Release Of Copper Ions Research Articles

Tailoring Copper-Doped Bioactive Glass/Chitosan Coatings with Angiogenic and Antibacterial Properties.

Implant coatings are frequently applied to modulate tissue response and delivery of drugs. Copper (Cu)-containing coatings on dental implant abutments have been proposed to improve soft tissue integration and reduce the risk for peri-implant infections. However, precise control over Cu loading and release kinetics remains a major challenge. In this study, we introduced a bottom-up coating deposition method based on nanoparticle assembly to allow for local release of Cu ions from implant surfaces. We first doped mesoporous bioactive glass (MBG) nanoparticles with various amounts of Cu. Subsequently, we suspended these Cu-doped MBG (Cu-MBG), Cu-free MBG nanoparticles, or mixtures thereof in chitosan solution and prepared a series of composite coatings on commercially pure titanium disks as model surfaces for transmucosal components of bone implants through electrophoretic deposition (EPD). By changing the Cu-MBG:MBG ratio of the composite coatings, we controlled the Cu release kinetics without changing other coating properties. Human gingival fibroblasts proliferated on the composite coatings except for coatings with the highest amount of Cu, which inhibited their proliferation. The migration rate of human umbilical vein endothelial cells cultured on the composite coatings was highest on coatings containing equal amounts of Cu-MBG and Cu-free MBG. Antibacterial tests confirmed that Cu-containing coatings reduced the growth of Porphyromonas gingivalis up to fivefold compared with uncoated implants. In conclusion, our data indicate that the EPD method is suitable to deposit nanoparticle-based coatings onto dental implants, which enhance endothelial cell migration and reduce bacterial growth. Impact statement Precise control over the release of therapeutic agents remains a major challenge for implant coatings. In this study, we introduce a simple and cost-effective way to tune the release of angiogenic and antibacterial copper ions using the electrophoretic deposition technique. Due to the flexibility and mild processing conditions of this technique, our method can also be used to incorporate other therapeutic agents onto implant surfaces.

Cu(II)-functionalized silk fibroin films for the catalytic generation of nitric oxide.

In situ release of nitric oxide (NO) has been suggested to be a potential functionalization strategy for blood-contacting implants. In this study, the NO generation capability catalyzed by the copper ion-incorporated silk fibroin (SF) films in the presence of S-nitroso-N-acetyl-dl-penicillamine (SNAP) is demonstrated. Cu(II) is effectively bound to the surface of the SF film based on metal-protein coordination. The x-ray photoelectron spectroscopy results indicate that copper ions may exist on the surface of the SF film in the form of Cu(II)/Cu(I) coexistence. The degradation behavior showed that the bound copper ions on the surface of the SF films can maintain a slow release in phosphate-buffered saline (PBS) or collagenase IA solution for 7 days. There was no significant difference in the release of copper ions between PBS degradation and enzyme degradation. The loading of copper ions significantly improved the release of NO from SNAP through catalysis. Based on the biological effects of copper ions and the ability to catalyze the release of NO from S-nitrosothiols, copper ion loading provides an option for the construction of bioactive SF biomaterials.

Inhalation toxicity of copper compounds: Results of 14-day range finding study for copper sulphate pentahydrate and dicopper oxide and 28-day subacute inhalation exposure of dicopper oxide in rats

