How the Aggregates Determine Bound Rubber Models in Silicone Rubber? A Contrast Matching Neutron Scattering Study

The correlation between aggregates and bound rubber structures in silicone rubbers(S(phr)) with various silica fractions(ΦSi) has been investigated by contrast matching small-angle neutron scattering(SANS), swelling kinetics, and low-field nuclear magnetic resonance(NMR).Mixed solvents with deuterated cyclohexane fractions of 4.9% and 53.7% were chosen to match the scattering length densities of the matrix(SMP(phr)) and the filler(SMS(phr)), respectively. All the data consistently suggest that:(i) There is a critical threshold ΦSic between 10 and 30 phr;below ΦSic, the isolated aggregates are dominant, while beyond ΦSic, some rubber fraction is trapped among the agglomerate;(ii) ΦSiindependent thicknesses around 7.5 nm(NMR) and 8.6 nm(SANS) suggest that the bound rubber formation is determined by inherent properties of the components, and the power-law around 4.2 suggests an exponential changed gradient density of the bound rubber;(iii) SMS(80) presents a bicontinuous bound rubber with three characteristic lengths of 41, 100, and 234 nm. The expanded correlation length, a 20 nm smaller aggregate sizes suggest that such existent bicontinuous network in dry samples with less ΦSi is kind of impacted by swelling. With the obtained bound rubber models, the reinforcing mechanism of filled silicone rubber is elucidated.     

Thienylmethylene Oxindole Based Conjugated Polymers via Direct Arylation Polymerization and Their Electrochromic Properties

Direct arylation methods have been used to polymerize thienylmethylene oxindoles(TEIs) and 3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2 H-thieno-[3,4-b][1,4]dioxepin(ProDOT) for new donor-acceptor conjugated polymers. The polymers exhibited blue hues in neutralstate with distinct color-to-transmissive reversible electrochromic switching under applied potentials from 0 V to +1.5 V, and showed high coloration efficiencies(436-438 cm~2·C~(-1)) in near-infrared regions with high switching speeds around 1-2 s under ambient conditions.     

Surface-assembled highly flexible Na_3(VOPO_4)_2F nanocube cathode for high-rate binder-free Na-ion batteries

Flexible Na-ion storage cathodes are still very few due to the challenge in achieving both reliable mechanical flexibility and excellent electrochemical performances.Herein,a new type of flexible Na_3(VOPO_4)_2F cathode with nanocubes tightly assembled on carbon cloth is fabricated by a facile solvothe rmal method for the first time.The cathode is able to exhibit superior rate capability and stable cycling performa nce up to 1000 cycles,due to the surface-assembling of crystalline nanocubes on carbon fibers.In addition,it shows good mechanical flexibility,nearly no capacity decay is observed after continuous bending of 500 times.With this novel cathode and a directly-grown Na_2Ti_2O_5 anode,a fully binde r-free Na-ion battery is assembled.It can deliver a high wo rking voltage and increased gravimetric energy/power densities(maximum values:220.2 Wh/kg;5674,7 W/kg),and can power a LED indicator at bending angles fro m 0° to 180°.     

Fabrication and characteristics of self‐aggregation nanoparticles used for conformance control treatment

In order to alleviate the contradiction between injectability of the profile control agent and its profile control performance, a novel core‐shell heterogeneous structure colloidal particles (CSA) were synthesized, and the mechanism of self‐aggregation plugging was proposed. Cross‐linking inside the nanoparticles and chain‐growth polymerization via capturing acrylamide in the aqueous phase result in the formation of core‐shell heterogeneous structures as proved by TEM observation and XPS analysis. Moreover, CSA nanoparticles exhibit good hydrophilic properties, outstanding thermal stability and limited expansion capacity. Effects of different metal cations and surface group on the self‐aggregation time of CSA nanoparticles were systematically studied. Results showed that divalent cations contributed to more significant aggregation of CSA nanoparticles in comparison to monovalent cations. The increasing cations concentration and valency decreased the thickness of electric double layer, which lead to a decrease in the zeta potential. Core flooding test shows that the injection of nanoparticles which diameter is much smaller that of pore‐throats into the target reservoir can not only successfully enter the depth of porous media, but also effectively block the high permeability areas by the formation of self‐aggregation particle clusters. This study provides a new method for the equilibrium between nanoparticles injectivity and in‐depth profile control of nanoparticles.     

