聚丙交酯立体寡聚物的合成及微结构分析

聚合物物理性质与其主链的立体结构密切相关,精确表征和定量分析聚合物微结构是该领域的重要研究内容之一。以具有确定分子量的立构规整性寡聚物为模型,对其核磁碳谱进行分析,是精确归属聚合物微观结构的关键。以L-丙交酯为起始原料,通过迭代发散/收敛方法,选择苄基和叔丁基二甲基硅基作为一对正交保护基,设计并合成了全同立构的八聚体、十聚体和十二聚体丙交酯寡聚物。通过分析这一系列模型化合物的碳谱,完成了全同聚丙交酯的微结构归属。结果表明：全同立构丙交酯寡聚物的羰基、次甲基和甲基的核磁碳谱信号分别对应δ 169.74、 69.15和16.78,并且随着重复单元数的增加,端位基团对寡聚物结构的影响逐渐变小,特征峰向丙交酯聚合物靠近。     

PS-PMMA嵌段共聚物/PMMA在选择性溶剂中的自组装行为

用动态光散射和透射电镜研究了嵌段共聚物聚苯乙烯-聚甲基丙烯酸甲酯(PS-b-PMMA)和其对应的均聚物聚甲基丙烯酸甲酯(PMMA)在选择性溶剂四氢呋喃/环己烷(THF/CYH)中的自组装行为.选择性溶剂对PS嵌段是良溶剂,对PMMA嵌段和均聚物PMMA是非良溶剂,实验结果表明,在适当的分子量及组成条件下,PS-PMMA/PMMA在选择性溶剂中形成了单分散的纳米胶束,均聚物PMMA与PMMA嵌段一同形成了胶束的核,通过控制均聚物PMMA的量可以在较大的范围内调整胶束的尺寸.     

寡聚物型A-D-A结构高效有机太阳能电池材料与器件

近年来有机太阳能电池发展迅速,活性层材料起到至关重要的作用.在众多活性层材料中,由于其化学结构确定、能级和吸收易调控以及其特殊的电子云分布等特点,寡聚物型A-D-A结构活性层材料成为领域研究的热点和重点.本文围绕A-D-A结构寡物聚型小分子光伏材料,首先对基于寡聚噻吩以及苯并[1,2-b:4,5-b']二噻吩的A-D-A给体材料进行系统的分析和讨论,对分子的结构-性能关系进行总结;然后讨论基于芴和苯并[1,2-b:4,5-b']二噻吩的两类A-D-A受体材料;总结了我们基于A-D-A分子叠层器件进展;最后,从能量转换效率、器件稳定性、柔性及大面积器件等方面对有机太阳能电池的发展进行了展望.     

聚甲基丙烯酸甲酯锥形量热仪标准物质候选物的均匀性和稳定性考察

介绍聚甲基丙烯酸甲酯锥形量热仪标准物质候选物的制备过程,对其配方设计、制备工艺、均匀性检验、稳定性考察进行了研究。采用锥形量热仪研究了炭黑的种类、炭黑的添加量、聚甲基丙烯酸甲酯的熔融指数对标准物质候选物热释放速率的影响。当添加质量分数0.5%的炭黑于熔融指数为16.0 g/(10 min)的聚甲基丙烯酸甲酯中时,该标准物质候选物具有良好的均匀性和稳定性。     

铟酞菁/聚甲基丙烯酸甲酯复合物固体光限幅器性能

将在溶液中表现出优良非线性光学和光限幅性能的铟酞菁及其二聚物嵌入到非光学活性的聚甲基丙烯酸甲酯(PMMA)中, 用传统的旋转涂膜法制备得到具有较高光学质量的复合物薄膜, 用开孔Z-扫描方法在532 nm 处研究了复合物薄膜材料的线性光学和非线性光学性能. 结果表明, 无论是铟酞菁单体还是轴向氧桥联的铟酞菁二聚物, 其PMMA复合材料的光限幅性能均显著优于相应的酞菁分子在溶液中的光限幅性能.     

聚(苯乙烯-甲基丙烯酸甲酯-砜)的合成及其紫外光降解

本文研究了苯乙烯、甲基丙烯酸甲酯、二氧化硫三元共聚合反应。其产品的特性用元素分析,红外和紫外光谱,NMR,DSC,TG等进行了详细地表征。该产品只有一个玻璃化温度132.5℃,故认为它是一个共聚物——聚(苯乙烯-甲基丙烯酸甲酯-砜),而不是一个均聚物的混合物。将聚(苯乙烯-砜)、聚(苯乙烯-甲基丙烯酸甲酯-砜)、聚甲基丙烯酸甲酯分别加热时,它们分别在252℃、272℃、282℃开始分解。当这些产品的溶液用三支30瓦的低压汞灯辐照时,聚(苯乙烯-砜)溶液的粘度下降速度比聚(苯乙烯-甲基丙烯酸甲酯-砜)快,聚甲基丙烯酸甲酯最慢。     

