ZnO/Cu nanocomposite: a platform for direct electrochemistry of enzymes and biosensing applications

Unique structured nanomaterials can facilitate the direct electron transfer between redox proteins and the electrodes. Here, in situ directed growth on an electrode of a ZnO/Cu nanocomposite was prepared by a simple corrosion approach, which enables robust mechanical adhesion and electrical contact between the nanostructured ZnO and the electrodes. This is great help to realize the direct electron transfer between the electrode surface and the redox protein. SEM images demonstrate that the morphology of the ZnO/Cu nanocomposite has a large specific surface area, which is favorable to immobilize the biomolecules and construct biosensors. Using glucose oxidase (GOx) as a model, this ZnO/Cu nanocomposite is employed for immobilization of GOx and the construction of the glucose biosensor. Direct electron transfer of GOx is achieved at ZnO/Cu nanocomposite with a high heterogeneous electron transfer rate constant of 0.67 ± 0.06 s(-1). Such ZnO/Cu nanocomposite provides a good matrix for direct electrochemistry of enzymes and mediator-free enzymatic biosensors.     

Synthesis,characterization, and biosensing application of ZnO/SnO2 heterostructured nanomaterials

In this work, zinc oxide/tin oxide (ZnO/SnO₂) heterostructured nanomaterials were synthesized by hydrothermal method. Transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction measurements revealed that the product was composed of ZnO nanowires and SnO₂ nanobranches. The novel ZnO/SnO₂ heterostructured nanocrystals were for the first time used as a supporting matrix to explore a novel immobilization and biosensing platform of redox proteins. UV–visible absorption investigation indicated that hemoglobin (Hb) intercalated well in the ZnO/SnO₂ heterostructured nanocrystals retained its native structure. Comparative experiments have confirmed that the ZnO/SnO₂-based biosensor not only had enhanced direct electron transfer capacity but also displayed excellent electrocatalytic properties such as higher sensitivity and wider linear range to the detection of hydrogen peroxide in comparison with the ZnO- and SnO₂-based biosensors.     

三维花状ZnO纳米材料的制备及发光性质

常压下用溶胶凝胶和化学溶液生长两步法在3种不同的衬底上制备出三维花状ZnO纳米材料.采用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、选区电子衍射(SAED)、紫外吸收(UV)光谱和光致发光光谱(PL)对样品进行分析,结果表明,花状ZnO的组成单元为沿c轴方向生长的ZnO纳米棒,直径约为100 nm,...     

Chemical stability of ZnO nanostructures in simulated physiological environments and its application in determining polar directions

The in vitro chemical stability and etching of ZnO nanostructures in simulated physiological solution (SPS) were studied using electron microscopy. Calcium hydrogen phosphate thin layers were observed to be uniformly deposited on the surfaces of ZnO nanomaterials in SPS. Electron diffraction and high-resolution transmission electron microscopy revealed that the calcium hydrogen phosphate layers were amorphous and had excellent interfacial contact with the nanocrystals. ZnO nanostructures fabricated by thermal evaporation were found to survive much longer in SPS than those fabricated using a hydrothermal solution method. The shapes of the voids formed in the ZnO nanostructures by the etching in SPS can be used to deduce the polar directions of ZnO nanostructures.     

Controlled Synthesis of Sea-urchin-like ZnO Nanomaterials with the Aid of Ethylene Glycol Using a Solvothermal Method

Sea-urchin-like ZnO nanomaterials were successfully synthesized by decomposition of zinc acetate precursor in the presence of sodium hydroxide and ethylene glycol(EG) in an ethanol solution using a solvothermal method at 180 ℃ for 12 h.The crystalline phase and morphology of the resultant nanomaterials were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),selected-area electronic diffraction(SAED) and high-resolution electron microscopy(HRTEM).Interestingly,the sizes and prod length of the samples can be easily tuned by changing the amount of directing agent EG and keeping other reaction conditions unchangeable.On the basis of our experimental outcomes,EG-controlled-nucleation-growth formation mechanism was proposed to correspond for the sea-urchin-like ZnO growth processes.And the photoluminescence(PL) spectra of the as-selected samples were measured at room temperature,presenting two emission peaks centered at～388 and 480 nm.     

