P(DMAA-co-AM)水凝胶制备及其固定α-淀粉酶研究

采用氧化还原引发体系,水溶液聚合法制备P(DMAA-co-AM)水凝胶,并以其作为载体固定α-淀粉酶。采用单一变量法研究交联剂(N,N’-亚甲基双丙烯酰胺)用量、引发剂(过硫酸铵)用量、单体浓度和单体配比对凝胶性能的影响。以水凝胶的最大平衡溶胀度为指标,得出制备P(DMAA-co-AM)水凝胶的优化条件:交联剂用量为0.3%,引发剂用量为0.6%,单体浓度为20%,N,N′-二甲基丙烯酰胺与丙烯酰胺的摩尔比为2∶1。在优化条件下,采用原位聚合法固定α-淀粉酶,测定不同单体配比的P(DMAA-co-AM)水凝胶固定化α-淀粉酶的活性。     

生物素-亲和素体系测定雌酮

雌酮与牛血清白蛋白共价结合,合成雌酮的完全抗原。利用此抗原免疫小鼠,通过细胞融合技术制备了雌酮的单克隆抗体,经纯化表征知,抗体是IgG1型,相对分子量为164000,与固定抗的亲和常数为8.2×10^8L/mol。以生物素化的羊抗鼠免疫球蛋白及辣根过氧化物酶标记的链亲和素为标记体系,通过竞争抑制的方式测定游离的雌酮,结果表明：雌酮在10～10000pg/mL内呈线性关系。     

P（DMAA-co—AM）水凝胶制备及其固定a-淀粉酶研究

采用氧化还原引发体系,水溶液聚合法制备P（DMAA-co-AM）水凝胶,并以其作为载体固定a-淀粉酶。采用单一变量法研究交联剂（N,N＇-亚甲基双丙烯酰胺）用量、引发剂（过硫酸铵）用量、单体浓度和单体配比对凝胶性能的影响。以水凝胶的最大平衡溶胀度为指标,得出制备P（DMAA-co-AM）水凝胶的优化条件：交联剂用量为0．3％,引发剂用量为0．6％,单体浓度为20％,N,N’-二甲基丙烯酰胺与丙烯酰胺的摩尔比为2：1。在优化条件下,采用原位聚合法固定a-淀粉酶,测定不同单体配比的P（DMAA-co-AM）水凝胶固定化a-淀粉酶的活性。     

温度及pH敏感N-异丙基丙烯酰胺/β-环糊精水凝胶的合成与性能研究

用顺丁烯二酸酐 (MAH)对具有分子包结能力的 β 环糊精 (β CD)进行化学改性 ,合成出了丁烯二酸单酯化 β CD单体 (MAH β CD) .通过氧化还原自由基引发MAH β CD与N 异丙基丙烯酰胺 (NIPA)聚合 ,合成出含 β CD结构单元的新型水凝胶 .用核磁共振、红外光谱及元素分析对MAH β CD单体及共聚物的结构和组成进行了表征 .溶胀研究结果表明 ,该水凝胶具有较好的pH、温度及离子强度敏感性 ;并且水凝胶在较高羧基(—COOH)含量和弱碱环境中 ,仍能表现出明显的温敏性     

甲基丙烯酸N,N-二甲氨基乙酯与丙烯酰β-环糊精共聚水凝胶的合成及其性能研究

用不同的方法合成了两种结构不同的丙烯酰 β 环糊精酯 (β CD 3 A和 β CD 6 A) ,以此为单体与甲基丙烯酸N ,N 二甲氨基乙酯 (DMAEMA)通过氧化还原自由基引发聚合 ,合成出两类含 β 环糊精结构单元的新型水凝胶 .用核磁共振 ,红外光谱及元素分析对两种单体及共聚物的结构和组成进行了表征 .溶胀实验结果表明 ,两类水凝胶均具有较好的pH、温度及离子强度敏感性 ,且因其交联网络结构不同 ,其溶胀性能有所差异     

