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1.  One-Step Synthesis of Monodisperse In-Doped ZnO Nanocrystals 
Nanoscale Research Letters  2010;5(5):882-888.
A method for the synthesis of high quality indium-doped zinc oxide (In-doped ZnO) nanocrystals was developed using a one-step ester elimination reaction based on alcoholysis of metal carboxylate salts. The resulting nearly monodisperse nanocrystals are well-crystallized with typically crystal structure identical to that of wurtzite type of ZnO. Structural, optical, and elemental analyses on the products indicate the incorporation of indium into the host ZnO lattices. The individual nanocrystals with cubic structures were observed in the 5% In–ZnO reaction, due to the relatively high reactivity of indium precursors. Our study would provide further insights for the growth of doped oxide nanocrystals, and deepen the understanding of doping process in colloidal nanocrystal syntheses.
doi:10.1007/s11671-010-9579-0
PMCID: PMC2894350  PMID: 20672040
ZnO; Nanocrystal; Doping; Indium; Monodisperse
2.  One-Step Synthesis of Monodisperse In-Doped ZnO Nanocrystals 
Nanoscale Research Letters  2010;5(5):882-888.
A method for the synthesis of high quality indium-doped zinc oxide (In-doped ZnO) nanocrystals was developed using a one-step ester elimination reaction based on alcoholysis of metal carboxylate salts. The resulting nearly monodisperse nanocrystals are well-crystallized with typically crystal structure identical to that of wurtzite type of ZnO. Structural, optical, and elemental analyses on the products indicate the incorporation of indium into the host ZnO lattices. The individual nanocrystals with cubic structures were observed in the 5% In–ZnO reaction, due to the relatively high reactivity of indium precursors. Our study would provide further insights for the growth of doped oxide nanocrystals, and deepen the understanding of doping process in colloidal nanocrystal syntheses.
doi:10.1007/s11671-010-9579-0
PMCID: PMC2894350  PMID: 20672040
ZnO; Nanocrystal; Doping; Indium; Monodisperse
3.  High-Frequency EPR and ENDOR Spectroscopy on Semiconductor Quantum Dots 
Applied Magnetic Resonance  2010;39(1-2):151-183.
It is shown that high-frequency electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy are excellent tools for the investigation of the electronic properties of semiconductor quantum dots (QDs). The great attractions of these techniques are that, in contrast to optical methods, they allow the identification of the dopants and provide information about the spatial distribution of the electronic wave function. This latter aspect is particularly attractive because it allows for a quantitative measurement of the effect of confinement on the shape and properties of the wave function. In this contribution EPR and ENDOR results are presented on doped ZnO QDs. Shallow donors (SDs), related to interstitial Li and Na and substitutional Al atoms, have been identified in this material by pulsed high-frequency EPR and ENDOR spectroscopy. The shallow character of the wave function of the donors is evidenced by the multitude of ENDOR transitions of the 67Zn nuclear spins and by the hyperfine interaction of the 7Li, 23Na and 27Al nuclear spins that are much smaller than for atomic lithium, sodium and aluminium. The EPR signal of an exchange-coupled pair consisting of a shallow donor and a deep Na-related acceptor has been identified in ZnO nanocrystals with radii smaller than 1.5 nm. From ENDOR experiments it is concluded that the deep Na-related acceptor is located at the interface of the ZnO core and the Zn(OH)2 capping layer, while the shallow donor is in the ZnO core. The spatial distribution of the electronic wave function of a shallow donor in ZnO semiconductor QDs has been determined in the regime of quantum confinement by using the nuclear spins as probes. Hyperfine interactions as monitored by ENDOR spectroscopy quantitatively reveal the transition from semiconductor to molecular properties upon reduction of the size of the nanoparticles. In addition, the effect of confinement on the g-factor of SDs in ZnO as well as in CdS QDs is observed. Finally, it is shown that an almost complete dynamic nuclear polarization (DNP) of the 67Zn nuclear spins in the core of ZnO QDs and of the 1H nuclear spins in the Zn(OH)2 capping layer can be obtained. This DNP is achieved by saturating the EPR transition of SDs present in the QDs with resonant high-frequency microwaves at low temperatures. This nuclear polarization manifests itself as a hole and an antihole in the EPR absorption line of the SD in the QDs and a shift of the hole (antihole). The enhancement of the nuclear polarization opens the possibility to study semiconductor nanostructures with nuclear magnetic resonance techniques.
