The tert-butyl-NNO-azoxy group in the synthesis of 1,2,4-benzotriazin-3(4H)-one 1-oxides

Treatment of 2-(tert-butyl-NNO-azoxy)anilines with phosgene at 20 °C was proposed as a novel route to 1,2,4-benzotriazin-3(4H )-one 1-oxides. This method involves a new reaction, viz., an intramolecular interaction of the tert-butyl-NNO-azoxy group with a C-electrophile (leading to the formation of the N(2)—C(3) bond of the triazine ring) followed by elimination of the tert-butyl group. Complete assignment of the signals in the ¹H and ¹³C NMR spectra of the compounds obtained was performed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1507–1509, August, 2007.     

Two‐stage copolycondensation of preformed oligomers with bisphenols by tosyl chloride/dimethylformamide/pyridine from distributions of resulting oligomers determined by a combination of gel permeation chromatography and NMR

A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (n_x‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation n_x (mol %) = n_x (% mol by GPC) × n₀ (mol % by NMR)/n₀ (% mol by GPC), where n_x (% mol) = n_x (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004     

Polarized Raman scattering of concentrated solutions of poly(dimethyl siloxane) in benzene

Raman depolarization (ρ) measurements have been made over the temperature range 20 > T > 60°C for solutions of poly(dimethyl siloxane) (mol wt 7.7 × 10⁴ and 2.0 × 10⁴) for several concentrations up to 100%. The band studied was the highly polarized methyl stretch at 2907 cm^?1. Computer calculations of the probability p_t of a rotational isomer being trans allow the ρ values to be related to ΔG, the free energy of mixing. ΔG is plotted as a function of concentration and minima are observed at 60 ± 3% (mol wt = 7.7 × 10⁴) and 70 ± 3% (mol wt = 2 × 10⁴).     

New concept for a toxicity assay based on multiple indexes from the wave shape of damped metabolic oscillation induced in living yeast cells (part I): characterization of the phenomenon

The damped glycolytic oscillation phenomenon occurring in starved cells of the yeast Saccharomyces cerevisiae (NBRC 0565) was characterization for application to a toxicity bioassay. S. cerevisiae was grown under semi-anaerobic conditions. The transient oscillations were observed photometrically as the time course of the fluorescent intensity of reduced pyridine nucleotide resulting from instantaneous addition of glucose to a cell suspension. In this study, simple and reproducible conditions inducing damped oscillations were obtained by modifying a literature method. For estimation of the wave shapes of the damped oscillations we used six indexes. To investigate the total reproducibility as the averaged relative standard deviation (RSD_av) for the six indexes obtained from the wave shapes, the damped oscillations were induced under the optimum conditions and the RSD_av values were calculated as 14% in a buffer cell suspension (n = 62) and 22% in a water cell suspension (n = 78). Finally, the effects of glucose concentration on the six indexes were examined, and all the indexes changed when the glucose concentration was changed. Excellent correlations were obtained between the index of oscillation-state time and the concentration of glucose in a buffer cell suspension (r = 0.9985, 0.5–250 mmol L⁻¹, 10 points) and in a water cell suspension (r = 0.9989, 2.5 μmol L⁻¹–250 mmol L⁻¹, 12 points), respectively. Figure Characterization of damped glycolytic oscillation, (a) typical shape, and (b) its estimation Electronic supplementary material The online version of this article (doi:)contains supplementary material, which is available to authorized users.     

