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1.  Sustained Release of a Monoclonal Antibody from Electrochemically Prepared Mesoporous Silicon Oxide 
Advanced functional materials  2010;20(23):4168-4174.
Nanostructured mesoporous silica (SiO2) films are used to load and release the monoclonal antibody bevacizumab (Avastin) in vitro. A biocompatible and biodegradable form of mesoporous SiO2 is prepared by electrochemical etching of single crystalline Si, followed by thermal oxidation in air at 800 °C. Porous SiO2 exhibits a negative surface charge at physiological pH (7.4), allowing it to spontaneously adsorb the positively charged antibody from an aqueous phosphate buffered saline solution. This electrostatic adsorption allows bevacizumab to be concentrated by >100× (300 mg bevacziumab per gram of porous SiO2 when loaded from a 1 mg mL−1 solution of bevacziumab). Drug loading is monitored by optical interferometric measurements of the thin porous film. A two-component Bruggeman effective medium model is employed to calculate percent porosity and film thickness, and is further used to determine the extent of drug loading into the porous SiO2 film. In vitro drug release profiles are characterized by an enzyme-linked immunosorbent assay (ELISA), which confirms that the antibody is released in its active, VEGF-binding form. The nanostructured delivery system described here provides a sustained release of the monoclonal antibody where approximately 98% of drug is released over a period of one month.
PMCID: PMC3026353  PMID: 21274422
2.  Biogenic Hierarchical TiO2/SiO2 Derived from Rice Husk and Enhanced Photocatalytic Properties for Dye Degradation 
PLoS ONE  2011;6(9):e24788.
Rice husk, an agricultural bioresource, is utilized as a non-metallic bio-precursor to synthesize biogenic hierarchical TiO2/SiO2 (BH-TiO2/SiO2) and the products are applied to dye degradation.
Methodology/Principal Findings
The as-prepared BH-TiO2/SiO2 samples are characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), nitrogen-adsorption measurement, UV-vis spectroscopy and electronic paramagnetic resonance (EPR). The results show that BH-TiO2/SiO2 possesses both anatase and rutile phases with amorphous SiO2 as background, which contains mesopore structure, and nitrogen derived from original rice husk is self-doped into the lattice. Besides, the light-harvesting within the visible-light range of BH-TiO2/SiO2 has been enhanced. Moreover, the catalytic activity of BH-TiO2/SiO2 has been proven by EPR, and both the photocatalytic activity and stability of BH-TiO2/SiO2 are improved as well, which has been illustrated by cycled degradation of methylene blue dye under irradiation.
This work provides a good way to combine natural hierarchical porous structure with synthetic material chemistry based on available biomass in the vast natural environment for the sustainable development of human society, and extends potentials of biomass in applications such as photocatalysts, sunlight splitting water and so forth.
PMCID: PMC3170388  PMID: 21931853
3.  Multi-Directional Growth of Aligned Carbon Nanotubes Over Catalyst Film Prepared by Atomic Layer Deposition 
Nanoscale Research Letters  2010;5(10):1555-1560.
The structure of vertically aligned carbon nanotubes (CNTs) severely depends on the properties of pre-prepared catalyst films. Aiming for the preparation of precisely controlled catalyst film, atomic layer deposition (ALD) was employed to deposit uniform Fe2O3 film for the growth of CNT arrays on planar substrate surfaces as well as the curved ones. Iron acetylacetonate and ozone were introduced into the reactor alternately as precursors to realize the formation of catalyst films. By varying the deposition cycles, uniform and smooth Fe2O3 catalyst films with different thicknesses were obtained on Si/SiO2 substrate, which supported the growth of highly oriented few-walled CNT arrays. Utilizing the advantage of ALD process in coating non-planar surfaces, uniform catalyst films can also be successfully deposited onto quartz fibers. Aligned few-walled CNTs can be grafted on the quartz fibers, and they self-organized into a leaf-shaped structure due to the curved surface morphology. The growth of aligned CNTs on non-planar surfaces holds promise in constructing hierarchical CNT architectures in future.
Electronic supplementary material
The online version of this article (doi:10.1007/s11671-010-9676-0) contains supplementary material, which is available to authorized users.
PMCID: PMC2956049  PMID: 21076673
Aligned carbon nanotubes; Atomic layer deposition; Chemical vapor deposition; Catalysis; Nanotechnology
4.  Multi-Directional Growth of Aligned Carbon Nanotubes Over Catalyst Film Prepared by Atomic Layer Deposition 
Nanoscale Research Letters  2010;5(10):1555-1560.
