Novel Organic-Inorganic Nanocomposite Hybrids Based on Bioactive Glass Nanoparticles and Their Enhanced Osteoinductive Properties.

Inorganic-organic hybrid biomaterials have been proposed for bone tissue repair, with improved mechanical flexibility compared with scaffolds fabricated from bioceramics. However, obtaining hybrids with osteoinductive properties equivalent to those of bioceramics is still a challenge. In this work, we present for the first time the synthesis of a class II hybrid modified with bioactive glass nanoparticles (nBGs) with osteoinductive properties. The nanocomposite hybrids were produced by incorporating nBGs in situ into a polytetrahydrofuran (PTHF) and silica (SiO2) hybrid synthesis mixture using a combined sol-gel and cationic polymerization method. nBGs ~80 nm in size were synthesized using the sol-gel technique. The structure, composition, morphology, and mechanical properties of the resulting materials were characterized using ATR-FTIR, 29Si MAS NMR, SEM-EDX, AFM, TGA, DSC, mechanical, and DMA testing. The in vitro bioactivity and degradability of the hybrids were assessed in simulated body fluid (SBF) and PBS, respectively. Cytocompatibility with mesenchymal stem cells was assessed using MTS and cell adhesion assays. Osteogenic differentiation was determined using the alkaline phosphatase activity (ALP), as well as the gene expression of Runx2 and Osterix markers. Hybrids loaded with 5, 10, and 15% of nBGs retained the mechanical flexibility of the PTHF-SiO2 matrix and improved its ability to promote the formation of bone-like apatite in SBF. The nBGs did not impair cell viability, increased the ALP activity, and upregulated the expression of Runx2 and Osterix. These results demonstrate that nBGs are an effective osteoinductive nanoadditive for the production of class II hybrid materials with enhanced properties for bone tissue regeneration.

Structure of amorphous materials in the NASICON system Na1+xTi2SixP3-xO12.

The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system Na1+xTi2SixP3-xO12withx= 0.8 andx= 1.0 was explored by combining neutron and high-energy x-ray diffraction with29Si,31P and23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The29Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si4units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The31P{23Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the31P MAS NMR line shape originates from four-coordinated Pnunits, wheren= 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their31P-23Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na+modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti-O coordination number of 5.17(4) forx= 0.8 and 4.86(4) forx= 1.0. A mismatch between the P-O and Si-O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure.

Solid-State Nuclear Magnetic Resonance Techniques for the Structural Characterization of Geminal Alane-Phosphane Frustrated Lewis Pairs and Secondary Adducts.

The first comprehensive solid-state nuclear magnetic resonance (NMR) characterization of geminal alane-phosphane frustrated Lewis pairs (Al/P FLPs) is reported. Their relevant NMR parameters (isotropic chemical shifts, direct and indirect 27 Al-31 P spin-spin coupling constants, and 27 Al nuclear electric quadrupole coupling tensor components) have been determined by numerical analysis of the experimental NMR line shapes and compared with values computed from the known crystal structures by using density functional theory (DFT) methods. Our work demonstrates that the 31 P NMR chemical shifts for the studied Al/P FLPs are very sensitive to slight structural inequivalences. The 27 Al NMR central transition signals are spread out over a broad frequency range (>200 kHz), owing to the presence of strong nuclear electric quadrupolar interactions that can be well-reproduced by the static 27 Al wideband uniform rate smooth truncation (WURST) Carr-Purcell-Meiboom-Gill (WCPMG) NMR experiment. 27 Al chemical shifts and quadrupole tensor components offer a facile and clear distinction between three- and four-coordinate aluminum environments. For measuring internuclear Al⋅⋅⋅P distances a new resonance-echo saturation-pulse double-resonance (RESPDOR) experiment was developed by using efficient saturation via frequency-swept WURST pulses. The successful implementation of this widely applicable technique indicates that internuclear Al⋅⋅⋅P distances in these compounds can be measured within a precision of ±0.1 Å.

Composition-Structure-Solubility Relationships in Borosilicate Glasses: Toward a Rational Design of Bioactive Glasses with Controlled Dissolution Behavior.

Owing to their fast but tunable degradation kinetics (in comparison to silicates) and excellent bioactivity, the past decade has witnessed an upsurge in the research interest of borate/borosilicate-based bioactive glasses for their potential use in a wide range of soft tissue regeneration applications. Nevertheless, most of these glasses have been developed using trial-and-error approaches wherein SiO2 has been gradually replaced by B2O3. One major reason for using this empirical approach is the complexity of short-to-intermediate range structures of these glasses which greatly complicate the development of a thorough understanding of composition-structure-solubility relationships in these systems. Transitioning beyond the current style of composition design to a style that facilitates the development of bioactive glasses with controlled ion release tailored for specific patients/diseases requires a deeper understanding of the compositional/structural dependence of glass degradation behavior in vitro and in vivo. Accordingly, the present study aims to decipher the structural drivers controlling the dissolution kinetics and ion-release behavior of potentially bioactive glasses designed in the Na2O-B2O3-P2O5-SiO2 system across a broad compositional space in simulated body environments (pH = 7.4). By employing state-of-the-art spectroscopy-based characterization techniques, it has been shown that the degradation kinetics of borosilicate glasses depend on their R (Na2O/B2O3) and K (SiO2/B2O3) ratios, while the release of particular network-forming moieties from the glass into solution is strongly influenced by their role in-and effect on-the short-to-intermediate-range molecular structure. The current study aims to promote a rational design of borosilicate-based bioactive glasses, where a delicate balance between maximizing soft tissue regeneration and minimizing calcification and cytotoxicity can be achieved by tuning the release of ionic dissolution products (of controlled identity and abundance) from bioactive glasses into physiological media.

