青铜在土壤中局部腐蚀过程的化学行为

用模拟闭塞电池法(O.C.)对青铜文物在模拟土壤溶液（0.028 mol•L^-1NaCl + 0.01 mol•L^-1Na₂SO₄+0.016 mol•L^-1NaHCO₃）中的腐蚀行为进行了研究,清楚地演示了青铜局部腐蚀过程中环境介质离子、阳极腐蚀产生的阳离子等物质的迁移、富集和沉积规律,得出铜的溶解因子f_Cu随通电时间的变化关系,即从最初锡的溶解速度大于铜的溶解速度逐渐演变为铜的溶解速度大于锡的溶解速度.闭塞区内的阳离子明显地向主体溶液中迁移.     

化学计量比、雾化压力对电站锅炉SNCR脱硝的影响

引言 电厂锅炉作为化学能向蒸汽热能转换的一种设备,是火电生产过程中一个重要的环节.但是,锅炉燃烧化石燃料进行能量转化的同时也向环境排放了各种污染物质.     

循环流化床中颗粒旋转特性

利用由高速数字摄影设备及大功率激光构成的测试系统在一截面为200 mm×200 mm、高为4 m的冷态循环流化床实验台上进行了床内颗粒旋转特性的实验研究.对在距布风板3.54 m高度的稀相区的1/4截面内13个测试点拍摄获得的图像序列利用Matlab、PhotoShop和ACDSee软件进行分析处理,采用人工直接判别获得颗粒转速,用双帧频验证法进行颗粒转速校验.结果表明：循环流化床气固两相流中固相颗粒普遍存在旋转现象,截面边壁区内的颗粒平均转速高于中心区域;粒径小或径向速度大的颗粒,其平均转速较大,反之亦然;不规则颗粒的平均转速明显高于球[JP2]形颗粒;当空截面气体速度V_g=5 m•s^-1,固体质量循环流率G_s=1.5 kg•m^-2•s^-1,玻璃珠颗粒平均粒径d_p=0.5 mm时,颗粒转速最高可达2000 r•s^-1,平均转速300 r•s^-1.     

The structural roles of conserved Pro196, Pro197 and His199 in the mechanism of thymidylate synthase

We generated replacement sets for three highly conserved residues,Pro196, Pro197 and His199, that flank the catalytic nucleophile,Cys198. Pro196 and Pro197 have restricted mobility that couldbe important for the structural transitions known to be essentialfor activity. To test this hypothesis we obtained and characterized13 amino acid substitutions for Pro196, 14 for Pro197 and 14for His199. All of the Pro196 and Pro197 variants, except P197R,and four of the His199 variants complemented TS-deficient Escherichiacoli cells, indicating they had at least 1% of wild-type activity.For all His199 mutations, k_cat/K_m for substrate and cofactordecreased more than 40-fold, suggesting that the conserved hydrogenbond network co-ordinated by His199 is important for catalysis.Pro196 can be substituted with small hydrophilic residues withlittle loss in k_cat, but 15- to 23-fold increases in K_m^dUMP.Small hydrophobic substitutions for Pro197 were most active,and the most conservative mutant, P197A, had only a 5-fold lowerk_cat/K_m^dUMP than wild-type TS. Several Pro196 and Pro197 variantswere temperature sensitive. The small effects of Pro196 or Pro197mutations on enzyme kinetics suggest that the conformationalrestrictions encoded by the Pro–Pro sequence are largelymaintained when either member of the pair is mutated. Received February 24, 2003; revised June 19, 2003; accepted June 20, 2003.     

Improvement of binding of Puumala virus neutralization site resembling peptide with a second-generation phage library

We have previously selected a peptide insert FPCDRLSGYWERGIPSPCVRrecognizing the Puumala virus (PUUV) G2-glycoprotein-specificneutralizing monoclonal antibody (MAb) 1C9 with K_d of 2.85x10^–8from a random peptide library X₂CX₁₄CX₂ expressed on the pIIIprotein of the filamentous phage fd-tet. We have now createda second-generation phage-displayed peptide library in whicheach amino acid of the peptide was mutated randomly to anotherwith a certain probability. Peptides were selected for higheraffinity for MAb 1C9 and for a common binding motif for MAb4G2 having an overlapping epitope with MAb 1C9 in G2 glycoprotein.The resulting peptides were synthesized as spots on cellulosemembrane. Amino acid changes which improved the reactivity ofthe peptides to MAb 1C9 were combined in the peptide ATCDKLFGYYERGIPLPCALwith K_d of 1.49x10^–9 in biosensor measurements. Our resultsshow that the binding properties of peptides, the affinity andthe specificity can be improved and the binding specificitydetermining amino acids and structural factors can be analyzedby combining binding assays with synthetic peptides on membranewith the use of second-generation phage display libraries. Received October 18, 2002; revised April 16, 2003; accepted May 26, 2003.     

