发光铱(Ⅲ)配合物抗肿瘤活性研究及应用

铱(Ⅲ)配合物因其发光量子产率高且波长易调控、发光寿命长和光稳定性好的特点,在发光材料领域备受关注。铱(Ⅲ)配合物细胞渗透能力强,能靶向多种细胞组织并影响其结构和功能,表现出独特的抗肿瘤活性,是目前金属抗肿瘤药物特别是PDT光敏剂方向的研究热点。本文重点关注铱(Ⅲ)配合物的结构对其发光性能与抗肿瘤性能的影响,综述了近期铱(Ⅲ)配合物在生物成像、探针与传感、抗肿瘤诊疗等领域的研究进展,并对目前研究中存在的问题及其应用前景进行探讨和展望。     

有机张力半导体及其光电特性

分子张力作为空间设计的重要组成部分正成为调控有机半导体的重要手段。由于分子内产生的拉伸张力、扭曲/弯曲张力以及空间张力而导致p轨道排布重组和构型构象结构发生变化,最近各种几何与拓扑结构的高张力有机半导体材料相继被报道,这使得高张力有机半导体材料成为有机电子领域研究的焦点。为了进一步梳理分子张力在有机半导体材料中扮演的角色与价值,该综述从分子张力的类型、实验与理论量化以及可视化出发,总结了高张力共轭芳烃的分子设计策略、与其光电性能分子张力之间的关系,以及这类新兴材料在光电领域的应用。最后,对高张力共轭芳烃的研究前景进行了展望,阐述了该类材料所面临的机遇与挑战。     

汽配件颜色喷涂顺序问题的TSP转化与建模

汽配件颜色喷涂顺序问题通常以生产线上相邻汽配件颜色切换次数少为最优目标,以进一步降低生产成本.该类问题具有所有汽配件都必须喷涂一次且只喷涂一次的特点,为此提出了TSP转化与建模的方法.将待喷涂汽配件定义为TSP顶点,任意两个待喷涂汽配件的颜色切换定义为顶点的距离,仿照TSP问题构建0-1规划模型;类似于顶点距离,将某些汽配件的颜色或类别不相邻要求定义为0-1矩阵,巧妙地构造了喷涂生产的约束条件.该建模方法简单快速,通用性高,适用于具有类似特点的各类生产实践问题.     

Modifying the physicochemical properties,solubility and foaming capacity of milk proteins by ultrasound-assisted alkaline pH-shifting treatment

This study investigated the effects of different treatment of alkaline pH-shifting on milk protein concentrate (MPC), micellar casein concentrate (MCC) and whey protein isolate (WPI) assisted by the same ultrasound conditions, including changes in the physicochemical properties, solubility and foaming capacity. The solubility of milk proteins had a significant increase with gradual enhancement of ultrasound-assisted alkaline pH-shifting (p < 0.05), especially for MCC up to 99.50 %. Also, treatment made a significant decline in the particle size of MPC and MCC, as well as the turbidity of the proteins (p < 0.05). The foaming capacity of MPC, MCC, and WPI was all improved, especially at pH 11, and at this pH, the milk protein also showed the highest surface hydrophobicity. The best foaming capacity at pH 11 was the result of the combined effect of particle size, potential, protein conformation, solubility, and surface hydrophobicity. In conclusion, ultrasound-assisted pH-shifting treatment was found to be effective in improving the physicochemical properties and solubility and foaming capacity of milk proteins, especially MCC, with promising application prospect in food industry.     

Substitution‐Pattern‐ and Counteranion‐Depending Ion‐Pairing Assemblies Based on Electron‐Deficient Porphyrin–AuIII Complexes

Porphyrin–Au^III complexes, which were partially or totally modified with C₆F₅ at the meso positions, were synthesized. The highly electron‐withdrawing substituents induced electron‐deficient states and Lewis acid properties. Single‐crystal X‐ray analysis of the ion pairs revealed ion‐pairing assemblies with characteristics dependent on the number and substitution pattern of the C₆F₅ units and the geometries of the anions.     

