Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

某金矿尾矿提纯石英应用对比试验研究

针对某金矿，在回收金银的基础上，对金银浮选尾矿进行云母和长石浮选，以及提纯石英试验，最终获得SiO2品位99.91%的石英产品。提纯石英产品与比利时矽比科矿业有限公司石英产品进行对比试验，通过化学成分、粒度组成、熔制、粘度和热膨胀系数测试对比试验，得出金矿提纯石英达到甚至超过矽比科进口石英产品的各项技术指标。     

The Antibacterial Drug Candidate SBC3 is a Potent Inhibitor of Bacterial Thioredoxin Reductase

Antibiotic resistance is a growing problem for public health and associated with increasing economic costs and mortality rates. Silver and silver-related compounds have been used for centuries due to their antimicrobial properties. In this work, we show that 1,3-dibenzyl-4,5-diphenyl-imidazol-2-ylidene silver(I) acetate/NHC*-Ag-OAc (SBC3) is a reversible, high affinity inhibitor of E. coli thioredoxin reductase (TrxR; K_i=10.8±1.2 nM). Minimal inhibition concentration (MIC) tests with different E. coli and P. aeruginosa strains demonstrated that SBC3 can efficiently inhibit bacterial cell growth, especially in combination with established antibiotics like gentamicin. Our results show that SBC3 is a promising antibiotic drug candidate targeting bacterial TrxR.     

Synthesis and Characterization of Co Nanocomposite Based on Poly(benzimidazole-amide) Matrix and Their Behavior as Catalyst in Oxidation Reaction

2,6-Bis(5-amino-1H-benzimidazol-2-yl)pyridine was prepared and characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H-NMR, and ¹³C-NMR spectroscopic methods. Then a new poly(benzimidazole-amide) was synthesized by polymerization of the corresponding diamine and isophthalic acid. The obtained poly(benzimidazole-amide) exhibited good yield and high thermal stability. Due to the existence of benzimidazole moieties in polymer’s structure, it has the tendency to form complexes with metal ions. So, a new poly(benzimidazole-amide)/Co nanocomposite was prepared. Morphological studies revealed that metal nanoparticles were dispersed in the polymer matrix without any aggregation. poly(benzimidazole-amide)/Co nanocomposite was used as a catalyst in the oxidation of ethyl benzene to acetophenone with tert-butyl hydroperoxide.     

Unraveling the effect of alumina-supported Y- doped ceria composition and method of preparation on the WGS activity of gold catalysts

The demands for high-purity hydrogen required in fuel-cell applications impose new goals and challenges for design of well performing water-gas shift (WGS) catalysts. Gold-based catalysts have exhibited high activity in the WGS reaction at low temperature. Preparation of appropriate and economically viable supports with complex composition by various synthesis procedures is an attractive approach to WGS performance improvement. The effect of two different preparation methods (wet impregnation or mechanical mixing) and ceria content (10, 20 or 30 wt%) on textural, structural, surface and reductive properties and WGS activity of gold catalysts was studied. Additionally, the role of Y₂O₃ as a promoter of ceria was examined. Long-term stability test was carried out at 260 °C over the most active catalyst. The composition of the best performing sample (composed of about 70 wt% alumina), prepared by mechanical mixing, was considered promising in case of practical applications because of its cost efficiency. The combination of gold nanoparticles and alumina supported Y-doped ceria proved an advantageous approach for developing new catalytic formulations with high effectiveness in clean hydrogen production.     

Encapsulation and Ostwald Ripening of Au and Au–Cl Complex Nanostructures in Silica Shells

We report a general template strategy for rational fabrication of a new class of nanostructured materials consisting of multicore shell particles. Our approach is demonstrated by encapsulating Au or Pt nanoparticles in silica shells. Other superstructures of these hollow shells, like dimers, trimers, and tetramers can also be formed by nanoparticle‐mediated self‐assembly. We have also used the as‐prepared multicore Au–silica hollow particles to perform the first studies of Ostwald ripening in confined microspace, in which chloride was found to be an efficient mediating ligand. After treatment with aqua regia, Au–Cl complex is formed inside the shell, and is found to be very active under in situ transmission electron microscopy observations while confined in a microcell. This aspect of the work is expected to motivate further in situ studies of confined crystal growth.     

A Donor–Acceptor Polymer with a Peculiar Negative‐Charge‐“Trapping” Characteristic

Voltammetric and spectrophotometric measurements of poly(3,3″‐dipentoxy‐3′‐dicyanoethenyl‐2,2′:5′,2″‐terthiophene) (polyCN) films, in connection with other experimental evidence, reveal a normal oxidative, but a peculiar reductive behavior consisting of trapping of the negative charge during the cathodic scan. Another interesting property of polyCN films is the tendency to form strong intramolecular and intermolecular associations, probably charge‐transfer (CT) complexes. These properties could account for the fact that the photovoltaic performance does not improve when polyCN is blended with a polythiophene donor.     

An application of chemometric techniques to analyze the effects of the wave function modifications on the intermolecular stretching frequencies of the hydrogen-bonded complexes

Factorial design and principal component models are used to determine how ab initio H-bond stretching frequencies depend on characteristics of the molecular orbital wave functions of acetylene–HX, ethylene–HX and cyclopropane–HX π-type hydrogen complexes with X=F, Cl, CN, NC and CCH. The results obtained for the three sets of complexes show that factorial design and principal component analyses complement each other. Factorial design calculations clearly show that these frequencies are affected mostly by inclusion of electron correlation on the calculation level. On average, their values are increased by about 25 cm⁻¹ due to a change from the Hartree–Fock (HF) to Möller–Plesset 2 (MP2) level. Valence, diffuse and polarization main effects as well as valence–diffuse, diffuse–correlation and polarization–correlation interaction effects are also important to better describe a factorial model to the H-bond stretching frequencies of these hydrogen complexes. This simplified model has been successful in reproducing the complete ab initio results, which correspond to two hundred and forty calculations. Principal component analyses applied only to hydrogen-bonded complexes whose experimental frequencies are known, has revealed that the six-dimensional original space can be accurately represented by a bidimensional space defined by two principal components. Its graphical representation reveals that the experimental intermolecular stretching frequencies are in closest agreement with the MP2/6–31+G and MP2/6–311+G ab initio results.