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1、基于环糊精的分子组装,基于天然环糊精的分子组装 基于单修饰环糊精的分子组装 基于桥联双环糊精的分子组装,-环糊精与2,2-联吡啶形成头对头通道结构及其联吡啶骨架,-环糊精与2,2-联吡啶和4,4-联吡啶的键合 能力及其组装行为,-环糊精与4,4-联吡啶形成头对头通道结构及其联吡啶骨架,(a) (b),(a) -环糊精与2,2-联吡啶以及与 (b) 4,4-联吡啶在水溶 液中的可能结构.,J. Org. Chem. 2004, 69(10), 3383-3390.,在25 C的水溶液中-环糊精与联吡啶包结络合作用的稳定常数(KS)、自由能变化(G) 、焓变(H)和熵变(TS).,通过环糊精、有机
2、分子和金属离子构筑多聚轮烷示意图,通过-环糊精与4,4-联吡啶的包结络合物与二价镍离子的配位作用构筑多聚轮烷,Angew. Chem. Int. Edit. 2003, 42(28), 3260-3263,联吡啶、环糊精包合物1以及聚轮烷2的核磁氢谱,聚轮烷2的STM 图象,聚轮烷2的TEM 图象,a,b,聚轮烷2的 (a) 低倍，和(b)高分辨率TEM 图象,由,和-环糊精与联吡啶包结配合物构筑的拥有多金属中心的线性假聚轮烷,Inorg. Chem., 2006, 45(7), 3014-3022.,环糊精/联吡啶包合物1-3在25C水溶液中的圆二色光谱,环糊精/联吡啶包合物1-3可能的构象
3、,环糊精/联吡啶包合物(a)1和(b)3在D2O中的ROESY光谱，混合时间200 ms.,假聚轮烷4的TEM图像， 假聚轮烷4的高分辨TEM图像,(c) 假聚轮烷6的TEM图像， (d) 假聚轮烷6的高分辨TEM图像,a b,c d,(a) 假聚轮烷6的STM图像，(b) a图的局部放大图，(c) b图的3D图像 (d) b图和c图的线装轮廓图,Chem. Mater., 2006, 18(18), 4423-4429 .,以Co2+ 和Zn2+ 配位中心和环糊精/联吡啶 包结配合物构筑的纳米构建物,The TEM images of polypseudorotaxane aggregati
4、on 2, showing the square nanostructures.,The TEM images of polypseudorotaxane aggregation 3, showing the rod nanotructures.,The TEM images of polypseudorotaxane aggregation 4, showing the square nanotructures.,The TEM images of polypseudorotaxane aggregation 5, showing the rod nanotructures.,The TEM
5、 images of polypseudorotaxane aggregation 6, showing the rod nanotructures.,The TEM images of polypseudorotaxane aggregation 7, showing the square nanostructures.,(a) The molecular modeling structure of a short oligomer of the polypseudorotaxanes. (b) Possible assembly mode for nanosquare superstruc
6、ture of polypseudorotaxanes. (c) Possible assembly mode for nanorod superstructure of polypseudorotaxanes.,The colors of polypseudorotaxanes 2 (blue), 3 (pink), and 4 (pink).,Synthetic route of AuNP aggregation 2.,Org. Lett., 2006, 8(7), 1267-1270.,以金纳米离子为中心的多聚2轮烷,Synthesis of rotaxane-capped gold n
7、anoparticle 4.,(a-c) Typical TEM images of 4. The size labels are 20 nm for (a) and (b), 10 nm for (c). (d) size-dependent histogram of 4.,通过-环糊精的包合物直接制备含共轭 体系的超分子聚轮烷,超分子聚轮烷及其高分子链的合成途径,1,2,具有“头-头”通道结构的包合物2的晶体结构,(a) 聚轮烷3在石墨基底上的STM图象， (b) 对应的三维图象， (c) 它的示意图,Macromolecules 2004, 37(17), 6362-6369.,从双吡啶
8、钌/环糊精轮烷构筑超分子聚轮烷,1H NMR spectra of Ru(bpy)2Cl2 (bottom), CD-BPD (middle) and complex 1 (top) in D2O.,TEM image of 2.,(a) Tridimensional and (b) planar STM images of assemblies 2.,Fluorescence spectra (a) Ru(bpy)2Cl2, (b) complex 1 and (c) assembly 2 in phosphate buffer solution (pH 7.2) at 25C.,Fluor
