Antibacterial and Photocatalytic Activity of ZnO/Au and ZnO/Ag Nanocomposites.

The use of a combination of nanoparticles as antimicrobial agents can be one strategy to overcome the tendency of microbes to become resistant to antibiotic action. Also, the optimization of nano-photocatalysts to efficiently remove persistent pollutants from wastewater is a hot topic. In this study, two composites ZnO/Au (1% wt.) and ZnO/Ag (1% wt.) were synthesized by simple aqueous solution methods. The structure and morphology of the r nanocomposites were analyzed by structural and optical characterization methods. The formation of AuNPs and AgNPs in these experiments was also discussed. The antimicrobial properties of ZnO, ZnO/Au, and ZnO/Ag nanomaterials were investigated against Gram-negative bacteria (Pseudomonas aeruginosa) and Gram-positive bacteria (Staphylococcus aureus). The results showed an increase of 80% in the antimicrobial activity of ZnO/Au against Pseudomonas aeruginosa compared with 30% in the case of ZnO/Ag. Similarly, in the case of the S. aureus strain tests, ZnO/Au increased the antimicrobial activity by 55% and ZnO/Ag by 33%. The photocatalytic tests indicated an improvement in the photocatalytic degradation of methylene blue (MB) under UV irradiation using ZnO/Au and ZnO/Ag nanocomposites compared to bare ZnO. The photocatalytic degradation efficiency of ZnO after 60 min of UV irradiation was ∼83%, while the addition of AuNPs enhanced the degradation rate to ∼95% (ZP2), and AgNP presence enhanced the efficiency to ∼98%. The introduction of noble metallic nanoparticles into the ZnO matrix proved to be an effective strategy to increase their antimicrobial activity against P. aeruginosa and S. aureus, and their photocatalytic activity was evaluated through the degradation of MB dye. Comparing the enhancing effects of Au and Ag, it was found that ZnO/Au was a better antimicrobial agent while ZnO/Ag was a more effective photocatalyst under UV irradiation.

Light-Sensing Properties of Amorphous Vanadium Oxide Films Prepared by RF Sputtering.

In this study we analyzed the structure and light-sensing properties of as-deposited vanadium oxide thin films, prepared by RF sputtering in different Ar:O2 flow rate conditions, at low temperature (e.g., 65 °C). X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDX), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed to analyze the film microstructure, composition and the oxidation states of vanadium ions. The SEM micrographs evidence VxOy films with smooth surfaces, whereas the XRD patterns show their amorphous structure. Raman spectra indicate an increased structural disorder in the films deposited in Ar:O2 flow comparatively with those deposited solely in Ar flow. The XPS data suggest the modification of the oxidation state from V4+ to V5+, thus proving the formation of the V2O5 phase when increasing the oxygen content, which further affects the films' optical properties. We observed a good stability of the photogenerated current in Si/SiO2/VxOy/TiN heterostructures upon excitation with pulses of UV (360 nm), VIS (white light) and NIR (860 nm) light. The responsivity, detectivity and linear dynamic range parameters increase with the O/V ratio in the VxOy films, reaching comparable values with photodetectors based on crystalline V2O5 or VO2.

Self-Sustained Three-Dimensional Macroporous TiO2-Graphene Photocatalyst for Sunlight Decolorization of Methyl Orange.

The development of highly efficient sunlight-driven photocatalysts has triggered increased attention due to their merit in effluent treatment through a chemically green approach. To this end, we present herein the synthesis and characterization of the TiO2/3D-GF/Ni hybrid emphasizing the main structural and morphological properties and the photodegradation process of a highly resistant aromatic azo dye, methyl orange, under both UV light and simulated sunlight. Three-dimensional (3D) graphene was grown by the thermal CVD method on the nickel foam and subsequently coated with thin films of anatase employing the sol-gel method. Thereafter, it was gratifyingly demonstrated that the hybrid nanomaterial, TiO2/3D-GF-Ni, was able to bring about more than 90% decolorization of methyl orange dye after 30 min under simulated sunlight irradiance. Moreover, the efficiency of the methyl orange decolorization was 99.5% after three successive cycles. This high-performance photocatalyst which can effectively decolorize methyl orange will most likely make a great contribution to reducing environmental pollution by employing renewable solar energy.

New Amorphous Hydrogels with Proliferative Properties as Potential Tools in Wound Healing.

