Superhydrophobic photosensitizers. Mechanistic studies of (1)O2 generation in the plastron and solid/liquid droplet interface.
Superhydrophobic photosensitizers. Mechanistic studies of (1)O2 generation in the plastron and solid/liquid droplet interface.
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DOI：
10.1021/ja410529q
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发表时间：
2013-12-18
影响因子：
15
通讯作者：
Greer A
中科院分区：
文献类型：
--
作者：
Aebisher D;Bartusik D;Liu Y;Zhao Y;Barahman M;Xu Q;Lyons AM;Greer A
我们在这里描述了在水滴中光氧化的第一种三相超疏水敏化剂的物理有机研究。对合成参数的控制使“临界”两相和三相超疏水敏化剂表面的机理研究成为可能，其中1O2是在湿的、部分湿的或在板层（即液滴下方的空气层）中保持干燥的隔室中产生的。超疏水表面是通过将部分酞菁硅（Pc）敏化颗粒嵌入到以正方形阵列印刷的聚二甲基硅氧烷（PDMS）柱（1mm高，0.5 mm间距）的特定位置来合成的。在红光和氧气存在下，单线态氧在超疏水表面形成，并在独立水滴内与9,10-蒽二丙酸dianion(1)反应生成内过氧化物，产率为54-72%。通过在PDMS末端末端或PDMS后基上合成富含Pc粒子的超疏水表面来控制1O2的化学反应。液滴中与蒽1反应的大部分o2是由敏化剂“润湿”Pc颗粒/水滴界面产生的，并产生最高的内过氧化物产率。大约20%的氧可以从血小板引入液滴。结果表明，超疏水敏化剂表面提供了一种独特的体系来研究1O2的转移途径，在相同的超疏水表面内，1O2的气液贡献平衡是可调的。
We describe here a physical-organic study of the first triphasic superhydrophobic sensitizer for photooxidations in water droplets. Control of synthetic parameters enables the mechanistic study of “borderline” two- and three-phase superhydrophobic sensitizer surfaces where 1O2 is generated in compartments that are wetted, partially wetted, or remain dry in the plastron (i.e., air layer beneath the droplet). The superhydrophobic surface is synthesized by partially embedding silicon phthalocyanine (Pc) sensitizing particles to specific locations on polydimethylsiloxane (PDMS) posts printed in a square array (1 mm tall posts on 0.5 mm pitch). In the presence of red light and oxygen, singlet oxygen is formed on the superhydrophobic surface and reacts with 9,10-anthracene dipropionate dianion (1) within a freestanding water droplet to produce an endoperoxide in 54–72% yields. Control of the 1O2 chemistry was achieved by the synthesis of superhydrophobic surfaces enriched with Pc particles either at the PDMS end-tips or at PDMS post bases. Much of the 1O2 that reacts with anthracene 1 in the droplets was generated by the sensitizer “wetted” at the Pc particle/water droplet interface and gave the highest endoperoxide yields. About 20% of the 1O2 can be introduced into the droplet from the plastron. The results indicate that the superhydrophobic sensitizer surface offers a unique system to study 1O2 transfer routes where a balance of gas and liquid contributions of 1O2 is tunable within the same superhydrophobic surface.
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影响因子：
11.4
作者：
HAAG, WR;HOIGNE, J
通讯作者：
HOIGNE, J
影响因子：
15
作者：
Jensen, Rasmus Lybech;Arnbjerg, Jacob;Ogilby, Peter R.
通讯作者：
Ogilby, Peter R.
影响因子：
11.4
作者：
Bartusik, Dorota;Aebisher, David;Lyons, Alan M.;Greer, Alexander
通讯作者：
Greer, Alexander
影响因子：
15
作者：
Davies, HML;Walji, AM;Nagashima, T
通讯作者：
Nagashima, T
影响因子：
15
作者：
Davies, IW;Matty, L;Reider, PJ
通讯作者：
Reider, PJ