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We employ intense and short pulses of energetic lithium (Li+) ions to investigate the relaxation dynamics of radiation induced defects in single crystal silicon samples. Ions both create damage and track damage evolution simultaneously at short time scales when we use the channeling effect as a diagnostic tool. Ion pulses, ∼20 to 600 ns long and with peak currents of up to ∼1 A are formed in an induction type linear accelerator, the Neutralized Drift Compression eXperiment at Lawrence Berkeley National Laboratory. By rotating silicon (<100>) membranes of different thicknesses and changing the incident ion energy, the fraction of channeled ions in the transmitted beam could be varied. In preliminary experiments we find that the Li ion intensity is not high enough to generate overlapping cascades (in time and space) that would be necessary to measure a change in the shape of the current waveform of the transmitted ion beam. We discuss the concept of pump-probe type experiments with short ion beam pulses to access defect dynamics in materials and outline a path to increasing damage rates with heavier ions and by the application of longitudinal and lateral pulse compression techniques.
We have quantified lithium dendrite growth in an optically accessible symmetric Li-metal cell, charged under imposed temperatures on the electrode surface. We have found that the dendrite length measure is reduced up to 43% upon increasing anodic temperature of about 50°C. We have deduced that imposing higher temperature on the electrode surface will augment the reduction rate relative to dendritic peaks and therefore lithium holes can draw near with the sharp deposited tips. We have addressed this mechanism via fundamentals of electrochemical transport.
For structural investigation, highly (112) oriented tetragonal Cu2ZnSnS4 (CZTS) thin films on hexagonal sapphire (0001) single crystal substrates were obtained by radio frequency (RF) magnetron sputtering. The influences of the deposition parameters, such as substrate temperature (Tsub) and working Ar pressure (PAr) on the chemical composition and structural properties of as deposited CZTS films were investigated. The film sputtered at 500°C has the only orientation of (112), also, it bears the best structural quality with pure CZTS phase and an estimated band gap of 1.51eV.
Matrix diffusion is a key process for radionuclide retention in crystalline rocks. Within the LTD project (Long-Term Diffusion), an in-situ diffusion experiment in unaltered non-fractured granite was performed at the Grimsel Test Site (www.grimsel.com, Switzerland). The tracers included 3H as HTO, 22Na+, 134Cs+ and 131I- with stable I- as carrier.
The dataset (except for 131I- because of complete decay) was analyzed with different diffusion-sorption models by different teams (NAGRA / IDAEA-CSIC, UJV-Rez, JAEA, Univ. Poitiers) using different codes, with the goal of obtaining effective diffusion coefficients (De) and porosity (ϕ) or rock capacity (α) values. A Borehole Disturbed Zone (BDZ), which was observed in the rock profile data for 22Na+ and 134Cs+, had to be taken into account to fit the experimental observations. The extension of the BDZ (1-2 mm) was about the same magnitude as the mean grain size of the quartz and feldspar grains.
De and α values for the different tracers in the BDZ are larger than the respective values in the bulk rock. Capacity factors in the bulk rock are largest for Cs+ (strong sorption) and smallest for 3H (no sorption). However, 3H seems to display large α values in the BDZ. This phenomenon will be investigated in more detail in a second test starting in 2013.
The aim of this study was to prepare various sized nano-pits on 316 L stainless steel and examine their effects on the attachment and proliferation of fibroblasts. In this study, 316L stainless steel with tunable pit sizes (0, 25, 50, and 60 nm) were fabricated by an anodization procedure in an ethylene glycol electrolyte solution containing 5 vol.% perchloric acid. The surface morphology of 316L stainless steel were characterized by scanning electron microscopy (SEM). The nano-pit arrays on all the 316L stainless steel samples were in a regular arrangement. The surface properties of the 316L stainless steel nano-pit surface showed improved wettability properties as compared to the untreated 316L stainless steel. The nano-pit surfaces with 50 nm and 60 nm diameter were rougher at the nanoscale than other samples. The attachment and proliferation of fibroblasts were investigated for up to 3 days in culture using MTT assays. Compared to unanodized (that is, nano-smooth) and smooth surfaces, 50 and 60 nm diameter nano-pit surfaces dramatically enhanced the initial fibroblast attachment and growth up to 3 days in culture. The results reported in this study showed that the 50 and 60 nm nano-pit surfaces promoted fibroblast adhesion and proliferation by increasing the surface roughness and adsorption of fibronectin. Such nano-pit surfaces can be designed to support fibroblast growth and be important for improving the use of 316L stainless steel for various implant applications (such as for improved skin healing for amputee devices or for percutaneous implants).
