Preparation of nanocellulose/reduced graphene oxide matrix loaded with cuprous oxide nanoparticles for efficient catalytic reduction of 4-nitrophenol.

The paper reports on the preparation of cellulose nanocrystals/reduced graphene oxide matrix loaded with cuprous oxide nanoparticles (CNC/rGO-Cu2O) through a simple solvothermal method and its application for 4-nitrophenol reduction to 4-aminophenol using sodium borohydride. The CNC/rGO-Cu2O nanocomposite was formed chemically by first mixing CNC and graphene oxide (GO) followed by complexation of the negatively charged functional groups of CNC/GO with Cu2+ ions and subsequent heating at 100°C. This resulted in the simultaneous reduction of GO to rGO and the formation of Cu2O nanoparticles. The as-elaborated nanocomposite was firstly characterized using different techniques such as atomic force microscopy, scanning electron microscopy, transmission electron microscopy, UV-Vis spectrophotometry, Raman spectroscopy and x-ray photoelectron spectroscopy. Then, it was successfully applied for efficient catalytic reduction of 4-nitrophenol to 4-aminophenol using sodium borohydride: the reduction was completed in about 6 min. After eight times use, the catalyst still maintained good catalytic performance. Compared to CNC/rGO, rGO/Cu2O and free Cu2O nanoparticles, the CNC/rGO-Cu2O nanocomposite exhibits higher catalytic activity even at lower copper loading.

Triazine-based covalent-organic framework embedded with cuprous oxide as the bioplatform for photoelectrochemical aptasensing Escherichia coli.

A superior photoelectrochemical (PEC) aptasensor was manufactured for the detection of Escherichia coli (E. coli) based on a hybrid of triazine-based covalent-organic framework (COF) and cuprous oxide (Cu2O). The COF synthesized using 1,3,5-tris(4-aminophenyl)-benzene (TAPB) and 1,3,5-triformylphloroglucinol (Tp) as building blocks acted as a scaffold for encapsulated Cu2O nanoparticles (denoted as Cu2O@TAPB-Tp-COF), which then was employed as the bioplatform for anchoring E. coli-targeted aptamer. Cu2O@Cu@TAPB-Tp-COF demonstrated enhanced separation of the photogenerated carriers and photoabsorption ability and boosted photoelectric conversion efficiency. The developed Cu2O@TAPB-Tp-COF-based PEC aptasensor exhibited a lower detection limit of 2.5 CFU mL-1 toward E. coli within a wider range of 10 CFU mL-1 to 1 × 104 CFU mL-1 than most of reported aptasensors for determining foodborne bacteria, together with high selectivity, good stability, and superior ability and reproducibility. The recoveries of E. coli spiked into milk and bread samples ranged within 95.3-103.6% and 96.6-102.8%, accompanying with low RSDs of 1.37-4.48% and 1.74-3.66%, respectively. The present study shows a promising alternative for the sensitive detection of foodborne bacteria from complex foodstuffs and pathogenic bacteria-polluted environment.

Differential Analysis of Three Copper-Based Nanomaterials with Different Morphologies to Suppress Alternaria alternata and Safety Evaluation.

The overuse of copper-based fertilizers and pesticides over the last few decades has resulted in detrimental risks to our environment. Nano-enabled agrichemicals with a high effective utilization ratio have shown great potential for maintaining or minimizing environmental issues in agriculture. Copper-based nanomaterials (Cu-based NMs) serve as a promising alternative to fungicides. Three types of Cu-based NMs with different morphologies were analyzed for their different antifungal effects on Alternaria alternata in this current study. Compared to commercial copper hydroxide water power (Cu(OH)2 WP), all tested Cu-based NMs, including cuprous oxide nanoparticles (Cu2O NPs), copper nanorods (Cu NRs) and copper nanowires (Cu NWs), especially Cu2O NPs and Cu NWs, showed higher antifungal activity against Alternaria alternata. Its EC50 were 104.24 and 89.40 mg L-1, respectively, achieving comparable activity using a dose approximately 1.6 and 1.9-fold lower. Cu-based NMs could introduce the downregulation of melanin production and soluble protein content. In contrast to trends in antifungal activity, Cu2O NPs showed the strongest power in regulating melanin production and protein content and similarly exhibited the highest acute toxicity to adult zebrafish compared to other Cu-based NMs. These results demonstrate that Cu-based NMs could offer great potential in plant disease management strategies.

