水基Fe3O4磁流体的制备工艺研究

用共沉淀法制备Fe3O4磁流体,总结出用十二烷基磺酸钠与聚乙二醇作为表面活性剂制备水基磁流体的合适条件:(1)反应温度为室温或不高于35℃;(2)表面活性剂十二烷基磺酸钠的最佳用量为0.0030～0.0040 g/80 mL;(3)第一次包裹的最佳pH为9～10;(4)聚乙二醇作为第二次包裹的表面活剂时,体系最佳温度为40℃左右;(5)表面活性剂聚乙二醇的最佳用量为0.0050～0.0060 g/80 mL。通过实验制得了能稳定存在180 d的水基磁流体。并用透射电镜、红外光谱、分光光度计、古埃磁天平等进行了初步表征。     

石油磺酸盐及其与脂肪醇醚磺酸盐复配体系的耐盐性能和界面性能

通过对胜利馏分油的磺化制得一种石油磺酸盐(PS),并对其与不同碳链脂肪醇醚磺酸盐(AnESO,EO=3,n=1214,16,18)复配体系的耐盐(NaCl、CaCl2)性能和界面性能进行了研究。结果表明:(1)PS耐盐性能较差,当NaCl质量浓度达到30 g/L或CaCl2质量浓度达到0.15 g/L时,即有沉淀生成,且与胜利原油间的界面张力值较高(≥10-1 mN/m)。(2)将PS和AnESO以m(PS)∶m(AnESO)=9∶1复配,复配体系的耐盐性能均明显提高。其中PS/A18ESO复配性能最好,复配体系NaCl质量浓度能达到80 g/L,CaCl2质量浓度则达到2.4 g/L;而且界面张力在一定NaCl和CaCl2含量下可以降至10-2 mN/m数量级。     

Inhibition of horse liver and yeast alcohol dehydrogenase by aromatic and aliphatic aldehydes

The reactivity of yeast alcohol dehydrogenase (YADH) and horse liver alcohol dehydrogenase (HLADH) towards 12 different aldehydes was tested. YADH was inhibited by pre-incubation with citral, citronellal, p-cuminaldehyde, p-anisaldehyde, m-tolualdehyde, trans-cinnamaldehyde, salicylaldehyde, p-hydroxybenzaldehyde and benzaldehyde, although of these aldehydes only trans-cinnamaldehyde acted as a substrate for the enzyme. HLADH was inhibited, to a much smaller extent, by pre-incubation with citral, salicylaldehyde, citronellal, p-anisaldehyde, piperonaldehyde, trans-cinnamaldehyde, p-hydroxybenzaldehyde and p-cuminaldehyde and all of these aldehydes acted as substrates for the HLADH. Immobilisation of the enzymes on CNBr-activated Sepharose 4B gave protection against inhibition by the aldehydes, suggesting a means of significantly extending the useful lifetime of the enzymes when they are used in industrial processes.     

嗜水气单胞菌胞内聚3-羟基丁酸-3-羟基己酸酯（PHBHHx）提取方法的研究

以嗜水气单胞菌利用月桂酸发酵生产PHBHHx,比较多种溶剂对提取率和产品质量的影响,建立了嗜水气单胞菌胞内提取PHBHHx的新方法。本方法使用湿细胞提取,节省干燥细胞的能耗,仲丁醇无异味、毒性小、价格低廉,而且可以循环多次利用、对相对分子质量影响小,解决了工业生产上能耗高,生产成本高,溶剂回收难,安全隐患多,提取率不高、产品质量低等问题。用仲丁醇作溶剂,预处理细胞提取率提高13％,相对分子质量达83万,提取率达78％,产品纯度达99％以上。     

Chemoenzymatic One‐Pot Synthesis of γ‐Butyrolactones

The synthesis of enantio‐ and diastereomerically pure γ‐butyrolactones is described using a one‐pot, two‐enzyme cascade. Ethyl 2‐methyl‐4‐oxopent‐2‐enoate ( 2 ) was reduced selectively first in a 1,4‐reduction using the old yellow enzyme (OYE1) [EC 1.6.99.1] and consecutively in a 1,2‐reduction by an alcohol dehydrogenase [EC 1.1.1.2].     

