Prominent antibacterial effect of sub 5 nm Cu nanoparticles/MoS2composite under visible light.

Achieving an efficient and inexpensive bactericidal effect is a key point for the design of antibacterial agent. Recent advances have proved molybdenum disulfide (MoS2) as a promising platform for antimicrobial applications, while the combination of metal nanoparticle would promote the antibacterial efficiency. Nevertheless, the dispersivity, cheapness and safety of metal nanoparticle loaded on MoS2raised some concerns. In this paper, we successfully realized a uniform decoration of copper nanoparticles (CuNPs) on surface of MoS2nanosheets, and the size of CuNPs could be controlled below 5 nm. Under 5 min irradiation of 660 nm visible light, the synthesized CuNPs/MoS2composite demonstrated superior antibacterial performances (almost 100% bacterial killed) towards both Gram-negativeE. coliand Gram-positiveS. aureusover the single component (Cu or MoS2), while the bactericidal effect could last for at least 6 h. The synergism of photodynamic generated hydroxyl radical (·OH), oxidative stress without reactive oxygen species production and the release of Cu ions was considered as the mechanism for the antibacterial properties of CuNPs/MoS2. Our findings provided new insights into the development of two-dimensional antibacterial nanomaterials of high cost performance.

Point-of-care testing of butyrylcholinesterase activity through modulating the photothermal effect of cuprous oxide nanoparticles.

Butyrylcholinesterase (BChE) is an important indicator for clinical diagnosis of liver dysfunction, organophosphate toxicity, and poststroke dementia. Point-of-care testing (POCT) of BChE activity is still a challenge, which is a critical requirement for the modern clinical diagnose. A portable photothermal BChE assay is proposed through modulating the photothermal effects of Cu2O nanoparticles. BChE can catalyze the decomposition of butyrylcholine, producing thiocholine, which further reduce and coordinate with CuO on surface of Cu2O nanoparticle. This leads to higher efficiency of formation of Cu9S8 nanoparticles, through the reaction between Cu2O nanoparticle and NaHS, together with the promotion of photothermal conversion efficiency from 3.1 to 59.0%, under the excitation of 1064 nm laser radiation. An excellent linear relationship between the temperature change and the logarithm of BChE concentration is obtained in the range 1.0 to 7.5 U/mL, with a limit of detection of 0.076 U/mL. In addition, the portable photothermal assay shows strong detection robustness, which endows the accurate detection of BChE in human serum, together with the screening and quantification of organophosphorus pesticides. Such a simple, sensitive, and robust assay shows great potential for the applications to clinical BChE detection and brings a new horizon for the development of temperature based POCT.

An enhanced photoelectrochemical biosensor for colitoxin DNA based on HKUST-1/TiO2 and derived HKUST-CuO/TiO2 heterogeneous composites.

HKUST-1 MOFs and its derivative HKUST-CuO were coupled with TiO2 nanoparticles to form the heterogeneous composites of HKUST-1/TiO2 and HKUST-CuO/TiO2 based on their well-suitable bandgap energies (Eg). Compared with mono-component HKUST-1 or HKUST-CuO, the prepared composites displayed photoelectrochemical (PEC) response due to the synergistic effect from their heterogeneous structure. Higher photocurrent response was obtained on HKUST-CuO/TiO2-modified ITO electrode (HKUST-CuO/TiO2/ITO), which could be attributed to the hollow structure with a thin shell of HKUST-CuO greatly enhancing visible spectra harvesting. The CuO component in HKUST-CuO not only could accelerate electron transfer on the heterojunction interface but also effectively separate the photo-generated charge carriers (e-1/h+). Based on the excellent PEC performance of prepared photoactive composite material, under visible-light excitation (λ ≥ 420 nm) and with a working potential of 0 V (vs. Ag/AgCl), the S1 (probe DNA)/HKUST-CuO/TiO2/ITO PEC platform was successfully fabricated for colitoxin DNA detection without using ascorbic acid (AA) as an electron donor. Compared with the analysis results on S1/HKUST-1/TiO2/ITO electrode, S1/HKUST-CuO/TiO2/ITO displayed a wider linear response range from 1.0 × 10-6 to 4.0 × 10-1 nM with a lower detection limit of 3.73 × 10-7 nM (S/N = 3), the linear regression equation was ΔI (10-6 A) =0.5549-0.1858 log (CS2/M), which confirmed the HKUST-CuO could improve sensitivity because of its prominent PEC property. The relative standard deviation (RSD) of the PEC sensor for target DNA detection of 2.0 × 10-4 nM was 7.4%. The proposed DNA biosensor also possessed good specificity and stability. Hence, this reported work was a promising strategy for molecular diagnosis in the bio-analysis field. (A) Schematic illustration of the preparation process of the proposed PEC biosensors for colitoxin DNA detection. (B) The preparation process of HKUST-1 and HKUST-CuO.

