三萜骨架功能分子

具有独特立体结构的三萜化合物是一类重要的生物活性天然产物,在消炎、降血脂、保肝护肾、抗菌、抗肿瘤、抗真菌等方面有着重要药用价值。利用其独特手性结构、亲脂性、生物活性以及生物相容性等特性,设计合成新型功能分子,可作为药物载体,发挥其识别功能以及用于医用材料等方面具有重要的作用。本文介绍了近年来以三萜为骨架设计合成的新型功能分子在离子、分子识别和自组装性能方面研究现状及其潜在的应用前景。     

高度支化状二茂铁基聚合物研究进展*

高度支化状二茂铁基聚合物具有丰富的拓扑结构形态和独特的电、磁、催化和氧化还原性能,而且这类材料具有独特的流动性能、低的粘度和进一步的可反应性,从而使得它们展现出良好的应用前景,开发二茂铁基功能高分子材料正日益受到重视.本文介绍高度支化状二茂铁基聚合物的合成、结构、性能以及应用的研究进展.     

中空碳材料用于钠离子电池负极的研究进展

实现钠离子电池等储能设备的大规模应用对于能源的可持续发展以及完成“碳达峰碳中和”目标具有重要意义.开发高性能的负极材料可提升钠离子电池的能量密度和循环稳定性,是实现钠离子电池大规模应用的关键性因素.中空碳材料因其独特的结构而具有优异的倍率性能与循环稳定性,作为钠离子负极材料具有广阔的应用前景.本文从多角度出发,综合评述了中空碳材料的合成方法,以及其形貌、杂原子修饰策略与储钠性能之间的关系,并对其未来发展方向进行了展望.     

纳米晶体材料研究进展

综述了目前纳米晶体材料合成、结构、性质和应用的研究和发展现状。通过惰性气体凝结、机械合金、等离子体技术和其他许多方法可以制得纳米晶体材料。尽管早期的研究者认为纳米晶体材料的晶粒边界结构不同于常规材料, 但目前有关纳米晶体材料结构的研究表明其具有与常规晶体材料相同的晶粒边界结构。纳米晶体材料所具有的诸如扩散和烧结、力学、陶瓷和金属间化合物的延展性、电学、热膨胀、光学、磁学、催化和腐蚀行为等性质优于常规多晶材料, 这些性质具有巨大的潜在应用价值。     

荧光量子点的水相合成及其在化学和生物分析中的应用

荧光量子点(又称为半导体纳米晶体)是一种新兴的无机发光材料, 由于其具有独特的结构和光电性能, 在发光二极管、太阳能电池及生命科学等领域有广泛的应用. 目前, 有机相合成法和水相合成法已被成功地用于荧光量子点的合成. 与有机相合成法相比, 水相合成量子点方法简单、绿色且廉价, 合成的量子点水溶性好, 在生物医学等领域具有很好的应用前景. 本文主要介绍荧光量子点的水相合成方法及其在化学和生物分析中的应用, 并对其发展趋势进行了展望.     

二维分子筛的制备及其催化应用研究进展

沸石分子筛是一种具有独特孔道结构的硅铝酸盐晶体,因其具有较大的比表面积、优异的孔道择形性、良好的热稳定性以及适宜的酸性质等特点,被广泛应用于催化、吸附、分离等领域。与常规三维沸石分子筛相比,二维分子筛由于其独特的形貌结构带来的可调变的多级孔结构、适宜的表面酸性以及良好的扩散传质性能等优点,已在吸附和催化领域显示出巨大的应用潜力。本文系统总结了二维MFI、SAPO-34、MCM-n、Y型分子筛等的合成以及此类分子筛催化应用研究方面的最新进展。最后,对二维沸石分子筛材料的新合成方法及新应用领域进行了展望。     

高稳定性金属有机骨架UiO-66的合成与应用

金属有机骨架(metal-organic frameworks,MOFs)是一种由金属中心与有机配体自组装而成的、具有三维网状有序孔结构的新型多孔晶体材料,其具有超高的比表面积、种类和结构多样性、可化学功能化等特点,在多个研究领域显示出了潜在的应用前景,已成为当前化学、材料学科的研究热点之一。 然而大多数MOFs材料的稳定性较差,极大地束缚了MOFs材料的发展。 以Zr为金属中心,对苯二甲酸为有机配体的UiO-66具有较好的热稳定性,结构可在500 ℃保持稳定,并且其还具有很高的耐酸性和一定的耐碱性,引起了人们的关注。 本文主要综述了UiO-66在合成调控、功能化合成和后改性方面的研究现状,以及其在吸附和催化等领域的应用前景。     

六苯基苯衍生物的合成及其应用

六苯基苯衍生物是一类具有独特三维结构的化合物。它可被认为是苯环的6个氢原子均被苯基所取代而成。由于外围6个苯环的空间位阻效应,构成了所谓螺旋桨型的空间结构。基于其独特的刚性立体结构、高的对称性以及其电荷环形离域等特点,六苯基苯衍生物在晶体工程、多孔聚合物、有机电子材料以及骨架材料等领域都受到了极大的关注。本文综述了近年来六苯基苯衍生物的合成及在上述领域中的应用。     

离子液体中制备无机材料

离子液体作为潜在的“绿色”溶剂,具有许多传统溶剂无法比拟的优异性能,在有机合成、催化、液液分离和萃取等领域引起了广泛的研究。而在离子液体领域无机材料的制备是一个较新的发展分支,现已利用其合成出多种具有独特结构和性能的无机材料。本文就离子液体在无机材料制备方面的应用及发展趋势进行了综述。目前,对于制备无机材料,离子液体主要是作为电解液、表面活性剂或溶剂,本文介绍了其在应用中的优缺点,并指出该领域未来的发展趋势是离子热合成和集模板-溶剂-反应物于一身的离子液体反应。     

两性离子聚合物的合成及应用

两性离子聚合物因独特的链结构,使其具有卓越的化学性能、良好的热稳定性与水化性能,尤其是具有"反聚电解质效应溶液行为"这一特点,近年来引起了广泛关注。因大多数两性离子聚合物链内引入了—OH,—COOH,—SO3H等亲水基团,使其具有抗蛋白质污染、抗细菌黏附及抗凝血等性能。迄今为止,人们已合成了很多新型的、功能化的两性离子聚合物并将其应用于石油工业、生物医用材料、药物合成和污水处理等各个领域。本文主要对两性离子聚合物的结构、性质、合成方法、应用、最新研究成果及发展前景等作了简单的概述和分析,并对它的合成方法和应用作了主要介绍,以期对两性离子聚合物的研究和发展有所借鉴。     

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.