The structure of vertically aligned carbon nanotubes (CNTs) severely depends on the properties of pre-prepared catalyst films. Aiming for the preparation of precisely controlled catalyst film, atomic layer deposition (ALD) was employed to deposit uniform Fe2O3 film for the growth of CNT arrays on planar substrate surfaces as well as the curved ones. Iron acetylacetonate and ozone were introduced into the reactor alternately as precursors to realize the formation of catalyst films. By varying the deposition cycles, uniform and smooth Fe2O3 catalyst films with different thicknesses were obtained on Si/SiO2 substrate, which supported the growth of highly oriented few-walled CNT arrays. Utilizing the advantage of ALD process in coating non-planar surfaces, uniform catalyst films can also be successfully deposited onto quartz fibers. Aligned few-walled CNTs can be grafted on the quartz fibers, and they self-organized into a leaf-shaped structure due to the curved surface morphology. The growth of aligned CNTs on non-planar surfaces holds promise in constructing hierarchical CNT architectures in future.
PMCID: PMC2956049  PMID: 21076673
Aligned carbon nanotubes; Atomic layer deposition; Chemical vapor deposition; Catalysis; Nanotechnology
5.  Resolution Enhancement in Surface Plasmon Resonance Sensor Based on Waveguide Coupled Mode by Combining a Bimetallic Approach 
Sensors (Basel, Switzerland)  2010;10(12):11390-11399.
In this study, we present and demonstrate a new route to a great enhancement in resolution of surface plasmon resonance sensors. Basically, our approach combines a waveguide coupled plasmonic mode and a kind of Au/Ag bimetallic enhancement concept. Theoretical modeling was carried out by solving Fresnel equations for the multilayer stack of prism/Ag inner-metal layer/dielectric waveguide/Au outer-metal layer. The inner Ag layer couples incident light to a guided wave and makes more fields effectively concentrated on the outer Au surface. A substantial enhancement in resolution was experimentally verified for the model stack using a ZnS-SiO2 waveguide layer.
PMCID: PMC3231050  PMID: 22163533
waveguide coupled surface plasmon resonance; bimetallic approach; high resolution SPR sensor
6.  A Single-Walled Carbon Nanotube Network Gas Sensing Device 
Sensors (Basel, Switzerland)  2011;11(8):7763-7772.
The goal of this research was to develop a chemical gas sensing device based on single-walled carbon nanotube (SWCNT) networks. The SWCNT networks are synthesized on Al2O3-deposted SiO2/Si substrates with 10 nm-thick Fe as the catalyst precursor layer using microwave plasma chemical vapor deposition (MPCVD). The development of interconnected SWCNT networks can be exploited to recognize the identities of different chemical gases by the strength of their particular surface adsorptive and desorptive responses to various types of chemical vapors. The physical responses on the surface of the SWCNT networks cause superficial changes in the electric charge that can be converted into electronic signals for identification. In this study, we tested NO2 and NH3 vapors at ppm levels at room temperature with our self-made gas sensing device, which was able to obtain responses to sensitivity changes with a concentration of 10 ppm for NO2 and 24 ppm for NH3.
PMCID: PMC3231699  PMID: 22164044
single-walled carbon nanotube (SWCNT) networks; gas sensing device; chemical vapors
7.  Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation 
Nanoscale Research Letters  2011;6(1):586.
Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions.
PMCID: PMC3240672  PMID: 22067075
8.  Effect of surrounding environment on atomic structure and equilibrium shape of growing nanocrystals: gold in/on SiO2 
Nanoscale Research Letters  2007;2(5):240-247.
We report on the equilibrium shape and atomic structure of thermally-processed Au nanocrystals (NCs) as determined by high resolution transmission electron microscopy (TEM). The NCs were either deposited on SiO2surface or embedded in SiO2layer. Quantitative data on the NCs surface free energy were obtained via the inverse Wulff construction. Nanocrystals inside the SiO2layer are defect-free and maintain a symmetrical equilibrium shape during the growth. Nanocrystals on SiO2surface exhibit asymmetrical equilibrium shape that is characterized by the introduction of twins and more complex atomic defects above a critical size. The observed differences in the equilibrium shape and atomic structure evolution of growing NCs in and on SiO2is explained in terms of evolution in isotropic/anisotropic environment making the surface free energy function angular and/or radial symmetric/asymmetric affecting the rotational/translational invariance of the surface stress tensor.