基于配位键和次级作用力协同效应构建的两个Co (Ⅱ)/Cd (Ⅱ)配位超分子网络的结构及荧光性质

以3-羧基-1-（4-羧基苄基）吡啶溴酸盐（（H₂L） Br）分别与Co （Ⅱ）和Cd （Ⅱ）金属盐反应,制备了2个配合物[Co （L）₂（H₂O）₄]·2H₂O （1）和[Cd （L）2（H₂O）]·3H₂O （2）。晶体结构分析揭示配合物1是一个中性的单核配合物,其拥有丰富的并可作为超分子合成子的氢键和π-π作用力组分。对于1,单核的[Co （L）₂（H₂O）₄]实体首先通过氢键形成具有孔道结构的二维层,该二维层进一步通过π-π堆积作用形成三维的多孔配位超分子。配合物2具有一维的“之”字形链状结构,该链通过悬挂的L配体之间的π-π作用力形成一维梯形结构。该一维梯形链进一步通过梯形边之间存在的2种π-π堆积作用形成波浪状的二维层。二维层进一步通过8种类型的O—H…O氢键连接形成三维的超分子结构。根据拓扑的观点,配合物2中的一维链采取胶合板排列。此外,配合物2显示了强的紫外荧光发射,平均寿命为2.54 ns。     

柔性双咪唑配体导向的Co(Ⅱ)⁃戊二酸金属有机骨架材料的合成、结构和性能

在水热条件下合成并表征了2例基于柔性配体构筑的Co(Ⅱ)-MOFs:{[Co(glu)(bimb)]·4H2O}n (1),[Co(glu)(bix)0.5]n (2)(H2glu=戊二酸;bimb=1,4-双(咪唑-1-基)-丁烷;bix=1,4-双(咪唑-1-基-亚甲基)-苯)。配合物1显示非穿插的(4,4)-菱形网格,通过层间氢键和π…π作用拓展为三维超分子结构。加热失水后1的结构不可逆地降解。配合物2呈现典型的柱-层状三维结构,其拓扑符号为41263,中心Co(Ⅱ)离子采用四方锥构型。此外,性质研究表明:配合物1在水溶液中对染料甲基橙具有显著的吸附活性,配合物2表现出弱的反铁磁行为。     

热活化延迟荧光蓝光小分子取代基效应的研究进展

近年来, 作为第三代有机发光二极管(organic light-emitting diodes, OLED)发光材料的热活化延迟荧光(thermally activated delayed fluorescence, TADF)材料受到了学术界和产业界的广泛关注. TADF分子由于其单线态与三线态之间的能级差较小, 三线态激子可以被环境热活化而通过反系间窜越上转换至单线态, 理论上可实现100%的激子利用率, 从而使得OLED器件外量子效率显著提高. TADF材料被认为是突破高效稳定有机电致蓝光发射瓶颈的潜在解决方案. 一般, TADF分子为含有电子给体(donor, D)和电子受体(acceptor, A)的纯有机推拉电子体系. 通过改变给体单元和受体单元的结构、数量和取代基及其位置可以有效调节TADF分子的单线态-三线态能级差、前线轨道分布、聚集态结构、电致发光颜色及其性能. 同时取代基在调控给、受体单元的推拉电子能力及TADF材料的分子构型、聚集态结构和稳定性等物化特性方面扮演着非常重要的角色. 本综述分别对D-A型和多重共振型TADF蓝光分子的取代基效应进行了综述, 以期为高效稳定的蓝光TADF分子的设计合成提供有效借鉴.     

CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest

In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO₂ responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO₂,1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO₂ and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.     

碳点的性质及其在生物传感器领域的应用

碳点(carbon dots,CDs)作为一种具有优良生物相容性、低毒性和表面功能可调的新型碳基纳米材料,在生物传感领域具有极大的应用潜力.本文对碳点的生物效应、发光性质及其发光机理进行了简述,并根据传感机制的不同,将CDs在生物传感领域的应用分为荧光(fluorescence,FL)传感器、电致发光(electrochemiluminescence,ECL)传感器以及化学发光(chemiluminescence,CL)传感器三类进行综述.最后分析了CDs目前在生物传感器领域应用中存在的问题,并对其发展进行了展望.     

手性配体在钯催化不对称碳氢键活化反应中的应用

目前,手性配体辅助钯催化的区域和对映选择性碳氢键活化是过渡金属催化的前沿领域.在过去的十年中,它作为一种越来越重要的合成工具,用于合成含有各种不对称元素(中心手性、轴手性和平面手性)的手性分子,也是快速构建各种碳碳键和碳杂原子键的最有效方法之一.本文介绍了一些典型手性配体在钯催化不对称sp²和sp³碳氢键活化/官能团化反应中的应用,如单齿配体亚磷酰胺、手性磷酸(CPAs)和双功能氮端单保护的氨基酸(MPAAs)配体;探讨了这些手性配体辅助催化反应的创新性和特点,在理清这一研究领域发展脉络的同时,展望了未来研究工作的方向.此外,本文还介绍了这一不对称合成策略在天然产物、药物分子全合成中的应用.