Pore graded borosilicate bioactive glass scaffolds: in vitro dissolution and cytocompatibility.

3D borosilicate bioactive glass (1393B20 and B12.5MgSr) scaffolds were prepared by robocasting, with and without a dense layer at the top. Pore graded scaffolds are promising as they allow for membrane deposition and could limit the risk of soft tissue infiltration. In vitro dissolution was studied in tris(hydroxymethyl)aminomethane (TRIS) and Simulated Body Fluid (SBF). 1393B20 scaffolds dissolved faster than B12.5MgSr in TRIS whereas they dissolved slower in SBF. The difference in dissolution profiles, as a function of the medium used, is assigned to the different rates of precipitation of hydroxyapatite (HA). While the precipitation of calcium phosphate (CaP) in the form of HA, first sign of bioactivity, was confirmed by ICP, FTIR-ATR and SEM-EDX analysis for both compositions, 1393B20 was found to precipitate HA at a faster rate. The presence of a dense top layer did not significantly impact the dissolution rate and CaP precipitation. In vitro cell culture was performed using human adipose-derived stem cells (hADSCs). Prior to cell plating, a preincubation of 3 days was found optimum to prevent burst ion release. In direct contact, cells proliferate and spread on the scaffolds while maintaining characteristic spindle morphology. Cell plated on 1393B20 scaffolds showed increased viability when compared to cell plated on B12.5MgSr. The lower cell viability, when testing B12.5MgSr, was assigned to the depletion of Ca2+ ions from culture medium and higher pH. Static cell culture leads to believe that the scaffold produced from the 1393B20 glass composition are promising in bone regeneration applications.

Exceptional Microscale Plasticity in Amorphous Aluminum Oxide at Room Temperature.

Oxide glasses are an elementary group of materials in modern society, but brittleness limits their wider usability at room temperature. As an exception to the rule, amorphous aluminum oxide (a-Al2 O3 ) is a rare diatomic glassy material exhibiting significant nanoscale plasticity at room temperature. Here, it is shown experimentally that the room temperature plasticity of a-Al2 O3 extends to the microscale and high strain rates using in situ micropillar compression. All tested a-Al2 O3 micropillars deform without fracture at up to 50% strain via a combined mechanism of viscous creep and shear band slip propagation. Large-scale molecular dynamics simulations align with the main experimental observations and verify the plasticity mechanism at the atomic scale. The experimental strain rates reach magnitudes typical for impact loading scenarios, such as hammer forging, with strain rates up to the order of 1 000 s-1 , and the total a-Al2 O3 sample volume exhibiting significant low-temperature plasticity without fracture is expanded by 5 orders of magnitude from previous observations. The discovery is consistent with the theoretical prediction that the plasticity observed in a-Al2 O3 can extend to macroscopic bulk scale and suggests that amorphous oxides show significant potential to be used as light, high-strength, and damage-tolerant engineering materials.

Halogen-bonded shape memory polymers.

Halogen bonding (XB), a non-covalent interaction between an electron-deficient halogen atom and a Lewis base, is widely adopted in organic synthesis and supramolecular crystal engineering. However, the roadmap towards materials applications is hindered by the challenges in harnessing this relatively weak intermolecular interaction to devise human-commanded stimuli-responsive soft materials. Here, we report a liquid crystalline network comprising permanent covalent crosslinks and dynamic halogen bond crosslinks, which possess reversible thermo-responsive shape memory behaviour. Our findings suggest that I···N halogen bond, a paradigmatic motif in crystal engineering studies, enables temporary shape fixation at room temperature and subsequent shape recovery in response to human body temperature. We demonstrate versatile shape programming of the halogen-bonded polymer networks through human-hand operation and propose a micro-robotic injection model for complex 1D to 3D shape morphing in aqueous media at 37 °C. Through systematic structure-property-performance studies, we show the necessity of the I···N crosslinks in driving the shape memory effect. The halogen-bonded shape memory polymers expand the toolbox for the preparation of smart supramolecular constructs with tailored mechanical properties and thermoresponsive behaviour, for the needs of, e.g., future medical devices.