PMCID: PMC3246344  PMID: 21798104
Nanocrystal; Crystal growth; Transmission electron microscopy; Wulff plot; Surface energy; Gold; SiO2
9.  Silicon nanowires prepared by electron beam evaporation in ultrahigh vacuum 
Nanoscale Research Letters  2012;7(1):243.
One-dimensional silicon nanowires (SiNWs) were prepared by electron beam evaporation in ultrahigh vacuum (UHV). The SiNWs can be grown through either vapor–liquid-solid (VLS) or oxide-assisted growth (OAG) mechanism. In VLS growth, SiNWs can be formed on Si surface, not on SiO2 surfaces. Moreover, low deposition rate is helpful for producing lateral SiNWs by VLS. But in OAG process, SiNWs can be grown on SiO2 surfaces, not on Si surfaces. This work reveals the methods of producing large-scale SiNWs in UHV.
PMCID: PMC3403976  PMID: 22559207
Silicon nanowires; Preparation; Vapor–liquid-solid; Oxide-assisted growth; Ultrahigh vacuum
10.  Macroscale adhesion of gecko setae reflects nanoscale differences in subsurface composition 
Surface energies are commonly used to determine the adhesion forces between materials. However, the component of surface energy derived from long-range forces, such as van der Waals forces, depends on the material's structure below the outermost atomic layers. Previous theoretical results and indirect experimental evidence suggest that the van der Waals energies of subsurface layers will influence interfacial adhesion forces. We discovered that nanometre-scale differences in the oxide layer thickness of silicon wafers result in significant macroscale differences in the adhesion of isolated gecko setal arrays. Si/SiO2 bilayer materials exhibited stronger adhesion when the SiO2 layer is thin (approx. 2 nm). To further explore how layered materials influence adhesion, we functionalized similar substrates with an octadecyltrichlorosilane monolayer and again identified a significant influence of the SiO2 layer thickness on adhesion. Our theoretical calculations describe how variation in the SiO2 layer thickness produces differences in the van der Waals interaction potential, and these differences are reflected in the adhesion mechanics. Setal arrays used as tribological probes provide the first empirical evidence that the ‘subsurface energy’ of inhomogeneous materials influences the macroscopic surface forces.
PMCID: PMC3565786  PMID: 22993246
van der Waals forces; gecko adhesion; surface energy
11.  Engineering functional protein interfaces for immunologically modified field effect transistor (ImmunoFET) by molecular genetic means 
The attachment and interactions of analyte receptor biomolecules at solid–liquid interfaces are critical to development of hybrid biological–synthetic sensor devices across all size regimes. We use protein engineering approaches to engineer the sensing interface of biochemically modified field effect transistor sensors (BioFET). To date, we have deposited analyte receptor proteins on FET sensing channels by direct adsorption, used self-assembled monolayers to tether receptor proteins to planar FET SiO2 sensing gates and demonstrated interface biochemical function and electrical function of the corresponding sensors. We have also used phage display to identify short peptides that recognize thermally grown SiO2. Our interest in these peptides is as affinity domains that can be inserted as translational fusions into receptor proteins (antibody fragments or other molecules) to drive oriented interaction with FET sensing surfaces. We have also identified single-chain fragment variables (scFvs, antibody fragments) that recognize an analyte of interest as potential sensor receptors. In addition, we have developed a protein engineering technology (scanning circular permutagenesis) that allows us to alter protein topography to manipulate the position of functional domains of the protein relative to the BioFET sensing surface.
PMCID: PMC2605506  PMID: 17580287
biosensors; interface engineering; surface modifications; protein engineering
12.  Electrical behavior of MIS devices based on Si nanoclusters embedded in SiOxNy and SiO2 films 
Nanoscale Research Letters  2011;6(1):170.
