CuS Nanorods Research Articles

Incorporation of CuS nanorods in polyelectrolyte multilayer microcapsules improved cancer cell cytotoxicity and signal intensity in ultrasound imaging

The fabrications of hollow microcapsules (MCs) with new architecture and ability to incorporate different nanomaterials have received great interest for targeted cancer therapy. Recently, CuS based nanomaterials have been demonstrated to possess the ability to mimic Fenton-like activity in tumor environment and inducing cancer cell apoptosis by generating highly reactive oxygen species (ROS). In this study, we have developed poly(allylamine) hydrochloride (PAH)/dextran sulfate (DS) polyelectrolyte MCs capable of carrying doxorubicin (DOX) for targeted cancer therapy and ultrasound imaging. The electron microscopy investigations showed the formation of polymeric MCs of 3 µm in size with incorporated CuS NRs in their interior structure. The surface modification of MCs with folic acid (FA), and encapsulation of model hydrophilic molecules in MCs was studied by UV–Visible (UV–Vis) spectroscopy, Fourier transform infra-red (FTIR) spectroscopy and confocal laser scanning microscopy. The encapsulation efficiency of DOX was found to be 56 % and the release was found to be linear at pH 5.5 and 7.4 in the absence of ultrasound exposure. The ultrasound exposure resulted in sudden rupture of MCs at 1 MHz and 1 W/cm2 and caused burst release of DOX at both pH conditions. The FA decorated PAH/DS/CuS NR MCs exhibited improved anti-cancer activity against MDA-MB-231 cancer cells due to the synergistic effects of ultrasound mediated burst release of chemotherapeutic drug (DOX), glutathione-stimulated ROS and targeted cancer therapy. Further, the capsules showed better echogenicity than that of control PAH/DS MCs when imaged under medical ultrasound-scanning system. Hence, the MCs demonstrated in this study have huge potential for targeted cancer theranostics by offering an option to image the cancer cells during the treatment period.

The role of surface modification in improving the effectiveness of CuS nanorods for cancer ablation therapy and antibacterial applications

We report a new methodology to synthesize CuS nanorods (CuS NRs) via hydrothermal route, and surface modified with chitosan (CS) and folic acid (FA) to demonstrate the role of surface modification in photo-thermal heat generation and cancer photo ablation therapy. The electron microscopy investigations showed the formation of rod-shaped CuS nanomaterial and the length and diameter of nanorods (NRs) were found to be ∼55 and 22 nm, respectively. The surface modification of CuS NRs was investigated by UV–Vis spectroscopy, FTIR spectroscopy, dynamic light scattering technique, and Raman spectroscopy. Without any compromise in photo-thermal heat generation, the surface modification significantly improved biocompatibility, cancer cell cytotoxicity, and anti-bacterial activity. The photothermal heat generation experiments with 808 nm laser light revealed that the temperature increase was found to be 54 ℃ for surface modified FA-CS@CuS NRs at 500 µg/mL which increased to ∼100 ℃ when the laser power intensity was increased from 0.5 to 1.5 W/cm2. The photothermal conversion efficiency (PCE) was estimated to be 38.6% for FA-CS@CuS NRs. Notably, the photothermal heat generation is significantly influenced by CuS NRs concentration and laser power intensity. The anticancer activity investigations against HCT116 cancer cells revealed enhanced cytotoxicity for cancer cells owing to synergistic effects of hyperthermia and generation of highly toxic hydroxyl radicals (·OH) induced by the release of Cu2+ions. The surface-modified FA-CS@CuS NRs showed excellent antibacterial activity against Escherichia coli and Staphylococcus aureus. Hence, the proposed FA-CS@CuS NRs can be a suitable nanoagent for effective targeted anticancer and photothermal ablation treatment.