A number of systems based on synthetic molecules, among them cationic liposomes and poly(ethylene imine)-based polymers, have been proposed as delivery vehicles for nucleic acids. Some of these systems have even reached the market, ensuring efficient and transient transfection levels in a variety of cell types. However, toxicity issues have limited their application in vivo. In this context, chitosan, a biocompatible and biodegradable polysaccharide, has been proposed as a promising alternative for the delivery of nucleic acid-based molecules. Here we present an overview of the state of the art of chitosan-based vectors for nucleic acid delivery and the most recent data on the in vivo testing of the proposed systems. We additionally express our view on the barriers that might be hampering the translation of this knowledge into clinical practice and the challenges that need to be fulfilled for these promising vehicles to reach patients.
This paper investigated the silicon substrate orientation dependence on the electrical properties of high-κ HfN gate insulator formed by electron-cyclotron-resonance (ECR) plasma sputtering. The effect of N2/4.9%H2 forming-gas annealing (FGA) was studied. By using N2/4.9%H2 FGA at 500°C for 20 min, the interfacial layer (IL) formation was not formed and led to the zero-interface layer (ZIL). The EOTs of 0.47 and 0.51 nm with leakage current of 1.1 and 1.4 A/cm2 (@VFB -1 V) were obtained on p-Si(100) and p-Si(110), respectively. The density of interface states (Dit) with the order of 1011 cm-2eV-1 was obtained on both p-Si(100) and p-Si(110). This suggests that the direct deposition of HfN film with ZIL prevented the degradation of electrical characteristics on the p-Si(100) and p-Si(110) substrate in comparison to the case of oxide-based hafnium gate insulator.
In this paper we present a multilayer device based on a-Si:H/a-SiC:H that operates as photodetector and optical filter. The use of such device in protein detection applications is pertinent in Fluorescence Resonance Energy Transfer (FRET) measurements that demand the detection of visible fluorescent signals located at specific wavelengths bands. This device was designed to operate in the visible range with a selective sensitivity dependent on the applied electrical bias. Several nanosensors were tested with a commercial spectrophotometer to judge the performance of the FRET signals using glucose solutions of different concentrations. Two nanosensors (FLIPglu-90μM and FLIPglu-600μM) were tested with a commercial spectrofluorimeter to judge the performance of the FRET signals by using glucose solutions of different concentrations. These measurements were carried out by using these nanosensors both in the free form and immobilized form on inner epidermis of onion bulb scale. The proposed device was used to demonstrate the possibility of FRET signals detection, using visible signals of similar wavelength and intensity. The device sensitivity was tuned to enhance the wavelength band of interest using adequate electrical biasing.
We demonstrate fluidically tuned fluorescence enhancement on the colorimetric substrate with the plasmonic effects induced by the periodic gold nanocup arrays. The fluorescence enhancement by the plasmonic effect has been studied extensively by varying the geometries of nanostructures or the morphology of nanoparticles. In this study, however, the fluorescence enhancement without changing these parameters but simply by varying surrounding media on the colorimetric plasmonic surface is accomplished. The dynamic responses of fluorescence from self-assembled monolayer of dyes on the surface were monitored by flowing various fluids with different refractive indices. The dependence of the radiative decay rate as well as the scattering cross-section on the surrounding dielectric properties results into the selective enhancement of the fluorescence intensity, having a maximum at different surrounding refractive index for different fluorophores with different emission band centers.
The colored component of several important ancient pigments, including Egyptian blue and Han blue, are based on alkali earth copper tetrasilicate materials. In recent work, we have found that these layered materials can be chemically exfoliated into their constituent monolayers to provide alkali earth copper tetrasilicate nanosheets—defined by nanometer thickness and lateral dimensions that are on the order of several microns. The facile exfoliation of these materials into nanosheets is especially surprising in view of their long history on artifacts under a variety of environmental conditions, and we have examined the issue of whether archaeological samples are affected by this exfoliation mechanism. We have characterized the properties of these nanosheets by an array of analytical techniques, including powder x-ray diffraction, photoluminescence measurements, and Raman spectroscopy. In all cases, we observe differences between nanosheet and bulk samples that originate from the loss of coupling between layers when going from three-dimensional to two- dimensional structures. Both CaCuSi4O10 nanosheets (derived from Egyptian blue) and BaCuSi4O10 nanosheets (derived from Han blue) have strong near-infrared luminescence properties like their bulk counterparts, yet they are amenable to modern solution processing methods. We have demonstrated ink jet printing with CaCuSi4O10 nanosheet inks, as well as the fabrication of nanosheet-based papers. Potential applications for these materials include NIR-based biomedical imaging and security inks.