We examined and compared the electrical properties of silica (SiO2) and silicon oxynitride (SiOxNy) layers embedding silicon nanoclusters (Sinc) integrated in metal-insulator-semiconductor (MIS) devices. The technique used for the deposition of such layers is the reactive magnetron sputtering of a pure SiO2 target under a mixture of hydrogen/argon plasma in which nitrogen is incorporated in the case of SiOxNy layer. Al/SiOxNy-Sinc/p-Si and Al/SiO2-Sinc/p-Si devices were fabricated and electrically characterized. Results showed a high rectification ratio (>104) for the SiOxNy-based device and a resistive behavior when nitrogen was not incorporating (SiO2-based device). For rectifier devices, the ideality factor depends on the SiOxNy layer thickness. The conduction mechanisms of both MIS diode structures were studied by analyzing thermal and bias dependences of the carriers transport in relation with the nitrogen content.
PMCID: PMC3211223  PMID: 21711698
13.  Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals 
Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF3@CeF3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, ‘the products’, with an average diameter around 10 nm, showed an increase in the concentration of Tb3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO2 shell.
Graphical Abstract
PMCID: PMC3825480  PMID: 24273438
Nanoparticles; Core/shell; Silica; Luminescence; Rare earth fluorides; Cytotoxicity
14.  Low Magnetic Field Detection Using a CuPt Nano Structure Made on a SiO2/Si Structure 
Sensors (Basel, Switzerland)  2009;9(12):9734-9740.
A Si/SiO2/CuPt structure is formed by depositing a very thin SiO2 layer between CuPt and P-type Si layers using e-beam evaporation. SEM images show the formation of CuPt nano clusters with an average size of less than 100 nm. This structure shows high sensitivity to applied magnetic fields at 77K and at low and high dc voltages such that magnetic field as low as 6 mT is detected using I-V and I–B measurements. The variation of current with various magnetic field strength at the constant voltage shows also an oscillatory behavior. The sensitivity of this structure to magnetic fields is believed to be due to small nano size of the platinum–copper structures as well as their discrete energy states and the tunneling of carriers into the insulating layer. Our results indicate that this structure may be a good candidate for small, simple, low cost and sensitive low magnetic field detectors.
PMCID: PMC3267195  PMID: 22303147
Cu-Pt nano clusters; I-V Curve; magnetic field detection
15.  Simultaneous Adsorption and Degradation of Cr(VI) and Cd(II) Ions from Aqueous Solution by Silica-Coated Fe0 Nanoparticles 
Core-shell silica-coated Fe0 nanoparticles (Fe@SiO2) were prepared in one-step synthesis by aqueous reduction combined with modified Stöber method. The as-prepared Fe@SiO2 were then used for simultaneous removal of Cr(VI) and Cd(II) from aqueous solution. Batch tests indicated that Fe@SiO2 exhibited high removal capacity toward Cr(VI) and Cd(II). Cr(VI) was removed by Fe@SiO2 through reduction rather than adsorption, while Cd(II) removal was mainly through adsorption. The removal rate increased with increasing initial Fe NPs dose and decreased with increasing initial Cr(VI) and Cd(II) concentrations. Cd(II) adsorption was also strengthened by Cr(VI) reduction with the release of OH−. The removals of Cr(VI) and Cd(II) were weakened in the presence of cations or humic acid, as a result of aggregation and less active site of Fe@SiO2. Overall, the simply prepared Fe@SiO2 were potential material for the heavy metals removed from water.
PMCID: PMC3876921  PMID: 24455425
16.  Evaluation of Complexation Ability Using a Sensor Electrode Chip Equipped with a Wireless Screening System 
Sensors (Basel, Switzerland)  2012;12(6):8405-8425.
