十二烷基苯磺酸钠氧化降解的研究

随着工农业的发展,表面活性剂已广泛应用于各个领域,表面活性剂废水的大量排放成为水体CODCr的重要来源.目前对此类废水的降解研究主要集中于生物法和光催化法[1].高铁酸盐具有强氧化性,在水处理方面可用于杀灭藻类和细菌[2],氧化降解水中的污染物[3,4]等,本研究以十二烷基苯磺酸钠(SDBS)水溶液作为表面活性剂模拟废水,研究高铁酸盐(FeO42-)对其处理效果和降解机理.实验结果表明,新型水处理剂高铁酸盐可以有效降解SDRS.     

草酸在Ti/IrO2-Ta2O5阳极圆柱形电解槽中的电催化氧化降解动力学

从电催化氧化降解有机污染物的机理出发,研究了草酸在Ti/IrO2-Ta2O5阳极圆柱形电解槽中的电催化氧化过程,建立了描述整个降解过程的瞬时电流效率与溶液本体有机物浓度的关系式. 通过实验对模型进行了验证,实验结果与模型计算结果基本一致,并讨论了误差产生的原因.     

有机涂层环境适应性研究进展

综述了有机涂层自然环境试验方法和实验室加速试验方法。自然环境试验方法主要有大气环境试验和海水环境试验;实验室加速试验方法不但包括模拟太阳光、热、湿热、盐雾等环境的实验室试验,还有综合模拟试验。还介绍了检测有机涂层老化的宏观分析方法、微观分析方法和电化学分析方法。其中宏观分析方法主要介绍了涂层附着力试验方法,微观分析方法则主要介绍了扫描电镜(SEM)、X射线光电子能谱仪(XPS)、傅里叶红外光谱(FTIR)及电化学交流阻抗谱法(EIS)。讨论了近年发展起来的有机涂层老化的各种机理,例如自由基降解的光老化降解机理,亲水性基团的水降解机理,热氧机理,臭氧及污染物影响的老化机理等。     

水相中POPs光化学降解研究进展

综述了近年来12种持久性有机污染物(POPs)在水体中光化学降解行为,从水体中POPs的光解途径、光解机理和定量结构-性质关系(QSPR)三个方面探讨了POPs在水体中的光化学行为,展望了水体中POPs光化学行为的研究前景.     

BiVO4光催化去除废水中的四环素和环丙沙星

利用微波水热法制备单斜白钨矿型BiVO4为光催化剂,探讨其对抗生素类污染物的去除效果.同时利用X射线衍射(XRD)、傅里叶红外(FT-IR)和场发射扫描电镜(FE-SEM)等测试手段对样品结构和性能进行了表征.以四环素(TC)和环丙沙星(CIP)为目标污染物,研究光照时间、pH及Cu(Ⅱ)共存对BiVO4光催化降解抗生素性能的影响.结果表明:BiVO4对TC和CIP的光催化具有较为宽泛的pH适用范围,其中TC在pH为5~12之间具有良好的效果,pH=8时,降解效率达到74%;CIP在pH为4~9之间适用范围最好,降解率由26%升高到37%.此外,对TC和CIP光催化降解机理和可能的降解途径进行探讨,光催化降解主要机理是有效光生电子-空穴与OH-和O2结合,将TC和CIP分解为中间产物CO2和H2O.总之,单斜白钨矿型BiVO4用于模拟抗生素废水的研究,取得一定效果,可为实际抗生素废水的处理提供参考.     

漆酶催化氧化水中有机污染物*

漆酶是一种含铜的多酚氧化酶, 属于铜蓝氧化酶蛋白, 能催化氧化多种难降解的有机污染物。漆酶催化氧化水中有机污染物具有底物广泛、能耗低、易操作、环境友好等优点,是一项前景广阔的生物处理技术。本文综述了漆酶对水中有机污染物的催化降解,主要从漆酶的化学组成、结构、催化降解机理、漆酶的固定化、影响因素（溶液pH值、温度、金属离子、营养因子、有机溶剂、漆酶的浓度、底物的初始浓度等）、降解的动力学以及漆酶在处理水中有机污染物的应用等五个方面介绍了相关的研究进展。漆酶催化氧化有机物的机理主要表现在底物自由基中间体的产生和氧气还原成水两个方面。本文提出了目前漆酶催化氧化水中有机污染物存在的主要问题,并展望了漆酶降解水体中有机污染物的发展方向。     

有毒难降解有机污染物的光催化降解

有毒难降解有机污染物的光催化降解在原理、过程和效率等方面仍然存在着巨大的挑战,特别是光催化剂的构效关系、可见光的利用、分子氧的活化和污染物分子矿化分解的机理仍然是今后的研究热点.本文就近年来在半导体光催化和负载型铁离子光催化降解有毒有机污染物的两个重要方面的研究进展进行了评述.     

环境中有机磷污染物碱性的理论研究

有机膦化合物的碱度对深入了解有机膦类污染物的降解有着重要的意义. 发展基于第一性原理的理论方法精确计算有机膦化合物的pKa值有重要意义. 本研究工作发展了精确计算有机膦阳离子化合物pKa值的方法: 用B3LYP/6- 31＋G(d)优化气相结构, PBEPBE计算单点能量, IEFPCM/Bondi (f＝1.0)计算溶剂化能. 理论值与实验值比较, 其平均偏差和均方根差分别为－0.6 pKa单位和0.7 pKa单位. 基于此方法, 我们研究了常见有机膦污染物阳离子的碱性, 定量计算其pKa值. 并进一步讨论了这类化合物的α取代效应和远程取代效应对其碱性的影响, 总结了影响杂环有机膦化合物阳离子酸性的因素.     

双配体仿酶催化剂的制备及其光催化降解水中对苯二酚

以天然氯化血红素和咪唑为原料,制备了咪唑轴向五配位型的双配体配合物,并将其负载于羟基功能化的纤维素磁微球表面。 通过紫外-可见分光光度、傅里叶变换红外光谱、透射电子显微镜、热重分析和振动样品磁强（VSM）对催化剂进行表征。 在模拟太阳光照射下,以水中溶解氧为氧化剂,考察了该催化剂降解模拟废水中有机污染物对苯二酚（HQ）的性能。 结果表明,在300 W氙灯照射下,当催化剂用量0.2 g/L、HQ初始浓度20 mg/L及pH值为6的条件下,6 h后HQ的降解率达到96.97%,催化剂重复使用5次后,降解率仍可达92%以上。同时对该催化剂光催化降解对苯二酚的机理进行了初步研究。     

高分子金属卟啉光催化氧化处理废水

 将高分子金属卟啉聚中位四（4,4’－联苯二磺酰基）氧基苯基钴卟啉用于多相光催化体系,在温和条件下成功地降解了有机染料吖啶橙．实验结果表明,降解反应符合一级动力学方程lnct＝2．52052－0．56546t（R＝－0．99704）,经8h的反应以后,染料溶液完全褪色．将此光催化剂用于混合染料、染料废水、化工厂废水及生活污水的处理,脱色率可达68％,COD去除率可达58％．通过对高压汞灯、碘钨灯和自然光等各种光源进行比较,发现在太阳光照射下,金属卟啉光催化氧化降解有机污染物的效率更高、速度更快、降解更完全．     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.