Computational simulations of solid state NMR spectra: a new era in structure determination of oxide glasses

The application of the MD-GIPAW approach to the calculation of NMR parameters, line widths and shapes of the spectra of oxide glasses is reviewed. Emphasis is given to the decisive role of this approach both as an interpretative tool for a deeper understanding of the spectral behavior of complex systems and as a predictive instrument to map NMR data in a distribution of structural parameters and vice versa (structural inversion method). After a brief overview of the basic features of oxide glasses and the experimental techniques routinely employed to investigate their structure, a general description of the computational methods usually adopted to generate sound structural models of amorphous materials is offered. The computational recipe used to compute the solid state NMR spectra of oxide glasses and to establish quantitative structural-NMR property relationships is then described. Finally, these concepts are applied to 'simple' network former glasses and more complex silicates, aluminosilicate, phosphosilicate and borosilicate glasses of scientific relevance. The final section is dedicated to the future developments that will hopefully improve the computational approach described overcoming some of the current limitations

Assessment of the basis set effect on the structural and electronic properties of organic-protected gold nanoclusters

We have investigated the structural and optical properties of five monolayer-protected gold nanoclusters with a combination of exchange–correlation functionals, namely B-PBE for the geometry relaxation and CAM-B3LYP for the time-dependent calculations. We have tested the accuracy of five different basis sets in reproducing the experimental structures of these nanoclusters, and we have found that even a rather small basis set (single zeta) can outperform a significantly larger one (double zeta) if some selected atoms are treated with polarization functions. Namely, the sulfur and phosphorous atoms of the capping thiols and phosphines usually are hypervalent when bonded to the gold inner core; therefore, polarization functions allow them significantly more structural flexibility. With the two best performing basis sets, we carried out optical calculations and found that the resulting UV–Vis profiles are largely similar, in particular the energy and orbital contributions of the optical gaps are very close. The results support the use of the small basis set proposed here to investigate larger nanoclusters with general hybrid and range-corrected hybrid functionals

An atomic-level look at the structure-property relationship of cerium-doped glasses using classical molecular dynamics

Ce-containing bioactive glasses are of great interest in biomedical field since they exert antioxidant properties associated with low toxicity and a broad spectrum of bacteriostatic activities. The results obtained by classical molecular dynamics simulations allow the elucidation of the correlations between the effect of the inclusion of cerium doping ions into the structure of phosphosilicate and silicate bioactive glasses and their properties. The addition of small quantities of Ce to the silicate bioglass favours the depolymerisation of the silicate network with a positive effect on the ability to dissolve in body fluid. Moreover, the under coordination of both the Ce3+ and Ce4+ species in these glasses enhances their catalytic activity towards hydrogen peroxide. Conversely, the formation of cerium phosphate domains in the phosphosilicate glasses leads to detrimental effects for both the solubility and the catalytic activity of the glasses. Finally, a new quantitative view of the structure-activity relationships governing the macroscopic properties of these glasses has been obtained by means of structural descriptor that takes into account the fragmentation of the Si network and the consequent rearrangement of the modifier ions and the network destruction per cerium unit descriptor

Accurate First-Principle Prediction of 29Si and 17O NMR Parameters in SiO2 Polymorphs: The Cases of Zeolites Sigma-2 and Ferrierite

Abstract: The magnetic shielding tensors of silica polymorphs have been investigated by meansof quantum chemical calculations. Several levels of theory, from Hartree-Fock to the lastgeneration of Density Functional Theory based approaches, have been tested on predicting29Si and 17O isotropic and principal components of the chemical shift tensors together with 17Oquadrupolar coupling constants. The NMR parameters have been computed on all known silicasystems, namely, R-quartz, R-cristobalite, coesite, Sigma-2, and ferrierite zeolites. Besides, clusterbased approaches have been compared to a hybrid Quantum-Mechanics/Molecular-Mechanics(QM/MM) method, within the ONIOM scheme. The convergence of computed 17O NMRparameters with respect to cluster size is found to be system-dependent. Excellent agreementbetween computed and experimental data has been found for 29Si NMR parameters of thedifferent Si sites of silica polymorphs and of Sigma-2 and ferrierite zeolites

Alginate Beads Containing Cerium-Doped Mesoporous Glass and Curcumin: Delivery and Stabilization of Therapeutics