微量聚四氢呋喃-聚甲基丙烯酸甲酯/聚四氢呋喃共混体系稀固体溶液中共聚物胶束的抑制成核作用

本工作将Leibler、Whitmore和Mayes等近期关于非晶嵌段共聚物共混体系胶束理论应用于结晶嵌段共聚物共混体系的熔融态,对聚甲基丙烯酸甲酯-聚四氢呋喃两嵌段共聚物与聚四氢呋喃均聚物共混体系的结晶行为进行了研究.结果表明,很低的共聚物浓度(如1％),其胶束在共混体系的结晶过程中即可显著地起到抑制成核的作用.这对改善结晶均聚物的形态及性能有一定的应用价值.     

微量聚四氢呋喃-聚甲基丙烯酸甲酯/聚四氢呋喃共混体系稀固体溶液中共聚物胶束的抑制成核作用

 本工作将Leibler、Whitmore和Mayes等近期关于非晶嵌段共聚物共混体系胶束理论应用于结晶嵌段共聚物共混体系的熔融态,对聚甲基丙烯酸甲酯-聚四氢呋喃两嵌段共聚物与聚四氢呋喃均聚物共混体系的结晶行为进行了研究.结果表明,很低的共聚物浓度(如1％),其胶束在共混体系的结晶过程中即可显著地起到抑制成核的作用.这对改善结晶均聚物的形态及性能有一定的应用价值.     

纳米CeO2的制备及其在PMMA中的分散

制备得到一Ce-三乙醇胺(TEA)配合物,以该配合物作为制备纳米CeO2的前驱体.将甲基丙烯酸甲酯(MMA)分散于配合物水溶液中,然后在同一反应器中依次进行水解、乳液聚合反应,得到纳米CeO2分散于聚甲基丙烯酸甲酯(PMMA)基质中的复合物粉末.分别运用XRD,TEM,TGA和DSC对复合物进行了表征.结果表明,纳米CeO2粒径为3～5nm,其均匀分散于聚合物基质中且单分散性良好.聚合物的热稳定性和玻璃化温度得到提高.     

寡聚表面活性剂的合成及其聚集行为的研究

寡聚表面活性剂是由2个或2个以上单头单链的表面活性剂在头基处或靠近头基处由连接基团通过化学键连接而成的二聚、三聚、四聚乃至更高寡聚度的分子.Gemini表面活性剂(二聚表面活性剂)是最简单,也是最早被发现的寡聚表面活性剂,已经被大量报道.已有综述很好地总结了Gemini表面活性剂的物理化学性质.本文主要综述三聚及三聚以上寡聚表面活性剂的研究进展,包括寡聚表面活性剂的合成和结构、表/界面性质以及溶液中的聚集行为等,以期使研究者比较全面地认识寡聚表面活性剂领域的研究进展.     

A Scalable and High‐Yield Strategy for the Synthesis of Sequence‐Defined Macromolecules

The efficient synthesis of a sequence‐defined decamer, its characterization, and its straightforward dimerization through self‐metathesis are described. For this purpose, a monoprotected AB monomer was designed and used to synthesize a decamer bearing ten different and selectable side chains by iterative Passerini three‐component reaction (P‐3CR) and subsequent deprotection. The highly efficient procedure provided excellent yields and allows for the multigram‐scale synthesis of such perfectly defined macromolecules. An olefin was introduced at the end of the synthesis, allowing the self‐metathesis reaction of the resulting decamer to provide a sequence‐defined 20‐mer with a molecular weight of 7046.40 g mol^?1. The obtained oligomers were carefully characterized by NMR and IR spectroscopy, GPC and GPC coupled to ESI‐MS, and mass spectrometry (FAB and orbitrap ESI‐MS).     

