Synchrotron X-ray imaging via ultra-small-angle scattering: principles of quantitative analysis and application in studying bone integration to synthetic grafting materials

Optimized experimental conditions for extracting accurate information at subpixel length scales from analyzer-based X-ray imaging were obtained and applied to investigate bone regeneration by means of synthetic beta-TCP grafting materials in a rat calvaria model. The results showed a 30% growth in the particulate size due to bone ongrowth/ingrowth within the critical size defect over a 1-month healing period.

Characterization and spectroscopic analysis of phenol-ethanol hydrogen bonded clusters

Different hydrogen bonded clusters involving phenol and ethanol are studied theoretically using MP2/aug-cc-pVDZ. Nine different 1: 1 clusters are obtained and analyzed according to their stability and spectroscopic properties. Different isomeric forms of ethanol are considered. Attention is also devoted to the spectral shift of the characteristic pi -> pi* transition of phenol. Using TDHF, CIS, CIS(D) and TDB3LYP in aug-cc-pVDZ basis set, all results agree that a red shift is obtained when phenol is the hydrogen donor and a blue shift is obtained in the opposite case. These results are used to rationalize the red shift observed for phenol in liquid ethanol. (C) 2010 Elsevier B.V. All rights reserved.

Thermodynamic Stabillity of Hydrogen-Bonded Systems in Polar and Nonpolar Environments

The thermodynamic properties of a selected set of benchmark hydrogen-bonded systems (acetic acid dimer and the complexes of acetic acid with acetamide and methanol) was studied with the goal of obtaining detailed information on solvent effects on the hydrogen-bonded interactions using water, chloroform, and n-heptane as representatives for a wide range in the dielectric constant. Solvent effects were investigated using both explicit and implicit solvation models. For the explicit description of the solvent, molecular dynamics and Monte Carlo simulations in the isothermal isobaric (NpT) ensemble combined with the free energy perturbation technique were performed to determine solvation free energies. Within the implicit solvation approach, the polarizable continuum model and the conductor-like screening model were applied. Combination of gas phase results with the results obtained from the different solvation models through an appropriate thermodynamic cycle allows estimation of complexation free energies, enthalpies, and the respective entropic contributions in solution. Owing to the strong solvation effects of water the cyclic acetic acid dimer is not stable in aqueous solution. In less polar solvents the double hydrogen bond structure of the acetic acid dimer remains stable. This finding is in agreement with previous theoretical and experimental results. A similar trend as for the acetic acid dimer is also observed for the acetamide complex. The methanol complex was found to be thermodynamically unstable in gas phase as well as in any of the three solvents. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 31: 2046-2055, 2010

Many-body energy decomposition of hydrogen-bonded glycine clusters in gas-phase

A detailed analysis of the many-body contribution to the interaction energies of the gas-phase hydrogen-bonded glycine clusters, (Gly)(N), N = 1-4 is presented. The energetics of the hydrogen-bonded dimer, trimer and tetramer complexes have been analyzed using density-functional theory. The magnitude of the two-through four-body energy terms have been calculated and compared. The relaxation energy and the two-body energy terms are the principal contributors to the total binding energy. Four-body contribution is negligible. However, the three-body contribution is found to be sizable and the formation of the cyclic glycine trimer presents geometric strains that make it less favorable. (C) 2010 Elsevier B.V. All rights reserved.

Ab Initio Calculations of Structural Evolution and Conductance of Benzene-1,4-dithiol on Gold Leads

By performing at) initio density functional theory (DFT) calculations and electronic transport simulations based on the OFT nonequilibrium Green`s functions method we investigate how the conformational changes of a benzene-1,4-dithiol molecule bonded to gold affect the molecular transport as the electrodes are separated from each other. In particular we consider the full evolution of the stretching process until the Junction breaking point and compare results obtained with a standard semilocal exchange and correlation functional to those computed with a self-interaction corrected method. We conclude that the inclusion of self-interaction corrections is fundamental for describing both the molecule conductance and its stability against conformational fluctuations.

Oxygen-mediated electron transport through hybrid silicon-organic interfaces

We investigate from first principles the electronic and transport properties of hybrid organic/silicon interfaces of relevance to molecular electronics. We focus on conjugated molecules bonded to hydrogenated Si through hydroxyl or thiol groups. The electronic structure of the systems is addressed within density functional theory, and the electron transport across the interface is directly evaluated within the Landauer approach. The microscopic effects of molecule-substrate bonding on the transport efficiency are explicitly analyzed, and the oxygen-bonded interface is identified as a candidate system when preferential hole transfer is needed.