Inhalation exposure to copper may occur during a range of occupational activities and the purpose of this study was to characterise the toxicological response to repeated inhalation of two copper compounds, representative of copper substances in large-scale production/use. Crl:CD(SD) rats were repeatedly exposed to aerosols of dicopper oxide (Cu2O) or copper sulphate pentahydrate (CuSO4.5 H2O) for 14-days as part of a range finding study at normalised copper doses of 0.18, 0.71, 1.78 and 8.9 mg/m3 Cu. Within a 28-days main study (Cu2O only), animals were repeatedly exposed to 0.2, 0.4, 0.8 and 2.0 mg/m3 Cu2O following OECD TG 412. The main study also consisted of satellite groups exposed for 1-, 2- or 3- weeks as well as a 13-week post-exposure recovery period group. Repeated exposure for 14-days to both copper compounds, normalised for copper content, led to an acute influx of polymorphonuclear leukocytes (neutrophils) and macrophages whilst only CuSO4.5 H2O exposure resulted in epithelial hyperplasia. This differential response may reflect the highly dissolvable nature of CuSO4.5 H2O in lung lining fluid leading to a release of copper ions at the epithelial surface whilst Cu2O is relatively indissolvable at neutral pH. In the 28-day study with Cu2O, an increase in cellularity was also evident in both histological and BALF samples and was dose-related with minimal to mild (neutrophilic) inflammation observed > 0.4 mg/m3 in the lung tissue sections and significant increases from 0.2 mg/m3 in BALF. There were no minimal haematological findings, no clinical findings and systemic organs were unaffected by inhalation exposure to dicopper oxide. The lung cellular response was limited to alveolar histiocytosis and neutrophil influx with no evidence of epithelial hyperplasia or fibrosis and all lung biomarkers returned to control levels within the post-exposure recovery period. Interestingly, the satellite groups showed that this acute cellular response followed a biphasic rather than monotonic pattern with a peak in lung biomarkers between weeks 1–3 and reduction thereafter. This reduction in lung biomarkers occurred during continued exposure and may indicate an adaptive response to copper exposure. Overall, these results show that repeated exposure to copper compounds results in an acute cellular response with no associated pathology and which fully resolved after the cessation of exposure. Therefore, the cellular response is evidence of a controlled and adaptive response associated with the removal of Cu2O from the alveolar surface.

Oxygen-Independent Sulfate Radical for Stimuli-Responsive Tumor Nanotherapy.

Variant modalities are quested and merged into the tumor nanotherapy by leveraging the excitation from external or intratumoral incentives. However, the ubiquitous hypoxia and the insufficient content of hydrogen peroxide (H2O2) in tumor microenvironments inevitably hinder the effective production of reactive oxygen species (ROS). To radically extricate from the shackles, peroxymonosulfate (PMS: HSO5 −)‐loaded hollow mesoporous copper sulfide (CuS) nanoparticles (NPs) are prepared as the distinct ROS donors for sulfate radical (•SO4 −)‐mediated and stimuli‐responsive tumor nanotherapy in an oxygen‐independent manner. In this therapeutic modality, the second near‐infrared laser irradiation, together with the released copper ions as well as the heat produced by CuS after illumination, work together to activate PMS thus triply ensuring the copious production of •SO4 −. Different from conventional ROS, the emergence of •SO4 −, possessing a longer half‐life and more rapid reaction, is independent of the oxygen (O2) and H2O2 content within the tumor. In addition, this engineered nanosystem also exerts the function of photoacoustic imaging and skin restoration on the corresponding animal models. This study reveals the enormous potential of sulfate radical in oncotherapy and broadens pave for exploring the application of multifunctional and stimuli‐responsive nanosystems in biomedicine.

Development of Functional Composite Cu(II)-Polyoxometalate/PLA with Antimicrobial Properties.

Novel composite self-disinfecting films of polylactic acid (PLA) filled with nanosized particles of double sodium–copper(II) paratungstate B Na2Cu3(CuOH)2[W12O40(OH)2]·32H2O (POM) were developed. The solvent casting (POM/PLA film) and solvent-free melt extrusion methods (Extr. POM/PLA film) were applied for film preparation. The copper (II) ion release to water from both types of the films after 10 days at different temperatures demonstrated that the PLA matrix acts as a diffusion barrier, and the resulting concentration of released copper in water at room temperature remained low, at 0.79% for POM/PLA film and 0.51% for Extr. POM/PLA film. The POM-containing films reveals a significant inhibitory effect against E. coli ATCC 25922 in the agar diffusion test. The numbers of CFUs in washes of the films after incubation for 24 h were found to be 3.6 log CFU mL–1 (POM/PLA film) and 4.1 log CFU mL–1 (Extr. POM/PLA film). The films combine the antibacterial properties of POM and a bio-based polymer matrix, which makes them a prospective coating material for applications in hospital indoor environments. Excellent thermal stability of POM gives a technological advantage for industrial manufacturing to allow the processing of novel composite material in the solvent free (molten) state.

CuS-PNIPAm nanoparticles with the ability to initiatively capture bacteria for photothermal treatment of infected skin.