Modeling of aqueous poly(oxyethylene) solutions. 2. Mesoscale simulations

We extend our work on aqueous solutions of poly(oxyethylene) oligomers H-(CH2-O-CH2)n -H (POEn). On the basis of atomistic simulations of trimer and decamer solutions (first part of this series of papers), different sets of coarse-grained implicit-solvent potentials have been constructed using the iterative Boltzmann inversion technique. The comparison of structures obtained from coarse-grained simulations (gyration radii, end-to-end distances, radial distribution functions) with atomistic reference simulations and experiments shows that the state-specific potentials are transferable both to a wide concentration range, if the same molecule size is considered, and to at least 2 orders of magnitude larger molecules (in terms of molecular mass). Comparing the performance of different mesoscale potentials, we find different applicability ranges in terms of molecule sizes. The experimental gyration radii for chains comprising up to 1500 monomers are reproduced almost quantitatively by the decamer-fitted potentials with dihedral interactions included. The trimer-fitted potentials reproduce experimental chain dimensions of up to some hundred monomers but seem to become metastable beyond a certain chain length, as we evidenced some chain collapses. Relaxation of large-scale features is 1-2 orders of magnitude faster in the mesoscale simulations than in the atomistic simulations. The diffusion behavior in dependence of concentration is captured correctly when the decamer potential is applied to the decamer itself. For all other chain lengths, we find that time mapping from coarse-grained to atomistic trajectories has to be determined separately for each concentration. Overall, diffusion is 1-2 orders of magnitude faster on the mesoscale, depending considerably on the Lowe-Andersen thermostat parameters. The CG simulations provide an overall speed-up of about 3 orders of magnitude.     

Synthesis of a C-linked glycosylated thymine-based PNA monomer and its incorporation into a PNA oligomer

Backbone modification of peptide nucleic acids (PNAs) by glycosylation has been shown to enhance selective biodistribution and cellular targeting of PNA oligomers based on sugar and cell surface lectin interactions. Here we report the synthesis of a new backbone-glycosylated thymine-based PNA monomer (T(gal)). The sugar residue was attached to the backbone of PNA via a stable carbon-carbon linkage between the sugar and the PNA monomers. Also, incorporation of the modified monomer into a PNA decamer (H-Ala(gal)-G-G-G-T(gal)-C-A-G-C-T(gal)-T-Lys-NH2) was successfully performed. Melting temperature (UV-Tm) of the modified PNA against the complementary DNA was only slightly lower than unmodified PNA.     

Monitoring oligomer formation from self-aggregating amylin peptides using ESI-IMS-MS

Amyloid diseases are a serious cause for concern world-wide. To understand the mechanism of formation of the fibrillar structures associated with such disorders, it is necessary to study the progression from soluble protein or peptide monomer through an array of oligomers to the final, insoluble, fibrils. The protein IAPP is found in vivo in the form of insoluble amyloid deposits in the pancreatic islets of diabetes type II sufferers. Here, we have studied the in vitro self-aggregation of three fibril-forming peptides from the amyloidogenic core of IAPP. Using electrospray ionization—mass spectrometry coupled with ion mobility spectrometry, the mass and cross-sectional area of each oligomer present in the heterogeneous assembly mixtures can be determined individually in a single, rapid experiment over time. For the three peptides studied, oligomers ≤20-mer were characterized. Conversely, no oligomers higher than a dimer were detected for a non-assembling peptide control. The rate in which the cross-sectional area of the oligomers increases with increasing number of peptide sub-units indicates that assembly for the amyloid-forming peptides proceeds in a linear fashion until an oligomer of a certain size is attained. After this, a step increase in cross-sectional area occurs for the next higher-order oligomer. This behaviour can be explained by molecular modelling of singly, doubly, triply and quadruply stacked β-stranded structures. Using one peptide as an example, the cross-sectional areas of the lower order oligomers (dimer to pentamer) were found to be consistent with a single β-sheet model, whereas the higher order oligomers were consistent with double-stranded (hexamer to decamer oligomers), triply-stranded (11-mers to 15-mers) and quadruply-stranded (16-mers to 20-mers) β-sheet models.     

Cryoscopy on sulfuric acid solutions of a heterocyclic polymer (BBB) and related compounds

Cryoscopic measurements have been carried out on solutions in sulfuric acid of a heterocyclic polymer, its monomers, and certain of its oligomers. The polymer, BBB, is prepared by the polycondensation of 1,4,5,8-naphthalenetetracarboxylic acid (NTC) with 3,3′-diaminobenzidine (DAB). The results show that the polymer, its oligomers and one of its monomers, DAB, are all extensively protonated in sulfuric acid, whereas its other monomer is not. The degree of protonation appears to be greater for the polymer than for its low molecular weight oligomers.     

Calorimetric study of mixtures of butyl methacrylate oligomers with methanol

Heats of mixing of methanol with butyl isobutyrate and with oligomers of butyl methacrylate (monomer to tetramer) having a butoxyl group on one chain end have been measured. To discuss the effect of hydrogen bonding on the heat values, it is appropriate to correlate the heat per mole of binding sites with the binding site fraction. This dependence can be described by a single curve for all oligomers studied, in contrast to the results obtained in a previous paper for the same oligomers with chloroform. This fact suggests that the binding parameters for methanol are not influenced by the degree of polymerization.     

