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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.
doi:10.1002/adfm.201000907
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.
Background
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.
Conclusions/Significance
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.
doi:10.1371/journal.pone.0024788
PMCID: PMC3170388  PMID: 21931853
3.  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.
doi:10.1186/1556-276X-6-586
PMCID: PMC3240672  PMID: 22067075
4.  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.
doi:10.1007/s11671-007-9058-4
PMCID: PMC3246344  PMID: 21798104
Nanocrystal; Crystal growth; Transmission electron microscopy; Wulff plot; Surface energy; Gold; SiO2
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.
doi:10.3390/s101211390
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.
doi:10.3390/s110807763
PMCID: PMC3231699  PMID: 22164044
single-walled carbon nanotube (SWCNT) networks; gas sensing device; chemical vapors
7.  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.
doi:10.1186/1556-276X-7-243
PMCID: PMC3403976  PMID: 22559207
Silicon nanowires; Preparation; Vapor–liquid-solid; Oxide-assisted growth; Ultrahigh vacuum
8.  Density functional theory calculations on graphene/α-SiO2(0001) interface 
Nanoscale Research Letters  2012;7(1):158.
In this work, the graphene/α-SiO2(0001) interface is calculated using density functional theory. On the oxygen-terminated SiO2 surface, atomic structure reconstruction occurs at the graphene/SiO2 interface to eliminate the dangling bonds. The interface interaction is 77 meV/C atom, which indicates that van der Waals force dominates the interaction, but it is stronger than the force between the graphene layers in graphite. The distance between graphene and the SiO2 surface is 2.805 Å, which is smaller than the 3.4 Å interlayer distance of graphite. In addition, the SiO2 substrate induces p-type doping in graphene and opens a small gap of 0.13 eV at the Dirac point of graphene, which is desirable for electronic device applications.
doi:10.1186/1556-276X-7-158
PMCID: PMC3305479  PMID: 22373326
9.  Degradation of poliovirus by adsorption on inorganic surfaces. 
Alteration of the specific infectivity of 3H-labeled ribonucleic acid and 14C-protein labeled poliovirus type 1 by adsorption on inorganic surfaces is investigated by application of kinetic theory to data obtained from sequential extractions of adsorbed virus. Some surfaces, e.g., SiO2, appear to have no significant effect. On the other hand, CuO substantially decreases the specific infectivity of adsorbed preparations. Differences in kinetic plots between 3H-labeled ribonucleic acid and 14C-labeled protein suggest that the inactivation observed involves physical disruption of virions. Van der Waals interactions between solid surfaces and virus are suspected to induce spontaneous virion disassembly. Surface catalyzed disassembly in aquatic and soil environments is implicated as an important mechanism controlling enterovirus dissemination. Methods developed here to evaluate complete recovery of adsorbed virus have potenital application to other degradation studied and problems concerning virus recovery from adsorbents used in virus concentrators.
PMCID: PMC243242  PMID: 222209
10.  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.
doi:10.1186/1556-276X-6-170
PMCID: PMC3211223  PMID: 21711698
11.  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.
doi:10.1186/1556-276X-6-148
PMCID: PMC3211198  PMID: 21711632
12.  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.
doi:10.1007/s11671-008-9180-y
PMCID: PMC3244952  PMID: 21752308
Nanocrystal; Surface energy; Gold; SiO2; Cohesive energy; Melting temperature; Vacancy formation energy
13.  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).
doi:10.1186/1556-276X-7-27
PMCID: PMC3265400  PMID: 22221978
mesoporous; titania; template; gold; nanostructures; shape control; photocatalysis; surface plasmon resonance
14.  Tribo-mechanical properties of thin boron coatings deposited on polished cobalt alloy surfaces for orthopedic applications 
Thin solid films  2008;516(10):3070-3080.