doi:10.1007/s00723-010-0151-y
PMCID: PMC2941054  PMID: 20936163
4.  Cellulose Nanocrystals/ZnO as a Bifunctional Reinforcing Nanocomposite for Poly(vinyl alcohol)/Chitosan Blend Films: Fabrication, Characterization and Properties 
In this study, cellulose nanocrystals/zinc oxide (CNCs/ZnO) nanocomposites were dispersed as bifunctional nano-sized fillers into poly(vinyl alcohol) (PVA) and chitosan (Cs) blend by a solvent casting method to prepare PVA/Cs/CNCs/ZnO bio-nanocomposites films. The morphology, thermal, mechanical and UV-vis absorption properties, as well antimicrobial effects of the bio-nanocomposite films were investigated. It demonstrated that CNCs/ZnO were compatible with PVA/Cs and dispersed homogeneously in the polymer blend matrix. CNCs/ZnO improved tensile strength and modulus of PVA/Cs significantly. Tensile strength and modulus of bio-nanocomposite films increased from 55.0 to 153.2 MPa and from 395 to 932 MPa, respectively with increasing nano-sized filler amount from 0 to 5.0 wt %. The thermal stability of PVA/Cs was also enhanced at 1.0 wt % CNCs/ZnO loading. UV light can be efficiently absorbed by incorporating ZnO nanoparticles into a PVA/Cs matrix, signifying that these bio-nanocomposite films show good UV-shielding effects. Moreover, the biocomposites films showed antibacterial activity toward the bacterial species Salmonella choleraesuis and Staphylococcus aureus. The improved physical properties obtained by incorporating CNCs/ZnO can be useful in variety uses.
doi:10.3390/ijms150611040
PMCID: PMC4100197  PMID: 24945313
biocomposites; cellulose nanocrystals; bi-functional filler; poly(vinyl alcohol)/chitosan blend; UV absorption
5.  Greater fibroblast proliferation on an ultrasonicated ZnO/PVC nanocomposite material 
There has been a significant and growing concern over nosocomial medical device infections. Previous studies have demonstrated that embedding nanoparticles alone (specifically, zinc oxide [ZnO]) in conventional polymers (eg, polyvinyl chloride [PVC]) can decrease bacteria growth and may have the potential to prevent or disrupt bacterial processes that lead to infection. However, little to no studies have been conducted to determine mammalian cell functions on such a nanocomposite material. Clearly, for certain medical device applications, maintaining healthy mammalian cell functions while decreasing bacteria growth is imperative (yet uncommon). For this reason, in the presented study, ZnO nanoparticles of varying sizes (from 10 nm to >200 nm in diameter) and functionalization (including no functionalization to doping with aluminum oxide and functionalizing with a silane coupling agent KH550) were incorporated into PVC either with or without ultrasonication. Results of this study provided the first evidence of greater fibroblast density after 18 hours of culture on the smallest ZnO nanoparticle incorporated PVC samples with dispersion aided by ultrasonication. Specifically, the greatest amount of fibroblast proliferation was measured on ZnO nanoparticles functionalized with a silane coupling agent KH550; this sample exhibited the greatest dispersion of ZnO nanoparticles. Water droplet tests showed a general trend of decreased hydrophilicity when adding any of the ZnO nanoparticles to PVC, but an increase in hydrophilicity (albeit still below controls or pure PVC) when using ultrasonication to increase ZnO nanoparticle dispersion. Future studies will have to correlate this change in wettability to initial protein adsorption events that may explain fibroblast behavior. Mechanical tests also provided evidence of the ability to tailor mechanical properties of the ZnO/PVC nanocomposites through the use of the different ZnO nanoparticles. Coupled with previous antibacterial studies, the present study demonstrated that highly dispersed ZnO/PVC nanocomposite materials should be further studied for numerous medical device applications.
doi:10.2147/IJN.S54897
PMCID: PMC3883596  PMID: 24403831
ZnO; nanoparticles; PVC; fibroblast; dispersion; nanotechnology
6.  Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process 
Summary
Zinc oxide (ZnO) nanorods decorated with gold (Au) nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC). The picosecond-resolved, time-correlated single-photon-count (TCSPC) spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption of the Au nanoparticles, enhanced power-conversion efficiency (PCE) of 6.49% for small-area (0.1 cm2) ZnO/Au-nanocomposite DSSC was achieved compared to the 5.34% efficiency of the bare ZnO nanorod DSSC. The TCSPC studies revealed similar dynamics for the charge transfer from dye molecules to ZnO both in the presence and absence of Au nanoparticles. A slower fluorescence decay associated with the electron recombination process, observed in the presence of Au nanoparticles, confirmed the blocking of the electron transfer from ZnO back to the dye or electrolyte by the Schottky barrier formed at the ZnO/Au interface. For large area DSSC (1 cm2), ~130% enhancement in PCE (from 0.50% to 1.16%) was achieved after incorporation of the Au nanoparticles into the ZnO nanorods.