The study and discovery of bioactive compounds and new formulations as potential tools for promoting the repair of dermoepidermal tissue in wound healing is of continuing interest. We have developed a new formulation of amorphous hydrogel based on sodium alginate (NaAlg); type I collagen, isolated by the authors from silver carp tails (COL); glycerol (Gli); Aloe vera gel powder (AV); and silver nanoparticles obtained by green synthesis with aqueous Cinnamomum verum extract (AgNPs@CIN) and vitamin C, respectively. The gel texture of the amorphous hydrogels was achieved by the addition of Aloe vera, demonstrated by a rheological analysis. The evaluations of the cytotoxicity and cell proliferation capacity of the experimental amorphous hydrogels were performed against human foreskin fibroblast Hs27 cells (CRL-1634-ATCC). The developed gel formulations did not show a cytotoxic effect. The hydrogel variant containing AgNPs@CIN in a concentration of 8 µg Ag/gel formulation and hydrogel variant with vitamin C had proliferative activity. In addition, the antibacterial activity of the hydrogels was evaluated against S. aureus ATCC 6538, Ps. aeruginosa ATCC 27853, and E. coli ATCC 25922. The results demonstrated that the gel variant based on AgNPs@CIN in a concentration of 95 µg Ag/gel formulation and the hydrogel based on vitamin C show antibacterial activity. Therefore, the developed hydrogels with AgNPs@CIN and vitamin C could be promising alternatives in wound healing.

Influence of Random Plasmonic Metasurfaces on Fluorescence Enhancement.

One of the strategies employed to increase the sensitivity of the fluorescence-based biosensors is to deposit chromophores on plasmonic metasurfaces which are periodic arrays of resonating nano-antennas that allow the control of the electromagnetic field leading to fluorescence enhancement. While artificially engineered metasurfaces realized by micro/nano-fabrication techniques lead to a precise tailoring of the excitation field and resonant cavity properties, the technological overhead, small areas, and high manufacturing cost renders them unsuitable for mass production. A method to circumvent these challenges is to use random distribution of metallic nanoparticles sustaining plasmonic resonances, which present the properties required to significantly enhance the fluorescence. We investigate metasurfaces composed of random aggregates of metal nanoparticles deposited on a silicon and glass substrates. The finite difference time domain simulations of the interaction of the incident electromagnetic wave with the structures reveals a significant enhancement of the excitation field, which is due to the resonant plasmonic modes sustained by the nanoparticles aggregates. We experimentally investigated the role of these structures in the fluorescent behaviour of Rhodamine 6G dispersed in polymethylmethacrylate finding an enhancement that is 423-fold. This suggests that nanoparticle aggregates have the potential to constitute a suitable platform for low-cost, mass-produced fluorescent biosensors.

The Physicochemical and Antimicrobial Properties of Silver/Gold Nanoparticles Obtained by "Green Synthesis" from Willow Bark and Their Formulations as Potential Innovative Pharmaceutical Substances.

Green chemistry is a pharmaceutical industry tool, which, when implemented correctly, can lead to a minimization in resource consumption and waste. An aqueous extract of Salix alba L. was employed for the efficient and rapid synthesis of silver/gold particle nanostructures via an inexpensive, nontoxic and eco-friendly procedure. The nanoparticles were physicochemically characterized using ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS), X-ray diffraction (XRD) and scanning electron microscopy (SEM), with the best stability of up to one year in the solution obtained for silver nanoparticles without any chemical additives. A comparison of the antimicrobial effect of silver/gold nanoparticles and their formulations (hydrogels, ointments, aqueous solutions) showed that both metallic nanoparticles have antibacterial and antibiofilm effects, with silver-based hydrogels having particularly high antibiofilm efficiency. The highest antibacterial and antibiofilm efficacies were obtained against Pseudomonas aeruginosa when using silver nanoparticle hydrogels, with antibiofilm efficacies of over 75% registered. The hydrogels incorporating green nanoparticles displayed a 200% increased bacterial efficiency when compared to the controls and their components. All silver nanoparticle formulations were ecologically obtained by "green synthesis" and were shown to have an antimicrobial effect or potential as keratinocyte-acting pharmaceutical substances for ameliorating infectious psoriasis wounds.

SPR detection of protein enhanced by seedless synthesized gold nanorods.

