Zingaretti Lilian, Mariano Correa N, Boscatto Liliana, Chiacchiera Stella M, Durantini Edgardo N, Bertolotti Sonia G, Rivarola Claudia R, Silber Juana J
Departamento de Química, Universidad Nacional de Río Cuarto, Agencia Postal No. 3, 5800 Río Cuarto, Argentina.
J Colloid Interface Sci. 2005 Jun 1;286(1):245-52. doi: 10.1016/j.jcis.2004.12.057.
The distribution of different aliphatic and aromatic amines: n-butylamine (n-BA), isobutylamine (i-BA), tert-butylamine (t-BA), piperidine (PIP), N,N-dimethylaniline (DMA) and N-methylaniline (MA) in water/sodium 1,4-bis(2-ethylhexyl)sulfosuccinate(AOT)/n-hexane reverse micelles was investigated by steady-state fluorescence measurements. The partition constants were measured by an indirect method based on the effect that amine partitioning exert on the bimolecular rate of the reaction between a microphase incorporated fluorophore (Ru(bpy)2+(3)) and the quencher, (Fe(CN)3-(6)). For MA, that can act as a quencher of the fluorophore a direct method was used. The results show that primary amines have larger partition constants than the secondary ones. For tertiary amines the distribution constants were practically negligible. Laser flash photolysis experiments confirmed that tertiary amines, both aliphatic and aromatic, are not incorporated to the micellar pseudophase. The effect of the amine structure on the partition constant was analyzed through linear solvation free energy relationships (LSER) using solute parameters and compared with those obtained for alcohols. Hydrogen bond interactions with the AOT polar heads appear to be the main driving force for the distribution of amines between the organic and micellar pseudophases, whereas the size of the alkyl or aromatic group tends to hinder it.
正丁胺（n-BA）、异丁胺（i-BA）、叔丁胺（t-BA）、哌啶（PIP）、N，N-二甲基苯胺（DMA）和N-甲基苯胺（MA）在水/1,4-双（2-乙基己基）磺基琥珀酸钠（AOT）/正己烷反胶束中的分布情况。基于胺分配对掺入微相的荧光团（Ru（bpy）2 +（3））与猝灭剂（Fe（CN）3 -（6））之间反应的双分子速率的影响，采用间接方法测量分配常数。对于可作为荧光团猝灭剂的MA，使用了直接方法。结果表明，伯胺的分配常数大于仲胺。对于叔胺，分布常数实际上可以忽略不计。激光闪光光解实验证实，脂肪族和芳香族叔胺均未掺入胶束假相。通过使用溶质参数的线性溶剂化自由能关系（LSER）分析了胺结构对分配常数的影响，并与醇类的结果进行了比较。与AOT极性头的氢键相互作用似乎是胺在有机相和胶束假相之间分布的主要驱动力，而烷基或芳基的大小则倾向于阻碍这种分布。