Influence of the photodeposition sequence on the photocatalytic activity of plasmonic Ag-Au/TiO2 nanocomposites.

Bimetallic Ag-Au/TiO2 nanocomposites were synthesized by sequential photodeposition in order to investigate the effect of surface plasmon resonance (SPR) properties on photocatalytic activity for solar water splitting and methylene blue (MB) degradation. The photodeposition times were optimized for monometallic Ag/TiO2 and Au/TiO2 nanocomposites to yield maximum SPR absorption in the visible range. It was found that the photocatalytic activity of bimetallic Ag-Au/TiO2 nanocomposites outperformed monometallic nanocomposites only when Au was photodeposited first on TiO2, which was attributed to Au-core-Ag-shell nanoparticle morphology. In contrast, reversing the photodeposition order resulted in Ag-Au alloy nanoparticle morphology, which was mediated by the galvanic replacement reaction during the second photodeposition. Alloying was not beneficial to the photocatalytic activity. These results demonstrate alloying during sequential photodeposition providing new insights for the synthesis of TiO2-based photocatalysts with plasmon-enhanced absorption in the visible range.

Formation and use of biogenic jarosite carrier for high-rate iron oxidising biofilms.

Jarosite precipitates formed in iron oxidising bioreactors have been shown to harbour iron-oxidisers. The aim of this study was to develop an iron oxidising bioprocess where microorganisms are retained solely on biogenic jarosite particles. Based on preliminary experiments using a fluidised-bed bioreactor (FBR), the formed jarosite particles started to disintegrate and wash out at upflow velocities of ≥0.21 cm/s. Therefore, the generation and use of biogenic jarosite carrier was studied in an expanded-bed bioreactor (J-EBR) with an upflow velocity of 0.19 cm/s. Inside J-EBR, the jarosite particles formed granules of 0.5-3 mm containing 200-460 mg/g of attached biomass. The performance of J-EBR was compared with an activated carbon biofilm FBR at 0.82 cm/s upflow velocity (AC-FBR). At 35 ± 2 °C with a feed ferrous iron concentration of 10 g/l, the highest obtained iron oxidation rate of J-EBR (6.8 g/l/h) was 33% lower than that of AC-FBR (10.1 g/l/h). This was likely due to the 80% lower recirculation rate and subsequently higher oxygen mass transfer limitation in J-EBR compared to AC-FBR. The present study demonstrates that biogenic jarosite can be used for retainment of iron oxidising biofilms in expanded-bed bioreactors that oxidise iron at high rates.

Highly ductile amorphous oxide at room temperature and high strain rate.

Oxide glasses are an integral part of the modern world, but their usefulness can be limited by their characteristic brittleness at room temperature. We show that amorphous aluminum oxide can permanently deform without fracture at room temperature and high strain rate by a viscous creep mechanism. These thin-films can reach flow stress at room temperature and can flow plastically up to a total elongation of 100%, provided that the material is dense and free of geometrical flaws. Our study demonstrates a much higher ductility for an amorphous oxide at low temperature than previous observations. This discovery may facilitate the realization of damage-tolerant glass materials that contribute in new ways, with the potential to improve the mechanical resistance and reliability of applications such as electronic devices and batteries.

Carbon coated TiO2 nanoparticles prepared by pulsed laser ablation in liquid, gaseous and supercritical CO2.

We report on the synthesis of TiO2 nanoparticles using nanosecond pulse laser ablation of titanium in liquid, gaseous and supercritical CO2. The produced particles were observed to be mainly anatase-TiO2 with some rutile-TiO2. In addition, the particles were covered by a carbon layer. Raman and x-ray diffraction data suggested that the rutile content increases with CO2 pressure. The nanoparticle size decreased and size distribution became narrower with the increase in CO2 pressure and temperature, however the variation trend was different for CO2 pressure compared to temperature. Pulsed laser ablation in pressurized CO2 is demonstrated as a single step method for making anatase-TiO2/carbon nanoparticles throughout the pressure and temperature ranges 5-40 MPa and 30 °C-50 °C, respectively.