We fabricated an electrode chip with a structure coated by an insulation layer that contains dispersed SiO2 adsorbent particles modified by an amino-group on a source-drain electrode. Voltage changes caused by chelate molecule adsorption onto electrode surfaces and by specific cation interactions were investigated. The detection of specific cations without the presence of chelate molecules on the free electrode was also examined. By comparing both sets of results the complexation ability of the studied chelate molecules onto the electrode was evaluated. Five pairs of source-drain electrodes(×8 arrays) were fabricated on a glass substrate of 20 × 30mm in size. The individual Au/Cr (1.0/0.1μm thickness) electrodes had widths of 50 μm and an inter-electrode interval of 100μm.The fabricated source-drain electrodes were further coated with an insulation layer comprising a porous SiO2 particle modified amino-group to adsorb the chelate molecules. The electrode chip was equipped with a handy-type sensor signal analyzer that was mounted on an amplifier circuit using a Miniship™ or a system in a packaged LSI device. For electrode surfaces containing different adsorbed chelate molecules an increase in the sensor voltage depended on a combination of host-guest reactions and generally decreased in the following order:5,10,15,20-tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphine, tetrakis(p-toluenesulfonate) (TMPyP)as a Cu2+chelator and Cu2+>2-nitroso-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol(nitroso-PSAP) as an Fe2+chelator and Fe2+>4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, disodium salt (BPDSA) as an Fe2+chelatorand Fe2+>3-[3-(2,4-dimethylphenylcarbamoyl)-2-hydroxynaphthalene-1-yl-azo]-4-hydroxybenzenesulfonic acid, sodium salt (XB-1) as a Mg2+chelator and Mg2+>2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, disodium salt (BCIDSA) as a Cu2+chelator and Cu2+, respectively. In contrast, for the electrode surfaces with adsorbed O,O′-bis(2-aminoethyl)ethyleneglycol-N,N,N′,N′-tetraacetic acid (GEDTA) or O,O′-bis(2-aminophenyl)ethyleneglycol-N,N,N′,N′-tetraacetic acid, tetrapotassium salt, hydrate (BAPTA) as a Ca2+chelator no increase in the detection voltage was found for all the electrode tests conducted in the presence of Ca2+.To determine the differences in electrode detection, molecular orbital (MO) calculations of the chelate molecules and surface molecular modeling of the adsorbents were carried out. In accordance with frontier orbital theory, the lowest unoccupied MO (LUMO) of the chelate molecules can accept two lone pair electrons at the highest occupied MO (HOMO) of the amino group on the model surface structure of the SiO2 particle. As a result, a good correlation was obtained between the LUMO-HOMO difference and the ion response of all the electrodes tested. Based on the results obtained, the order of adsorbed chelate molecules on adsorption particles reflects the different metal ion detection abilities of the electrode chips.
PMCID: PMC3436036  PMID: 22969407
chemical adsorption; electrode; chelate; metal ion
17.  Reversible optical doping of graphene 
Scientific Reports  2013;3:2355.
The ultimate surface exposure provided by graphene monolayer makes it the ideal sensor platform but also exposes its intrinsic properties to any environmental perturbations. In this work, we demonstrate that the charge carrier density of graphene exfoliated on a SiO2/Si substrate can be finely and reversibly tuned between hole and electron doping with visible photons. This photo-induced doping happens under moderate laser power conditions but is significantly affected by the substrate cleaning method. In particular, it requires hydrophilic substrates and vanishes for suspended graphene. These findings suggest that optically gated graphene devices operating with a sub-second time scale can be envisioned and that Raman spectroscopy is not always as non-invasive as generally assumed.
PMCID: PMC3733054  PMID: 23912707
18.  In Vivo Biodistribution and Pharmacokinetics of Silica Nanoparticles as a Function of Geometry, Porosity and Surface Characteristics 
The in vivo biodistribution and pharmacokinetics of silica nanoparticles (SiO2) with systematically varied geometries, porosities, and surface characteristics were investigated in immune-competent CD-1 mice via the intravenous injection. The nanoparticles were taken up extensively by the liver and spleen. Mesoporous SiO2 exhibited higher accumulation in the lung than nonporous SiO2 of similar size. This accumulation was reduced by primary amine modification of the nanoparticles. High aspect ratio, amine-modified mesoporous nanorods showed enhanced lung accumulation compared to amine-modified mesoporous nanospheres. Accumulation of the nanoparticles was mainly caused by passive entrapment in the discontinuous openings in the endothelium of the liver and spleen or in the pulmonary capillaries, and was highly dependent on nanoparticle hydrodynamic size in circulation. The SiO2 were likely internalized by the reticulo-endothelial system (RES) following physical sequestration in the liver and spleen. The nanoparticles that were transiently associated with the lung were re-distributed out of this organ without significant internalization. Pharmacokinetic analysis showed that all SiO2 were rapidly cleared from systemic circulation. Amine-modified or nonporous nanoparticles possessed a higher volume of distribution at steady state than their pristine counterparts or mesoporous SiO2. In all, surface characteristics and porosity played important roles in influencing SiO2 biodistribution and pharmacokinetics. Increasing the aspect ratio of amine-modified mesoporous SiO2 from 1 to 8 resulted in increased accumulation in the lung.