Two-Dimensional Metal-Organic Framework Film for Realizing Optoelectronic Synaptic Plasticity.

2D metal-organic framework (MOF) film as the active layer show promising application prospects in various fields including sensors, catalysis, and electronic devices. However, exploring the application of 2D MOF film in the field of artificial synapses has not been implemented yet. In this work, we fabricated a novel 2D MOF film (Cu-THPP, THPP=5,10,15,20-Tetrakis(4-hydroxyphenyl)-21H,23H-porphine), and further used it as an active layer to explore the application in the simulation of human brain synapses. It shows excellent light-stimulated synaptic plasticity properties, and exhibits the foundation function of synapses such as long-term plasticity (LTP), short-term plasticity (STP), and the conversion of STP to LTP. Most critically, the MOF based artificial synaptic device exhibits an excellent stability in atmosphere. This work opens the door for the application of 2D MOF film in the simulation of human brain synapses.

Catalytic and Photochemical Strategies to Stabilized Radicals Based on Anomeric Nucleophiles.

Carbohydrates, one of the three primary macromolecules of living organisms, play significant roles in various biological processes such as intercellular communication, cell recognition, and immune activity. While the majority of established methods for the installation of carbohydrates through the anomeric carbon rely on nucleophilic displacement, anomeric radicals represent an attractive alternative because of their functional group compatibility and high anomeric selectivities. Herein, we demonstrate that anomeric nucleophiles such as C1 stannanes can be converted into anomeric radicals by merging Cu(I) catalysis with blue light irradiation to achieve highly stereoselective C(sp3)-S cross-coupling reactions. Mechanistic studies and DFT calculations revealed that the C-S bond-forming step occurs via the transfer of the anomeric radical directly to a sulfur electrophile bound to Cu(II) species. This pathway complements a radical chain observed for photochemical metal-free conditions where a disulfide initiator can be activated by a Lewis base additive. Both strategies utilize anomeric nucleophiles as efficient radical donors and achieve a switch from an ionic to a radical pathway. Taken together, the stability of glycosyl nucleophiles, a broad substrate scope, and high anomeric selectivities observed for the thermal and photochemical protocols make this novel C-S cross coupling a practical tool for late-stage glycodiversification of bioactive natural products and drug candidates.

Self-powered cathodic photoelectrochemical aptasensor based on in situ-synthesized CuO-Cu2O nanowire array for detecting prostate-specific antigen.

A facile and sensitive self-powered cathodic photoelectrochemical (PEC) aptasensor is reported for the detection of prostate-specific antigen (PSA) based on CuO-Cu2O nanowire array grown on Cu mesh (CuO-Cu2O NWA/CM) as electrode. The mixed narrow band gaps of the CuO-Cu2O heterostructure ensured its wide absorption band, effective electron/hole separation, and high photocatalytic activity in the visible region. In addition, nanowires directly grown on the substrate provided high specific surface area and exposed abundant active sites, thus guaranteeing its high photocatalytic efficiency. Therefore, the self-powered sensor exhibited favorable analytical performance with fast response, wide linear ranges of 0.01 to 5 ng/mL and 5 to 100 ng/mL, an acceptable detection limit of 3 pg/mL, and reasonable selectivity and stability. The proposed CuO-Cu2O NWA/CM can be considered a promising visible light-responsive photoactive material for fabrication of PEC aptasensor with high performance. Graphical abstract a Schematic illustration of construction process of PEC sensing platform based on the CuO-Cu2O composite for PSA detection. b Schematic mechanism of the operating PEC system.

