Photocatalytic Degradation of Crystal Violet on Cu, Zn Doped BiVO4 Particles.

Fabrication of codoped photocatalysts is a developing area of research. Herein, we explore the visible light photocatalytic properties of Cu, Zn codoped BiVO4 particles. Doping lower valent cations (Cu and Zn) makes the BiVO4 surface more acidic and enables us to target the basic crystal violet (CV) dye. The adopted hydrothermal protocol of synthesis results in the formation of Cu-Zn codoped monoclinic BiVO4 particles. Undoped monoclinic BiVO4, prepared by the same protocol, showed significant formation of oxygen vacancies. XPS analyses confirm the coexistence of Cu2+/Cu+ and Zn2+ dopants. Increased dopant percentage reduced oxygen vacancies. XRD indicates that Cu2+/Cu+ or Zn2+ dopants generally substitute Bi3+ in BiVO4. All photocatalysis activities for CV degradation are reported under near-neutral pH conditions. A typical codoped BiVO4 photocatalyst with 1% Zn and 2% Cu demonstrated the best CV degradation photocatalytic activity. The activity of this Zn, Cu codoped photocatalyst is better than that of pure, Zn-doped, and Cu-doped BiVO4 samples. Active species trapping experiments indicated the possible photocatalysis mechanism. The photocatalysts exhibited appropriate recyclability and photostability.

Silver nanoparticle-decorated NiFe2O4/CuWO4 heterostructure electrocatalyst for oxygen evolution reactions.

In this work, Ag nanoparticles decorated with NiFe2O4/CuWO4 heterostructure were synthesized using the step-wise precipitation method. The influence of varying Ag loading on the NiFe2O4/CuWO4 heterostructure and its electrochemical OER performance was extensively studied in 1 M KOH electrolyte. The obtained LSV profile was analyzed to determine the overpotential, Tafel slope, and onset potential. The heterostructure with an optimal Ag loading of 5 wt% required the least overpotential (1.60 V vs. RHE) for generating a current density of 10 mA cm-2 with a lower Tafel slope of 44.5 mV dec-1, indicating its faster OER kinetics. Furthermore, the composite remained stable over a period of 24 hours with a minimum rise in the overpotential after the stability test. The enhanced OER performance of the as-prepared catalyst can be attributed to the presence of multiple metallic elements in the Ag-loaded NiFe2O4/CuWO4 composite, which created a diverse array of oxygen-vacant sites with varying reactivity, enhancing the charge-transfer kinetics; and thus contributing to the overall efficiency of OER. Therefore, optimizing the Ag concentration and engineering a microstructure represents an encouraging strategy for developing cost-effective catalysts for next-generation energy-conversion applications.

The E3 ligase Itch and deubiquitinase Cyld act together to regulate Tak1 and inflammation.

Chronic inflammation has been strongly associated with tumor progression, but the underlying mechanisms remain elusive. Here we demonstrate that E3 ligase Itch and deubiquitinase Cyld formed a complex via interaction through 'WW-PPXY' motifs. The Itch-Cyld complex sequentially cleaved Lys63-linked ubiquitin chains and catalyzed Lys48-linked ubiquitination on the kinase Tak1 to terminate inflammatory signaling via tumor necrosis factor. Reconstitution of wild-type Cyld but not the mutant Cyld(Y485A), which cannot associate with Itch, blocked sustained Tak1 activation and proinflammatory cytokine production by Cyld(-/-) bone marrow-derived macrophages. Deficiency in Itch or Cyld led to chronic production of tumor-promoting cytokines by tumor-associated macrophages and aggressive growth of lung carcinoma. Thus, we have identified an Itch-Cyld-mediated regulatory mechanism in innate inflammatory cells.

The bandgap of sulfur-doped Ag2O nanoparticles.

