Kinetic Analysis of Terminal and Unactivated C?H Bond Oxyfunctionalization in Fatty Acid Methyl Esters by Monooxygenase‐Based Whole‐Cell Biocatalysis

The alkane monooxygenase AlkBGT from Pseudomonas putida GPo1 constitutes a versatile enzyme system for the ω‐oxyfunctionalization of medium chain‐length alkanes. In this study, recombinant Escherichia coli W3110 expressing alkBGT was investigated as whole‐cell catalyst for the regioselective biooxidation of fatty acid methyl esters to terminal alcohols. The ω‐functionalized products are of general economic interest, serving as building blocks for polymer synthesis. The whole‐cell catalysts proved to functionalize fatty acid methyl esters with a medium length alkyl chain specifically at the ω‐position. The highest specific hydroxylation activity of 104 U g_CDW⁻¹ was obtained with nonanoic acid methyl ester as substrate using resting cells of E. coli W3110 (pBT10). In an optimized set‐up, maximal 9‐hydroxynonanoic acid methyl ester yields of 95% were achieved. For this specific substrate, apparent whole‐cell kinetic parameters were determined with a V_max of 204±9 U g_CDW⁻¹, a substrate uptake constant (K_S) of 142±17 μM, and a specificity constant V_max/K_S of 1.4 U g_CDW⁻¹ μM ⁻¹ for the formation of the terminal alcohol. The same E. coli strain carrying additional alk genes showed a different substrate selectivity. A comparison of biocatalysis with whole cells and enriched enzyme preparations showed that both substrate availability and enzyme specificity control the efficiency of the whole‐cell bioconversion of the longer and more hydrophobic substrate dodecanoic acid methyl ester. The efficient coupling of redox cofactor oxidation and product formation, as determined in vitro, combined with the high in vivo activities make E. coli W3110 (pBT10) a promising biocatalyst for the preparative synthesis of terminally functionalized fatty acid methyl esters.     

坐姿下人体振动特性建模及实验分析

为客观评价垂直振动条件下人体生物力学响应,依据多体动力学原理建立了七自由度无靠背坐姿下人体振动模型。根据不同频率下人体振动实验数据,采用最小二乘参数识别法以及加权计算得到人体动力学参数,根据识别出的参数进行人体振动特性分析,得到了特定频率下人体头部振动加速度响应特性。应用近红外光谱法无创检测脑部组织血氧参量,分析了不同频率下血氧参数变化。实验结果表明:该模型有较高的预测精度,可为动态环境下人机界面设计提供重要参考,对于客观评价人体坐姿舒适性,提高汽车人机界面设计宜人性有指导意义。     

4H-SiC npn双极型晶体管的研制

采用国产的4H-SiC外延材料和自行开发的SiC双极晶体管的工艺技术,实现了4H-SiC npn双极晶体管特性。为避免二次外延或高温离子p+注入等操作,外延形成n+/p+/p/n-结构材料,然后根据版图设计进行相应的刻蚀,形成双台面结构。为保证p型基区能实现良好的欧姆接触,外延时在n+层和p层中间插入适当高掺杂的p+层外延,但也使双极晶体管发射效率降低,电流放大系数降低。为提高器件的击穿电压,在尽量实现低损伤刻蚀时,采用牺牲氧化等技术减少表面损伤及粗糙度,避免表面态及尖端电场集中,并利用SiC能形成稳定氧化层的优势来形成钝化保护。器件的集电结反向击穿电压达200 V,集电结在100 V下的反向截止漏电流小于0.05 mA,共发射极电流放大系数约为3。     

曝气设备的氧转移效率

从某污水处理厂技术改造失败的教训入手,深入分析了曝气设备各指标间的关系,区分了设备的效能指标与规格指标,探讨了曝气设备选择上的困惑,估算了曝气设备选择不当可能造成的经济损失,提出了如下观点动力效率是曝气设备唯一的效能指标,应大力推广动力效率高的设备,坚决淘汰动力效率低的设备;充氧能力和氧转移效率是规格指标;在评价曝气设备性能、选择曝气设备类型时,氧转移效率不应考虑．     

超临界火电机组的金属腐蚀特点和沉积规律

介绍了超临界水的物理化学性质,包括密度、离子积、介电常数、氢键和扩散系数等方面的特性.阐述了超临界火电机组的金属腐蚀特点和沉积规律,并通过实例加以说明.提出了抑制超临界机组金属腐蚀与沉积的措施,即机组投产前对高压给水系统进行充分、有效的化学清洗和机组投产后给水处理尽快转入加氧处理(OT)方式.     

