Synthesis of Polymer Brushes on Tannic Acid-Coated Copper Particles and Surface Co-Assembly.

The synthesis of polymer brushes on inorganic particles is an effective approach to surface modification. The polymer brushes on the surface endow the substrates with new surface properties. However, the lack of functional groups and the difficulty of surface modification have made it difficult to develop an effective method for the synthesis of polymer brushes on metal surfaces. Herein, a simple and versatile strategy for synthesizing polymer brushes on copper particles is reported. Tannic acid (TA) molecules are adsorbed onto the surfaces of copper particles, forming TA coatings. Quaternized poly(2-(dimethylamino)ethyl methacrylate)-block-polystyrene (qPDMAEMA-b-PS) block copolymer (BCP) chains are grafted on the TA coatings through hydrogen bonding and electrostatic interaction, and PS brushes are grafted on the copper particles. The effects of TA concentration on the adsorption of TA and PS brush synthesis are discussed. The PS brushes are able to form surface nanostructures on the copper particles through co-assembly with PDMAEMA-b-PS BCP chains. The effect of BCP concentration on the surface nanostructures is investigated. It is reasonable to expect that polymer brushes and surface nanostructures can be synthesized on different metal surfaces by using the TA-coating approach reported in this paper.

Review on Generation and Characterization of Copper Particles and Copper Composites Prepared by Mechanical Milling on a Lab-Scale.

This review aims to expose mechanical milling as an alternative method for generating copper-based particles (copper particles (CuP) and copper composites (CuC)); more specifically, via a top-down or bottom-up approach, on a lab-scale. This work will also highlight the different parameters that can affect the size distribution, the type, and the morphology of the obtained CuP or CuC, such as the type of mechanical mill, ball-to-powder ratios (BPR), the milling speed, milling time, and the milling environment, among others. This review analyzes various papers based on the Cu-based particle generation route, which begins with a pretreatment step, then mechanical milling, its approach (top-down or bottom-up), and the post-treatment. Finally, the characterization methods of the resulting CuP and CuC through mechanical milling are also discussed.

Green Synthesis of Gold, Silver, Copper, and Magnetite Particles Using Poly(tartaric acid) Simultaneously as Coating and Reductant.

Poly(tartaric acid) is a relatively recently described polymer that can be easily synthesized and scaled up from a readily available renewable material (tartaric acid). This article demonstrates its use in a green synthesis of gold nanoparticles, silver nanoparticles, copper particles, and magnetite nanoparticles. In this case poly(tartaric acid) acts both as a reductant and as a coating agent. To our knowledge this is the first green synthesis of several different types of nanoparticles using only one reagent (polytartrate) as both reductant and coating. The resulting particles were analyzed by XRD, TEM/SEM, EDX, FTIR, DLS, zeta-potential, XPS, and UV/VIS spectroscopy. Preliminary studies of the thermal behavior of mixtures of different types of particles with poly(tartaric acid) were also conducted. The obtained particles show different sizes depending on the material, and the coating allows for better dispersibility as well as potential further functionalization, making them potentially useful also for other applications, besides the inclusion in polymer composites.

In Situ-Generated, Dispersed Cu Catalysts for the Catalytic Hydrogenolysis of Glycerol.

The present study is dedicated to the experimental verification of a concept for the hydrogenolysis of glycerol over in situ-generated Cu dispersed particles (Cu-DP). The Cu-DP were generated by in situ reduction of a precursor salt (Cu(OAc)2, CuSO4, CuCl2) in the presence of KOH and were active in glycerol conversion under hydrogen (T = 200-220 °C, p(H2) = 1-4 MPa), where 1,2-propylene glycol (PG) and lactic acid (LA) were detected to be the main products. The influence of the reaction conditions (temperature, hydrogen pressure, reaction time, catalyst-to-feed ratio and the KOH/Cu ratio) on the yields of the products is described. It was shown that the selectivity between the PG and LA could be tuned by changing p(H2) or by the KOH amount, i.e., higher yields of LA corresponded to lower p(H2) and higher alkalinity of the reaction media. The activity of the in situ-generated Cu-DP was found to be comparable to that of an industrial Cu-Cr2O3 catalyst. The Cu-DP catalysts were characterized by XRD, XPS, HRTEM and SEM. During the reaction, the catalyst evolved by the sintering and recrystallization of the separate Cu-DP; the crystallite sizes after 1 and 15 h reaction times amounted to 35 and 49 nm, respectively.

Antibacterial Activity of Copper Particles Embedded in Knitted Fabrics.