Photoelectrochemical aptasensor for thrombin based on Au-rGO-CuS as signal amplification elements.

A photoelectrochemical platform for thrombin determination was developed based on Au-rGO-CuS as multiple signal amplification elements. CuInS2 QDs was used to sensitize burr-shape TiO2 (b-TiO2) to obtain a strong photocurrent. Under the specific recognition between aptamer and thrombin, a sandwichlike structure was formed and the Au-rGO-CuS-labeled aptamer (S2@Au-rGO-CuS) was immobilized on the electrode surface. This induced a sharp decrease in photocurrent. The phenomenon is mainly due to the fact that CuS NPs can competitively consume the light energy and electron donor with CuInS2/b-TiO2. The rGO can increase the amount of CuS NPs and the Au NPs can accelerate charge transferring which depress the recombination of photogenerated electrons and holes in CuS to further enhance the competitive capacity of CuS. The sandwichlike structure has a steric hindrance effect. Therefore, the S2@Au-rGO-CuS has a multiple signal amplification function for thrombin determination. Under optimal conditions, the PEC aptasensor exhibited a wide linear concentration range from 0.1 pM to 10 nM with a low detection limit of 30 fM (S/N = 3) for thrombin. Besides, the designed aptasensor performed well in the assay of human serum sample, indicating good potential for the determination of thrombin in real samples. Graphical abstract.

Antibacterial Properties of Superhydrophilic Textured Copper in Contact with Bacterial Suspensions.

The method of pulsed laser processing with a nanosecond pulse duration was employed to obtain a nanotexture on the surface of copper alloys. The effect of the obtained micro- and nanotexture on the bactericidal properties of the surface upon its contact with suspensions containing of E. coli K12 C600 or K. pneumoniae 811 cells in a nutrient medium were studied. The evolution of cell morphology after on the nanotextured surface was analyzed using scanning electron microscopy, and changes in biological fluid during this contact were studied by mass spectrometry. It was shown that massive death of bacterial cells both in the suspension and on the nanotextured surface was determined by combined toxic effects of the hierarchically textured surface and high concentration of Cu2+ ions in the medium.

Copper-Catalyzed Trifluoromethylation of Alkyl Bromides.

Copper oxidative addition into organohalides is a challenging two-electron process. In contrast, formal oxidative addition of copper to Csp2 carbon-bromine bonds can be accomplished by employing latent silyl radicals under photoredox conditions. This novel paradigm for copper oxidative addition has now been applied to a Cu-catalyzed cross-coupling of Csp3-bromides. Specifically, a copper/photoredox dual catalytic system for the coupling of alkyl bromides with trifluoromethyl groups is presented. This operationally simple and robust protocol successfully converts a variety of alkyl, allyl, benzyl, and heterobenzyl bromides into the corresponding alkyl trifluoromethanes.

Photothermal Soft Nanoballs Developed by Loading Plasmonic Cu2- xSe Nanocrystals into Liposomes for Photothermal Immunoassay of Aflatoxin B1.

Photothermal effects (PTEs) have been greatly concerned with the fast development of new photothermal nanomaterials. Herein we propose a photothermal immunoassay (PTIA) by taking mycotoxins (AFB1) as an example based on the PTEs of plasmonic Cu2- xSe nanocrystals (NCs). By loading plasmonic Cu2- xSe NCs into liposomes to form photothermal soft nanoballs (ptSNBs), on which aptamer of AFB1 previously assembled, a sandwich structure of AFB1 could be formed with the aptamer on ptSNBs and capture antibody. The heat released from the ptSNBs under NIR irradiation, owing to the plasmonic photothermal light-to-heat conversion through photon-electron-phonon coupling, makes the temperature of substrate solution increased, and the increased temperature has a linear relationship with the AFB1 content. Owing to the large amounts of plasmonic Cu2- xSe NCs in the ptSNBs, the PTEs get amplified, making AFB1 higher than 1 ng/mL detectable in food even if with a rough homemade immunothermometer. The proposal of PTIA opens a new field of immunoassay including developing photothermal nanostructures, new thermometers, PTIA theory, and so on.

