Improved visible-light-driven photocatalytic removal of Bisphenol A using V2O5/WO3 decorated over Zeolite: Degradation mechanism and toxicity.

WO3/Zeolite/V2O5 (TZV) composite synthesized through co-precipitation was used for the degradation of Bisphenol-A (BpA). XRD and Raman spectra were employed to ascertain the crystallinity of the composite. The pristine nature of the compound without any free particles over the zeolite surface was established through FESEM, thus, substantiating the composite character of the material. The enhancement in activity after doping with WO3 was ascertained by DRS-UV. Photocatalytic degradation studies clearly established the superiority of TZV 10 over bare V2O5. Complete BpA degradation (100%) was attained at 50 min of incubation with 0.75 g/L TZV-10 in acidic medium (pH 3) for an initial BpA concentration of 100 mg/L. HPLC-MS/MS analysis was used to decipher the degradation pathway. The catalyst was stable even after 9 cycles. Phytotoxicity studies and lake water treatment results proved the environmental efficiency of the synthesized material.

Carbon-Based Ternary Nanocomposite: Bullet Type ZnO-SWCNT-CuO for Substantial Solar-Driven Photocatalytic Decomposition of Aqueous Organic Contaminants.

A facile two-step synthesis of ternary hetero-composites of ZnO, CuO, and single-walled carbon nanotubes (SWCNTs) was developed through a recrystallization process followed by annealing. A series of nanocomposites were prepared by varying the weight ratio of copper(II) acetate hydrate and zinc(II) acetate dihydrate and keeping the weight ratio of SWCNTs constant. The results revealed the formation of heterojunctions (ZnO-SWCNT-CuO, ZSC) of three crystal structures adjacent to each other, forming a ternary wurtzite-structured nanoparticles along with defects. Enhanced charge separation (electron-hole pairs), reduced band gap, defect-enhanced specific surface area, and promoted oxidation potential were key factors for the enhanced photocatalytic activity of the ternary nanocomposites. OH• radicals were the main active species during dye degradation, and O2-• and h+ were also involved to a lesser extent. A type II heterojunction mechanism approach is proposed based on the charge carrier migration pattern. Among the synthesized nanocomposites, the sample prepared using copper(II) acetate hydrate and zinc(II) acetate dihydrate in a 1: 9 ratio (designated a ZSC3) showed the highest photocatalytic activity. ZSC3 achieved 99.2% photodecomposition of methylene blue in 20 min, 94.1% photodecomposition of Congo red in 60 min, and 99.6% photodecomposition of Rhodamine B in 40 min under simulated sunlight. Additionally, ZSC3 showed excellent reusability and stability, maintaining 96.7% of its activity even after five successive uses. Based on overall results, the ZSC sample was proposed as an excellent candidate for water purification applications.

Orientation-specific switching of inelastic electron tunneling in an oxygen-pyridine complex adsorbed onto an Ag(110) surface.

Here, we report the development of a molecular rotary switch (a "stator-rotor" consisting of a single oxygen molecule as a stator and a single pyridine molecule as a rotor) on a silver surface. The pyridine molecule was bonded to the oxygen molecule and was found to rotate to enable "ON" or "OFF" vibrational conductance through the oxygen molecule. Four stable sites around the oxygen molecule were observed, and vibration conductance turned on and off depending on the site at which the pyridine molecule bonded. The spatially resolved mapping of the vibrational change revealed two locations of maximal vibration intensity, separated by ∼3 Å. These positions acted as two conducting channels. The two distinct vibrational energy levels were associated with the switching process. Adsorption-induced electron transfer between the silver layers and the molecules enhanced the local interactions between the molecules. The two vibration modes were excited by resonant tunneling despite substantial interactions between the molecules, which resulted in a decrease in tunneling conductance. An independent pathway exists for the vibrational excitation process by tunneling electrons and intermolecular interactions.

Direct observation of the conformational transitions of single pyridine molecules on a Ag(110) surface induced by long-range repulsive intermolecular interactions.

