惠东县乡镇学龄前儿童血铅水平分析

为了解惠东县乡镇3～6岁儿童血铅水平。采取随机与特定结合的方法,于2 0 0 4年1 0月～1 1月对惠东县5个乡镇的790名3～6岁儿童进行了血铅水平测定。检测采用全国统一的BH -2 1 0 0钨舟原子吸收仪及随机专用试剂进行。所有操作均严格按照要求进行。结果表明,惠东县乡镇3～6岁儿童血铅水平为(70 70±2 4 89) μg/L达到我国近年来5 2个调查结果所示的普通市区儿童血铅水平70～90 μg/L的下限。其中高于国际儿童铅中毒标准占9 6%。儿童的血铅水平存在明显的区域差异,制鞋工业乡镇较高。同时儿童血铅水平存在着性别差异。男童较女童偏高。提示不能忽视乡镇儿童铅污染情况,尤其是制鞋工业乡镇的儿童高血铅水平应引起有关部门重视。     

Structure and sorption characteristics of bioaffinity membranes

The new bioaffinity membranes comprise mammalian blood and tissue cells immobilized in the polymer matrix. The method of immobilization does not assume the retention of physiological and enzymatic activity of immobilized cells, but it ensures the safety of cellular membrane receptors that are used as specific ligands. Macroporous polymer carriers based on polyacrylonitrile maintain the accessibility of the cellular receptors for all blood plasma components including immunoglobulins and viral particles. The sorption capacity of membranes with respect to model substances in a batchwise technique is evaluated. Although the results are of a preliminary nature, the membranes may be used in crossflow modules for selective blood plasma correction of endogenous substances.     

Chemistry of novolac resins. X. Polymerization studies of HMTA and strategically synthesized model compounds

The reactions between hexamethylenetetramine (HMTA) and compounds which model novolac resins have been studied by ¹³C‐ and ¹⁵N‐NMR techniques. The dimer and tetramer compounds vary in molecular size and structure and react with HMTA to yield benzylamines and benzoxazine as the major initial‐formed intermediates and convert to methylene linked compounds at increased temperatures. The reaction of the compounds with only ortho reactive sites paralleled the 2,4‐xylenol–HMTA case reported by us previously; however, increasing molecular weight favored the formation of benzylamines and not benzoxazines. Those compounds with only para reactive sites paralleled the 2,6‐xylenol–HMTA case. The reactivity of the systems containing both ortho and para reactive sites depends on the ratio of ortho/para sites and various aspects such as the chemical structure and molecular weight of the compound, the HMTA level, and the melting point and pH of the system. These results parallel those obtained from novolac/HMTA systems. The xylenol/HMTA reactions formed similar products but showed quite different relative reaction rates by varying the HMTA ratio and structures of the materials. The importance of careful selection of model systems is also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1347–1355, 1999     

Peroxide initiated maleic anhydride grafting: Structural studies on an ester‐containing copolymer and related substrates

Maleic anhydride (MAn) was grafted onto the low molecular weight esters methyl decanoate (MD) and methyl 2‐ethylhexanoate (MEH) using the free‐radical initiators Lupersol‐101 and ‐130; the esters were used as model compounds for the copolymer poly(ethylene‐co‐methyl acrylate). The grafted products in both cases were isolated from the unreacted ester and were subjected to extensive analysis using spectroscopic and chromatographic techniques. Analysis of the grafted material indicated the presence of one or more succinic anhydride (SAn) residues grafted to the ester. In the case of the multiply grafted material it has been established conclusively by ¹³C‐NMR using 2,3‐¹³C₂ labeled MAn that the multiple grafts exist as single units. A limited number of grafting experiments was performed on the copolymer in the melt and the graft‐modified copolymer was characterized spectroscopically. Single graft units were observed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1609–1618, 1999     

Enzymatic polymerization: A new method of polymer synthesis

Enzymatic polymerization denotes an in vitro polymerization via nonbiosynthetic pathways catalyzed by an isolated enzyme. This article describes the recent progress of this polymerization technique, developed mainly during this decade. The polymerization utilizes enzymes of hydrolases and oxidoreductases as catalysts. This new method of polymer synthesis provided natural polysaccharides like cellulose, amylose, xylan, and chitin, and unnatural polysaccharides catalyzed by a glycosidase from well-designed monomers, various functionalized polyesters catalyzed by lipase from a variety of monomers, and polyaromatics materials catalyzed by an oxidoreductase and an enzyme model complex from phenols and anilines. An oxidoreductase also initiated vinyl polymerizations. Characteristic features of enzymatic polymerizations are discussed, including the importance of the combination of substrate monomer and enzyme. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3041–3056, 1999     

