过渡金属的液晶基元配合物纳米胶束的自组装

以异烟酸和溴代十二烷为原料合成液晶基元异烟酸十二烷基酯,在水和无水乙醇混合反应体系中,室温下分别与Pd(Ⅱ)、Cu(Ⅱ)和Ni(Ⅱ)过渡金属按4∶1的摩尔比混合反应,通过自组装形成配合物。透射电镜形态观测表明,配合物之间借助超分子力和配体的液晶性协同作用构建成25～40nm左右的棒状形态的纳米胶束。并利用红外光谱,紫外可见吸收光谱,荧光光谱等手段对其结构和性质进行了表征。     

Porous polyurethane film fabricated via the breath figure approach for sustained drug release

The breath figure (BF) method is an effective process for fabricating porous polymeric films. In this study, we fabricated porous polymer films from thermoplastic polyurethane (PU) through static BF with CHCl₃ as a solvent under 55–80% relative humidity. The porous PU films were prepared within various pore structures and sizes, which were adjustable, depending on the fabrication conditions. The humidity and exposure time were examined as variable parameters affecting the surface morphology, wettability, and cytotoxicity. Atorvastatin calcium, a hyperlipidemic agent, was loaded into the porous films during the casting process, and the drug-loading and drug-releasing behaviors of the porous PU membranes were evaluated. Approximately 60–80% of the drug was released in 14 days. The films exhibited sustained drug-release performances because of the hydrophobicity and nonbiodegradable nature of PU for perivascular drug administration. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47658.     

Covalently Assembled Dipeptide Nanoparticles with Adjustable Fluorescence Emission for Multicolor Bioimaging

Peptide self-assembly, inspired by the naturally occurring fabrication principle, remains the most attractive in constructing fluorescent nanoagents towards bioimaging. However, the noncovalent interactions that drive peptide self-assembly are usually susceptible to the complex physiological environment; thus leading to disassembly and dysfunction of fluorescent nanoagents. Herein, a covalently crosslinked assembly strategy for fabrication of stable peptide-based nanoparticles with adjustable emission is introduced. In the process of cationic diphenylalanine peptide (H-Phe-Phe-NH₂ ⋅ HCl) self-assembly, glutaraldehyde is used as a crosslinker and the resulting product of the Schiff base reaction can be fluorescent. More importantly, the emission wavelength can be readily tuned by controlling the covalent reaction time. It has been demonstrated that the nanoparticles are stable, even after intracellular uptake, and can be used for sustainable multicolor fluorescent imaging. The strategy with integrating peptide self-assembly and covalent crosslinking could be promising for the design and engineering of functional fluorescent nanoparticles with robust physiological stability and adjustable emission towards improved bioimaging applications.     

Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

TiO_2/FeOOH/硅藻土纳米复合材料的制备和光催化性能研究

采用分子组装的方法,以硅藻土为基底制备TiO_2/硅藻土、TiO_2/FeOOH/硅藻土纳米复合材料,通过UV-Vis、TEM方法对材料进行表征,以甲基橙溶液为目标降解物探究纳米复合材料的光催化性能,结果表明,基底制备TiO_2/硅藻土、TiO_2/FeOOH/硅藻土纳米复合材料对甲基橙均有不错的降解率,其中TiO_2/FeOOH/硅藻土纳米复合材料降解率达到67.16%。     

酸碱度对金纳米结构形貌的调控及其机理研究

本文通过调节环境pH酸碱度改变聚电解质膜中氨基基团的键合状态,以控制聚电解质膜表面金纳米粒子的原位还原与自组装过程中的聚集行为,发现当聚电解质膜经pH为5.40的去离子水处理后可在其表面制备出片状金纳米结构;经pH为0.65的强酸溶液处理后,可在膜表面制备出树枝状的金纳米结构,且尺寸比pH为5.40条件下增大一倍;经pH为12.77的强碱溶液处理后,金纳米粒子的聚集状态发生改变,形成了球形纳米结构;对金纳米粒子形貌的调控机理进行了初步探讨.     

层层自组装法制备碳纳米管薄膜研究进展

综述了近年来通过层层自组装法制备碳纳米管薄膜的一些最新研究进展,重点介绍了通过物理吸附和化学吸附两种方式来制备碳纳米管组装膜,并对如何提高碳纳米管薄膜的电化学稳定性方面进行了论述。     

丙烯腈嵌段共聚物的合成及其自组装研究进展

综述了含聚丙烯腈(PAN)嵌段共聚物的合成方法及其在溶液中的自组装技术。对常用的活性自由基聚合方法,如原子转移自由基聚合(ATRP)、可逆加成断裂链转移(RAFT)聚合、氮氧自由基聚合(NMP)以及钴调介自由基聚合(CMRP)等方面的研究进行了总结,同时对PAN类嵌段共聚物在溶液中的自组装技术进行了概括。最后提出了现有技术存在的问题,并对其今后发展方向进行了展望。     

Transition Metal Ion–Mediated Tyrosine‐Based Short‐Peptide Amphiphile Nanostructures Inhibit Bacterial Growth

We report the design and synthesis of a biocompatible small‐peptide‐based compound for the controlled and targeted delivery of encapsulated bioactive metal ions through transformation of the internal nanostructures of its complexes. A tyrosine‐based short‐peptide amphiphile (sPA) was synthesized and observed to self‐assemble into β‐sheet‐like secondary structures. The self‐assembly of the designed sPA was modulated by application of different bioactive transition‐metal ions, as was confirmed by spectroscopic and microscopic techniques. These bioactive metal‐ion‐conjugated sPA hybrid structures were further used to develop antibacterial materials. As a result of the excellent antibacterial activity of zinc ions the growth of clinically relevant bacteria such as Escherichia coli was inhibited in the presence of zinc ? sPA conjugate. Bacterial testing demonstrated that, due to high biocompatibility with bacterial cells, the designed sPA acted as a metal ion delivery agent and might therefore show great potential in locally addressing bacterial infections.     

Polyoxometalate-Incorporated Supramolecular Self-Assemblies: Structures and Functional Properties

As a family of functional inorganic clusters, polyoxometalates (POMs) were introduced into hybrid self-assemblies with the assistance of the supramolecular interaction with diverse organic cationic molecules, which reinforced both the processibility and functionality of the POMs. This method not only improved the surface properties of the POMs, but also provided excellent amphiphilic building blocks for the construction of advanced self-assembled nanostructures. In this review, we summarize the fundamental aspects of surfactant-encapsulated POMs (SEPs) and the most recent progress in potential applications of SEPs and the related POM-containing systems (hybrids composed of POMs and polymers and other cationic molecules beyond surfactants). The functionalization of such organic/inorganic hybrids in self-assembled systems is also described. Furthermore, perspectives regarding self-assemblies and possible applications of POM complexes with synergetic interactions between organic and inorganic components are outlined.