Surface plasmon resonance (SPR) is a label-free, real-time bio-sensing technique with high potential in the diagnostic area, especially when a signal amplification strategy is used to improve the detection limit. We report here a simple method for enhancing the detection limit of bovine serum albumin (BSA), by attaching gold nanorods (AuNRs). AuNRs were obtained by a seedless synthesis technique and characterized using scanning electron microscopy (SEM), UV-VIS spectroscopy, FT-IR spectroscopy and dynamic light scattering (DLS). Finite element method (FEM) simulations were employed to explore the enhancement of the SPR signal by adding AuNRs on the SPR sensor's metallic layer. SPR spectroscopy was used to analyze the changes in the refractive index brought by the immobilization of unconjugated BSA and BSA modified with AuNRs. The results confirmed that the AuNRs conjugated with the protein increase the SPR signal ~ 10 times, leading to a limit of detection of 1.081 × 10-8 M (0.713 µg/mL).

Plasmon-Enhanced Photoresponse of Self-Powered Si Nanoholes Photodetector by Metal Nanowires.

In this work, we report the development of self-powered photodetectors that integrate silicon nanoholes (SiNHs) and four different types of metal nanowires (AgNWs, AuNWs, NiNWs, PtNWs) applied on the SiNHs' surface using the solution processing method. The effectiveness of the proposed architectures is evidenced through extensive experimental and simulation analysis. The AgNWs/SiNHs device showed the highest photo-to-dark current ratio of 2.1 × 10-4, responsivity of 30 mA/W and detectivity of 2 × 1011 Jones along with the lowest noise equivalent power (NEP) parameter of 2.4 × 10-12 WHz-1/2 in the blue light region. Compared to the bare SiNHs device, the AuNWs/SiNHs device had significantly enhanced responsivity up to 15 mA/W, especially in the red and near-infrared spectral region. Intensity-modulated photovoltage spectroscopy (IMVS) measurements revealed that the AgNWs/SiNHs device generated the longest charge carrier lifetime at 470 nm, whereas the AuNWs/SiNHs showed the slowest recombination rate at 627 nm. Furthermore, numerical simulation confirmed the local field enhancement effects at the MeNWs and SiNHs interface. The study demonstrates a cost-efficient and scalable strategy to combine the superior light harvesting properties of SiNHs with the plasmonic absorption of metallic nanowires (MeNWs) towards enhanced sensitivity and spectral-selective photodetection induced by the local surface plasmon resonance effects.

From Chip Size to Wafer-Scale Nanoporous Gold Reliable Fabrication Using Low Currents Electrochemical Etching.

We report a simple, scalable route to wafer-size processing for fabrication of tunable nanoporous gold (NPG) by the anodization process at low constant current in a solution of hydrofluoric acid and dimethylformamide. Microstructural, optical, and electrochemical investigations were employed for a systematic analysis of the sample porosity evolution while increasing the anodization duration, namely the small angle X-ray scattering (SAXS) technique and electrochemical impedance spectroscopy (EIS). Whereas the SAXS analysis practically completes the scanning electronic microscopy (SEM) investigations and provides data about the impact of the etching time on the nanoporous gold layers in terms of fractal dimension and average pore surface area, the EIS analysis was used to estimate the electroactive area, the associated roughness factor, as well as the heterogeneous electron transfer rate constant. The bridge between the analyses is made by the scanning electrochemical microscopy (SECM) survey, which practically correlates the surface morphology with the electrochemical activity. The results were correlated to endorse the control over the gold film nanostructuration process deposited directly on the substrate that can be further subjected to different technological processes, retaining its properties. The results show that the anodization duration influences the surface area, which subsequently modifies the properties of NPG, thus enabling tuning the samples for specific applications, either optical or chemical.

Comparative analysis of honey and citrate stabilized gold nanoparticles: In vitro interaction with proteins and toxicity studies.

Gold nanoparticles of comparable size were synthetized using honey mediated green method (AuNPs@honey) and citrate mediated Turkevich method (AuNPs@citrate). Their colloidal behavior in two cell media DMEM and RPMI, both supplemented with 10% FBS, was systematically investigated with different characterization techniques in order to evidence how the composition of the media influences their stability and the development of protein/NP complex. We revealed the formation of the protein corona which individually covers the nanoparticles in RPMI media, like a dielectric spacer according to UV-Vis spectroscopy, while DMEM promotes more abundant agglomerations, clustering together the nanoparticles, according to TEM investigations. In order to evaluate the biological impact of nanoparticles, B16 melanoma and L929 mouse fibroblasts cells were used to carry out the viability assays. Generally, the L929 cells were more sensitive than B16 cells to the presence of gold nanoparticles. Measurements of cell viability, proliferation and apoptotic activities of B16 cells indicated that the effects induced by AuNPs@honey were slightly similar to those induced by AuNPs@citrate, however, the toxic response improved in the L929 fibroblast cells following the treatment with AuNPs@honey within the same concentration range from 1 µg/ml to 15 µg/ml for 48 h. Results showed that honey mediated synthesis generates nanoparticles with reduced toxicity trends depending on the cell type, concentration of nanoparticles and exposure time toward various biomedical applications.