The composition and antibacterial properties of copper particles synthesized by a very simple reduction method were studied. For the preparation of particles in knitted fabrics, copper(II) sulfate was used as a precursor and ascorbic acid as a reducing natural agent. X-ray diffraction analysis showed the crystalline nature of the obtained particles. The round or oval particles and their agglomerates in knitted fabrics consisted of copper with traces of copper(I) oxide-cuprite. The element maps and energy dispersive X-ray spectra showed a high content of copper in the samples. The samples of wool and cotton knitted fabrics with copper particles had excellent antibacterial activity against gram-positive Staphylococcus aureus (S. aureus) and gram-negative Escherichia coli (E. coli) bacterial strains. The maximum zones of inhibition were 19.3 mm for S. aureus and 18.3 mm for E. coli using wool knitted fabric and 14.7 mm and 15.3 mm using cotton knitted fabric, respectively. The obtained results showed that the modified wool and cotton fabrics are suitable for use as inserts in reusable masks due to their noticeable and long-term activity against pathogenic bacteria.

Novel Rubber Composites Based on Copper Particles, Multi-Wall Carbon Nanotubes and Their Hybrid for Stretchable Devices.

New technologies are constantly addressed in the scientific community for updating novel stretchable devices, such as flexible electronics, electronic packaging, and piezo-electric energy-harvesting devices. The device promoted in the present work was found to generate promising ~6V and durability of >0.4 million cycles. This stretchable device was based on rubber composites. These rubber composites were developed by solution mixing of room temperature silicone rubber (RTV-SR) and nanofiller, such as multi-wall carbon nanotube (MWCNT) and micron-sized copper particles and their hybrid. The hybrid composite consists of 50:50 of both fillers. The mechanical stretchability and compressive modulus of the composites were studied in detail. For example, the compressive modulus was 1.82 MPa (virgin) and increased at 3 per hundred parts of rubber (phr) to 3.75 MPa (MWCNT), 2.2 MPa (copper particles) and 2.75 MPa (hybrid). Similarly, the stretching ability for the composites used in fabricating devices was 148% (virgin) and changes at 3 phr to 144% (MWCNT), 230% (copper particles) and 199% (hybrid). Hence, the hybrid composite was found suitable with optimum stiffness and robust stretching ability to be useful for stretching electronic devices explored in this work. These improved properties were tested for a real-time stretchable device, such as a piezoelectric energy-harvesting device and their improved voltage output and durability were reported. In the end, a series of experiments conducted were summarized and a discussion on the best candidate with higher properties useful for prospective applications was reported.

O-carboxymethyl chitosan/gelatin/silver-copper hydroxyapatite composite films with enhanced antibacterial and wound healing properties.

Wound dressing composite films of O-carboxymethyl chitosan (OCMC) and gelatin were prepared and mixed with hydroxyapatite (HA) composited with Silver (Ag) and Copper (Cu) at different concentrations. The chemical, thermal, morphological, and biological properties of the composite films were studied. The analysis by FTIR confirmed the presence of interactions between gelatin and OCMC, and at the same time, the polymer matrix interactions with Ag-Cu/HA complex. The inclusion of nanoparticle to the composite was associated with an improvement of the thermal stability, morphological roughness, a 9-12% more hydrophobic behavior (composite C1, C5, and C8), increase in antibacterial activity from 23.2 to 33.1% for gram negative bacteria and from 37.28 to 40.59% for gram positive bacteria, and with a cell viability greater than 100% for 24 and 72 h. The films obtained can serve as a wound healing dressing and regenerating biomaterial.

Inhibition of SARS-CoV-2 Alpha Variant and Murine Noroviruses on Copper-Silver Nanocomposite Surfaces.

With the continued scenario of the COVID-19 pandemic, the world is still seeking out-of-the-box solutions to break its transmission cycle and contain the pandemic. There are different transmission routes for viruses, including indirect transmission via surfaces. To this end, we used two relevant viruses in our study. The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) causing the pandemic and human norovirus (HuNV), both known to be transmitted via surfaces. Several nanoformulations have shown attempts to inhibit SARS-CoV-2 and other viruses. However, a rigorous, similar inactivation scheme to inactivate the cords of two tedious viruses (SARS-CoV-2 Alpha variant and HuNV) is lacking. The present study demonstrates the inactivation of the SARS-CoV-2 Alpha variant and the decrease in the murine norovirus (MNV, a surrogate to HuNV) load after only one minute of contact to surfaces including copper-silver (Cu-Ag) nanocomposites. We thoroughly examined the physicochemical characteristics of such plated surfaces using diverse microscopy tools and found that Cu was the dominanting element in the tested three different surfaces (~56, ~59, and ~48 wt%, respectively), hence likely playing the major role of Alpha and MNV inactivation followed by the Ag content (~28, ~13, and ~11 wt%, respectively). These findings suggest that the administration of such surfaces within highly congested places (e.g., schools, public transportations, public toilets, and hospital and live-stock reservoirs) could break the SARS-CoV-2 and HuNV transmission. We suggest such an administration after an in-depth examination of the in vitro (especially on skin cells) and in vivo toxicity of the nanocomposite formulations and surfaces while also standardizing the physicochemical parameters, testing protocols, and animal models.