脂肪醇醚磺酸盐类表面活性剂的合成进展

综述了国内外不同工艺路线:卤化脂肪醇醚法、烯基加成法、丙烷磺内酯法、羟乙基磺酸钠法、脂肪醇醚硫酸酯盐转化法和氯乙基磺酸钠法等合成脂肪醇醚磺酸盐类阴离子表面活性剂的研究工作,并从反应路线、产率、原料性能及工艺流程等方面进行了分析比较,讨论了各工艺中存在的问题及工业化的可行性。     

脂肪醇聚氧乙烯醚磺酸盐表面活性剂合成进展

综述了当前耐温、耐盐脂肪醇聚氧乙烯醚磺酸盐表面活性剂的制备方法和研究进展。介绍了各种方法的优缺点，并进一步讨论了其工业化生产的可行性。     

Role of Iron-Containing Alcohol Dehydrogenases in Acinetobacter baumannii ATCC 19606 Stress Resistance and Virulence

Most bacteria possess alcohol dehydrogenase (ADH) genes (Adh genes) to mitigate alcohol toxicity, but these genes have functions beyond alcohol degradation. Previous research has shown that ADH can modulate quorum sensing in Acinetobacter baumannii, a rising opportunistic pathogen. However, the number and nature of Adh genes in A. baumannii have not yet been fully characterized. We identified seven alcohol dehydrogenases (NAD⁺-ADHs) from A. baumannii ATCC 19606, and examined the roles of three iron-containing ADHs, ADH3, ADH4, and ADH6. Marker-less mutation was used to generate Adh3, Adh4, and Adh6 single, double, and triple mutants. Disrupted Adh4 mutants failed to grow in ethanol-, 1-butanol-, or 1-propanol-containing mediums, and recombinant ADH4 exhibited strongest activity against ethanol. Stress resistance assays with inorganic and organic hydroperoxides showed that Adh3 and Adh6 were key to oxidative stress resistance. Virulence assays performed on the Galleria mellonella model organism revealed that Adh4 mutants had comparable virulence to wild-type, while Adh3 and Adh6 mutants had reduced virulence. The results suggest that ADH4 is primarily involved in alcohol metabolism, while ADH3 and ADH6 are key to stress resistance and virulence. Further investigation into the roles of other ADHs in A. baumannii is warranted.     

Thermogravimetric analysis of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The thermal degradation of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐HV)] was studied using thermogravimetry (TG). In the thermal degradation of PHB, the temperature at the onset of weight loss (T_o) was derived by T_o = 0.97B + 259, where B represents the heating rate (°C/min). The temperature at which the weight loss rate was maximum (T_p) was T_p = 1.07B + 273, and the final temperature (T_f) at which degradation was completed was T_f = 1.10B + 280. The percentage of the weight loss at temperature T_p (C_p) was 69 ± 1% whereas the percentage of the weight loss at temperature T_f (C_f) was 96 ± 1%. In the thermal degradation of P(HB‐HV) (7:3), T_o = 0.98B + 262, T_p = 1.00B + 278, and T_f = 1.12B + 285. The values of C_p and C_f were 62 ± 7 and 93 ± 1%, respectively. The derivative thermogravimetric (DTG) curves of PHB confirmed only one weight loss step change because the polymer mainly consisted of the HB monomer only. The DTG curves of P(HB‐HV), however, suggested multiple weight loss step changes; this was probably due to the different evaporation rates of the two monomers. The incorporation of 10 and 30 mol % of the HV component into the polyester increased the various thermal temperatures (T_o, T_p, andT_f) by 7–12°C (measured at B = 20°C/min). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2237–2244, 2001     

Production of (R)-3-Quinuclidinol by E. coli Biocatalysts Possessing NADH-Dependent 3-Quinuclidinone Reductase (QNR or bacC) from Microbacterium luteolum and Leifsonia Alcohol Dehydrogenase (LSADH)

We found two NADH-dependent reductases (QNR and bacC) in Microbacterium luteolum JCM 9174 (M. luteolum JCM 9174) that can reduce 3-quinuclidinone to optically pure (R)-(−)-3-quinuclidinol. Alcohol dehydrogenase from Leifsonia sp. (LSADH) was combined with these reductases to regenerate NAD⁺ to NADH in situ in the presence of 2-propanol as a hydrogen donor. The reductase and LSADH genes were efficiently expressed in E. coli cells. A number of constructed E. coli biocatalysts (intact or immobilized) were applied to the resting cell reaction and optimized. Under the optimized conditions, (R)-(−)-3-quinuclidinol was synthesized from 3-quinuclidinone (15% w/v, 939 mM) giving a conversion yield of 100% for immobilized QNR. The optical purity of the (R)-(−)-3-quinuclidinol produced by the enzymatic reactions was >99.9%. Thus, E. coli biocatalysis should be useful for the practical production of the pharmaceutically important intermediate, (R)-(−)-3-quinuclidinol.     