doi:10.3762/bjnano.2.73
PMCID: PMC3201621  PMID: 22043457
dye-sensitized solar cell; gold nanoparticle; picosecond spectroscopy; Schottky barrier; zinc oxide nanorod
7.  Novel conductive polypyrrole/zinc oxide/chitosan bionanocomposite: synthesis, characterization, antioxidant, and antibacterial activities 
An antibacterial and conductive bionanocomposite (BNC) film consisting of polypyrrole (Ppy), zinc oxide (ZnO) nanoparticles (NPs), and chitosan (CS) was electrochemically synthesized on indium tin oxide (ITO) glass substrate by electrooxidation of 0.1 M pyrrole in aqueous solution containing appropriate amounts of ZnO NPs uniformly dispersed in CS. This method enables the room temperature electrosynthesis of BNC film consisting of ZnO NPs incorporated within the growing Ppy/CS composite. The morphology of Ppy/ZnO/CS BNC was characterized by scanning electron microscopy. ITO–Ppy/CS and ITO–Ppy/ZnO/CS bioelectrodes were characterized using the Fourier transform infrared technique, X-ray diffraction, and thermogravimetric analysis. The electrical conductivity of nanocomposites was investigated by a four-probe method. The prepared nanocomposites were analyzed for antioxidant activity using the 2,2-diphenyl-1-picrylhydrazyl assay. The results demonstrated that the antioxidant activity of nanocomposites increased remarkably by addition of ZnO NPs. The electrical conductivity of films showed a sudden decrease for lower weight ratios of ZnO NPs (5 wt%), while it was increased gradually for higher ratios (10, 15, and 20 wt%). The nanocomposites were analyzed for antibacterial activity against Gram-positive and Gram-negative bacteria. The results indicated that the synthesized BNC is effective against all of the studied bacteria, and its effectiveness is higher for Pseudomonas aeruginosa. The thermal stability and physical properties of BNC films were increased by an increase in the weight ratio of ZnO NPs, promising novel applications for the electrically conductive polysaccharide-based nanocomposites, particularly those that may exploit the antimicrobial nature of Ppy/ZnO/CS BNCs.
doi:10.2147/IJN.S69740
PMCID: PMC4284024  PMID: 25565815
bionanocomposite; electrodeposition; conductive; antibacterial; antioxidant
8.  Low-temperature solution growth of ZnO nanotube arrays 
Summary
Single crystal ZnO nanotube arrays were synthesized at low temperature in an aqueous solution containing zinc nitrate and hexamethylenetetramine. It was found that the pH value of the reaction solution played an important role in mediating the growth of ZnO nanostructures. A change in the growth temperature might change the pH value of the solution and bring about the structure conversion of ZnO from nanorods to nanotubes. It was proposed that the ZnO nanorods were initially formed while the reaction solution was at a relatively high temperature (~90 °C) and therefore enriched with colloidal Zn(OH)2, which allowed a fast growth of ZnO nanocrystals along the [001] orientation to form nanorods. A decrease in the reaction temperature yielded a supersaturated solution, resulting in an increase in the concentration of OH− ions as well as the pH value of the solution. Colloidal Zn(OH)2 in the supersaturated solution trended to precipitate. However, because of a slow diffusion process in view of the low temperature and low concentration of the colloidal Zn(OH)2, the growth of the (001) plane of ZnO nanorods was limited and only occurred at the edge of the nanorods, eventually leading to the formation of a nanotube shape. In addition, it was demonstrated that the pH might impact the surface energy difference between the polar and non-polar faces of the ZnO crystal. Such a surface energy difference became small at high pH and hereby the prioritized growth of ZnO crystal along the [001] orientation was suppressed, facilitating the formation of nanotubes. This paper demonstrates a new strategy for the fabrication of ZnO nanotubes on a large scale and presents a more comprehensive understanding of the growth of tube-shaped ZnO in aqueous solution at low temperature.
doi:10.3762/bjnano.1.15
PMCID: PMC3045914  PMID: 21977402
growth from solutions; nanorods; nanotubes; supersaturation; ZnO
9.  Preparation and properties of poly(vinyl alcohol)/chitosan blend bionanocomposites reinforced with cellulose nanocrystals/ZnO-Ag multifunctional nanosized filler 
A series of novel bionanocomposites were cast using different contents of zinc oxide-silver nanoparticles (ZnO-AgNPs) stabilized by cellulose nanocrystals (CNC) as multifunctional nanosized fillers in poly(vinyl alcohol)/chitosan (PVA/Cs) matrices. The morphological structure, mechanical properties, ultraviolet-visible absorption, and antimicrobial properties of the prepared films were investigated as a function of their CNC/ZnO-AgNP content and compared with PVA/chitosan/CNC bionanocomposite films. X-ray diffraction and field emission scanning electron microscopic analyses showed that the CNC/ZnO-AgNPs were homogeneously dispersed in the PVA/Cs matrix and the crystallinity increased with increasing nanosized filler content. Compared with pure PVA/Cs, the tensile strength and modulus in the films increased from 0.055 to 0.205 GPa and from 0.395 to 1.20 GPa, respectively. Ultraviolet and visible light can be efficiently absorbed by incorporating ZnO-AgNPs into a PVA/Cs matrix, suggesting that these bionanocomposite films show good visibility and ultraviolet-shielding effects. The bionanocomposite films had excellent antimicrobial properties, killing both Gram-negative Salmonella choleraesuis and Gram-positive Staphylococcus aureus. The enhanced physical properties achieved by incorporating CNC/ZnO-AgNPs could be beneficial in various applications.
doi:10.2147/IJN.S60274
PMCID: PMC4003268  PMID: 24790433
multifunctional nanofiller; bionanocomposite; cellulose nanocrystals; antimicrobial properties; poly(vinyl alcohol)/chitosan blend
10.  Effect of different spiking procedures on the distribution and toxicity of ZnO nanoparticles in soil 
Ecotoxicology (London, England)  2012;21(7):1797-1804.
