Hu Teh-Min, Lin Chien-Yu, Wu Meng-Ju
Faculty of Pharmacy, School of Pharmaceutical Sciences, National Yang-Ming University Taipei 112 Taiwan
Center for Advanced Pharmaceutics and Drug Delivery Research, National Yang-Ming University Taipei 112 Taiwan.
RSC Adv. 2019 Sep 6;9(48):28028-28037. doi: 10.1039/c9ra05509f. eCollection 2019 Sep 3.
Reactions involving hydrophobic reactants in water can be much accelerated in organic solvent-free solutions containing amphiphiles at neutral pH and room temperature. Previously, we demonstrated that organosilica colloidal particles could be conveniently synthesized by a versatile salt-catalysis method in solutions modified with various amphiphilic molecules. The method precludes the use of any solvent, any added form of energy (thermal or mechanical), and any strong (or hazardous) acids/bases. Herein, the kinetic properties of the reaction were systematically investigated for fluoride-catalysed synthesis of colloidal organosilica from a thiol-functionalized organosilane precursor, (3-mercaptopropyl)trimethoxysilane. Continuous, real-time ATR-FTIR measurements allowed probing the time evolution of organosilica condensation in different reaction systems, containing one of the following: non-ionic surfactants (Tween 20, Tween 40, Tween 60, Tween 80, Triton X-100), anionic surfactant (sodium dodecyl sulphate; SDS), cationic surfactant (cetyltrimethylammonium bromide; CTAB), and amphiphilic polymers (polyvinyl alcohol and polyvinylpyrrolidone). Overall, while some amphiphile-specific properties were revealed, fluoride-catalysed synthesis was ultrafast with a universal two-phase kinetic scheme ( transition within 5-10 min) for all amphiphiles studied.
在中性pH和室温下,涉及水中疏水反应物的反应在含有两亲物的无有机溶剂溶液中可大大加速。此前,我们证明了通过通用的盐催化方法,在经各种两亲分子改性的溶液中可以方便地合成有机硅胶体颗粒。该方法无需使用任何溶剂、任何外加形式的能量(热或机械)以及任何强酸/强碱。在此,系统研究了以硫醇官能化的有机硅烷前体(3-巯基丙基)三甲氧基硅烷为原料,氟化物催化合成胶体有机硅的反应动力学性质。连续实时的衰减全反射傅里叶变换红外光谱(ATR-FTIR)测量能够探测不同反应体系中有机硅缩合的时间演变,这些体系包含以下之一:非离子表面活性剂(吐温20、吐温40、吐温60、吐温80、曲拉通X-100)、阴离子表面活性剂(十二烷基硫酸钠;SDS)、阳离子表面活性剂(十六烷基三甲基溴化铵;CTAB)以及两亲聚合物(聚乙烯醇和聚乙烯吡咯烷酮)。总体而言,虽然揭示了一些两亲物的特定性质,但对于所有研究的两亲物,氟化物催化合成均具有超快的通用两相动力学方案(5-10分钟内转变)。