The transition between two conformations of pyridine molecules adsorbed on a Ag(110) surface at 13 K was investigated by performing single-molecule manipulation at a very low coverage and the track-imaging of pyridines for various surface coverages using a variable low-temperature scanning tunneling microscope. A single tilted conformer was converted to an upright conformer when another coadsorbed tilted pyridine molecule approached to within ∼2 nm. The conversion probability depends on the molecular separation. The tilted conformers that are prevalent at a very low coverage were converted to upright conformers with an increasing surface coverage. The minimum molecular separation before this transition is induced was determined to be 2.2 nm using molecular track-imaging and statistical analysis of the pyridine separation as a function of the molecular coverage. The conformation transition was attributed to substrate-mediated long-range repulsive interactions between the pyridine molecules, which are produced by charge redistribution that occurs upon pyridine adsorption on the silver surface.

TCNQ Interlayers for Colloidal Quantum Dot Light-Emitting Diodes.

CdSe/CdS/ZnS quantum dot light-emitting diodes (QD-LEDs) show increased brightness (from ca. 18 000 to 27 000 cd m(-2) ) with 7,7,8,8-tetracyanoquinodimethane (TCNQ) between the QD and electron-transfer layers of ZnO nanoparticles. As QD/ZnO layers are known to have interface defects, our finding leads to the importance of interface engineering for QD-LEDs. Although the photoluminescent intensity and decay lifetime of ZnO/TCNQ/QD layers are similar to those of ZnO/QD layers, cyclic voltammetry suggests improved charge transfer of TCNQ/ZnO layers compared to that of pure ZnO layers. This helps us to understand the mechanism of electrically driven QD-LED behavior, which differs from that of conventional solid-state LEDs, and enables the rational design of QD-based optoelectronic devices.

Extended two-temperature model for ultrafast thermal response of band gap materials upon impulsive optical excitation.

Thermal modeling and numerical simulations have been performed to describe the ultrafast thermal response of band gap materials upon optical excitation. A model was established by extending the conventional two-temperature model that is adequate for metals, but not for semiconductors. It considers the time- and space-dependent density of electrons photoexcited to the conduction band and accordingly allows a more accurate description of the transient thermal equilibration between the hot electrons and lattice. Ultrafast thermal behaviors of bismuth, as a model system, were demonstrated using the extended two-temperature model with a view to elucidating the thermal effects of excitation laser pulse fluence, electron diffusivity, electron-hole recombination kinetics, and electron-phonon interactions, focusing on high-density excitation.

Ultrafast photocarrier dynamics in nanocrystalline ZnOxNy thin films.

We examined the ultrafast dynamics of photocarriers in nanocrystalline ZnOxNy thin films as a function of compositional variation using femtosecond differential transmittance spectroscopy. The relaxation dynamics of photogenerated carriers and electronic structures are strongly dependent on nitrogen concentration. Photocarriers of ZnOxNy films relax on two different time scales. Ultrafast relaxation over several picoseconds is observed for all chemical compositions. However, ZnO and oxygen-rich phases show slow relaxation (longer than several nanoseconds), whereas photocarriers of films with high nitrogen concentrations relax completely on subnanosecond time scales. These relaxation features may provide a persistent photocurrent-free and prompt photoresponsivity for ZnOxNy with high nitrogen concentrations, as opposed to ZnO for display applications.

A comparison between centralized and asynchronous federated learning approaches for survival outcome prediction using clinical and PET data from non-small cell lung cancer patients.

