PMMA纳米球的制备及其银膜包覆技术

采用无皂乳液聚合法制备了单分散、直径为170 nm左右的聚甲基丙烯酸甲酯(PMMA)纳米球, 然后利用3-甲基丙烯酰氧基丙基三甲氧基硅烷(MATS)和3-巯丙基三甲氧基硅烷(MPTMS)对PMMA纳米球进行表面改性, 在其表面包覆一层均匀的巯基, 通过巯基与银离子之间的相互作用, 使银在PMMA纳米球表面成核长大, 从而合成PMMA/Ag纳米球壳粒子. 通过扫描电子显微镜、投射电子显微镜和紫外-可见吸收光谱测试技术对产物性能进行了表征, 研究结果表明, 制备的PMMA/Ag纳米球壳粒子的分散性好、包覆均匀.     

乙烯基化的中空二氧化硅球的制备与表征

在乙醇/氨水介质中,以分散法制备的聚苯乙烯微球为模板,通过乙烯基三乙氧基硅烷水解缩合反应在聚苯乙烯表面形成包覆层.然后将聚苯乙烯球核溶解而制备了乙烯基化二氧化硅空心微球.     

细乳液聚合制备载有CdTe的交联聚苯乙烯荧光微球

利用改进的正相细乳液聚合法, 对疏水的CdTe纳米晶进行包覆, 得到了纳米级的交联聚苯乙烯荧光微球. 研究发现, 较高的引发剂浓度和较高的交联度有利于抑制相分离的发生和荧光的保持. 进而将3-甲基丙烯酰氧基丙基三甲氧基硅烷作为共聚单体, 得到了表面硅羟基功能化的聚苯乙烯荧光微球, 改善了微球在水相中的分散性, 并将此类荧光功能微球成功用于细胞成像.     

CdTe纳米晶-BaSO4复合荧光微球的制备

利用表面活性剂双层修饰技术在水溶性荧光CdTe纳米晶表面先后包覆了双十八烷基二甲基溴化铵和十二烷基硫酸钠, 从而在纳米晶外表面引入—SO-4反应位点, 以—SO-4为活性中心进一步制备了包覆CdTe纳米晶的BaSO4复合荧光微球. 通过扫描电子显微镜、透射电子显微镜、共聚焦荧光显微镜和X射线粉末衍射等方法确定了复合微球的尺寸及组成. 由于BaSO4的保护, CdTe-BaSO4复合微球荧光的耐酸性比CdTe原液的提高明显.     

生物功能化纳米SiO2 微球的构建及对谷胱甘肽S-转移酶的捕获分离

采用巯基丙基三甲氧基硅烷(MPS)一步水解法制备了表面带有巯基(-SH)的纳米SiO2微球(nSiO2-SH), 探讨了水/醇体积比、 反应温度、 MPS初始浓度及反应时间对nSiO2-SH微球形貌的影响, 并分析了反应机理. 制备的nSiO2-SH微球进一步与还原型谷胱甘肽(GSH)中的-SH反应生成双硫键(-S-S-), 在微球表面键合上GSH分子, 得到了生物功能化的纳米nSiO2-GSH微球. 通过扫描电子显微(SEM)、 透射电子显微镜(TEM)、 傅里叶变换红外光谱(FTIR)和热重分析仪(TG)对样品的表面形貌、 尺寸和组成等进行了表征. 利用十二烷基磺酸钠-聚丙烯酰胺凝胶电泳法(SDS-PAGE)检测样品对谷胱甘肽S-转移酶(GST)的分离效果, 结果表明, nSiO2-GSH微球能从混合蛋白中特异性吸附GST, 达到了分离GST的目的.     

