Iridium oxide-modified reference screen-printed electrodes for point-of-care portable electrochemical cortisol detection.

Cortisol is a well-known stress biomarker; this study focuses on using electrochemical immuno-sensing to measure the concentration of cortisol selectively and sensitively in artificial samples. Anti-cortisol antibodies have been immobilised on polycrystalline Au electrodes via strong covalent thiol bonds, fabricating an electrochemical bio-immunosensor for cortisol detection. IrOx was then anodically electrodeposited as a reference electrode on a commercial screen-printed electrode and electrochemical impedance spectrometry (EIS) studies were used to correlate the electrochemical response to cortisol concentration and the induced changes in charge transfer resistance (Rct). A linear relationship between the Rct and the logarithm of cortisol concentration was found in concentrations ranging from 1 ng/mL to 1 mg/mL with limit of detection at 11.85 pg/mL (32.69 pM). The modification of the reference electrode with iridium oxide has greatly improved the reproducibility of the screen-printed electrode. The sensing system can provide a reliable and sensitive detection approach for cortisol measurements.

A feasible interlayer strategy for simultaneous light and heat management in photothermal catalysis.

Photothermal conversion represents one crucial approach for solar energy harvesting and its exploitation as a sustainable alternative to fossil fuels; however, an efficient, cost-effective, and generalized approach to enhance the photothermal conversion processes is still missing. Herein, we develop a feasible and efficient photothermal conversion strategy that achieves simultaneous light and heat management using supported metal clusters and WSe2 interlayer toward enhanced CO2 hydrogenation photothermal catalysis. The interlayer can simultaneously reduce heat loss in the catalytic layer and improve light absorption, leading to an 8-fold higher CO2 conversion rate than the controls. The optical and thermal performance of WSe2 interlayered catalysts on different substrates was quantified using Raman spectroscopy. This work demonstrates a feasible and generalized approach for effective light and heat management in solar harvesting. It also provides important design guidelines for efficient photothermal converters that facilitate the remediation of the energy and environmental crises faced by humans.

Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to (Z)-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry.

While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives (Z)-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ5-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals. Four of these are characterised by X-ray diffraction with two involving the bidentate ligand forming a five-membered ring metallacycle and two with the ligand coordinating to the metal only through phosphorus.

Plasmonic enhanced Cu2O-Au-BFO photocathodes for solar hydrogen production.

A novel Cu2O-Au-BFO heterostructure photocathode was constructed which significantly improved the efficiency of photo-generated carrier transfer for solar hydrogen production. A BiFeO3 (BFO) ferroelectric film was synthesized on top of a Cu2O layer by a sputtering process. The BFO layer acted to protect the Cu2O layer from photochemical corrosion, increasing photoelectrochemical (PEC) stability. The p-n heterojunction between Cu2O and BFO layers enhanced the PEC properties by suppressing charge recombination and improved interfacial charge transfer efficiency. When Cu2O and BFO are interfaced by Au Nanoparticles (NPs) the PEC performance was further enhanced, due to hot-electron transfer at the plasmonic resonance. After positive poling, the depolarization field across the whole volume of BFO film drove electrons into the electrolyte solution, inducing a significant anodic shift, Vop of 1.01 V vs. RHE, together with a significantly enhanced photocurrent density of -91 µA/cm2 at 0 V vs. RHE under 100 mW/cm2 illumination. The mechanism was investigated through experimental and theoretivcal calculations.

Morphology dependent adsorption of methylene blue on trititanate nanoplates and nanotubes prepared by the hydrothermal treatment of TiO2.

The adsorption properties of two nanomorphologies of trititanate, nanotubes (TiNT) and plates (TiNP), prepared by the hydrothermal reaction of concentrated NaOH with different phases of TiO2, were examined. It was found that the capacity for both morphologies towards methylene blue (MB), an ideal pollutant, was extremely high, with the TiNP having a capacity of 130 mg/g, higher than the TiNT, whose capacity was 120 mg/g at 10 mg/L MB concentration. At capacity, the well-dispersed powders deposit on the floor of the reaction vessel. The two morphologies had very different structural and adsorption properties. TiNT with high surface area and pore volume exhibited exothermic monolayer adsorption of MB. TiNP with low surface area and pore volume yielded a higher adsorption capacity through endothermic multilayer adsorption governed by pore diffusion. TiNP exhibited a higher negative surface charge of -23 mV, compared to -12 mV for TiNT. The adsorption process appears to be an electrostatic interaction, with the cationic dye attracted more strongly to the nanoplates, resulting in a higher adsorption capacity and different adsorption modes. We believe this simple, low cost production of high capacity nanostructured adsorbent material has potential uses in wastewater treatment.