Structural and Biochemical Analysis of the Furan Aldehyde Reductase YugJ from Bacillus subtilis

NAD(H)/NADP(H)-dependent aldehyde/alcohol oxidoreductase (AAOR) participates in a wide range of physiologically important cellular processes by reducing aldehydes or oxidizing alcohols. Among AAOR substrates, furan aldehyde is highly toxic to microorganisms. To counteract the toxic effect of furan aldehyde, some bacteria have evolved AAOR that converts furan aldehyde into a less toxic alcohol. Based on biochemical and structural analyses, we identified Bacillus subtilis YugJ as an atypical AAOR that reduces furan aldehyde. YugJ displayed high substrate specificity toward 5-hydroxymethylfurfural (HMF), a furan aldehyde, in an NADPH- and Ni²⁺-dependent manner. YugJ folds into a two-domain structure consisting of a Rossmann-like domain and an α-helical domain. YugJ interacts with NADP and Ni²⁺ using the interdomain cleft of YugJ. A comparative analysis of three YugJ structures indicated that NADP(H) binding plays a key role in modulating the interdomain dynamics of YugJ. Noticeably, a nitrate ion was found in proximity to the nicotinamide ring of NADP in the YugJ structure, and the HMF-reducing activity of YugJ was inhibited by nitrate, providing insights into the substrate-binding mode of YugJ. These findings contribute to the characterization of the YugJ-mediated furan aldehyde reduction mechanism and to the rational design of improved furan aldehyde reductases for the biofuel industry.     

The kinetics of the thermal decomposition of poly(3‐hydroxybutyrate) and maleated poly(3‐hydroxybutyrate)

The thermal decomposition mechanism of maleated poly(3‐hydroxybutyrate) (PHB) was investigated by FTIR and ¹H NMR. The results of experiments showed that the random chain scission of maleated PHB obeyed the six‐membered ring ester decomposition process. The thermal decomposition behavior of PHB and maleated PHB with different graft degree were studied by thermogravimetry (TGA) using various heating‐up rates. The thermal stability of maleated PHB was evidently better than that of PHB. With increase in graft degree, the thermal decomposition temperature of maleated PHB gradually increased and then declined. Activation energy E_a as a kinetic parameter of thermal decomposition was estimated by the Flynn‐Wall‐Ozawa and Kissinger methods, respectively. It could be seen that approximately equal values of activation energy were obtained by both methods. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1789–1796, 2002; DOI 10.1002/app.10463     

磺酸盐表面活性剂研究进展

综述了磺酸盐表面活性剂的研究现状和正在开发的新品种,并对其合成技术路线和方法进行了概述,尤其是对链烃磺酸盐、脂肪酸酯磺酸盐、双芳环醚磺酸盐、二聚磺酸盐表面活性剂的合成和性质进行了重点介绍。我国应大力开发原料易得、活性高的脂肪酸磺酸盐、脂肪醇醚磺酸盐表面活性剂,注重结构新颖、性能独特的Gem in i表面活性剂的基础研究以适应各行业的需求。引用文献41篇。     

Carbon dioxide sorption and diffusion in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐CO‐3‐hydroxyvalerate)

CO₂ sorption and diffusion in poly(3‐hydroxybutyrate) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers were investigated gravimetrically at temperatures from 25° to 50°C and pressures up to 1 atm. The sorption behavior proved to be linear for all the copolymers studied. An additional set of measurements performed in a pressure decay apparatus at 35°C showed that the linearity could be extrapolated to pressures up to 25 atm. The sorption results obtained from both techniques were in good agreement. The poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) sorption kinetics were increasingly non‐Fickian at the higher temperatures, thus preventing the calculation of diffusion coefficients above 35°C. Interestingly, this was not the case for poly(3‐hydroxybutyrate), and diffusion coefficients and permeabilities could be calculated at all of the investigated temperatures. The 35°C permeabilities were fairly low, which is attributed to the high degree of crystallinity of this polyester family. Finally, the poly(3‐hydroxybutyrate) barrier properties against CO₂ are successfully compared with those of some selected common thermoplastics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2391–2399, 1999     