Friedel–crafts crosslinking methods for polystyrene modification. IV. Macromolecular structure of crosslinked particles

Crosslinked polystyrene particles were prepared by Friedel–Crafts suspension crosslinking of polystyrene using 2,4-dichloromethyl-2,5-dimethyl benzene as crosslinking agent. The polymer was dissolved in nitrobenzene and reaction occurred in a 70 wt % aqueous solution of ZnCl₂ with poly(vinyl alcohol) as a suspending agent. The spherical particles produced were swollen in toluene, chloroform, and tetrahydrofuran to determine their equilbrium polystyrene volume fraction. Analysis of the crosslinked macromolecular structure gave values of number-average molecular weight between crosslinks of M?_c = 900–5900 increasing as the nominal crosslinking ratio X decreased from 0.75 to 0.0625 mol of crosslinking agent per mole of polystyrene repeating unit. Porosimetric analysis contributed to the understanding of the importance of the pore structure for swelling behavior.     

Influence of molecular weight on the microhardness of poly(ethylene terephthalate)

 Poly(ethylene terephthalate) (PET) was annealed in vacuum at different temperatures (190–260 °C) for different times (10 min–24 h) in order to examine the mechanical properties (microhardness) of PET samples with a wide range of molecular weights (10 000–120 000). Short annealing times result in a twofold decrease in mol. wt. due to hydrolytic decomposition. However, long annealing times give rise to a substantial molecular weight increase. It is found that microhardness (H) rises linearly with the degree of crystallinity obtained during up-grading of mol. wt. and its extrapolation leads to H-values of completely crystalline PET, H ^PET _c=405 MPa for samples with conventional mol. wt. and of 426 MPa for samples with mol. wt. higher than 30 000. It is shown that the increase of mol. wt. for each set of samples with a given range of degree of crystallinity also causes a slight increase of H. The influence of mol. wt. upon hardness is discussed in the light of the changes in the physical structure (crystallinity, crystal thickness) which is formed at given heat treatment conditions. Received: 29 April 1997 Accepted: 23 September 1997     

Vibrational spectra and structure ofN,N-dinitromethylamine

The vibrational (IR and Raman) spectra ofN,N-dinitromethylamine were studied. The assignments of the bands were carried out using a comparison of spectra obtained in different aggregate states, invoking the results of normal coordinate analysis. The most probable symmetry of the molecule was shown to beC _s with a planar configuration of the N(NO₂)₂ moiety.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1503–1507, August, 1995.     

Comparative energetics of glucose and xylose metabolism in ethanologenic recombinantEscherichia coli B

This study compared the anaerobic catabolism of glucose and xylose by a patented, recombinant ethanologenicEscherichia coli B 11303:pLOI297 in terms of overall yields of cell mass (growth), energy (ATP), and end product (ethanol). Batch cultivations were conducted with pH-controlled stirred-tank bioreactors using both a nutritionally rich, complex medium (Luria broth) and a defined salts minimal medium and growth-limiting concentrations of glucose or xylose. The value of Y_ATP was determined to be 9.28 and 8.19 g dry wt cells/mol ATP in complex and minimal media, respectively. Assuming that the nongrowth-associated energy demand is similar for glucose and xylose, the mass-based growth yield (Y _x/s , g dry wt cells/g sugar) should be proportional to the net energy yield from sugar metabolism. The value ofY _x/s was reduced, on average, by about 50% (from 0.096 g/g glu to 0.051 g/g xyl) when xylose replaced glucose as the growth-limiting carbon and energy source. It was concluded that this observation is consistent with the theoretical difference in net energy (ATP) yield associated with anaerobic catabolism of glucose and xylose when differences in the mechanisms of energy-coupled transport of each sugar are taken into account. In a defined salts medium, the net ATP yield was determined to be 2.0 and 0.92 for glucose and xylose, respectively.     