Copper sulfide nanoparticles (CuS NPs) have shown great potential in various application fields, especially in biomedical engineering fields. CuS NPs, with the ability to actively capture and kill bacteria and without the worry of biocompatibility, will greatly expand their applications. Herein, a four-arm star thermo-sensitive polyisopropylacrylamide (4sPNIPAm) was used to modify CuS NPs (CuS-PNIPAm NPs). The obtained NPs displayed the controlled release of copper ions and higher photothermal conversion ability in comparison with contrast materials CuS-PEG NPs and CuS NPs. Aggregation of CuS-PNIPAm NPs at above 34°C resulted in capturing bacteria by forming the aggregates of NPs-bacteria. Both Staphylococcus aureus and Escherichia coli co-cultured with CuS-PNIPAm NPs were completely killed upon near-infrared irradiation in minutes. Furthermore, CuS-PNIPAm NPs were verified to be a photothermal agent without toxic effect. In in vivo experiment, the NPs effectively killed the bacteria in the wound and accelerated the process of wound repairment. Overall, photothermal treatment by CuS-PNIPAm NPs demonstrates the ability to actively capture and kill bacteria, and has a potential in the treatment of infected skin and the regeneration of skin tissues. The therapy will exert a far-reaching impact on the regeneration of stubborn chronic wounds.

Behavior and toxicity assessment of copper nanoparticles in aquatic environment: A case study on red swamp crayfish

With the wide use of copper nanoparticles (CuNPs) in various industrial and commercial applications, they inevitably enter the aquatic environment. However, their behavior in the aquatic environment and potential toxicity to aquatic organisms remain little known. In this study, we investigated the behavior of CuNPs in freshwater, as well as the toxicity and bioaccumulation of CuNPs and copper sulfate (CuSO4), used as a positive control for copper ions toxicity, in red swamp crayfish (Procambarus clarkii). The results showed that CuNPs released copper ions into freshwater and aggregated rapidly in freshwater, and their release of copper ions and aggregation slowed down at a higher concentration of CuNPs. The calculated 72-h LC50 values for crayfish were 1.18 and 0.54 mg/L for CuNPs and CuSO4, respectively. Cu accumulation in the gill and hepatopancreas from CuSO4 treatments was significantly higher than that from CuNPs, and the highest Cu bioaccumulation level in crayfish was found in the gill, followed by hepatopancreas and muscle with the exposure of copper. The activities of the antioxidative enzymes in the crayfish significantly decreased after exposure to CuNPs for 48 h, compared to the control (without CuNPs or CuSO4). Histological examination revealed that there was no significant alteration of hepatopancreas in the crayfish exposed to CuNPs. Meanwhile, the growth of crayfish was not significantly inhibited by CuNPs. These results suggested that CuNPs exposure can induce oxidative stress in the crayfish, gill is the main tissue for their accumulation, and their toxicity is mainly caused by the released copper ions.

A Copper Peroxide Fenton Nanoagent-Hydrogel as an In Situ pH-Responsive Wound Dressing for Effectively Trapping and Eliminating Bacteria.

Bacterial infection has been a great threat to wounds due to the abuse of antibiotics and drug resistance. Elaborately constructing an efficient antibacterial strategy for accelerated healing of bacteria-infected wounds is of great importance. Herein, we develop a transferrin-conjugated copper peroxide nanoparticle-hydrogel (denoted as CP@Tf-hy) wound dressing with no toxicity to mammalian cells at a test dosage. When exposed to an initial acidic wound environment, the CP@Tf-hy simultaneously displays in situ self-supplied H2O2 and pH-responsive release of Fenton catalytic copper ions accompanied by highly toxic hydroxyl radical (•OH) generation against antibiotic-resistant bacteria. Meanwhile, the positively charged CP@Tf-hy can efficiently trap and restrain negatively charged bacteria to the range of •OH destruction to greatly overcome its intrinsic disadvantages of short life and diffusion distance. Importantly, the CP@Tf-hy consumes the bacterial overexpressed antioxidant glutathione while boosting Fenton catalytic copper(I) ions to generate more •OH. The synergistic effects of the enhanced Fenton reaction, responsive copper ion release, and bacterial trapping can achieve high bacterial elimination efficacy (7 log reduction). In vivo investigations demonstrate that the porous CP@Tf-hy significantly promotes hemostasis, cell proliferation, and migration of the wound, consequently accelerating bacteria-infected wound healing. The safe, low-cost, and all-in-one CP@Tf-hy holds great prospects as an antibacterial dressing for rapid resistant bacteria-infected purulent wound healing.