BACKGROUND AND OBJECTIVE: Survival analysis plays an essential role in the medical field for optimal treatment decision-making. Recently, survival analysis based on the deep learning (DL) approach has been proposed and is demonstrating promising results. However, developing an ideal prediction model requires integrating large datasets across multiple institutions, which poses challenges concerning medical data privacy. METHODS: In this paper, we propose FedSurv, an asynchronous federated learning (FL) framework designed to predict survival time using clinical information and positron emission tomography (PET)-based features. This study used two datasets: a public radiogenic dataset of non-small cell lung cancer (NSCLC) from the Cancer Imaging Archive (RNSCLC), and an in-house dataset from the Chonnam National University Hwasun Hospital (CNUHH) in South Korea, consisting of clinical risk factors and F-18 fluorodeoxyglucose (FDG) PET images in NSCLC patients. Initially, each dataset was divided into multiple clients according to histological attributes, and each client was trained using the proposed DL model to predict individual survival time. The FL framework collected weights and parameters from the clients, which were then incorporated into the global model. Finally, the global model aggregated all weights and parameters and redistributed the updated model weights to each client. We evaluated different frameworks including single-client-based approach, centralized learning and FL. RESULTS: We evaluated our method on two independent datasets. First, on the RNSCLC dataset, the mean absolute error (MAE) was 490.80±22.95 d and the C-Index was 0.69±0.01. Second, on the CNUHH dataset, the MAE was 494.25±40.16 d and the C-Index was 0.71±0.01. The FL approach achieved centralized method performance in PET-based survival time prediction and outperformed single-client-based approaches. CONCLUSIONS: Our results demonstrated the feasibility and effectiveness of employing FL for individual survival prediction in NSCLC patients, using clinical information and PET-based features.

Sonophotocatalytic water splitting by BaTiO3@SrTiO3 core shell nanowires.

Sonophotocatalysis has garnered significant attention due to its potential to enhance advanced oxidation processes, particularly water splitting, by employing materials with combined sonocatalytic and photocatalytic properties. In this study, we synthesized and investigated core-shell BaTiO3@SrTiO3 nanowires (BST NWs) with varying Sr/Ba molar ratios (2.5:7.5, 5.0:5.0, 7.5:2.5 mM, denoted as BST-1, BST-2, and BST-3, respectively) as catalysts for hydrogen production through water splitting. The piezoelectric nanowires demonstrated hydrogen evolution via both sonocatalysis and photocatalysis. In the sonophotocatalysis process, the ultrasonic vibration induced mechanical forces on the BST nanowires, thereby establishing a built-in electric field. This built-in electric field facilitated the effective separation of photo-generated charge carriers and prolonged their lifetimes, leading to a synergistic enhancement of hydrogen evolution. The pristine BaTiO3 and SrTiO3 nanowires exhibited relatively low hydrogen evolution rates (HER) of 7.0 and 6.0 µmol·g-1min-1, respectively. In contrast, the core-shell nanowires exhibited a substantial improvement in the hydrogen evolution rate. The HER increased with the addition of Sr, and BST-1, BST-2, and BST-3 achieved HERs of 12.0, 13.5, and 18.0 µmol·g-1min-1, respectively. The superior performance of BST-3 nanowires can be attributed to their highest piezoelectric potential and largest surface area. Additionally, BST-3 nanowires demonstrated remarkable stability over multiple cycles, validating their practical applicability as efficient photocatalysts.

Cobalt-molybdenum-selenide nanoflowers for bifunctional visible light photocatalysis.

The renewability and zero carbon emissions of hydrogen make it a promising clean energy resource to meet future energy demands. Owing to its benefits, photocatalytic water-splitting has been extensively investigated for hydrogen production. However, the low efficiency poses a serious challenge to its implementation. Herein, we attempted to synthesize bimetallic transition metal selenides, namely Co/Mo/Se (CMS) photocatalysts, with varying atomic compositions (CMSa, CMSb, and CMSc) and investigated their photocatalytic water splitting efficiencies. The observed hydrogen evolution rates were as follows: 134.88 µmol g-1 min-1 for CoSe2, 145.11 µmol g-1 min-1 for MoSe2, 167.31 µmol g-1 min-1 for CMSa, 195.11 µmol g-1 min-1 for CMSb, and 203.68 µmol g-1 min-1 for CMSc. Hence, we deemed CMSc to be the most potent photocatalytic alternative among the compounds. CMSc was also tested for its efficiency towards degradation of triclosan (TCN), and results substantiated that CMSc succeeded degrading 98% TCN while CMSa and b were able to degrade 80 and 90% TCN respectively-the attained efficiency being exponentially higher than CoSe2 and MoSe2 taken for comparative analysis in addition to complete degradation of the pollutants leaving no harmful intermediaries during the process. Thus, CMSc shall be identified as a highly potential photocatalyst with respect to both environmental and energy applications.