: Cancer is a leading cause of death worldwide, its genesis and progression are caused by homeostatic errors, and reactive oxygen species play a major role in promoting aberrant cancer homeostasis. In this scenario, curcumin could be an interesting candidate due to its versatile antioxidant, anti-inflammatory, anti-tumor, anti-HIV, and anti-infection properties. Nonetheless, the major problem related to its use is its poor oral bioavailability, which can be overcome by encapsulating it into small particles, such as hydrogel beads containing mesoporous silica. In this work, various systems have been synthesized: starting from mesoporous silica glasses (MGs), cerium-containing MGs have been produced; then, these systems have been loaded with 4 to 6% of curcumin. Finally, various MGs at different compositions have been included in alginate beads. In vitro studies showed that these hybrid materials enable the stabilization and effective delivery of curcumin and that a synergic effect can be achieved if Ce3+/Ce4+ and curcumin are both part of the beads. From swelling tests, it is possible to confirm a controlled curcumin release compartmentalized into the gastrointestinal tract. For all beads obtained, a curcumin release sufficient to achieve the antioxidant threshold has been reached, and a synergic effect of cerium and curcumin is observed. Moreover, from catalase mimetic activity tests, we confirm the well-known catalytic activity of the couple Ce3+/Ce4+. In addition, an extremely good radical scavenging effect of curcumin has been demonstrated. In conclusion, these systems, able to promote an enzymatic-like activity, can be used as drug delivery systems for curcumin-targeted dosing

A first step towards the understanding of the 5-HT3 receptor subunitheterogeneity from a computational point of view

The functional serotonin type-3 receptor (5-HT3-R), which is the target of many neuroactive drugs, isknown to be a homopentamer made of five identical subunits A (5-HT3A-R) or a binary heteropentamermade of subunits A and B (5-HT3A/B-R) with a still debated arrangement and stoichiometry. Thiscomplex picture has been recently further complicated by the discovery of additional 5-HT3-R subunits,C, D, and E, which, similarly to the B subunit, are apparently able to form functional receptors only ifco-expressed with subunit A. Being the binding site for both serotonin and antagonists (i.e. drugs)located at the extracellular interface between two adjacent subunits, the large variability of the 5-HT3-Rcomposition becomes a crucial issue, since it can originate many different interfaces providing nonequivalentligand binding sites and complicating the pharmacological modulation. Here, the different5-HT3-R interfaces are analysed, on the bases of the structural conformations of previously built 3Dhomology models and of the known subunit sequences, by addressing their physicochemicalcharacterization. The results confirm the presence of an aromatic cluster located in the core of the A–Ainterface as a key determinant for having an interface both stable and functional. This is used as adiscriminant to make hypotheses about the capability of all the other possible interfaces constituted bythe known 5-HT3-R sequences A, B, C, D, and E to build active receptors

The antioxidant properties of Ce-containing bioactive glass nanoparticles explained by Molecular Dynamics simulations

Molecular dynamics simulations of two glass nanoparticles with composition 25Na2O\ub725CaO 50SiO2 mol% (Ce-K NP) and 46.1SiO2\ub724.4Na2O\ub726.9CaO\ub7 2.6P2O5 mol.% (Ce-BG NP) doped with 3.6 mol% of CeO2 have been carried out in order to explain the enhanced antioxidant properties of the former glass with respect to the latter. The present models show that the different catalase mimetic activity of the two NPs is related to the Ce3+/Ce4+ ratio exposed at their surface. In fact, this ratio is about 3.5 and 13 in the bulk and at the surface of the Ce-BG NP, and 1.0 and 2.1 in the bulk and at the surface of the Ce-K NPs, respectively. Since both oxidation states are necessary for the catalysis of the dismutation reaction of hydrogen peroxides, NPs with a very high Ce3+/Ce4+ ratio possess poorer antioxidant properties. Moreover, our simulations reveal that the already low silicate connectivity found in the bulk glasses examined here is further reduced on the nanoparticle surface, whereas the Na+/Ca2+ ratio rapidly increases. Sodium, calcium and cerium sites in proximity of the surface are found to be under-coordinated, prone to quickly react with water present in physiological environments, thus accelerating the glass biodegradatio

DFT and TD-DFT Study of the Chemical Effect in the SERS Spectra of Piperidine Adsorbed on Silver Colloidal Nanoparticles

The surface-enhanced Raman scattering (SERS) spectra of piperidine adsorbed on silver/chloride colloids were studied by a combined density functional theory (DFT)/time dependent DFT (TD-DFT) approach. The mechanism of chemical enhancement on the Raman signals is due to at least two contributions: the first comes from the changes in the molecular force constants and the dynamic polarizabilities of the normal modes, when the molecule is chemisorbed. DFT calculations satisfactorily reproduce the SERS spectra of piperidine adsorbed on silver, showing that the species formed on the silver particle is a complex formed by a deprotonated piperidine linked to a silver cation. A second contribution to the SERS chemical enhancement is due to a resonance Raman effect occurring when the wavelength of the Raman excitation falls within the electronic excitation band of the molecule/metal complex. Actually, the SERS spectra of piperidine show a significant dependence on the wavelength of the laser excitation, with a marked enhancement in the green-light region. TD-DFT calculations on the most-probable complex explain this behavior, because a strong excitation band of the complex is calculated in the green spectral region. This pinpoints that a resonance between the exciting radiation and the absorption band of this complex is responsible for this enhancement effect

Bioglasses: glasses for medical applications

bioglasses for medical application