Fabrication of copper nanoparticle composite nanogel for high-efficiency management of Pseudomonas syringae pv. tabaci on tobacco.

Copper nanoparticles (CuNPs) can release copper ions (Cu2+ ) to control bacterial diseases on crops. However, the high concentration of the CuNPs applied in disease controlling can highly limit their application. In this work, by in situ reducing CuNPs in alginate nanogels and coated with cetyl trimethyl ammonium chloride (CTAC), a CuNP composite nanogel was fabricated as a new nanopesticide with low copper content. Data showed that the CTAC coating would affect the antibacterial activity and leaf surface adhesion of the nanogel, while CuNP content could also influence the membrane damage ability of the gel. The nanogel could depress the growth of bacteria by rupturing its membrane and show a minimum inhibitory concentration (MIC) as low as 500 μg mL-1 , which only contain 58 μg mL-1 CuNP, and achieve a 64% of therapeutic efficiency (with 1000 μg mL-1 nanogel) in in vivo experiments, higher than that of commercial bactericide thiodiazole copper. Furthermore, the application of the nanogel can also perform a growth-promoting effect on the plant, which may be due to the supplement of copper element provided by CuNP. The CuNP composite nanogel fabricated in this work performed high leaf disease controllability and safety compared to the commercial bactericide thiodiazole copper. We hope this nanogel can provide a potential high-efficiency nano-bactericide that can be used in the leaf bacterial disease control.

In vitro degradation, photo-dynamic and thermal antibacterial activities of Cu-bearing chlorophyllin-induced Ca-P coating on magnesium alloy AZ31.

Surgical failures, caused by postoperative infections of bone implants, are commonly met, which cannot be treated precisely with intravenous antibiotics. Photothermal therapy (PTT) and photodynamic therapy (PDT) have attracted widespread attention due to their non-invasive antibacterial effects on tissues and no bacterial resistance, which may be an excellent approach to solve infections related to bone implants for biodegradable magnesium alloys. Herein, a sodium copper chlorophyllin (SCC) with a porphyrin ring induced Ca–P coating was prepared on AZ31 magnesium alloy via layer-by-layer (LbL) assembly. The morphology and composition of the samples were characterized through field emission scanning electron microscope (FE-SEM) with affiliated energy dispersive spectrometer (EDS), X-ray diffractometer (XRD), and Fourier infrared spectrometer (FTIR) and X-ray photoelectron spectrometer (XPS) as well. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and hydrogen evolution experiments were employed to evaluate the corrosion behavior of the samples. Atomic absorption spectrophotometer was used to measure Cu elemental content of different immersion periods. Cytocompatibility and antibacterial performance of the coatings were probed using in vitro cytotoxicity tests (MTT assay), live/dead cell staining and plate counting method. The results showed that the obtained (Ca–P/SCC)10 coating exhibited good corrosion resistance, antimicrobial activity (especially under 808 nm irradiation) and biocompatibility. The antibacterial rates for E. coli and S. aureus were 99.9% and 99.8%, respectively; and the photothermal conversion efficiency was as high as 42.1%. Triple antibacterial mechanisms including photodynamic, photothermal reactions and copper-ions release were proposed. This coating exhibited a promising application for biodegradable magnesium alloys.

Enhanced antibacterial behavior of a novel Cu-bearing high-entropy alloy.

Contact infection of bacteria and viruses has been a critical threat to human health. The worldwide outbreak of COVID-19 put forward urgent requirements for the research and development of the self-antibacterial materials, especially the antibacterial alloys. Based on the concept of high-entropy alloys, the present work designed and prepared a novel Co0.4FeCr0.9Cu0.3 antibacterial high-entropy alloy with superior antibacterial properties without intricate or rigorous annealing processes, which outperform the antibacterial stainless steels. The antibacterial tests presented a 99.97% antibacterial rate against Escherichia coli and a 99.96% antibacterial rate against Staphylococcus aureus after 24 h. In contrast, the classic antibacterial copper-bearing stainless steel only performed the 71.50% and 80.84% antibacterial rate, respectively. The results of the reactive oxygen species analysis indicated that the copper ion release and the immediate contact with copper-rich phase had a synergistic effect in enhancing antibacterial properties. Moreover, this alloy exhibited excellent corrosion resistance when compared with the classic antibacterial stainless steels, and the compression test indicated the yield strength of the alloy was 1015 MPa. These findings generate fresh insights into guiding the designs of structure-function-integrated antibacterial alloys.