Pyrrolidine PNA: a novel conformationally restricted PNA analogue

[reaction:see text] A new conformationally restricted PNA adenine monomer has been synthesized in 13 steps from cis-4-hydroxy-D-proline. A fully modified adenine decamer displayed improved binding affinity toward complementary DNA and RNA oligonucleotides as compared to that of the parent PNA adenine decamer.     

Radical polymerization of tetrafluoroethylene that forms a colloid solution and gel of oligomers

As the concentration of tetrafluoroethylene (TFE) in the solvent increases, its polymerization is shown to be accompanied by a transformation of the resulting homogeneous solution of oligomers into a colloid one, which then transforms into gel. The micron-sized colloid particles consist of oligomers and solvent molecules, whose number per TFE unit in the oligomer decreases from 15–20 at the threshold of dense phase formation to 4–6 in a gel. A kinetic model of polymerization was suggested. In this model, the chain propagation is limited by monomer diffusion to the growing macroradical and the chain transfer (oligomer formation and regeneration of the prime radical) is limited by the reaction of the growing macroradical with the solvent molecule. The model that allows for the decrease in the diffusion coefficients with increasing of the oligomer chain length and their local concentration leads to a spatially inhomogeneous molecular mass distribution, with long oligomers accumulated in the vicinity of the macroradical and short ones in the distant zone. The formation of colloid particles and gel occurs when the concentration of long oligomers shaped as rigid rods exceeds the critical value for the dense phase formation and the percolation threshold, respectively. The transition from the initial spatial distribution to the equilibrium distribution described by the phase diagram was considered using the model of viscoelastic separation so that phases retain spatial continuity.     

芳香环状低聚物组分分布与单体结构关系的研究

根据Jacoson-Stockmayer(J-S)环化理论,应用基质辅助激光解吸离子化飞行时间质谱(MAIDL-TOFMS),对一系列芳香环状低聚物组分分布进行分析,研究了芳香环状低聚物的组分分布与单体结构的关系,结果表明,在芳香聚酯、聚膦酸酯及芳香聚醚环状低聚物系列中,Incn与Inn呈良好的线性关系,符合J-S理论分布,在环状聚酯及聚膦酸酯系列中,低聚物的组分分布受双酚单体的中心键角影响,单体的中心键角在100°～120°之间,其中心键角愈小,γ值愈大,而在聚醚系列中,在固定一种单体的前提下,环化物的组分分布受另一单体键角的影响与环状聚酯和聚膦酸酯相一致.     

Synthesis and physical investigation of donor-donor and acceptor-acceptor end-functionalized monodisperse poly(triacetylene) oligomers

Two series of monodisperse, terminally donor-donor [D-D, D=4-(dimethylamino)phenyl] and acceptor-acceptor [A-A, A=4-nitrophenyl] functionalized poly(triacetylene) (PTA) oligomers ranging from monomer to hexamer were synthesized by oxidative Hay oligomerization under end-capping conditions. The corresponding D-D and A-A end-substituted polymers with an average degree of polymerization (DP) of n approximately 18 and n approximately 12, respectively, were also prepared and served as reference points for the corresponding infinitely long polymers. These terminally functionalized PTA oligomers and polymers are yellow- to orange-colored compounds, displaying excellent solubility in aprotic solvents with melting points above 200 degrees C for the hexamers. For the 4-(dimethylamino)phenyl substituted compounds, a consistent first oxidation potential around +0.42 V versus Fc/Fc+ (ferrocene/ferricinium) was observed, whereas the 4-nitrophenyl functionalized systems underwent a reversible reductive two-electron transfer around -1.40V versus Fc/Fc+. The nature of the end-groups has a dramatic influence on the electronic absorption spectra. Saturation of the linear optical properties in the D-D series occurs at significantly shorter chain-length [effective conjugation length (ECL) of n approximately 4 monomer units] than in the A-A substituted or the previously reported Me3Si- and Et3Si-end-capped PTA oligomer series (ECL: n approximately 10 monomer units). Similar observations with respect to the ECL were made by measurement of the Raman-active v(C triple bound C) stretches. Third-harmonic generation (THG) and degenerate four-wave mixing (DFWM) experiments showed that shorter oligomers of terminally D-D or A-A functionalized PTAs display higher second hyperpolarizabilities gamma than the corresponding R3Si-end-capped series (R=alkyl). Moreover, they disclose a distinct peak of the nonlinearity per monomer unit at intermediate backbone lengths. In THG experiments, the second hyperpolarizabilities for long D/A-functionalized PTA oligomers attained the same saturation values as observed for the corresponding R3Si-end-capped rods. The nonlinearities measured by DFWM of the D-D and A-A substituted PTAs were found to be larger than for the silylated ones, which can be explained by the closeness of the two-photon resonance.