Real-time monitoring of cellular oxidative stress during aerosol sampling: a proof of concept study.

The Portable In Vitro Exposure Cassette (PIVEC) was developed for on-site air quality testing using lung cells. Here, we describe the incorporation of a sensor within the PIVEC for real time monitoring of cellular oxidative stress during exposure to contaminated air. An electrochemical, enzymatic biosensor based on cytochrome c (cyt c) was selected to measure reactive oxygen species (ROS), including hydrogen peroxide and super oxides, due to the stability of signal over time. Human A549 lung cells were grown at the air-liquid interface and exposed within the PIVEC to dry 40 nm copper nanoparticle aerosols for 10 minutes. The generation of ROS compounds was measured during exposure and post-exposure for one hour using the biosensor and compared to intracellular ROS determined using the 2',7'-dichlorodihydrofluoroscein diacetate (DCFH-DA) assay. A similar increase in oxidative stress upon aerosol exposure was measured using both the cyt c biosensor and DCFH-DA assay. The incorporation of a biosensor within the PIVEC is a unique, first-of-its-kind system designed to monitor the real-time effect of aerosols.

Nanosized copper particles induced mesangial cell toxicity via the autophagy pathway

Nanosized copper particles (nano Cu) have been incorporated into products in multiple industries, although studies have demonstrated that these particles are nephrotoxic. We investigated the cytotoxicity of nanosized copper particles on rat mesangial cells and measured rates of apoptosis, the expression of caspase-3, and generation of reactive oxygen species. We also measured autophagy through the acridine orange (AO) staining and expression of Beclin-1, microtubule-associated protein 1 light chain 3, and p62 to screen the underlying mechanism of toxicity. Nanosized copper particles inhibited mesangial cell viability, up-regulated the activity of caspase-3, and increased the rates of apoptosis and the generation of reactive oxygen species in a concentration-dependent manner. Exposure to nano Cu increased the formation of acidic vesicular organelles and the expression of Beclin-1, microtubule-associated protein 1 light chain 3, and p62, and treatment with an autophagy inhibitor reduced nephrotoxicity. This indicated that the autophagy pathway is involved in the toxicity induced by nanosized copper particles to mesangial cells. This finding can contribute to the development of safety guidelines for the evaluation of nanomaterials in the future.

Investigations on Melt Flow Rate and Tensile Behaviour of Single, Double and Triple-Sized Copper Reinforced Thermoplastic Composites.

Thermoplastic composite materials are emerging rapidly due to the flexibility of attaining customized mechanical and melt flow properties. Due to high ductility, toughness, recyclability, and thermal and electrical conductivity, there is ample scope of using copper particles in thermoplastics for 3d printing applications. In the present study, an attempt was made to investigate the Melt Flow Index (MFI), tensile strength, and electrical and thermal conductivity of nylon 6 and ABS (acrylonitrile butadiene styrene) thermoplastics reinforced with copper particles. Thus, the experiments were conducted by adding different-sized copper particles (100 mesh, 200 mesh, and 400 mesh) in variable compositions (0% to 10%) to ABS and nylon 6 matrix. The impact of single, double, and triple particle-sized copper particles on MFI was experimentally investigated followed by FTIR and SEM analysis. Also, the tensile, electrical, and thermal conductivity testing were done on filament made by different compositions. In general, higher fluidity and mechanical strength were obtained while using smaller particles even with higher concentrations (up to 8%) due to improved bonding strength and adhesion between the molecular chains. Moreover, thermal and electrical conductivity was improved with an increase in concentration of copper particles.

Fabrication of Carbon Nanomaterials Using Laser Scribing on Copper Nanoparticles-Embedded Polyacrylonitrile Films and Their Application in a Gas Sensor.

