Universal Antifouling and Photothermal Antibacterial Surfaces Based on Multifunctional Metal-Phenolic Networks for Prevention of Biofilm Formation.

Biofilms formed from the pathogenic bacteria that attach to the surfaces of biomedical devices and implantable materials result in various persistent and chronic bacterial infections, posing serious threats to human health. Compared to the elimination of matured biofilms, prevention of the formation of biofilms is expected to be a more effective way for the treatment of biofilm-associated infections. Herein, we develop a facile method for endowing diverse substrates with long-term antibiofilm property by deposition of a hybrid film composed of tannic acid/Cu ion (TA/Cu) complex and poly(ethylene glycol) (PEG). In this system, the TA/Cu complex acts as a multifunctional building block with three different roles: (i) as a versatile "glue" with universal adherent property for substrate modification, (ii) as a photothermal biocidal agent for bacterial elimination under irradiation of near-infrared (NIR) laser, and (iii) as a potent linker for immobilization of PEG with inherent antifouling property to inhibit adhesion and accumulation of bacteria. The resulted hybrid film shows negligible cytotoxicity and good histocompatibility and could prevent biofilm formation for at least 15 days in vitro and suppress bacterial infection in vivo, showing great potential for practical applications to solve the biofilm-associated problems of biomedical materials and devices.

NIR-Driven Intracellular Photocatalytic O2 Evolution on Z-Scheme Ni3S2/Cu1.8S@HA for Hypoxic Tumor Therapy.

Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, Ni3S2/Cu1.8S nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O2 evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron-hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide H2O into O2, directly. Meanwhile, the photostimulated electrons can capture the dissolved O2 to form a toxic reactive oxygen species (ROS). Moreover, Ni3S2/Cu1.8S nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous H2O2 into ·OH and O2, which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated via feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for Ni3S2/Cu1.8S. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and Ni3S2/Cu1.8S@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.

Dual-Modal FexCuySe and Upconversion Nanoparticle Assemblies for Intracellular MicroRNA-21 Detection.

In situ quantification and imaging of low-level intracellular microRNAs (miRs) are important areas in biosensor research. Herein, DNA-driven FexCuySe@upconversion nanoparticle (UCNP) core@satellite nanostructures were developed to probe microRNA-21 (miR-21). FexCuySe@UCNP probes displayed dual signals: upconversion luminescence (UCL) and magnetic resonance imaging (MRI). In the presence of miR-21, the luminescence signal was restored and the T2 value was significantly increased because of dissociation of UCNPs from the assemblies. There was a good linear relationship between the dual signals and the expression levels of miR-21 in the range of 0.035-31.824 amol/ngRNA. The limit of detection (LOD) was 0.0058 amol/ngRNA for the luminescence intensity and 0.0182 amol/ngRNA for the MRI signal. This method opens a new avenue for intracellular miR-21 detection with high sensitivity and specificity.

Eco-biocompatibility of chitosan coated biosynthesized copper oxide nanocomposite for enhanced industrial (Azo) dye removal from aqueous solution and antibacterial properties.

In the present study, the biogenic synthesis of an ecofriendly and non-toxic chitosan (CS) coated copper oxide NPs (CS-CuO nanocomposite) using Psidium guajava aqueous leaf extract. The biogenic synthesized CS-CuO nanocomposite was characterized by using UV-vis spectroscopy analysis (UV-Vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Field emission scanning electron microscopy with energy dispersive X-ray spectroscopy (FE-SEM-EDS), Dynamic light scattering (DLS), and Transmission electron microscopy (TEM). The prepared CS-CuO nanocomposite was evaluated for antibacterial activity by agar well diffusion method as well as minimum inhibitory concentrations (MIC) were assessed against both Gram-positive Streptococcus pneumoniae, Staphylococcus epidermidis and Gram-negative Escherichia coli, Proteus mirabilis with good inhibition effects on Gram-negative bacteria than the Gram-positive bacteria. The interaction of the CS-CuO nanocomposite with the bacterial membrane was visually observed by confocal laser scanning microscopy and the live/dead cells were differentiated by treatment with acridine orange and ethidium bromide dyes.