Synthesis and characterization of poly(vinyl amine)‐based amphiphilic comb‐like dextran glycopolymers by a two‐step method

Poly(vinyl amine) (PVAm)‐based amphiphilic glycopolymers were synthesized by a two‐step method, that is dextran molecules (Dex, M_w = 1500) were attached to the PVAm backbone by reacting amine groups with dextran lactone, and then, hexanoyl groups (Hex) were attached by reacting the PVAm free amine groups with N‐(hexanoyloxy)succinimide. By adjustment of the feed ratios of Dex/Hex, amphiphilic comb‐like glycopolymers with various hydrophilic and hydrophobic balances were prepared, and their structures were characterized by ¹H NMR. Surface activity of the amphiphilic glycopolymers at the air/water interface was demonstrated by reduction in water surface tension. Adsorption of the amphiphilic glycopolymers at the solid/water interface was examined on octadecyltrichlorosilane (OTS)‐coated coverslips by water contact angle measurements. The results show that the amphiphilic glycopolymers need about 20 mol % of dextran attachment to make an effective hydrophilic coating. In comparison with the one‐step reaction by addition of dextran lactone and alkyl succinimide simultaneously, the two‐step approach can attach Dex on PVAm as high as possible in the first step, and offers quantitative advantages in controlling the ratio of hydrophilic and hydrophobic chains along the PVAm backbone, resulting in increased water solubility for the final amphiphilic glycopolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 192–199, 2006     

Characteristic properties of film prepared from poly(L‐lactide)‐grafted dextran of a relatively high sugar unit content as a degradable biomaterial

To develop novel biomedical soft materials with degradability, amphiphilic poly(L ‐lactide)‐grafted dextrans (Dex‐g‐PLLAs) of relatively high sugar unit contents were synthesized with the trimethylsilyl protection method. The characteristic properties of solution‐cast films prepared from the obtained Dex‐g‐PLLAs were investigated. The water absorption and degradation rate of the Dex‐g‐PLLA films increased with increasing sugar unit content. The morphology of the bulk phase and top surface of the Dex‐g‐PLLA films was evaluated with transmission electron microscopy and atomic force microscopy, respectively. The bulk phase of the Dex‐g‐PLLA films with a sugar unit content of 16–25 wt % was found by transmission electron microscopy to form a lamellar type of phase‐separated structure composed of approximately 80–100‐nm‐wide nanodomains because of their amphiphilic and branched structures. The hydrophobic top surface for a Dex‐g‐PLLA film with a sugar unit content of 25 wt % covered with PLLA segments was confirmed by atomic force microscopy phase images to be easily converted to a wettable top surface covered with hydrophilic dextran aggregates showing an 8–10‐nm‐wide honeycomb pattern by means of annealing in water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6402–6409, 2006     

Orientation and mechanical properties of PBT and its blends with a liquid-crystalline copolyester

Blends of poly (butylene terephthalate) (PBT) and a liquid-crystalline copolyester (60 mol % poly(p-hydroxy benzoic acid)/40 mol % polyethylene terephthalate) (LCP) were prepared in the melt state. The investigation of mechanical properties indicated that, for the processing conditions used, neither the addition of up to 30 wt % LCP to PBT nor the cooling history affected significantly the tensile modulus E. For oriented specimens, a marked improvement of E was obtained for all the blends, and increased with the LCP content. This improvement was more marked for slowly cooled samples. X-ray diffraction was used to quantify the orientation of the crystalline PBT and liquid-crystalline LCP phases. It was shown that neither the thermal history nor the presence of up to 30 wt % LCP affected the orientation behavior of the PBT crystalline phase. For the LCP phase, measurements were not possible for concentrations lower than 10 wt %, and were more difficult and less precise than for PBT. Nevertheless, it was possible to show that a better orientation was obtained for the slowly cooled samples and for higher concentrations of LCP in the blends. This correlated with the enhancement of mechanical properties observed for the oriented samples.     

Synthesis and transformations of 3-acetylpyridine-2(1<Emphasis Type="Italic">H</Emphasis>)-thiones

Reactions of substituted 3-cyanopyridine-2(1H)-thiones with methyllithium gave 3-acetylpyridine-2(1H)-thiones. The best results were achieved by adding a solid-state thione to a solution of methyllithium in ether (thione: MeLi = 1: 3). The compounds obtained and their 3-pentanoyl analogs were used to synthesize a number of fused heterocyclic systems. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1504–1507, July, 2008.     