Due to the difficulty in dispersing some engineered nanomaterials in exposure media, realizing homogeneous distributions of nanoparticles (NP) in soil may pose major challenges. The present study investigated the distribution of zinc oxide (ZnO) NP (30 nm) and non-nano ZnO (200 nm) in natural soil using two different spiking procedures, i.e. as dry powder and as suspension in soil extract. Both spiking procedures showed a good recovery (>85 %) of zinc and based on total zinc concentrations no difference was found between the two spiking methods. Both spiking procedures resulted in a fairly homogeneous distribution of the ZnO particles in soil, as evidenced by the low variation in total zinc concentration between replicate samples (<12 % in most cases). Survival of Folsomia candida in soil spiked at concentrations up to 6,400 mg Zn kg−1 d.w. was not affected for both compounds. Reproduction was reduced in a concentration-dependent manner with EC50 values of 3,159 and 2,914 mg Zn kg−1 d.w. for 30 and 200 nm ZnO spiked as dry powder and 3,593 and 5,633 mg Zn kg−1 d.w. introduced as suspension. Toxicity of ZnO at 30 and 200 nm did not differ. We conclude that the ZnO particle toxicity is not size related and that the spiking of the soil with ZnO as dry powder or as a suspension in soil extract does not affect its toxicity to F. candida.
doi:10.1007/s10646-012-0914-3
PMCID: PMC3431463  PMID: 22552447
Zinc oxide nanoparticles; Soil; Spiking; Folsomia candida; Ecotoxicity
11.  Characterization of the nonlinear optical properties of nanocrystals by Hyper Rayleigh Scattering 
Journal of Nanobiotechnology  2013;11(Suppl 1):S8.
Background
Harmonic Nanoparticles are a new family of exogenous markers for multiphoton imaging exerting optical contrast by second harmonic (SH) generation. In this tutorial, we present the application of Hyper-Rayleigh Scattering (HRS) for a quantitative assessment of the nonlinear optical properties of these particles and discuss the underlying theory and some crucial experimental aspects.
Methods
The second harmonic properties of BaTiO3, KNbO3, KiTiOPO4 (KTP), LiNbO3 and ZnO nanocrystals (NCs) are investigated by HRS measurements after careful preparation and characterization of colloidal suspensions.
Results
A detailed analysis of the experimental results is presented with emphasis on the theoretical background and on the influence of some experimental parameters including the accurate determination of the nanocrystal size and concentration. The SH generation efficiency and averaged nonlinear optical coefficients are then derived and compared for six different types of NCs.
Conclusions
After preparation of colloidal NC suspensions and careful examination of their size, concentration and possible aggregation state, HRS appears as a valuable tool to quantitatively assess the SH efficiency of noncentrosymmetric NCs. All the investigated nanomaterials show high SH conversion efficiencies, demonstrating a good potential for bio-labelling applications.
doi:10.1186/1477-3155-11-S1-S8
PMCID: PMC4029443  PMID: 24564891
12.  Improvement of Flame-made ZnO Nanoparticulate Thick Film Morphology for Ethanol Sensing 
Sensors (Basel, Switzerland)  2007;7(5):650-675.
ZnO nanoparticles were produced by flame spray pyrolysis using zinc naphthenate as a precursor dissolved in toluene/acetonitrile (80/20 vol%). The particles properties were analyzed by XRD, BET. The ZnO particle size and morphology was observed by SEM and HR-TEM revealing spheroidal, hexagonal, and rod-like morphologies. The crystallite sizes of ZnO spheroidal and hexagonal particles ranged from 10-20 nm. ZnO nanorods were ranged from 10-20 nm in width and 20-50 nm in length. Sensing films were produced by mixing the nanoparticles into an organic paste composed of terpineol and ethyl cellulose as a vehicle binder. The paste was doctor-bladed onto Al2O3 substrates interdigitated with Au electrodes. The morphology of the sensing films was analyzed by optical microscopy and SEM analysis. Cracking of the sensing films during annealing process was improved by varying the heating conditions. The gas sensing of ethanol (25-250 ppm) was studied at 400 °C in dry air containing SiC as the fluidized particles. The oxidation of ethanol on the surface of the semiconductor was confirmed by mass spectroscopy (MS). The effect of micro-cracks was quantitatively accounted for as a provider of extra exposed edges. The sensitivity decreased notably with increasing crack of sensing films. It can be observed that crack widths were reduced with decreasing heating rates. Crack-free of thick (5 μm) ZnO films evidently showed higher sensor signal and faster response times (within seconds) than cracked sensor. The sensor signal increased and the response time decreased with increasing ethanol concentration.
PMCID: PMC3785690
ZnO; Flame spray pyrolysis; Crack; Ethanol sensor
13.  In vivo imaging of immune cell dynamics in skin in response to zinc-oxide nanoparticle exposure 
Biomedical Optics Express  2013;4(10):1817-1828.