Antibacterial Composites of Cuprous Oxide Nanoparticles and Polyethylene.

Cuprous oxide nanoparticles (Cu2ONPs) were used for preparing composites with linear low-density polyethylene (LLDPE) by co-extrusion, thermal adhesion, and attachment using ethyl cyanoacrylate, trimethoxyvinylsilane, and epoxy resin. The composites were examined by Scanning electron microscope and tested for their antibacterial activity against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. All of these composites-except for the one obtained by extrusion-eradicated cells of both bacteria within half an hour. The composite prepared by thermal adhesion of Cu2ONPs on LLDPE had the highest external exposure of nanoparticles and exhibited the highest activity against the bacteria. This composite and the one obtained using ethyl cyanoacrylate showed no leaching of copper ions into the aqueous phase. Copper ion leaching from composites prepared with trimethoxyvinylsilane and epoxy resin was very low. The antibacterial activity of the composites can be rated as follows: obtained by thermal adhesion > obtained using ethyl cyanoacrylate > obtained using trimethoxyvinylsilane > obtained using epoxy resin > obtained by extrusion. The composites with the highest activity are potential materials for tap water and wastewater disinfection.

Rapid and Sensitive Determination of Vanillin Based on a Glassy Carbon Electrode Modified with Cu2O-Electrochemically Reduced Graphene Oxide Nanocomposite Film.

A facile cuprous oxide nanoparticles functionalized electro-reduced graphene oxide modified glassy carbon electrode (denoted as Cu2O NPs-ERGO/GCE) was fabricated via a simple physical adsorption and electrochemical reduction approach. Cyclic voltammetry and second-order derivative linear scan voltammetry were used to investigate the electrocatalysis oxidation of vanillin on the Cu2O NPs-ERGO/GCE. The compound yielded a well-defined voltammetric response in 0.1 M H2SO4 at 0.916 V (vs. saturated calomel electrode (SCE)). A linear calibration graph was obtained in the concentration range of 0.1 µM to 10 µM and 10 µM to 100 µM, while the detection limit (S/N = 3) is 10 nM. In addition, the Cu2O NPs-ERGO/GCE presented well anti-interference ability, stability, and reproducibility. It was used to detect vanillin sensitively and rapidly in different commercial food products, and the results were in agreement with the values obtained by high performance liquid chromatography.

Novel Electrochemical Sensors Based on Cuprous Oxide-Electrochemically Reduced Graphene Oxide Nanocomposites Modified Electrode toward Sensitive Detection of Sunset Yellow.

Control and detection of sunset yellow is an utmost demanding issue, due to the presence of potential risks for human health if excessively consumed or added. Herein, cuprous oxide-electrochemically reduced graphene nanocomposite modified glassy carbon electrode (Cu2O-ErGO/GCE) was developed for the determination of sunset yellow. The Cu2O-ErGO/GCE was fabricated by drop-casting Cu2O-GO dispersion on the GCE surface following a potentiostatic reduction of graphene oxide (GO). Scanning electron microscope and X-ray powder diffractometer was used to characterize the morphology and microstructure of the modification materials, such as Cu2O nanoparticles and Cu2O-ErGO nanocomposites. The electrochemical behavior of sunset yellow on the bare GCE, ErGO/GCE, and Cu2O-ErGO/GCE were investigated by cyclic voltammetry and second-derivative linear sweep voltammetry, respectively. The analytical parameters (including pH value, sweep rate, and accumulation parameters) were explored systematically. The results show that the anodic peak currents of Cu2O-ErGO /GCE are 25-fold higher than that of the bare GCE, due to the synergistic enhancement effect between Cu2O nanoparticles and ErGO sheets. Under the optimum detection conditions, the anodic peak currents are well linear to the concentrations of sunset yellow, ranging from 2.0 × 10-8 mol/L to 2.0 × 10-5 mol/L and from 2.0 × 10-5 mol/L to 1.0 × 10-4 mol/L with a low limit of detection (S/N = 3, 6.0 × 10-9 mol/L). Moreover, Cu2O-ErGO/GCE was successfully used for the determination of sunset yellow in beverages and food with good recovery. This proposed Cu2O-ErGO/GCE has an attractive prospect applications on the determination of sunset yellow in diverse real samples.

Effects of Cu2O nanoparticles on the kinetic characteristics of rapid chlorophyll fluorescence induction and related genes in wheat seedlings.