Automated solvent vapor annealing with nanometer scale control of film swelling for block copolymer thin films.

Molecular self-assembly of block copolymers has been pursued as a next generation high-resolution, low-cost lithography technique. Solvent vapor annealing is a promising way of achieving self-assembled patterns from polymers with high interaction parameters, χ, or high molecular weights. Compared to thermal annealing, the assembly in a solvated state can be much faster, but the film swelling process is typically challenging to control and reproduce. We report the design and implementation of an automated solvent annealing system that addresses these issues. In this system the film swelling is controlled via local heating or cooling, which enables exceptionally fast and precise modulation of the swelling. The swelling of the polymer films follows preprogrammed annealing profiles with the help of a feedback loop that compares and tunes the film thickness with respect to the set point. The system therefore enables complex annealing profiles such as rapid cyclic swelling and deswelling. We show that the orientation of the pattern morphology and the amount of lattice defects are influenced by the used annealing profile. We demonstrate that optimized profiles significantly shorten the annealing time (<15 min) of high-χ and high-molecular weight poly(styrene-b-2-vinylpyridine).

An Unexpected Role of Hyaluronic Acid in Trafficking siRNA Across the Cellular Barrier: The First Biomimetic, Anionic, Non-Viral Transfection Method.

Circulating nucleic acids, such as short interfering RNA (siRNA), regulate many biological processes; however, the mechanism by which these molecules enter the cell is poorly understood. The role of extracellular-matrix-derived polymers in binding siRNAs and trafficking them across the plasma membrane is reported. Thermal melting, dynamic light scattering, scanning electron microscopy, and computational analysis indicate that hyaluronic acid can stabilize siRNA via hydrogen bonding and Van der Waals interactions. This stabilization facilitated HA size- and concentration-dependent gene silencing in a CD44-positive human osteosarcoma cell line (MG-63) and in human mesenchymal stromal cells (hMSCs). This native HA-based siRNA transfection represents the first report on an anionic, non-viral delivery method that resulted in approximately 60 % gene knockdown in both cell types tested, which correlated with a reduction in translation levels.

High molecular weight block copolymer lithography for nanofabrication of hard mask and photonic nanostructures.

An unusual dot pattern was realized via self-assembly of high molecular weight polystyrene-block-polydimethylsiloxane (PS-b-PDMS) copolymer by a simple one-step solvent annealing process, optimized based on Hansen solubility parameters. Annealing PS-b-PDMS under neutral solvent vapors at room temperature produces an ordered arrangement of dots with ∼112 nm spacing and ∼54 nm diameter. The template is highly resistant to dry etching with chlorine-based plasma, enabling its utilization on a variety of hard masks and substrates. The self-assembled PDMS dots were further exploited as a template for direct patterning of silicon, metal, and dielectric materials. This nanopatterning methodology circumvents expensive and time-consuming atomic layer deposition, wet processes, and sequential infiltration techniques. Application-wise, we show a process to fabricate nanostructured antireflection surfaces (nanocones) on a 2 in. silicon wafer, reducing the reflectance of planar silicon from 35% to below 0.5% over a broad wavelength range. Alternatively, nanocones made of TiO2 on silicon exhibit low reflectance (<3%) and improved transmittance into the substrate at the visible wavelength range. The measured optical properties concur with the simulation results. The versatility of the PS-b-PDMS templates was further utilized for nanopatterning materials such as silicon-on-insulator substrates, gallium arsenide, aluminum indium phosphide, and gallium nitride, which are important in electronics and photonics.

Ion Beam Assisted E-Beam Deposited TiN Microelectrodes-Applied to Neuronal Cell Culture Medium Evaluation.