9、escence spectra of Ru(bpy)2Cl2, complex 1 and assembly 2 in solid state.,Chem. Commun., 2005, (13), 1702-1704.,富勒烯调控的内锁式环糊精-卟啉双聚轮烷,TEM images of 4,STM image of the end of 4 on HOPG surface,Macromelecules, 2005, 38(22), 9095-9099.,环糊精封端的聚轮烷及其组装行为,假聚轮烷1，聚轮烷2和聚集体3的制备,Macromolecules 2005, 38(13), 5838-5
10、840 .,(a)假聚轮烷1和(b)聚轮烷2在DMSO-d6的核磁光谱,(a)假聚轮烷1(0.6毫克/毫升)，(b)聚轮烷2(0.6毫克/毫升)和(c)聚集体3(0.6 毫克/毫升)在pH 7.4的水溶液中的紫外(UV-vis)谱图,聚集体3的TEM图像,Synthetic route of AuNP aggregation 2.,Macromol. Rapid Commun., 2005, 26(5), 401-406.,巯基修饰环糊精假聚轮烷调控的金纳米 粒子超分子组装,(a) High-resolution TEM image of 3, and (b) size-dependent h
11、istograms for AuNPs 3.,(a) Typical TEM and (b) high-resolution TEM images of 2, and (c) sizedependent histograms for AuNPs in aggregate 2.,DNA-cleavage ability of 2 in phosphate buffer (pH 7.4) at 25 C. 1: DNA; 2: DNA + 2.,环糊精假聚轮烷与金纳米粒子形成的 超分子聚集体:作为富勒烯的捕获器,J. Am. Chem. Soc., 2005, 127(2), 657-666.,A
12、u,TEM images of (a) Au colloid paricles, (b) Au-PPR aggregates 5, (c) 6, (d) 7; (e-g) high- resolution TEM images of (e) 5, (f) 6, (g) 7; (h) TEM image of Au-PPR aggregate 8,Time-dependent UV/Vis spectra of aggregate 6 (0.3 mg/mL). The curves from top tobottom correspond to the gradual increment of
13、time: 0, 1, 2, 3, 5, 10, 15, 20, 25, 32, 45, 60, 90,120, 150, 180, 190 min,528 nm,665 nm,Sedimentation rates of aggregates 5-7 denoted by the SPR intensities of aggregates 5 (0.1 mg/mL), 6 (0.3 mg/mL), and 7 (0.6 mg/mL),捕获富勒烯,UV/Vis spectra of (a) aggregate 8 (0.2 mg / mL) and (b) 60fullerene-absorb
14、ed aggregate 8 in aqueous solution.,将20.3毫克的富勒烯60加到10毫升饱和的聚集体8的溶液中，混合物室温 搅拌12h，不溶的物质离心除去，得到的上层清液减压旋干，所得的吸附有富 勒烯60的固体真空干燥。,富集能力检测,实验结果表明1毫克的聚集体8可以富集1.83毫克的富勒烯60。 在控制试验中，1毫克的聚集体6只能富集0.08毫克的富勒烯60，而 金溶胶和假聚轮烷2，4未表现出对富勒烯60的富集能力。这些溶解 实验都重复了3遍，误差在10%以内。,将2.3毫克的聚集体8溶于1毫升的水中，然后向该溶液中加入5.0 mg的 富勒烯60，混合体系超声反应10分
15、钟，不溶的富勒烯60离心收集， 真空干燥，称重。,DNA切割实验,Agarose gel electrophoretic patterns of plasmid DNA. The reaction samples contained 2.0g of pBR322 plasmid. Line 1: no reagent in 50 mM Tris-HCl buffer (pH 7.4). Lines 2 and 5: 2.5 g/L of PPR 2. Lines 3 and 6: 2.5 g/L of 8. Lines 4 and 7: 2.5 g/L of 8-C60 system. Lin
16、es 1-4:incubated in the dark for 6 h. Lines 5-7: incubated under visible light irradiation at 20C for 6 h. Electrophoresis was performed by using 1% agarose gel containing ethidium bromide (0.5g/L),双纳米管的有序高级结构,双纳米管的制备途径,TEM spectrum of bis(molecular tube)s 20,AFM spectrum of bis(molecular tube)s 20: (a) tubular structure; (b) rectangles composed of four -cyclodextrin units.,
