大分子光引发剂的研究进展

综述了大分子光引发剂的研究现状和进展。简要叙述了大分子光引发剂的制备方法、引发机理。对小分子光引发剂和大分子光引发剂进行了对比,着重讨论了分子结构因素对引发性能的影响。     

光聚合引发剂研究进展

对最近几年光敏聚合引发体系的研究进展进行了评述，并就一些新型光敏引发体系及引发机理进行了介绍。     

铈盐－过硫酸盐复合引发体系的研究

铈盐－过硫酸盐复合引发体系的研究李朝阳，丘坤元（北京大学化学系，北京，１００８７１）关键词复合引发体系，铈盐，过硫酸盐，氧化还原引发本文研究了一种新的复合引发体系，即在传统的单独钟盐引发体系中引人过硫酸盐这一本身具有强氧化性的新组分，提高原体系的引发...     

无机纳米材料表面引发自由基可控聚合反应

无机纳米-高分子杂化材料具有优异的性能及广阔的应用前景,引起人们的广泛关注.本文综述了无机纳米材料表面引发自由基可控聚合反应在合成无机-高分子纳米杂化材料方面的广泛应用,包括表面引发原子转移自由基聚合(ATRP)、表面引发可逆加成-断裂链转移自由基聚合(RAFT)、表面引发稳定氮氧自由基聚合(NMP). 着重总结了近几年来这类杂化材料在功能性研究上新的进展,并对今后研究的发展趋势进行了展望.     

新型水溶性硫杂蒽酮类光引发剂的光引发性能研究

利用红外光谱技术对六种新型水溶性硫杂蒽酮类光引发剂在紫外光聚合反应中的引发性能进行了测试,用相对峰面积法计算了聚合反应的转化率,并据此对引发剂结构与光化学性能之间的关系做了一定的探讨。结果表明该类光引发剂具有很高的光化学活性,而引发剂的结构直接影响引发性能。研究发现硫杂蒽酮母体上甲基的引入使引发剂的引发效率增大,而引发剂侧链上羟基的引入,则由于降低了质量转移的有效性并有可能使引发剂分子缔合,致命引     

环氧树脂的紫外光引发阳离子／自由基固化

研究了两类阳离子引发剂复合苯基硫钅翁盐和芳茂铁盐的紫外光引发活性以及它们分别与自由基引发剂的复合体系的增强光引发活性，并讨论了强氧化剂异丙苯过氧化氢对于芳茂铁盐引发效率的促进作用以及适量多元醇对于提高阳离子固化体系交联度所起的作用     

水性光引发剂研究进展及其在生物医学中的应用

近年来,水性光固化技术被越来越多地应用于生物医学领域,如牙科材料、3D生物打印、体外聚合、细胞封装等。水溶性好、细胞毒性低、引发效率高的水性光引发剂是光固化技术在生物医学领域广泛发展应用的关键物质。为此,研究人员做了大量的工作,设计开发了一系列性能优良的水性光引发剂,并研究了其在药物控释、生物仿生解毒器、细胞传感器、软骨修复、断层扫描体积生物打印、生物组织粘合剂、光动力肿瘤治疗等方面的应用效果。本文概述了水性光引发剂的种类、作用机制以及在生物医学中的一些应用研究,并对水性光引发剂的发展方向进行了展望,希望能为水性光引发剂的发展以及应用带来一些启发。     

铈离子氧化还原引发体系与铈离子引发接枝或嵌段共聚合研究的新进展

本文介绍Ce⁴⁺/酰胺引发体系;Ce⁴⁺/聚酰胺、带酰苯胺侧基的聚合物引发接枝共聚合;Ce⁴⁺/氨基甲酸酯引发体系;Ce⁴⁺/聚醚氨酯引发接枝共聚合;Ce⁴⁺/羰基化合物引发体系;Ce⁴⁺引发嵌段共聚合6个方面的研究新进展.     

GC—MS方法测定等离子体引发丙烯酸酯聚合引发活性种

在等离子体引发的液态丙烯酸酯类单体聚合体系中加入大量链转移剂乙硫醇,得到了端基带有引发活性种的低聚物,利用气相色谱-质谱的多离子检测手段,测定了活性种的结构,结果表明:引发活性种是单体在等离子体区裂解生成的酯基碎片[-C—O—R].进而解释了丙烯酸酯类单体可以由等离子体引发聚合,而苯乙烯不能引发聚合的问题.     

双官能度引发剂引发苯乙烯聚合微观动力学

采用 2 ,5 二甲基 2 ,5 二己酰基过氧化己烷 (DMDEHPH)为引发剂 ,在 5 5～ 80℃下引发苯乙烯聚合 .通过研究影响聚合速率的各种因素 ,得出了聚合速率对单体浓度和引发剂浓度的级数分别为 1 0和 0 5次、聚合活化能为 92 0kJ mol、引发效率为 0 5 5± 0 0 3.温度一定 ,引发效率随引发剂浓度的增加而减小 .求得 6 0和70℃下DMDEHPH向引发剂的链转移常数分别为 0 0 37和 0 0 4 8、向单体的链转移常数分别为 0 5 9× 10 - 4和0 75× 10 - 4.     

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.     

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.     

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.     

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.