对位酚类衍生物作为化学发光分析的增强剂研究

在化学发光分析中，常常要用到碱性条件下鲁米诺与过氧化氢的反应系统，通过催化剂辣根过氧化物酶使反应顺利进行。如果再加入适当的增强剂，则灵敏度提高且发光时间延长，可改善测定的重现性。实验证明，对位酚类衍生物，如：对叔丁基苯酚，对甲苯酚的发光增强作用明显，其发光效率可上升几十倍，发光时间也获得有效延长。     

取代对苯二酚醚化物的合成研究

本文从取代的对苯三酚３出发、利用Ｗｉｌｌｉａｍｓｏｎ醚化反应合成了一系列它的醚化产物４ａ－４Ｈ，给出了它们的核磁共振数据（氢谱和碳谱）。讨论了影响醚化反应的一些因素，比较了不同烷化剂发生醚化反应的活泼性。     

Influence of heat treatment conditions on the porosity changes of sulfonated styrene/divinylbenzene copolymers

Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca²⁺ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m²/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m²/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc.     

Phenol biosensor based on electrochemically controlled integration of tyrosinase in a redox polymer

An amperometric biosensor for the detection of phenolic compounds was developed based on the immobilization of tyrosinase within an Os-complex functionalized electrodeposition polymer. Integration of tyrosinase within the redox polymer assures efficient catechol recycling between the enzyme and the polymer bound redox sites. The non-manual immobilization procedure improves the reproducibility of fabrication process, greatly reduces the desorption of the enzyme from the immobilization layer, and, most importantly prevents fast inactivation of the enzyme by its substrate due to fast redox cycling. A two-layer sensor architecture was developed involving ascorbic acid oxidase entrapped within an electrodeposition polymer in a second layer on top of the redox polymer/tyrosinase layer. Using this sensor architecture it was possible to eliminate the current interference arising from direct ascorbate oxidation up to a concentration of 630 μM ascorbic acid. The effects of the polymer thickness, the enzyme/polymer ratio, and the applied potential were evaluated with respect to optimal sensor properties. The sensitivity of the optimized sensors for catechol was 6.1 nA μM⁻¹ with a detection limit of 10 nM, and for phenol 0.15 nA μM⁻¹ with a detection limit of 100 nM.     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

Highly Effective Phenol Hydroxylation over Ti-ZSM-5 Catalyst Prepared Using B-ZSM-5 as Precursor 以B-ZSM-5为母体合成Ti-ZSM-5高效苯酚羟基化催化剂

 以改进方法合成的B-ZSM-5为母体,采用气固相同晶取代法合成了较小晶粒的Ti-ZSM-5分子筛. 考察了样品的物化性能和催化苯酚羟基化性能. 结果表明: 所合成的小晶粒Ti-ZSM-5具有较高的结晶度,尺寸为100~200 nm,且不含锐钛矿型TiO2,对苯酚羟基化反应的催化性能优异.     

铁－铜－锰氧化物／海泡石催化剂对苯羟基化为苯酚的催化作用

铁－铜－锰氧化物／海泡石催化剂对苯羟基化为苯酚的催化作用曹声春，黄孟光，李克，杜兴军（湖南大学化工系，长沙４１００８２）关键词氧化铁，氧化钢，二氧化锰，海泡石，负载型催化剂，苯，羟基化，苯酚由苯合成苯酚的现行方法存在着反应步骤多，工艺过程复杂，总转化...     

镀铜铁屑-H_2O_2催化氧化降解含酚废水

采用镀铜铁屑代替传统Fenton体系中的FeSO4作为催化剂,通过改变H2O2与镀铜铁屑的投加量、溶液的pH值、反应温度、反应时间等条件,研究了该体系对处理苯酚废水的影响。结果表明,常温下处理实际含酚印染废水,在pH值为4~6,30%H2O2 12mL/L,镀铜铁屑5g/L,反应时间为45min时,COD去除率可达96%,其CODCr从5827mg/L降至419mg/L,色度从2000降至30,符合国家三级排放标准。     

镍(Ⅱ)与3-噻唑偶氮-5-氨基苯酚体系络合吸附波的研究

3-噻唑偶氮-5-氨基苯酚(3-thiazolyazo-5-am ino phenol,3-TAP)是一种高灵敏度新型杂环偶氮类显色剂,在极谱分析中的应用尚未见报道。镍(Ⅱ)的测定已有较多方法报道[1~5]。为了进一步扩大3-TAP的应用范围,作者研究了镍(Ⅱ)与3-TAP络合物吸附波的最佳实验条件及络合物的极谱波性     

含铜三元类水滑石化合物的合成及其性质

 以Cu（NO3）2，Zn（NO3）2和Al（NO3）3为原料，以NaOH为沉淀剂，利用共沉淀法合成了含铜三元类水滑石化合物CuZnAl－HTLcs．从不同Cu／Zn／Al比的混合原料溶液的滴定曲线入手，详细探讨了溶液pH值、原料加入方式、组分配比及水热处理条件对类水滑石合成的影响，利用XRD，ICP及比表面积测定对合成物进行了表征，并以苯酚羟基化为探针反应评价了催化剂的催化性能．结果表明，在体系pH＝5．0～6．2，（Cu＋Zn）／Al摩尔比＝2．0，Cu／Zn摩尔比≤1．0及室温条件下共沉淀后，于100℃水热处理3h，即可得到晶相单一和结晶度高的CuZnAl－HTLcs．变化pH法合成的样品的相对结晶度为100％，低过饱和法为76．5％，高过饱和法为75．9％．合成的CuZnAl－HTLcs中Cu2＋的含量均比原料液中Cu2＋的含量有所增加，这可能是由于在pH＝5．8时Cu2＋对Al（OH）3的同晶取代能力比Zn2＋强．随着CuZnAl－HTLcs中Cu含量的增加，催化剂对苯酚羟化反应的催化活性逐渐增大．