Photopolymerization mechanisms of acrylates in poly(methyl methacrylate) films

Photoinitiation processes for photopolymer coating layers have been investigated with respect to quenching rates by a laser flash photolysis using a total reflection cell, as well as to the decomposition‐quantum yield of a sensitizer dye and a radical‐generating reagent by a gel permeative chromatographic analysis (GPC); the sensitizer dye,2‐[p‐(diethylamino)styryl]naphtho[1,2‐d]‐thiazole (DNT) and the radical‐generating reagent, 2,2′‐bis(2‐chlorophenyl)‐4,4′,5,5′‐tetraphenyl‐1,1′‐bi‐1H‐imidazole (BI). From experiments using flash photolysis, strong fluorescence was observed at excitation of 355 nm laser pulse, though no transient absorption was observed. The fluorescence was statically quenched by BI with a quenching distance, R = 11 Å. From the experiments using GPC, the high‐quantum yield of decomposition (Φ) was obtained as Φ (DNT) = 3 and Φ (BI) = 9 for DNT and BI in the presence of acrylate monomers, trimethyrolpropanetri‐acrylate (TMPTA), at 488 nm exposure of 3.36 mJ cm which was required to form a photo‐hardened image, however no decomposition of DNT and BI was detected in the absence of TMPTA. The results imply that the photoinitiator system undergoes efficient static‐dye sensitization and efficient polymerization of the acrylate monomers accompanied with the chain decomposition of DNT and BI. Copyright © 1999 John Wiley & Sons, Ltd.     

双染料复合敏化SnO2纳米多孔膜光电极的研究

光电化学;光电转换;双染料复合敏化SnO2纳米多孔膜光电极的研究     

制备方法对煤焦油模型化合物裂解催化剂Ni/Al_2O_3结构及性能的影响

采用等体积浸渍法、浸渍沉淀法和机械化学法(市售载体和自制载体)制备了Cat-1、Cat-2、Cat-3和Cat-4四种催化剂,通过BET、H_2-TPR、XRD、XPS和NH_3-TPD等表征催化剂的结构特征,考察了各催化剂对煤焦油模型化合物甲苯和芘(3%,质量分数)裂解反应性能的影响。结果表明,四种催化剂均为介孔材料,且Cat-4的介孔有序度更高,比表面积最大,达235 m~2/g。Cat-4催化剂中,NiAl_2O_4尖晶石的还原峰面积最高,占总面积的85.2%,还原后Ni的分散度最大,粒径最小,约为10.0 nm,意味着活性位点多。实验表明,除Cat-1外,其他催化剂对芘的裂解活性基本相当,其中,Cat-4作用下的析碳量最低,为10.84%,经Cat-1、Cat-2和Cat-3裂解后,体系中的析碳量分别较Cat-4增加了35.0%、74.7%和45.7%。可见,机械化学法制备的催化剂不仅具有最高的比表面积利于活性组分分散,而且NiAl_2O_4尖晶石含量最高,可抑制裂解过程中积炭的生成,因而最适宜于甲苯+芘裂解体系。     

不同结构扩孔分子筛催化MTP反应行为及表面积炭物种表征

采用TEAOH溶液处理MFI结构ZSM-5分子筛、MWW结构MCM-22分子筛,NaOH溶液处理TON结构ZSM-22分子筛、CHA结构SSZ-13分子筛得到四种结构的扩孔分子筛。在反应温度480℃、反应压力0.1 MPa、甲醇与水质量比1∶1、甲醇质量空速1.5 h~(-1)的条件下,考察了四种扩孔分子筛的甲醇制丙烯(MTP)催化性能,并采用XRD、N_2吸附-脱附、NH_3-TPD、TG、UV-Raman和GC-M S等方法表征催化剂的物化性质及M TP反应2 h后的分子筛积炭性质。结果表明,四种分子筛扩孔改性后均出现介孔,其中,T-ZSM-5分子筛在MTP反应中寿命最长;T-MCM-22分子筛寿命次之且失活速率慢;而一维孔道结构N-ZSM-22分子筛和八元环尺寸较小的N-SSZ-13分子筛均失活迅速。受拓扑结构和孔道扩散的影响,MTP反应2 h后,分子筛积炭量增加的顺序为T-ZSM-5N-ZSM-22T-MCM-22N-SSZ-13且可溶焦分子质量随积炭量增加而增重,即从五甲基苯增重到菲、芘等多环芳烃。     

盐析辅助液液萃取交联聚维酮净化-靶向单一离子监测/高分辨质谱法测定蜂蜜中新烟碱类农药残留

基于盐析辅助液液萃取(LLE)交联聚维酮(PVPP)净化技术,建立了蜂蜜中7种新烟碱类农药的靶向单一离子监测(TSIM)/高分辨质谱检测方法。样品用乙腈基于盐析辅助LLE-PVPP提取净化,采用BEH C18色谱柱为分析柱,甲醇-水体系(两相均含0.1%甲酸和5 mmol/L甲酸铵)作为流动相,梯度洗脱,采用高分辨质谱TSIM模式检测目标化合物,内标法定量。结果表明,盐析辅助LLE-PVPP净化技术可实现提取净化一步式样品制备,TSIM扫描模式则显示了更宽的线性动态范围和更高的灵敏度与准确度。7种新烟碱类农药在0.01~100μg/L或0.02~100μg/L范围内具有良好的线性关系(r20.999);方法检出限为0.03~0.07μg/kg,定量下限为0.1~0.2μg/kg。在0.2、2、20μg/kg 3种加标水平下,7种新烟碱类农药在蜂蜜中的平均回收率为84.8%~112.7%,日内精密度(RSDr)为0.9%~5.7%,日间精密度(RSDR)为3.7%~9.7%。该方法前处理简单快速、成本较低,灵敏度高、重现性好,可广泛应用于蜂蜜中新烟碱类农药残留的快速检测。