Carbon nanomaterials have attracted significant research attention as core materials in various industrial sectors owing to their excellent physicochemical properties. However, because the preparation of carbon materials is generally accompanied by high-temperature heat treatment, it has disadvantages in terms of cost and process. In this study, highly sensitive carbon nanomaterials were synthesized using a local laser scribing method from a copper-embedded polyacrylonitrile (CuPAN) composite film with a short processing time and low cost. The spin-coated CuPAN was converted into a carbonization precursor through stabilization and then patterned into a carbon nanomaterial of the desired shape using a pulsed laser. In particular, the stabilization process was essential in laser-induced carbonization, and the addition of copper promoted this effect as a catalyst. The synthesized material had a porous 3D structure that was easy to detect gas, and the resistance responses were detected as -2.41 and +0.97% by exposure to NO2 and NH3, respectively. In addition, the fabricated gas sensor consists of carbon materials and quartz with excellent thermal stability; therefore, it is expected to operate as a gas sensor even in extreme environments.

Preparation of functional bamboo by combining nano-copper with hemicellulose and lignin under high voltage electric field (HVEF).

A simple and effective method for preparing functional bamboo by combining nano-copper with hemicellulose and lignin was proposed. The influences of HVEF treatment time and voltage on the reaction of nano-copper with hemicellulose and lignin were studied. The combination was characterized by scanning electron microscopy-X-ray energy dispersive spectrometer (ESEM-EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results indicated that the O/C ratio and OH content of the treated bamboo decreased, the number of CHO groups decreased, the number of CO groups increased, and the nano-copper interacted with the hemicellulose and lignin in the bamboo. Copper was presented in the treated bamboo in the form of Cu0, Cu+ and Cu2+. The concentration of copper increased with the increasing treatment time or voltage. The bamboo underwent the high-voltage electrostatic in situ impregnation copper treatment had significant antibacterial properties and excellent UV protection performance. Therefore, the in situ impregnation of nano-copper particles with an HVEF treatment is simple and effective to produce functionalized bamboo, and has broad application prospects.

Flux-Free Diffusion Joining of SiCp/6063 Al Matrix Composites Using Liquid Gallium with Nano-Copper Particles in Atmosphere Environment.

A new method for flux-free diffusion joining of aluminum matrix composites reinforced with SiC particles (SiCp/Al MMCs) in atmosphere environment has been developed. Liquid gallium and nano-copper particles were employed as filler metal under joining temperatures ranging between 400 °C to 480 °C, with a holding time of 2 h and pressure of 3 MPa. The results showed that 65 vol.% SiCp/6063 Al MMCs were successfully joined together. X-ray diffraction (XRD) analysis confirmed the presence of Ga2O3 at the fracture. Meanwhile, neither copper oxide nor aluminum oxide was detected. The formation of Ga2O3 can protect nano-copper particles and SiCp/6063 Al MMCs from oxidation. The width of weld seam tended to be narrowed from 40 µm to 14 µm gradually with increasing temperature from 400 °C to 480 °C. The maximum shear strength level of 41.2 MPa was achieved with a bonding temperature of 450 °C. The change of the strength was due to the adequate elements' mutual diffusion and solution, as well as the change of the quantity and morphology of intermetallic compounds in the weld seam, such as Al2Cu and Cu3Ga. When the diffusion joining temperature reached 440 °C or above, the leak rate of the specimen remained under 10-10 Pa·m3/s.

Manufacturing Graphene-Encapsulated Copper Particles by Chemical Vapor Deposition in a Cold Wall Reactor.

Functional fillers, such as Ag, are commonly employed for effectively improving the thermal or electrical conductivity in polymer composites. However, a disadvantage of such a strategy is that the cost and performance cannot be balanced simultaneously. Therefore, the drive to find a material with both a cost efficient fabrication process and excellent performance attracts intense research interest. In this work, inspired by the core-shell structure, we developed a facile manufacturing method to prepare graphene-encapsulated Cu nanoparticles (GCPs) through utilizing an improved chemical vapor deposition (CVD) system with a cold wall reactor. The obtained GCPs could retain their spherical shape and exhibited an outstanding thermal stability up to 179 °C. Owing to the superior thermal conductivity of graphene and excellent oxidation resistance of GCPs, the produced GCPs are practically used in a thermally conductive adhesive (TCA), which commonly consists of Ag as the functional filler. Measurement shows a substantial 74.6 % improvement by partial replacement of Ag with GCPs.

Eddy current evaluation of recovered conductive waste purity.

