手性聚二炔组装体*

本文介绍了手性聚双炔制备的研究进展,重点介绍从非手性的含有光活性基团的偶氮双炔单体小分子出发,采用一种全新的技术即手性圆偏振紫外光辐照聚合技术,制备偶氮聚双炔手性Langmuir–Blodgett（LB）膜,研究了偶氮聚双炔手性LB膜在光致旋光性调控过程中的光学和其它物理性质变化,并展望其在光子学器件领域中的应用。     

可见光对双炔酸Langmuir膜UV聚合的影响

测量了10,12-二炔廿五碳酸单体及其聚合物的π-A曲线,Langmuir膜在10mN/m膜压10,12-二炔廿五碳酸下的紫外光聚合的分子占据面积曲线,可见光对Langmuir膜聚合的加速行为以及该聚合物的紫外可见光谱。并从聚合机理和反应中间体的电子态等角度对可见光在链增长中的作用加以讨论。     

侧链带有L-氨基酸乙酯的螺旋聚苯乙炔衍生物的手性识别能力研究

采用Rh(nbd)BPh4催化剂合成了3种侧链带有L-氨基酸乙酯的螺旋聚苯乙炔衍生物PPA-S-Phe、PPA-S-Leu和PPA-A-Leu,并将其涂覆在氨丙基硅胶上制备高效液相色谱(HPLC)手性固定相(CSP),研究其对7种对映体的手性识别能力.由于侧链手性基团或主链与手性基团之间的链接基团不同,PPA-S-Phe、PPA-S-Leu和PPA-A-Leu形成了不同的螺旋构象,并表现出对对映体不同的手性识别能力.PPA-S-Phe和PPA-S-Leu的主链与手性基团之间的链接基团均为磺酰胺基,侧链手性基团为L-亮氨酸乙酯的PPA-S-Leu的手性识别能力优于侧链手性基团为L-苯丙氨酸乙酯的PPA-S-Phe.PPA-S-Leu和PPA-A-Leu的侧链手性基团均为L-亮氨酸乙酯,以酰胺基为链接基团的PPA-A-Leu的手性识别能力明显优于以磺酰胺基为链接基团的PPA-S-Leu.螺旋聚苯乙炔主链与侧链手性基团之间的链接基团、侧链手性基团在手性识别中均发挥十分着重要作用.     

乙烯基二联苯单体的螺旋选择性自由基聚合

为了深入理解乙烯基二联苯单体自由基聚合过程中的手性传递,进行了手性单体(+)-2-[(S)-异丁氧羰基-5-(4′-己氧基苯基)苯乙烯、非手性单体2-丁氧羰基-5-(4′-己氧基苯基)苯乙烯的均聚反应及它们二者的共聚反应,探讨了聚合温度和溶剂性质对手性单体均聚物旋光活性、手性单体含量对共聚物旋光活性以及聚合反应溶剂的超分子手性对共聚物旋光活性的影响.研究发现,降低聚合温度、采用液晶性反应介质有利于得到旋光度大的聚合物;少量手性单体的引入即可诱导共聚物形成某一方向占优的螺旋构象,比旋光度随手性单体的含量增加呈线性增长;在胆甾相液晶中制备的非手性单体聚合物不具有光学活性.这些结果表明,该类乙烯基二联苯聚合物具有动态螺旋构象,其光学活性主要依赖于主链的立构规整度和侧基不对称原子的手性.     

螺旋聚苯乙炔膜的制备及其气体透过性能

利用非手性((nbd)Rh~+[η~6-(C_6 H_5)B~-(C_6 H_5)_3])为催化剂,将3种手性苯乙炔单体与非手性苯乙炔单体按照不同的比例进行共聚,得到了高分子量的可溶苯乙炔共聚物。将得到共聚物利用溶剂挥发法进行制膜,然后采用圆二色光谱仪(CD)对共聚物的二级结构进行测试。结果表明:该膜对CO_2有优先透过性能,共聚物主链上形成单手性螺旋结构。     

8,10-二炔二十五碳酸LB膜的聚合

Langmuir-Blodgett膜(LB膜)具有特殊的功能和生物活性,在现代高技术中有广泛的应用^[1]。本文合成了一个长链炔酸-8,10-二炔二十五碳酸,并研究其LB膜的聚合。     

