Cui Renfa, Li Qing, Gross Dustin E, Meng Xin, Li Bo, Marquez Manuel, Yang Ronghua, Sessler Jonathan L, Shao Yuanhua
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
J Am Chem Soc. 2008 Nov 5;130(44):14364-5. doi: 10.1021/ja804631p. Epub 2008 Oct 8.
The facilitated transfer of four hydrophilic anions, i.e., Cl-, Br-, NO2-, and CH3CO2-, at the micro-water/1,2-dichloroethane interface supported at the tip of a micropipet has been observed successfully using beta-octafluoro-meso-octamethylcalix[4]pyrrole 2 as the receptor. We have also shown for the first time that the dynamics of this process can be studied by micropipet voltammetry. The standard kinetic rate constants (kdegrees) for facilitated anion transfer at such an interface were determined to be (2.11 +/- 0.90) x 10(-2) and (0.75 +/- 0.50) x 10(-2) cm/s in the case of Cl- and CH3CO2-, respectively. These values are much smaller than those associated with the facilitated transfer of analogous alkali metal ions. This difference is thought to reflect a number of underlying factors, including the higher hydration of anions as compared to similar sized cations. Studies such as these are expected to be useful in understanding the mechanism of anion transport at soft interfaces and for the design of yet-improved anion receptors and carriers.
使用β-八氟-间-八甲基杯[4]吡咯2作为受体,已成功观察到在微量移液管尖端支撑的微水/1,2-二氯乙烷界面上四种亲水性阴离子(即Cl-、Br-、NO2-和CH3CO2-)的促进转移。我们还首次表明,该过程的动力学可以通过微量移液管伏安法进行研究。在这种界面上促进阴离子转移的标准动力学速率常数(k°)在Cl-和CH3CO2-的情况下分别确定为(2.11±0.90)×10(-2)和(0.75±0.50)×10(-2) cm/s。这些值远小于与类似碱金属离子促进转移相关的值。这种差异被认为反映了许多潜在因素,包括与类似大小阳离子相比阴离子更高的水合作用。此类研究有望有助于理解软界面上阴离子传输的机制,并用于设计改进的阴离子受体和载体。