Novel Bis-arylPheDOT Synthons for Electrochromic Polymers

Two terthiophenes incorporating the synthon 3,4-(1,2-phenylenedioxy)thiophene (PheDOT) have been developed. Specifically, 2,5-bisthienyl-3,4-(1,2-phenylenedioxy)thiophene (BTh-PheDOT 1) and 2,5-bisethylenedioxythienyl-3,4-(1,2-phenylenedioxy)thiophene (BEDOT-PheDOT 2) were electropolymerized to form electroactive polymer films (P1 and P2) that switched between two highly colored states with the more electron-rich EDOT derivative P2 observed to switch at a lower potential. Additionally, both P1 and P2 displayed moderate to low optical bandgaps of 1.8 and 1.6 eV, respectively. Crystal structures of BTh-PheDOT showed the monomer to be nearly planar with π -stacking observable between monomers. These findings demonstrate the potential of PheDOT as an electroactive synthon for the formation of well-ordered systems.     

Synthesis and Characterization of Novel Liquid Crystalline Epoxides with Lateral Substituent Showing Imposing Shape Memory Properties

In this work, a series of novel shape memory liquid crystalline (LC) epoxides with lateral substituent were prepared and characterized. Dynamic mechanical analysis (DMA) and shape memory testing were used to investigate on the thermo-mechanical properties and shape memory effects of prepared samples. The results showed that the modulus in the rubbery region (E_R ) decreased as the length of lateral alkyl group increases. And more than 95% of the deformation can be fixed as the sample was cooled down below the glass transition temperature (T_g), which was determined by differential scanning calorimetry (DSC) measurement, and can be recovered completely as heating. Effects of the curing agent and substituent on the shape memory behavior were also studied. We found that LC epoxides cured by aromatic diamine have a higher recovery speed. The recovering speeds of the shape memory decreased as the length of lateral alkyl group inscreased. The local ordered structures and the lateral substituent played an important role in shape memory effects.     

Cyclopentadienyl(iron)arene-bis-(p-N,N-dimethylaminobenzylidene)-cyclopentanone Photoinitiated Polymerization of Methyl Methacrylate and Styrene

Abstract

Polymerization of methyl methacrylate and styrene can be effectively photoinitiated by a binary photoinitiator system consisting of cyclopentadienyl(iron)arene hexafluorophosphonate salt and bis(p-N, N-dimethylaminobenzylidene)cyclopentanone in the spectral range of 400–500 nm. The amine-type radical formed from the exciplex of the binary photoinitiator system is probably responsible for the radical polymerization of vinyl monomers. A probable mechanism of initiation of polymerization is discussed.     

Multi-responsive cyclodextrin vesicles assembled by ‘supramolecular bola-amphiphiles’

Multi-responsive cyclodextrin vesicles (CDVs) self-assembled by ‘supramolecular bola-amphiphiles’, consisting of a guest (N,N′-bis(ferrocenylmethylene)-diaminohexane, 1) and a host (γ-hydroxybutyric-β-cyclodextrin, γ-HB-β-CD), were prepared and investigated for the first time. The morphologies and sizes of these novel vesicles in water were observed by transmission electron microscopy (TEM), scanning electron microscopy and dynamic light scattering. The effects of the host–guest ratio, the concentration and the solvent composition are also discussed. The host–guest interactions, complex stoichiometry and structures of 1·γ-HB-β-CD in water were investigated by cyclic voltammetry, UV and NMR spectroscopy. According to the complex stoichiometry, TEM observations and Chem3D estimation, the ‘supramolecular bola-amphiphiles’, made from 1·γ-HB-β-CD and assumed for the first time, formed the membranes of the CDVs. The CDV system was responsive to an oxidising agent, which is the first report on redox-responsive systems in this field. The CDVs are also responsive to pH and the presence of metal ions, such that they disassemble upon addition of acetic acid or Cu²⁺ ions, providing possible routes to drug delivery systems.     

Lanthanide‐Catalyzed Selective Addition of Diethyl Phosphite to Chalcones

Lanthanide‐catalyzed addition of diethyl phosphite with chalcones was achieved under mild conditions. The reaction exhibited good product selectivity using different catalysts. γ‐Oxophosphonates were obtained in high yields in the reactions catalyzed by Yb(OAr)₃(THF)₂, while those catalyzed by [(Me₃Si)₂N]₃La(μ‐Cl)Li(THF)₃ afforded 1,2‐oxaphospholane‐5‐phosphonates as the main products in moderate to good yields. This methodology provides facile and practical approaches to the corresponding organophosphorus compounds with biological interest.     