This paper presents experimental evidence that thin (<∼200 nm) boron coatings, deposited with a (vacuum) cathodic arc technique on pre-polished Co-Cr-Mo surfaces, could potentially extend the life of metal-on-polymer orthopedic devices using cast Co-Cr-Mo alloy for the metal component. The primary tribological test used a linear, reciprocating pin-on-disc arrangement, with pins made of ultra-high molecular weight polyethylene. The disks were cast Co-Cr-Mo samples that were metallographically polished and then coated with boron at a substrate bias of 500 V and at about 100 °C. The wear tests were carried out in a saline solution to simulate the biological environment. The improvements were manifested by the absence of a detectable wear track scar on the coated metal component, while significant polymer transfer film was detected on the uncoated (control) samples tested under the same conditions. The polymer transfer track was characterized with both profilometry and Rutherford Backscattering Spectroscopy. Mechanical characterization of the thin films included nano-indentation, as well as additional pin-on-disk tests with a steel ball to demonstrate adhesion, using ultra-high frequency acoustic microscopy to probe for any void occurrence at the coating-substrate interface.
doi:10.1016/j.tsf.2007.10.111
PMCID: PMC2435378  PMID: 19340285
Boron; amorphous materials; coatings; biomaterials; deposition process; Rutherford back-scattering spectroscopy; tribology; cobalt alloy
15.  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.
doi:10.1007/s11671-010-9676-0
PMCID: PMC2956049  PMID: 21076673
Aligned carbon nanotubes; Atomic layer deposition; Chemical vapor deposition; Catalysis; Nanotechnology
16.  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.
doi:10.1007/s11671-010-9676-0
PMCID: PMC2956049  PMID: 21076673
Aligned carbon nanotubes; Atomic layer deposition; Chemical vapor deposition; Catalysis; Nanotechnology
17.  Evaluation of environmental filtration control of engineered nanoparticles using the Harvard Versatile Engineered Nanomaterial Generation System (VENGES) 
Applying engineering controls to airborne engineered nanoparticles (ENPs) is critical to prevent environmental releases and worker exposure. This study evaluated the effectiveness of two air sampling and six air cleaning fabric filters at collecting ENPs using industrially relevant flame-made engineered nanoparticles generated using a versatile engineered nanomaterial generation system (VENGES), recently designed and constructed at Harvard University. VENGES has the ability to generate metal and metal oxide exposure atmospheres while controlling important particle properties such as primary particle size, aerosol size distribution, and agglomeration state. For this study, amorphous SiO2 ENPs with a 15.4 nm primary particle size were generated and diluted with HEPA-filtered air. The aerosol was passed through the filter samples at two different filtration face velocities (2.3 and 3.5 m/min). Particle concentrations as a function of particle size were measured upstream and downstream of the filters using a specially designed filter test system to evaluate filtration efficiency. Real time instruments (FMPS and APS) were used to measure particle concentration for diameters from 5 to 20,000 nm. Membrane-coated fabric filters were found to have enhanced nanoparticle collection efficiency by 20–46 % points compared to non-coated fabric and could provide collection efficiency above 95 %.
PMCID: PMC3569546  PMID: 23412707
Engineered nanoparticles; Aerosol emission; Filter; Engineering control; Silica; Environmental and health effects
18.  FTIR and Raman Spectroscopy of Carbon Nanoparticles in SiO2, ZnO and NiO Matrices 
Nanoscale Research Letters  2008;3(11):421-426.
Coatings of carbon nanoparticles dispersed in SiO2, ZnO and NiO matrices on aluminium substrates have been fabricated by a sol–gel technique. Spectrophotometry was used to determine the solar absorptance and the thermal emittance of the composite coatings with a view to apply these as selective solar absorber surfaces in solar thermal collectors. Cross-sectional high resolution transmission electron microscopy (X-HRTEM) was used to study the fine structure of the samples. Raman spectroscopy was used to estimate the grain size and crystallite size of the carbon clusters of the composite coatings. X-HRTEM studies revealed a nanometric grain size for all types of samples. The C–SiO2, C–ZnO and C–NiO coatings contained amorphous carbon nanoparticles embedded in nanocrystalline SiO2, ZnO and NiO matrices, respectively. Selected area electron diffraction (SAED) showed that a small amount of Ni grains of 30 nm diameter also existed in the NiO matrix. The thermal emittances of the samples were 10% for C–SiO2, 6% for the C–ZnO and 4% for the C–NiO samples. The solar absorptances were 95%, 71% and 84% for the C–SiO2, C–ZnO and C–NiO samples, respectively. Based on these results, C–NiO samples proved to have the best solar selectivity behaviour followed by the C–ZnO, and last were the C–SiO2samples. Raman spectroscopy studies revealed that both the C–ZnO and C–NiO samples have grain sizes for the carbon clusters in the range 55–62 nm and a crystallite size of 6 nm.
doi:10.1007/s11671-008-9172-y
PMCID: PMC3244956
FTIR spectroscopy; Raman spectroscopy; Carbon nanoparticles; Oxide matrices
19.  Transmission electron microscope observation of organic–inorganic hybrid thin active layers of light-emitting diodes 
Nanoscale Research Letters  2012;7(1):591.