Tunable photoluminescence from interconnected graphene network with potential to enhance the efficiency of a hybrid Si nanowire solar cell.

An interconnected graphene network (IGN) structure with excellent photoluminescence (PL) properties was synthesized using a one-pot microwave-assisted hydrothermal carbonization route. The material exhibited intense and excitation-wavelength dependent PL emission located mainly in the UV-blue light range (300-450 nm). The result demonstrates that graphene networks could also be included in the emerging class of tunable PL carbon nanomaterials. Furthermore, we have taken a first step towards their incorporation into solar cell devices by fabricating IGN/p-SiNWs radial heterojunctions using the versatile potentiostatic electrodeposition technique. The IGN modified p-SiNW solar cell showed the best performance with an overall enhancement of power conversion efficiency of 7.5 times higher than the reference cell. We emphasize that the structural and electronic characteristics of the as-prepared IGN combined with tapering effects are directly responsible for the tripled short circuit current density and 9% improvement of open circuit voltage with respect to the reference cell. Finally, we have demonstrated that the IGN successfully passivated the Si nanowires' surface using intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). These promising findings indicate that further IGN exploitation may help to gain efficiency in future energy conversion applications.

High-performance solid state supercapacitors assembling graphene interconnected networks in porous silicon electrode by electrochemical methods using 2,6-dihydroxynaphthalen.

The challenge for conformal modification of the ultra-high internal surface of nanoporous silicon was tackled by electrochemical polymerisation of 2,6-dihydroxynaphthalene using cyclic voltammetry or potentiometry and, notably, after the thermal treatment (800 °C, N2, 4 h) an assembly of interconnected networks of graphene strongly adhering to nanoporous silicon matrix resulted. Herein we demonstrate the achievement of an easy scalable technology for solid state supercapacitors on silicon, with excellent electrochemical properties. Accordingly, our symmetric supercapacitors (SSC) showed remarkable performance characteristics, comparable to many of the best high-power and/or high-energy carbon-based supercapacitors, their figures of merit matching under battery-like supercapacitor behaviour. Furthermore, the devices displayed high specific capacity values along with enhanced capacity retention even at ultra-high rates for voltage sweep, 5 V/s, or discharge current density, 100 A/g, respectively. The cycling stability tests performed at relatively high discharge current density of 10 A/g indicated good capacity retention, with a superior performance demonstrated for the electrodes obtained under cyclic voltammetry approach, which may be ascribed on the one hand to a better coverage of the porous silicon substrate and, on the other hand, to an improved resilience of the hybrid electrode to pore clogging.

Engineering Graphene Quantum Dots for Enhanced Ultraviolet and Visible Light p-Si Nanowire-Based Photodetector.

In this work, a significant improvement of the classical silicon nanowire (SiNW)-based photodetector was achieved through the realization of core-shell structures using newly designed GQDPEIs via simple solution processing. The poly(ethyleneimine) (PEI)-assisted synthesis successfully tuned both optical and electrical properties of graphene quantum dots (GQDs) to fulfill the requirements for strong yellow photoluminescence emission along with large band gap formation and the introduction of electronic states inside the band gap. The fabrication of a GQDPEI-based device was followed by systematic structural and photoelectronic investigation. Thus, the GQDPEI/SiNW photodetector exhibited a large photocurrent to dark current ratio (Iph/Idark up to ∼0.9 × 102 under 4 V bias) and a remarkable improvement of the external quantum efficiency values that far exceed 100%. In this frame, GQDPEIs demonstrate the ability to arbitrate both charge-carrier photogeneration and transport inside a heterojunction, leading to simultaneous attendance of various mechanisms: (i) efficient suppression of the dark current governed by the type I alignment in energy levels, (ii) charge photomultiplication determined by the presence of the PEI-induced electron trap levels, and (iii) broadband ultraviolet-to-visible downconversion effects.