Microwave-hydrothermal synthesis of copper sulphide nanorods embedded on graphene sheets as an efficient electrocatalyst for excellent hydrogen evolution reaction

Fabrication of non-precious and highly efficient electro-catalyst to accelerate the production of hydrogen evolution reaction (HER) at lower potential is a great challenging task in today’s energy generation era. In the present work, copper sulphide (CuS) nanorods tailored on reduced graphene oxide (rGO) nanosheets were synthesised by microwave-assisted hydrothermal method for highly stable and efficient material for HER is reported to newest. CuS nanorods decorated on rGO sheets showed a very low onset potential value of 0.0891 V with high current density when compared to pure CuS, rGO and better than commercially available Pt/C in 0.5 M H2SO4 solution with 100% Faradaic yield in HER activity. Importantly the present synthesis approach can be readily extended to prepare composites of CuS tailored structure and morphology for potential application in energy storage and conversion. The CuS@rGO nanocomposites can strongly accommodate a large volume changes by supplying the conducting network and in turn increasing the charge transferability. Oxygen cluster ions and sulphur edges on Cu surface that decreases the interface equilibrium distance between CuS, rGO and strong interactive coordination showing excellent synergism.

Temperature dependent structural, optical and electrical properties of CuS nanorods in aloe vera matrix

Coper sulphide nanorods were synthesized in an aqueous solution by a simple chemical route using copper acetate monohydrate and thiourea as reactants in different ambient temperatures with aloe vera as a green capping material. The as prepared nanorods were characterized with XRD, HRTEM, UV–Vis. absorption and PL spectroscopy, FTIR and EDAX analysis. The electrical conductivity of the electrolytic ionic CuS solution was measured by a standard conductivity cell. The XRD confirmed the polycrystalline hexagonal structure of CuS nanorods. The HRTEM exhibited well defined nanorods distributed in large areas. The UV–Vis. absorption and the PL spectra showed a systematic blue shift of absorption and UV-blue emission confirming quantum confinement effect in the synthesized nanorods. Optical band gap as estimated from Tauc-plot increased from 3.0eV to 3.8eV with increase of temperature. The particle sizes calculated from XRD results by Debye–Scherrer and W–H plots are in well agreement with those obtained from HRTEM results. Aloe vera acted as a good green capping material in quantum confinement of nanorods. FTIR spectra exhibited Cu–S stretching peak at 620 cm−1 which is characteristic of CuS. Electrical properties of ionic solution of CuS indicated good semiconducting nature of CuS. Ionic parameters are estimated and correlated to molar concentration. The EDAX analysis confirmed atomic % of copper and sulphur in CuS. The synthesized material may be used in fabrication of an optoelectronic device in UV-blue region.

Cu(OH)2 nanorods undergo sulfidation in water: in situ formation of CuO nanorods as intermediates and enhanced toxicity to Escherichia coli

Fate and risk of nanomaterials in the environment have attracted wide attention over the years. Copper hydroxide (Cu(OH)2) nanorods have been used as antibacterial nanomaterials in agricultural products, leading to their release into the environment. Yet, knowledge about the transformation of Cu(OH)2 nanorods is currently scarce, representing a potential for the environment. Here we investigated the sulfidation process of Cu(OH)2 nanorods by dissolved sulfide (Na2S) in aqueous solutions with varied molar ratios of Cu(OH)2 nanorods versus Na2S. The solid products were characterized with focus on the roles of dissolved oxygen (DO) and dissolved sulfide on CuS formation. The impact of sulfidation on the toxicity of Cu(OH)2 nanorods for Escherichia coli was also investigated. Copper oxide (CuO) nanorods with comparable morphology to Cu(OH)2 nanorods were identified as the intermediate of Cu(OH)2 nanorods sulfidation. We proposed that in situ formation of self-assembly CuS nanorods was achieved through an anion-exchange reaction between O2− of CuO and S2− of Na2S. We found that sulfidation enhanced the toxicity of Cu(OH)2 nanorods to E. coli: the inhibition of E. coli growth increased from 1.2 to 22.6% with increasing sulfidation due to an increase of dissolved Cu concentration.

