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The nanostructure of engineered bioscaffolds has a profound impact on cell response, yet its understanding remains incomplete as cells interact with a highly complex interfacial layer rather than the material itself. For bioactive glass scaffolds, this layer comprises of silica gel, hydroxyapatite (HA)/carbonated hydroxyapatite (CHA), and absorbed proteins-all in varying micro/nano structure, composition, and concentration. Here, we examined the response of MC3T3-E1 pre-osteoblast cells to 30 mol% CaO-70 mol% SiO 2 porous bioactive glass monoliths that differed only in nanopore size (6-44 nm) yet resulted in the formation of HA/CHA layers with significantly different microstructures. We report that cell response, as quantified by cell attachment and morphology, does not correlate with nanopore size, nor HA/CHO layer micro/nano morphology, or absorbed protein amount (bovine serum albumin, BSA), but with BSA's secondary conformation as indicated by its β-sheet/α-helix ratio. Our results suggest that the β-sheet structure in BSA interacts electrostatically with the HA/CHA interfacial layer and activates the RGD sequence of absorbed adhesion proteins, such as fibronectin and vitronectin, thus significantly enhancing the attachment of cells. These findings provide new insight into the interaction of cells with the scaffolds' interfacial layer, which is vital for the continued development of engineered tissue scaffolds.

For hard tissue regeneration, the bioactivity of a material is measured by its ability to induce the formation of hydroxyapatite (HA) under physiological conditions. It depends on the dissolution behavior of the glass, which itself is determined by the composition and structure of glass. The enhanced HA growth on nanoporous than on nonporous glass has been attributed by some to greater specific surface area (SSA), but to nanopore size distribution by others. To decouple the influence of nanopore size and SSA on HA formation, we have successfully fabricated homogeneous 30CaO-70SiO 2 (30C70S) model bioactive glass monoliths with different nanopore sizes, yet similar SSA via a combination of sol-gel, solvent exchange, and sintering processes. After incubation in PBS, HA, and Type-B carbonated HA (HA/B-CHA) form on nanoporous monoliths. The XPS, FTIR, and SEM analyses provide the first unambiguous demonstration of the influence of nanopore size alone on the formation pathway, growth rate, and microstructure of HA/CHA. Due to pore-size limited diffusion of PO 4 , two HA/CHA formation pathways are observed: HA/CHA surface deposition and/or HA/CHA incorporation into nanopores. HA/CHA growth rate on the surface of a nanoporous glass monolith is dominated by the pore-size limited transport of Ca 3- ions dissolved from nanoporous glass substrates. Furthermore, with increasing nanopore size, HA/CHA microstructures evolve from needle-like, plate-like, to flower-like appearance. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 886-899, 2019.2+ ions dissolved from nanoporous glass substrates. Furthermore, with increasing nanopore size, HA/CHA microstructures evolve from needle-like, plate-like, to flower-like appearance. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 886-899, 2019., (© 2018 Wiley Periodicals, Inc.)

Tissue regeneration is a significantly improved alternative to tissue replacement by implants. It requires porous bioscaffolds for the restoration of natural tissue rather than relying on bio-inactive, often metallic implants. Recently, we developed technology for fabricating novel, nano-macroporous bioactive 'tailored amorphous multi-porous (TAMP)' hard tissue scaffolds using a 70 mol% SiO 2 -30 mol% CaO model composition. The TAMP silicate scaffolds, fabricated by a modified sol-gel process, have shown excellent biocompatibility via the rapid formation of hydroxyapatite in biological fluids as well as in early tests with bone forming cells. Here we report an in depth investigation of the response of MC3T3-E1 pre-osteoblast cells and bone marrow derived (BMD) osteoclasts to these TAMP scaffolds. Light and electron microscopic imaging, gene and protein expression, and enzyme activity analyses demonstrate that MC3T3-E1 pre-osteoblasts adhere, proliferate, colonize, and differentiate on and inside the bioactive TAMP scaffolds. Additionally, BMD precursor cells mature into active osteoclasts and remodel the scaffold, highlighting the exceptional qualities of this novel scaffold material for bone tissue regeneration.