Aerogelation of Polymer-Coated Photoluminescent, Plasmonic, and Magnetic Nanoparticles for Biosensing Applications.

Macroscopic materials with nanoscopic properties have recently been synthesized by self-assembling defined nanoparticles to form self-supported networks, so-called aerogels. Motivated by the promising properties of this class of materials, the search for versatile routes toward the controlled assembly of presynthesized nanoparticles into such ultralight macroscopic materials has become a great interest. Overcoating procedures of colloidal nanoparticles with polymers offer versatile means to produce aerogels from nanoparticles, regardless of their size, shape, or properties while retaining their original characteristics. Herein, we report on the surface modification and assembly of various building blocks: photoluminescent nanorods, magnetic nanospheres, and plasmonic nanocubes with particle sizes between 5 and 40 nm. The polymer employed for the coating was poly(isobutylene-alt-maleic anhydride) modified with 1-dodecylamine side chains. The amphiphilic character of the polymer facilitates the stability of the nanocrystals in aqueous media. Hydrogels are prepared via triggering the colloidally stable solutions, with aqueous cations acting as linkers between the functional groups of the polymer shell. Upon supercritical drying, the hydrogels are successfully converted into macroscopic aerogels with highly porous, open structure. Due to the noninvasive preparation method, the nanoscopic properties of the building blocks are retained in the monolithic aerogels, leading to the powerful transfer of these properties to the macroscale. The open pore system, the universality of the polymer-coating strategy, and the large accessibility of the network make these gel structures promising biosensing platforms. Functionalizing the polymer shell with biomolecules opens up the possibility to utilize the nanoscopic properties of the building blocks in fluorescent probing, magnetoresistive sensing, and plasmonic-driven thermal sensing.

Effect of boron incorporation on the bioactivity, structure, and mechanical properties of ordered mesoporous bioactive glasses.

B2O3 doped (0.5-15 mol%) ordered mesoporous bioactive glasses (MBG) with the composition 80% SiO2-15% CaO-5% P2O5 were synthesized via a sol-gel based evaporation-induced self-assembly process using the block-copolymer P123 as a structure directing agent and characterized by biokinetic, mechanical and structural investigations. Nitrogen physisorption isotherms and electron microscopy indicate no detrimental effect of B2O3 on the ordered hexagonal pore structure. Boron incorporation increases both the bulk modulus and hardness of the glasses. In vitro bioactivity tests reveal a rapid initial release of Ca2+ and PO43- ions, followed by formation of hydroxyapatite carbonate within a few hours. Contrary to the tight incorporation of Al in Al-doped MBGs, the rapid release of borate species into simulated-body-fluid suggests loosely bound species localized at the internal surfaces of the mesopores. 29Si, 11B, 31P, and 1H solid state NMR spectroscopy reveal that the majority of the borate is present as anionic BO4/2- species. The need for charge compensation leads to an increase in the average degree of polymerization of the phosphate species for high boron contents. 11B{31P} rotational echo double resonance NMR results reveal the absence of B-O-P linkages. This structural model explains the rapid release of borate and the enhanced dissolution kinetics of the Ca2+ and phosphate species.

Rare-earth solid-state NMR spectroscopy of intermetallic compounds: The case of the 175Lu isotope.

The feasibility of high-resolution 175Lu solid-state NMR spectroscopy in intermetallic compounds crystallizing with cubic crystal structures is explored by magic-angle spinning NMR at different magnetic flux densities. The large quadrupole moment of this isotope (3.49 × 10-28 m2) restricts observation of the NMR signal to nearly perfectly ordered crystalline samples. Signals are successfully detected and analyzed in the binary pnictides LuPn (NaCl-type structure; Pn = P, As, Sb) and the intermetallic compounds LuPtSb and LuAuSn, both crystallizing with the MgAgAs-type structure. Sources of line broadening are discussed based on field-dependent static and MAS-NMR spectra, providing guidance with respect to measurement conditions resulting in reliable results. The results highlight the importance of ionic/covalent bonding effects for the detectability of the signal, which reduce the probability of real structure effects commonly observed in intermetallic compounds. No 175Lu NMR signals can be observed in various cubic Heusler compounds. This is attributed to mixed site occupancies and other structural defects producing electric field gradients whose interaction with the 175Lu quadrupole moments broadens the signal beyond detection.

Recoupling dipolar interactions with multiple I=1 quadrupolar nuclei: A 11B{6Li} and 31P{6Li} rotational echo double resonance study of lithium borophosphate glasses.

The case of rotational echo double resonance (REDOR) experiments on the observe nuclei 11B and 31P interacting with multiple I=1 quadrupolar nuclei is analyzed in detail by SIMPSON simulations and experimental studies. The simulations define the region within the parameter space spanned by nutation frequency, quadrupolar coupling constant and spinning frequency where the parabolic analysis of the initial REDOR curve in terms of dipolar second moments has validity. The predictions are tested by experimental studies on the crystalline model compounds lithium diborate and lithium pyrophosphate, which are subsequently extended to measure dipolar second moments M2(11B{6Li}) and M2(31P{6Li}) in three borophosphate glasses. The data indicate that the lithium cations interact significantly more strongly with the phosphate than with the borate species, despite the formally anionic character of four-coordinate boron and the formally neutral character of the ultraphosphate (P(3)) units to which they are linked.