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.     

Atomic-level insights into the modification mechanism of Fe (III) ion on smithsonite (1 0 1) surface from DFT calculation

Fe(III) ion can strongly inhibit the sulphidation amine flotation of smithsonite. However, its modification mechanism on smithsonite surface is still obscure. In this work, a systematic study of the modification of Fe(III) ion on smithsonite (1 0 1) surface was performed using DFT calculation. The optimal number of H₂O ligands for Fe(III) ion hydrates in aqueous conditions was probed, and [Fe(OH)₂(H₂O)₄]⁺ and [Fe(OH)₄]^? were identified as the major modification species, then their adsorption and bonding mechanisms were further revealed by analyzing the frontier orbitals, density of state, Mulliken population, and electron density. The calculated adsorption structures were consistent with the former experiment, and we found the O site that bonded to the C atom on smithsonite surface was the most favorable position for [Fe(OH)₂(H₂O)₄]⁺ and [Fe(OH)₄]^? adsorptions. Besides, their adsorption mechanisms on smithsonite surface were principally due to the combined effect of FeO bond and hydrogen bonding. Simultaneously, hydrogen bonding greatly enhanced the stability of the adsorption structures. Moreover, the dominant orbital contribution for the bonding of FeO was primarily due to the orbital hybridization between Fe 3d and O 2p orbitals. This work can help in deeper understanding of the depression of Fe(III) ion on the sulphidation amine flotation of smithsonite.     

Numerical investigation of a convective hybrid nanofluids around a rotating sheet

Hybrid nanofluids are formulated with various kinds of base fluids. They are designed to provide good heat transfer performance. They can achieve this by dispersing various kinds of nanoparticles in the base materials. This new technology of formulating hybrid nanofluids has a wide range of applications in various industries such as solar energy, medical equipment, and aerospace. Keeping these applications in view, this study provides an insight into the effects of convective heat transport on a Hybrid nanofluid, across a rotating sheet with a variable heat source. In this investigation, the governing boundary layer partial differential equations were modified into the ordinary differential equations, by using the proper similarity transformations. Later, they were solved numerically, with the support of the Lobatto IIIA technique in MATLAB. The influence of the Richardson number on flow parameters was studied, and it was discovered that increasing Ri increases the velocity while decreasing temperature and concentration profiles. The impact of various other flow parameters on the flow fields and also on the behavior of Nusselt number, coefficient skin friction, and Sherwood number were studied and represented graphically. The outcomes were found to be in excellent accord when compared with quoted studies.     

Dynamic Oscillation via Negative Differential Resistance in Type III Junction Organic/Two-Dimensional and Oxide/Two-Dimensional Transition Metal Dichalcogenide Diodes

Among many of 2D semiconductor-based devices, type III PN junction diodes are given special attentions due to their unique function, negative differential resistance (NDR). However, it has been found uneasy to achieve well-matched type III PN junctions from 2D–2D van der Waals heterojunctions. Here, the authors present other alternatives of type III heterojunctions, using 2D p-MoTe₂/organic n-type dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN) and 2D p-WSe₂/n-MoO_x systems. Those junction diodes appear to well-demonstrate static and dynamic NDR behavior via resonant tunneling and electron–hole recombination. Extended to an inverter circuit, p-MoTe₂/n-HAT-CN diode enables multilevel inverter characteristics as monolithically integrated with p-MoTe₂ channel field effect transistor. The same NDR diode shows dynamic LC oscillation behavior under a constant DC voltage, connected to an external inductor. From p-WSe₂/n-MoO_x oxide diode, similar NDR behavior to those of p-MoTe₂/n-HAT-CN is again observed along with LC oscillations. The authors attribute these visible oscillation results to high peak-to-valley current ratios of their organic or oxide/2D heterojunction diodes.     