We analyzed the biological performance of spinodally and droplet-type phase-separated 45S5 Bioglass ® generated by quenching the melt from different equilibrium temperatures. MC3T3-E1 pre-osteoblast cells attached more efficiently to 45S5 Bioglass® with spinodal than to the one with droplet morphology, providing the first demonstration of the role of micro-/nano-scale on the bioactivity of Bioglass®. Upon exposure to biological solutions, phosphate buffered saline (PBS) and cell culture medium (α-MEM), a layer of hydroxyapatite (HA) formed on both glass morphologies. Although both Bioglass® varieties were incubated under identical conditions, and physico-chemical characteristics of the HA layers were similar, the adsorption magnitude of a model protein, bovine serum albumin (BSA, an abundant blood serum component) and its β-sheet/β-turn ratio and α-helix content were significantly higher on spinodal than droplet type Bioglass®. These results indicate that: (i) a protein layer quickly adsorbs on the surface of 45S5 Bioglass® varieties (with or without HA layer), (ii) the amount and the conformation of adsorbed proteins are guided by the glass micro-/nano-structure, and (iii) cell attachment and proliferation are influenced by the concentration and the conformation of attached proteins with a significantly better cell adhesion to spinodal type 45S5 Bioglass® substrate. Taken together, our results indicate that the biological performance of 45S5 Bioglass® can be improved further with a relatively simple, inexpensive fabrication procedure that provides a superior glass micro-/nano-structure. A simple modification to the fabrication procedure of classic 45S5 Bioglass® generates spinodal (A(a)) and droplet (A(b)) varieties and has a significant impact on protein adsorption (B) and cell adhesion (C).

Nanoporosity is known to impact the performance of implants and scaffolds such as bioactive glass (BG) scaffolds, either by providing a higher concentration of bioactive chemical species from enhanced surface area, or due to inherent nanoscale topology, or both. To delineate the role of these two characteristics, BG scaffolds have been fabricated with nearly identical surface area (81 and 83±2 m(2)/g) but significantly different pore size (av. 3.7 and 17.7 nm) by varying both the sintering temperature and the ammonia concentration during the solvent exchange phase of the sol-gel fabrication process. In vitro tests performed with MC3T3-E1 preosteoblast cells on such scaffolds show that initial cell attachment is increased on samples with the smaller nanopore size, providing the first direct evidence of the influence of nanopore topography on cell response to a bioactive structure. Furthermore, in vivo animal tests in New Zealand rabbits (subcutaneous implantation) indicate that nanopores promote colonization and cell penetration into these scaffolds, further demonstrating the favorable effects of nanopores in tissue-engineering-relevant BG scaffolds.

Laser-fabrication of complex, highly oriented three-dimensional ferroelectric single crystal architecture with straight lines and bends is demonstrated in lanthanum borogermanate model glass using a high repetition rate femtosecond laser. Scanning micro-Raman microscopy shows that the c-axis of the ferroelectric crystal is aligned with the writing direction even after bending. A gradual rather than an abrupt transition is observed for the changing lattice orientation through bends up to approximately 14 degrees. Thus the single crystal character of the line is preserved along the bend through lattice straining rather than formation of a grain boundary.

We report the kinetics of below band-gap light induced photodarkening in (80-x)GeS(2)-20Ga(2)S(3)-xAgI (x = 0 and 20 mol %) bulk chalcogenide glasses by measuring the time evolution of transmission spectra at every 10 milliseconds. The results prove clearly the enhancement of photosensivity upon doping of AgI compound in glasses. It is interesting to find that PD observed in AgI-doped glass totally disappears two hours later after the laser exposing even at room temperature. In significant contrast to 80GeS(2)-20Ga(2)S(3) glass that the metastable part of PD remains for a long time. We expect such a fast auto-recovery property in AgI-doped glass can be utilized for optical signal processing.

Thermal poling is a widely used method for creating glass surfaces with modified structure and altered properties by application of DC voltage. The mechanism of structural change has remained controversial, especially as poling is performed well below the glass transition temperature. Specifically, the role of Joule heating in facilitating structural transformation has remained an open question, conceivably through local heating to temperatures approaching Tg. Here, we investigate this possibility directly by in situ measurements of the local glass temperature during poling using infrared imaging. Examination near the anode region reveals only a slight temperature increase (~10°C) above the furnace temperature at the start of poling, and remains a few hundred degrees below Tg throughout. SIMS analysis revealed a ~1‐µm thick alkali depletion layer next to the anode. XPS analysis of the anode, cathode, and unpoled regions shows complex changes in structure and composition including migration of alkali ions, injection of hydrogen at the anode interface, removal of non‐bridging oxygen, and polymerization of the network via electrolysis. All these changes arise as a result of high electric field (~106 V/cm) produced across the highly resistive depletion layer, and refutes any significant increase in the temperature by Joule heating as the cause of their creation. [ABSTRACT FROM AUTHOR]