Metal nanoparticles could be accumulated in soils, which threatens the ecological stability of crops. Investigating the effects of cuprous oxide nanoparticles (Cu2O-NPs) on photosystem Ⅱ (PSⅡ) of wheat seedling leaves holds considerable importance in comprehending the implications of Cu2O-NPs on crop photosynthesis. Following the hydroponic method, we investigated the effects of 0, 10, 50, 100, and 200 mg·L-1 Cu2O-NPs on chlorophyll fluorescence induction kinetics and photosynthetic-related genes in wheat seedlings of "Zhoumai 18". The results showed that, with the increases of Cu2O-NPs concentrations, chlorophyll contents in wheat leaves decreased, and the standardization of the OJIP curve showed a clearly K-phase (ΔK＞0). Cu2O-NPs stress increased the parameters of active PSⅡ reaction centers, including the absorption flux per active RC (ABS/RC), the trapping flux per active RC (TRo/RC), the electron transport flux per active RC (ETo/RC), and the dissipation flux per active RC (DIo/RC). Cu2O-NPs stress decreased the parameters of PSⅡ energy distribution ratio including the maximum quantum yield of PSⅡ (φPo), the quantum yield of electron transport from QA (φEo), and the probability that a trapped exciton moved an electron further than QA (Ψo), while increased the quantum ratio for heat dissipation (φDo). Moreover, there was a decrease in photosynthetic quantum yield Y(Ⅱ), photochemical quenching coefficient (qP), net photosynthetic rate (Pn), stomatal conductance (gs), intercellular CO2 concentration (Ci), and transpiration rate (Tr) of leaves with the increases of Cu2O-NPs concentration. Under Cu2O-NPs stress, the expression levels of genes which included PSⅡ genes (PsbD, PsbP, Lhcb1), Rubisco large subunit genes (RbcL), cytochrome b6/f complex genes (PetD, Rieske), and ATP synthase genes (AtpA, AtpB, AtpE, AtpI) were downregulated. These results indicated that Cu2O-NPs stress altered the activity and structure of PSⅡ in wheat seedlings, affected the activity of PSⅡ reaction centers, performance parameters of PSⅡ donor and acceptor sides. PSⅡ related genes were downregulated and exhibited significant concentration effects.

Double-Layered Hollow Mesoporous Cuprous Oxide Nanoparticles for Double Drug Sequential Therapy of Tumors.

Cancer stem cells (CSCs) are one of the determinants of tumor heterogeneity and are characterized by self-renewal, high tumorigenicity, invasiveness, and resistance to various therapies. To overcome the resistance of traditional tumor therapies resulting from CSCs, a strategy of double drug sequential therapy (DDST) for CSC-enriched tumors is proposed in this study and is realized utilizing the developed double-layered hollow mesoporous cuprous oxide nanoparticles (DL-HMCONs). The high drug-loading contents of camptothecin (CPT) and all-trans retinoic acid (ATRA) demonstrate that the DL-HMCON can be used as a generic drug delivery system. ATRA and CPT can be sequentially loaded in and released from CPT3@ATRA3@DL-HMCON@HA. The DDST mechanisms of CPT3@ATRA3@DL-HMCON@HA for CSC-containing tumors are demonstrated as follows: 1) the first release of ATRA from the outer layer induces differentiation from CSCs with high drug resistance to non-CSCs with low drug resistance; 2) the second release of CPT from the inner layer causes apoptosis of non-CSCs; and 3) the third release of Cu+ from DL-HMCON itself triggers the Fenton-like reaction and glutathione depletion, resulting in ferroptosis of non-CSCs. This CPT3@ATRA3@DL-HMCON@HA is verified to possess high DDST efficacy for CSC-enriched tumors with high biosafety.

Cu2O nanoparticles synthesized by green and chemical routes, and evaluation of their antibacterial and antifungal effect on functionalized textiles.

The potential for the application of metal-containing nanomaterials at the nanoscale promotes the opportunity to search for new methods for their elaboration, with special attention to those sustainable methods. In response to these challenges, we have investigated a new method for green synthesis of cuprous oxide nanoparticles (Cu2O NPs) using Myrciaria dubia juice as an organic reductant and, comparing it with chemical synthesis, evaluating in both cases the influence of the volume of the organic (juice) and chemical (ascorbic acid) reductants, for which a large number of techniques such as spectrophotometry, EDX spectrometry, TEM, SEM, DLS, FTIR spectroscopy have been used. Likewise, the nanomaterial with better morphological characteristics, stability, and size homogeneity has been applied in the functionalization of textiles by means of in situ and post-synthesis impregnation methods. The success of the synthesis process has been demonstrated by the antimicrobial activity (bacteria and fungi) of textiles impregnated with Cu2O NPs.

