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二棕榈酰基磷脂酰胆碱(DPPC)单层中内嵌富勒烯(Dy@C82)的研究。

Studies of dipalmitoylphosphatidylcholine (DPPC) monolayers embedded with endohedral metallofullerene (Dy@C82).

机构信息

Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.

出版信息

Langmuir. 2009 Nov 17;25(22):12968-73. doi: 10.1021/la9017932.

Abstract

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.

摘要

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。

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