Cell stretching measurement utilizing viscoelastic particle focusing.

We present an efficient method for measuring cell stretching based on three-dimensional viscoelastic particle focusing. We suspended cells in a biocompatible viscoelastic medium [poly(vinylpyrrolidone) solution in phosphate-buffered saline]. The medium viscoelasticity significantly homogenized the trajectories of cells along the centerline of a simple straight channel, which could not be achieved in conventional Newtonian media. More than 95% of red blood cells (RBCs) were successfully delivered to the stagnation point of a cross-slot microchannel and stretched by extensional flow. By computational simulations, we proved that this method prevents inaccuracies due to random lateral distributions of cells and, further, guarantees rotational-free cell stretching along the shear-free channel centerline. As a demonstration, we characterized the differences in RBC deformabilities among various heat treatments. Furthermore, we monitored the decrease of deformability due to nutrient starvation in human mesenchymal stem cells. We envisage that our novel method can be extended to versatile applications such as the detection of pathophysiological evolution in impaired RBCs due to malaria or diabetes and the monitoring of cell quality in stem cell therapeutics.

Photocatalytic degradation of tetracycline using hybrid Ag/Ag2S@BiOI nanowires: Degradation mechanism and toxicity evaluation.

The wide use of antibiotics has caused their continual release and persistence in the eco-system, subsequently giving birth to antibiotic resistant bacterial species in the aquatic environment, thereby necessitating immediate and efficient remediation of the contaminated environment. In the present study, we synthesized Ag/Ag2S@BiOI nanowires with an average diameter of ∼150 nm and length of 3-5 µm using a hydrothermal method and employed them as photocatalysts for photocatalytic degradation of tetracycline as a model antibiotic. The nanowire achieved nearly complete degradation of tetracycline (∼99%) within 60 min at the optimal condition of 100 mg/L TC concentration and pH 2. The degradation followed pseudo-first order kinetics, with a rate constant of 0.06228 min- 1. Our toxicity tests showed that the nanowire has negligible toxicity towards PBMC cells, suggesting it as a promising photocatalyst.

Zinc iron selenide nanoflowers anchored g-C3N4 as advanced catalyst for photocatalytic water splitting and dye degradation.

Hydrogen has been considered as a promising clean energy source owing to its renewability and zero carbon emission. Accordingly, photocatalytic water splitting has drawn much attention as a key green technology of producing hydrogen. However, it has remained as a great challenge due to the low production rate and expensive constituents of photocatalytic systems. Herein, we synthesised nanostructures consisting of transition metal selenide and g-C3N4 for photocatalytic water splitting reaction. They include ZnSe, FeSe2, Zn/FeSe2 and ZnFeSe2 nanoflowers and a nanocomposite made of Zn/FeSe2 and g-C3N4. Hydrogen evolution rates in the presence of ZnSe, FeSe2, Zn/FeSe2 and ZnFeSe2 photocatalysts were measured as 60.03, 128.02, 155.11 and 83.59 µmolg-1 min-1, respectively. On the other hand, with the nanocomposite consisting of Zn/FeSe2 and g-C3N4, the hydrogen and oxygen evolution rates were significantly enhanced up to 202.94 µmol g-1min-1 and 90.92 µmol g-1min-1, respectively. The nanocomposite was also examined as a photocatalyst for degradation of rhodamine B showing that it photodegrades the compound two times faster compared to pristine Zn/FeSe2 nanoflowers without g-C3N4. Our study suggests the nanocomposite of Zn/FeSe2 and g-C3N4 as a promising photocatalyst for energy and environmental applications.

Highly efficient visible light photocatalysis of Nix Zn1-x Fe2O4 (x= 0, 0.3, 0.7) nanoparticles: Diclofenac degradation mechanism and eco-toxicity.

