Biosynthesis of poly(3-hydroxybutyrate-co-3-hydroxyalkanoates) by metabolically engineered Escherichia coli strains

Biosynthesis of polyhydroxyalkanoates (PHAs) consisting of 3-hydroxyalkanoates (3HAs) of 4 to 10 carbon atoms was examined in metabolically engineered Escherichia coli strains. When the fadA and/or fadB mutant E. coli strains harboring the plasmid containing the Pseudomonas sp. 61-3 phaC2 gene and the Ralstonia eutropha phaAB genes were cultured in Luria-Bertani (LB) medium supplemented with 2 g/L of sodium decanoate, all the recombinant E. coli strains synthesized PHAs consisting of C4, C6, C8, and C10 monomer units. The monomer composition of PHA was dependent on the E. coli strain used. When the fadA mutant E. coli was employed, PHA containing up to 63 mol% of 3-hydroyhexanoate was produced. In fadB and fadAB mutant E. coli strains, 3-hydroxybutyrate (3HB) was efficiently incorporated into PHA up to 86 mol%. Cultivation of recombinant fadA and/or fadB mutant E. coli strains in LB medium containing 10 g/L of sodium gluconate and 2 g/L of sodium decanoate resulted in the production of PHA copolymer containing a very high fraction of 3HB up to 95 mol%. Since the material properties of PHA copolymer consisting of a large fraction of 3HB and a small fraction of medium-chain-length 3HA are similar to those of low-density polyethylene, recombinant E. coli strains constructed in this study should be useful for the production of PHAs suitable for various commercial applications.     

Near-crater discoloration of white lead in wall paintings during laser induced breakdown spectroscopy analysis

During Laser-Induced Breakdown Spectroscopy (LIBS) analysis of white lead pigment (basic lead carbonate, 2PbCO₃·Pb(OH)₂), used in wall paintings of historical interest, a yellow–brown discoloration has been observed around the crater. This phenomenon faded after a few days exposure under ambient atmosphere. It was established that the mechanism of this discoloration consists in lead oxides (PbO) formation. It was verified by further experiments under argon atmosphere that recombination of lead with oxygen in the plasma plume produces the oxides, which settle around the crater and induce this discoloration. The impact of discoloration on the artwork's aesthetic aspect and the role of atmosphere on discoloration attenuation are discussed. The mechanism is studied on three other pigments (malachite, Prussian blue and ultramarine blue) and threshold for discoloration occurrence is estimated.     

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO₂) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO₂ proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc.     

Preparation and swelling properties of hydrolysis-resistant superabsorbent composite based on acrylic acid and sodium bentonite

Abstract

A novel hydrolysis-resistant superabsorbent composite was prepared via the solution polymerization based on acrylic acid (AA) and sodium bentonite (SBT) as monomers, tetraallylammonium bromine (TAAB) as crosslinker and ammonium persulfate (APS) as initiator. The mechanism of polymerization and the structure of the superabsorbent polymer (SAP) were studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (X-ray), and scanning electron microscopy (SEM). The reaction conditions such as different mass ratios of APS to AA, TAAB to AA, SBT to AA, neutralization degree of AA were optimized by orthogonal experiment, and the influence of each reaction condition on the capacity of water absorption at 150?°C was investigated via single-factor controlled experiment. The hydrolysis resistance and swelling kinetics of the SAP were studied in different solutions at 150?°C. Compared to traditional SAPs, the SAP synthesized with TAAB as crosslinker performed a more excellent hydrolysis resistance and water absorbency capacity at high temperatures. The water absorbency in distilled water or 0.1?mol L^?1 NaCl solution could reach 392.6 and 145.2?g g^?1at 150?°C, respectively. The SAP maintaining high swelling capacity in the pH range of 5–9 indicated its wide application values in the acidic or alkaline environment at high temperature. In addition, the SAP exhibited good reusability which could still retain about 73% of its initial water absorbency after reswelling six times at 150?°C.     

Conductometric study of cationic and anionic complexes in propylene carbonate

Conductivity data are used to determine thermodynamic complex formation constants for cases in which both the initial electrolyte and the complexed electrolyte form ion pairs. Using the method described in the text, the complex formation constants of Li⁺, Na⁺ and K⁺ with the crown ether 18-crown-6 and of Li⁺ with the ligand triphenylphosphine oxide in propylene carbonate have been evaluated from conductance data. The complexation of AgBr in propylene carbonate solutions of n-etrabutylammonium bromide has also been studied by the measurement of molar conductivities. The results of these studies indicate that ion pairing should not be neglected, even in high permittivity solvents such as propylene carbonate, and that the ion pair association constants correlate well with structural studies on cation-crown ether molecular conformations.     

