Photochemical Synthesis of Oligomeric Amphiphiles from Alkyl Oxoacids in Aqueous Environments.
Photochemical Synthesis of Oligomeric Amphiphiles from Alkyl Oxoacids in Aqueous Environments.
复制标题
DOI：
10.1021/jacs.7b01707
复制
发表时间：
2017-05-24
影响因子：
15
通讯作者：
Vaida V
中科院分区：
文献类型：
--
作者：
Rapf RJ;Perkins RJ;Yang H;Miyake GM;Carpenter BK;Vaida V
研究了一系列具有不同线性烷基链长度的两亲性 α-酮酸的水相光化学，证明了阳光引发的反应在环境相关条件下构建分子复杂性的能力。我们表明，α-酮酸在水溶液中的光化学反应机制是稳健的，并且可以在烷基链长度上推广。光解过程中产生的有机自由基是不加区别的，导致使用高分辨率电喷雾电离质谱法观察到大量光产物混合物，但这些产物可以按照文献光化学机制进行识别。这里研究的烷基含氧酸可以经历 Norrish II 型反应生成丙酮酸，从而增加观察到的光产物的多样性。这种光化学的主要产物是起始含氧酸的共价键合二聚体和三聚体，其中许多是多尾脂质。讨论了这些低聚物的特性，包括它们自发自组装成聚集体。
The aqueous phase photochemistry of a series of amphiphilic α-keto acids with differing linear alkyl chain lengths was investigated, demonstrating the ability of sunlight-initiated reactions to build molecular complexity under environmentally relevant conditions. We show that the photochemical reaction mechanisms for α-keto acids in aqueous solution are robust and generalizable across alkyl chain lengths. The organic radicals generated during photolysis are indiscriminate, leading to a large mixture of photoproducts that are observed using high-resolution electrospray ionization mass spectrometry, but these products are identifiable following literature photochemical mechanisms. The alkyl oxoacids under study here can undergo a Norrish Type II reaction to generate pyruvic acid, increasing the diversity of observed photoproducts. The major products of this photochemistry are covalently bonded dimers and trimers of the starting oxoacids, many of which are multitailed lipids. The properties of these oligomers are discussed, including their spontaneous self-assembly into aggregates.
登录
查看更多内容
DOI：
10.1073/pnas.1105715108
发表时间：
2011-08-23
影响因子：
11.1
作者：
Cooper, George;Reed, Chris;Wang, Yi
通讯作者：
Wang, Yi
影响因子：
15
作者：
CLOSS, GL;MILLER, RJ
通讯作者：
MILLER, RJ
影响因子：
1.8
作者：
DAVIDSON, RS;GOODWIN, D;DEVIOLET, PF
通讯作者：
DEVIOLET, PF
影响因子：
5.2
作者：
Chiu, R.;Tinel, L.;Volkamer, R.
通讯作者：
Volkamer, R.
影响因子：
6.3
作者：
Bregonzio-Rozier, L.;Giorio, C.;Doussin, J. -F.
通讯作者：
Doussin, J. -F.