Water transport properties in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biopolymers

Water sorption and diffusion have been investigated in poly(3‐hydroxybutyrate) (PHB) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers [P(HB‐HV)] by means of a Cahn electromicrobalance. Permeability of these samples have been determined using a gravimetric permeation cell. Two experimental setups were used for the gravimetric sorption measurements, under dynamic and static conditions, respectively. The differences observed in the results obtained using these techniques are discussed. The sorption measurements have evidenced the tendency of water molecules to form aggregates or clusters in the polymer. In addition, the static sorption method revealed the potential of PHB and P(HB‐HV) to undergo molecular relaxations, eventually leading to a partial desorption of the previously sorbed water after an induction period. The clustering effect was adequately described by the polycondensation model. On the other hand, the interpretation of the diffusivity in terms of mobility coefficients has revealed a competition between a plasticization effect and clustering. As a whole, water transport properties in PHB and its copolymers can be considered to be very close in magnitude to those of common thermoplastics such as PVC and PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 455–468, 1999     

Synthesis and Biochemical Evaluation of Nicotinamide Derivatives as NADH Analogue Coenzymes in Ene Reductase

Nicotinamide and pyridine-containing conjugates have attracted a lot of attention in research as they have found use in a wide range of applications including as redox flow batteries and calcium channel blockers, in biocatalysis, and in metabolism. The interesting redox character of the compounds’ pyridine/dihydropyridine system allows them to possess very similar characteristics to the natural chiral redox agents NAD⁺/NADH, even mimicking their functions. There has been considerable interest in designing and synthesizing NAD⁺/NADH mimetics with similar redox properties. In this research, three nicotinamide conjugates were designed, synthesized, and characterized. Molecular structures obtained through X-ray crystallography were obtained for two of the conjugates, thereby providing more detail on the bonding and structure of the compounds. The compounds were then further evaluated for biochemical properties, and it was found that one of the conjugates possessed similar functions and characteristics to the natural NADH. This compound was evaluated in the active enzyme, enoate reductase; like NADH, it was shown to help reduce the C=C double bond of three substrates and even outperformed the natural coenzyme. Kinetic data are reported.     

碳酸钠对烷基苯磺酸钠／脂肪醇聚氧乙烯醚／H2O体系相行为和流变性的影响

研究了NaCO3对烷基苯磺酸钠／脂肪醇聚氧乙烯醚／H2O（LAS／Neodol25-9/H2O)体系相行为的影响,确认了L1 La与L1＋La相界面的存在,并得到了不同Na2CO3浓度下体系的相图,结果表明,碳酸钠的加入使L1相和La相缩小,H缩小至消失,层状分散扩大,但其分散稳定性下降,LAS／Neodol25-9混合体系的稳定性明显高于纯的LAS或Neodol25-9体系。     

Tailoring the surface architecture of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) scaffolds

This study was designed to determine whether the surface modifications of the various poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3HB‐co‐4HB)] copolymer scaffolds fabricated would enhance mouse fibroblast cells (L929) attachment and proliferation. The P(3HB‐co‐4HB) copolymer with a wide range of 4HB monomer composition (16–91 mol %) was synthesized by a local isolate Cupriavidus sp. USMAA1020 by employing the modified two‐stage cultivation and by varying the concentrations of 4HB precursors, namely γ‐butyrolactone and 1,4‐butanediol. Five different processing techniques were used in fabricating the P(3HB‐co‐4HB) copolymer scaffolds such as solvent casting, salt‐leaching, enzyme degradation, combining salt‐leaching with enzyme degradation, and electrospinning. The increase in 4HB composition lowered melting temperatures (T_m) but increased elongation to break. P(3HB‐co‐91 mol % 4HB) exhibited a melting point of 46°C and elongation to break of 380%. The atomic force analysis showed an increase in the average surface roughness as the 4HB monomer composition increased. The mouse fibroblasts (L929) cell attachment was found to increase with high 4HB monomer composition in copolymer scaffolds. These results illustrate the importance of a detailed characterization of surface architecture of scaffolds to provoke specific cellular responses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012