Dynamical Analysis of a New Chaotic Fractional Discrete-Time System and Its Control

This article proposes a new fractional-order discrete-time chaotic system, without equilibria, included two quadratic nonlinearities terms. The dynamics of this system were experimentally investigated via bifurcation diagrams and largest Lyapunov exponent. Besides, some chaotic tests such as the 0–1 test and approximate entropy (ApEn) were included to detect the performance of our numerical results. Furthermore, a valid control method of stabilization is introduced to regulate the proposed system in such a way as to force all its states to adaptively tend toward the equilibrium point at zero. All theoretical findings in this work have been verified numerically using MATLAB software package.     

Excited-State Dynamics of Non-Luminescent and Luminescent π-Radicals

Recently, the potential use of organic π-radicals and related spin systems has been expanded to modern technological applications. The unique excited-state dynamics of organic π-radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up-conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π-radicals have been recently reported, which are especially interesting for application in organic light-emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited-state nature of stable π-radicals as well as the control of their excited-state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited-state dynamics of both photostable non(weakly)-luminescent and luminescent π-radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high-spin photoexcited states and control of the excited-state dynamics by using non-luminescent π-radicals, 2) unique excited-state dynamics of luminescent π-radicals and radical excimers, and 3) applications utilizing excited-state dynamics of π-radicals.     

Chloride‐Selective Electrodes Based on “Two‐Wall” Aryl‐Extended Calix[4]Pyrroles: Combining Hydrogen Bonds and Anion–π Interactions to Achieve Optimum Performance

The performance of chloride‐selective electrodes based on “two‐wall” aryl‐extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso‐positions. When the meso‐phenyl groups are decorated with strong electron‐withdrawing substituents, attractive anion–π interactions may exist between the receptor’s aromatic walls and the sandwiched anion. These anion–π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p‐nitro withdrawing group on each of the meso‐phenyl rings, afforded sensors that display anti‐Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion‐specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids.     

Rhodium‐Catalyzed Stitching Polymerization of 1,5‐Hexadiynes and Related Oligoalkynes

A new mode of polymerization, rhodium‐catalyzed stitching polymerization, has been developed for the synthesis of π‐conjugated polymers with bridged repeating units from nonconjugated 1,5‐hexadiynes containing both terminal and internal alkyne moieties as monomers. The polymerization proceeded smoothly with a high degree of stitching efficiency under mild conditions, and 1,5,9‐decatriyne and 1,5,9,13‐tetradecatetrayne monomers could also be employed. The present polymerization strategy would be particularly beneficial for the synthesis of polymers consisting of a repeating unit that is difficult to prepare as a stable monomer because it does not require the use of a preformed bridged π‐conjugated monomer.     

A stable pillared metal–organic framework constructed by H4TCPP ligand as luminescent sensor for selective detection of TNP and Fe3+ ions

A novel luminescent metal–organic framework ( Zn‐TCPP/BPY ) with pillared structure based on 2,3,5,6‐tetrakis(4‐carboxyphenyl)pyrazine (H₄TCPP) and 4,4′‐bipyridine (BPY) has been designed and synthesized through a solvothermal reaction. The [Zn₂(COO)₄] paddlewheel units are linked by TCPP^4? ligands to form two‐dimensional layers and further connected by BPY ligands as pillars to construct the twofold interpenetrating three‐dimensional framework. Interestingly, Zn‐TCPP/BPY possesses outstanding stability in organic solvents and water as well as maintains its structural rigidity in aqueous solutions of different pH values (3–12). After activation, Zn‐TCPP/BPY possesses permanent porosity with Brunauer–Emmett–Teller surface area of 630 m² g^–1. Remarkably, Zn‐TCPP/BPY displays excellent fluorescent property in virtue of the aggregation‐induced emission effect of the H₄TCPP ligand, which can be highly active and quenched by small amounts of 2,4,6‐trinitrophenol (TNP) and Fe³⁺ ions. Furthermore, the detection effect of Zn‐TCPP/BPY remains basically the same even after five cycles. The excellent stability, high sensitivity, and recyclability of Zn‐TCPP/BPY make it an outstanding chemical sensor for detecting TNP and Fe³⁺ ions.