Copper oxide nanoparticles doped with lanthanum, magnesium and manganese: optical and structural characterization.

Copper oxide (Cu2O) is a promising semiconductor for photovoltaic and photocatalytic applications since this material has a high optical absorption coefficient and lower band gap (2.17 eV). Doped lanthanum (La), magnesium (Mg) and manganese (Mn) Cu2O nanoparticles (Cu2O Nps) were prepared by a displacement reaction. The doped and undoped Cu2O Nps were characterized with scanning electron microscopy-energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. The EDS results confirm the presence of La, Mg and Mn in the Cu2O Nps. The XRD results confirm the formation a single cubic phase of Cu2O with a cuprite structure. TEM images confirm the formation of Nps with mean diameters between 12.0 ± 6.1 and 30.8 ± 11.0 nm. Doped and undoped Nps present a narrow band gap (2.40 eV), blue shifted with respect to bulk Cu2O.

Novel nanoformulated diethyldithiocarbamate complexes with biosynthesized or green chemosynthesized copper oxide nanoparticles: An in vitro comparative anticancer study.

Developing more soluble and stable nanoformulation for the potent anticancer complex of copper diethyldithiocarbamate (CD) is extremely desired. Herein, for the first time, CD nanoparticles (NPs) were formulated by chelating diethyldithiocarbamate to bacterially and green chemically prepared copper oxide NPs (Bio CO NPs and Chemo CO NPs, respectively). Chemo CO NPs were produced in simpler and less time-consuming manner with higher NPs homogeneity. These CO NPs were identified, by X-ray diffractometer, as CuO and Cu2O, respectively. The nanoformulated CD complexes (Bio CD NPs and Chemo CD NPs) which have nanosizes (215.7 nm and 148.1 nm, respectively) with negative zeta potentials (∼-20 mv), exhibited not only high serum stability and solubility but also a potent anticancer effect. More importantly, Chemo CD NPs outperformed Bio CD NPs in the terms of synergistic anticancer index, apoptosis induction (>81% and <54%, respectively) and anti-migration efficacy (≥80% and <71%, respectively). This could be attributed to smaller nanosize and Cu2O of Chemo CD NPs causing higher cellular uptake with stronger inhibition of aldehyde dehydrogenase 1A1 and more free radical generation in Chemo CD NPs-treated cancer cells than Bio CD NPs. This distinct anticancer efficacy of novel Chemo CD NPs deserves further investigation using animal models.

LLDPE Composites with Nanosized Copper and Copper Oxides for Water Disinfection.

Consumption of contaminated water may lead to dangerous and even fatal water-borne diseases. Disinfection of drinking water is the most effective solution for this problem. The most common water treatment methods are based on the use of toxic disinfectants. Composites of polymers with nanosized metals and their oxides may become a good alternative to the existing methods. Expanding the scope of our previous publication, copper, cuprous, and copper oxide nanoparticles were immobilized onto linear low-density polyethylene by a simple thermal adhesion method. The antibacterial efficiency of the immobilized nanoparticles was tested against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus in batch experiments and for the first time the efficiency of these composites is reported for continuous flow regime. Immobilized copper and cuprous oxide nanoparticles demonstrated a high ability to eradicate bacteria after 30 min. These composites showed no or very limited leaching of copper ions into the aqueous phase both in the presence and in the absence of a bacterial suspension. Immobilized copper and cuprous oxide nanoparticles can be used for batch or continuous disinfection of water.

Cuprous oxide nanoparticle-inhibited melanoma progress by targeting melanoma stem cells.