We performed transmission electron microscope (TEM) observation of organic–inorganic hybrid thin films fabricated by the sol–gel reaction and used as the active layers of organic light-emitting diodes. The cross-sectional TEM images show that the films consist of a triple-layer structure. To evaluate the composition of these layers, the distribution of atoms in them was measured by energy-dispersive X-ray fluorescence spectroscopy. As a result, most of the organic emissive material, poly(9,9-dioctyl-fluorene-co-N-4-butylphenyl-diphenylamine (TFB), was found to be distributed in the middle layer sandwiched by SiO and SiO2 layers. The surface SiO layer was fabricated due to the lack of oxygen. This means that the best sol–gel condition was changed due to the TFB doping; thus, the novel best condition should be found.
doi:10.1186/1556-276X-7-591
PMCID: PMC3499159  PMID: 23095451
Organic light-emitting diodes; TEM; sol–gel; Hybrid thin films; EDS
20.  Focused electron beam induced deposition: A perspective 
Summary
Background: Focused electron beam induced deposition (FEBID) is a direct-writing technique with nanometer resolution, which has received strongly increasing attention within the last decade. In FEBID a precursor previously adsorbed on a substrate surface is dissociated in the focus of an electron beam. After 20 years of continuous development FEBID has reached a stage at which this technique is now particularly attractive for several areas in both, basic and applied research. The present topical review addresses selected examples that highlight this development in the areas of charge-transport regimes in nanogranular metals close to an insulator-to-metal transition, the use of these materials for strain- and magnetic-field sensing, and the prospect of extending FEBID to multicomponent systems, such as binary alloys and intermetallic compounds with cooperative ground states.
Results: After a brief introduction to the technique, recent work concerning FEBID of Pt–Si alloys and (hard-magnetic) Co–Pt intermetallic compounds on the nanometer scale is reviewed. The growth process in the presence of two precursors, whose flux is independently controlled, is analyzed within a continuum model of FEBID that employs rate equations. Predictions are made for the tunability of the composition of the Co–Pt system by simply changing the dwell time of the electron beam during the writing process. The charge-transport regimes of nanogranular metals are reviewed next with a focus on recent theoretical advancements in the field. As a case study the transport properties of Pt–C nanogranular FEBID structures are discussed. It is shown that by means of a post-growth electron-irradiation treatment the electronic intergrain-coupling strength can be continuously tuned over a wide range. This provides unique access to the transport properties of this material close to the insulator-to-metal transition. In the last part of the review, recent developments in mechanical strain-sensing and the detection of small, inhomogeneous magnetic fields by employing nanogranular FEBID structures are highlighted.
Conclusion: FEBID has now reached a state of maturity that allows a shift of the focus towards the development of new application fields, be it in basic research or applied. This is shown for selected examples in the present review. At the same time, when seen from a broader perspective, FEBID still has to live up to the original idea of providing a tool for electron-controlled chemistry on the nanometer scale. This has to be understood in the sense that, by providing a suitable environment during the FEBID process, the outcome of the electron-induced reactions can be steered in a controlled way towards yielding the desired composition of the products. The development of a FEBID-specialized surface chemistry is mostly still in its infancy. Next to application development, it is this aspect that will likely be a guiding light for the future development of the field of focused electron beam induced deposition.
doi:10.3762/bjnano.3.70
PMCID: PMC3458607  PMID: 23019557
atomic force microscopy; binary systems; electron beam induced deposition; granular metals; micro Hall magnetometry; radiation-induced nanostructures; strain sensing
21.  Stable Encapsulation of QD Barcodes with Silica Shells** 
Advanced functional materials  2010;20(21):3721-3726.
Quantum dot-doped mesoporous microbeads (QDMMs) are encapsulated with silica shells for enhanced chemical stability. The results show that a micro-emulsion procedure is highly efficient in coating QDMMs with polyvinyl alcohol (PVA), which is important in the subsequent deposition of a silica shell. Incorporation of fluorescent silane precursors allows direct observation of silica shells by fluorescence microscopy. The resulting silica coated QDMMs (QDMM@SiO2) exhibit remarkable stability against solvent-induced QD leaching and chemical-induced fluorescence quenching compared with uncoated QDMMs. Further development of this technology such as optimization of silica shell thickness, surface modification with non-fouling polymers, and conjugation with biomolecular probes will enable clinical translation of the optical barcoding technology for highly multiplexed detection and screening of genes and proteins.
doi:10.1002/adfm.201000711
PMCID: PMC3290339  PMID: 22389642
mesoporous; quantum dots; barcoding; silica; encapsulation
22.  The temperature effect on electrokinetic properties of the silica–polyvinyl alcohol (PVA) system 
Colloid and Polymer Science  2010;289(3):341-344.
