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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Lateral Diffusion of Reconstituted Alkylferrocenecarboxamide/Phosphatidylcholine Lipid Monolayer at the Air/Water Interface Studied with Electrochemistry
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Lateral Diffusion of Reconstituted Alkylferrocenecarboxamide/Phosphatidylcholine Lipid Monolayer at the Air/Water Interface Studied with Electrochemistry

机译：重构的烷基二茂铁羧酰胺/磷脂酰胆碱脂质单层在空气/水界面的横向扩散研究

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摘要

Lateral diffusion of alkylferrocenecarboxamide (FcCONHC_n)/1,2-dilauroyl-sn-glycero-3-phosphatidylcholine lipid monolayer at the air/water interface was determined with electrochemical techniques using a fabricated microline electrode. The prepared homogeneous Langmuir monolayer of electroactive FcCONH_n/phospholipid was identified with pressure-area isotherms in the subphase of 50 mM HClO_4. The diffusion constant of electroactive FcCONHC_n in the lipid monolayer was approximately between 0.1 * 10~(-6) and 2.6 * 10~(-6) cm~2/s at room temperature. The diffusion constant of ferrocenes in a phospholipid monolayer at the air/water interface was greater for the ferrocene with longer alkyl chains. This is interpreted as the extent of hydrodynamic coupling of the hydrophilic ferrocene moiety of FcCONHC_n to the subphase, which was less for ferrocenes with longer alkyl chains. This lets the position of the hydrophilic headgroup of FcCONHC_n with respect to the air/water interface be shifted upward for the longer alkyl chain because of greater hydrophobic entanglement. The electrochemistry with the microline electrode was possible in the mean molecular area range 60-100 A~2/mol because of monolayer adsorption in a mean molecular area that is less than 60 A~2/mol. The linear decrease of the diffusion constant of ferrocenes with decreasing mean molecular area is explained by the decreasing free volume of the moving headgroup. This is well explained by the modified Cohen-Turnbull free volume model.
机译：使用制造的微线电极，通过电化学技术确定了烷基二茂铁羧酰胺（FcCONHC_n）/ 1,2-二茂铁基-sn-甘油-3-磷脂酰胆碱脂质单层在空气/水界面的横向扩散。在50 mM HClO_4的亚相中，通过压力-面积等温线鉴定了制备的电活性FcCONH_n /磷脂的均质Langmuir单层。在室温下，电活性FcCONHC_n在脂质单层中的扩散常数约为0.1 * 10〜（-6）至2.6 * 10〜（-6）cm〜2 / s。对于具有较长烷基链的二茂铁，二茂铁在空气/水界面处的磷脂单层中的扩散常数更大。这被解释为FcCONHC_n的亲水二茂铁部分与亚相的流体动力学偶联程度，对于具有更长烷基链的二茂铁而言，该程度较小。对于较长的烷基链，这使FcCONHC_n亲水性头基相对于空气/水界面的位置向上移动，因为疏水缠结更大。用微线电极进行的电化学在平均分子面积范围60-100 A〜2 / mol内是可能的，因为在平均分子面积内的单层吸附小于60 A〜2 / mol。二茂铁的扩散常数随平均分子面积的减少而线性降低，这是由于移动头基的自由体积减少所致。修改后的Cohen-Turnbull自由体积模型很好地解释了这一点。

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