NIR-Driven Water Splitting H2 Production Nanoplatform for H2-Mediated Cascade-Amplifying Synergetic Cancer Therapy.

As a newly emerging treatment strategy for many diseases, hydrogen therapy has attracted a lot of attention because of its excellent biosafety. However, the high diffusivity and low solubility of hydrogen make it difficult to accumulate in local lesions. Herein, we develop a H2 self-generation nanoplatform by in situ water splitting driven by near-infrared (NIR) laser. In this work, core-shell nanoparticles (CSNPs) of NaGdF4:Yb,Tm/g-C3N4/Cu3P (UCC) nanocomposites as core encapsulated with zeolitic imidazolate framework-8 (ZIF-8) modified with folic acid as shell are designed and synthesized. Due to the acid-responsive ZIF-8 shell, enhanced permeability and retention (EPR) effect, and folate receptor-mediated endocytosis, CSNPs are selectively captured by tumor cells. Upon 980 nm laser irradiation, CSNPs exhibit a high production capacity of H2 and active oxygen species (ROS), as well as an appropriate photothermal conversion temperature. Furthermore, rising temperature increases the Fenton reaction rate of Cu(I) with H2O2 and strengthens the curative effect of chemodynamic therapy (CDT). The excess glutathione (GSH) in tumor microenvironment (TME) can deplete positive holes produced in the valence band of g-C3N4 in the g-C3N4/Cu3P Z-scheme heterojunction. GSH also can reduce Cu(II) to Cu(I), ensuring a continuous Fenton reaction. Thus, a NIR-driven H2 production nanoplatform is constructed for H2-mediated cascade-amplifying multimodal synergetic therapy.

Industrial textile effluent treatment and antibacterial effectiveness of Zea mays L. Dry husk mediated bio-synthesized copper oxide nanoparticles.

Zea mays L. dry husk extract was used to bio synthesize copper oxide nanoparticles. Red coloured cubic Cu2O nanoparticles were obtained for the first time via this simple, eco- friendly, green synthesis route. The Cu2O nanoparticles were thermally oxidized to pure monoclinic CuO nanoparticles at 600 °C. The phases of the copper oxides were confirmed from the x-ray diffraction (XRD) studies. The nanoparticle sizes as obtained from high resolution transmission electron microscope (HRTEM) analysis range from 10 to 26 nm, 36-73 nm and 30-90 nm for the unannealed Cu2O, 300 °C and 600 °C annealed CuO respectively. The values of the bandgap energies obtained from diffuse reflectance of the nanoparticles are 2.0, 1.30 and 1.42 eV respectively for the unannealed, 300 °C, and 600 °C annealed copper oxide nanoparticles. The 600 °C annealed copper oxide nanoparticles showed 91% and 90% degradation ability for methylene blue dye (BM) and textile effluent (TE) respectively under visible light irradiation. While CuO_300 is more effective to inhibit the growth of Escherichia coli 518,133 and Staphylococcus aureus 9144, Cu2O is better for Pseudomonas aeruginosa and Bacillus licheniformis. The results confirm the photo-catalytic and anti-microbial effectiveness of the copper oxide nanoparticles.

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.

Red emissive CuInS2-based nanocrystals: a potential phosphor for warm white light-emitting diodes.

We here report the integration of red emissive CuInS(2) based nanocrysals as a potential red phosphor for warm light generation. By combining red emissive CuInS(2) based nanocrysals with commercial yellow emissive YAG:Ce and green emissive Eu(2+) doped silicate phosphors, we fabricated warm white light-emitting diodes with high color rendering index up to ~92, high luminous efficiency of 45~60 lm/W and color temperature less than 4000K.

Adsorptional photocatalytic degradation of methylene blue onto pectin-CuS nanocomposite under solar light.