Zinc oxide (ZnO) nanoparticles (NPs) are widely used in cosmetic and sunscreen products which are applied topically to the skin. Despite their widespread use, the safety and biological response of these particles remains an active area of investigation. In this paper we present methods based on in vivo multiphoton microscopy (MPM) in skin to address relevant questions about the potential toxicity and immunological response of ZnO NPs. Registration of time-lapse volumetric MPM images allows the same skin site to be tracked across multiple days for visualizing and quantifying cellular and structural changes in response to NP exposure. Making use of the unique optical properties of ZnO enables high contrast detection of the NPs in the presence of strong autofluorescence and second harmonic generation (SHG) background from the skin. A green fluorescent protein (GFP) bone marrow (BM) transplanted mouse model is used to visualize and assess the dynamic response of BM-derived immune cells. These cells are visualized to assess the potential for ZnO NPs to interact with immune cells and elicit an immune reaction in skin. We investigate both topical and dermal exposure of the ZnO NPs. The methods and findings presented in this paper demonstrate a novel approach for tracking ZnO NPs in vivo and for visualizing the cellular response of the exposed tissue to assess the immunological response and potential toxicity of these particles.
doi:10.1364/BOE.4.001817
PMCID: PMC3799648  PMID: 24156046
(180.4315) Nonlinear microscopy; (170.0170) Medical optics and biotechnology; (160.4236) Nanomaterials; (170.1420) Biology
14.  Optical properties of ZnO/BaCO3 nanocomposites in UV and visible regions 
Nanoscale Research Letters  2014;9(1):399.
Pure zinc oxide and zinc oxide/barium carbonate nanoparticles (ZnO-NPs and ZB-NPs) were synthesized by the sol–gel method. The prepared powders were characterized by X-ray diffraction (XRD), ultraviolet–visible (UV–Vis), Auger spectroscopy, and transmission electron microscopy (TEM). The XRD result showed that the ZnO and BaCO3 nanocrystals grow independently. The Auger spectroscopy proved the existence of carbon in the composites besides the Zn, Ba, and O elements. The UV–Vis spectroscopy results showed that the absorption edge of ZnO nanoparticles is redshifted by adding barium carbonate. In addition, the optical parameters including the refractive index and permittivity of the prepared samples were calculated using the UV–Vis spectra.
PACS
81.05.Dz; 78.40.Tv; 42.70.-a.
doi:10.1186/1556-276X-9-399
PMCID: PMC4145363  PMID: 25177218
Optical; Composite materials; Ceramic materials
15.  Gas sensing properties of conducting polymer/Au-loaded ZnO nanoparticle composite materials at room temperature 
Nanoscale Research Letters  2014;9(1):467.
In this work, a new poly (3-hexylthiophene):1.00 mol% Au-loaded zinc oxide nanoparticles (P3HT:Au/ZnO NPs) hybrid sensor is developed and systematically studied for ammonia sensing applications. The 1.00 mol% Au/ZnO NPs were synthesized by a one-step flame spray pyrolysis (FSP) process and mixed with P3HT at different mixing ratios (1:1, 2:1, 3:1, 4:1, and 1:2) before drop casting on an Al2O3 substrate with interdigitated gold electrodes to form thick film sensors. Particle characterizations by X-ray diffraction (XRD), nitrogen adsorption analysis, and high-resolution transmission electron microscopy (HR-TEM) showed highly crystalline ZnO nanoparticles (5 to 15 nm) loaded with ultrafine Au nanoparticles (1 to 2 nm). Film characterizations by XRD, field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, and atomic force microscopy (AFM) revealed the presence of P3HT/ZnO mixed phases and porous nanoparticle structures in the composite thick film. The gas sensing properties of P3HT:1.00 mol% Au/ZnO NPs composite sensors were studied for reducing and oxidizing gases (NH3, C2H5OH, CO, H2S, NO2, and H2O) at room temperature. It was found that the composite film with 4:1 of P3HT:1.00 mol% Au/ZnO NPs exhibited the best NH3 sensing performances with high response (approximately 32 to 1,000 ppm of NH3), fast response time (4.2 s), and high selectivity at room temperature. Plausible mechanisms explaining the enhanced NH3 response by composite films were discussed.
doi:10.1186/1556-276X-9-467
PMCID: PMC4159556  PMID: 25246871
P3HT; Au-loaded ZnO; Composite films; NH3 sensor; Flame spray pyrolysis
16.  Effects of Palladium Loading on the Response of a Thick Film Flame-made ZnO Gas Sensor for Detection of Ethanol Vapor 
Sensors (Basel, Switzerland)  2007;7(7):1159-1184.
