The current limitations in utilizing metal-organic frameworks for (photo)electrochemical applications stem from their diminished electrochemical stability. In our study, we illustrate a method to bolster the activity and stability of (photo)electrocatalytically active metal-organic frameworks through ligand engineering. We synthesize four distinct mixed-ligand versions of zeolitic imidazolate framework-67, and conduct a comprehensive investigation into the structural evolution and self-reconstruction during electrocatalytic oxygen evolution reactions.
View Article and Find Full Text PDFA novel series of Zn--AB porphyrins and benzoporphyrins bearing phenyl and thiophene-based -substituents was successfully synthesized and characterized by spectroscopic and electrochemical techniques. Systematic comparison among the compounds in this series, together with the corresponding A analogs previously studied by our group, led to the understanding of the effects of π-conjugated system extension of a porphyrin core through β-fused rings, replacement of the phenyl with the thiophene-based -groups, and introduction of additional thiophene rings on thienyl substituents on photophysical and electrochemical properties. Oxidative electropolymerization through bithiophenyl units of both A and -AB analogs was achieved, resulting in porphyrin- and benzoporphyrin-oligothiophene conjugated polymers, which were characterized by cyclic voltammetry and absorption spectrophotometry.
View Article and Find Full Text PDFProduction of green hydrogen (H) is a sustainable process able to address the current energy crisis without contributing to long-term greenhouse gas emissions. Many Ag-based catalysts have shown promise for light-driven H generation, however, pure Ag-in its bulk or nanostructured forms-suffers from slow electron transfer kinetics and unfavorable Ag─H bond strength. It is demonstrated that the complexation of Ag with various chalcogenides can be used as a tool to optimize these parameters and reach improved photocatalytic performance.
View Article and Find Full Text PDFThe organic semiconductor 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), a widely used industrial pigment, has been identified as a diffusion-less Na-ion storage material, allowing for exceptionally fast charging/discharging rates. The elimination of diffusion effects in electrochemical measurements enables the assessment of interaction energies from simple cyclic voltammetry experiments through the theoretical work of Laviron and Tokuda. In this work, the two N-substituted perylenes, ,'-dimethyl-3,4,9,10-perylenetetracarboxylic diimide (MePTCDI) and ,'-diphenyl-3,4,9,10-perylenetetracarboxylic diimide (PhPTCDI), as well as the parent molecule 3,4,9,10-perylenetetracarboxylic diimide (HPTCDI) are investigated as thin-film composite electrodes on carbon fibers for sodium-ion batteries.
View Article and Find Full Text PDFThe objective of the present study was to assess the inactivation kinetics of γ-irradiation of selected foodborne pathogens in instant soup. O157:H7 (ATCC 25922), subsp. serovar Enteritidis (ATCC 13076) (ATCC 2592), and (ATCC 11778) were inoculated into instant soup and irradiated at various doses of 0 (control), 0.
View Article and Find Full Text PDFCuAl layered double hydroxide (LDH) and polymeric carbon nitride (g-CN, GCNN) were assembled to construct a set of novel 2D/2D CuAl-LDH/GCNN heterostructures. These materials were tested towards H and O generation from water splitting using visible-light irradiation. Compared to pristine materials, the heterostructures displayed strongly enhanced visible-light H evolution, dependent on the LDH content, which acts as a cocatalyst, replacing the benchmark Pt.
View Article and Find Full Text PDFGrape juice is a widely consumed fruit due to its bioactive compounds, minerals, and aroma components. Our objective was to investigate ultrasound treatment of black grape juice affects its bioactive components due to using response surface methodology (RSM) and artificial neural network (ANN) optimization. At the same time, mineral components, sugar components, organic acids, and volatile aroma profiles were compared in black grape juice treated with thermal and ultrasound pasteurization.
View Article and Find Full Text PDFToday, many essential industrial processes depend on syngas. Due to a high energy demand and overall cost as well as a dependence on natural gas as its precursor, alternative routes to produce this valuable mixture of hydrogen and carbon monoxide are urgently needed. Electrochemical syngas production via two competing processes, namely carbon dioxide (CO) reduction and hydrogen (H) evolution, is a promising method.
View Article and Find Full Text PDFCo-doping represents a valid approach to maximize the performance of photocatalytic and photoelectrocatalytic semiconductors. Albeit theoretical predictions in hematite suggesting a bulk n-type doping and a surface p-type doping would deliver best results, hematite co-doping with coupled cations possessing low and high oxidation states has shown promising results. Herein, we report, for the first time, Sb and Li co-doping of hematite photoanodes.
View Article and Find Full Text PDFAims: Dysregulated immune response contributes to inefficiency of treatment strategies to control hypertension and reduce the risk of end-organ damage. Uncovering the immune pathways driving the transition from the onset of hypertensive stimulus to the manifestation of multi-organ dysfunction are much-needed insights for immune targeted therapy.
