Center for Chemical Engineering, St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 St. Petersburg, Russia.
Institute of Macromolecular Compounds, Russian Academy of Sciences, 199004 St. Petersburg, Russia.
Int J Mol Sci. 2022 Aug 15;23(16):9142. doi: 10.3390/ijms23169142.
Vesicles formed by DMPC liposomes externally conjugated with branched polyglycerol-dendrons as well as linear PEG in water solution were simulated using the DPD method. Such a structure of vesicles corresponds to the structure of polymer-grafted liposomes obtained experimentally by the post-insertion method, in which polymer chains are fixed on the outer surface of the liposome. The grafting density, generation number and spacer length of grafted dendrons were varied. It was shown that modification of the outer surface of liposomes due to grafting of hydrophilic dendrons has practically no effect on the size and shape of the vesicle, as well as on the morphology of the lipid membrane up to certain critical thresholds of grafting density, degree of polymerization, and generation number of grafted molecules. Exceeding the threshold values of these structural parameters leads to irreversible deformation of the lipid membrane. Diffusion through the membrane and the transition of grafted molecules from the outer surface of the liposome to the inner surface is not observed for dendrons with a generation number higher than one, even at high grafting densities. The critical values of the generation number and the characteristics of the molecular coating at these values were determined for various grafting densities and spacer lengths of the grafted chains. It was shown that the chemical potential of the grafted dendron can serve as a stability metric for the conjugated liposome. The chemical potential of grafted molecules was calculated using the mean field model of the spherical brush on the liposome surface. An analysis of the simulation data shows that, within the framework of the applicability of the mean field approach, the value of the chemical potential is a sufficient criterion for separating vesicles into stable and unstable forms. These results can be used as a guide for the experimental design of nanocontainers based on lipid vesicles with an external protective coating of branched macromolecules.
在水溶液中,通过 DMPC 脂质体外部接枝支化聚甘油-树枝状大分子以及线性 PEG 来模拟囊泡。这种囊泡的结构与通过后插入法实验获得的聚合物接枝脂质体的结构相对应,其中聚合物链固定在脂质体的外表面。改变接枝树枝状大分子的接枝密度、代数量和间隔长度。结果表明,由于亲水性树枝状大分子的接枝修饰,脂质体的外表面的修饰对囊泡的大小和形状以及脂质膜的形态几乎没有影响,直到接枝密度、聚合度和接枝分子的代数量的某些临界阈值。超过这些结构参数的阈值会导致脂质膜的不可逆变形。对于代数量高于一的树枝状大分子,即使在高接枝密度下,也不会观察到通过膜的扩散以及接枝分子从脂质体的外表面向内表面的转变。对于各种接枝密度和接枝链的间隔长度,确定了代数量的临界值和分子涂层的特性。结果表明,接枝树枝状大分子的化学势可以作为共轭脂质体的稳定性度量。使用脂质体表面的球形刷的平均场模型计算接枝分子的化学势。对模拟数据的分析表明,在平均场方法的适用性范围内,化学势的值是将囊泡分离成稳定和不稳定形式的充分标准。这些结果可作为具有支化大分子外部保护层的脂质囊泡的纳米容器的实验设计指南。