Montmorillonite-perlite-iron ceramic membranes for the adsorption/removal of As(III) and other constituents from surface water

In this study, ceramic membranes made of montmorillonite, perlite and iron were used to remove As(III) from water. Membranes prepared with 0.0, 0.5, 1.0, and 1.5 wt% of iron content were used to filtrate As(III) synthetic water and surface water solutions. As(III) adsorption capacity and removal efficiency, and other parameters such as cations and anions content, turbidity, pH, electrical conductivity were used to evaluate the membranes' performance. Results show that the As(III) adsorption/removal capacity of membranes was improved by the addition of iron. Adsorption capacity of 7.5 μg As(III)/g and removal efficiency of 97% can be achieved in membranes with 1.0 wt% of iron filings content for surface water; however, a greater amount of iron in the membrane structure limits the adsorption capacity of As(III). Besides the capacity of ceramic membranes to adsorb/remove As(III), membranes were also effective to remove other ions, turbidity, and electrical conductivity from the surface water. The addition of iron to the ceramic membranes enhanced their capacity to remove such surface water constituents. These results are important from the practical viewpoint showing the potential of ceramic membranes for the removal of metalloids and other water constituents. Langmuir isotherm model best described the adsorption process in ceramic membranes, suggesting that adsorption of As(III) happened on a monolayered surface of the ceramic membrane.     

Analysis of P. aeruginosa disinfectant sensitivity and microbial adhesions to worn cosmetic contact lenses

PurposeTo compare the sensitivity of two genotypes of P. aeruginosa to various disinfectant solutions and analyze the attached bacteria on worn cosmetic contact lenses (cosCLs).MethodsIn this prospective study, healthy volunteers wore etafilcon (brown), nelfilcon (gray), or hilafilcon (black) cosCLs and microbial adhesion analysis was performed. A rub-off test determined pigment dislodgement. Disinfectant sensitivity to Optifree Replenish (Alcon), Optifree Pure Moist (Alcon), Renu Fresh (Bausch & Lomb), and AoSept Plus (Ciba Vision) was tested at various disinfection times and compared between various genotypes and Type III secretion (T3S) system mutants.ResultsOf the 1152 cosCLs collected, 364 were culture positive (32%). The highest rate of culture-positive lens was hilafilcon (chi square, P = 0.0001). Hilafilcon also had a significantly greater number of isolates than etafilcon (P < 0.0001). Hilafilcon was the only lens to fail the rub-off test. Cytotoxic strains were significant more resistant to Renu Fresh than were invasive strains, even at 100% of recommended disinfection time (P = 0.0005). Of the tested disinfectants, Renu Fresh was significantly less effective in killing both genotypes of P. aeruginosa compared to AoSept Plus at all time points (25%, 50%, 75%, and 100% recommended disinfection time, P = 0.0001, 0.0001, 0.0005, and 0.0005, respectively). When the T3S system was dysfunctional, mutant strains were all susceptible to disinfectants (P = 0.0001 for both invasive and cytotoxic strains).ConclusionPseudomonas species is commonly found on cosCLs of asymptomatic individuals. Wearers of cosCLs that dislodge pigments may be predisposed to microbial contamination. Cytotoxic strains are more resistant to disinfectant solutions, especially to Renu Fresh. P. aeruginosa disinfectant resistance requires a functional T3S system.     

Modified three-phase-lag Green–Naghdi models for thermomechanical waves in an axisymmetric annular disk

Abstract

A novel modification for Green and Naghdi thermoelasticity model of type III is proposed in this article. This model is joined to other ones to treat a thermoelastic wave propagation problem in an annular disk. The closed-form solution of thermoelastic analysis of the annular disks has been presented to deduce temperature, radial displacement, dilatation and stresses. Results are illustrated and reported to compare the simple Green–Naghdi II and III and their modified single-, dual- and three-phase-lag models. Concluding remarks are added.     

