Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Langmuir. 2009 Nov 17;25(22):12968-73. doi: 10.1021/la9017932.
Toxicological effects of carbon nanomaterials have attracted increasing attention. In this work, we studied the interaction between Dy@C(82) and dipalmitoylphosphatidylcholine (DPPC) in a monolayer at the N(2)/Tris buffer interface by thermodynamic analysis of surface pressure-area (pi-A) and surface potential-area (DeltaV-A) isotherms. Dy@C(82) was found to impact considerably more on the physical properties of the monolayers than C(60) because of its elliptical structure and distinctive dipole. The addition of Dy@C(82) essentially closed down the liquid expanded-liquid condensed (LE-LC) phase coexistence region of the mixed monolayers. Furthermore, Dy@C(82) reduced elasticity of the monolayers, as indicated by the decreasing elastic modulus (C(s)(-1)) with increasing molar ratio of Dy@C(82) (X(Dy@C82)). Brewster angle microscopy (BAM) and atomic force microscopy (AFM) revealed that the dispersion of Dy@C(82) depend on the state of the mixed films. Dy@C(82) formed flocs from aggregation of Dy@C(82) towers in the LE and LE-LC coexistence regions, accompanied by gradual falling down of Dy@C(82) from the towers and permeation of the falling metallofullerenes into the LE phase during their compression-induced reorientation process. In the LC and solid phases, the Dy@C(82) flocs were dispersed into isolated towers, accompanied by the partial squeezing out of the embedded metallofullerenes to above the DPPC monolayer. The continuous falling down of Dy@C(82) from the towers resulted in their height decrease but diameter enlargement. When the surface pressure was increased to the kink value (53 mN/m), Dy@C(82) was almost completely extruded from the DPPC monolayers. These findings are believed to be important for understanding the impact of fullerenes, metallofullerenes, and nanomaterials in general on biological membranes.
碳纳米材料的毒理学效应引起了越来越多的关注。在这项工作中,我们通过表面压-面积(pi-A)和表面电势-面积(DeltaV-A)等温线的热力学分析,研究了 Dy@C(82)与二棕榈酰磷脂酰胆碱(DPPC)在 N(2)/Tris 缓冲界面单层中的相互作用。由于 Dy@C(82)的椭圆形结构和独特的偶极矩,它对单层的物理性质的影响比 C(60)大得多。添加 Dy@C(82)基本上关闭了混合单层的液体膨胀-液体凝聚(LE-LC)相共存区。此外,Dy@C(82)降低了单层的弹性,这表现为随着 Dy@C(82)摩尔比(X(Dy@C82))的增加,弹性模量(C(s)(-1))逐渐减小。掠入射显微镜(BAM)和原子力显微镜(AFM)表明,Dy@C(82)的分散取决于混合膜的状态。在 LE 和 LE-LC 共存区,Dy@C(82)通过 Dy@C(82)塔的聚集形成絮状物,同时 Dy@C(82)从塔上逐渐落下,并且在压缩诱导的重排过程中,落入的金属富勒烯渗透到 LE 相中。在 LC 和固态中,Dy@C(82)絮状物分散成孤立的塔,同时部分嵌入的金属富勒烯被挤出 DPPC 单层之上。Dy@C(82)从塔上不断落下导致其高度降低但直径增大。当表面压增加到拐点值(53 mN/m)时,Dy@C(82)几乎完全从 DPPC 单层中挤出。这些发现对于理解富勒烯、金属富勒烯和一般纳米材料对生物膜的影响具有重要意义。