聚甲基丙烯酸单层保护金纳米粒子的制备及pH响应性聚集

通过可逆断裂链转移加成聚合,制备了单分散的聚甲基丙烯酸叔丁酯,并一步水解获得了具有硫醇端基的聚甲基丙烯酸(PMAA).在还原氯金酸为金纳米粒子的同时,利用硫醇端基与金纳米粒子(GNPs)的耦合作用,一步获得了聚甲基丙烯酸单层保护的金纳米粒子.通过紫外光谱和透射电镜表征证实,金纳米粒子为单分散的球型颗粒,在水溶液中具有长期稳定性.聚甲基丙烯酸单层保护的金纳米粒子的光学性质和聚集状态,具有明显的pH响应性.在酸性条件下,由于PMAA被质子化发生疏水性转变,聚合物链收缩聚集,促使金纳米粒子之间互相靠近并聚集,其表面等离子共振吸收峰发生红移.从酸性调节为碱性后,(PMAA-@-GNPs)能重新分散,吸收峰发生蓝移.在多次循环后,溶液的光学信号能可逆互变且变化不大.     

金纳米粒子杂化超分子水凝胶的制备与性能

在制备水溶性硫辛酸酯封端的甲氧基聚乙二醇-聚己内酯嵌段共聚物(MPEG-PCL-ALA)单层包覆金纳米粒子的基础上, 在水溶液中, 利用α-环糊精(α-CD)与单层包覆金纳米粒子的包合作用构建杂化超分子水凝胶. 透射电子显微(TEM)照片显示, 金纳米粒子的尺寸为6～8 nm. X射线衍射测试表明, 所制备的水凝胶中含有α-环糊精与MPEG-PCL嵌段共聚物包合形成的多聚准轮烷的特征衍射峰(2θ＝19.7°). 紫外-可见吸收光谱显示, 单层包覆金纳米粒子的水溶液及其与α-CD包合形成的水凝胶在525 nm处均出现表面等离子共振吸收峰, 单层包覆金纳米粒子溶液存放3个月后, 其表面等离子共振吸收峰未发生明显红移, 表明单层包覆金纳米粒子的水溶液具有较好的稳定性.     

嵌段聚合物修饰的金纳米粒子的制备及表征

通过RAFT合成聚(甲基丙烯酸缩水甘油酯)-b-聚(乙二醇甲基丙烯酸酯)嵌段共聚物(PGMA-bPMAPEG),再用半胱氨酸(Cys)使PGMA中的环氧基团开环,制备含有巯基的两亲水嵌段聚合物PMAPEG-bP(GMA-Cys)。并以其作为修饰剂,通过原位还原法使HAuCl4在NaBH4的还原下制备金/聚合物纳米复合粒子(Au@PMAPEG-b-P(GMA-Cys)NPs)。经FT-IR、UV-vis、TG、XRD、TEM和DLS表征,发现金纳米复合粒子呈均匀分散的球形,平均粒径约为10nm,在527nm处出现了金纳米粒子的表面等离子共振吸收峰,金约占总重量的49%。由于外层嵌段共聚物的修饰作用,金纳米复合粒子在室温下放置6个月未发生粒子间的聚集。     

金纳米粒子表面自组装巯基十一烷醇单分子层体系的制备及其光散射特性研究

采用柠檬酸钠还原法制备了水相金纳米粒子, 通过巯基的自组装, 成功获得了巯基十一烷醇(MUN)单分子层保护的金纳米粒子. 用紫外可见光谱、透射电子显微镜、激光散射粒度分析、同步散射光谱和发射光谱等手段对组装前后的金纳米粒子的性质进行了研究. 结果表明: 制备的金纳米粒子最大吸收波长518 nm, 形状规则, 粒度均匀, 平均粒径为14.6 nm, 每个粒子含有约9.64×10⁴原子; 组装之后的金纳米粒子表面等离子体共振吸收峰红移17.0 nm, 平均粒径增大为20.2 nm, 组装层的平均厚度2.8 nm, 与MUN分子长度相当, 结合量实验证明每一个金纳米粒子可以结合约7.52×10³个MUN, 表面覆盖率为83.6%, 粒子分散均匀, 稳定性增强可长期保存; 同步散射光谱变化和发射光谱中分频、差频和倍频峰的存在证明, 金纳米粒子组装前后均具有非线性光学特性.     