This study describes the effect of adsorption on methylene blue degradation using pectin-CuS nanocomposite (PCSNC). The nanocomposite was synthesized using co-precipitation methods followed by direct encapsulation with pectin. The synthesized nanocomposite was characterized by SEM, TEM, XRD, FTIR and UV-vis spectral technique. The adsorption and photocatalytic efficiencies of PCSNC were compared with copper sulphide nanoparticle (CSNP). The dye removal was studied under different reaction conditions. The adsorption capacity of pectin based nanocomposite was higher due to other free functional group on pectin surface after connecting to nanoparticles. The simultaneous adsorption and photodegradation process (A+P) was the most efficient process due to rapid destruction of adsorbed dye molecules. The complete COD removal was attained in 10h using PCSNC/A+P process. On comparing with CSNP, pectin-CuS nano composite showed more degradation efficiency and reusability for MB degradation.

Microwave-hydrothermal synthesis and characterization of nanostructured copper substituted ZnM2O4 (M = Al, Ga) spinels as precursors for thermally stable Cu catalysts.

Nanostructured Cu(x)Zn(1-x)Al(2)O(4) with a Cu:Zn ratio of »:¾ has been prepared by a microwave-assisted hydrothermal synthesis at 150 °C and used as a precursor for Cu/ZnO/Al(2)O(3)-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m(2) g(-1)). Cu nanoparticles of an average size of 3.3 nm can be formed by reduction of the spinel precursor in hydrogen and the accessible metallic Cu(0) surface area of the reduced catalyst was 8 m(2) g(-1). The catalytic performance of the material in CO(2) hydrogenation and methanol steam reforming was compared with conventionally prepared Cu/ZnO/Al(2)O(3) reference catalysts. The observed lower performance of the spinel-based samples is attributed to a lack of synergetic interaction of the Cu nanoparticles with ZnO due to the incorporation of Zn(2+) in the stable spinel lattice. Despite its lower performance, however, the nanostructured nature of the spinel catalyst was stable after thermal treatment up to 500 °C in contrast to other Cu-based catalysts. Furthermore, a large fraction of the re-oxidized copper migrates back into the spinel upon calcination of the reduced catalyst, thereby enabling a regeneration of sintered catalysts after prolonged usage at high temperatures. Similarly prepared samples with Ga instead of Al exhibit a more crystalline catalyst with a spinel particle size around 20 nm. The slightly decreased Cu(0) surface area of 3.2 m(2) g(-1) due to less copper incorporation is not a significant drawback for the methanol steam reforming.

Long-term fade study of the DT-702 LiF: Mg,Cu,P TLD.

LiF thermoluminescent dosemeters (TLDs) are used by the US Navy to record radiation exposure of personnel. The Model DT-648 LiF:Mg,Ti TLD has been replaced by a new Model DT-702 LiF:Mg,Cu,P TLD. The DT-648 was used for many years and has undergone extensive testing to identify its pre- and post-irradiation fade operating characteristics. Studies have shown that the addition of copper increases the thermoluminesence sensitivity of the TLD for improved low-level radiation monitoring. This study evaluates various fading characteristics of the new copper-doped dosemeter using current equipment for processing of TLDs and calibrating to a National Institute of Standards and Technology standard source. The 57-week study took place at the Naval Dosimetry Center, Bethesda, MD, USA. TLDs were stored for various lengths of time before and after being exposed to a National Institute of Standards and Technology calibrated radiation sources. TLDs were then processed using current US Navy instructions and the resulting dose compared with the calibrated exposure. Both loss of signal and loss of sensitivity were evaluated. The results of this study have shown that the DT-702 TLD has no statistically significant change in sensitivity or change in signal with up to 57 weeks of pre- or post-irradiation time. The results of this study will increase the accuracy of exposure record keeping for the Navy and will allow longer issue periods. This will increase flexibility with international and domestic shipping procedures, as well as reduce workload requirements for dosimetry processing.

Microwave-assisted copper-catalyzed preparation of diaryl chalcogenides.