巯基化壳聚糖包覆CdS量子点荧光猝灭法测定环境水样中的Hg~(2+)

合成了新型巯基化壳聚糖,并采用一步法合成了巯基化壳聚糖包覆的水溶性CdS量子点(QDs)。结果表明制备的巯基化壳聚糖包覆CdS QDs粒径均匀,该量子点在水溶液中稳定性好并且Hg2+对其荧光具有明显的猝灭作用。在最佳测定条件下,标准曲线的线性范围为3.0×10-7~5.0×10-5 mol/L,检出限为5.3×10-8 mol/L,且方法抗干扰性好,日内及日间精密度在5.8%之内。该方法应用于实际水样检测,回收率在86.4%~104.6%之间。     

基于金/巯基相互作用的功能分子在磁性高分子复合微球表面可控组装研究

建立了一种基于金纳米粒子与巯基相互作用的在磁性高分子复合微球表面高效组装功能分子的新方法.首先制备了粒径均一的介孔磁性纳米粒子簇(MSP),利用蒸馏沉淀技术在MSP上包覆一层―S―S―键交联的聚甲基丙烯酸壳层(P(MAA-Cy)),并将直径10~30 nm的金纳米粒子沉积在MSP@P(MAACy)复合微球表面,从而获得MSP@P(MAA-Cy)-Au NP复合微球.调控HAu Cl4的投料量可以控制金纳米粒子沉积数量和尺寸.利用金粒子和巯基之间的强相互作用,将巯基修饰的荧光分子快速可控组装在MSP@P(MAA-Cy)-Au NP微球上.作为模型示范,实现了一次在MSP@P(MAA-Cy)-Au NP微球上快速固定单种或多种功能分子,为即时、高效、定量在功能微球(靶向药物载体等)上修饰功能分子提供了一种可选择的解决方案.     

Eu(dbm)_3phen/SiO_2@KH570-NH_2核壳结构微球的制备及其性能表征

将由二苯甲酰甲烷、1,10-菲罗啉及氯化铕三者合成的荧光配合物Eu(dbm)3phen嵌入于用水刻蚀法制得的二氧化硅微球,得到Eu(dbm)3phen/SiO_2复合微球。为解决上述复合微球易泄漏的问题,在微球表面包覆了一层约10nm厚的γ-甲基丙烯酰氧基丙基三甲氧基硅烷,形成核-壳结构,并通过与甲基丙烯酸缩水甘油酯的聚合反应,使微球表面带上环氧基团。通过环氧基团与乙二胺的开环反应,使微球表面带有氨基,其荧光强度可保持为原强度的72%,并便于与抗体连接。通过激发粒径仪、扫描电镜等多种方法对此材料的结构及性能作了表征。结果表明该材料有条件用作荧光免疫检测中生物分子的标记。     

载有量子点的介孔二氧化硅微球的制备与性能研究

采用自组装方法制备了一种磁核/介孔二氧化硅壳的微球, 调节体系中C₁₈TMS的加入量可控制介孔硅球的比表面积; 并通过化学修饰的方法对介孔微球表面进行巯基功能化修饰. 利用巯基与量子点之间的相互作用可将一定尺寸的量子点吸附于介孔二氧化硅球的孔中, 令介孔微球具有荧光效应; 同时可以利用吸附不同粒径的量子点的荧光光谱对介孔二氧化硅微球孔径的大小进行近似考察.     

同轴电喷法制备PCL-蛋清体系复合微胶囊

以鸡蛋的卵清蛋白作为蛋白质药物模板、生物可降解材料聚己内酯(PCL)为药物载体模板,采用同轴电喷法制备PCL-蛋清体系的复合微球.研究了电导率、黏度对于电喷微球成型的影响.核壳溶液推进速率比、电压、溶液质量分数和接收距离等对于所得微球表面形态和结构的影响.利用扫描电子显微镜(SEM)研究了微球的表面形态,用荧光显微镜表征了微球的包覆模式.结果表明:同轴电喷法可以制备PCL-蛋清体系的复合结构微胶囊,其中推进速率比对微球形貌、粒径及其分布的影响比较明显,当PCL与蛋清溶液推进速率比大于10时,将出现具有包覆结构的微球.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.