Single‐crystal architectures in glass, formed by a solid‐solid transformation via laser heating, are novel solids with a rotating lattice. To understand the process of lattice formation that proceeds via crystal growth, we have observed in situ Sb2S3 crystal formation under X‐ray irradiation with simultaneous Laue micro X‐ray diffraction (μXRD) pattern collection. By translating the sample with respect to the beam, we form rotating lattice single (RLS) crystal lines with a consistently linear relationship between the rotation angle and distance from nucleation site. The lines begin with a seed crystal, followed by a transition region comprising of sub‐grain or very similarly oriented grains, followed by the presence of a rotating lattice single crystal of unrestricted length. The results demonstrate that the primary cause of lattice rotation within RLS crystals is the densification accompanying the glass → crystal transformation, rather than stresses produced from the difference in thermal expansion coefficient of the two phases or paraelectric → ferroelectric transition during cooling to ambient temperature. [ABSTRACT FROM AUTHOR]

Abstract: Electric field‐induced softening (EFIS) is a recently discovered phenomenon leading to significant reduction in the furnace temperature at which glass softens under the application of DC voltage. Unfortunately, it is accompanied by local compositional changes due to migration of ions that could limit its usefulness. To overcome this drawback, we have investigated the same phenomenon using AC voltage, that is, AC‐EFIS on a sodium disilicate glass and a 50/50 mixed lithium‐sodium disilicate glass of very different ionic resistivity yet similar network structure. The results show that the magnitude of EFIS temperature reduction is significantly greater for AC compared to DC for both glass compositions. The enhancement of EFIS under AC voltage appears to be due to a more uniform power dissipation and self‐healing of changes than under DC voltage. This uniformity allows for the overall sample temperature to increase throughout the bulk and provides a better technique for practical applications than the DC case which produces potentially undesirable changes, especially in the anode region. [ABSTRACT FROM AUTHOR]

Positron annihilation lifetime measurements are performed for sol–gel-derived 70 mol% SiO2–30 mol% CaO bioactive glass. Strong positronium formation processes are shown to be an inherent feature for these kinds of materials. Observed orthopositronium (o-Ps) lifetimes show a three-modal distribution with lifetime values weighed at ∼2, ∼18, and ∼70 ns. The exposure of the investigated sol–gel-derived bioactive glasses to water vapor significantly modifies o-Ps lifetime distribution due to the penetration of water molecules into the nanopores, indicating high ratio of their interconnectivity. Classic Tao–Eldrup equation is used to relate the o-Ps lifetimes with the size of nanopores, whose distribution is verified by nitrogen adsorption porosimetry. [ABSTRACT FROM AUTHOR]

Abstract: The mixed electronic–ionic conduction in 0.5[xAg2O–(1−x)V2O5]–0.5TeO2 glasses with x=0.1–0.8 has been investigated over a wide temperature range (70–425K). The mechanism of dc conductivity changes from predominantly electronic to ionic within the 30⩽mol% Ag2O⩽40 range; it is correlated with the underlying change in glass structure. The temperature dependence of electronic conductivity has been analyzed quantitatively to determine the applicability of various models of conduction in amorphous semiconducting glasses. At high temperature, T>θ D/2 (where θ D is the Debye temperature) the electronic dc conductivity is due to non-adiabatic small polaron hopping of electrons for 0.1⩽x⩽0.5. The density of states at Fermi level is estimated to be N(E F)≈1019–1020 eV−1 cm−3. The carrier density is of the order of 1019 cm−3, with mobility ≈2.3×10−7–8.6×10−9 cm2 V−1 s−1 at 300K. The electronic dc conductivity within the whole range of temperature is best described in terms of Triberis–Friedman percolation model. For 0.6⩽x⩽0.8, the predominantly ionic dc conductivity is described well by the Anderson–Stuart model. [Copyright &y& Elsevier]

High-resolution X-ray photoelectron spectroscopy is used to identify the mechanism of X-ray-induced Ag diffusion into Ge30Se70 chalcogenide glass thin films, which are prepared in situ to avoid oxygen contamination. From the analysis of Ge 3d, Se 3d, and Ag 3d core levels, and valence band spectra, changes in the electronic structure are determined as Ag diffuses gradually with increasing irradiation. The ternary phase based on Ge2Se6 units, which contains homopolar Ge–Ge bonds, forms when diffusion approaches equilibrium where Ag content ∼30 at.%. The formation of a Se-rich composition is indicated in the near-surface region at the initial stage of the process, but the previously assumed Ag2Se phase is not detected. [ABSTRACT FROM AUTHOR]

Using a novel, selective heating by Nd:YAG laser, a single-crystal architecture is created in a model glass system, Sm0.5La0.5BGeO5, which devitrifies congruently into a ferroelectric phase of the same composition as the parent glass. The Sm3+ ions in glass absorb the light and heat the matrix locally resulting in devitrification. Initially, a polycrystalline spot is formed. However, with optimum laser power, scanning speed, and the depth of focus, one of the grains acts as the seed for further growth as a single crystal. By programming the relative displacement of the glass with respect to laser spot, desired single ferroelectric crystal architecture is created. The optical functionalities (guiding of light and second harmonic generation) of the architectures are shown, which demonstrate the viability of this method for constructing active elements in optical integrated circuits. The single-crystal nature of the architecture is confirmed from the electron backscattered diffraction results. [ABSTRACT FROM AUTHOR]

The article offers information on a study on the fabrication of nano-macro porous soda-lime phosphosilicate bioactive glass by the melt-quench method presented at the 31st International Conference on Advanced Ceramics and Composites. Heat treatment of 45S and 49S glasses exhibits highly interconnected microstructure due to the coalescence and growth of second-phase particles. Chemical and thermal treatments that produce initial composition influence hydroxyapatite (HA) formation and bioactivity.