Diaryl chalcogenide synthesis employing diaryl dichalcogenides and aryl halides as starting materials in the presence of excess magnesium and a catalytic amount of CuI/bipyridyl is significantly improved by microwave heating. Reaction times can be reduced from 2 to 3 days to 6-8 h. Both aryl bromides and aryl chlorides can be used as substrates in the substitution reaction. The procedure is useful not only for diaryl sulfide and diaryl selenide synthesis but also for the preparation of unsymmetrical diaryl tellurides. Starting from suitable aryl halides, the novel microwave-assisted procedure was used for the facile preparation of novel chalcogen analogues (PhS-, PhSe-, and PhTe-) of various antioxidants (ethoxyquin and 3-pyridinol). Attempts to use dialkyl dichalcogenides for the coupling of alkylchalcogeno moieties to aryl halides were only successful in the case of long-chain (such as n-octyl) disulfides and diselenides.

The application of LiF:Mg,Cu,P to large scale personnel dosimetry: current status and future directions.

LiF:Mg,Cu,P is starting to replace LiF:Mg,Ti in a variety of personnel dosimetry applications. LiF:Mg,Cu,P has superior characteristics as compared to LiF:Mg,Ti including, higher sensitivity, improved energy response for photons, lack of supralinearity and insignificant fading. The use of LiF:Mg,Cu,P in large scale dosimetry programs is of particular interest due to the extreme sensitivity of this material to the maximum readout temperature, and the variety of different dosimetry aspects and details that must be considered for a successful implementation in routine dosimetry. Here we discuss and explain the various aspects of large scale LiF:Mg,Cu,P based dosimetry programs including the properties of the TL material, new generation of TLD readers, calibration methodologies, a new generation of dose calculation algorithms based on the use of artificial neural networks and the overall uncertainty of the dose measurement. The United States Navy (USN) will be the first US dosimetry processor who will use this new material for routine applications. Until June 2002, the Navy used two types of thermoluminescent materials for personnel dosimetry, CaF2:Mn and LiF:Mg,Ti. A program to upgrade the system and to implement LiF:Mg,Cu,P, started in the mid 1990s and was recently concluded. In 2002, the new system replaced the LiF:Mg,Ti and is scheduled to start replacing the CaF2:Mn system in 2006. A pilot study to determine the dosimetric performance of the new LiF:Mg,Cu,P based dosimetry system was recently completed, and the results show the new system to be as good or better than the current system in all areas tested. As a result, LiF:Mg,Cu,P is scheduled to become the primary personnel dosimeter for the entire US Navy in 2006.

Determination of LiF:Mg,Ti and LiF:Mg,Cu,P TL efficiency for X-rays and their application to Monte Carlo simulations of dosemeter response.

The simulation of response of a new passive area dosemeter for measuring ambient dose equivalent H*(10) for photons has been performed using the Monte Carlo code MCNP and experimentally determined responses of LiF:Mg,Ti and LiF:Mg,Cu,P thermoluminescent (TL) detectors for hard-filtered X-ray spectra from 20 to 300 keV and for 137Cs and 60Co gamma radiation. Relative TL efficiency for both types of detectors, determined in experiments with bare detectors and similar Monte Carlo simulations, compared favourably with prediction of microdosimetric models for proposed microdosimetric target sizes in the range of 20-40 nm. The concluding verification experiment showed small deviations between measured and simulated dosemeter energy response values in the range of a few percent.

Low temperature radioluminescence of LiF:Mg,Cu,P.

Low temperature radioluminescence spectra of LiF, variously co-doped with Mg, Cu and P, show highly unusual temperature dependencies which resemble thermoluminescence data. The signals include intense peaks and a relatively weak continuous background. One peak occurs below 30 K, together with a major peak near 125 K. The signals are highly sensitive to the dopants and slightly sensitive to X-ray dose rate. The role of donor acceptor pairs and the perturbations from intrinsic defects formed by ionisation can be used to describe all the observations. The 290 nm emission band is linked to H center annealing.

Comparison of two extremity dosemeters based on LiF:Mg,Cu,P thin detectors for mixed beta-gamma fields.