浆态光催化反应器有机模拟废水光催化氧化特性与动力学

采用循环式浆态光催化反应器对苯甲酰胺模拟废水光催化氧化特性和动力学进行了研究,系统地考察了操作条件对模拟污染物光催化降解的影响,并与搅拌式和鼓泡床式浆态光催化反应器中苯甲酰胺的降解效果进行对比.结果表明,循环式浆态光催化反应器中光催化剂的用量、污染物的初始浓度和初始pH值对模拟污染物光催化降解性能的影响存在适宜值;体系中H₂PO^-₄、Cl^-、Cu²⁺、Al³⁺对其光催化降解过程有明显的抑制作用.与传统的搅拌式和鼓泡床式浆态光催化反应器相比,循环式浆态光催化反应器中催化剂和废水的混合效果较好,光利用率高,较大程度上减少催化剂的用量和提高废水处理能力.同时,对不同催化剂的用量和污染物初始浓度下的光催化氧化反应动力学研究表明,此过程符合拟一级动力学,催化剂表面反应速率常数k₀和催化剂吸附平衡常数K_TiO2分别为0.0279 min^-1和17.99 L•g^-1.     

电化学还原脱氯用GC负载Pd-Ni电极的制备及表征

通过电沉积法在玻碳板（GC）电极上负载钯镍双金属颗粒,并利用正交实验对其进行循环伏安（CV）研究,得到Pd-Ni/GC电极的最佳制备条件为：Ni²⁺=8.5 mmol·L^-1,Pd²⁺=3 mmol·L^-1,pH=7.0,J_k=15 mA·cm^-2,T=30 min。可以在-500 mV（以Hg/Hg₂SO₄为参比电极）左右获得-24.83 mA的氢吸附峰。用聚吡咯(PPy)修饰GC制备Pd-Ni/PPy/GC电极,CV结果表明,Pd-Ni/PPy/GC电极具有比Pd-Ni/GC电极更大的氢吸附峰值,可以在-500 mV（以Hg/Hg₂SO₄为参比电极）左右获得-32.33 mA的氢吸附峰。扫描电镜（SEM）分析表明,聚吡咯的修饰明显改变了Pd-Ni颗粒的沉积形态,使其沉积粒径更小,分散度更高。     

饮用水中摇蚊幼虫的臭氧灭活及其臭氧-活性炭工艺协同去除

进行了臭氧、二氧化氯和液氯灭活低龄期摇蚊幼虫的对比试验,对影响臭氧灭活效果的主要因素进行了考察,在此基础上,探讨了臭氧-活性炭工艺去除水中摇蚊幼虫的可行性.研究表明：与其他两种化学氧化剂相比,臭氧对滤后水中的低龄期摇蚊幼虫具有更显著的灭活作用,臭氧投加量1.0 mg•L^-1,接触25 min可以达到100%的灭活率;增加臭氧反应器水深有利于提高灭活率,在水质中性条件,COD_Mn对灭活效果影响较大.动态试验中,臭氧投加量1.0 mg•L^-1,接触11 min,臭氧对滤后水中的低龄期摇蚊幼虫可以达到100%灭活率;投加量0.8 mg•L^-1,臭氧-活性炭工艺的协同作用可以完全去除水中生物活性减低的摇蚊幼虫.     

Effect of mutations involving charged residues on the stability of staphylococcal nuclease: a continuum electrostatics study

A continuum electrostatics model is used to calculate the relativestabilities of 117 mutants of staphylococcal nuclease (SNase)involving the mutation of a charged residue to an unchargedresidue. The calculations are based on the crystallographicstructure of the wild-type protein and attempt to take implicitlyinto account the effect of the mutations in the denatured stateby assuming a linear relationship between the free energy changescaused by the mutation in the native and denatured states. Agood correlation (linear correlation coefficient of 0.8) isfound with published experimental relative stabilities of thesemutants. The results suggest that in the case of SNase (i) chargedresidues contribute to the stability of the native state mainlythrough electrostatic interactions, and (ii) native-like electrostaticinteractions may persist in the denatured state. The continuumelectrostatics method is only moderately sensitive to modelparameters and leads to quasi-predictive results for the relativemutant stabilities (error of 2–3 kJ mol^–1 or ofthe order of k_BT), except for mutants in which a charged residueis mutated to glycine. Received March 24, 2003; revised August 11, 2003; accepted September 12, 2003.     

