Oxotitanium(IV) complexes of some bis‐unsymmetric Schiff bases: Synthesis,structural elucidation and biomedical applications

A number of oxotitanium(IV) complexes of the type TiOL with bis‐unsymmetric dibasic tetradentate Schiff base (LH₂) containing ONNO donor atoms have been synthesized. Mono‐Schiff base (OPD‐HNP) was prepared by the condensation of 1:3 molar ratio of 2‐hydroxy‐1‐naphthaldehyde (HNP) with o‐phenylenediamine (OPD). Dibasic unsymmetric tetradentate diamine Schiff bases were prepared by the reaction of OPD‐HNP with 2‐hydroxyacetophenone, 2‐hydroxypropeophenone, benzoylacetone, acetylacetone and ethylacetoacetate. Further, titanylacetylacetonate was reacted with these ligands to obtain their metal complexes. On the basis of analytical and physiochemical data, the formation of complexes as TiOL was suggested having square pyramidal geometry. Quantum mechanical approach also confirmed this geometry. The assessment of the synthesized ligands and their complexes showed that some behave as good inhibitors of mycelial growth against selected phytopathogic fungi but weak inhibitors against some selected bacteria. A few of them also showed antioxidant properties.     

Ultrasonic assisted synthesis of nanocrystalline cellulose as support and reducing agent for Ag nanoparticles: green synthesis and novel effective nanocatalyst for degradation of organic dyes

In this study, nanocrystalline cellulose (NCC) prepared from microcrystalline cellulose using high‐intensity ultrasonication as mechanical method without any chemical treatment. The obtained NCC with around 30–50 nm diameters, utilized as support, reducing and stabilizing agent for in‐situ green and eco‐friendly synthesis of silver nanoparticles (Ag NPs). The catalytic activity of composite was examined for degradation of environmental pollutants. The structure of as‐synthesized composite (Ag@NCC) was characterized by ultraviolet–visible spectroscopy (UV–vis), field emission scanning electron microscopy (FE‐SEM); Transmission electron microscopy (TEM); Energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA). The results of the catalytic reaction experiments showed that spherically shaped silver nanoparticles of around 20 nm distributed on the surface of nanocellulose demonstrated high catalytic efficiency towards the removal of methyl orange (MO) and 4‐nitrophenol (4‐NP).     

磷酸化调控泛素单体与Rad23A/Ubiquilin-1中泛素结合域互作的检测

泛素（ubiquitin，Ub）是一种广泛存在、高度保守的信号蛋白质，它能够特异性识别成千上万种靶蛋白，以非共价方式行使不同的功能，其中包含蛋白质降解．Ubiquilin-1（Ubql-1）和Rad23A作为两种蛋白降解的转运因子，都包含有与泛素结合的结构域，被称为泛素结合域（ubiquitin-associated domain，UBA）．2014年，泛素S65位磷酸化修饰的特异性激酶PINK1被发现，磷酸化使泛素在溶液中呈现舒展态与收缩态两种互相转换的构象．本文通过核磁共振（nuclear magnetic resonance，NMR）技术对UBA和磷酸化泛素之间的相互作用进行检测，观测磷酸化对UBA和泛素结合的影响．实验结果表明Rad23A-UBA2与Ubql-1 UBA都特异性的与磷酸化泛素的舒展态相互作用，但是磷酸化未改变泛素与UBA之间的亲和力．值得注意的是与Ubql-1 UBA相互作用时，磷酸化促进了泛素收缩态向舒展态的转换．     

Novel thionin-functionalised core shell magnetic nanoparticles for dispersive solid-phase extraction of Hg(II) in food and water samples

To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L^?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g^?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%.     

Enhancing the Viscosity-Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

Molecular rotors are a class of fluorophores that enable convenient imaging of viscosity inside microscopic samples such as lipid vesicles or live cells. Currently, rotor compounds containing a boron-dipyrromethene (BODIPY) group are among the most promising viscosity probes. In this work, it is reported that by adding heavy-electron-withdrawing −NO₂ groups, the viscosity-sensitive range of a BODIPY probe is drastically expanded from 5–1500 cP to 0.5–50 000 cP. The improved range makes it, to our knowledge, the first hydrophobic molecular rotor applicable not only at moderate viscosities but also for viscosity measurements in highly viscous samples. Furthermore, the photophysical mechanism of the BODIPY molecular rotors under study has been determined by performing quantum chemical calculations and transient absorption experiments. This mechanism demonstrates how BODIPY molecular rotors work in general, why the −NO₂ group causes such an improvement, and why BODIPY molecular rotors suffer from undesirable sensitivity to temperature. Overall, besides reporting a viscosity probe with remarkable properties, the results obtained expand the general understanding of molecular rotors and show a way to use the knowledge of their molecular action mechanism for augmenting their viscosity-sensing properties.     

Room temperature suzuki cross‐coupling polymerizations of aryl dihalides and aryldiboronic acid/acid esters with t‐Bu3P‐coordinated 2‐phenylaniline‐based palladacycle complex as the precatalyst

Room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t‐Bu₃P‐coordinated 2‐phenylaniline‐based palladacycle complex, [2′‐(amino‐kN)[1,1′‐biphenyl]‐2‐yl‐kC]chloro(tri‐t‐butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross‐coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand‐coordinated palladacycle complexes including other electron‐rich monophosphine‐coordinated ones for room temperature cross‐coupling polymerizations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1606–1611     

A Methodology for Estimating Kinetic Parameters and Reactivity Ratios of Multi‐site Type Catalysts Using Polymerization,Fractionation, and Spectroscopic Techniques

This work describes a polymer reaction engineering framework for understanding how catalyst kinetic parameters affect the microstructure of polyolefins made with single‐ or multi‐site catalysts. Moreover, a methodology for deconvolution and kinetic parameters estimation is presented to estimate the reactivity ratios of multi‐site catalysts based on the combination of polymerization, fractionation, and spectroscopic techniques, namely, gel permeation chromatography‐IR and carbon‐13 nuclear magnetic resonance spectroscopy. The methodology capabilities are then demonstrated and validated using a case study simulated via a Monte Carlo model including random noise in order to better represent experimental result uncertainties. The methodology can reverse engineer experimental results and estimate all relevant reaction performance parameters.     

Two novel Co (II)-coordination polymers as bifunctional materials for efficient photocatalytic degradation of dyes and electrocatalytic water oxidation

Two novel Co (II)- coordination polymers (CPs) based on 2,5-bis(4-carboxylpheny)-1,3,4-oxadiazole (bcpo), namely [Co/(bcpo)_0.5(tib)(H₂O)₂]_n (1) and [Co (bcpo)_0.5(bidpe)(H₂O)₂]_n (2) (tib = 1,3,5-tirs(1-imidazolyl)benzene, bidpe = 4,4′-bis (imidazolyl)diphenyl ether) have been synthesized under solvothermal conditions and characterized by powder X-ray diffraction (PXRD), single crystal X-ray diffraction, photochemistry as well as electrochemistry. The investigation of the photo-degradation methyl blue and methyl violet (MB, MV) properties of CPs 1–2 demonstrates that CP 1 shows great performance for the degradation of MB, and CP 2 could efficiently degrade MB/MV. Meanwhile, the possible photo-degradation mechanism has been proposed and explored. Simultaneously, electrochemistry studies show that both CPs 1 and 2 can catalyze water oxidation under an alkaline condition at the potential around 1.20 V vs. NHE with relatively low overpotential of 330–510 mV vs. NHE.