A narrow band gap restricts photocatalytic applications of Ag2O nanoparticles, but appropriate doping can favorably modify this aspect. Given this, density functional theory (DFT) calculations were conducted, revealing that substitutional sulfur doping of Ag2O could increase its bandgap and stabilize oxygen vacancies. A hydrothermal precipitation protocol was employed to prepare sulfur-doped (S-doped) Ag2O nanoparticles. The band gap of the prepared nanoparticles increased to 1.89 eV with 1.25-mole percent S-doping. XPS analysis of the samples also revealed that S-doping increased oxygen vacancies in the prepared Ag2O nanoparticles. Furthermore, S-doping caused a major shift in the valence band position to a negative value. These doped Ag2O nanoparticles showed an enhanced visible-light photocatalytic activity towards rhodamine B (RhB) degradation.

Genesis of copper oxide nanoparticles from waste printed circuit boards and evaluation of their photocatalytic activity.

Discarded Printed Circuit Boards (PCBs) are one of the secondary resources of high-purity copper, and precious materials, which if disposed off inappropriately may present several environmental risks. This study focuses on the production of copper oxide nanoparticles (CuO NPs) from reclaimed copper via a facile precipitation route to obtain a value-added nanoproduct. The synthesis involved the dissolution of downsized PCBs, leaching of Cu into the solution phase and the precipitation of nanoparticles (NPs) in an alkaline medium. XRD analysis confirmed the as-synthesized NPs were monoclinic CuO of size 19.23 nm without any impurity. HRTEM analysis confirmed that the NPs were nearly round spheres with average particle size of 19.973 ± 6.036 nm. The NPs have a specific surface area of 200 m2/g and mesoporous structure with mean pore diameter of 18.051 nm. The CuO NPs photocatalyzed the degradation of Congo Red under visible light irradiation. Hence, the PCB e-waste was utilized to produce nanomaterials with added-values, decreasing environmental problems.

Visible-Light Plasmonic Enhancement of Catalytic Activity of Anisotropic Silver Nanoparticles.

Synthesis of silver nanoparticles (AgNPs) in presence of copper salt (as the etchant) led to the formation of nanoparticle samples with different fractions of anisotropic particles. The proportion of anisotropic nanoparticles decreased with increase in ratio of precursor Cu salt in the preparation protocol. These AgNPs samples were found to catalyse p-nitrophenol reduction by glycerol and Fenton oxidation of methyl orange. The catalytic activity of these AgNPs samples for these reactions increased with the fraction of anisotropic nanoparticles in the catalyst samples. On conducting these reactions under cool white LED visible light, the catalytic activity of AgNPs catalyst samples increased by 2 to 3 times compared to that observed in dark. The photo-Fenton MO degradation catalytic activity obtained is among the best reported in literature. However, the order of the reaction did not change whether the reaction was conducted under visible light or in dark. Direct plasmonic catalytic mechanisms are proposed to explain the enhancement in reactivity under visible light.

Bosutinib inhibits migration and invasion via ACK1 in KRAS mutant non-small cell lung cancer.

The advent of effective targeted therapeutics has led to increasing emphasis on precise biomarkers for accurate patient stratification. Here, we describe the role of ACK1, a non-receptor tyrosine kinase in abrogating migration and invasion in KRAS mutant lung adenocarcinoma. Bosutinib, which inhibits ACK1 at 2.7 nM IC50, was found to inhibit cell migration and invasion but not viability in a panel of non-small cell lung cancer (NSCLC) cell lines. Knockdown of ACK1 abrogated bosutinib-induced inhibition of cell migration and invasion specifically in KRAS mutant cells. This finding was further confirmed in an in vivo zebrafish metastatic model. Tissue microarray data on 210 Singaporean lung adenocarcinomas indicate that cytoplasmic ACK1 was significantly over-expressed relative to paired adjacent non-tumor tissue. Interestingly, ACK1 expression in "normal" tissue adjacent to tumour, but not tumour, was independently associated with poor overall and relapse-free survival. In conclusion, inhibition of ACK1 with bosutinib attenuates migration and invasion in the context of KRAS mutant NSCLC and may fulfil a therapeutic niche through combinatorial treatment approaches.

Synthesis and characterization of titanium-substituted nanocrystalline Co2-Y hexaferrite: magnetically retrievable photocatalyst for treatment of methyl orange contaminated wastewater.

