热敏性聚(N-乙烯基异丁酰胺)接枝高分子微球的合成

用自由基聚合和端基反应法合成了大分子单体聚 (N 乙烯基异丁酰胺 ) (PNVIBA) ,将其与苯乙烯在乙醇 水的混合溶剂中进行分散共聚 ,得到了PNVIBA接枝聚苯乙烯 (PNVIBA g PSt)高分子微球 .用GPC、激光光散射和电子显微镜等对聚合物的分子量和微球直径及形态进行了表征 .研究结果表明 ,大分子单体PNVIBA和PNVIBA g PSt高分子微球具有明显的热敏性 ,并且发现PNVIBA g PSt微球直径和形态可通过改变反应条件加以控制 ,得到了一种新形态的亚微米级高分子微球     

种子聚合制备表面磺酸基功能化聚苯乙烯微球

首先采用分散聚合法制备得到单分散的粒径约1.4～2.7 μm的聚苯乙烯(PS)种子微球,并研究了控制微球粒径及其分布的工艺参数.然后采用种子聚合法,使用苯乙烯磺酸钠(NaSS)作为具有磺酸基的功能单体与苯乙烯(St)单体进行共聚.通过扫描电子显微镜(SEM)和X-射线光电子能谱(XPS)对最终微球的表面形貌和组成成分进行表征,结果表明:成功获得了表面磺酸基功能化的聚苯乙烯微球;苯乙烯磺酸钠与苯乙烯单体共聚的最佳摩尔比为1:3.     

功能化PVA-g-PSt微球对牛血清蛋白的吸附研究

由大分子单体法制得了聚醋酸乙烯酯接枝聚苯乙烯(PVAc-g-PSt)微球,使该微球在碱性条件下醇解形成了聚乙烯醇接枝聚苯乙烯(PVA-g-PSt)微球.经X射线光电子能谱对PVA-g-PSt微球表层组成的表征,发现微球具有以PVA为壳、PSt为核的核壳结构.进而利用汽巴蓝F3GA(CB)与PVA-g-PSt微球进行亲核反应,制得了CB功能化的PVA-g-PSt微球,由元素分析定量出了固定在微球表面的CB含量.用透射电子显微镜对微球的粒径与形态进行了表征,发现微球表面在CB功能化后变得相对粗糙,粒径大小基本保持不变,但形态更加规整.比较了3种不同微球对蛋白质的吸附,考察了吸附动力学和影响吸附的因素,发现起始牛血清蛋白(BSA)浓度、pH值、离子强度对微球吸附BSA有明显的影响,并利用Zeta电位探讨了微球与蛋白质间的相互作用机理.最后用硫氰酸钠(NaSCN)进行解吸,计算解吸率最高可达到95.7%,该CB功能化微球可以重复利用,吸附率仅减少5.3%.     

PAm-g-PMAA亲水性聚合物微球的合成

利用链转移自由基聚合和端基置换反应法 ,合成了苯乙烯基单封端的聚甲基丙烯酸叔丁酯 (PBMA)大分子单体 .在N ,N′ 亚甲基二丙烯酰胺 (Bis A)存在的条件下 ,使PBMA大分子单体与亲水性单体丙烯酰胺(Am)在乙醇 水的混合介质中进行分散共聚反应 ,得到了表面为PBMA接枝的聚丙烯酰胺 (PAm g PBMA)聚合物微球 .将所得PAm g PBMA微球在酸性条件下水解 ,得到了整体亲水的聚甲基丙烯酸接枝的聚丙烯酰胺(PAm g PMAA)聚合物微球 .用激光光散射、透射电子显微镜和X射线光电子能谱仪等对聚合物微球的直径、形态及表面组成进行了表征 .研究结果表明 ,在共聚反应中PBMA大分子单体的分子量与浓度、Bis A浓度和介质的组成对微球的形成与颗粒直径的大小有明显影响 ;所形成的聚合物颗粒是以PBMA为壳、以交联PAm为核的核壳结构微球 .     