Interaction of unmodified and partially silylated nanosilica with red blood cells

Interaction of red blood cells (RBCs) with unmodified and partially (50%) silylated fumed silica A-300 (nanosilica)was studied by microscopic, XRD and thermally stimulated depolarisation current (TSDC) methods. Nanosilica at a low concentration C _A-300 < 0.01 wt.% in buffered aqueous suspension is characterised by a weak haemolytic effect on RBCs. However, at C _A-300 = 1 wt% all RBCs transform into shadow corpuscles because of 100% haemolysis. Partial (one-half) hydrophobization of nanosilica leads to reduction of the haemolytic effect in comparison with unmodified silica at the same concentrations. A certain portion of the TSDC spectra of the buffered suspensions with RBC/A-300 is independent of the amounts of silica. However, significant portions of the low-and high-temperature TSDC bands have a lower intensity at C _A-300 = 1 wt% than that for RBCs alone or RBC/A-300 at C _A-300 = 0.01 wt.% because of structural changes in RBCs. Results of microscopic and XRD investigations and calculations using the TSDC-and NMR-cryoporometry suggest that the intracellular structures in RBCs (both organic and aqueous components) depend on nanosilica concentration in the suspension.      

Covalent modification of mushroom tyrosinase with different amphiphic polymers for pharmaceutical and biocatalysis applications

Two different poly(ethylene glycol) derivatives (linear, mol wt 5000 and a branched form, mol wt 10000) and a new polymer (poly [acryloylmorfoline], mol wt 5500) were covalently bound to the enzyme tyrosinase. The polymer-protein conjugates were studied with a view to their potential pharmaceutical application and to their use for the bioconversion of phenolic substrates in organic solvents.V _max andK _m for the dopa-dopaquinone conversion, thermostability, stability toward inactivation by dopa oxidation products, half-life in blood circulation, and behavior in organic solvents for the different adducts were investi gated. Arrhenius plots for the dopa-dopaquinone conversion were also obtained in order to study the effects of temperature on the different enzyme forms. Covalent attachment of the polymers increased enzyme stability in aqueous solution and the solubility in organic solvents. However, organic solvent solubilization brought about loss of enzyme conformation as assessed by CD measurements, which is accompanied by a nonreversible loss of catalytic activity.     

Effects of filler–polymer interactions on cold‐crystallization kinetics in crosslinked,silica‐filled polydimethylsiloxane/polydiphenylsiloxane copolymer melts

Crystallization in a series of variable crosslink density poly(dimethyl‐diphenyl)siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), nuclear magnetic resonance (NMR), and X‐ray diffraction (XRD). The silicone composite studied was composed of 94.6 mol % dimethoylsiloxane, 5.1 mol % diphenylsiloxane, and 0.3 mol % methyl‐vinyl siloxane (which formed crosslinking after peroxide cure). The polymer was filled with a mixture of 21.6 wt % fumed silica and 4.0 wt % precipitated silica previously treated with 6.8 wt % ethoxy‐end‐blocked siloxane processing aid. Molecular weight between crosslinks and filler–polymer interaction strength were modified by exposure to γ‐irradiation in either air or in vacuo. Isothermal DMA experiments illustrated that crystallization at ?85 °C occurred over a 1.8 hour period in silica‐filled systems and 2.2–2.6 hours in unfilled systems. The crystallization kinetics for irradiated samples were found to be dependent on crosslink density. Irradiation in vacuo resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface for samples irradiated in air. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1898–1906, 2006     

Polystyrene/decahydronaphthalene/propane phase equilibria and polymer conformation properties from intrinsic viscosities