Investigation of photocatalytic performance of CuS/Bi2WO6 and degradation pathway of RhB in water

Abstract A series of CuS/Bi2WO6 composites were synthesized by solvothermal synthesis, which showed enhanced photocatalytic activity. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, photoluminescence ultraviolet–visible absorption spectroscopy, transient photocurrent and EIS. The results showed that as-prepared CuS/Bi2WO6 has flower-like nano microspheres self-assembled by nanoplates and CuS nanorods are uniformly dispersed on its surface. The CuS/Bi2WO6 forms heterojunctions between CuS and Bi2WO6 and shows a wide light response range and a strong light response intensity. The CuS/Bi2WO6 exhibits a better Rhodamine B (RhB) degradation effect than pure Bi2WO6 and CuS, and it can degrade 90% RhB in 50 min and achieve complete degradation in 70 min under Xe lamp irradiation. The CuS/Bi2WO6 has photocatalytic activity in a low pH environment and good stability. The formation of a heterojunction between CuS and Bi2WO6 can effectively separate photo-generated electrons and holes, greatly improving the photocatalytic activity. In the CuS/Bi2WO6-RhB reaction system, O2− is the main active species, and it can rapidly remove the ethyl group from the amino group linked to benzene rings to achieve the N-de-ethylation reaction in the process of RhB degradation. The N-de-ethylated products are simultaneously degraded to small organic molecules and even mineralized into CO2 and H2O.

Facile hydrothermal bio-synthesis of cellulose acetate templated CuS nanorods like fibres: antibacterial, cytotoxicity effects and DNA cleavage properties against A549 lung cancer cells.

In this research, the hydrothermal method was used for synthesising cellulose acetate (CA) templated nanorods like CuS fibres using vegetable extract (Brassica oleracea var. italica). These extracts act as a reducing agent in the presence of CA. Surprisingly, when the same reaction was carried out in the absence of CA and broccoli extract, structural morphology disappeared and was found as agglomerated. In the presence of cellulose templated extract mediated CuS has revealed as nanorods like fibres and was confirmed by field emission scanning electron microscope analysis. Their crystallinity property of CuS nanoparticles (NPs) and cellulose templated biosynthesised CuS NPs was analysed and compared using X-ray diffraction technique. The biological activities of the obtained product were examined for antibacterial assessment against two bacterial strains that include two-gram negative strains (E.Coli and S. aureus). The nanostructured product found to exhibit excellent antibacterial agent against all the strains. Biosynthesised nanostructure showed its efficacy against A549 lung cancer cells which might attribute to a larger surface to volume ratio of nanorods like fibres. The authors observation suggest that CuS nanorods like fibres can significantly reduce the cell growth with IC50 value of 31.2 μg/ml.

Synthesis of randomly oriented self assembled CuS nanorods by co-precipitation route

In this paper, we have reported undoped and Co doped CuS nanorods by using co-precipitation method. Dehydrated Copper Chloride and Thiourea were used as main precursors and NaOH as a complexing agent in this synthesis process. The reaction takes place at room temperature. The powder samples were obtained under 100 °C using an oven for 3 h and analyzed by using various techniques like X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and UV–Vis spectroscopy. X-ray diffraction spectra exhibit the poly crystalline behavior with hexagonal phase. FESEM micrographs exhibit the randomly oriented few micrometer long CuS nanorods in vertical directions with diameter 10–15 nm. With the addition of cobalt, the nanorod converts into nanosheets with average length 2 µm and diameter 80 nm. Optical studies show the optical band gap of about 1.09–1.19 nm which is good for optoelectronic devices.

In Situ Microwave‐Assisted Fabrication of Hierarchically Arranged Metal Sulfide Counter Electrodes to Boost Stability and Efficiency of Quantum Dot‐Sensitized Solar Cells