PSt种子与“花瓣”形PSt/PAN复合颗粒的制备

以过硫酸钾为引发剂,在乙醇/水的混合介质中使苯乙烯进行无皂乳液聚合,得到了单分散亚微米级聚苯乙烯(PSt)微球.用扫描电子显微镜研究了引发剂浓度、单体浓度、反应温度和溶剂组成对PSt微球粒径的影响.结果表明,改变上述条件能明显影响其粒径.以所得单分散聚苯乙烯微球为种子,在丙烯酸单封端聚乙二醇大分子单体存在的条件下,使丙烯腈和少量苯乙烯进行新的无皂种子乳液聚合,在合适的条件下制得到了“花瓣”形的聚合物复合颗粒,为深入探讨这类特殊形态聚合物颗粒的形成机理提供了新的佐证.     

两亲高分子微球的合成与表征

通过苯乙烯和聚氧乙烯大分子单体的共聚,合成了粒径在0.5μm～1.5μm的两亲高分子微球.随着聚氧乙烯大分子单体浓度的增加,微球粒径减小.通过扫描电镜,IR等分析手段对微球进行了表征.     

PEG大分子单体的合成及纳米级微球的制备

以端基反应法合成苯乙烯封端的聚乙二醇（PEG）大分子单体,用凝胶色谱和核磁共振表征它们的相对分子量和末端官能度,发现得到的大分单体的末端有较高的官能度,使该大分子单体与苯乙烯进行接枝共聚,将得到的产物逐步滴加到各种比例的甲醇－水的混合溶剂中,实验发现,接枝共聚物浓度,共聚物中PEG的含量和混合溶剂的比例对纳米微球的形成与聚集形态有明显的影响,X－射线能谱研究表明,微球表面为亲水性PEO,核为疏水的聚苯乙烯,即形成的聚集物为核－壳复合结构的纳米微球。     

热敏性高分子接枝聚苯乙烯微球的制备

通过使聚N－乙烯基异丁酰胺（PNVIBA）大分子单体与苯乙烯在乙醇／水的混合溶剂中进行自由基分散共聚，得到热敏性PNVIBA接枝聚苯乙烯（PNVIBA－g-PSt)高分子微球。用TEM对微球的形态进行了观察，同时考察了起始PNVIBA大分子单体浓度、苯乙烯浓度、引发剂浓度、聚合温度和混合溶剂中水对微球直径的影响。发现在较宽的聚合反应条件下，得到的接枝高分子颗粒均保持球形并具有单分散性，微球的数均直径（D）与反应条件的关系遵循：D＝K[PNVIBA]^-0.39[St]^0.80[I]^-0.14;微球直径随聚合温度的升高和混合溶剂中水含量增加而降低；颗粒形态可以通过改变聚合反应条件或添加第二小分子单体加以控制。     

特殊形态聚合物微球原位负载Ag纳米粒子

以苯乙烯单封端的聚N-异丙基丙烯酰胺(St-PNIPAAm)大分子单体为反应性分散稳定剂,使之与丙烯腈(AN)和少量苯乙烯(St)在醇/水混合介质中进行三元分散共聚反应,制得了以聚苯乙烯(PS)为核,表面接枝PNIPAAm的聚合物微球(PNIPAAm-g-PAN/PS).利用扫描电子显微镜(SEM)观察证实:所得聚合物微球的粒径和表面凸起均一,形态结构规整,其粒径和形态可通过改变聚合反应条件加以控制.以典型配方的聚合物微球为媒介,AgNO3为金属源,乙醇为还原剂,在90 ℃下使Ag纳米粒子原位负载在PNIPAAm-g-PAN/PS聚合物微球表面.利用透射电子显微镜(TEM),紫外光谱(UV)及傅立叶红外光谱(FT-IR)对表面负载Ag纳米粒子的聚合物微球样品进行了表征,结果表明:Ag纳米粒子在特殊形态聚合物微球表面负载均匀,通过改变银离子的用量可将Ag纳米粒子的大小控制在3～32 nm范围内,最小平均粒径约为6 nm.     

分散聚合法制备单分散交联聚苯乙烯微球

以苯乙烯为单体、二乙烯基苯为交联剂,通过优化反应条件,制备了平均粒径为3.28～9.04 μm的单分散聚苯乙烯微球和平均粒径为6.60 μm的单分散交联聚苯乙烯微球.探讨了单体浓度、引发剂含量、分散稳定剂用量对微球粒径和分散性的影响.热稳定性分析表明:交联聚苯乙烯微球耐热性明显优于线性聚苯乙烯.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.     

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.