Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst

In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.     

基于荧光效应的小分子抗癌药物释放体系研究进展

近年来,随着癌症发病率的不断升高,癌症治疗技术的更新和发展显得尤为重要,特别是化学疗法(Chemotherapy)的提出促进了荧光小分子抗癌药物释放体系的研究。 将具有荧光效应的有机小分子与抗癌药物结合在一起,使得药物释放体系表现出低毒性、优异的癌细胞靶向性和方便药物跟踪监测等特点。 因此,设计不同性能的前药可以研究抗癌药物释放的动力学过程,为实现癌症的精准治疗提供有力的工具。 本文主要介绍了基于喜树碱、SN-38和阿霉素等前药的研究进展,并对其发展前景作了展望。     

Structural characterization of disperse black 9 based Cu (II) complex and investigation of its some properties

We obtained the azo‐imine ligand (2,2′‐[4‐(5‐methoxy salicylidene‐4‐iminophenylazo)phenylimino]diethanol) (HL) and its Cu (II) complex (CuL) from the ethanol solution. The complex Cu(L)₂ was obtained as single crystals from the CH₃OH solution and structurally characterized. The electronic and photoluminescence properties of the ligand and its Cu (II) complex were investigated both in DMF solution and solid state. The oxidation and reduction behaviours of the compounds were studied in the solution and found that the redox processes are irreversible. Thermal studies show that the ligand has higher thermal stability than the CuL complex. Single crystals of the complex were obtained from slow evaporation of a DMF solution of the complex. Crystals of the complex showed a diffraction pattern; however, the structure of the complex was able to be solved.     

Versatile light‐responsive organogels: Evaluation of their dye releasing and photoinitiation behaviors

Light‐responsive crosslinked structures were prepared by a straightforward quaternization strategy using chloride functional polystyrene copolymers and commercially available Michler's ketone with varying feed ratios. Resulting organogels demonstrated excellent solvent absorption and their swelling characteristics were altered by UV‐light irradiation. According to scanning electron microscope images, UV‐illuminated samples showed an obvious photodecomposition, which enhanced their solvent uptake capacity with increase of UV exposure. Additionally, release behavior of eosin Y as a model compound was determined by UV–vis and fluorescence spectrometers. Achieved photoactive gels were also employed as the reusable heterogeneous initiators for photoinduced free‐radical polymerization of methyl methacrylate. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1275–1282     

Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480     

Thermally Responsive Materials for Bioimaging

The last decade has witnessed multiple thermally responsive materials emerge as a significant class of stimuli‐responsive materials. These materials are elaborately designed and exert interesting properties. Herein, an overview of thermally responsive materials with respect to design strategies, fabrication procedures, and their applications is presented. Recently reported thermally responsive materials are highlighted. Then, applications of thermally responsive materials in bioimaging are summarized.     

Electrochemical Signal‐triggered Release of Biomolecules Functionalized with His‐tag Units

His‐tagged molecular species, a ferrocene derivative and Protein A, were immobilized on electrode surfaces (Au and graphite) through formation of a chelated complex in the presence of Cu²⁺ cations used as bridging units. The complex was cleaved and the attached molecules were released from the electrode surface by applying reductive potential to the electrodes resulting in Cu²⁺ reduction, thus decomposing the chelate complex. The molecule release process was followed by cyclic voltammetry in case of the ferrocene derivative. His‐tagged Protein A was additionally labeled with a fluorescent tag and its release was followed by fluorescence measurements in the solution and by impedance spectroscopy at the electrode. The studied release of the His‐tagged redox species and biomolecules was considered as a new generic approach to the signal‐controlled molecule release applicable in various biotechnological and biomedical applications.     

Hybrid Organic–Inorganic Thermoelectric Materials and Devices

Hybrid organic–inorganic materials have been considered as a new candidate in the field of thermoelectric materials since the last decade owing to their great potential to enhance the thermoelectric performance by utilizing the low thermal conductivity of organic materials and the high Seebeck coefficient, and high electrical conductivity of inorganic materials. Herein, we provide an overview of interfacial engineering in the synthesis of various organic–inorganic thermoelectric hybrid materials, along with the dimensional design for tuning their thermoelectric properties. Interfacial effects are examined in terms of nanostructures, physical properties, and chemical doping between the inorganic and organic components. Several key factors which dictate the thermoelectric efficiency and performance of various electronic devices are also discussed, such as the thermal conductivity, electric transportation, electronic band structures, and band convergence of the hybrid materials.     

Determination of nanolayer thickness and effective thermal conductivity of nanofluids

Nanofluids having high thermal conductivity enhancement relative to conventional pure fluids are fluids engineered by suspending solid nanoparticles into base fluids. In the present study, calculating the Van der Waals interaction energy between a nanoparticle and an ordered liquid nanolayer around it, the nanolayer thickness was determined, the average velocity of the Brownian motion of nanoparticles in a fluid was estimated, and by taking into account both the aggregation of nanoparticles and the presence of a nanolayer a new thermal conductivity model for nanofluids was proposed. It has been shown that the nanolayer thickness in nanofluids is independent on the radius of nanoparticles when the radius of the nanoparticles is much greater than the nanolayer thickness and determines by the specific interaction of the given liquid and solid nanoparticle through the Hamaker constant, the surface tension and the wetting angle. It was proved that the frequency of heat exchange by fluid molecules is two orders of magnitude higher than the frequency of heat transfer by nanoparticles, so that the contribution due to the Brownian motion of nanoparticles in the thermal conductivity of nanofluids can be neglected. The predictions of the proposed model of thermal conductivity were compared with the experimental data and a good correlation was achieved.     

Synthesis and characterization of processable polyamides containing polar quinoxaline unit in the main chain and evaluation of its hydrophilicity

Here we report a new five polyamides prepared via solution-phase polycondensation under Yamazaki-Higashi conditions to prove the suitability of this method. The synthesized polyamides were characterized by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, inherent viscosity, solubility and wettability tests. These polyamides were amorphous in nature and they are completely soluble in many organic solvents and they could easily be solution-cast into transparent, flexible films. The as-prepaired polymers showed excellent thermal properties. The glass transition temperatures of these polymers are in the range of 251–274?°C under nitrogen atmosphere. The decomposition temperature in nitrogen for a 10% weight-loss temperature is more than 744?°C, and char yield at 900?°C ranged from 43 to 56% in nitrogen. Water contact angles were also tested to know the hydrophilicity of the polyamide films. As-synthesized polyamides showed smallest quantact angles indicating hydrophilic surface.