X-ray transmission through nanostructured and microstructured CuO materials

This study presents a comparison of the X-ray transmission through microsized and nanosized materials. For this purpose CuO nanoparticles, with 13.4 nm average grain size, and CuO microparticles, with a mean particle size of 56 mu m, were incorporated separately to beeswax in a concentration of 5%. Results show that the transmission through the above material plates with microsized and nanosized CuO was almost the same for X-ray beams generated at 60 and 102 kV tube voltages. However, for the radiation beams generated at 26 and 30 kV tube voltages the X-rays are more attenuated by the nanostructured CuO plates by a factor of at least 14%. Results suggest that the difference in the low energy range may be due to the higher number of particles/gram in the plates designed with CuO nanoparticles and due to the grain size effect on the X-ray transmission. (C) 2010 Elsevier Ltd. All rights reserved.

FT-IR spectroscopy assessment of aesthetic dental materials irradiated with low-dose therapeutic ionizing radiation

The aim of the present study was to evaluate the effects of low-dose therapeutic ionizing radiation on different aesthetic dental materials. Forty five specimens (n = 45) of three different aesthetic restorative materials were prepared and randomly divided into five groups: G1 (control group); G2, G3, G4, G5 experimental groups irradiated respectively with 0.25, 0.50, 0.75, and 1.00 Gy of gamma radiation by the (60)Co teletherapy machine. Chemical analyses were performed using a FT-IR Nicolet 520 spectrophotometer with reflectance diffuse technique. Even a minimal exposition at ionizing radiation in therapeutic doses can provide chemical changes on light-cured composite resins. The three studied restorative materials showed changes after exposure at gamma radiation, however the increase of the radiation dose did not contribute to an increase in this effect.

Crystal Engineering of an Anti-HIV Drug Based on the Recognition of Assembling Molecular Frameworks

A rational strategy was employed for design of an orthorhombic structure of lamivudine with maleic acid. On the basis of the lamivudine saccharinate structure reported in the literature, maleic acid was chosen to synthesize a salt with the anti-HIV drug because of the structural similarities between the salt formers. Maleic acid has an acid-ionization constant of the anti first proton and an arrangement of their hydrogen bonding functionalities similar to those of saccharin. Likewise, there is a saccharin-like conformational rigidity in maleic acid because of the hydrogen-bonded ring formation and the Z-configuration around the C=C double bond. As was conceivably predicted, lamivudine maleate assembles into a structure whose intermolecular architecture is related to that of saccharinate salt of the drug. Therefore, a molecular framework responsible for crystal assembly into a lamivudine saccharinate-like structure could be recognized in the salt formers. Furthermore, structural correlations and structure-solubility relationships were established for lamivudine maleate and saccharinate. Although there is a same molecular framework in maleic acid and saccharin, these salt formers are Structurally different in some aspects. When compared to saccharin, neither out-of-plane SO(2) oxygens nor a benzene group occur in maleic acid. Both features could be related to higher solubility of lamivudine maleate. Here, we also anticipate that multicomponent molecular crystals of lamivudine with other salt formers possessing the molecular framework responsible for crystal assembly can be engineered successfully.

Adhesion as a tool for in-built nanotechnology design in cementitious materials

Confined water, such as those molecules in nanolayers of 2-3 nm in length, plays an important role in the adhesion of hydrophilic materials, mainly in cementitious ones. In this study, the effects of water containing kosmotropic substances on adhesion, known for their ability of enhancing the hydrogen bond (H-bond) network of confined water, were evaluated using mechanical strength tests. Indeed, to link adhesion provided by water confined in nanolayers to a macro-response of the cementitious samples, such as the bending strength, requires the evaluation of local water H-bond network configuration in the presence of kosmotropes, considering their influences on the extent and the strength of H-bonds. Among the kosmotropes, trimethylamine and sucrose provided a 50% increase in bending strength compared to the reference samples, the latter just using water as an adhesive, whereas trehalose was responsible for reducing the bending strength to a value close to the samples without any adhesive. The results attained opened up perspectives regarding exploring the confined water behavior which naturally occurs throughout the hydration process in cement-based materials.

MATERIALS EDUCATION AND INNOVATION: GLOBALIZATION OPENS NEW FRONTIERS, OPPORTUNITIES AND CHALLENGES

In this paper we consider evolutionary pressures that will influence materials education and its role in the present scenario of Globalization: Challenges, Opportunities and needs. The main evolutionary pressures are related to some major control variables: increase of global population, new emerging technologies such as nanotechnology, alternative energies related to climate change, multimedia convergence in global communications, health, hunger, economic asymmetries and violence. Of course, many other factors could be identified, but this paper considers these as an adequate minimum basis for strategic considerations related to current materials education planning for the 21st century. In conclusion, we propose an International Network Program for Materials Education Strategy, thinking globally but acting regionally.