Rapid industrial growth causes considerable environmental havoc, adversely affecting human and aqueous life. It becomes a significant concern to deal with adequate wastewater treatment strategies by converging on water scarcity. This research work explored the synthesis of titanium-substituted Y-type barium hexaferrite (Co2-Y), having a general formula of Ba2Co2Fe12-xTixO22 (x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5), using a facile nitrate-based sol-gel auto-combustion route and its suitability was investigated as a heterogeneous catalyst within the photo-Fenton-based degradation of methyl orange (MO), one of the significant pollutants generated from textile industries. Developing a thermochemically stable and magnetically separable heterogeneous catalyst for photocatalytic decomposition of nonbiodegradable organic dye from wastewater was also emphasized. The as-prepared nanocrystalline Co2-Y powders were analyzed using XRD, FTIR, DLS, UV-visible spectroscopy, SEM, VSM, and XPS. Furthermore, the photocatalytic degradation performance of pristine and titanium substituted Ba2Co2Fe11.6Ti0.4O22 ferrite, having the lowest bandgap value among all samples, was quantified and compared in terms of apparent rate constant (karc) value and turnover frequency values. The enriched photocatalytic performance was correlated with the existence of multi-valance states of transition metal cations and the availability of oxygen vacancy, confirmed by the surface chemistry using the XPS analysis. The modified (enhanced thermal and chemical stability) hexaferrite catalyst was magnetically separable and reusable without significant losses to its catalytic performance. This promising catalyst may be considered as a replacement for soft ferrite materials to catalyze the degradation of several other nonbiodegradable organic pollutants from wastewater in large-scale industries.

Magnetic Ni@C nanoadsorbents for methyl orange removal from water.

In this study, Ni@C nanoparticles were produced and used as an adsorbent for removing methyl orange (MO) from an aqueous solution. The sol-gel method was utilized for the preparation of the particles. The X-ray diffraction pattern and transmission electron microscopy (TEM) were utilized to determine the phase, morphology, and size. The electron micrograph indicated the coating of carbon over Ni having size between 43 and 94 nm, and the Raman spectrum supported it. Among three, the maximum specific magnetization of the Ni@C nanocomposite was 55.78 emu/g for the N7 sample. From the BET approach, specific surface areas of 2.29 × 105, 3.66 × 105, and 5.48 × 105 cm2/g as well as average pore size of 49.30, 37.25, and 35.27 nm were observed for N5, N6, and N7, respectively. The Ni@C nanoparticles were magnetically separable and exhibited rapid adsorption of MO of different concentrations from their aqueous solutions. The N7 adsorbent displayed the highest MO adsorption capacity (~ 32 mg·g-1) along with maintaining an adsorption capacity of 81% even after 5 cycles. Adsorption isotherm and kinetic analysis gave critical inputs toward the possible adsorption mechanism.

Waste remediation: Low-temperature synthesis of hybrid Cu(OH)2/CuO and CuO nanostructures from spent printed circuit boards and their dye degradation studies.

The demand for environmentally friendly and sustainable resource utilization techniques for recycling waste printed circuit boards is significant due to their status as valuable secondary resources, containing high-purity copper and precious metals. In this context, Cu(OH)2/CuO and CuO nanostructures were fabricated using alkaline precipitation and low-temperature aging methods using the strip solution originated from laboratory-scale spent mobile phone printed circuit board recovery process. XRD, FTIR, FESEM-EDX, and TEM were utilized to characterize the as-recovered nanoproducts. A hybrid structure of Cu(OH)2/CuO was formed at 70°, and monoclinic CuO phase was formed at 80 °C aging time. The results show that Cu(OH)2/CuO nanoflakes have an average crystallite size of 24.06 nm and a particle width of 22 ± 3 nm. Cu(OH)2/CuO nanoflakes formed at 70 °C aging temperature and 24-h residence time have finer crystallite and particle sizes than CuO-ridged nanospheres formed at 80 °C aging temperature. The optical band gap energy of Cu(OH)2/CuO and CuO nanostructures formed was found to be 2.28 eV and 2.22 eV, respectively. The hybrid Cu(OH)2/CuO nanostructure photocatalyzed the decomposed 97.28% rhodamine blue using a visible light source, whereas the CuO nanostructure degraded only 14.64% rhodamine blue dye under similar conditions. A surfactant-less hybrid structure is developed without the use of any chemical precursor. Thus, a high value-added product is produced using one waste material to remove another waste in wastewater treatment.