Synthesis and characterization of novel poly(1-naphthylamine)/zinc oxide nanocomposites: Application in catalytic degradation of methylene blue dye

The organic–inorganic poly(1-naphthylamine)/ZnO (PNA/ZnO) nanocomposites were synthesized by in situ chemical oxidative polymerization of 1-naphthylamine monomer and ZnO nanomaterials for the photocatalytic degradation of methylene blue (MB) dye under visible light. The surface properties of PNA molecules were altered by adding the ZnO nanomaterials. The crystalline and the optical properties of PNA/ZnO nanocomposites were improved with the increased contents of ZnO nanomaterials in PNA molecules due to the effective interaction of PNA to the surface of ZnO nanomaterials. The prepared PNA/ZnO nanocomposites presented moderate photocatalytic MB dye degradation of ~22% under visible light. The occurrence of dye degradation under visible light might attribute to high-charge separation of ē-h⁺ pairs at the interfaces of PNA and ZnO nanomaterials in its excited state under light irradiation.     

An effective nanocomposite of polyaniline and ZnO: preparation,characterizations, and its photocatalytic activity

The polyaniline/zinc oxide (PANI/ZnO) nanocomposites were prepared by in situ polymerization of aniline monomer with ZnO nanomaterials and applied as a photocatalyst for the degradation of methylene blue (MB) dye. The morphological observations elicited the agglomerations of PANI sheets which occurred due to the interaction between PANI and ZnO nanomaterials in PANI/ZnO nanocomposites. As compared to pristine PANI, the UV–vis spectra exhibited that the absorption peak of π–π* transitions considerably shifted to higher wavelength at 360 nm from 325 nm in the nanocomposites. The photocatalytic activity results indicated the substantial degradation of MB dye by ~76% over the surface of PANI/ZnO nanocomposite catalyst under light illumination. The PANI/ZnO nanocomposites showed three times higher photocatalytic activity to MB dye degradation compared to pristine PANI might due to high photogenerated electron (ē)–hole (h⁺) pairs charge separation.     

Electrons Transfer Between Mercaptoacetic Acid and ZnO Nanocrystal Thin Film

ZnO nanoorystals thin film were prepared by means of the self-assembly mothed. The complex films of mercaptoacetic acid(MPA) and ZnO nanocrystals(ZNCs) were prepared by means of the self-assembly technique. The interaction between the MPA and ZnO within the MPA and ZnO nanocrystal thin film decreases the photoluminescence intensity of the ZnO. The interaction was manifested by the X-ray photoelectron spectra. The intensity change of the photoluminescence of the ZnO is discussed on the basis of taking into account the process of electron transfer on the interface between the ZnO and MPA. The electron transfer of ZnO depends on the distance between the ZnO and MPA.     

Enhanced UV photosensing properties of ZnO nanowires prepared by electrodeposition and atomic layer deposition

A new process enabling the synthesis of zinc oxide (ZnO) and Al-doped ZnO nanowires (NWs) for photosensing applications is reported. By combining atomic layer deposition (ALD) for the seed layer preparation and electrodeposition for the NW growth, high-quality ZnO nanomaterials were prepared and tested as ultraviolet (UV) sensors. The obtained NWs are grown as arrays perpendicular to the substrate surface and present diameters between 70 and 130 nm depending on the Al doping, as seen from scanning electron microscopy (SEM) studies. Their hexagonal microstructure has been determined using X-ray diffraction and Raman spectroscopy. An excellent performance in UV sensing has been observed for the ZnO NWs with low Al doping, and a maximal photoresponse current of 11.1 mA has been measured. In addition, initial studies on the stability have shown that the NW photoresponse currents are stable, even after ten UV on/off cycles.     