ZnO nanoparticles doped with 0-5 mol% Pd were successfully produced in a single step by flame spray pyrolysis (FSP) using zinc naphthenate and palladium (II) acetylacetonate dissolved in toluene-acetonitrile (80:20 vol%) as precursors. The effect of Pd loading on the ethanol gas sensing performance of the ZnO nanoparticles and the crystalline sizes were investigated. The particle properties were analyzed by XRD, BET, AFM, SEM (EDS line scan mode), TEM, STEM, EDS, and CO-pulse chemisorption measurements. A trend of an increase in specific surface area of samples and a decrease in the dBET with increasing Pd concentrations was noted. ZnO nanoparticles were observed as particles presenting clear spheroidal, hexagonal and rod-like morphologies. The sizes of ZnO spheroidal and hexagonal particle crystallites were in the 10-20 nm range. ZnO nanorods were in the range of 10-20 nm in width and 20-50 nm in length. The size of Pd nanoparticles increased and Pd-dispersion% decreased with increasing Pd concentrations. The sensing films were produced by mixing the particles into an organic paste composed of terpineol and ethyl cellulose as a vehicle binder. The paste was doctor-bladed onto Al2O3 substrates interdigitated with Au electrodes. The film morphology was analyzed by SEM and EDS analyses. The gas sensing of ethanol (25-250 ppm) was studied in dry air at 400°C. The oxidation of ethanol on the sensing surface of the semiconductor was confirmed by MS. A well-dispersed of 1 mol%Pd/ZnO films showed the highest sensitivity and the fastest response time (within seconds).
PMCID: PMC3923181
Flame spray pyrolysis; ZnO; Palladium; Ethanol sensor
17.  Core/Shell NaGdF4:Nd3+/NaGdF4 Nanocrystals with Efficient Near-Infrared to Near-Infrared Downconversion Photoluminescence for Bioimaging Applications 
ACS nano  2012;6(4):2969-2977.
We have synthesized core/shell NaGdF4:Nd3+/NaGdF4 nanocrystals with an average size of 15 nm and exceptionally high photoluminescence (PL) quantum yield. When excited at 740 nm, the nanocrystals manifest spectrally distinguished, near infrared to near infrared (NIR-to-NIR) downconversion PL peaked at ~900, ~1050, and ~1300 nm. The absolute quantum yield of NIR-to-NIR PL reached 40% for core-shell nanoparticles dispersed in hexane. Time-resolved PL measurements revealed that this high quantum yield was achieved through suppression of nonradiative recombination originating from surface states and cross relaxations between dopants. NaGdF4:Nd3+/NaGdF4 nanocrystals, synthesized in organic media, were further converted to be water-dispersible by eliminating the capping ligand of oleic acid. NIR-to-NIR PL bioimaging was demonstrated both in vitro and in vivo through visualization of the NIR-to-NIR PL at ~900 nm under incoherent lamp light excitation. The fact that both excitation and the PL of these nanocrystals are in the biological window of optical transparency, combined with their high quantum efficiency, spectral sharpness and photostability, makes these nanocrystals extremely promising as optical biomaging probes.
doi:10.1021/nn2042362
PMCID: PMC3430515  PMID: 22401578
near-infrared; photoluminescence; nanocrystals; lanthanide; bioimaging
18.  Enhanced Sensitivity of Anti-Symmetrically Structured Surface Plasmon Resonance Sensors with Zinc Oxide Intermediate Layers 
Sensors (Basel, Switzerland)  2013;14(1):170-187.
We report a novel design wherein high-refractive-index zinc oxide (ZnO) intermediary layers are used in anti-symmetrically structured surface plasmon resonance (SPR) devices to enhance signal quality and improve the full width at half maximum (FWHM) of the SPR reflectivity curve. The surface plasmon (SP) modes of the ZnO intermediary layer were excited by irradiating both sides of the Au film, thus inducing a high electric field at the Au/ZnO interface. We demonstrated that an improvement in the ZnO (002) crystal orientation led to a decrease in the FWHM of the SPR reflectivity curves. We optimized the design of ZnO thin films using different parameters and performed analytical comparisons of the ZnO with conventional chromium (Cr) and indium tin oxide (ITO) intermediary layers. The present study is based on application of the Fresnel equation, which provides an explanation and verification for the observed narrow SPR reflectivity curve and optical transmittance spectra exhibited by (ZnO/Au), (Cr/Au), and (ITO/Au) devices. On exposure to ethanol, the anti-symmetrically structured showed a huge electric field at the Au/ZnO interface and a 2-fold decrease in the FWHM value and a 1.3-fold larger shift in angle interrogation and a 4.5-fold high-sensitivity shift in intensity interrogation. The anti-symmetrically structured of ZnO intermediate layers exhibited a wider linearity range and much higher sensitivity. It also exhibited a good linear relationship between the incident angle and ethanol concentration in the tested range. Thus, we demonstrated a novel and simple method for fabricating high-sensitivity, high-resolution SPR biosensors that provide high accuracy and precision over relevant ranges of analyte measurement.
doi:10.3390/s140100170
PMCID: PMC3926552  PMID: 24361929
intermediary layer; surface plasmon resonance (SPR); zinc oxide (ZnO); full width at half maximum (FWHM)
19.  Direct synthesis and characterization of optically transparent conformal zinc oxide nanocrystalline thin films by rapid thermal plasma CVD 
Nanoscale Research Letters  2011;6(1):568.