Promotion of diabetic wound healing using novel Cu2O/Pt nanocubes through bacterial killing and enhanced angiogenesis in rats

Chronic bacterial infection, local inflammation, and insufficient angiogenesis contribute to poor healing of diabetic wounds. Here, Cu2O/Pt nanocubes (CPN) are successfully developed with good biocompatibility for treatment of diabetic wounds in rats. The synthesized CPN are characterized using SEM, XPS, and XRD. CPN exhibit triple-enzyme mimetic activity: oxidase-like, peroxidase-like, and catalase-like activities. Moreover, CPN show significant antibacterial activity against Gram-negative and Gram-positive bacteria when combined with low concentration of H2O2, via generation of highly reactive ROS. CPN also exhibit significantly accelerated wound healing in a full-layer deprivation rat model infected by Staphylococcus aureus, which is ascribed to the constant release of copper ions, subsequently activating the VEGF/AKT/ERK1/2 signaling pathway and promoting angiogenesis. CPN are able to catalyze H2O2 to generate O2 for local hypoxia alleviation. Furthermore, in vivo results indicate that treatment with CPN promotes the expression of transforming growth factor and matrix metalloproteinases, causing enhanced cell proliferation and collagen deposition, as well as extracellular matrix remodeling. In contrast, CPN decrease the expression of proinflammatory cytokines, such as TNF-ɑ and IL-1β, which are induced by bacterial infection and hyperglycemia. These results suggest a novel strategy for the treatment of diabetic wound healing.

Copper stabilized bimetallic alloy Cu–Bi by convenient strategy fabrication: A novel Fenton-like and photothermal synergistic antibacterial platform

The release of pollutants from bacterial pathogens in air or water, which causes a serious threat to human health and well-being. Traditional antibiotics have exhibited insufficient ability in combating bacteria owing to the emergence of drug-resistant bacteria. Hence, effective antibacterial candidates urgently need to be explored as an alternative for overcoming the antibiotic barrier. It is highly necessary to find an effective stable disinfection system with the nature of environmental-friendly, high activity and stability, convenient synthesis procedure, low energy, cleaner, and low economic consumption. Considering these aspects, optical strategy and chemical treatment bring convenience and advantages in bacterial inactivation. In this work, the bimetallic Cu–Bi alloy was explored using a simple one-pot solvothermal strategy. On the one hand, the bimetallic structure can prevent copper from oxidation to decrease potential secondary pollution activity caused by excessive release of copper ions, and maintain copper's highly biological activity. On the other hand, the as-prepared Cu–Bi alloy was employed to perform antibacterial applications. Hyperthermia is driven by near-infrared light and the introduction of ROS from Cu Fenton-like reaction that can effectively promote the death of bacteria, and perform a better antibacterial ability than that of single Ag + or Cu2+ release, resulting in the significant growth inhibition of E. coli. Overall, the combination of the multiple disinfection ability of the Cu–Bi alloy, involving highly efficient ROS generation and effective photothermal performance, not only shows the potential in fighting against pathogenic bacteria but also provides an important insight for the exploration of antibacterial platforms based on the bimetallic materials.

Copper Surface Treatment Method with Antibacterial Performance Using "Super-Spread Wetting" Properties.

In this work, a copper coating is developed on a carbon steel substrate by exploiting the superwetting properties of liquid copper. We characterize the surface morphology, chemical composition, roughness, wettability, ability to release a copper ion from surfaces, and antibacterial efficacy (against Escherichia coli and Staphylococcus aureus). The coating shows a dense microstructure and good adhesion, with thicknesses of approximately 20–40 µm. X-ray diffraction (XRD) analysis reveals that the coated surface structure is composed of Cu, Cu2O, and CuO. The surface roughness and contact angle measurements suggest that the copper coating is rougher and more hydrophobic than the substrate. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) measurements reveal a dissolution of copper ions in chloride-containing environments. The antibacterial test shows that the copper coating achieves a 99.99% reduction of E. coli and S. aureus. This study suggests that the characteristics of the copper-coated surface, including the chemical composition, high surface roughness, good wettability, and ability for copper ion release, may result in surfaces with antibacterial properties.