铑催化剂的制备及其催化取代苯乙炔不对称聚合研究

以1,5-环辛二烯(cod)和2,5-降冰片二烯(nbd)为配体,合成了[Rh(cod)Cl]_2和[Rh(nbd)Cl]_2两种铑催化剂,利用红外吸收光谱、核磁共振对其进行测试表征,准确确定其结构,且[Rh(nbd)Cl]_2的收率高达79.4%。再用四种手性氨作为助催化剂和[Rh(cod)Cl]_2或[Rh(nbd)Cl]_2形成催化体系催化含十二烷基的取代苯乙炔单体(1)聚合,聚合物重均分子量最高达49.39万,按照螺旋选择聚合机理诱起了聚合物主链上的螺旋结构;此外,首次在无助催化剂的作用下,用[Rh(nbd)Cl]_2催化含有L-丙氨醚、L-缬氨醚、L-苯丙氨醚取代基的苯乙炔单体(2、3、4)进行不对称聚合,三种聚合物产率高且分子量大,通过自配位螺旋选择聚合诱起三大分子主链上的螺旋结构,所得聚合物Poly(2)、Poly(3)、Poly(4)的主链顺式构型所占百分比分别为70%、77%、77%,因此取得了比较理想的催化效果。     

手性乙烯基二联苯单体的合成与螺旋选择性聚合反应

设计、合成了一系列含有手性烷氧基末端的乙烯基二联苯单体,进行了普通自由基、原子转移自由基以及负离子聚合反应.所有单体中,只有手性烷氧基苯基位于乙烯基邻位的聚合物的比旋光度与其单体相比有比较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明可能形成了某一方向占优的螺旋构象.在所研究范围内,聚合条件和聚合物分子量对聚合物的旋光度没有明显的影响.比较负离子聚合和自由基聚合所获得聚合物的比旋光度发现,负离子聚合有利于增加聚合物螺旋链构象的完整性.切除能形成螺旋链的聚合物侧基上的手性烷氧基,所得到的聚合物虽然不含手性原子但依然表现出光学活性,说明其具有一定的手性记忆效应.     

1,4-丁炔二醇的均聚及与苯乙炔的共聚研究

<正> 炔类聚合物由于具有长链π体系的结构特点,理论上可作为结构型导电聚合物,这一领域的研究工作正在迅速展开。 1,4-丁炔二醇(BD)可用PdCl_2,ZnCl_2,(Ph_3P)_2PdCl_2等多种催化剂催化聚合,得到长链共轭的聚(1,4-丁炔二醇)(PBD)。苯乙炔(PA)可用热聚合,光聚合、电聚合、自由基聚合、等离子体聚合、催化聚合等聚合方法,得到长链共轭的聚苯乙炔     

TS单晶体及其聚合物PTS的介电和动态力学行为

<正> 聚丁二炔类宏观单晶体以其极大的尺寸,完整性和立体规整的共轭主链,为我们提供了一个准一维体系模型化合物。它们的电性能,非线性光学性能及形成聚合LB膜的能力等具有潜在的应用前景,近年来研究工作非常活跃。丁二炔类化合物中最能培养咸大晶体,从而研究得最多的是双(对甲苯磺酸)-2,4-己二炔-1,6-二醇酯(TS)及其聚合物PTS。我们先后测量过它们的热电势率、电导、膨胀系数、介电性能、光声效     

Supramolecular chirality formation of bisazobenzene-substituted polydiacetylene LB films

In order to investigate the exact effect of stereoregular packing of head group in the side chain on the helical structure formation of polydiacetylene backbone, the larger size of bisazobenzene-substituted diacetylene monomer, 4-(4-nitrophenylazo) azobenzene-10, 12-pentacosadiynoate (BNADA) was synthesized successfully. Owing to overcrowded packing of bisazobenzene chromophores, the BNADA Langmuir-Blodgett (LB) films showed macroscopic supramolecular chirality, although BNADA molecules were achiral. Under circularly polarized UV light (CPUL) irradiation, supramolecular helix of bisazobenzene chromophores always maintained, due to the large size and lower photo-isomerization rate of bisazeobenzene chromophores. While for polydiacetylene backbone, the helical direction of the polymer chain should be decided by the competition of the effect of stereoregular packing of bisazobenzene chromophores and the interaction between the CPUL and the diacetylene dimer.     