苯乙烯在阴离子型聚氨酯纳米水分散液中聚合过程的研究

采用自乳化法制备出阴离子聚氨酯纳米水分散液,以其作为乳化剂使苯乙烯单体在其中进行聚合,制备出不同聚苯乙烯与聚氨酯质量比的阴离子型PS/PU纳米复合物水分散液;对苯乙烯单体的聚合过程进行了研究;采用光子相关谱仪和透射电镜对其微观结构、粒径及其分布进行了测试,结果表明,该方法能够制备出稳定的具有核壳结构的PS/PU纳米复合物水分散液,但当苯乙烯单体浓度增大到一定程度(PS/PU质量比为50∶100)时,粒子不稳定而发生聚集.     

沉淀法高效制备聚多巴胺纳米粒子

为得到分散性和稳定性较好的聚多巴胺纳米粒子,利用“沉淀-再分散法”高效制备了聚多巴胺纳米粒子水分散液。 首先利用溶液氧化法制备了分散在水/乙醇中的聚多巴胺纳米粒子,然后向分散液中加入丙酮使聚多巴胺纳米粒子絮凝。 收集沉降物,用丙酮冲洗并干燥后,加水重新分散得到纯化的聚多巴胺纳米粒子水分散液。 丙酮沉淀法得到的聚多巴胺纳米粒子形貌规整,分散性好,粒径分布在250 nm左右,在水中具有良好的储存稳定性和光热性能,与传统的超速离心提纯法相比,产率可提高57.4%。 此方法为其之后在药物载体及光热治疗等方面的应用研究提供了便利。     

基于点击化学和活性自由基聚合方法制备双重响应金纳米粒子

采用点击化学和可逆加成断裂链转移活性自由基聚合方法制备了温度和pH双重响应的金纳米粒子. 通过红外光谱(FTIR)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)及热重分析(TGA)等方法对双重响应性金纳米粒子进行了表征. 该金纳米杂化粒子具有良好的分散性, 其表面接枝聚合物的密度约为0.6 Chain/nm2. 通过改变温度和pH条件, 考察了金纳米杂化粒子的可逆响应行为. 实验结果表明, 点击化学和可逆加成断裂链转移活性自由基聚合方法实现了金纳米粒子修饰的简单化、可控化以及功能化.     

聚合物-纳米金在油水界面的自组装及有序结构的构筑

聚合物-纳米金复合物既具有金纳米粒子的光、电及催化性能,又具有聚合物的可加工性及对外界的刺激响应性,因此已成为高分子科学及材料科学研究的热点。本文主要介绍了我们实验室在聚合物-纳米金在油水界面的自组装及有序结构的构筑研究方面的相关工作:(1)利用界面聚合的方法制备侧链接枝亲水性金纳米粒子的聚苯乙烯及杂化聚合物在水溶液中的自组装;(2)亲水性金纳米粒子及疏水性聚合物(或疏水性磁性纳米粒子)在油水界面的自组装研究;(3)利用金纳米粒子为交联点制备具有温度响应性聚合物微凝胶的研究。     

金纳米粒子的阳光光化学合成和晶种媒介生长

在柠檬酸盐-HAuCl4溶液体系中, 于高原太阳紫外线辐射下光化学合成了分散良好、尺寸分布窄的胶体金纳米粒子. 研究了溶液的酸度和太阳辐射条件对Au(Ⅲ)离子光化学还原反应速率和形成金纳米粒子尺寸的影响; 采用晶种媒介生长技术, 通过改变Au(0)/Au(Ⅲ)比合成了平均直径为4.9~9.7 nm的球形金粒子. 根据紫外-可见吸收光谱和透射电子显微镜的表征和分析, 讨论了光化学反应中自由基反应、金纳米粒子成核和生长机理.     

聚甲基丙烯酸单层修饰金纳米粒子的制备及pH响应性催化

采用可逆加成断裂链转移(RAFT)聚合制备了具有硫醇端基的聚甲基丙烯酸叔丁酯(PtBMA),通过其水解得到具有pH刺激响应的聚甲基丙烯酸(PMAA)。利用硫醇端基与金之间的强耦合作用获得了聚甲基丙烯酸单层修饰的金纳米粒子(PMAA-GNPs)催化体系。利用UV-Vis光谱和透射电子显微镜(TEM)研究了PMAA-GNPs催化剂在不同pH值下的分散状态。以NaBH4还原对硝基苯酚的反应,验证了此催化体系的pH响应性。结果表明,调节体系的pH值为酸性,PMAA塌缩和包覆在金纳米粒子(GNPs)的表面,引起GNPs的聚集,从而降低了催化效率。反之,在碱性环境中,在PMAA链的排斥作用下,GNPs能较好的分散,提高催化效率。     

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%.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.