The main goal of this paper is to present a new approach to evaluate the recovered conductive granular waste purity. For this purpose, the eddy current approach which is commonly applied in nondestructive evaluation has been used. The experimental tests consist of several samples composed of copper particles mixed with sand inserted in a cylindrical container with solenoidal coil. The impedance of the coil is measured, using precision LRC-meter, for several frequencies per sample and used according to the Experiment Design Methodology (EDM) to determinate the relationship between input and output of experiments, to have a quadratic model that will be used for inversion. The input and output are successively impedance and percentage of copper particles contained in the container. The results show the capability of the proposed approach to evaluate the conductive recovered waste purity.

Release of copper-amended particles from micronized copper-pressure-treated wood during mechanical abrasion.

BACKGROUND: We investigated the particles released due to abrasion of wood surfaces pressure-treated with micronized copper azole (MCA) wood preservative and we gathered preliminary data on its in vitro cytotoxicity for lung cells. The data were compared with particles released after abrasion of untreated, water (0% MCA)-pressure-treated, chromated copper (CC)-pressure-treated wood, and varnished wood. Size, morphology, and composition of the released particles were analyzed. RESULTS: Our results indicate that the abrasion of MCA-pressure-treated wood does not cause an additional release of nanoparticles from the unreacted copper (Cu) carbonate nanoparticles from of the MCA formulation. However, a small amount of released Cu was detected in the nanosized fraction of wood dust, which could penetrate the deep lungs. The acute cytotoxicity studies were performed on a human lung epithelial cell line and human macrophages derived from a monocytic cell line. These cell types are likely to encounter the released wood particles after inhalation. CONCLUSIONS: Our findings indicate that under the experimental conditions chosen, MCA does not pose a specific additional nano-risk, i.e. there is no additional release of nanoparticles and no specific nano-toxicity for lung epithelial cells and macrophages.

Understanding the transformation, speciation, and hazard potential of copper particles in a model septic tank system using zebrafish to monitor the effluent.

Although copper-containing nanoparticles are used in commercial products such as fungicides and bactericides, we presently do not understand the environmental impact on other organisms that may be inadvertently exposed. In this study, we used the zebrafish embryo as a screening tool to study the potential impact of two nano Cu-based materials, CuPRO and Kocide, in comparison to nanosized and micron-sized Cu and CuO particles in their pristine form (0-10 ppm) as well as following their transformation in an experimental wastewater treatment system. This was accomplished by construction of a modeled domestic septic tank system from which effluents could be retrieved at different stages following particle introduction (10 ppm). The Cu speciation in the effluent was identified as nondissolvable inorganic Cu(H2PO2)2 and nondiffusible organic Cu by X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), diffusive gradients in thin-films (DGT), and Visual MINTEQ software. While the nanoscale materials, including the commercial particles, were clearly more potent (showing 50% hatching interference above 0.5 ppm) than the micron-scale particulates with no effect on hatching up to 10 ppm, the Cu released from the particles in the septic tank underwent transformation into nonbioavailable species that failed to interfere with the function of the zebrafish embryo hatching enzyme. Moreover, we demonstrate that the addition of humic acid, as an organic carbon component, could lead to a dose-dependent decrease in Cu toxicity in our high content zebrafish embryo screening assay. Thus, the use of zebrafish embryo screening, in combination with the effluents obtained from a modeled exposure environment, enables a bioassay approach to follow the change in the speciation and hazard potential of Cu particles instead of difficult-to-perform direct particle tracking.

Ion-exchange chromatography combined with direct current amperometric detection at CuNPs/reduced graphene oxide-chitosan composite film modified electrode for determination of monosaccharide composition of polysaccharides from Phellinus igniarius.

A novel Cu nanoparticles/reduced graphene oxide-chitosan (CuNPs/r-GO-chitosan) composite film modified glassy carbon electrode (GCE) was fabricated by dispersing CuNPs uniformly on a stable r-GO-chitosan thin film through electrodeposition process. The modified electrode was characterized by cyclic voltammetry, scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS), and exhibited efficiently electrocatalytic oxidation toward monosaccharides with high stability. The good electrocatalytic activity of this modified electrode might be attributed to the synergistic effect of r-GO and CuNPs, and the stability might be attributed to the r-GO and chitosan thin matrix film. When the CuNPs/r-GO-chitosan/GCE was used as an electrochemical sensor in high performance anion exchange chromatography-direct current amperometric detection (HPAEC-DC) flowing system for the determination of monosaccharides under constant working potential of +0.55 V, the detection limits (S/N=3) ranged from 0.006 to 0.02 mg L(-1) for the analyzed sugars, and the dynamic linear ranges spanned from 0.02 to 500 mg L(-1). The proposed method has been applied for the determination of monosaccharide composition of crude polysaccharides from phellinus igniarius real samples, and the results were satisfactory.