Metal ion modulated organization and function of the Langmuir-Blodgett films of amphiphilic diacetylene: photopolymerization, thermochromism, and supramolecular chirality

Some novel properties of organized molecular films of 10,12-tricosadiynoic acid (TDA), which were modulated by transition metal ions, were investigated. It was found that metal ions such as Cu(2+), Zn(2+), Ni(2+), Cd(2+), and Ag(+) in the subphase can greatly affect the monolayer formation of TDA and the properties of the subsequently deposited Langmuir-Blodgett (LB) films, particularly in the case of Ag(+), Zn(2+), and Cu(2+) ions. TDA LB film from the subphase containing Ag(+) ion could not be photopolymerized. It was suggested that both the strong chelating property to the carboxylate and the easy reduction of Ag(+) in the film disrupted the topochemical sequence of TDA and resulted in no polymerization in the film. Zinc ion coordinated TDA film could be photopolymerized into a blue polydiacetylene (PDA) film, which showed a reversible thermochromism between blue and purple color upon thermal stimulation. Fourier transform infrared spectra revealed the difference of the Zn(2+)-PDA film from those of the other ions, and the mechanism of the thermochromism was discussed. Copper ion coordinated TDA film could only be photopolymerized to a red PDA film, which showed supramolecular chirality although TDA itself was achiral. Atomic force microscopic measurements revealed the nanofiber structure in the Cu(2+)-PDA film. The supramolecular chirality of the Cu(2+)-PDA film was suggested to be due to the arrangement of the polymer backbone in a helical sense. Furthermore, it was found that the chiral assemblies from the achiral TDA molecules were very stable and the chirality could be kept even upon heating or treating with alkaline solution. While many synthetic efforts have been devoted to the functionalization of PDA films, we provided a simple method of modulating the organization and function of PDA films through metal ions.     

Photo‐controlled Hierarchical Assembly and Fusion of Coumarin‐containing Polydiacetylene Vesicles

Herein, we synthesize a coumarin‐substituted diacetylene monomer (CODA) and report the novel photo‐controlled reversible assembly and disassembly behavior of the polymerized CODA (PCODA) vesicles. The photo‐triggered dimerization and cleavage reactions of the coumarin groups within the surface of the adjacent PCODA vesicles can be utilized as the driving force to induce assembly and disassembly of PCODA vesicles. Moreover, the boundary of PCODA vesicles in the aggregates becomes more obscure when the irradiation time exceeds 30 min. Fusion occurs upon close docking of target membranes, driven by sufficient dimerization of the coumarin groups within the surface of PCODA vesicles.     

Chirality of photopolymerized organized supramolecular polydiacetylene films

Photopolymerized organized molecular films of polydiacetylene showed chirality although the monomeric amphiphilic diacetylene was achiral.     

Self-assembled spiral nanoarchitecture and supramolecular chirality in Langmuir-Blodgett films of an achiral amphiphilic barbituric acid

An amphiphilic barbituric acid derivative was found to form stable monolayers showing a clear phase transition at the air/water interface. It is interesting to find that the deposited Langmuir-Blodgett (LB) films of the compound showed circular dichroism (CD) although the molecule itself was achiral. AFM measurements on the transferred one-layer LB film revealed that spiral nanoarchitectures were formed. It was further found that the supramolecular chirality of the LB films was related to symmetry breaking at the interface. Hydrogen bonding and the pi-pi stacking between the neighboring molecules resulted in chiral fibers which formed the spiral structures. To the best of our knowledge, this is the first report on the chirality of the molecular assemblies and spiral nanostructures formed through the air/water interface by achiral molecules.     

Aminopyridine-containing supramolecular polydiacetylene: film formation,thermochromism and micropatterning

Polydiacetylenes (PDAs) are intrinsically supramolecular conjugated polymers that are prepared by polymerisation of self-assembled diacetylene (DA) supramolecules. Owing to their highly aggregating nature and insolubility, fabrication of transparent and homogeneous films has been challenging. By taking advantage of multiple hydrogen bonding, a transparent and thin PDA film was readily prepared with an aminopyridine-containing DA monomer. The PDA film displayed an irreversible blue-to-red colour change between 30 and 90 °C and a reversible red-to-yellow thermochromism between 30 and 190 °C. Micropatterned colour and fluorescence PDA images were readily fabricated by employing a simple photolithographic approach.     

