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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Chromosomal instability-induced senescence potentiates cell non-autonomous tumourigenic effects.

Chromosomal instability (CIN), a high rate of chromosome loss or gain, is often associated with poor prognosis and drug resistance in cancers. Aneuploid, including near-polyploid, cells contain an abnormal number of chromosomes and exhibit CIN. The post-mitotic cell fates following generation of different degrees of chromosome mis-segregation and aneuploidy are unclear. Here we used aneuploidy inducers, nocodazole and reversine, to create different levels of aneuploidy. A higher extent of aneuploid and near-polyploid cells in a given population led to senescence. This was in contrast to cells with relatively lower levels of abnormal ploidy that continued to proliferate. Our findings revealed that senescence was accompanied by DNA damage and robust p53 activation. These senescent cells acquired the senescence-associated secretory phenotype (SASP). Depletion of p53 reduced the number of senescent cells with concomitant increase in cells undergoing DNA replication. Characterisation of these SASP factors demonstrated that they conferred paracrine pro-tumourigenic effects such as invasion, migration and angiogenesis both in vitro and in vivo. Finally, a correlation between increased aneuploidy and senescence was observed at the invasive front in breast carcinomas. Our findings demonstrate functional non-equivalence of discernable aneuploidies on tumourigenesis and suggest a cell non-autonomous mechanism by which aneuploidy-induced senescent cells and SASP can affect the tumour microenvironment to promote tumour progression.

Autophagy Governs Protumorigenic Effects of Mitotic Slippage-induced Senescence.

The most commonly utilized class of chemotherapeutic agents administered as a first-line therapy are antimitotic drugs; however, their clinical success is often impeded by chemoresistance and disease relapse. Hence, a better understanding of the cellular pathways underlying escape from cell death is critical. Mitotic slippage describes the cellular process where cells exit antimitotic drug-enforced mitotic arrest and "slip" into interphase without proper chromosome segregation and cytokinesis. The current report explores the cell fate consequence following mitotic slippage and assesses a major outcome following treatment with many chemotherapies, therapy-induced senescence. It was found that cells postslippage entered senescence and could impart the senescence-associated secretory phenotype (SASP). SASP factor production elicited paracrine protumorigenic effects, such as migration, invasion, and vascularization. Both senescence and SASP factor development were found to be dependent on autophagy. Autophagy induction during mitotic slippage involved the autophagy activator AMPK and endoplasmic reticulum stress response protein PERK. Pharmacologic inhibition of autophagy or silencing of autophagy-related ATG5 led to a bypass of G1 arrest senescence, reduced SASP-associated paracrine tumorigenic effects, and increased DNA damage after S-phase entry with a concomitant increase in apoptosis. Consistent with this, the autophagy inhibitor chloroquine and microtubule-stabilizing drug paclitaxel synergistically inhibited tumor growth in mice. Sensitivity to this combinatorial treatment was dependent on p53 status, an important factor to consider before treatment.Implications: Clinical regimens targeting senescence and SASP could provide a potential effective combinatorial strategy with antimitotic drugs. Mol Cancer Res; 16(11); 1625-40. ©2018 AACR.

Curcumin-Functionalized Ag/Ag2 O Nanocomposites: Efficient Visible-Light Z-scheme Photocatalysts.

Curcumin-functionalized Ag/Ag2 O (c-Ag/Ag2 O) nanocomposites with varying proportions of curcumin and Ag/Ag2 O were prepared by a simple one pot green synthesis protocol in aqueous medium. The plasmonic band undergoes slight redshift, broadening and decrease in intensity with increase in the proportion of Ag2 O formed. These composite nanoparticles were found to be efficient visible-light photocatalysts for aerobic oxidation of methyl orange and rhodamine B (RhB). Functionalization by curcumin significantly enhanced the photocatalytic activity with good reusability. The photocatalytic oxidation rate showed super linear increase with light intensity because of localized surface plasmon resonance (LSPR)-induced strong near field. The trapping experiments confirmed that superoxide radicals were the main active species responsible for the degradation reaction. A plasmonic Z-scheme photocatalytic mechanism is proposed to explain the possible charge transfer and separation behavior of electron-hole pairs among Ag, Ag2 O and curcumin under visible-light irradiation.