PMCID: PMC3476833  PMID: 22684119
silica nanoparticles; nanotoxicity; biodistribution; geometry; porosity
19.  Probing the Chemical Stability of Mixed Ferrites: Implications for MR Contrast Agent Design 
Nanomaterials with mixed composition, in particular magnetic spinel ferrites, are emerging as efficient contrast agents for magnetic resonance imaging (MRI). Many factors, including size, composition, atomic structure, and surface properties are crucial in the design of such nanoparticle-based probes due to their influence on the magnetic properties. Silica-coated iron oxide (IO-SiO2) and cobalt ferrite (CoIO-SiO2) nanoparticles were synthesized using standard high temperature thermal decomposition and base-catalyzed water-in-oil microemulsion techniques. Under neutral aqueous conditions, it was found that 50–75% of the cobalt content in the CoIO-SiO2 nanoparticles leached out of the core structure. Leaching caused a 7.2-fold increase in longitudinal relaxivity and an increase in the saturation magnetization from ~48 emu/g core to ~65 emu/g core. X-ray absorption fine structure studies confirmed that the atomic structure of the ferrite core was altered following leaching, while TEM and DLS confirmed that the morphology and size of the nanoparticle remained unchanged. The CoIO-SiO2 nanoparticles converted from a partially inverted spinel cation arrangement (unleached state) to an inverse spinel arrangement (leached state). The control IO-SiO2 nanoparticles remained stable with no change in structure and negligible changes in magnetic behavior. This detailed analysis highlights how important understanding the properties of nanomaterials is in the development of reliable agents for diagnostic and therapeutic applications.
PMCID: PMC3097046  PMID: 21603070
MRI; ferrite; nanoparticle; leaching; magnetic properties
20.  Properties of silicon dioxide layers with embedded metal nanocrystals produced by oxidation of Si:Me mixture 
Nanoscale Research Letters  2011;6(1):148.
A two-dimensional layers of metal (Me) nanocrystals embedded in SiO2 were produced by pulsed laser deposition of uniformly mixed Si:Me film followed by its furnace oxidation and rapid thermal annealing. The kinetics of the film oxidation and the structural properties of the prepared samples were investigated by Rutherford backscattering spectrometry, and transmission electron microscopy, respectively. The electrical properties of the selected SiO2:Me nanocomposite films were evaluated by measuring C-V and I-V characteristics on a metal-oxide-semiconductor stack. It is found that Me segregation induced by Si:Me mixture oxidation results in the formation of a high density of Me and silicide nanocrystals in thin film SiO2 matrix. Strong evidence of oxidation temperature as well as impurity type effect on the charge storage in crystalline Me-nanodot layer is demonstrated by the hysteresis behavior of the high-frequency C-V curves.
PMCID: PMC3211198  PMID: 21711632
21.  Thermodynamic Properties of Supported and Embedded Metallic Nanocrystals: Gold on/in SiO2 
Nanoscale Research Letters  2008;3(11):454-460.
We report on the calculations of the cohesive energy, melting temperature and vacancy formation energy for Au nanocrystals with different size supported on and embedded in SiO2. The calculations are performed crossing our previous data on the surface free energy of the supported and embedded nanocrystals with the theoretical surface-area-difference model developed by W. H. Qi for the description of the size-dependent thermodynamics properties of low-dimensional solid-state systems. Such calculations are employed as a function of the nanocrystals size and surface energy. For nanocrystals supported on SiO2, as results of the calculations, we obtain, for a fixed nanocrystal size, an almost constant cohesive energy, melting temperature and vacancy formation energy as a function of their surface energy; instead, for those embedded in SiO2, they decreases when the nanocrystal surface free energy increases. Furthermore, the cohesive energy, melting temperature and vacancy formation energy increase when the nanocrystal size increases: for the nanocrystals on SiO2, they tend to the values of the bulk Au; for the nanocrystals in SiO2 in correspondence to sufficiently small values of their surface energy, they are greater than the bulk values. In the case of the melting temperature, this phenomenon corresponds to the experimentally well-known superheating process.
PMCID: PMC3244952  PMID: 21752308
Nanocrystal; Surface energy; Gold; SiO2; Cohesive energy; Melting temperature; Vacancy formation energy
22.  Peel-and-Stick: Mechanism Study for Efficient Fabrication of Flexible/Transparent Thin-film Electronics 
Scientific Reports  2013;3:2917.