Mitochondria- and nucleolus-targeted copper(i) complexes with pyrazole-linked triphenylphosphine moieties for live cell imaging.

The labelling and imaging of mitochondria and nucleolus have attracted great attention because of the involvement of these cellular organelles in critical cellular activities. Therefore, a large number of mitochondria- or nucleolus-labelling probes have been developed throughout the world. However, in the current study, we successfully developed two pyrazole-based, copper-linked triphenylphosphine-coupled emissive metallo-complexes (C1 and C2) for the simultaneous visualization of mitochondria and nucleolus in a single run. These complexes were very inexpensive and could be synthesized by a simple one-pot multicomponent reaction scheme. The complexes were very specific, and only a small concentration of 5 µM was found to be sufficient to probe both the organelles efficiently. Additionally, even under a shorter incubation period (half hour), the fluorescence intensity from the cells was appreciable. Also, both the compounds were found to be photostable when torched with 10% of a 100 mW laser for up to 10 min. All these results indicate that both the complexes may contribute towards the future development of cell imaging tools. To the best of our knowledge, this is the first report on the development of multifunctional live cell imaging tools for simultaneous mitochondria and nucleolus imaging and within the shortest incubation time of about 30 minutes.

An CuInS2 photocathode for the sensitive photoelectrochemical determination of microRNA-21 based on DNA-protein interaction and exonuclease III assisted target recycling amplification.

A photocathode is described for the determination of microRNA-21 by using CuInS2 as an active photocathode material. Exonuclease III assisted target recycling amplification was employed to enhance the detection sensitivity. The TATA-binding protein (TBP) was applied to enhance steric hindrance which decreases the photoelectrochemical intensity. This strategy is designed by combining the anti-interference photocathode material, enzyme assisted target recycling amplification and TBP induced signal off, showing remarkable amplification efficiency. Under the optimized conditions, the detection limit for microRNA-21 is as low as 0.47 fM, and a linear range was got from 1.0 × 10-15 M to 1.0 × 10-6 M. Graphical abstract Schematic representation of sensitive photoelectrochemical detection of microRNA-21.CuInS2 is used as an active photocathode material. Combined Exonuclease III assisted target recycling amplification and TATA-binding protein decreased of photoelectrochemical intensity, the detection limit was 0.47 fM with good selectivity. (miR-21: microRNA-21; CS: chitosan).

Biogenic synthesis of copper nanoparticles by natural polysaccharides and Pleurotus ostreatus fermented fenugreek using gamma rays with antioxidant and antimicrobial potential towards some wound pathogens.

Mono-dispersed copper nanoparticles (CuNPs) were constructed using cheap polysaccharides (citrus pectin, chitosan, and sodium alginate), and by appropriating aqueous fermented fenugreek powder (FFP) under the action of Pleurotus ostreatus (as reducing and preserving means), through the influence of gamma irradiation. The synthesized CuNPs are described by UV-Vis. spectroscopy TEM, DLS, XRD, and FT-IR. XRD study of the CuNPs confirmed the generation of metallic CuNPs. The nucleation and the production mechanism of CuNPs are moreover explained. TEM unveiled that, the ordinary diameter of CuNPs incorporated by various polysaccharides, and FFP taken in the range of 31.0 and 36.0 nm respectively. CuNPs size is influenced by many parameters such as the variety of stabilizer, pH within the organization and applied gamma dose. Evaluation of the antioxidant and antimicrobial activities of CuNPs was performed against some selected wound pathogens. The results showed that, CuNPs were a strong antimicrobial agents against microbes caused burn skin infection such as Klebsiella pneumoniae, Staphylococcus aureus, and Candida albicans (16.0, 15.0, and 15.0 mm ZOI, respectively). Additionally, CuNPs have a strong antioxidant with 70% scavenging activity against DPPH. So, due to unique characteristics of CuNPs (cost-effective with continued-term stabilization and effective features), they can recover reasonable potential in biomedical, industrial, agricultural, cosmetics, dermal products and pharmaceutical purposes.

Quantum chaos and breaking of all anti-unitary symmetries in Rydberg excitons.

