基于环糊精的分子组装课件.ppt

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1、二、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、有机分子和金属离子构筑多

2、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,环糊精/联吡啶包合物(a)1和(b)3在D

3、2O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,ab,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 aggregation 2,showing the square nanostructures.,

4、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 images of polypseudorotaxane aggregation 6,

5、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 superstructure of polypseudorotaxanes.(c)Possible assembly

6、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 nanoparticle 4.,(a-c)Typical TEM images of 4.The size labels

7、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 compl

8、ex 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.,Fluorescence spectra of Ru(bpy)2Cl2,complex 1 and assembly 2 in solid state.,Chem.Commun.,2005,(13)

9、,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),5838-5840.,(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

10、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 histograms for AuNPs 3.,(a)Typical TEM and(b)high-resolution TEM images of 2,and(c)sizedependent histograms for AuN

11、Ps 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.,Au,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

12、 Au-PPR aggregate 8,Time-dependent UV/Vis spectra of aggregate 6(0.3 mg/mL).The curves from top to bottom correspond to the gradual increment of 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

13、 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-absorbed 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

14、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 2.0 g of pBR322 plasmid.Line 1:no reagent in 50 mM Tris-HCl buffer(pH 7.4).

15、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.Lines 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

16、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.,a b,Nano Lett.2001,1(11),613-616.,由环糊精与杯芳烃的分子间相互作用构筑纳米线,Nano Lett.2002,2(4),257-261.,STM images of the supramolecular aggregates:(a)li

17、near assemblies;(b)host-guest inclusion complexes composed of four-cyclodextrins and a calix4arene units.,ab,TEM images of the supramolecular aggregates,SEM images of(a)calixarene,(b)cyclodextrin and(c)the supramolecular aggregates,a,b,c,通过桥联双环糊精的选择性键合控制纳米线的致密性,Chem.Lett.,2003,32(10),884-8845.,STM i

18、mages of(a)Nanowires 5,a,假聚轮烷有序高级结构的构筑,Macromelecules 2002,35(27),9934-9938.,The STM image of(a)3 and(b)its chematic structure,The STM image of(a,c)4 and(b)its chematic structure,金属桥联环糊精调控的水溶性超分子富勒烯组装体,富勒烯（C60）拥有一个球形的电子体系，表现出有趣的磁性、超导、电子和生物化学性能。然而由于富勒烯在一般有机溶剂中低的溶解性和几乎不溶于水的特点极大的限制了它的性能开发于应用。,富勒烯组装体的制备

19、途径,Angew.Chem.Int.Edit.2004,43(20),2690-2694.,金属桥联双环糊精2与富勒烯组装体3的紫外-可见光谱图,金属桥联双环糊精2（上图）与富勒烯组装体3（下图）的核磁共振光谱图,金属桥联双环糊精2(a)在石墨基底上的STM图象，(b)图象的线性轮廓，(c)局部图，(d)它的示意图,富勒烯组装体3(a)在石墨基底上的STM图象，(b)图象的线性轮廓，(c)它的示意图,富勒烯组装体3的TEM图象,被富勒烯组装体3蚀刻的琼脂糖凝胶电泳图。线1：Tris-HCl 缓冲溶液中没有切割剂；线2和5：含有20 mol dm-3 的桥联双环糊精1；线3和6：含有20 mol

20、 dm-3的金属桥联双环糊精2；线4和7：含有73 mg dm-3的富勒烯组装体3。线1-4：20oC下可见光照射6小时；线5-7：暗室里孵育6小时.,含有杯4芳烃和环糊精的金属帽式聚轮烷及其对Ca2+的高选择性,金属帽式聚轮烷的制备途径,(a)(b),金属帽式聚轮烷在石墨基底上的(a)STM图象，和(b)它的高分辨STM图象,金属帽式聚轮烷的TEM图像,在25 C的水溶液中聚轮烷与金属离子包结络合作用的有效键合常数(KES)和吉布斯自由能(-G)变化.,金属帽式聚轮烷键合金属离子示意图,Chem.Comm.2004,(20)2266-2267.,水溶性的环糊精修饰金纳米粒子作为60富勒烯的循

21、环萃取器,环糊精修饰金纳米粒子2的制备,环糊精修饰金纳米粒子2对60富勒烯的循环萃取路线,(a)代表性的2的高分辨TEM图像；(b)C60诱导的2的组装体的低分辨TEM 图像；(c)C60诱导的2的组装体加入2-金刚烷醇后的代表性的高分辨TEM图像,a b c,(a)2(0.1 mg/mL)的紫外光谱；(b)C60/2组装体(0.1 mg/mL)的紫外光谱；(c)C60/2组装体水溶液的甲苯萃取液的紫外光谱,C60诱导的环糊精修饰金纳米例子聚集体示意图,Chem.Commun.,2005,(33),4208-4210.,由多金属桥联环糊精形成的双假聚轮烷以及其分子组装的热力学起源,双假聚轮烷的

22、制备途径,桥联双环糊精1(a)在石墨基底上的STM图象，(b)局部放大图，(c)它的示意图，(d)图象的线性轮廓,双假聚轮烷的STM图象,双假聚轮烷的结构示意图,PPG与金属桥式双环糊精2在20C,25C,30C,35C,40C,45 C时的穿插过程的logKS 对1/T作图,log KS=5.05 M-1H=54.0 kJmol1 TS=82.8 kJmol1,Macromolecules 2004,37(17),6370-6375.,Bundle-Shaped Cyclodextrin-Tb Nano-Supramolecular Assembly Mediated by C60:Intr

23、amolecular Energy Transfer,(a-b)STM images of assembly 3 on a HOPG surface.(c)Line profile of image shown in(b).(d)Schematic structure of 3.,d,(a)TEM and(b)HR-TEM images of 3(1 10-4 M);(c)TEM images of 3(5 10-6 M).,Luminescence spectra of polyad 2 and assembly 3(1 10-6 calculated as Tb3+)in a pH 7.2 Tris-HCl buffer solution;excitation wavelength:275 nm,slit width 5 nm.(inset)Visible emission observed from(a)polyad 2 and(b)assembly 3.,Nano Lett.,2006,6(11),2196-2200.,