The metal-catalyzed step-growth radical polymerization was achieved to enable two systems for preparing tailored polymeric structures, i.e., sequence-regulated vinyl copolymer and periodically-functionalized polymer. The former is a novel strategy for preparing sequence-regulated vinyl copolymers by step-polymerization of sequence-regulated vinyl oligomers prepared from common vinyl monomers as building blocks. The later deals the simultaneous chain- and step-growth radical polymerization, which resulted in the polymers with periodic functional groups.
In this work we have investigated the mechanical properties and fracture patterns of some graphene nanowiggles (GNWs). Graphene nanoribbons are finite graphene segments with a large aspect ratio, while GNWs are nonaligned periodic repetitions of graphene nanoribbons. We have carried out fully atomistic molecular dynamics simulations using a reactive force field (ReaxFF), as implemented in the LAMPPS (Large-scale Atomic/Molecular Massively Parallel Simulator) code. Our results showed that the GNW fracture patterns are strongly dependent on the nanoribbon topology and present an interesting behavior, since some narrow sheets have larger ultimate failure strain values. This can be explained by the fact that narrow nanoribbons have more angular freedom when compared to wider ones, which can create a more efficient way to accumulate and to dissipate strain/stress. We have also observed the formation of linear atomic chains (LACs) and some structural defect reconstructions during the material rupture. The reported graphene failure patterns, where zigzag/armchair edge terminated graphene structures are fractured along armchair/zigzag lines, were not observed in the GNW analyzed cases.
In the previous investigation, piezoelectric properties of the ‘Aligned-type’ in which the piezoelectric-ceramic particles are formed in linear aggregates in the rubber, remarkable piezoelectric properties were confirmed. In this investigation, to further enhance the piezoelectric properties of the Aligned-type, the influence of the matrix properties was investigated. The properties on which we focused were the dielectric constant and the Young’s modulus. Four kinds of matrix materials whose dielectric constant and Young’s modulus are different from each other; Silicone gel, Silicone rubber, Urethane rubber and Poly-methyl-methacrylate were investigated. As a result of measurement of the piezoelectric strain constant d33 of the Aligned-Type, it was confirmed that though the influence of the dielectric constant of the matrix material was small, the lower the Young’s modulus of the matrix was, the higher d33 was.
Transparent UV protective coatings were developed by incorporating nano-TiO2 into waterborne acrylic systems to provide long-term UV protection for UV sensitive cool color roofing. Water based high crystalline TiO2 nanoparticle suspension was prepared via a gel-sol method at a basic pH. The TiO2 nanoparticles have an average size of 20 nm and are stable against agglomeration. As prepared TiO2 nanosuspension is ready to be well dispersed in commercial waterborne acrylic resin system without extra surface modification. The fabricated TiO2/acrylic nanocomposite coating achieved an UV cut-off below 350 nm with a visible transmission greater than 85% at 700 nm. It is also demonstrated that surface modification of Nano-TiO2 with a SiO2 insulation layer would suppress the catalytic activity of Nano-TiO2 and improve the UV protection for UV and photocatalysis sensitive dyes.
Articular cartilage is prone to degeneration and possesses extremely poor self-healing capacity due to its low cell density and absence of blood vessels. It has extensively reported tissue engineered scaffold can be a promising approach for cartilage repair. However, there still remains an inherent lack of desirable scaffolds that stimulate cartilage regrowth with appropriate functional properties. Therefore, in this study, we develop a biomimetic cartilage substitute comprising of electrospun polycaprolactone (PCL) with cold atmospheric plasma (CAP) modified cell favorable surface and sustained bioactive factor (bovine serum albumin (BSA) or transforming growth factor beta 1 (TGF-β1)) incorporated microspheres inside for improving stem cell chondrogenesis and cartilage regeneration. Scanning electron microscopy (SEM) analysis showed the drug delivery spheres homogeneously distribution in the fibrous scaffold. Furthermore, CAP treatment renders the scaffold’s surface more hydrophilic and results in more specific vitronectin adsorption as illustrated by contact angle and ELISA testing. Our results showed that the CAP treated scaffold can greatly improve growth and chondrogenic differentiation (such as increased glycosaminoglycan (GAG) synthesis) of human bone marrow-derived mesenchymal stem cells (MSCs).