We report a rapid, self-catalyzed, solid precursor-based thermal plasma chemical vapor deposition process for depositing a conformal, nonporous, and optically transparent nanocrystalline ZnO thin film at 130 Torr (0.17 atm). Pure solid zinc is inductively heated and melted, followed by ionization by thermal induction argon/oxygen plasma to produce conformal, nonporous nanocrystalline ZnO films at a growth rate of up to 50 nm/min on amorphous and crystalline substrates including Si (100), fused quartz, glass, muscovite, c- and a-plane sapphire (Al2O3), gold, titanium, and polyimide. X-ray diffraction indicates the grains of as-deposited ZnO to be highly textured, with the fastest growth occurring along the c-axis. The individual grains are observed to be faceted by (103) planes which are the slowest growth planes. ZnO nanocrystalline films of nominal thicknesses of 200 nm are deposited at substrate temperatures of 330°C and 160°C on metal/ceramic substrates and polymer substrates, respectively. In addition, 20-nm- and 200-nm-thick films are also deposited on quartz substrates for optical characterization. At optical spectra above 375 nm, the measured optical transmittance of a 200-nm-thick ZnO film is greater than 80%, while that of a 20-nm-thick film is close to 100%. For a 200-nm-thick ZnO film with an average grain size of 100 nm, a four-point probe measurement shows electrical conductivity of up to 910 S/m. Annealing of 200-nm-thick ZnO films in 300 sccm pure argon at temperatures ranging from 750°C to 950°C (at homologous temperatures between 0.46 and 0.54) alters the textures and morphologies of the thin film. Based on scanning electron microscope images, higher annealing temperatures appear to restructure the ZnO nanocrystalline films to form nanorods of ZnO due to a combination of grain boundary diffusion and bulk diffusion.
PACS: films and coatings, 81.15.-z; nanocrystalline materials, 81.07.Bc; II-VI semiconductors, 81.05.Dz.
doi:10.1186/1556-276X-6-568
PMCID: PMC3227690  PMID: 22040295
zinc oxide; transparent nanocrystalline film; thermal plasma chemical vapor deposition; annealing; nanorods
20.  The role of particle size of particulate nano-zinc oxide wood preservatives on termite mortality and leach resistance 
Nanoscale Research Letters  2011;6(1):427.
Historically most residential wood preservatives were aqueous soluble metal formulations, but recently metals ground to submicron size and dispersed in water to give particulate formulations have gained importance. In this study, the specific role nano-zinc oxide (ZnO) particle size and leach resistance plays in termite mortality resulting from exposure to particulate ZnO-treated wood was investigated. Southern yellow pine (SYP) sapwood impregnated with three concentrations of two particle sizes (30 and 70 nm) of ZnO were compared to wood treated with soluble zinc sulphate (ZnSO4) preservative for leach resistance and termite resistance. Less than four percent leached from the particulate nano-ZnO-treated specimens, while 13 to 25% of the zinc sulphate leached from the soluble treated wood. Nano-ZnO was essentially non-leachable from wood treated with 5% formulation for the 30-nm particle size. In a no-choice laboratory test, eastern subterranean termites (Reticulitermes flavipes) consumed less than 10% of the leached nano-ZnO-treated wood with 93 to 100% mortality in all treatment concentrations. In contrast, termites consumed 10 to 12% of the leached ZnSO4-treated wood, but with lower mortality: 29% in the 1% treatment group and less than 10% (5 and 8%, respectively) in the group of wood blocks treated with 2.5 and 5.0% ZnSO4. We conclude that termites were repelled from consuming wood treated with nano-ZnO, but when consumed it was more toxic to eastern subterranean termites than wood treated with the soluble metal oxide formulation. There were no differences in leaching or termite mortality between the two particle sizes of nano-ZnO.
doi:10.1186/1556-276X-6-427
PMCID: PMC3211844  PMID: 21711491
21.  Titanium dioxide and zinc oxide nanoparticles in sunscreens: focus on their safety and effectiveness 
Sunscreens are used to provide protection against adverse effects of ultraviolet (UV)B (290–320 nm) and UVA (320–400 nm) radiation. According to the United States Food and Drug Administration, the protection factor against UVA should be at least one-third of the overall sun protection factor. Titanium dioxide (TiO2) and zinc oxide (ZnO) minerals are frequently employed in sunscreens as inorganic physical sun blockers. As TiO2 is more effective in UVB and ZnO in the UVA range, the combination of these particles assures a broad-band UV protection. However, to solve the cosmetic drawback of these opaque sunscreens, microsized TiO2 and ZnO have been increasingly replaced by TiO2 and ZnO nanoparticles (NPs) (<100 nm). This review focuses on significant effects on the UV attenuation of sunscreens when microsized TiO2 and ZnO particles are replaced by NPs and evaluates physicochemical aspects that affect effectiveness and safety of NP sunscreens. With the use of TiO2 and ZnO NPs, the undesired opaqueness disappears but the required balance between UVA and UVB protection can be altered. Utilization of mixtures of micro- and nanosized ZnO dispersions and nanosized TiO2 particles may improve this situation. Skin exposure to NP-containing sunscreens leads to incorporation of TiO2 and ZnO NPs in the stratum corneum, which can alter specific NP attenuation properties due to particle–particle, particle–skin, and skin–particle–light physicochemical interactions. Both sunscreen NPs induce (photo)cyto- and genotoxicity and have been sporadically observed in viable skin layers especially in case of long-term exposures and ZnO. Photocatalytic effects, the highest for anatase TiO2, cannot be completely prevented by coating of the particles, but silica-based coatings are most effective. Caution should still be exercised when new sunscreens are developed and research that includes sunscreen NP stabilization, chronic exposures, and reduction of NPs’ free-radical production should receive full attention.