One-pot fabrication of a polydopamine-based nanoplatform for GSH triggered trimodal ROS-amplification for cancer therapy.

Reactive oxygen species (ROS) based nanoplatforms have been considered as attractive and feasible candidates for cancer therapy. However, the activated endogenous antioxidant defense of cancer cells in response to the ROS attack greatly hinders their therapeutic efficacy. Although cancer-specific ROS amplification strategies have been widely explored, most of them suffer from tedious synthesis procedures and complex components, which will bring about undesired side effects and unsatisfactory results. Herein, we design a cancer-specific oxidative stress amplification nanomedicine (CA-Cu-PDA), which is simply fabricated through integrating the glutathione (GSH) responsive/depleting nanocarrier of copper-polydopamine (Cu-PDA) nanoparticles with a ROS-generating drug cinnamaldehyde (CA) via a facile one-pot polymerization route. It is verified that GSH could trigger the breakage of CA-Cu-PDA networks and the subsequent release of both copper ions and CA in cancer cells. The released copper ions efficiently oxidize GSH, thereby weakening the antioxidant system of cancer cells and increasing the ROS levels. On the other hand, extra ROS are generated by the reduced copper ions through a Fenton reaction, so that a synergistic ROS therapy with CA is achieved. Consequently, oxidative stress is specifically increased within cancer cells, leading to efficient cancer cell apoptosis, significant tumor suppression and minimized side effects. Such an ingenious structure realizes the interlocking cooperation and full utilization of each component's function, presenting promising perspectives for nanomedicine design.

Characterization of the copper rich phase precipitation behavior and comprehensive properties of austenitic stainless steel

Antibacterial austenitic stainless steel was nominated as a new biomaterial material. The copper rich phase precipitation behavior and comprehensive properties in copper-containing austenitic stainless steel after different aging treatment were systematically studied. It was found that a large number of dispersed copper rich phases developed at 750–800 °C. At 800 °C, copper rich phase precipitated quickly within 1 h, but grew and coarsened slowly in the later stage. The hardness of the material increased gradually with the precipitation of copper rich phase, until it reached the maximum after 6 h and tended to be stable. However, with the extension of aging time, high concentration of copper rich phase destroyed the passive film on the surface of stainless steel and accelerated the matrix corrosion, but promoted the release of copper ions and improved the antibacterial property. Therefore, the comprehensive experimental results indicated that 3.60% Cu-304L stainless steel treated by solid solution at 1050 °C for 5 min and aged at 800 °C for more than 6 h had good corrosion resistance and antibacterial property. These results could provide theoretical guidance for the optimal design of copper containing antibacterial stainless steel in production process.

The effect of high temperature aging on the corrosion resistance, mechanical property and antibacterial activity of Cu-2205 DSS

The effects of high temperature aging on the corrosion resistance, mechanical property and antibacterial activity of a copper–bearing 2205 duplex stainless steel (Cu-2205 DSS) were investigated. The results from scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and EDS analysis showed that after aging the proportion of γ phase in microstructure was increased and new σ phase and copper-rich precipitates were formed. The mechanical properties including hardness and tensile and yield strengths of the aged Cu-2205 DSS were significantly enhanced compared to the solution-treated Cu-2205 DSS as well as the 2205 DSS. Electrochemical measurements including electrochemical impedance spectroscopy, potentiodynamic polarization curves and potentiostatic polarization scan were performed to evaluate the corrosion behavior of the Cu-2205 DSS. It was found that aging increased the uniform corrosion resistance but had slightly adverse effect on the pitting corrosion resistance. Additionally, the antibacterial performance of aged Cu-2205 DSS was significantly improved compared to the solution treated Cu-2205 DSS, which was attributed to the more release of copper ions from the matrix that killed the bacteria cells and inhibited the biofilm formation on the surface. The above results suggest that Cu-2205 DSS after high temperature aging revealed good mechanical property, antibacterial performance, and corrosion resistance, which will further expand the application of duplex stainless steel in marine engineering fields.

Water- and Acid-Sensitive Cu2O@Cu-MOF Nano Sustained-Release Capsules with Superior Antifouling Behaviors.