Osmium‐Catalyzed Selective Oxidations of Methane and Ethane with Hydrogen Peroxide in Aqueous Medium

Various transition metal chlorides including FeCl₃, CoCl₂, RuCl₃, RhCl₃, PdCl₂, OsCl₃, IrCl₃, H₂PtCl₆, CuCl₂ and HAuCl₄ were studied for the selective oxidations of methane and ethane with hydrogen peroxide in aqueous medium. Among the metal chlorides investigated, osmium(III) chloride (OsCl₃) exhibited the highest turnover frequency (TOF) for the formation of organic oxygenates (mainly alcohols and aldehydes) from both methane and ethane. For the OsCl₃‐catalyzed oxidation of methane with hydrgen peroxide, methyl hydroperoxide was also formed together with methanol and formaldehyde. The effects of various kinetic factors on the catalytic behavior of the OsCl₃‐H₂O₂ system were investigated, and TOF values of 12 and 41 h⁻¹ could be obtained for oxygenate formation during the oxidations of methane and ethane, respectively. In the presence of OsCl₃, NaClO, NaClO₄ or NaIO₄ as oxidant was incapable of oxidizing methane and ethane to the corresponding oxygenates, and the use of tert‐butyl hydroperoxide (TBHP) instead of H₂O₂ provided remarkably lower rates of formation of oxygenates. UV‐Vis spectroscopic measurements suggested that OsCl₃ was probably oxidized into an Os(IV) species by H₂O₂ in aqueous medium, and the Os(IV) species might be involved in the oxygenation of methane or ethane. The result that the conversions of both methane and ethane to oxygenates were suppressed by the addition of a radical scavenger suggested that the reactions proceeded via a radical pathway.     

Solving the problem at the source: Controlling Mn release at the sediment-water interface via hypolimnetic oxygenation

One of the primary goals of hypolimnetic oxygenation systems (HOx) from a drinking water perspective is to suppress sediment-water fluxes of reduced chemical species (e.g., manganese and iron) by replenishing dissolved oxygen (O₂) in the hypolimnion. Manganese (Mn) in particular is becoming a serious problem for water treatment on a global scale. While it has been established that HOx can increase sediment O₂ uptake rates and subsequently enhance the sediment oxic zone via elevated near-sediment O₂ and mixing, the influence of HOx on sediment-water fluxes of chemical species with more complicated redox kinetics like Mn has not been comprehensively evaluated.This study was based on Mn and O₂ data collected primarily in-situ to characterize both the sediment and water column in a drinking-water-supply reservoir equipped with an HOx. While diffusive Mn flux out of the sediment was enhanced by HOx operation due to an increased concentration driving force across the sediment-water interface, oxygenation maintained elevated near-sediment and porewater O₂ levels that facilitated biogeochemical cycling and subsequent retention of released Mn within the benthic region. Results show that soluble Mn levels in the lower hypolimnion increased substantially when the HOx was turned off for as little as ∼48 h and the upper sediment became anoxic. Turning off the HOx for longer periods (i.e., several weeks) significantly impaired water quality due to sediment Mn release. Continual oxygenation maintained an oxic benthic region sufficient to prevent Mn release to the overlying source water.     

Functional MRI activation in children with and without dyslexia during pseudoword aural repeat and visual decode: Before and after treatment.

Children without dyslexia (n=10) received nonphonological treatment, and those with dyslexia received phonological (n=11) or nonphonological (n=9) treatment. Before and after treatment they performed aural repeat, visual decode, and aural match pseudoword tasks during functional MRI scanning that separated stimulus input from response production. Group map analysis indicated that children with dyslexia overactivated compared with good readers during the aural-repeat/aural-match contrast in bilateral frontal (Brodmann's area [BA] 3, 4, 5, 6, 9), left parietal (BA 2, 3), left temporal (BA 38), and right temporal (BA 20, 21, 37) regions (stimulus input) and underactivated in right frontal (BA 24, 32) and right insula (BA 48) regions (response production); they underactivated in BA 19/V5 during the visual-decode/aural-match contrast (response production). Individual brain analysis for children with dyslexia revealed that during the aural-repeat/aural-match contrast (stimulus input), phonological treatment decreased and normalized activation in left supramarginal gyrus and postcentral gyrus. Nonphonological treatment increased and normalized activation during the visual-decode/aural-match contrast (response production) in BA19/V5 and changed activation in the same direction as good readers during aural-repeat/aural-match contrast (stimulus input) in left postcentral gyrus. The significance of the findings for competing theories of dyslexia is discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

天铁新建15 000 Nm3/h制氧工程给排水设计

文章分别从设计参数、给排水系统、给排水构筑物及给排水设施主要设备几个方面对天铁15000Nm^3/h制氧工程给排水设计作了具体地介绍。该工程的给排水设施投入使用后运行良好。