Abstract: Low-Energy Ion Scattering (LEIS) spectroscopy is a technique with a unique sensitivity to the elemental composition of the surface top atomic layers of a solid. LEIS measurements of simple binary silicate glasses (with Na2O, Cs2O or BaO) have shown differences in composition between the as-cast glass surface and the vacuum-fracture surface. The as-cast surface is usually depleted of modifier ions compared to the nominal (batch) bulk glass composition, while the fracture surface is typically enriched with the monovalent modifier species, but not the divalent barium. While the melt surface depletion can probably be attributed to evaporation from the hot melt surface, the origin of the strong accumulation on the fracture surfaces is less clear. It is certainly possible that the fracture may have been preferentially guided by regions already alkali-enriched within the bulk of the glass. But considering the extreme surface sensitivity of this method, a surface-monolayer localized enrichment with alkali due to the stress gradient created by the fracture or the electric field created by dangling bonds on the vacuum-fractured surface is also possible. The Si/O ratio shows usually little deviation from the nominal glass batch value, falling within the estimated errors. [Copyright &y& Elsevier]

Photoinduced expansion is a special property of chalcogenide glasses, which makes them useful for various applications in photonics. A clear understanding of the kinetics and the topography of photoinduced effects is fundamental to improve potential applications. A detailed study on bulk glass is performed using in situ Atomic Force Microscope measurements. The corresponding expected thermal contribution is obtained by numerical simulation using Finite Elemental Analysis method. The results show a significant difference between the dynamics of metastable/permanent and transitory effects, with the permanent photoexpansion being much larger in magnitude and slower in kinetics than the transient or reversible changes. The former effect is of athermal origin. However, the dynamic response of the latter is similar to that expected from thermoelastic expansion, suggesting a close correlation between the two effects, which remains to be established. Image 1 • Thermal and athermal contributions for the dynamics of the laser induced effects in A s 2 S 3 bulk glass. • In situ laser-induced surface deformation measurement by Atomic Force Microscopy. • Numerical determination of the thermal contribution for the transient part of photoexpansion. [ABSTRACT FROM AUTHOR]

A carefully controlled femtosecond laser irradiation offers the possibility of fabricating high quality, 3D functional single-crystal patterns designed for integrated optical devices deep inside glass. Notwithstanding, a general theory relating particular irradiation conditions to crystal growth dynamics and resulting morphologies remains to be established. To overcome this challenge, crystal lines written in glass under varying conditions are investigated in this work by optical microscopy, scanning electron microscopy, and electron backscatter diffraction in the congruently crystallizing LaBGeO 5 model system. We show that despite a strongly preferential orientation of the optic axis along the direction of laser scanning, typical morphologies of fs laser-written crystals in this system are inhomogeneous due to low-angle grain boundaries and rotations or inversions of the preferential axis. Nevertheless, uniform single crystals can be produced under optimized irradiation conditions. The theoretical dynamics of crystal growth is developed within the unique environment of a moving laser-induced melt to explain these results, including the role of competitive growth in establishing the preferential lattice orientation; the effects of temperature gradient and focal scan rate in establishing crystal morphology and cross-section shape; and most notably, the specific design criteria that must be met for stable single-crystal growth. [ABSTRACT FROM AUTHOR]

Abstract: Glasses with compositions (40− x)PbO-- x ZnO--60(B2O3--SiO2) (x =5, 10, 15, 20) have been prepared. Substitution of ZnO for PbO increased glass bandgap (E g ) and crystallization ability greatly. Crystalline phases of bulk glasses after rapid thermal processing (RTP) were identified by X-ray diffraction (XRD). Transmission line model (TLM) was employed to measure the electrical performance of Ag electrodes screen printed on polycrystalline Si substrates using Ag thick-film pastes and by RTP. The conductivity (σ) decreased while specific contact resistance (ρ c ) was not monotonic varied with increasing ZnO content. The correlation between electrical performance and glass barrier formed on the Ag gridline and Si emitter interface has been investigated. [ABSTRACT FROM AUTHOR]