Bond Strength and Etching Pattern of Adhesive Systems to Enamel: Effects of Conditioning Time and Enamel Preparation

Statement of the problem: The performance of self-etch systems on enamel is controversial and seems to be dependent on the application technique and the enamel preparation. Purpose of the Study: To examine the effects of conditioning time and enamel surface preparation on bond strength and etching pattern of adhesive systems to enamel. Materials and Methods: Ninety-six teeth were divided into 16 conditions (N = 6) in function of enamel preparation and conditioning time for bond strength test. The adhesive systems OptiBond FL (Kerr, Orange, CA, USA), OptiBond SOLO Plus (Kerr), Clearfil SE Bond (Kuraray, Osaka, Japan), and Adper Prompt L-Pop (3M ESPE, St. Paul, MN, USA) were applied on unground or ground enamel following the manufacturers` directions or doubling the conditioning time. Cylinders of Filtek Flow (0.5-mm height) were applied to each bonded enamel surface using a Tygon tube (0.7 mm in diameter; Saint-Gobain Corp., Aurora, OH, USA). After storage (24 h/37 degrees C), the specimens were subjected to shear force (0.5 mm/min). The data were treated by a three-way analysis of variance and Tukey`s test (alpha = 0.05). The failure modes of the debonded interfaces and the etching pattern of adhesives were observed using scanning electron microscopy. Results: Only the main factor ""adhesive"" was statistically significant (p < 0.001). The lowest bond strength value was observed for OptiBond FL. The most defined etching pattern was observed for 35% phosphoric acid and for Adper Prompt L-Pop. Mixed failures were observed for all adhesives, but OptiBond FL showed cohesive failures in resin predominantly. Conclusions: The increase in the conditioning time as well as the enamel pretreatment did not provide an increase in the resin-enamel bond strength values for the studied adhesives. CLINICAL SIGNIFICANCE The surface enamel preparation and the conditioning time do not affect the performance of self-etch systems to enamel. (J Esthet Restor Dent 20:322-336, 2008)

Hybrid materials from intermolecular associations between cationic lipid and polymers

Intermolecular associations between a cationic lipid and two model polymers were evaluated from preparation and characterization of hybrid thin films cast on silicon wafers. The novel materials were prepared by spin-coating of a chloroformic solution of lipid and polymer on silicon wafer. Polymers tested for miscibility with the cationic lipid dioctadecyldimethylammonium bromide (DODAB) were polystyrene (PS) and poly(methyl methacrylate) (PMMA). The films thus obtained were characterized by ellipsometry, wettability, optical and atomic force microscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and activity against Escherichia coli. Whereas intermolecular ion-dipole interactions were available for the PMMA-DODAB interacting pair producing smooth PMMA-DODAB films, the absence of such interactions for PS-DODAB films caused lipid segregation, poor film stability (detachment from the silicon wafer) and large rugosity. In addition, the well-established but still remarkable antimicrobial DODAB properties were transferred to the novel hybrid PMMA/DODAB coating, which is demonstrated to be highly effective against E. coli.

Tryptophan photooxidation promoted by new hybrid materials prepared by condensation of naphthalene imides with silicate by the sol-gel process

Three novel hybrid organic/inorganic materials were synthesized from 4-substituted (NO(2), Br, H) 1,8-naphthalene imide-N-propyltriethoxysilane by the sol-gel process. These materials were obtained as a xerogel and partially characterized. The ability to photosensitize the oxidation and degradation of tryptophan indole ring by these materials was studied through photophysical and photochemical techniques. Although the derivatives containing Br and NO(2) as substituent do not cause efficient tryptophan photodamage, the hybrid material obtained from 1,8-naphthalic anhydride is very efficient to promote tryptophan photooxidation. By using laser flash photolysis it was possible to verify the presence of naphthalene imide transient radical species. The presence of oxygen causes an increase of the yield of radical formation. These results suggest that the mechanism of photodegradation of tryptophan occurs by type I, i.e. the transient radical (TrpH(center dot+)) formed by the direct reaction of the triplet state of the naphthalene imide moiety with tryptophan. Thus a inorganic-organic hybrid material that can be used to promote the oxidation of biomolecules was obtained. (C) 2009 Elsevier B.V. All rights reserved.

Platinum nanoparticle-modified electrodes, morphologic, and electrochemical studies concerning electroactive materials deposition

The present work describes the synthesis of platinum nanoparticles followed by their electrophoretic deposition onto transparent fluorine-doped tin oxide electrodes. The nano-Pt-modified electrodes were characterized by voltammetric studies in acidic solutions showing a great electrocatalytic behavior towards H(+) reduction being very interesting for fuel cell applications. Morphological characterization was performed by atomic force microscopy on different modified electrodes showing a very rough surface which can be tuned by means of time of deposition. Also, nickel hydroxide thin films were galvanostatically grown onto these electrodes showing an interesting electrochemical behavior as sharper peaks, indicating a faster ionic exchange from the electrolyte to the film.