构建巯基-Ce(Ⅳ)盐氧化还原引发体系实现丙烯腈在硅胶微粒表面的高效接枝聚合

使用偶联剂γ-巯丙基三甲氧基硅烷(MPMS,KH-590),对微米级硅胶微粒进行了表面化学改性,将巯基引入硅胶微粒表面(SiO2-MPMS),构成巯基-Ce(Ⅳ)盐氧化-还原引发体系,探索研究了丙烯腈在硅胶微粒表面的引发接枝聚合,制得了高接枝度(30 g/100g)的接枝微粒SiO2-MPMS-g-PAN.采用红外光谱(FTIR)、扫描电镜(SEM)及热重分析(TGA)等方法对接枝微粒SiO2-MPMS-g-PAN进行了表征.在此基础上,重点研究了主要因素对巯基-Ce(Ⅳ)盐体系引发AN接枝聚合的影响.研究结果表明,类似于羟基-Ce(Ⅳ)盐体系,巯基-Ce(Ⅳ)盐体系也可以有效地引发乙烯基单体在固体微粒表面接枝聚合.与在固体微粒表面引入可聚合双键的"grafting through"接枝聚合法相比,铈盐引发的接枝聚合,由于活性位点居于载体表面,故具有高的接枝度,是一种高效率的表面引发接枝法.为制得高接枝度的接枝微粒SiO2-MPMS-g-PAN,本研究体系适宜的酸浓度为0.25 mol/L;Ce(Ⅳ)盐浓度为5.0×10-3 mol/L;接枝聚合宜在50℃下进行.     

β-环糊精交联聚丙烯酸水凝胶的合成及其药物控制释放研究

采用1,3-二环己基碳化二亚胺(DCC)为缩合剂,通过β环糊精与丙烯酸的酯化反应合成了不同取代度的丙烯酸β环糊精酯(βCD6A),以此为单体与丙烯酸通过氧化还原自由基引发聚合,合成出了不同交联密度和不同环糊精含量的新型水凝胶(AAβCD6A).溶胀实验表明,该类水凝胶均具有pH敏感性,溶胀动力学实验进一步对其机理进行了探讨.选择苯丁酸氮芥(CHL)作为模型药物,考察了不同pH下AAβCD6A水凝胶对药物释放行为的影响.结果表明,pH=6.8时药物释放率均大于pH=2.0时药物释放率,环糊精的存在表现出促释作用.     

食品中罂栗碱金标快速检测试剂条的研究

首先以1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC·HCI)方法合成罂粟碱完全抗原;通过改变还原剂加入量,确定纳米金合成条件为每50.0 ml,氯金酸加入1.5 mL柠檬酸三钠;合成金标保护剂量为20.0 mL胶体金溶胶加入1100稀释抗体(12 mg/L)2.0 mL,标记pH值为8.65.以罂粟碱多克隆抗体-纳米金复合物作为分析探针,罂粟碱完全抗原作为竞争抗原,构建分析体系.点样条件抗原质量浓度为1.0 g/L(以蛋白浓度计算);抗原点样量1 μL/条;金标点样量5 μL/条;二抗浓度(羊抗兔)3.3 g/L稀释至13 500;二抗点样量1μL/条.同时在实验中确定了样品提取方法.检测的灵敏度达到10 μg/L,检测时间不超过20 min.与ELISA方法对照结果,对比检测123份样品,准确率100%.     

食品中罂粟碱金标快速检测试剂条的研究

首先以1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC·HCI)方法合成罂粟碱完全抗原;通过改变还原剂加入量,确定纳米金合成条件为每50.0 ml,氯金酸加入1.5 mL柠檬酸三钠;合成金标保护剂量为20.0 mL胶体金溶胶加入1:100稀释抗体(12 mg/L)2.0 mL,标记pH值为8.65.以罂粟碱多克隆抗体-纳米金复合物作为分析探针,罂粟碱完全抗原作为竞争抗原,构建分析体系.点样条件:抗原质量浓度为1.0 g/L(以蛋白浓度计算);抗原点样量:1 μL/条;金标点样量:5 μL/条;二抗浓度(羊抗兔)3.3 g/L稀释至1:3 500;二抗点样量:1μL/条.同时在实验中确定了样品提取方法.检测的灵敏度达到10 μg/L,检测时间不超过20 min.与ELISA方法对照结果,对比检测123份样品,准确率100%.     

泡沫聚合法制备超大多孔水凝胶

采用泡沫体系分散聚合法,过硫酸铵(APS)及N,N,N′,N′-四甲基乙二胺(TMEDA)为氧化还原引发体系,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,碳酸钠为发泡剂,聚氧化乙烯-氧化丙稀(PF127)为泡沫稳定剂,用羧甲基纤维素钠(CMC)接枝丙烯酸(AA)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)合成了CMC-g-(AA-co-AMPS)超大多孔水凝胶。通过FTIR、SEM表征,表明材料是具有超大多孔结构的CMC-g-(AA-co-AMPS)水凝胶。对各影响因素的研究表明,在m(CMC)∶m(AA)∶m(AMPS)为1∶4∶1,w(APS)为0.8%[其中m(APS)∶m(TMEDA)=2∶1],w(Na2CO3)=65%,w(PF127)=0.2%,温度为65℃时,制得的凝胶吸蒸馏水倍率可达1281g/g,吸0.9%盐水倍率达143g/g,10min时已基本达到溶胀平衡。     

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.     

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.     

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.     

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.     

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.     

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%).