, environmental safety, wide substrate scope, good yields, and PEG-400 can be recovered and reused. Most significant of all, this protocol is green.     

Synthesis of enantiomerically pure glycerol derivatives containing an organochalcogen unit: In vitro and in vivo antioxidant activity

We describe here the synthesis of enantiomerically pure chalcogenoethers obtained through the reaction of nucleophilic species of chalcogen (S, Se and Te), generated in situ from the respective diorganyl dichalcogenides, with (R)- and (S)-tosyl solketal. Furthermore, some of the chalcogenoethers were treated with acidic cation exchange resin Dowex-(H⁺) leading to the respective deprotected enantiomerically pure 3-phenylchalcogenyl-1,2-diols. In order to explore the biological potential of these molecules, the antioxidant activity of some organochalcogens was evaluated by several in vitro assays. Overall, the chalcogenoethers containing Te were better scavengers of DPPH and ABTS⁺ radicals, had higher ferric reducing capacity and prevented lipid peroxidation. To analyze the effects of these compounds in vivo, we used the alternative model Caenorhabditis elegans. Chalcogenoethers treatment, especially (S)- and (R)-2,2-dimethyl-4-(phenylselanylmethyl)-1,3-dioxolane, conferred protection against the mortality-induced by hydrogen peroxide. Accordingly, these chalcogenoethers were able to modulate the antioxidant enzyme catalase. Notably, the compounds did not present toxicity in worm’s reproduction. To sum up, our study demonstrated that Te- containing chalcogenoethers were promising in vitro scavengers, while Se molecules were more prone to protect against a stressor in vivo. In this sense, the antioxidant activity of chalcogenoethers, especially with Se and Te, indicates that these molecules may have biological application in an attempt to reduce the oxidative stress.     

Estimation of N-ethyl O-isopropyl Thionocarbamate (Dow: 2-200) in Mine Wastes by GLC

Abstract

Dow 2200 is a selective ore flotation agent, consisting mainly of Nethyl, 0-isopropyl thionocarbamate (IF'ETC). This paper describes a GLC method for the estimation of IPETC, and compares it with the conventional U.V. spectrophotometric procedure.

An aliquot of a cyclohexane extract of IPETC (prepared for spectrophotometric analysis) is chromatographed on a column of SE-30 or OV-17/QF-1 at 125°C and the IPETC peak is estimated in a ³H electron capture detector (ECD). The ECD is superior in sensitivity and linearity of response to the flame photometric detector operated in the S-mode. The ECD-GLC procedure is comparable in sensitivity to the conventional U.V. absorbance method, and offers an independent and complementary procedure useful for confirmation of low levels of IPETC.