Microelectrode material and cell culture medium have significant roles in the signal-to-noise ratio and cell well-being in in vitro electrophysiological studies. Here, we report an ion beam assisted e-beam deposition (IBAD) based process as an alternative titanium nitride (TiN) deposition method for sputtering in the fabrication of state-of-the-art TiN microelectrode arrays (MEAs). The effects of evaporation and nitrogen flow rates were evaluated while developing the IBAD TiN deposition process. Moreover, the produced IBAD TiN microelectrodes were characterized by impedance, charge transfer capacity (CTC) and noise measurements for electrical properties, AFM and SEM for topological imaging, and EDS for material composition. The impedance (at 1 kHz) of brand new 30 µm IBAD TiN microelectrodes was found to be double but still below 100 kΩ compared with commercial reference MEAs with sputtered TiN microelectrodes of the same size. On the contrary, the noise level of IBAD TiN MEAs was lower compared with that of commercial sputtered TiN MEAs in equal conditions. In CTC IBAD TiN electrodes (3.3 mC/cm2) also outperformed the sputtered counterparts (2.0 mC/cm2). To verify the suitability of IBAD TiN microelectrodes for cell measurements, human pluripotent stem cell (hPSC)-derived neuronal networks were cultured on IBAD TiN MEAs and commercial sputtered TiN MEAs in two different media: neural differentiation medium (NDM) and BrainPhys (BPH). The effect of cell culture media to hPSC derived neuronal networks was evaluated to gain more stable and more active networks. Higher spontaneous activity levels were measured from the neuronal networks cultured in BPH compared with those in NDM in both MEA types. However, BPH caused more problems in cell survival in long-term cultures by inducing neuronal network retraction and clump formation after 1-2 weeks. In addition, BPH was found to corrode the Si3N4 insulator layer more than NDM medium. The developed IBAD TiN process gives MEA manufacturers more choices to choose which method to use to deposit TiN electrodes and the medium evaluation results remind that not only electrode material but also insulator layer and cell culturing medium have crucial role in successful long term MEA measurements.

Effect of Partial Crystallization on the Structural and Luminescence Properties of Er3+-Doped Phosphate Glasses.

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al2O3, TiO2, and ZnO was investigated. The morphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO3)2 crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er3+ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al2O3, TiO2, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er3+ ions are incorporated in the precipitated crystals only in this glass ceramic.

Block Copolymer Patterning for Creating Porous Silicon Thin Films with Tunable Refractive Indices.

We investigated the use of block copolymer (BCP) self-assembly for tuning the optical properties of silicon. We fabricated porous silicon by etching a hexagonally ordered pore pattern onto the surface of silicon wafers using poly(styrene-2-vinylpyridine) to prepare the etch mask. Contrary to typical BCP lithography, we did not need to use a range of different polymers to vary the pore size. We used the dry etching time as a way to increase the pore diameter and thus the porosity. The optical properties of the fabricated porous thin films were characterized by two effective medium approximations. Both the volume-averaging theory and the 2D Maxwell-Garnett theory gave similar effective refractive index values, although the latter was more accurate in predicting the film porosity. The refractive indices of the produced thin films could be varied by controlling the porosity. A maximum decrease of 30% in the refractive index was observed at 34% porosity compared to bulk silicon. We also demonstrated over a 60% decrease in the reflectance of silicon at 500 nm wavelength. The presented BCP method can be used to tailor semiconductor and dielectric layers for photonic applications without the size limitations of conventional lithography or the unpredictability of other pore-forming fabrication methods.

Coating of gold nanoparticles made by pulsed laser ablation in liquids with silica shells by simultaneous chemical synthesis.

Coating of gold nanoparticles with silica shells by the well known Stöber-method requires the use of additional coupling agents to seed the growth of the shell as gold does not form a native oxide. Here we report a novel single-step process to create the gold nanoparticles directly into a mixture of tetraethyl orthosilicate and a catalyst by means of pulsed laser ablation in liquids. We observe that good silica shells are achieved only when all of the reagents are present during the production of the nanoparticles. Experiments with two different laser wavelengths: 515 nm and 1030 nm, show that the formation of the shell is efficient only with the laser wavelength close to the plasmon resonance of the gold nanoparticles. We propose a model indicating that the shell formation is initiated by laser-induced heating of the particles.