White light emission based on both upconversion and thermal processes from Nd3+ doped yttrium silicate

In the present study, white light emission based on both upconversion and thermal processes from single-phase yttrium silicate nanopowder doped with Neodymium (III) (Nd³⁺) was investigated at both room pressure and vacuum (0.01 mbar) with a diode laser excitation of 808 nm. 1% Nd³⁺ doped (per mole) yttrium silicate (Y₂O₃:SiO₂) nanopowder was synthesized by using the sol-gel method and annealed at 1250 °C for 12 h to obtain the powder form. Emission for upconverted white light mainly due to the transitions of Nd³⁺ ions was obtained below ~ 5.79 W of the laser beam power at atmospheric pressure. For powers exceeding ~ 5.79 W, the powder emitted a thermal white light (WL) due to the photon avalanche mechanism together with thermal processes. The threshold power to obtain thermal white light with the transitions of Nd³⁺ ions was decreased to ~ 3.51 W at the vacuum condition. These processes were investigated in detail by studying the spectral differences of the rise and decay patterns at atmospheric pressure and vacuum conditions.     

Hypoxia-Responsive Class III Peroxidases in Maize Roots: Soluble and Membrane-Bound Isoenzymes

Flooding induces low-oxygen environments (hypoxia or anoxia) that lead to energy disruption and an imbalance of reactive oxygen species (ROS) production and scavenging enzymes in plants. The influence of hypoxia on roots of hydroponically grown maize (Zea mays L.) plants was investigated. Gene expression (RNA Seq and RT-qPCR) and proteome (LC–MS/MS and 2D-PAGE) analyses were used to determine the alterations in soluble and membrane-bound class III peroxidases under hypoxia. Gel-free peroxidase analyses of plasma membrane-bound proteins showed an increased abundance of ZmPrx03, ZmPrx24, ZmPrx81, and ZmPr85 in stressed samples. Furthermore, RT-qPCR analyses of the corresponding peroxidase genes revealed an increased expression. These peroxidases could be separated with 2D-PAGE and identified by mass spectrometry. An increased abundance of ZmPrx03 and ZmPrx85 was determined. Further peroxidases were identified in detergent-insoluble membranes. Co-regulation with a respiratory burst oxidase homolog (Rboh) and key enzymes of the phenylpropanoid pathway indicates a function of the peroxidases in membrane protection, aerenchyma formation, and cell wall remodeling under hypoxia. This hypothesis was supported by the following: (i) an elevated level of hydrogen peroxide and aerenchyma formation; (ii) an increased guaiacol peroxidase activity in membrane fractions of stressed samples, whereas a decrease was observed in soluble fractions; and (iii) alterations in lignified cells, cellulose, and suberin in root cross-sections.     

Tris(dithiocarbamato)iron(III) complexes as precursors for iron sulfide nanocrystals and iron sulfide-hydroxyethyl cellulose composites

Iron(III) complexes of dimethyldithiocarbamate and imidazolyl dithiocarbamate were synthesized and characterized by elemental analyses, FTIR, UV–VIS and the ligands by NMR spectroscopy. The complexes were thermolysed as single molecule precursors at 180°C to prepare octadecylamine (ODA) capped iron sulfide nanocrystals and iron sulfide-hydroxyethyl cellulose (HEC) composites. UV–VIS, PL, FTIR, P-XRD, HRTEM, FESEM and EDS were used to characterize the iron sulfide nanocrystals and corresponding HEC nanocomposites. XRD confirmed iron sulfide nanocrystal (NP1) from dimethyldithiocarbamate to be hexagonal pyrrhotite-5H, Fe₉S₁₀ crystalline phase while iron sulfide nanocrystals (NP2) from imidazolyl dithiocarbamate is in pyrrhotite, Fe₁₁S₁₂ crystalline phase. TEM images show that the iron sulfide nanocrystals have particle sizes in the range 24–32?nm for NP1 and 18–25?nm for NP2 iron sulfide nanocrystals. The optical band gaps of the iron sulfide nanocrystals obtained from Tauc plots are 3.83 and 4.16?eV for NP1 and NP2, respectively. IR spectra, FESEM surface morphology and EDS spectra of iron sulfide/HEC composites confirmed dispersion of the iron sulfide nanocrystals within the hydroxyethyl cellulose (HEC) matrix.