In situ growth of ZnO nanocrystals from solid electrospun nanofiber matrixes

Porous fiber membranes consisting of 1D assemblies of ZnO nanocrystal-supported poly(vinyl alcohol) (PVA) nanofibers are described. These hybrid nanofiber membranes were assembled by first electrospinning a ZnO precursor-containing PVA aqueous solution. Subsequently, the electrospun composite nanofibers were submerged in a basic ethanol solution. As a result, ZnO precursors in solid PVA matrixes were hydrolyzed to generate ZnO crystals residing on the fiber surfaces. Photoluminescence spectroscopy analysis demonstrated the as-hydrolyzed fiber membranes possess white luminescence. Furthermore, the ZnO-encapsulated PVA nanofibers were prepared by directly electrospinning a ZnO nanocrystal-containing PVA solution as the contrast of the as-hydrolyzed hybrid nanofibers. The surface photovoltage spectroscopy (SPS) confirmed that the as-hydrolyzed hybrid fiber membranes had a strong SPS response, but the directly spun fiber membranes did not have any SPS response. This can be attributed to the favorable structure of the hydrolyzed hybrid nanofibers, that is, the surface residence of ZnO permits ZnO crystals to make direct contact with ITO electrodes to transfer the photogenerated electron originating from ZnO to ITO electrodes. By contrast, the transfer of the photogenerated electron is limited by PVA matrixes in the directly spun fiber system.     

Biogenic Synthesis of CuO,ZnO, and CuO–ZnO Nanoparticles Using Leaf Extracts of Dovyalis caffra and Their Biological Properties

Biogenic metal oxide nanoparticles (NPs) have emerged as a useful tool in biology due to their biocompatibility properties with most biological systems. In this study, we report the synthesis of copper oxide (CuO), zinc oxide (ZnO) nanoparticles (NPs), and their nanocomposite (CuO–ZnO) prepared using the phytochemical extracts from the leaves of Dovyalis caffra (kei apple). The physicochemical properties of these nanomaterials were established using some characterization techniques including X-ray diffraction analysis (XRD), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The XRD result confirmed the presence of a monoclinic CuO (Tenorite), and a hexagonal ZnO (Zincite) nanoparticles phase, which were both confirmed in the CuO–ZnO composite. The electron microscopy of the CuO–ZnO, CuO, and ZnO NPs showed a mixture of nano-scale sizes and spherical/short-rod morphologies, with some agglomeration. In the constituent’s analysis (EDX), no unwanted peak was found, which showed the absence of impurities. Antioxidant properties of the nanoparticles was studied, which confirmed that CuO–ZnO nanocomposite exhibited better scavenging potential than the individual metal oxide nanoparticles (CuO, and ZnO), and ascorbic acid with respect to their minimum inhibitory concentration (IC₅₀) values. Similarly, the in vitro anticancer studies using MCF7 breast cancer cell lines indicated a concentration-dependent profile with the CuO–ZnO nanocomposite having the best activity over the respective metal oxides, but slightly lower than the standard 5-Fluorouracil drug.     

生物模板法制备纳米氧化锌及其表征

本文以油菜花粉为生物模板,硝酸锌为锌源制备了一种分级多孔结构的纳米氧化锌。采用SEM、TEM、XRD和 FTIR等技术手段对其进行了表征。实验结果表明,采用油菜花粉为生物模板制备的氧化锌纳米材料为六方纤锌矿结构,较好的复制了花粉的分级多孔结构。同时,研究了制备条件诸如煅烧温度和反应物浓度对产物结构、形貌和尺度的影响。     

Synthesis,Characterization, and Assessment of Anti-Cancer Potential of ZnO Nanoparticles in an In Vitro Model of Breast Cancer

Advanced innovations for combating variants of aggressive breast cancer and overcoming drug resistance are desired. In cancer treatment, ZnO nanoparticles (NPs) have the capacity to specifically and compellingly activate apoptosis of cancer cells. There is also a pressing need to develop innovative anti-cancer therapeutics, and recent research suggests that ZnO nanoparticles hold great potential. Here, the in vitro chemical effectiveness of ZnO NPs has been tested. Zinc oxide (ZnO) nanoparticles were synthesized using Citrullus colocynthis (L.) Schrad by green methods approach. The generated ZnO was observed to have a hexagonal wurtzite crystal arrangement. The generated nanomaterials were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-visible spectroscopy. The crystallinity of ZnO was reported to be in the range 50–60 nm. The NPs morphology showed a strong absorbance at 374 nm with an estimated gap band of 3.20 eV to 3.32 eV. Microscopy analysis proved the morphology and distribution of the generated nanoparticles to be around 50 nm, with the elemental studies showing the elemental composition of ZnO and further confirming the purity of ZnO NPs. The cytotoxic effect of ZnO NPs was evaluated against wild-type and doxorubicin-resistant MCF-7 and MDA-MB-231 breast cancer cell lines. The results showed the ability of ZnO NPs to inhibit the prefoliation of MCF-7 and MDA-MB-231 prefoliation through the induction of apoptosis without significant differences in both wild-type and resistance to doxorubicin.     