AbstractThis study describes preparation of metal sulfide counter electrodes (CEs) through one‐pot microwave‐assisted route to improve power conversion efficiency (PCE) of quantum dot‐sensitized solar cells at a lower cost. The CuS nanorods, Ni0.96S nanoparticles, and PbS nanocubes are synthesized and deposited in situ on fluorine‐doped tin oxide substrate to serve as CEs without further post‐treatment. Effects of several reaction parameters including sulfur precursor (Na2S, C2H5NS, CH4N2S), Cu concentration, reaction time, and choice of cation (Cu, Ni, Pb) on the CEs morphology, electrochemical characteristics, and PCE are studied. Furthermore, nanostructure formation and thin film growth are studied and correlated with PCE, from which morphology‐ and composition‐performance relationships can be inferred. Hierarchically assembled nanorod CuS CEs exhibit higher electrochemical stability in the S2–/Sn2– redox reaction. Together with the efficient charge transfer and higher diffusion coefficient of polysulfide redox at the electrode/electrolyte interface, deduced from electrochemical impedance spectroscopy and Tafel analyses, a PCE of 8.32% is achieved for the CuS CE. The enhanced photovoltaic performance is ascribed to the 1D CuS nanorods forming a diffusive structure which decreases charge transfer impedance and facilitates regeneration of polysulfide redox leading to a higher short‐circuit current density and fill factor.

Modifying the lubricating and tribological properties via introducing the oleic acid in CuS nanomaterials for vehicle

Materials made from self-lubricating inorganic and organic composites have gained great attention due to advantages of the rust-resistance, light weight, low cost, and high compatibility. As a result, they have extensive applications in the friction and lubrication fields, typically for vehicle. With the help of the water bath and hydrothermal method, we have prepared the CuS nanomaterials with and without oleic acid modification. Various techniques, such as X-ray diffraction (XRD) spectra, transmission electron microscope (TEM), energy-dispersive X-ray spectroscopy (EDS) and vertical universal friction as well as wear testing, have been employed to analyze the structure information and characterize the related tribological properties of our CuS nanomaterials. Results show that the morphologies of the CuS nanomaterials are nanorods. Increasing the surface area and the concentration of CuS nanorod additives can significantly reduce the friction coefficient and wear rate of pins in both unmodified and oleic acid-modified CuS nanomaterials. More than that, we find that when compared to those without oleic acid modification, the oleic acid modification enable the CuS nanomaterials to exhibit higher anti-wear properties. The EDS analysis shows that there is still a uniform tribo-film in the surface of oleic acid-modified CuS nanomaterials, implying the prominent tribological performances of CuS nanorods additives. Our results indicate that the Oleic acid-modified CuS nanorods can be served as a new lubricating and tribological material for vehicle.

Morphology controlled synthesis and photocatalytic study of novel CuS-Bi2O2CO3 heterojunction system for chlorpyrifos degradation under visible light illumination

In this study, Bi2O2CO3 (BSC) nanoplates with high aspect ratio and hierarchical nanostructures were prepared by hydrothermal technique using urea/hexamethylenetetramine as hydrolysing agent and KCl as additive in different solvent systems. The relative molar proportion of urea and KCl was crucial for phase purity as well as thickness and planar dimension of the BSC plates. The BSC nanoplates were used as substrates to prepare CuS-Bi2O2CO3 (CuS/BSC) direct z-scheme heterojunction systems. The heterojunction materials were characterized by FESEM, HRTEM, XRD, PL, FTIR and UV–Vis-DRS techniques. The presence of crystalline tetragonal BSC and hexagonal covellite CuS phase was inferred from XRD study. Morphologically, the CuS/BSC material contained CuS nanorods and BSC nanoplates. HRTEM study suggested microscopic close contact between the CuS nanorods and BSC nanoplates. Optical property study revealed improvement in visible light absorption and enhanced separation of excitons. The CuS/BSC materials were used as photocatalyst for chlorpyrifos pesticide degradation under visible light irradiation. The heterojunction materials were highly active achieving >95% degradation within 3 h of reaction. The pathway and mechanism of CP degradation was elucidated using GCMS and radical scavenger experiments.