Dopamine Surface Modification of Trititanate Nanotubes: Proposed In-Situ Structure Models.

Two models for self-assembled dopamine on the surface of trititanate nanotubes are proposed: individual monomer units linked by π-π stacking of the aromatic regions and mono-attached units interacting through hydrogen bonds. This was investigated with solid state NMR spectroscopy studies and powder X-ray diffraction.

Binding mode and structure-activity relationships around direct inhibitors of the Nrf2-Keap1 complex.

An X-ray crystal structure of Kelch-like ECH-associated protein (Keap1) co-crystallised with (1S,2R)-2-[(1S)-1-[(1,3-dioxo-2,3-dihydro-1H-isoindol-2-yl)methyl]-1,2,3,4-tetrahydroisoquinolin-2-carbonyl]cyclohexane-1-carboxylic acid (compound (S,R,S)-1 a) was obtained. This X-ray crystal structure provides breakthrough experimental evidence for the true binding mode of the hit compound (S,R,S)-1 a, as the ligand orientation was found to differ from that of the initial docking model, which was available at the start of the project. Crystallographic elucidation of this binding mode helped to focus and drive the drug design process more effectively and efficiently.

Substituted azaquinazolinones as modulators of GHSr-1a for the treatment of type II diabetes and obesity.

Substituted azaquinazolinones were identified as antagonists of the GHSr-1A receptor for the treatment of type II diabetes and obesity. Optimisation for potency and LogD lead to the identification of orally bioavailable, potent antagonists with improved selectivity over hERG.

Design and synthesis of potent carboxylic acid DGAT1 inhibitors with high cell permeability.

A series of potent carboxylic acid DGAT1 inhibitors with high permeability were developed from a virtual screening hit. Strategies were employed to reduce Pgp substrate recognition and increase passive permeability, resulting in the discovery of a series showing good inhibition of cellular triglyceride synthesis. The mutagenic potential of prospective metabolites was evaluated in the Ames assay, and one aniline was shown to be devoid of mutagenicity.

The toxicity evaluation of nano-trititanate with bactericidal properties in vitro.

Three forms of nano-trititanate (H(2)Ti(3)O(7) nanomaterial) were prepared by a hydrothermal method to replace nano-TiO(2) for sterilizing the environment. The bactericidal capabilities of these nano-trititanates were observed to be more significant compared to nano-TiO(2) both with and without exposure to UV light. For the future commercial applications of those nano-trititanates, we investigated their cytotoxicity and genotoxicity to HEp-2 cells. As data in our study shows, nanoplate, one of the nano-trititanates, possesses the lowest toxicity to HEp-2 cells. The results indicated that the shape and length of the material only affect the toxicity of nano-trititanate but not its bactericidal effect. Thus, through manipulating the shape or length of nano-trititanate, we may obtain a more powerful bactericidal reagent with lower toxicity to the human body.

Accelerated electron beam induced breakdown of commercial WO3 into nanorods in the presence of triethylamine.

Tungsten oxide nanorods were prepared from commercial crystalline WO(3) particles treated with triethylamine under electron beam irradiation in an electron microscope operating at 200 kV. The amine acts as a molecular knife, cleaving the particles under beam irradiation.

Thermal rearrangement of thiocarbonyl-stabilised triphenylphosphonium ylides leading to (Z)-1-diphenylphosphino-2-phenylsulfenylalkenes.

While thermolysis of thiocarbonyl-stabilised phosphonium ylides generally results in extrusion of Ph(3)PS to give alkynes, those with a P=CH function instead undergo a novel P to S transfer of a phenyl group to give (Z)-configured 1-phosphino-2-sulfenylalkenes of interest as bidentate ligands.