Recent studies have shown that metal and metal oxide have a potential function in antitumor therapy. Our previous studies demonstrated that cuprous oxide nanoparticles (CONPs) not only selectively induce apoptosis of tumor cells in vitro but also inhibit the growth and metastasis of melanoma by targeting mitochondria with little hepatic and renal toxicities in mice. As a further study, our current research revealed that CONPs induced apoptosis of human melanoma stem cells (CD271+/high cells) in A375 and WM266-4 melanoma cell lines and could significantly suppress the expression of MITF, SOX10 and CD271 involved in the stemness maintenance and tumorigenesis of melanoma stem cells. CD271+/high cells could accumulate more CONPs than CD271-/low through clathrin-mediated endocytosis. In addition, lower dosage of CONPs exhibited good anti-melanoma effect by decreasing the cell viability, stemness and tumorigenesis of A375 and WM266-4 cells through reducing the expression of SOX10, MITF, CD271 and genes in MAPK pathway involved in tumor progression. Finally, CONPs obviously suppressed the growth of human melanoma in tumor-bearing nonobese diabetic-severe combined immunodeficiency (NOD-SCID) mice, accompanied with tumors structural necrosis and fibrosis remarkably and decreased expression of CD271, SOX10 and MITF. These results above proved the effectiveness of CONPs in inhibiting melanoma progress through multiple pathways, especially through targeting melanoma stem cells.

Antiviral activity of cuprous oxide nanoparticles against Hepatitis C Virus in vitro.

Small molecular inhibitors in combination with or without interferon have improved sustained antiviral responses against Hepatitis C Virus (HCV) infection. Nonetheless, resistance to these inhibitors is expected to emerge rapidly due to the high mutation rate of the virus. Thus, new antiviral drugs, in combination with currently available therapies, are urgently needed to treat HCV infection. In the present study, we evaluated the antiviral efficacy of cuprous oxide nanoparticles (CO-NPs) against HCV in the HCVcc/Huh7.5.1 cell culture system. CO-NPs were able to significantly inhibit the infectivity of HCVcc at a non-cytotoxic concentration. In addition, CO-NPs inhibited the entry of HCV pseudoparticle (HCVpp), including genotypes 1a, 1b, and 2a, while no effect on HCV replication was observed. Further time-of-addition experiment indicated that CO-NPs blocked HCV infection both at the attachment and entry stages. In conclusion, we report that CO-NPs can act as an anti-HCV agent by targeting the binding of infectious HCV particles to hepatic cells and the virus entry into the cells. These findings suggest that CO-NPs may have novel roles in the treatment of patients with chronic hepatitis C.

Serum adsorption, cellular internalization and consequent impact of cuprous oxide nanoparticles on uveal melanoma cells: implications for cancer therapy.

AIM: To investigate the biological fate of cuprous oxide nanoparticles (Cu2O-NPs) and to evaluate their potential in uveal melanoma therapy. MATERIALS & METHODS: The protein corona, cellular uptake mechanism and localization of Cu2O-NPs were investigated. Furthermore, the effect of Cu2O-NPs on uveal melanoma cell proliferation, migration and invasion, and possible mechanisms were studied in detail. RESULTS: Cu2O-NPs are able to adsorb serum proteins in cell culture medium, which are then internalized by uveal melanoma cells mainly through lipid raft-mediated endocytosis. Furthermore, Cu2O-NPs selectively inhibit cancer cell growth and impair the ability of uveal melanoma cell migration, invasion and the cytoskeleton assembly. The mechanism may be that Cu2O-NPs located in and damage mitochondria, autophagolysosomes and lysosomes, leading to elevated reactive oxygen species level and over-stimulated apoptosis and autophagy. CONCLUSION: The data provide detailed information of Cu2O-NPs for further application and indicate that Cu2O-NPs could be a potential agent for uveal melanoma therapy.

Synthesis of nano Cu2O on cotton: morphological, physical, biological and optical sensing characterizations.

In this paper, Cu2O nanoparticles were in situ synthesized on cotton fabric through a new simple and cost-effective chemical reduction method using copper sulfate, sodium hydroxide and ammonia. Cotton fabric participates as a reducing agent in reduction of copper sulfate and facilitates synthesis of cuprous oxide in nano-scale as a stabilizer. The produced cotton/nano Cu2O composite were characterized by X-ray diffraction, scanning electron microscopy and Energy-dispersive X-ray spectroscopy. Interaction of Cu2O with cotton fabric in addition to alteration of cotton functional groups were studied by Fourier transforms infrared spectroscopy. The intermediate solution, copper-amine complex, was analyzed by ultraviolet-visible spectroscopy. The mechanical properties of the cotton/nano Cu2O composite were studied using Instron indicated a higher tensile strain. The antibacterial activity of the fabric samples showed considerable behavior against S. aureus and E. coli. Further, the treated fabric became highly hydrophobic and sensed ammonia and hydrogen peroxide chromatically.