Photocatalytic degradation of alachlor using type-II CuS/BiFeO3 heterojunctions as novel photocatalyst under visible light irradiation

In this study, a sustainable visible light promoted photocatalytic route has been developed for mineralization of alachlor pesticide using CuS/BiFeO3 heterojunction materials. The heterojunctions were synthesized by a two-step process and characterized using XRD, FESEM, HRTEM, XPS, FTIR, UV–Vis-DRS and PL techniques. Morphologically, the heterojunction materials consist of BiFeO3 nanoplates with high aspect ratio and CuS nanorods. The intimate contact between the two phases was ascertained from the HRTEM study. Optical property study suggested that these materials show excellent absorption in visible region with superior charge carrier separation characteristics compared to the individual components. The transient photocurrent measurement and I-V plots revealed high mobility of the excitons across grain boundary due to heterojunction formation. The band positions of the two components were aligned favourably for a cyclic movement of electrons and holes resulting in a type-II heterojunctions. The CuS/BiFeO3 materials efficiently catalyse the mineralization of alachlor pesticide under visible light illumination achieving >95% degradation within 60 min. The mechanism of alachlor degradation over the catalyst surface was elucidated using GCMS and radical scavenger experiments. The attractive features of the developed photocatalytic method are the use of renewable energy, low cost, high efficiency, stability and recyclability of the catalyst material.

Hydrothermal synthesis of highly stable copper sulfide nanorods for efficient photo-thermal conversion

Copper sulfide (CuS) nanostructures have an important application prospect in the field of solar photo-thermal conversion because of their excellent photo-thermal stability. In this paper, nanostructured CuS nanorods were successfully prepared via hydrothermal reaction method. The crystal structure and surface morphology of the as-prepared CuS nanorods were characterized. The optical absorption and photo-thermal conversion performance of the CuS emulsions based on water were studied. The ultraviolet/visible/near infrared (UV/Vis/NIR) absorption spectra tests show that the prepared CuS emulsions have strong optical absorption in both visible light and near infrared light bands. And the photo-thermal conversion results indicate that the CuS emulsions possess good photo-thermal conversion performance, and the maximum temperature of the emulsion reaches about 74.44 °C with the mass fraction of 0.10%. Moreover, in a certain concentration range, the photo-thermal conversion performance will be effectively enhanced with increasing the mass fractions of the emulsions.

Facile synthesis of a hierarchical CuS/CuSCN nanocomposite with advanced energy storage properties

Facile fabrication of a CuS/CuSCN nanocomposite electrode for a supercapacitor with a high specific capacitance (1787.3 F g−1).

Preparation and tribological properties of unmodified and oleic acid-modified CuS nanorods as lubricating oil additives

Unmodified and oleic acid-modified CuS nanorods were prepared by water bath and hydrothermal method. The prepared CuS nanorods were characterized by X-ray diffraction and transmission electron microscope. The tribological properties of both types of CuS nanorods as additives in liquid paraffin (LP) were investigated using a vertical universal friction and wear testing machine. The addition of unmodified and oleic acid-modified CuS nanorods was found to significantly reduce the friction coefficient and wear rate of pins by increasing the surface area and addition concentration of CuS nanorod additives. The addition of oleic acid-modified CuS nanorod showed higher anti-wear properties than those of unmodified CuS nanorods. The prominent tribological performances of CuS nanorods additives were attributed to the formation of complete and uniform tribo-film，which is confirmed by the EDS analyses of tested worn surfaces of pins.

Self-assembly of complex hollow CuS nano/micro shell by an electrochemically active bacterium Shewanella oneidensis MR-1

In the present study, Shewanella oneidensis MR-1 was successfully exploited to produce CuS nanocrystals not only as a biotemplate but also as a supplier of sulfur source. The biogenic H2S produced via the thiosulfate reduction in periplasm grabbed Cu(II) ions bound with extracellular polymeric substance of Shewanella and precipitated as monodisperse CuS nanoparticles extracellularly. These nanoparticles aggregated in the extracellular matrix gradually and then formed CuS nanorods. Ultimately, a complex hollow CuS microshell self-assembled on the cell surface was observed for the first time. The biogenic CuS microshell could significantly enhance the adsorption ability of S. oneidensis MR-1 toward Cr(VI). This work may facilitate a better understanding about the biosynthesis mechanism of nanomaterials and contribute to the application in environmental remediation.