Strong metal-support interactions between gold nanoparticles and ZnO nanorods in CO oxidation

The catalytic performances of supported gold nanoparticles depend critically on the nature of support. Here, we report the first evidence of strong metal-support interactions (SMSI) between gold nanoparticles and ZnO nanorods based on results of structural and spectroscopic characterization. The catalyst shows encapsulation of gold nanoparticles by ZnO and the electron transfer between gold and the support. Detailed characterizations of the interaction between Au nanoparticles and ZnO were done with transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and FTIR study of adsorbed CO. The significance of the SMSI effect is further investigated by probing the efficiency of CO oxidation over the Au/ZnO-nanorod. In contrast to the classical reductive SMSI in the TiO(2) supported group VIII metals which appears after high temperature reduction in H(2) with electron transfer from the support to metals, the oxidative SMSI in Au/ZnO-nanorod system gives oxygen-induced burial and electron transfer from gold to support. In CO oxidation, we found that the oxidative SMSI state is associated with positively charged gold nanoparticles with strong effect on its catalytic activity before and after encapsulation. The oxidative SMSI can be reversed by hydrogen treatment to induce AuZn alloy formation, de-encapsulation, and electron transfer from support to Au. Our discovery of the SMSI effects in Au/ZnO nanorods gives new understandings of the interaction between gold and support and provides new way to control the interaction between gold and the support as well as catalytic activity.     

Molten salt route toward the growth of ZnO nanowires in unusual growth directions

ZnO nanowires with unusual growth directions, such as the approximate 102 and the 100 directions, were prepared by using the LiCl molten salt synthetic method. Intrinsic crystallographic structures and the growth directions of the as-prepared ZnO nanowires were investigated by using selected area electron diffraction and high-resolution transmission electron microscopy. In the present case, Li+ and Cl- ions of molten salts may bind with O2- and Zn2+ ions, respectively, of the {101} and {001} polar surfaces of the ZnO crystals, resulting in the decrease of their surface energies and tuning the growth directions by blocking the growth on the polar surfaces. A combination of the growth along the <102>, <100>, and <210> directions may lead to the formation of complex tree like ZnO dendrites. Strong green light emission was observed from room-temperature PL spectra of the as-prepared ZnO nanowires. This molten-salt synthetic process could be extended to synthesize other kinds of unusual 1D nanomaterials with specific crystal structures and properties.     

Synthesis, characterization and antimicrobial investigation of mechanochemically processed silver doped ZnO nanoparticles

The application of nanomaterials has gained considerable momentum in various fields in recent years due to their high reactivity, excellent surface properties and quantum effects in the nanometer range. The properties of zinc oxide (ZnO) vary with its crystallite size or particle size and often nanocrystalline ZnO is seen to exhibit superior physical and chemical properties due to their higher surface area and modified electronic structure. ZnO nanoparticles are reported to exhibit strong bacterial inhibiting activity and silver (Ag) has been extensively used for its antimicrobial properties since ages. In this study, Ag doped ZnO nanoparticles were synthesized by mechanochemical processing in a high energy ball mill and investigated for antimicrobial activity. The nanocrystalline nature of zinc oxide was established by X-ray diffraction (XRD) studies. It is seen from the XRD data obtained from the samples, that crystallite size of the zinc oxide nanoparticles is seen to decrease with increasing Ag addition. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) data also supported the nanoparticle formation during the synthesis. The doped nanoparticles were subjected to antimicrobial investigation and found that both increase in Ag content and decrease in particle size contributed significantly towards antimicrobial efficiency. It was also observed that Ag doped ZnO nanoparticles possess enhanced antimicrobial potential than that of virgin ZnO against the studied microorganisms of Escherichia coli and Staphylococcus aureus.     