Video abstract
doi:10.2147/NSA.S19419
PMCID: PMC3781714  PMID: 24198489
skin barrier; TiO2; ZnO; nanoparticles; physicochemical; scattering; blue shift; UV-radiation; (photo) toxicity; cancer
22.  Annealing temperature and environment effects on ZnO nanocrystals embedded in SiO2: a photoluminescence and TEM study 
Nanoscale Research Letters  2013;8(1):517.
We report on efficient ZnO nanocrystal (ZnO-NC) emission in the near-UV region. We show that luminescence from ZnO nanocrystals embedded in a SiO2 matrix can vary significantly as a function of the annealing temperature from 450°C to 700°C. We manage to correlate the emission of the ZnO nanocrystals embedded in SiO2 thin films with transmission electron microscopy images in order to optimize the fabrication process. Emission can be explained using two main contributions, near-band-edge emission (UV range) and defect-related emissions (visible). Both contributions over 500°C are found to be size dependent in intensity due to a decrease of the absorption cross section. For the smallest-size nanocrystals, UV emission can only be accounted for using a blueshifted UV contribution as compared to the ZnO band gap. In order to further optimize the emission properties, we have studied different annealing atmospheres under oxygen and under argon gas. We conclude that a softer annealing temperature at 450°C but with longer annealing time under oxygen is the most preferable scenario in order to improve near-UV emission of the ZnO nanocrystals embedded in an SiO2 matrix.
doi:10.1186/1556-276X-8-517
PMCID: PMC4029520  PMID: 24314071
ZnO nanocrystals; Photoluminescence; UV emission
23.  One-step DNA-programmed growth of luminescent and biofunctionalized nanocrystals 
Nature nanotechnology  2008;4(2):121-125.
Colloidal semiconductor nanocrystals are widely used as lumiphores in biological imaging because their luminescence is both strong and stable, and because they can be biofunctionalized. During synthesis, nanocrystals are typically passivated with hydrophobic organic ligands1, so it is then necessary either to replace these ligands or encapsulate the nanocrystals with hydrophilic moieties to make the lumiphores soluble in water. Finally, biological labels must be added to allow the detection of nucleic acids, proteins and specific cell types2-8. This multistep process is time- and labour-intensive and thus out of reach of many researchers who want to use luminescent nanocrystals as customized lumiphores. Here, we show that a single designer ligand—a chimeric DNA molecule—can controllably program both the growth and the biofunctionalization of the nanocrystals. One part of the DNA sequence controls the nanocrystal passivation and serves as a ligand, while another part controls the biorecognition. The synthetic protocol reported here is straightforward and produces a homogeneous dispersion of nanocrystal lumiphores functionalized with a single biomolecular receptor. The nanocrystals exhibit strong optical emission in the visible region, minimal toxicity and have hydrodynamic diameters of ∼6 nm, which makes them suitable for bioimaging4. We show that the nanocrystals can specifically bind DNA, proteins or cells that have unique surface recognition markers.
doi:10.1038/nnano.2008.373
PMCID: PMC2667941  PMID: 19197315
24.  Effect of substrate (ZnO) morphology on enzyme immobilization and its catalytic activity 
Nanoscale Research Letters  2011;6(1):450.
In this study, zinc oxide (ZnO) nanocrystals with different morphologies were synthesized and used as substrates for enzyme immobilization. The effects of morphology of ZnO nanocrystals on enzyme immobilization and their catalytic activities were investigated. The ZnO nanocrystals were prepared through a hydrothermal procedure using tetramethylammonium hydroxide as a mineralizing agent. The control on the morphology of ZnO nanocrystals was achieved by varying the ratio of CH3OH to H2O, which were used as solvents in the hydrothermal reaction system. The surface of as-prepared ZnO nanoparticles was functionalized with amino groups using 3-aminopropyltriethoxysilane and tetraethyl orthosilicate, and the amino groups on the surface were identified and calculated by FT-IR and the Kaiser assay. Horseradish peroxidase was immobilized on as-modified ZnO nanostructures with glutaraldehyde as a crosslinker. The results showed that three-dimensional nanomultipod is more appropriate for the immobilization of enzyme used further in catalytic reaction.
doi:10.1186/1556-276X-6-450
PMCID: PMC3211870  PMID: 21752255
25.  Functionalised zinc oxide nanowire gas sensors: Enhanced NO2 gas sensor response by chemical modification of nanowire surfaces 
Summary
Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.
doi:10.3762/bjnano.3.43
PMCID: PMC3388361  PMID: 23016141
gas sensor; nanowire; tris(hydroxymethyl)aminomethane; self-assembled monolayer; zinc oxide

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