Symmetries are the underlying principles of fundamental interactions in nature. Chaos in a quantum system may emerge from breaking these symmetries. Compared to vacuum, crystals are attractive for studying quantum chaos, as they not only break spatial isotropy, but also lead to novel quasiparticles with modified interactions. Here we study yellow Rydberg excitons in cuprous oxide which couple strongly to the vacuum light field and interact significantly with crystal phonons, leading to inversion symmetry breaking. In a magnetic field, time-reversal symmetry is also broken and the exciton states show a complex splitting pattern, resulting in quadratic level repulsion for small splittings. In contrast to atomic chaotic systems in a magnetic field, which show only a linear level repulsion, this is a signature of a system where all anti-unitary symmetries are broken simultaneously. This behaviour can otherwise be found only for the electro-weak interaction or engineered billiards.

Photosensitization of CuI - the role of visible light induced CuI→ CuII transition in photocatalytic degradation of organic pollutants and inactivation of microorganisms.

Bare and photosensitized copper iodides were tested in photocatalysed degradation of an organic dye (Acid Red 1) and inactivation of fungi (Saccharomyces cerevisiae). CuI, with the band gap energy slightly lower than that of TiO2, appeared to be highly efficient in these processes. Sensitization of copper iodide was achieved by surface modification with [Cu(SCN)2(phen)2]. The photosensitization mechanism encompasses a metal to metal charge transfer, CuI→ CuII. The applied photosensitizer binds to CuI through thiocyanate ligands resulting in the formation of an active CuII/CuI hybrid photocatalyst ([CuII(SCN)2(phen)2]@CuII). Its absorption edge is red shifted towards a lower energy when compared with bare CuI, resulting in enhanced visible light induced photocatalytic activity. The studied materials appeared to be photoactive in current generation, degradation of organic compounds and inactivation of fungi.

Preparation of BaTiO3/Cu2O and BaTiO3/Cu2O/Au Complexes: Their Photocatalytic and Antipathogenic Effect.

BaTiO3/Cu2O and BaTiO3/Cu2O/Au complexes were prepared from CuCl2, HAuCl4 solution, and BaTiO3 by the solution method. BaTiO3 particles were dispersed in a CuCl2 solution, and the BaTiO3/CuO complex was produced through crystallization of CuO onto the BaTiO3 surface by hydrolysis of CuCl2 in the first stage. After the reaction, CuO was reduced to Cu2O by treatment with glucose, thereby yielding the BaTiO3/Cu2O complex. The BaTiO3/Cu2O/Au complex was prepared by treating the BaTiO3/Cu2O particles with HAuCl4. Under visible light, the obtained BaTiO3/Cu2O0/Au complex showed higher photocatalytic activity than the Degussa P-25sample. In addition, the BaTiO3/Cu2O complex showed excellent antipathogenic effect.

Enhanced photoelectrocatalytic decomposition of copper cyanide complexes and simultaneous recovery of copper with a Bi2MoO6 electrode under visible light by EDTA/K4P2O7.

Simultaneous photoelectrocatalytic (PEC) oxidation of cyanides and recovery of copper in a PEC reactor with a Bi(2)MoO(6) photoanode was investigated at alkaline conditions under visible light irradiation. The surface variation of the Bi(2)MoO(6) photoanode and titanium cathode was characterized. The Cu mass distribution onto the anode, in the solution, and onto the cathode was fully investigated. In the individual PEC oxidation of copper cyanides, the formation of a black copper oxide on the anode occurred. By keeping the initial cyanide concentration at 0.01 mM, the effect of EDTA/K(4)P(2)O(7) was examined at different molar ratios of EDTA/K(4)P(2)O(7) to cyanide. It was indicated that the oxidation of cyanides increased and simultaneous copper electrodeposition with zero value onto the cathode was feasible at pH 11. Under the optimal conditions, the total cyanide concentration was lowered from 250 to 5.0 mg/L, and the Cu recovery efficiency deposited onto the cathode was higher than 90%. Cyanate was the only product. The role of the photogenerated hole in the oxidation of cyanide ions was confirmed.

Convenient Route to Well-Dispersed Cu2O Nanospheres and Their Use as Photocatalysts.

