磁性高分子微球的合成研究─—带醛基磁性高分子微球的合成及表征

用超声波分散处理Ｆｅ３Ｏ４粉末同稳定剂溶液的分散体系，使Ｆｅ３Ｏ４粉末能稳定地分散成细微粒子，同时增强了Ｆｅ３Ｏ４细微粒子同单体、引发剂的亲合性。苯乙烯—丙烯醛共聚物为高分子壳层，包裹Ｆｅ３Ｏ４得到了带醛基的磁性高分子复合微球。微球粒径可控制在５０～２００μｍ，微球中Ｆｅ３Ｏ４含量在０．４～１．５％之间，通过电导滴定法测定微球表面醛基含量在０．０４～０．１ｍｍｏＬ·ｇ－１范围内。着重考察了引发剂体系、稳定剂体系、分散介质等对微球粒径、表面醛基含量的影响。     

磁性高分子微球的合成研究——带醛基磁性高分子微球的合成及表征

用超声波分散处理Ｐｅ３Ｏ４粉末同稳定剂溶液的分散体系，使Ｆｅ３Ｏ４粉末能稳定地分散成细微粒子，同时增强了Ｆｅ３Ｏ４细微粒子同单体，引发剂的亲合性。苯乙烯－丙烯醛共聚物为高分子壳层，包裹Ｆｅ３Ｏ４得到了带醛基的磁性高分子复合微球。     

等瓣置换反应研究—异核四面体簇合物（μ2）FeMoCo（η^5—RC5H4）（C…

通过η＾５－ＣＨ３ＣＯＣ５Ｈ４（ＣＯ）３ＭｏＮａ与（μ３－Ｓ）ＦｅＣｏ２（ＣＯ）９的反应俣成了（μ３－Ｓ）ＦｅＭｏＣｏ（η＾５－ＣＨ３ＣＯＣ５Ｈ４（ＣＯ）８１，１进一步（η＾５－Ｃ５Ｈ５）Ｎｉ的反应合成了（μ３－Ｓ）－ＦｅＭｏＮｉ（η＾５－ＣＨ３ＣＯＣ５Ｈ４）（ＣＯ）５２，（μ３－Ｓ）ＦｅＭｏＮｉ（η＾５－Ｃ５Ｈ５（η＾５－Ｃ５Ｈ５）－（ＣＯ）５３及（μ３－Ｓ）ＦｅＭｏＣｏ（η５－Ｃ５Ｈ５）（ＣＯ     

等瓣置换反应的研究——手性簇合物[η^—MeO2CC5H4）（CO）2Mo…

用Ｘ射线衍微法测定了由η＾５－ＭｅＯ２ＣＣ５Ｈ４（ＣＯ）３ＭｏＮａ和〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ－（ＣＯ）３Ｃｏ（ＣＯ）３（μ３－Ｓ）的等瓣置换反应所生成的手性簇合物－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｍｏ〕－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ（ＣＯ）３（μ３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数ａ＝０．８７１６２（５）ｎｍ，ｂ＝０．８     

Fe_3O_4／P（St－AA）核－壳复合微球的制备和表征

以磁性氧化铁胶体粒子为种子，运用分散聚合法，制备出具有磁响应性的Ｆｅ_３Ｏ_４／Ｐ（Ｓｔ－ＡＡ）核－壳复合微球。考察了复合微球的形态及结构，测定了复合微球的粒径和磁响应性，研究了分散介质、引发剂、聚合单体和种子粒子等因素对复合微球形成的影响。     

Fe3O4／P（St—AA）核—壳复合微球的制备和表征

以磁性氧化铁胶体粒子为种子，运用分散聚合法，制备出具有磁响应性的Ｆｅ３Ｏ４／Ｐ（Ｓｔ－ＡＡ）核－壳复合微球，考察了复合微球的形态及结构，测定了复合微球的粒径和磁响应性，研究了分散介质，引发剂，聚合单体和种子粒子等因素对复合微球形成的影响。     

环状配合物Me_2Si［η~5－C_5H_4Fe（CO）_2］_2SnR_2的合

通过ＳｎＣｌ_２对化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（Ⅰ）中Ｆｅ－Ｆｅ键的插入反应以及Ⅰ被Ｎａ－Ｈｇ齐还原所生成的相应双铁负离子｛Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２｝~（２－）与ＳｎＲ_２Ｃｌ_２（Ｒ＝Ｍｅ，Ｐｈ）的亲核反应，合成了环状化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２ＳｎＲ_２［Ｒ＝Ｃｌ（１），Ｍｅ（２），Ｐｈ（３）］。以元素分析、ＩＲ和~１ＨＮＭＲ谱表征了它们的结构，并用Ｘ射线衍射测定了配合物３的晶体结构。３为单斜晶系，空间群Ｐ２_１／ｎ，ａ＝１．０３８４（３）ｎｍ，ｂ＝１．６３８４（１）ｎｍ，ｃ＝１．５７６２（５）ｎｍ，β＝９７．９３（２）°，Ｖ＝２．６５６（２）ｎｍ~３，Ｚ＝４，Ｄｘ＝１．７１ｇ／ｍＬ。     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

磁性壳聚糖微球用于脲激酶的固定化研究I. 磁性壳聚糖微球的制备和表征

为制备用于固定化酶的磁性壳聚糖微球,本文首先用化学共沉淀法制备了磁流体,随后在磁流体存在下进行壳聚糖和戊二醛的共聚反应。结果表明,磁流体中的Ｆｅ３Ｏ４以水化物的状态存在,其含量为２．０４％,平均粒径为０．２～０．５ｕｍ左右;磁性壳聚糖微球的弱碱交换量随交联度的增加而减小,质量磁化率与微球粒径成反比。该微球具有良好的磁响应性,在外加磁场下可被快速的从溶液中分离出来。     

钙钛矿型SrFeO3-λ对部分染料的光催化活性

本文用柠檬酸法合成钙钛矿型ＳｒＦｅＯ３－λ,并用水溶性染料在ＳｒＦｅＯ３－λ悬浮体系中进行光催化降解实验。实验发现了在ＳｒＦｅＯ３－λ化合物中,由于Ｆｅ＾３＋、Ｆｅ＾４＋、Ｆｅ＾５＋离子的共存使ＳｒＦｅＯ３－λ具有优异的光催化染料降解活性。     

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.     

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.     

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.