The influence of polyvinyl alcohol (PVA) adsorption on the structure of the diffuse layer of silica (SiO2) in the temperature range 15–35 °C was examined. The microelectrophoresis method was used in the experiments to determine the zeta potential of the solid particles in the absence and presence of the polymer. The adsorption of PVA macromolecules causes the zeta potential decrease in all investigated SiO2 systems. Moreover this, decrease is the most pronounced at the highest examined temperature. Obtained results indicate that the conformational changes of adsorbed polymer chains are responsible for changes in electrokinetic properties of silica particles. Moreover, the structure of diffuse layer on the solid surface with adsorbed polymer results from the following effects: the presence of acetate groups in PVA chains, the blockade of silica surface groups by adsorbed polymer and the shift of slipping plane due to macromolecules adsorption.
doi:10.1007/s00396-010-2341-4
PMCID: PMC3044228  PMID: 21472022
Polyvinyl alcohol; Silica; Polymer conformation; Zeta potential; Slipping plane; Temperature influence
23.  A Tunable Strain Sensor Using Nanogranular Metals 
Sensors (Basel, Switzerland)  2010;10(11):9847-9856.
This paper introduces a new methodology for the fabrication of strain-sensor elements for MEMS and NEMS applications based on the tunneling effect in nano-granular metals. The strain-sensor elements are prepared by the maskless lithography technique of focused electron-beam-induced deposition (FEBID) employing the precursor trimethylmethylcyclopentadienyl platinum [MeCpPt(Me)3]. We use a cantilever-based deflection technique to determine the sensitivity (gauge factor) of the sensor element. We find that its sensitivity depends on the electrical conductivity and can be continuously tuned, either by the thickness of the deposit or by electron-beam irradiation leading to a distinct maximum in the sensitivity. This maximum finds a theoretical rationale in recent advances in the understanding of electronic charge transport in nano-granular metals.
doi:10.3390/s101109847
PMCID: PMC3231023  PMID: 22163443
cantilevers; electron beam induced deposition; granular metals; strain sensors
24.  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.
doi:10.3390/s120608405
PMCID: PMC3436036  PMID: 22969407
chemical adsorption; electrode; chelate; metal ion
25.  Copper Oxide Nanoparticles Induce Oxidative Stress and Cytotoxicity in Airway Epithelial Cells 
Metal oxide nanoparticles are often used as industrial catalysts and elevated levels of these particles have been clearly demonstrated at sites surrounding factories. To date, limited toxicity data on metal oxide nanoparticles are available. To understand the impact of these airborne pollutants on the respiratory system, airway epithelial (HEp-2) cells were exposed to increasing doses of silicon oxide (SiO2), ferric oxide (Fe2O3) and copper oxide (CuO) nanoparticles, the leading metal oxides found in ambient air surrounding factories. CuO induced the greatest amount of cytotoxicity in a dose dependent manner; while even high doses (400 µg/cm2) of SiO2 and Fe2O3 were non-toxic to HEp-2 cells. Although all metal oxide nanoparticles were able to generate ROS in HEp-2 cells, CuO was better able to overwhelm antioxidant defenses (e.g. catalase and glutathione reductase). A significant increase in the level of 8-isoprostanes and in the ratio of GSSG to total glutathione in cells exposed to CuO suggested that ROS generated by CuO induced oxidative stress in HEp-2 cells. Co-treatment of cells with CuO and the antioxidant resveratrol increased cell viability suggesting that oxidative stress may be the cause of the cytotoxic effect of CuO. These studies demonstrated that there is a high degree of variability in the cytotoxic effects of metal oxides, that this variability is not due to the solubility of the transition metal, and that this variability appears to involve sustained oxidative stress possibly due to redox cycling.
doi:10.1016/j.tiv.2009.08.005
PMCID: PMC2756312  PMID: 19699289
Nanoparticles; HEp-2 cells; CuO; Oxidative stress; Resveratrol

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