Cyclin-dependent kinases control septin phosphorylation in Candida albicans hyphal development.

Cyclin-dependent kinases (Cdks) control cytoskeleton polarization in yeast morphogenesis. However, the target and mechanism remain unclear. Here, we show that the Candida albicans Cdk Cdc28, through temporally controlled association with two cyclins Ccn1 and Hgc1, rapidly establishes and persistently maintains phosphorylation of the septin cytoskeleton protein Cdc11 for hyphal development. Upon hyphal induction, Cdc28-Ccn1 binds to septin complexes and phosphorylates Cdc11 on Ser394, a nonconsensus Cdk target. This phosphorylation requires prior phosphorylation on Ser395 by the septin-associated kinase Gin4. Mutating Ser394 or Ser395 blocked Cdc11 phosphorylation on Ser394 and impaired hyphal morphogenesis. Reconstitution experiments using purified Cdc28-Ccn1, Gin4, and septins reproduced phosphorylations on the same residues. Transient septin-Cdc28 associations were also detected prior to bud and mating-projection emergence in S. cerevisiae. Our study uncovers a direct link between the cell-cycle engine and the septin cytoskeleton that may be part of a conserved mechanism underlying polarized morphogenesis.

Mechanism of phenol and p-nitrophenol adsorption on kaolinite surface in aqueous medium: A molecular dynamics study.

Very few aqueous medium experimental studies focus on the molecular interaction mechanism between the adsorbent and the adsorbate. Herein, we investigate the adsorption of two organic pollutants, phenol and p-nitrophenol (PNP) in dilute aqueous solution conditions on kaolinite (001) surface through classical molecular dynamics (MD) simulations. The present investigation addresses both adsorption isotherms and mechanistic issues. MD simulations at different solute concentrations generated density profiles and, thereby, adsorption isotherms. The data generated for phenol adsorption fitted both Langmuir and Freundlich isotherm models equally well. Alternatively, PNP adsorption data on the kaolinite surface followed the Langmuir model better. Overall, phenol exhibits a higher adsorption capacity on kaolinite than PNP. These results support the experimental observations made in earlier publications in the literature. Radial distribution functions (RDF) between various atom types on the adsorbent and molecules in the solution phase point toward hydrogen bond-dominated interaction mechanisms for organic pollutants.

Cd-doped Ag2O/BiVO4 visible light Z-scheme photocatalyst for efficient ciprofloxacin degradation.

Foreign element doping can produce new photocatalysts with different band edge positions and adsorption properties. A composite of such a doped semiconductor with another component should enhance its photocatalytic properties towards a target substrate. The present investigation used a simple hydrothermal protocol to prepare Cd-doped Ag2O nanoparticles. The Cd-doping of Ag2O nanoparticles changed its valence band maximum position from 0.8 eV (for undoped Ag2O nanoparticles) to 2.67 eV with a slight narrowing of the Ag2O bandgap. A combination of DFT calculation and XRD results showed that the dopant Cd substituted Ag in the Ag2O lattice. The doped material is an effective photocatalyst for ciprofloxacin degradation but with poor recyclability. The joining of a BiVO4 part to the Cd-doped Ag2O nanostructures gave a composite with improved photocatalytic activity and recyclability towards ciprofloxacin degradation. DFT calculations showed that BiVO4 has a higher oxygen affinity than Cd-doped Ag2O. The XPS characterization of the composite and appropriate active species scavenger experiments demonstrated a Z-scheme mechanism. Superoxide radicals play a critical role in CIP degradation.

Frequently used antiemetic agent dexamethasone enhances the metastatic behaviour of select breast cancer cells.

