Manuel Miguel, Martins Jorge
IBB-CBME and DQBF-FCT, Universidade do Algarve, Campus de Gambelas, Faro, Portugal.
Chem Phys Lipids. 2008 Aug;154(2):79-86. doi: 10.1016/j.chemphyslip.2008.04.007. Epub 2008 May 4.
Molecular partitioning into biomembranes is of fundamental importance in diverse biochemical processes and reactions. The majority of aqueous/membrane partition data using model membrane systems, is obtained with pure phosphatidylcholine bilayers, being lipid mixtures less used, while studies involving bilayers containing zwitterionic/anionic mixtures of phospholipids are even more scarce. In this study, the solvatochromic effects of 1-pyrenesulfonate observed at 375 nm in aqueous liposome suspensions, and monitored by second derivative absorption spectrophotometry, enabled the determination of its partition constants into defined phospholipid bilayers. We compare, under cautiously settled experimental conditions, the partition of the anionic amphiphile PSA into fluid zwitterionic bilayers of POPC (Kp=6.7 x 10(3), at 25 degrees C), and into fluid mixed zwitterionic/anionic bilayers containing small proportions of anionic phospholipids. At the same temperature, we found increasing K(p) values in parallel with the proportion of POPS mixed with POPC (Kp=3.4 x 10(4) and Kp=7.3 x 10(4), with 5 and 10 mol% of POPS, respectively). Our interpretation is based on the interfacial properties of fluid and flexible mixed zwitterionic/anionic phospholipid bilayers.
分子在生物膜中的分配在多种生化过程和反应中具有至关重要的意义。使用模型膜系统获得的大多数水相/膜分配数据是通过纯磷脂酰胆碱双层得到的,较少使用脂质混合物,而涉及含有两性离子/阴离子磷脂混合物的双层的研究则更为稀少。在本研究中,通过二阶导数吸收分光光度法监测,在水相脂质体悬浮液中于375 nm处观察到的1-芘磺酸盐的溶剂化显色效应,使得能够确定其在特定磷脂双层中的分配常数。在谨慎设定的实验条件下,我们比较了阴离子两亲物PSA在25℃时进入POPC的流体两性离子双层(Kp = 6.7×10³)以及进入含有少量阴离子磷脂的流体两性离子/阴离子混合双层中的分配情况。在相同温度下,我们发现K(p)值随着与POPC混合的POPS比例增加而升高(分别含有5 mol%和10 mol%的POPS时,Kp = 3.4×10⁴和Kp = 7.3×10⁴)。我们的解释基于流体且灵活的两性离子/阴离子混合磷脂双层的界面性质。