Surface-plasmon-enhanced band emission of ZnO nanoflowers decorated with Au nanoparticles

A simple strategy was used to enhance band emission through the transfer of defect emission from ZnO to Au by using the energy match between the defect emission of ZnO and the surface plasmon absorbance of Au NPs through decorating the surface of ZnO nanoflowers with Au nanoparticles (Au NPs). The ZnO nanostructure, which was comprised of six nanorods that were attached on one side in a flower-like fashion, was synthesized by using a hydrothermal method. The temperature-dependent morphology and detailed growth mechanism were studied. The influence of the density of the Au NPs that were deposited onto the surface of ZnO on photoluminescence was investigated to optimize the configuration of the ZnO/Au system in terms of the maximum band emission. The sequential transfer of defect energy from ZnO to Au and electron transfer from excited Au to ZnO was proposed as a possible mechanism for the enhanced band emission.     

Surface‐Plasmon‐Enhanced Band Emission of ZnO Nanoflowers Decorated with Au Nanoparticles

A simple strategy was used to enhance band emission through the transfer of defect emission from ZnO to Au by using the energy match between the defect emission of ZnO and the surface plasmon absorbance of Au NPs through decorating the surface of ZnO nanoflowers with Au nanoparticles (Au NPs). The ZnO nanostructure, which was comprised of six nanorods that were attached on one side in a flower‐like fashion, was synthesized by using a hydrothermal method. The temperature‐dependent morphology and detailed growth mechanism were studied. The influence of the density of the Au NPs that were deposited onto the surface of ZnO on photoluminescence was investigated to optimize the configuration of the ZnO/Au system in terms of the maximum band emission. The sequential transfer of defect energy from ZnO to Au and electron transfer from excited Au to ZnO was proposed as a possible mechanism for the enhanced band emission.     

Shape-controlled zinc(II) oxide nanomaterial constructed from three-dimensional zinc(II) coordination complex

Hydrothermal synthetic method has been used to prepare complex [ZnL]_n (1) (H₂L = 4-[(1H-imidazol-4-yl)methylamino]benzoic acid) as spherical microparticles. Slow morphological changes from small spindle-shaped particles to smoother spherical particles in the growth process of complex 1 were observed. Subsequently complex 1 was used as precursor as well as sacrificial template to synthesize hexagonal ZnO nanomaterials by calcination in air. The structure of the final products and the formation process were characterized by measurements of X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The formation mechanism of the final nanorods was proposed on the basis of the structural change of complex 1 in the calcination process. The photocatalytic properties of complex 1 and prepared ZnO have also been studied, and the results showed that all these nano-/micromaterials have photocatalytic properties and ZnO formed under lower calcinated temperature has higher photocatalytic activity.     

High-yield synthesis of pure ZnO nanoparticles by one-step solid-state reaction approach for enhanced photocatalytic activity

Zinc oxide (ZnO) nanostructures were synthesized via a one-step solid-state reaction approach in ammonia (NH₃) gas environment with different temperature ramp rates. The so-formed nanostructures were characterized using X-ray diffraction (XRD) for phase identification, where the typical wurtzite hexagonal structure was observed. Scanning electron microscopy (SEM) confirmed the particle size to be in the range 45–50 nm, the same as calculated by the XRD pattern for the ramp rate of 10 °C/min. Energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the chemical purity of the samples. The photoluminescence (PL) spectrum indicated multiple near-band-edge emissions and energy-band emissions. Then, these ZnO nanomaterials were used for the degradation of crystal violet (CV) dye under UV light irradiation. The CV solution was completely degraded in 2 hr. The initial photocatalyst and dye amounts of 0.2 g/100 ml and 0.5 mg/L, respectively, were found to be the optimum values for maximum degradation efficiency. The ZnO-based photocatalyst was stable up to three cycles of reuse. These results indicate that the high surface area and porosity of the nanomaterials are responsible for the high efficiency, which was confirmed by specific surface area analysis.