Glucocorticoids, such as dexamethasone (Dex), are used to prevent common side effects induced by chemotherapy and are heavily prescribed for solid cancers such as breast cancer. There is substantial pre-clinical data to support that Dex activation of the glucocorticoid receptor overrides chemotherapy-induced apoptosis in breast cancer cell lines. These findings are compounded by a recent study demonstrating that increased glucocorticoid receptor activation by endogenous stress hormones increased breast cancer heterogeneity and metastasis. Our study is the first to use both in vitro and in vivo models to thoroughly compare the Dex response on the migration of multiple estrogen receptor negative (ER-) and ER+ cancer cell lines. ER+ and ER- breast cancer cell lines were studied to compare their endogenous glucocorticoid activity as well as their metastatic ability in response to Dex treatment. We show that in the ER- breast cancer lines, Dex increases cell numbers, invasiveness, and migration, while decreasing apoptotic ability. Furthermore, we show that following Dex treatment, ER- breast cancer lines migrate further in an in vivo zebrafish model in comparison to ER+ cell lines. The use of ROR1 antibody to block WNT signaling diminished the metastatic properties of ER- cells, however recombinant WNT5A alone was not sufficient to induce migration. Taken together, we demonstrate that Dex treatment exacerbates the metastatic potential of ER- but not ER+ cells. These findings add to the growing body of data stressing the potential adverse role of endogenous and synthetic glucocorticoids in breast cancer biology.

Efficient removal of chromate ions from aqueous solution using a highly cost-effective ferric coordinated [3-(2-aminoethylamino)propyl]trimethoxysilane-MCM-41 adsorbent.

The present investigation involves synthesis and characterization of MCM-41-AEAPTMS-Fe(iii)Cl using coordinated Fe(iii) on MCM-41-AEAPTMS for efficient removal of hazardous Cr(vi) ions from aqueous solution. The adsorbent MCM-41-AEAPTMS-Fe(iii)Cl was characterized using small-angle X-ray diffraction (SAX), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier-transform infrared (FT-IR) and Brunauer-Emmett-Teller (BET) surface analyzer techniques. The BET surface area was found to be 87.598 m2 g-1. The MCM-41-AEAPTMS-Fe(iii)Cl effectively adsorbs Cr(vi) with an adsorption capacity acquiring the maximum value of 84.9 mg g-1 at pH 3 at 298 K. The data followed pseudo-second-order kinetics and obeyed the Langmuir isotherm model. The thermodynamic data proved the exothermic and spontaneous nature of Cr(vi) ion adsorption on MCM-41-AEAPTMS-Fe(iii). Further, the higher value of ΔH° (-64.339 kJ mol-1) indicated that the adsorption was chemisorption in nature.

Experimental and DFT calculation study of interaction between silver nanoparticle and 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid.

The mechanism of stabilization of silver nanoparticles (Ag NPs) by 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (IL) is elucidated from experimental spectroscopic investigations and density functional theory (DFT) calculations. FTIR spectrum of the synthesized IL stabilized silver nanoparticles reveals small red shift in B-F stretching frequency while C-H stretching remains unshifted. There is no shift in NMR peaks of IL before and after the synthesis of IL stabilized Ag NPs. This suggests that Ag NPs are surrounded by anions of ILs. The optimized structure obtained from density functional theory (DFT) calculations also shows the anionic part of the IL surrounding the Ag nanocluster. This is supported by the IR frequency data calculated using DFT. The calculated binding energy and interaction energy obtained between cluster and IL is considerably attractive. Density of State (DOS) calculation shows that the HOMO-LUMO gap of the Ag cluster-IL composite is significantly lesser than that of the IL alone.

AgI/CuWO4 Z-scheme photocatalyst for the degradation of organic pollutants: Experimental and molecular dynamics studies.