The influence of dissolved propane (up to 31.2 wt %) on the phase equilibria of 5 wt % polystyrene (PS) dissolved in 66/34 wt % trans/cis‐decahydronaphthalene (DHN) was measured over the temperature range of 323–423 K. A suitable temperature, pressure, and propane composition operating space was defined to measure intrinsic viscosities of a single fluid phase. Intrinsic viscosities of PS in cosolvent mixtures of propane and trans/cis‐DHN were measured between 323 and 423 K and between 70 and 208 bar. The addition of propane to the isomeric mixture of DHN resulted in a decreased solvent quality for PS, causing a contraction of the PS coil. The most dramatic decrease in solvent quality with the addition of propane occurred at 323 K and 70 bar with approximately a 36% reduction in the viscometric radius with the addition of 45 mol % propane to DHN. At 423 K, the solvent quality was less sensitive to the addition of propane and only a 13% reduction in the viscometric radius was observed at 70 bar and 45 mol % propane in DHN. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Syntheses of conductive adhesives based on epoxy resin and polyanilines by using N‐tert‐butyl‐5‐methylisoxazolium perchlorate as a thermally latent curing reagent

Conductive composites consisted of epoxy resin and polyanilines (PANIs) doped with dodecylbenzenesulfonic acid ( 1 ), dodecylsulfonic acid (2), di(2‐ethylhexyl)sulfosuccinic acid (3), and HCl were synthesized by use of N‐tert‐butyl‐5‐methylisoxazolium perchlorate (5) under various reaction conditions. It was found that the composites with PANI doped with acid 2 (PANI‐2) prepared by curing with 10 mol % of reagent 5 at 80 °C for 12 h showed high electroconductivity along with the low conducting percolation threshold (3 wt % of PANI‐2). Furthermore, the composite with even ?10 wt % of PANI‐2 exhibited ?10^?1 S/cm of electroconductivity. The UV–vis and IR measurements indicated that the conductive emeraldine salt form of PANI‐2 in the composite was maintained after the curing reaction. The thermal stability was studied by TGA and DSC measurements, and then, the T_d10 and T_g of the composite with 5 and 10 wt % of PANI‐2 were found to be similar to those with the cured epoxy resin itself. In addition, the similar investigation with an oxetane resin instead of the epoxy resin was also carried out. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 718–726, 2006     

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.     

Purification and characterization of a xylanase from the thermophilic ascomyceteThielavia terrestris 255b

Thielavia terrestris 255B, a thermophilic ascomycete, produced two major forms of xylanase with pIs of 4.6 (xylanase I) and 6.1 (xylanase II). The latter enzyme could be purified to > 99% homogeneity using anion-exchange chromatography and gel filtration. Xylanase II had a mol wt of 25.7 kDa (SDS-PAGE) and a pH and a temperature optimum of 3.6–4.0 and 60–65°C, respectively. The ratio of the enzyme’s activity against xylan and carboxymethylcellulose was 500–1000 to 1, indicating a possible application of this enzyme in biobleaching processes. The amino acid sequence of this protein is being determined, and initial data suggest that the enzyme belongs to a group of low-mol wt xylanases that have been isolated from both bacteria and fungi.     

Purification of a marine bacterial glucose dehydrogenase fromCytophaga marinoflava and its application for measurement of 1,5-anhydro-d-glucitol

A novel glucose dehydrogenase (GDH) from a marine bacteriumCytophaga marinoflava IFO 14170 was isolated from its membrane fraction. This GDH catalyzes the oxidation of a hydroxy group of glucose, but does not react in its C-l position. This enzyme is composed of a single peptide with a mol wt of 67,000. The GDH can react under high salinity. The optimum pH is around 8.0, showing a typical property of marine bacterial enzymes. Using this novel enzyme, an enzymatic determination of 1,5-anhydro-D-glucitol (1,5AG) utilizing 2,6-dichrolophenolindophenol (DCIP) and phenazine methosulfate (PMS) as electron mediators was caried out. A good linear correlation was observed from 0.5 mM to 4 mM of 1,5AG.