恒电位下原位电生成活性氯氧化降解蒽醌染料

在一个阳极为形稳阳极的分隔的流经式电化学反应器中,利用原位电生成活性氯对活性艳蓝KN-R模拟废水进行氧化降解.在恒电位模式下,分别以592nm、255nm波长处的吸光度为主要指标,对该种染料的脱色及其芳环结构的氧化降解进行了对比分析.实验结果表明,在一定实验条件下,经4h的电解,可使染料100%脱色,同时40%左右的染料芳环结构被破坏;阳极电位、氯化钠浓度、染料浓度、电解液pH值对染料的脱色及其芳环结构的氧化降解有较强的影响,而温度和支持电解质浓度影响较小;在整个电氧化过程中,电解液未发生明显的矿化.在本实验条件下,间接电氧化在染料的氧化脱色降解过程中起主导作用,而直接电氧化作用不明显.     

常温下ABR反应器处理低浓度有机废水降解动力学

本文研究了折流板厌氧反应器（ABR）在常温下处理低浓度有机废水有机污染物降解动力学方面的问题。根据对ABR反应器有机污染物降解动力学模型的研究,得出ABR处理效率与水力停留时间（HRT）、污泥浓度、分格数（m）及温度有关。小试采用葡萄糖配制的模拟生活污水进行试验,求得不同温度下减速增长的速度常数K₂值。由Arrhenius公式求得了活化能E值1.92×104 J.mol^-1,这表明本试验中温度对K₂值影响不大,从而在理论上说明在温度较低时ABR反应器仍有较好处理效果的原因。     

水在ZSM-5型分子筛中吸附的Monte Carlo模拟

构建了ZSM-5型分子筛物理模型,采用Connoly表面方法和Solvent表面方法对ZSM-5型分子筛的几何结构和性质进行了模拟分析。通过巨正则系综蒙特卡罗方法(GCMC)模拟研究了水蒸气在ZSM-5型分子筛上的吸附特性。通过模拟方法看到了实验难以表征的水蒸气在分子筛中具体吸附位,研究了压力、温度和硅铝比对ZSM-5型分子筛吸附性能的影响及其吸附热的变化规律。     

六氨氯化镁热解过程及其非等温动力学

利用热重（TG）分析技术对六氨氯化镁的热分解过程及动力学进行了研究,考察了六氨氯化镁在4、7、10、13、16 K·min^-1线性升温速率和空气气氛下热分解机理,六氨氯化镁热解过程分为3个阶段。提出了一种整体优化的多升温速率迭代的等转化率求取活化能方法,采用该方法,得到六氨氯化镁热解3个阶段的活化能分别为51.38、64.70、73.55 kJ·mol^-1。采用整体优化的多升温速率等温法确立了六氨氯化镁热解3个阶段的热解机理函数与指前因子：第1步反应的热解机理属于固体相边界反应机理（n=1/4）,指前因子为3.281×10⁵ s^-1;第2步反应的热解机理属成核与生长机理（n=1.8）,指前因子为5.624×10⁶ s^-1;第3步反应属化学反应机理（1.5级反应）,指前因子为5.862×10⁵ s^-1。     

Stability effects associated with the introduction of a partial and a complete Ca2+-binding site into human lysozyme

Two mutants of human lysozyme were synthesized. Mutant A92D,in which Ala92 was substituted by Asp, contains a partial Ca²⁺-bindingsite and mutant M4, in which Ala83, Gm86, Asn88 and Ala92 werereplaced by Lys, Asp, Asp and Asp respectively, contains thecomplete Ca -binding site of bovine a-lactalbumin. The Ca²⁺-bindingconstants of wild type human lysozyme and of mutants A92D andM4, measured at 25C and pH 7.5, were 2(1) x 102 M"1, 8(2)x l^M"1 and 9(0.5) x 10* M"1 respectively. Information gatheredfrom mkrocalorimetrk and CD spectro-scopic measurements indicatesthat the conformational changes of the M4 mutant lysozyme, inducedby Ca²⁺ binding, are smaller than those observed for bovinea-lactalbumin and for the Ca²⁺-binding equine lysozyme. At pH4.5, the thermostability of both the apo and Ca²⁺ forms of theA92D human was decreased in comparison with that of native humanlysozyme. In particular, within the apo form of this mutantan a-helix-containing sequence was destabilized. In contrast,at the same pH the thermostability of the apo and Ca²⁺ formsof the M4 mutant lysozyme was increased. The e-ammonium groupof the Lys83 side chain is assumed to be responsible for thestabilization of the apo form of this mutant.     