Methods And Results: To aid visualization of cellular events orchestrating multi-organ pathogenesis, we modelled hypertensive cardiovascular remodelling in zebrafish.
J Phys Chem C Nanomater Interfaces
February 2021
The ordering effects in anthraquinone (AQ) stacking forced by thin-film application and its influence on dimer solubility and current collector adhesion are investigated. The structural characteristics of AQ and its chemical environment are found to have a substantial influence on its electrochemical performance. Computational investigation for different charged states of AQ on a carbon substrate obtained via basin hopping global minimization provides important insights into the physicochemical thin-film properties.
View Article and Find Full Text PDFIn this report, we present results on the electrocatalytic activity of conducting polymers [polyaniline (PANI) and polypyrrole (PPy)] toward the electrochemical oxygen reduction reaction (ORR) to hydrogen peroxide (HO). The electropolymerization of the polymers and electrolysis conditions were optimized for HO production. On flat glassy carbon (GC) electrodes, the faradaic efficiency (FE) for HO production was significantly improved by the polymers.
View Article and Find Full Text PDFStressful experiences early in life can increase the risk of cardiovascular diseases. However, it remains largely unknown how stress influences susceptibility to the disease onset. Here, we show that exposure to brain-processed stress disrupts myocardial growth by reducing cardiomyocyte mitotic activity.
View Article and Find Full Text PDFIn this work 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) is investigated as electrode material for organic Na-ion batteries. Since PTCDI is a widely used industrial pigment, it may turn out to be a cost-effective, abundant, and environmentally benign cathode material for secondary Na-ion batteries. Among other carbonyl pigments, PTCDI is especially interesting due to its high Na-storage capacity in combination with remarkable high rate capabilities.
View Article and Find Full Text PDFWe report the synthesis and electrochemical properties of freebase tetraphenyltetrabenzoporphyrin and its complexes of Zn(ii), Co(ii), Ni(ii), Cu(ii) and Sn(iv) towards electrochemical reduction of carbon dioxide (CO). Based on cyclic voltammetry, it is shown that central metals significantly affect the electrocatalytic performance in the reduction of CO in terms of reduction potential and catalytic current enhancement. At an applied potential of -1.
View Article and Find Full Text PDFIn this article, we present the improvement in device performance and stability as well as reduction in hysteresis of inverted mixed-cation-mixed-halide perovskite solar cells (PSCs) using a low temperature, solution processed titanium oxide (TiO ) interlayer between [6,6]-phenyl-C butyric acid methyl ester (PCBM) and an Al electrode. Upon applying a TiO interlayer, device resistance was reduced compared to that of the control devices, which results in improved rectification of the characteristic current density-voltage (-) curve and improved overall performance of the device. PSCs with the TiO interlayer show an open-circuit voltage ( ) of around 1.
View Article and Find Full Text PDFFlavins are known to be extremely versatile, thus enabling routes to innumerable modifications in order to obtain desired properties. Thus, in the present paper, the group of bio-inspired conjugated materials based on the alloxazine core is synthetized using two efficient novel synthetic approaches providing relatively high reaction yields. The comprehensive characterization of the materials, in order to evaluate the properties and application potential, has shown that the modification of the initial alloxazine core with aromatic substituents allows fine tuning of the optical bandgap, position of electronic orbitals, absorption and emission properties.
View Article and Find Full Text PDFWe report on a self-assembled system comprising a molecular copper-porphyrin photoelectrocatalyst, 5-(4-carboxy-phenyl)-10,15,20-triphenylporphyrinatocopper(II) (CuTPP-COOH), covalently bound to self-organized, anodic titania nanotube arrays (TiO NTs) for photoelectrochemical reduction of oxygen. Visible light irradiation of the porphyrin-covered TiO NTs under cathodic polarization up to -0.3 V vs.
View Article and Find Full Text PDFExposure to low-intensity radiation in the near-infrared (NIR) spectral region matching the optically transparent "phototherapeutic window" of biological tissues can be applied to directly populate spin-restricted excited states of light-responsive compounds. This unconventional and unprecedented approach is introduced herein as a new strategy to overcome some of the major unresolved problems observed in the rapidly emerging fields of photopharmacology and molecular photomedicine, where practical applications in living cells and organisms are still limited by undesired side reactions and insufficient light penetration. Water-soluble and biocompatible metal complexes with a significant degree of spin-orbit coupling were identified as target candidates for testing our new hypothesis.
View Article and Find Full Text PDFControlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization.
View Article and Find Full Text PDFIn the recent decade, CO has increasingly been regarded not only as a greenhouse gas but even more as a chemical feedstock for carbon-based materials. Different strategies have evolved to realize CO utilization and conversion into fuels and chemicals. In particular, biological approaches have drawn attention, as natural CO conversion serves as a model for many processes.
View Article and Find Full Text PDFA broad review of homogeneous and heterogeneous catalytic approaches toward CO reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes.
View Article and Find Full Text PDFDeveloping efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT).
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