Pharmaceuticals and personal care products occupy a predominant position with respect to both utility and release into the ecosystem, thereby contributing to environmental pollution at alarming rates. Of the several methods identified to minimize the concentration of PPCPs, nanomaterial based photocatalysis seems to be a potential alternative for it being highly economical and eco-friendly. In this study, we synthesized Nickel zinc ferrite (Ni-ZF) [Nix Zn1-x Fe2O4 (x = 0, 0.3, 0.7)] nanoparticles with an average diameter of ∼400 nm by a co-precipitation method towards diclofenac degradation. The composite showed greater degrees of crystallinity devoid of any impurities. Nearly complete DCF degradation (∼99%) was achieved after 50 min reaction time with the nanoparticles at pH 7 for an initial DCF concentration of 50 mg/L. The degradation process followed a pseudo first-order rate law with the rate constant of 0.1657 min- 1. Microbial toxicity and phytotoxicity studies demonstrated negligible toxicity imposed by the contaminated water treated with the prepared composite, suggesting it as a promising photocatalyst benefitting in all aspects.

Enhanced visible light-driven photocatalytic activity of reduced graphene oxide/cadmium sulfide composite: Methylparaben degradation mechanism and toxicity.

Reduced graphene oxide/cadmium sulfide (RGOCdS) nanocomposite synthesized through solvothermal process was used for methylparaben (MeP) degradation. The crystallinity of the nanocomposite was ascertained through X-ray diffraction. High resolution transmission electron microscope (HRTEM) results proved the absence of any free particle beyond the catalyst surface ensuring the composite nature of the prepared material. The enhancement in the activity on doping with RGO was substantiated by diffuse reflectance spectroscopy (DRS-UV). It is evident from the photocatalytic degradation experiments that RGOCdS is more efficient than pure CdS. Maximum MeP degradation (100%) was achieved after 90 min of irradiation with 750 mg/L RGOCdS dosage at an acidic pH of 3, for an initial MeP concentration of 30 mg/L. The degradation mechanism substantiated through HPLC-MS/MS analysis showed the complete degradation of MeP without any residual intermediaries. The catalyst could be sustained and reused for up to 9 cycles of usage. Phytotoxicity and mycotoxicity results evidently ascertain the environmental implications of the photocatalyst material.

Highly efficient visible light driven photocatalytic activity of zinc/ferrite: Carbamazepine degradation, mechanism and toxicity assessment.

In this present study, spherical shaped zinc ferrite (Zn/Fe2O4) was prepared as uniformly sized (65 ± 0.5 nm) nanoparticles with band gap (2.00 eV) in a visible light regime and employed for the photocatalytic degradation of carbamazepine (CBZ). The doping of Zn decreased the band gap (from 2.00 to 1.98 eV) and enhanced the absorption of visible light. Zinc doping also induced effective separation of photogenerated carriers and subsequent charge migration to the surface of the Zn/Fe2O4 nanoparticle. On account of the advantages of the material, a high removal efficiency (~ 100%) of CBZ through photocatalytic degradation was achieved. Kinetics of CBZ degradation follows a pseudo first-order with the rate constant 0.0367 min-1. In-vitro and in-vivo toxicity of the nanoparticles were examined promoting the environmental implications.

Nickel decorated manganese oxynitride over graphene nanosheets as highly efficient visible light driven photocatalysts for acetylsalicylic acid degradation.

In this work, we prepared nanocomposites of nickel-decorated manganese oxynitride on graphene nanosheets and demonstrated them as photocatalysts for degradation of acetylsalicylic acid (ASA). The catalyst exhibited a high degradation efficiency over ASA under visible light irradiation and an excellent structural stability after multiple uses. Compared to manganese oxide (MnO) and manganese oxynitride (MnON) nanoparticles, larger specific surface area and smaller band gap were observed for the nanocomposite accounting for the enhanced photocatalytic efficiency. Besides the compositional effect of the catalyst, we also examined the influence of various experimental parameters on the degradation of ASA such as initial concentration, catalyst dose, initial pH and additives. The best performance was obtained for the nanocomposite when the catalyst dose was 10 mg/mL and the initial pH 3. Detection of intermediates during photocatalysis showed that ASA undergoes hydroxylation, demethylation, aromatization, ring opening, and finally complete mineralization into CO2 and H2O by reactive species. For practical applications as a photocatalyst, cytotoxicity of the nanocomposite was also evaluated, which revealed its insignificant impact on the cell viability. These results suggest the nanocomposite of nickel-decorated manganese oxynitride on graphene nanosheets as a promising photocatalyst for the remediation of ASA-contaminated water.