The efficiency of thin-film solar cells using a-Si:H is limited by the decrease in a-Si:H layer optical path length and its poor light absorption at red and NIR wavelengths. Metal NP such as Au have been shown to increase the absorption in the active material and then cell performances, by exhibiting localized surface plasmon (LSP) resonances. Our work’s goal is to understand NP influence in such cells, to perform an optimal structure by increasing the amount of light absorbed within the cell using NP scattering and luminescence. Modeling based on Mie theory is first carried out using bulk Palik data for Au spheres with various diameters and refractive medium indexes. Using modeling parameters, Au layers were deposited on glass and SnO2 substrates respectively by thermal evaporation in vacuum and sputtering, followed by thermal annealing (200 ∼ 500°C) in order to promote the NP growth. MEB pictures show quasispherical Au NP shape with a mean size of 150nm. This diameter range switches extinction of NP in scattering regime. Annealing temperature (T) strongly affects the NP morphology. Surface coverage decreases and sphericity appears to increase with T. UV-Visible spectroscopy displays distinct LSP resonances around 600nm after annealing with a red shift while T increases.
The use of generic sorption data in PA requires the transfer of the data to the PA-specific conditions. A site-specific Kd setting approach for PA calculations was tested, comparing two data transfer procedures. First transfer of sorption data can be done through semi-quantitative estimation procedures, by considering differences between experimental and PA geochemical conditions (sorption capacity, radionuclide speciation, competitive reactions, etc.). On the other hand, thermodynamic sorption models allow to estimate Kd variations directly, based on quasi-mechanistic understanding. The present paper focuses on illustrating example calculations regarding the derivation of Kd values, and their uncertainties, of Cs, Ni, Am and Th, for the mineralogical and geochemical conditions of the mudstone system at the Horonobe URL. Clay minerals (illite and smectite) were considered as sorption-relevant minerals in all cases. The Kd setting results were compared with Kd measured for Horonobe mudstone by batch experiments. The results indicate that Kd can be quantitatively evaluated from generic sorption data when adequate data and models are available. The careful evaluation and conjunctive use of calculated and measured Kd values can enhance the reliability of Kd setting and uncertainty assessments.
Semi-flexible polymer networks generate a diverse family of structures. The network generating behaviors of specific semi-flexible biological filaments are well known (i.e. F-actin, microtubules, DNA etc.), however recent developments in tunable synthetic filaments extend the range of accessible structures. A similarly tunable model was developed using the molecular dynamics platform NAMD to provide a guide for generating synthetic filament networks. Structural characteristics of simulated networks may be quantitatively examined using connectivity analysis, radial pair distribution functions and scaling analysis. These methods provide a basis to calculate morphological properties, including mesh size, packing order, network connectivity, avg. cluster size, filaments per bundle, and space-filling dimensionality. An analytic toolset for describing the structure of filament networks is thus provided by detailing these methods.
A facile technique was developed for a long-term increase in silicone elastomer surface hydrophilicity, eliminating the need for post-cure surface treatment (e.g. oxygen plasma or surface grafting). Well-defined silicones (1-4 kDa) with a central vinyl functionality and discrete PEG2, PEG3 and tetrahydrofurfuryl (THF) pendant endgroups were synthesized, characterized and used as comonomers in addition-cure, platinum catalyzed 2-part silicone elastomer formulations. The modified silicone elastomers were optically clear and maintained the mechanical performance characteristic of this class of material with up to 20 wt.% comonomer in the 2-part formulation. Contact angle measurements of deionized water on the silicone elastomer surface showed improved wettability with comonomer content. The elastomer surface shifted from hydrophobic (contact angle ∼120°C) to hydrophilic (contact angle < 90°C) at ∼5 wt.% comonomer loadings for extended time frames (> 5 months). Coefficient of friction measurements of the modified silicone elastomers revealed an increase in surface lubricity with comonomer loadings.