Configurational rules governing the stereochemical control of chiral initiators in ring-opening polymerizations of heterocyclic monomers

Configuration rules were established for the polymerization of cyclic monomers with chiral initiators. The latter recognize in the monomer an asymmetric carbon of homochiral configuration. The chirality of the initiator is defined by the “local” asymmetry of the ligand and by the overall asymmetry of the particular arrangement of catalytic aggregates. Two types of process called “homosteric” and “antisteric,” which apply to the polymerization of resolvable monomers and achiral monomers of meso structure, are defined. These configurational rules have a general character and are verified in many examples of differently substituted three- or four-membered cyclic monomers (oxiranes, thiiranes, β-lactones). Stereoelective polymerization appears to be an original method for the determination of the absolute configuration of some monomers of unknown chirality.     

Regulation of supramolecular chirality and morphology of the LB film of achiral barbituric acid by amphiphilic matrix molecules

Previously, we have found that an achiral barbituric acid (BA) derivative, 5-(4-(N-methyl-N-hexadecylaminobenzylidene))-2,4,6-(1H,3H)-pyrimidinetrione (BAC16), could form molecular assemblies showing supramolecular chirality through the organization at the air/water interface. To acquire more knowledge of the formation mechanism of such supramolecular assemblies, some achiral molecules, such as stearic acid (SA), octadecylamine (ODA), and an analogue of BA without an alkyl chain, were mixed into the BAC16 system. The effects of these matrix molecules on the supramolecular chirality and surface morphologies of Lanmuir-Blodgett (LB) films were investigated. It was observed that, at a low molar ratio of the matrix molecules (below 10%), the chirality of the BAC16 assemblies could be maintained with only a reduction in the intensity. When the matrix fraction was increased, the supramolecular chirality of the mixed films disappeared. The addition of the matrix molecules can greatly change the surface morphologies of the mixed films. When SA was mixed with BAC16, the spiral nanofibers of BAC16 were changed to long nanofibers. When ODA was mixed, the hydrolytic cleavage reaction of BAC16 took place at the air/water interface and disordered spirals were obtained. When the analogous BA derivate without an alkyl chain was mixed, the phase-separating morphology was observed. These changes in the chirality and surface morphologies indicated firmly that the supramolecular chirality of BAC16 films were formed due to the cooperative arrangement of the molecules. A certain amount of matrix molecules will destroy the cooperative arrangement and thus the chirality.     

Helix-sense-selective polymerization of phenylacetylene having two hydroxy groups using a chiral catalytic system

We have found a simple and novel synthetic method for obtaining a chiral polymer from an achiral monomer by using a chiral catalytic system. The chirality of the polymer was caused only by a one-handed helical backbone, and the polymer had no other chiral structures in the side groups. In addition, the helical conformation was stable in solution by itself. This is the first example of helix-sense-selective polymerization of a substituted acetylene. The stability of the helicity was found to be caused by intramolecular hydrogen bonds.     

Enantioselective recognition between polydiacetylene nucleolipid monolayers and complementary oligonucleotides

A two-dimensional bio/synthetic hybrid system at the air-solution interface made of a polymerized diacetylene Langmuir film with nucleobase modified headgroups is presented. The polymerized film presents a crystalline array of nucleobases, capable of specific binding of complementary mononucleoside or oligonucleotide sequences. Mixed monolayers of the linear polyconjugated polydiacetylene (PDA) films derivatized with cytosine (10,12-pentacosadiyne-cytidyl, PDC) monomers and alcohol-terminated diacetylene lipid (10,12-pentacosadiynol, PDOH) at a 3:1 ratio (PDC 75%) were compressed and polymerized at the air-water interface with circular polarized light (CPL) or nonpolarized UV light. Here we report a grazing incidence X-ray diffraction (GIXD) investigation of PDC films polymerized to different chirality and hybridized with complementary ssDNA strands. We have demonstrated enantioselective interactions on synthetic structured interfaces produced by Langmuir surface compression followed by polymerization with circular polarized UV light (CPL). The left- and right-CPL polymerized light exhibit the same well-defined crystalline structure. The observed difference between left- and right-CPL polymerized PDC 75% Langmuir films compressed over the complementary mononucleotide guanosine or hybridized with fully complementary ssG(12)T(5) oligonucleotide in the subphase suggests that they are indeed enantiomeric structures, capable of enantioselective binding of their natural ligand, guanosine, solely as a result of surface induced asymmetry in "left" but not in "right" form. This observation may also be related to the intriguing question of chiral selection during the early period of "Origin of Life". We show that achiral compounds, as a result of irradiation with circular polarized light, can organize in chiral surface structures capable of amplification of biopolymer binding of particular handedness.