A simple and facile method was developed to synthesize well-dispersed cuprous oxide nanospheres with uniform morphology and the size in the range of 400-600 nm. Cuprous oxide nanospheres were obtained through the chemical reduction of copper acetate by fructose in the presence of ethylene glycol and de-ionized water. X-ray powder diffraction (XRD), Energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), UV-Vis spectroscopy (UV-Vis) and transmission electron microscopy (TEM) as well as high-resolution transmission electron microscopy (HRTEM) were used to characterize the obtained nanoparticles. The influence of time, temperature and the solvent on the formation of cuprous oxide was investigated. The growth process of cuprous oxide was analyzed and the mechanism of crystal growth was proposed. The photocatalytic activity of degradation of methyl orange (MO) under visible light irradiation was also investigated. It was found that the product of cuprous oxide had efficient catalytic for degradation MO.

Hydrated copper ion chemistry: guided ion beam and computational investigation of Cu2+(H2O)n (n = 7-10) complexes.

Cross sections for the threshold collision-induced dissociation of Cu(2+)(H(2)O)(n), where n = 8 - 10, are measured using a guided ion beam tandem mass spectrometer. The primary dissociation pathway is found to be loss of a single water molecule followed by the sequential loss of additional water molecules until n = 8, at which point charge separation to form CuOH(+)(H(2)O)(4) (+) H(+)(H(2)O)(3) is observed to occur at a slightly lower energy than loss of a water molecule. Competition from charge separation prohibits the formation of appreciable amounts of the n = 7 or smaller complexes as reactants in the source. These findings indicate that Cu(2+) has a critical size of 8. Analysis of the data using statistical modeling techniques that account for energy distributions and lifetime effects yields primary and sequential bond dissociation energies (BDEs) for loss of one and two water molecules from n = 8 - 10 complexes as well as the barrier for charge separation from n = 8. More speculative analysis extends the thermochemistry obtained down to n = 5 and 6. Theoretical BDEs are determined from quantum chemical calculations using structures optimized at the B3LYP/6 311(+)G(d,p) level along with the lowest-energy isomers suggested by single point energies at the MP2(full), M06, B3LYP, and B3P86 levels of theory using a 6- 311(+)G(2d,2p) basis set. BDEs at 0K are converted to 298 K thermodynamic values using a rigid rotor/harmonic oscillator approximation. Experimental and theoretical entropies of activation suggest that a third solvent shell forms at n = 9, in accord with previous findings. The present work represents the first experimentally determined hydration enthalpies for the Cu(2+)(H(2)O)n system.

Effect of aqueous media on the copper-ion-mediated phototoxicity of CuO nanoparticles toward green fluorescent protein-expressing Escherichia coli.

Quantitative comparison of different aqueous media on the phototoxicity of copper oxide nanoparticles (CuO NPs) is crucial for understanding their ecological effects. In this study, the phototoxicity of CuO NPs toward the green fluorescent protein-expressing Escherichia coli (GFP-E. coli) under UV irradiation (365 nm) was investigated in Luria-Bertani medium (LB), NaCl solution, deionized water (DI) and phosphate-buffered saline (PBS). The phototoxicity of CuO NPs toward GFP-E. coli decreased in the order of DI>NaCl>PBS>LB because of different released concentrations of Cu(2+). The 3h released Cu(2+) concentrations by 10mg/L CuO NPs in DI water, NaCl solution, LB medium, and PBS were 1946.3 ± 75.6, 1242.5 ± 47.6, 1023.4 ± 41.2, and 1162.1 ± 41.9 µg/L, respectively. Transmission electron microscope and laser scanning confocal microscope images of E. coli exposed to CuO NPs demonstrated that the released Cu(2+) resulted in fragmentation of bacterial cell walls, leakage of intracellular components, and finally death of bacteria in four media after UV light irradiation. In each medium, the bacterial mortality rate logarithmically increased with the releasing concentrations of Cu(2+) by CuO NPs (R(2)>0.90) exposed to 3h UV light. This study highlights the importance of taking into consideration of water chemistry when the phototoxicity of CuO NPs is assessed in nanotoxicity research.