While the knowledge of the adsorption properties of components of a composite heterogeneous photocatalyst is critical to its applicability to a particular reaction, there has been little research in this direction. The present research is on the development of AgI/CuWO4 nanocomposites that photocatalytically degraded ciprofloxacin and rhodamine B in an aqueous medium under visible light irradiation. The nanocomposites were prepared by a step-wise precipitation protocol. XPS analysis and active species trapping experiments demonstrated that the photocatalysis proceeded by a Z-scheme mechanism. Large scale aqueous medium molecular dynamics simulations showed that oxygen and CIP adsorb on the AgI part, while water interacts intensely with the CuWO4 component. Information from experimental and molecular dynamics studies was combined to arrive at the photocatalysis mechanism.

Mechanism of visible light enhanced catalysis over curcumin functionalized Ag nanocatalysts.

There is little research on the visible light photocatalytic properties of the hybrids of plasmonic metals and organic molecules (OM) with the HOMO-LUMO gap in the visible range. Here, we investigate the mechanism of the visible light enhanced reduction of p-nitrophenol (PNP) by glycerol (a green reductant) at ambient temperature over curcumin functionalized Ag nanoparticles (c-AgNPs). The catalytic activity got significantly boosted under visible light irradiation. Reaction kinetics indicated that the catalytic mechanism followed under visible light and in the dark were different. DFT calculations showed that in the ground state, the HOMO resides on Ag while the LUMO is on the curcumin part of the composite. TD-DFT calculations demonstrated the transfer of charge from Ag to curcumin on photo-excitation. Based on this information, we propose a mechanism for understanding the role of curcumin in this photocatalytic phenomenon.

Ag-Cu Bimetallic Nanoparticles as Efficient Oxygen Reduction Reaction Electrocatalysts in Alkaline Media.

The alkaline medium oxygen reduction reaction (ORR) activities of Ag-Cu bimetallic nanoparticles (BNPs), consisting of neighboring Ag and Cu domains, were studied and compared with those of pure Ag and Cu nanoparticles prepared by the same polyol route. Three variations of Ag-Cu BNPs viz. Ag-Cu (4:1), Ag-Cu (2:1), Ag-Cu (1:1) BNPs were considered. The electrocatalytic performances of these nanoparticles were investigated by using different techniques, such as cyclic voltammetry (CV) and linear sweep voltammograms (LSV). The Ag-Cu bimetallics demonstrated synergistic ORR electrocatalytic activity compared to pure Ag or Cu. Optimum values of these parameters were observed for Ag-Cu (4:1) BNPs. According to LSV, the reduction peak position is at lower applied potential and showed higher intensity for the Ag-Cu (4:1) as compared to Ag-Cu (2:1) and Ag-Cu (1:1) BNPs. Density Functional Theory (DFT) calculations show that charge transfer from Cu to Ag (in the bimetallic nanoparticles) results in their stronger oxygen interaction and water activation properties relative to that of pure Ag nanoparticles.

ZnO/CuO nanocomposites from recycled printed circuit board: preparation and photocatalytic properties.

Cost-effective recycling of e-waste (from computer printed circuit boards, PCB's) for the synthesis of metal oxide nanocomposites is demonstrated. Metals in electronic components of waste memory slots were leached out using nitric acid (HNO3). Compositional analyses of the filtrate obtained after leaching were 66 wt.% Cu, 27.7 wt.% Zn, and 6.2 wt.% Ni. The leached out metal salt solutions were subjected to alkaline hydrothermal treatment to synthesize nanocomposites. Two nanoparticle samples were prepared, one without any stabilizing agent and another sample with PVP as a stabilizing agent. XRD, HR-XRD, HR-TEM, UV-DRS, UV-visible spectroscopy was used to characterize the as-prepared metal oxide nanoparticles. The analysis showed the formation of ZnO/CuO nanocomposites only. No nickel oxide component was precipitated under the studied hydrothermal experimental conditions. Most of the ZnO/CuO nanocomposite particles obtained by this route consisted of fine ZnO nanostructures precipitated on CuO cores. The ZnO and CuO components exhibit both direct and indirect band gaps in the visible range. The nanocomposites demonstrate good visible light photo-Fenton methyl orange (MO) degradation by pseudo-zero order kinetics.