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.     

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.     

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.     

Synthesis of heterocyclic metal complexes and their evaluation as marine antifoulants

4-Amino-3-thio-1,24-triazolidine (L₁) and 4-amino-5-thio-1,3,4-thiadiazole (L_II) as well as their metal complexes of the general formulae ML_I·2H₂O and ML_IICl (M; Pb(II), Cd(II) and Zn(II)) were prepared. With Sn(II), we obtained Sn(L_I)₂·2H₂O and SnL_IICl, respectively. The structures of the compounds were identified through elemental analysis, and IR and UV spectra measurements, in addition to thermal analysis in case of the metal complexes. The antifouling properties of the compounds were tested by their incorporation into paint formulations which were applied to PVC substrates and tested in water from Alexandria western harbour. When the compounds were added at 17·5% by volume, the coated panels were fouled after 3 months of immersion. The addition of 6·7% by volume of tributyltin oxide to 15·8% of the prepared compounds in one formulation elevated the paint efficiency and prevented fouling for 11 months. Paint containing solely tributyltin oxide at the same concentration was inactive against algae.     

Highly Efficient Orange and Green Solid‐State Light‐Emitting Electrochemical Cells Based on Cationic IrIII Complexes with Enhanced Steric Hindrance

Highly efficient orange and green emission from single‐layered solid‐state light‐emitting electrochemical cells based on cationic transition‐metal complexes [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ (where ppy is 2‐phenylpyridine, dFppy is 2‐(2,4‐difluorophenyl)pyridine, and sb is 4,5‐diaza‐9,9′‐spirobifluorene) is reported. Photoluminescence measurements show highly retained quantum yields for [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂ sb]PF₆ in neat films (compared with quantum yields of these complexes dispersed in m‐bis(N‐carbazolyl)benzene films). The spiroconfigured sb ligands effectively enhance the steric hindrance of the complexes and reduce the self‐quenching effect. The devices that use single‐layered neat films of [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ achieve high peak external quantum efficiencies and power efficiencies of 7.1 % and 22.6 lm W^–1) at 2.5 V, and 7.1 % and 26.2 lm W^–1 at 2.8 V, respectively. These efficiencies are among the highest reported for solid‐state light‐emitting electrochemical cells, and indicate that cationic transition‐metal complexes containing ligands with good steric hindrance are excellent candidates for highly efficient solid‐state electrochemical cells.     

Immunoelectron localization of mitochondrial F1 factor in cryosections of heart muscle cells

Immunocytochemistry was used to investigate the localization of F1 ATPase in mitochondria of cryosections of adult mouse heart muscle cells. The initial aldehyde fixation was the only denaturation step for antigens. The fine structure was preserved with contrast enhancement as the sections were maintained hydrated, with the advantage that the entire procedure is completed in one working day. The reaction was highly specific, and entire mitochondria were labeled with the Protein A-gold complex. A new analytical technique, electron spectroscopic imaging (ESI), contributed to a better visualization of the localization of the F1 factor.     

Synthesis and characterization of poly(ethylene aspartate)-metal complexes

Poly(ethylene aspartate) [PEA] was synthesized by the melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing pendent amino and carbonyl groups in its repeating chain was used as the polymeric ligand for complexation with transition metal ions, viz. Co(II), Ni(II), Cu(II), Mn(II), Zn(II), Cd(II), Ca(II), Mg(II), Pb(II) and Hg(II). Complexation was found to be most effective in DMSO. The resulting polyester-metal complexes were solid coloured materials which have been characterized by IR spectroscopy, elemental analysis and magnetic susceptibility measurements. The thermal stability of the polyester-metal complexes was investigated by thermogravimetric analysis (TGA). On the basis of the physico-chemical studies, an oxygen and nitrogen coordinated structure for the polyester-metal complexes is proposed.