SA/NaCS-CaCl2/PMCG微胶囊固定化枯草杆菌HL-1发酵生产纳豆激酶

制备了海藻酸钠/纤维素硫酸钠-CaCl₂/聚亚基二胍氯化氢微胶囊（SA/NaCS-CaCl₂/PMCG微胶囊）,并以该微胶囊固定化培养枯草杆菌HL-1用于发酵制备纳豆激酶,考察了PMCG对枯草杆菌生长的影响,比较了微囊化培养与游离培养过程中的菌体生长、耗糖速率以及纳豆激酶产物分泌能力.最后经过连续6批培养,酶活可达到2465 IU•ml^-1,是游离培养过程的3倍.     

固体氧化物质子传导膜H2S燃料电池

引　言H2 S固体氧化物燃料电池首先由美国学者Pujare等[1] 于 1987年提出 ,它是以废气中的H2 S作为燃料 ,固体氧化物YSZ (氧离子传导 )为离子传导膜 ,由于在脱除H2 S的同时可获得绿色能源———电能 ,引起了学术界与工业界的极大关注 .GeorgiaInstituteofTechnology的Yates等、     

Evidence for the involvement of tyrosine-69 in the control of stereospecificity of porcine pancreatic phospholipase A2

We have studied the role of Tyr-69 of porcine pancreatic phospholipaseA₂ in catalysis and substrate binding, using site-directed mutagenesis.A mutant was constructed containing Phe at position 69. Kineticcharacterization revealed that the Phe-69 mutant has retainedenzymatic activity on monomeric and micellar substrates, andthat the mutation has only minor effects on k_cat and K_m. Thisshows that Tyr-69 plays no role in the true catalytic eventsduring substrate hydrolysis. In contrast, the mutation has aprofound influence on the stereospecificity of the enzyme. Whereasthe wild-type phospholipase A₂ is only able to catalyse thedegradation of sn-3 phospholipids, the Phe-69 mutant hydrolysesboth the sn-3 isomers and, at a low (1–2%) rate, the sn-1isomers. Despite the fact that the stereospecificity of themutant phospholipase has been altered, Phe-69 phospholipasestill requires Ca²⁺ ions as a cofactor and also retains itsspecificity for the sn-2 ester bond. Our data suggest that inporcine pancreatic phospholipase A₂ the hydroxyl group of Tyr-69serves to fix and orient the phosphate group of phospholipidmonomers by hydrogen bonding. Because no such interaction canoccur between the Phe-69 side-chain and the phosphate moietyof the substrate monomer, the mutant enzyme loses part of itsstereospecificity but not its positional specificity.     

电晕-吸收法治理NOx废气技术

采用电晕结合现场化学吸收的方法对NO的去除效果进行了实验研究.电晕反应器为线筒式结构,作为吸收剂的Ca(OH)₂均匀地覆盖在筒壁的内表面.实验表明此法能有效地除去气流中的氮氧化物,NO的去除率大大高于反应器内没有固体吸收剂的情况,同时反应器出口NO₂的浓度小于12 mg•m^-3.可以认为反应器内的Ca(OH)₂吸收剂与NO的氧化产物NO₂或NO₃的吸收反应促进了NO的分解反应.研究还发现在气流中有氧气和水分存在时有利于NO的氧化反应和气固吸收反应,从而提高了NO的去除率.     

模拟土壤介质中仿古铸铁腐蚀产物的形貌及其生长过程

采用金相、显微激光拉曼和X射线衍射等技术研究了仿古铸铁在模拟土壤介质(0.06 mol•L^-1 NaCl+0.03 mol•L^-1 Na₂SO₄+0.01 mol•L^-1 NaHCO₃溶液)中的腐蚀形态、腐蚀产物的形貌及其生长和发展过程.结果表明,在最初的34 h内,铸铁发生铁的选择性腐蚀,在试样表面留下许多白色圈状的Fe(OH)₂沉淀,圈内则是分散状的Fe(OH)₂;浸泡120 h时,观察到试样表面有一层深绿色的腐蚀产物,其组分主要为GR(Cl^-)（化学式为Fe^Ⅱ₃Fe^Ⅲ（OH）₈Cl•2H₂O）和GR(SO^2-₄)（化学式为Fe^Ⅱ₄Fe^Ⅲ₂（OH）₁₂SO₄•2H₂O）,绿锈表面呈黄色;约288 h后,腐蚀产物呈现分层,内层主要由黑色结晶状的FeO和Fe₃O₄组成,外层主要为疏松多孔的砖红色γ-FeOOH,后者是铁器表面的一种有害锈.