Two types of thin LiF:Mg,Cu,P detectors, GR-200F and MCP-Ns, have been characterised for use in the design of an extremity dosemeter for mixed beta-photon radiation fields. Both detectors consist of an extremely thin layer of sensitive material with effective thicknesses of 5 and 8 mg cm(-2), respectively, held in a 5 mg cm(-2) PVC ring holder. Dosimetric performance was analysed according to the ISO 12794 standard and compared with 240 mg cm(-2) TLD-100 measurements. In particular, the energy response was obtained for ISO narrow X-ray spectra, (137)Cs, (60)Co, (204)Tl and (90)Sr/(90)Y. From these measurements a mean calibration factor was calculated to estimate H(p)(0.07). Subsequently, the performance of the dosemeters was checked for a set of 10 different mixed photon and beta-photon fields. The study shows that the proposed dosemeters can estimate H(p)(0.07) in a wide range of mixed beta-photon fields with a maximum deviation from the given dose of 30% and an overall uncertainty of the order of 25% (k = 1). However, the results also highlight a large variability among the different thin detectors and, thus, the standard TLD-100 material is recommended whenever the workplace does not include low-energy beta radiation.

Time-resolved spectroscopy of LiF:Mg,Cu,P.

Time-resolved spectroscopy measurements of LiF:Mg,Cu,P luminescence are presented to obtain a better understanding of the emission characteristics of this material. The intensities and decay of the emission bands were studied as a function of annealing temperature and ionising radiation (gamma) dose. Two peaks in the emission were observed at 367 and 466 nm when excited by the 266 nm laser radiation. The luminescence spectrum under band-to-band X-ray excitation shows a dominant emission approximately 390-400 nm, which resembles the reported thermoluminescence emission and is clearly different from the spectrum obtained using the 266 nm pulsed laser excitation. Annealing of the material to 300 degrees C increases the intensity of the 367 and 466 nm emission bands by an order of magnitude as well as changes the relative intensity of the bands. Additional emission bands, which are not evident in the thermoluminescence emission spectra, are seen at longer wavelengths that also increase with dose. Possible explanations for the observed emission spectra are discussed in this paper.

LiF:Mg,Cu,P glow curve shape dependence on heating rate.

The glow curve shape of LiF:Mg,Cu,P (MCP) material is studied in this research. The study is focused on the effects of the heating rate on the dosimetric peaks. Different configurations of dosemeters (chips, cards and powder) are studied. The shifting of the dominant dosimetric peak is observed and analysed. The curves are deconvoluted using the new Harshaw Glow Curve Analyser (GCA) program. Results of the study are presented, as well as possible explanations as to the observed effects.

The dose-response of Harshaw TLD-700H.

Harshaw TLD-700H (7LiF:Mg,Cu,P) was previously characterised for low- to high-dose ranges from 1 microGy to 20 Gy. This paper describes the studies and results of dose-response and linearity at much higher doses. TLD-700H is a near perfect dosimetric material with near tissue equivalence, flat energy response, and the ability to measure beta, gamma and X rays. These new results extend the applicability of Harshaw TLD-700H into more dosimetric measurement environments. The simple glow curve structure provides insignificant fade, eliminating special oven preparation methods experienced by other materials. The work presented in this paper quantifies the performance of Harshaw TLD-700H in extended ranges.

Energy response of a two-dimensional sheet-type LiF:Mg,Cu,P TL dosemeter to photons.

A 2-D tissue-equivalent sheet-type dosemeter (NTL sheet) was developed using thermoluminescent material of LiF:Mg,Cu,P (NTL-250). The energy responses of the NTL sheet and NTL-250 powder were measured with 10-150 keV monoenergetic photons from synchrotron radiation at SPring-8. The sample was irradiated by a rotational method for the uniform irradiation with the narrow beam. Linearity of the NTL-250 was confirmed up to 2 Gy. Energy responses of the NTL sheet and NTL-250 powder were close to that of soft tissue. On the other hand, the BaSO(4) sheet, which has been used practically, showed the response that the sensitivity approximately 60 keV was 100 times higher than that for (60)Co gamma rays. Therefore the NTL sheet can be said to have excellent properties for dose measurements.