Coarse-graining Calcium Dynamics on Stochastic Reaction-diffusion Lattice Model

We develop a coarse grained (CG) approach for efficiently simulating calcium dynamics in the endoplasmic reticulum membrane based on a fine stochastic lattice gas model. By grouping neighboring microscopic sites together into CG cells and deriving CG reaction rates using local mean field approximation, we perform CG kinetic Monte Carlo (kMC) simulations and find the results of CG-kMC simulations are in excellent agreement with that of the microscopic ones. Strikingly, there is an appropriate range of coarse proportion m, corresponding to the minimal deviation of the phase transition point compared to the microscopic one. For fixed m, the critical point increases monotonously as the system size increases, especially, there exists scaling law between the deviations of the phase transition point and the system size. Moreover, the CG approach provides significantly faster Monte Carlo simulations which are easy to implement and are directly related to the microscopics, so that one can study the system size effects at the cost of reasonable computational time.     

Two lanthanum(III) complexes containing η2‐pyrazolate and η2‐1,2,4‐triazolate ligands: intramolecular C—H...N/O interactions and coordination geometries

The lanthanum(III) complexes tris(3,5‐diphenylpyrazolato‐κ²N,N′)tris(tetrahydrofuran‐κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C₁₅H₁₁N₂)₃(C₄H₈O)₃]·C₄H₈O, (I), and tris(3,5‐diphenyl‐1,2,4‐triazolato‐κ²N¹,N²)tris(tetrahydrofuran‐κO)lanthanum(III), [La(C₁₄H₁₀N₃)₃(C₄H₈O)₃], (II), both contain La^III atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer‐distorted octahedral geometry, while complex (II) has a fac‐distorted configuration. The difference in the coordination geometries and the existence of asymmetric La—N bonding in the two complexes is associated with intramolecular C—H...N/O interactions between the ligands.     

NO2在黑碳表面的非均相反应

HONO是大气中OH自由基的重要来源,NO2在黑碳表面可反应生成HONO,因此NO2在黑碳表面的非均相反应引起了人们的关注。目前不同研究小组测量的摄取系数可相差7个数量级,选择不同的摄取系数去评估非均相反应的重要性将得到完全不同的结果。本文在深入分析NO2在黑碳表面反应机理的基础上,从反应体系、黑碳表面性质、反应条件等角度对不同小组测量的摄取系数存在差异的原因进行了分析,为模式中摄取系数的选取提供了依据。     

pH响应性P(MMA-co-MAA-co-HEMA)微凝胶的制备及其性能

利用预乳化乳液法制备了不同单体配比的聚(甲基丙烯酸甲酯-co-甲基丙烯酸-co-甲基丙烯酸羟乙酯)(P(MMA-co-MAA-co-HEMA))微凝胶分散液;采用透射电子显微镜、动态光散射仪研究了微凝胶的微观形态、粒径大小及其溶胀率;利用试管倒转法对微凝胶分散液的凝胶化相转变行为进行了研究,借助椎板流变仪考察了所形成胶态凝胶的储能模量与单体配比、微凝胶分散液浓度和温度的关系.结果表明,所制备的微凝胶的数均粒径为90 nm左右,当MMA与MAA的投料质量不变时,随着HEMA含量的增加,分散液凝胶化所需的临界最小浓度增大,临界最大pH值减小,胶态凝胶的储能模量增加.当保持单体MMA与HEMA的投料质量不变时,随着单体MAA投料质量的增多,微凝胶的数均粒径和溶胀率增大,胶态凝胶的储能模量先升高后降低;当MAA占单体总摩尔数的25%时,浓度为15 wt%的微凝胶分散液在扫描频率为100 rad/s时,胶态凝胶的储能模量最高可达2×104Pa.这类微凝胶分散液在组织工程支架材料方面有潜在的应用价值.     

荧光增白剂28的光漂白特性研究

荧光增白剂28(F-28)为欧盟标准EN 648-2006《与食品接触的纸和纸板-荧光增白剂牢度的测定》中判断食品接触材料所含荧光增白剂是否向食品中迁移的标样。我们发现,在规定的波长365nm紫外光激发下,F-28所制成的标样会出现光漂白现象。因此,本文对F-28的光漂白特性进行研究。结果表明,紫外辐照时间为60s时,四级(3mg/L)、三级(8mg/L)、二级(31mg/L)、一级(125mg/L)滤纸和玻纤的最大荧光值衰减率分别为0.16%、0.29%、0.92%、0.44%和2.59%、1.99%、0.49%、3.14%;当辐照时间延长到1800 s时,最大荧光值衰减率分别增加为4.67%、4.22%、5.51%、2.75%和35.37%、39.78%、28.09%、39.38%。因此,在对食品接触材料是否含有荧光增白剂以及是否迁移的测试中,必须考虑光漂白因素。同时,滤纸作为迁移实验载体,在降低光漂白和稳定性方面比玻纤更具优势。