Enhanced visible light-driven photocatalysis of iron-oxide/titania composite: Norfloxacin degradation mechanism and toxicity study.

A simulated visible light-mediated iron oxide-titania (IoT) nanocomposite was employed to degrade the antibiotic norfloxacin (NFN) photocatalytically. The photocatalyst were prepared using a sol-gel method with controlled titania loadings to iron oxide by altering the fabrications step. The nanocomposites were structurally characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), field emission high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, Diffuse reflectance UV-visible spectra (DRS-UV) spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy (XPS). It was observed that 100 mg/L of iron oxide doped titania loading at 1:4 (IoT-4) achieved the maximum photocatalytic activity in a 75 mg/100 mL of NFN solution within 60 min of the reaction time under visible light irradiation. The NFN degradation mechanism affirmed using HPLC-MS/MS analysis and the results confirmed the complete NFN degradation without residual intermediates. Significant, sustained recyclability was obtained by completely removing the contaminant up to 5 cycles with 90% degradation ability till nine cycles. Bacterial- and phytotoxicity data ascertain that the photocatalyzed and contaminant-free water is safe for the environment. The outstanding photocatalytic performance in removing organic pollutants indicates the potential application of IoT nanocomposites in real-time environmental remediation.

Virus-templated assembly of porphyrins into light-harvesting nanoantennae.

Biological molecules can be used as versatile templates for assembling nanoscale materials because of their unique structures and chemical diversities. Supramolecular organization of molecular pigments, as is found in the natural light-harvesting antenna, has drawn attention for its potential applications to sensors, photocatalytic systems, and photonic devices. Here we show the arrangement of molecular pigments into a one-dimensional light-harvesting antenna using M13 viruses as scaffolds. Chemical grafting of zinc porphyrins to M13 viruses induces distinctive spectroscopic changes, including fluorescence quenching, the extensive band broadening and small red shift of their absorption spectrum, and the shortened lifetime of the excited states. Based on these optical signatures we suggest a hypothetical model to explain the energy transfer occurring in the supramolecular porphyrin structures templated with the virus. We expect that further genetic engineering of M13 viruses can allow us to coassemble other functional materials (e.g., catalysts and electron transfer mediators) with pigments, implying potential applications to photochemical devices.

BTB proteins are substrate-specific adaptors in an SCF-like modular ubiquitin ligase containing CUL-3.

Programmed destruction of regulatory proteins through the ubiquitin-proteasome system is a widely used mechanism for controlling signalling pathways. Cullins are proteins that function as scaffolds for modular ubiquitin ligases typified by the SCF (Skp1-Cul1-F-box) complex. The substrate selectivity of these E3 ligases is dictated by a specificity module that binds cullins. In the SCF complex, this module is composed of Skp1, which binds directly to Cul1, and a member of the F-box family of proteins. F-box proteins bind Skp1 through the F-box motif, and substrates by means of carboxy-terminal protein interaction domains. Similarly, Cul2 and Cul5 interact with BC-box-containing specificity factors through the Skp1-like protein elongin C. Cul3 is required for embryonic development in mammals and Caenorhabditis elegans but its specificity module is unknown. Here we report the identification of a large family of BTB-domain proteins as substrate-specific adaptors for C. elegans CUL-3. Biochemical studies using the BTB protein MEL-26 and its genetic target MEI-1 (refs 12, 13) indicate that BTB proteins merge the functional properties of Skp1 and F-box proteins into a single polypeptide.