利用聚乙烯醇结晶辅助制备多重交联的高强度聚丙烯酰胺水凝胶

在表面带有C=C双键的乙烯基杂化二氧化硅纳米颗粒(vinyl hybrid silica nanoparticle,VSNP)上接枝丙烯酰胺(AM),所得到的纳米刷状凝胶因子通过聚丙烯酰胺(PAM)间的氢键形成物理交联点,则多官能化的VSNP可作为拟共价交联点构筑双重交联的单一网络纳米复合物理水凝胶(nanocomposite physical hydrogel,NCP gel),表现出较高的强度和超拉伸性.为了进一步提高凝胶的强度和韧性,将少量PVA和PAM/VSNP纳米刷混合制成凝胶,通过冷冻-融化处理,使与PAM分子链相互缠绕并形成氢键作用的PVA结晶,形成新的交联点进一步交联PAM NCP gel,得到多交联的PAM NCP gel体系.通过拉曼光谱和示差扫描量热分析,证明凝胶中的PVA通过氢键既可以与PAM相互作用,又形成微晶为新交联点,大大增强了NCP gel的力学性能,与PAM NCP gel相比,凝胶的拉伸强度和断裂能分别从313 k Pa和1.41×104 J/m~2提高到了557k Pa和4.65×104 J/m~2.     

羧甲基纤维素-壳聚糖水凝胶球的制备及性能

采用物理交联法制备了羧甲基纤维素(CMC)-壳聚糖(CS)共混水凝胶球;研究了共混球的耐酸碱性、溶胀性及对亚甲基蓝的吸附性能.结果表明,水凝胶球在弱酸和弱碱中具有一定的稳定性;随着羧甲基纤维素与壳聚糖质量比的增大,水凝胶的吸水溶胀率增加.在CMC与CS质量比为1∶4时制备的水凝胶呈规则球状.     

双重交联VSNPs-PAA纳米复合水凝胶的制备及其溶胀性能的研究

采用自由基聚合法合成了乙烯基硅纳米粒子-聚丙烯酸(VSNPs-PAA)双重交联复合水凝胶,考察了交联剂、引发剂、单体以及p H值、温度、盐溶液等对水凝胶溶胀行为的影响。结果表明,引发剂浓度为0.08%,交联剂浓度为0.1%,单体浓度为80%时,合成的水凝胶溶胀性能最大,吸水率达到5000%以上;该水凝胶不仅具有p H值敏感性和p H值变化下良好的反复性,而且在p H4的酸性溶液中表现出温度敏感性,其溶胀率随温度的升高而增大;水凝胶的溶胀率随着盐溶液浓度的增大而减小。     

磺化聚苯乙烯纳米微球-聚丙烯酰胺杂化水凝胶的制备及性能

首先通过乳液聚合法合成了聚苯乙烯(PS)微球,该微球经浓硫酸磺化后得到了磺化聚苯乙烯(SPS)微球;然后将合成的SPS微球作为多功能交联点加入丙稀酰胺(AAm)化学水凝胶网络中制备了SPS-PAAm杂化水凝胶。通过扫描电镜、透射电镜观察了SPS微球及杂化水凝胶的微观结构。研究了SPS微球对SPS-PAAm杂化水凝胶的凝胶分数、溶胀性能和力学性能的影响。结果显示:随着SPS微球用量的增加,SPS-PAAm水凝胶的凝胶分数先增加后降低,平衡溶胀度降低;SPS微球的加入能改善水凝胶的力学性能,随着SPS含量的增加,水凝胶的拉伸强度和能量损耗增加;SPS微球和PAAm分子链间存在物理相互作用。     

会变形的水凝胶

本实验是关于可变形水凝胶的制备及其复杂形变的设计和调控的新创综合实验。首先,利用自由基聚合交联法制备含有聚丙烯酸钠(PNaAAc)的聚乙烯基吡咯烷酮-聚丙烯酰胺(PVP-PAAm)水凝胶。该凝胶具有优良的力学性能,其中PNaAAc可与Fe3+等金属离子络合,从而增加水凝胶的交联密度,降低其溶胀程度。使用离子转移印花技术和新开发的离子墨水打印技术在凝胶单面或双面不同位置引入Fe3+交联,改变水凝胶局部表面的交联密度和溶胀性能。处理后的凝胶样品在溶胀或去溶胀时可发生由一维到二维、二维到三维以及简单三维到复杂三维的复杂可控形变。     