Engineering bacterial inclusion bodies as nanostructured depots of functional protein drugs

In the present study, Shewanella oneidensis MR-1 was successfully exploited to produce CuS nanocrystals not only as a biotemplate but also as a supplier of sulfur source. The biogenic H2S produced via the thiosulfate reduction in periplasm grabbed Cu(II) ions bound with extracellular polymeric substance of Shewanella and precipitated as monodisperse CuS nanoparticles extracellularly. These nanoparticles aggregated in the extracellular matrix gradually and then formed CuS nanorods. Ultimately, a complex hollow CuS microshell self-assembled on the cell surface was observed for the first time. The biogenic CuS microshell could significantly enhance the adsorption ability of S. oneidensis MR-1 toward Cr(VI). This work may facilitate a better understanding about the biosynthesis mechanism of nanomaterials and contribute to the application in environmental remediation.

Synthesis of sub-10 nm copper sulphide rods as high-performance anode for long-cycle life Li-ion batteries

Copper sulfide (CuS) nanorods with the size of sub-10 nm are synthesized via a facile sol–gel method without post–thermal treatment. The as-prepared CuS nanorods are characterized by X-ray diffraction, transmission electron microscope, and energy dispersive X-ray spectroscopy as hexagonal covellite CuS. The as-prepared CuS nanorods utilized as anode material exhibit a high reversible capacity and excellent cycling stability up to 250 cycles, as well as high Coulombic efficiency. The unique structure of the CuS nanorods should be responsible for their excellent electrochemical performance.

Copper Sulfide Self-Assembly Architectures with Improved Photothermal Performance

Copper chalcogenide nanomaterials are promising photothermal materials for establishing novel diagnostic and therapeutic methods owing to the low cost but high photothermal transduction efficiency. Further progresses of the correlated technologies greatly depend on the efforts on design and construction of novel nanostructures. In this paper, we demonstrate a facile one-pot route for constructing CuS nanostructures in aqueous media via a spontaneous assembly process. In the presence of polyvinylpyrrolidone (PVP) as the capping agents, a decomposition of Cu(CH3COSH)x precursors is induced by ammonia, which produces hexagonal CuS nanoparticles (NPs) with the diameter around 22 nm. The primary CuS NPs greatly tend to self-assembly into one-dimensional structures, which are triggered by short-range anisotropic dipolar attraction and enforced by long-range isotropic electrostatic repulsion. The further fusion of the assembled NPs generates 480 × 50 nm(2) CuS nanorods. Because the formation of nanorods enhances the internanorod van der Waals attraction, the nanorods finally self-assembly into shuttle-like bundles in micrometer size. In comparison to isolated NPs, the regular CuS assembly structures exhibit improved molar extinction coefficient up to 9.7 × 10(16) cm(-1) M(-1) by shortening the distance of neighboring CuS NPs and therewith generating new electronic structures of the CuS indirect transition. Consequently, better photothermal performance is achieved.

Synthesis of CuS nanorods grown at room temperature by electrodeposition method

CuS thin films were deposited on stainless steel substrates from an aqueous solution of CuSO4, Na2S2O3 and Triethanolamine. Deposited films were characterized by XRD, SEM, EDAX, Raman and Optical measurements. The electrodeposition bath concentration can be used to control the diameter of the electrodeposited nanorods within the range of 35–40 nm. The formation of complexes of copper ions and TEA was found to be a key factor in the nanorods growth process. Films are polycrystalline with hexagonal crystal structure. SEM images indicate that the film surfaces are smooth, homogeneous and well-covered. A new structure of CuS nanorods having length of 5–10 μm and diameter from 35 to 40 nm has been demonstrated. By changing bath concentration and keeping deposition time fixed the agglomeration of rods is enhanced due to the formation of large number of particles during growth process. Raman shifts of samples are detected at wave numbers 473 cm−1. Typical film deposited with optimized bath concentration shows optical band gap of about 2.73 eV.