Peel-and-stick process, or water-assisted transfer printing (WTP), represents an emerging process for transferring fully fabricated thin-film electronic devices with high yield and fidelity from a SiO2/Si wafer to various non-Si based substrates, including papers, plastics and polymers. This study illustrates that the fundamental working principle of the peel-and-stick process is based on the water-assisted subcritical debonding, for which water reduces the critical adhesion energy of metal-SiO2 interface by 70 ~ 80%, leading to clean and high quality transfer of thin-film electronic devices. Water-assisted subcritical debonding is applicable for a range of metal-SiO2 interfaces, enabling the peel-and-stick process as a general and tunable method for fabricating flexible/transparent thin-film electronic devices.
PMCID: PMC3794378  PMID: 24108063
23.  Simulation of electron transport during electron-beam-induced deposition of nanostructures 
We present a numerical investigation of energy and charge distributions during electron-beam-induced growth of tungsten nanostructures on SiO2 substrates by using a Monte Carlo simulation of the electron transport. This study gives a quantitative insight into the deposition of energy and charge in the substrate and in the already existing metallic nanostructures in the presence of the electron beam. We analyze electron trajectories, inelastic mean free paths, and the distribution of backscattered electrons in different compositions and at different depths of the deposit. We find that, while in the early stages of the nanostructure growth a significant fraction of electron trajectories still interacts with the substrate, when the nanostructure becomes thicker the transport takes place almost exclusively in the nanostructure. In particular, a larger deposit density leads to enhanced electron backscattering. This work shows how mesoscopic radiation-transport techniques can contribute to a model that addresses the multi-scale nature of the electron-beam-induced deposition (EBID) process. Furthermore, similar simulations can help to understand the role that is played by backscattered electrons and emitted secondary electrons in the change of structural properties of nanostructured materials during post-growth electron-beam treatments.
PMCID: PMC3869256  PMID: 24367747
electron backscattering; electron transport; (F)EBID; Monte Carlo simulation; PENELOPE
24.  Selective preparation of zero- and one-dimensional gold nanostructures in a TiO2 nanocrystal-containing photoactive mesoporous template 
Nanocrystallized SiO2-TiO2 with tubular mesopores was prepared via the sol-gel technique. Gold was deposited in the tubular mesopores of the nanocrystallized SiO2-TiO2. The shape of the gold was varied from one-dimensional [1-D] to zero-dimensional [0-D] nanostructures by an increase in TiO2 content and ultraviolet [UV] irradiation during gold deposition. 1-D gold nanostructures [GNSs] were mainly obtained in the mesopores when a small amount of TiO2-containing mesoporous SiO2-TiO2 was used as a template, whereas the use of a template containing a large amount of TiO2 led to the formation of shorter 1-D or 0-D GNSs. UV irradiation also resulted in the formation of 0-D GNSs.
PACS: 06.60.Jn (sample preparation); 81.07.Gf (nanowires); 81.16.Be (chemical synthesis methods).
PMCID: PMC3265400  PMID: 22221978
mesoporous; titania; template; gold; nanostructures; shape control; photocatalysis; surface plasmon resonance
25.  Real-time assessment of surface interactions with titanium passivation layer by surface plasmon resonance 
Acta Biomaterialia  2011;8(3):1260-1266.
The high corrosion resistance and strength-to-density ratio makes titanium widely used in major industry, but also in a gamut of medical applications. Here we report for the first time on our development of a titanium passivation layer sensor that makes use of surface plasmon resonance (SPR). The deposited titanium metal layer on the sensor was passivated in air, like titanium medical devices. Our ‘Ti-SPR sensor’ enables analysis of biomolecules interactions with the passivated surface of titanium in real time. As a proof of concept, corrosion of titanium passivation layer exposed to acid was monitored in real time. Also, the Ti-SPR sensor can accurately measure the time-dependence of protein adsorption onto titanium passivation layer with a sub-nanogram per square millimeter accuracy. Besides such SPR analyses, an SPR-imaging (SPRI) enables real-time assessment of chemical surface processes that occur simultaneously at ‘multiple independent spots’ on the Ti-SPR sensor, such as acid-corrosion or adhesion of cells. Our Ti-SPR sensor will therefore be very useful to study titanium-corrosion phenomena and biomolecular titanium-surface interactions with application in a broad range of industrial and biomedical fields.
PMCID: PMC3272143  PMID: 22154862
Titanium passivation layer; Surface plasmon resonance; Protein adsorption; Cell adhesion; Biosensor

Results 1-25 (419411)