Thermal properties of sodium acetylacetonate

Sodium acetylacetonate was prepared by the interaction of acetyl acetone with sodium hydroxide. The thermal conductivity, phonon velocity, mean free path, Yong's modulus, and the thermal expansion coefficient were studied. The thermal conductivity of the material decreases with increasing temperature due to the thermal lattice scattering of phonons. The velocity of phonons is also decreased due to the perturbation of thermal phonons. The linear thermal expansion coefficient increases with temperature due to the weakness of the attractive forces between the small Na⁺ cations and bulkier acetylacetonate anions in the lattice.

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Zusammenfassung Natriumacetylacetonat wurde durch die Wechselwirkung zwischen Acetylaceton und Natriumhydroxid gewonnen. Es wurde die Wärmeleitfähigkeit, die Phononengeschwindigkeit, die mittlere freie Wegstrecke, das Elastizitätsmodul und der Wärmeausdehnungskoeffizient untersucht. Die Wärmeleitfähigkeit der Substanz nimmt wegen der thermischen Gitterstreuung der Phononen mit steigender Temparatur ab. Die Geschwindigkeit der Phononen nimmt auf Grund der Perturbierung der thermischen Phononen ebenfalls ab. Der lineare Wärmeausdehnungskoeffizient steigt mit zunehmender Temperatur an, was auf die schwachen Anziehungskräfte zwischen den kleinen Na⁺ Ionen und den massigen Acetylacetonat-Anionen im Gitter zurückzuführen ist.

     

Quantum chemical models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media (MOH-H<Subscript>2</Subscript>O-DMSO,M = Li,Na, K)

Models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media have been constructed using Hartree Fock and DFT (B3LYP) quantum chemical methods; the structure and energies of anion complexes are considered. The hydroxide anion in the models is stabilized as complexes of OH^?·H₂O and OH^?· 2H₂O types.     

Carbonat-isostere Anionen [SnX3]5− in den Verbindungen Rb6[SnX3]O0,5 und Cs6[SnX3]O0,5 mit X = As,Sb und Bi

Carbonate Isostructural Anions [SnX₃]^5? in the Compounds Rb₆[SnX₃]O_0.5 and Cs₆[SnX₃]O_0.5 with X = As, Sb, and Bi The metallic shining compounds Rb₆[SnX₃]O_0.5 and Cs₆[SnX₃]O_0.5 with X = As, Sb, and Bi were prepared from the melt starting from adequate mixtures of the elements and SnO₂. They crystallize in the hexagonal system (space group P6₃/mmc, No. 194, Z = 2) with the lattice constants mentioned in ?Inhaltsübersicht”?. In the structures of the isotypic compounds tin and the main group(V) elements build up trigonal planar anions [SnX₃]^5? with X = As, Sb, and Bi isostructural to the carbonate anion, oxygen forms isolated O^2? ions. The bond lengths Sn? X are significantly shortened with respect to the sums of Pauling covalent radii. The atoms of the units [SnX₃]^5? are coordinated by alkali metal cations forming trigonal prisms and the O^2? anions occupy octahedral holes.     

用双氧水绿色氧化环己酮合成己二酸的研究

以30%的双氧水为氧化剂, 钨酸钠与含N或O的双齿有机配体(草酸)形成的络合物为催化剂, 在无有机溶剂、无相转移剂的条件下, 研究了环己酮氧化制己二酸的反应. 研究结果表明, 用廉价的草酸为配体, 最佳反应条件为钨酸钠∶草酸∶环己酮∶30%的双氧水的物质的量比为2.0∶3.3∶100∶350, 在92 ℃下反应12 h, 可制得80.6%的己二酸; 用GC-MS跟踪了氧化过程中三种主要物质环己酮、己内酯及己二酸含量随反应时间的变化关系, 提出了其主要氧化机理为环己酮首先经Beayer-Villiger氧化反应生成己内酯, 己内酯进一步氧化成己二酸.     

Liquid-liquid equilibria for mixtures of (ethylene carbonate + aromatic hydrocarbon + cyclohexane)

Liquid-liquid equilibrium data for mixtures of (ethylene carbonate + benzene + cyclohexane) at temperatures 303.15 and 313.15 K and (ethylene carbonate + BTX + cyclohexane) at temperature 313.15 K are reported, where the BTX is benzene, toluene and m-xylene. The compositions of liquid phases at equilibrium were determined by gas liquid chromatography. The selectivity factors and partition coefficients of ethylene carbonate for the extraction of benzene, toluene and m-xylene from (ethylene carbonate + BTX + cyclohexane) are calculated and presented. The obtained results are compared with the selectivity factors and partition coefficients of ethylene carbonate for the extraction of benzene from (ethylene carbonate + benzene + cyclohexane). The liquid-liquid equilibrium data were correlated with the UNIQUAC and NRTL activity coefficient models. The phase diagrams for the studied mixtures are presented and the correlated tie line results have been compared with the experimental data. The comparisons indicate the applicability of the UNIQUAC and NRTL activity coefficients model for liquid-liquid equilibrium calculations of the studied mixtures. The tie line data of the studied mixtures also were correlated using the Hand method.