Marine biofouling is one of the technical bottlenecks restricting the development of the global marine economy. Among the commercial self-polishing antifouling coatings, cuprous oxide is an irreplaceable component because of its efficiency and broad-spectrum antibacterial activity. However, one of the biggest obstacles to achieving long-term antifouling is the "initial burst and final decay" of cuprous oxide in the coating. Here, we lock the copper ions by establishing an antifouling unit composed of Cu2O (core) and Cu-based metal-organic framework (Cu-MOF, shell). Cu-MOF is densely grown in situ on the periphery of Cu2O by acid proton etching. The shell structure of Cu-MOF can effectively improve the stability of the internal Cu2O and thus achieve the stable and slow release of copper ions. Furthermore, Cu2O@Cu-MOF nanocapsules can also achieve active defense by rapid and complete dissolution of Cu2O@Cu-MOF at local acidic microenvironment (pH ≤ 5) where the adhesion of fouling organisms occurs. Super-resolution fluorescence microscopy is used to explain the sterilization mechanism. Relying on the water- and acid-sensitive properties of Cu-MOF shell, the stable, controlled and efficient release of copper ions has been achieved for the Cu2O@Cu-MOF nanocapsules in the self-polishing antifouling coatings. Thus, these controlled-release nanocapsules make long-term antifouling promising.

Electrospun Biodegradable Nanofibers Coated Homogenously by Cu Magnetron Sputtering Exhibit Fast Ion Release. Computational and Experimental Study.

Copper-coated nanofibrous materials are desirable for catalysis, electrochemistry, sensing, and biomedical use. The preparation of copper or copper-coated nanofibers can be pretty challenging, requiring many chemical steps that we eliminated in our robust approach, where for the first time, Cu was deposited by magnetron sputtering onto temperature-sensitive polymer nanofibers. For the first time, the large-scale modeling of PCL films irradiation by molecular dynamics simulation was performed and allowed to predict the ions penetration depth and tune the deposition conditions. The Cu-coated polycaprolactone (PCL) nanofibers were thoroughly characterized and tested as antibacterial agents for various Gram-positive and Gram-negative bacteria. Fast release of Cu2+ ions (concentration up to 3.4 µg/mL) led to significant suppression of E. coli and S. aureus colonies but was insufficient against S. typhimurium and Ps. aeruginosa. The effect of Cu layer oxidation upon contact with liquid media was investigated by X-ray photoelectron spectroscopy revealing that, after two hours, 55% of Cu atoms are in form of CuO or Cu(OH)2. The Cu-coated nanofibers will be great candidates for wound dressings thanks to an interesting synergistic effect: on the one hand, the rapid release of copper ions kills bacteria, while on the other hand, it stimulates the regeneration with the activation of immune cells. Indeed, copper ions are necessary for the bacteriostatic action of cells of the immune system. The reactive CO2/C2H4 plasma polymers deposited onto PCL-Cu nanofibers can be applied to grafting of viable proteins, peptides, or drugs, and it further explores the versatility of developed nanofibers for biomedical applications use.

Quantitative Evaluation of Nucleic Acid Degradability of Copper Alloy Surfaces and Its Correlation to Antibacterial Activity.

Copper (Cu) and its alloys have bactericidal activity known as “contact killing” with degradation of nucleic acids inside the bacteria, which is beneficial to inhibit horizontal gene transfer (HGF). In order to understand the nucleic acid degradability of Cu and its alloy surfaces, we developed a new in vitro method to quantitatively evaluate it by a swab method under a “dry” condition and compared it with that of commercially available antibacterial materials such as antibacterial stainless steel, pure silver, and antibacterial resins. As a result, only Cu and its alloys showed continuous degradation of nucleic acids for up to 6 h of contact time. The nucleic acid degradability levels of the Cu alloys and other antibacterial materials correlate to their antibacterial activities evaluated by a film method referring to JIS Z 2801:2012 for Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria. Nucleic acid degradation by copper (I) and (II) chlorides was confirmed at the ranges over 10 mM and 1–20 mM, respectively, suggesting that the copper ion release may be responsible for the degradation of the nucleic acids on Cu and its alloy surfaces. In conclusion, the higher Cu content in the alloys gave higher nucleic acid degradability and higher antibacterial activities.