微流控纺丝制备葡萄糖响应凝胶纤维

葡萄糖响应凝胶纤维在血糖监测传感器开发中有着潜在的应用前景。本文基于微流控纺丝方法和自由基聚合反应制备了化学交联和物理交联的葡萄糖响应聚(N-异丙基丙烯酰胺/3-丙烯酰胺基苯硼酸)(P(NIPAM-co-AAPBA))凝胶纤维。通过傅里叶变换红外光谱、扫描电子显微镜和力学性能测试等技术手段表征了凝胶纤维的结构和形态、力学性能、溶胀度动力学与葡萄糖响应性。结果表明,凝胶纤维具有多孔的微观结构,通过改变芯层与壳层溶液的流速可以调控凝胶纤维的直径。随着AAPBA质量分数的增加,凝胶纤维的溶胀速率和平衡溶胀度均有所降低,但葡萄糖响应性能提高。与化学交联的凝胶纤维相比,物理交联的凝胶纤维具有良好的力学性能。     

pH敏感的聚(L-谷氨酸)-交联聚丙烯酸水凝胶的合成与性能研究

通过在聚L-谷氨酸侧链部分接枝甲基丙烯酸2-羟乙酯得到含有双键的聚(L-谷氨酸),将其与丙烯酸共聚得到由聚(L-谷氨酸)侧链接枝并交联聚丙烯酸的pH敏感水凝胶.研究水凝胶在不同pH的缓冲溶液中的溶胀性、溶胀动力学,并通过SEM观察水凝胶的微观结构.结果表明,水凝胶在低pH环境下的溶胀率明显低于高pH环境中的溶胀率,不同...     

纳米复合水凝胶的力学行为与刺激响应性

纳米复合水凝胶（nanocomposite hydrogels,NC凝胶）由于其简便的制备方法、独特的组成、优异的力学性能、高光学透明度以及良好的溶胀/去溶胀性等,引起了广泛的关注.近年来,本课题组在NC凝胶的力学行为及刺激响应性NC凝胶的制备方面取得了可喜的研究成果.观察到新合成的和溶胀平衡的聚N-异丙基丙烯酰胺（PNIPAm）-锂藻土LaponiteNC凝胶的超拉伸性,发现了在大应变下的应变硬化现象;发现利用Mooney-Rivlin方程可以描述NC凝胶的压缩应力-应变,但不能描述较大的应变硬化;Creton模型能很好地描述NC凝胶在大形变下的应力-应变曲线,特别是凝胶的应变硬化;从NC凝胶小应变下的平衡剪切模量得到了有效交联密度,观察到NC凝胶形变-回复过程的迟滞现象,测定了NC凝胶的松弛指数.我们认为NC凝胶具有超拉伸性的原因是其较低的交联密度和适度的松弛速率;在响应性NC凝胶的制备方面,发现了溶胶型Laponite的水分散液的稳定窗口,避免了加入离子性单体引起的聚集沉淀;通过共聚制备了具有超拉伸性、pH响应或温度和pH双响应的透明NC凝胶.本文主要综述了我们课题组在NC凝胶力学行为及响应性NC凝胶领域的一些研究进展,并分析了NC凝胶研究领域仍然未解决的科学问题,以及今后可能的发展方向.     

丝素蛋白纤维/聚N-异丙基丙烯酰胺复合水凝胶的性能

以丝素蛋白纤维为填充材料,采用自由基聚合的方法制备复合聚N-异丙基丙烯酰胺(PNIPPAm)水凝胶,研究复合水凝胶的黏弹性能、溶胀性能和反复溶胀-收缩性能。结果表明:丝素蛋白纤维的加入改善了复合水凝胶的力学性能,其平衡溶胀率不仅与温度有关,而且与丝素蛋白纤维的含量有关。此外,处在表面的丝素蛋白纤维与水凝胶之间存在间隙,在反复溶胀-收缩过程中可以作为输水通道,有利于水分子进出,提高了PNIPPAm水凝胶对温度的响应速率并使其溶胀-收缩重复性更好。     

含有锂皂土/聚多巴胺复合纳米微粒的再生丝蛋白水凝胶

在辣根过氧化物酶/过氧化氢酶促交联(化学交联)制备再生丝蛋白化学交联凝胶的过程中,通过引入锂皂土/聚多巴胺复合纳米材料作为第二组分,以调节反应并提高化学交联效率;再经乙醇熟化后,再生丝蛋白化学交联凝胶中可进一步形成物理网络,进而得到双交联凝胶.结果表明,第二组分的引入不仅能够提高再生丝蛋白化学交联水凝胶的力学性能,并有利于后续均匀物理交联网络的形成,致使最终所得双交联水凝胶具有更好的力学性能.同时,由此制备的双交联水凝胶传承了再生丝蛋白良好的生物相容性以及与交联结构密切相关的生物降解性,并具备了诱导干细胞成骨分化的能力,因而在软骨修复等领域具有潜在的应用价值.     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.