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Chemical Interaction (chemical + interaction)
Selected AbstractsNucleation of Hydroxyapatite Crystal through Chemical Interaction with CollagenJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 11 2000Sang-Hoon Rhee The nucleation of hydroxyapatite (HAp) crystal through chemical interaction with collagen was investigated. A collagen membrane was soaked in a supersaturated simulated body fluid (1.5 SBF) solution with ion concentrations at 1.5 times that of normal simulated body fluid (1.0 SBF). A few carbonate-containing HAp crystals were formed mostly on the edge-side of the collagen membrane after 4 weeks. In the Fourier-transform infrared spectometry (FTIR) results, the carboxylate band of the collagen membrane showed red chemical shifts after the formation of HAp crystals, which coincided well with the decrease of the calculated bond orders of the carboxylate group when chelated with a calcium ion, which emulated the first-step nucleation of HAp crystal on the carboxylate group of collagen. The result implies that the binding of a calcium ion to the carboxylate group of collagen is one of the key factors for the nucleation of HAp crystals in a 1.5 SBF solution. [source] Chemical Interactions at Metal/Molecule Interfaces in Molecular Junctions,A Pathway Towards Molecular Recognition,ADVANCED MATERIALS, Issue 3 2009Mila Manolova A 4-aminothiophenol self-assembled monolayer (see image) is prepared on top of a Au(111) crystal, which is subsequently metallized by a nearly closed Pd overlayer of monoatomic height. Analysis of its structural setup and electronic properties reveals that the monolayer consists of a minimum of two molecular layers, and strong chemical interactions between the metal overlayer and the amino groups are found to play a decisive role in determining the overall electronic, and thus the transport properties, of the layer/metal contact. [source] Polyphase evolution and reaction sequence of compositional domains in metabasalt: a model based on local chemical equilibrium and metamorphic differentiationGEOLOGICAL JOURNAL, Issue 3-4 2000T. M. Toóth Abstract Eclogitic garnet amphibolite samples from the Southern Steep Belt of the Central Alps show evidence of several stages of metamorphic evolution and exhumation. A method for unravelling this evolution is presented and applied to these samples. It involves a combination of detailed petrographic analysis and microchemical characterization with quantitative models of the thermodynamically stable phase relations for specific compositional domains of each sample. Preserved mineral relics and textural evidence are compared to model predictions to identify the important irreversible reactions. The interpretation of the exhumation history is thus based on the consistency of a wide spectrum of observations with predicted phase diagrams, leading to robust reconstruction of a pressure,temperature (P,T) path even where the mineralogical relics in samples are insufficient, due to retrogression, to warrant application of multi-equilibrium thermobarometric techniques. The formation of compositionally different domains in the metabasalt samples studied is attributed to prograde growth of porphyroblasts (e.g. garnet, plagioclase, zoisite) in the matrix, implying substantial metamorphic differentiation at the scale of a few millimetres. Chemical interaction among different domains during the subsequent P,T evolution is shown to have been very limited. This led to different reaction sequences during exhumation, in which relics preserved in different domains reflect a range of continually changing P,T conditions. For samples from a single outcrop, we deduce a Barrovian prograde path to eclogite facies (23,±,3,kbar, 750,±,50°C), followed by (rapid) decompression to 8,±,1,kbar and 675,±,25°C, and a final heating phase at similar pressures reaching 750,±,40°C. This evolution is attributed to the Alpine cycle involving subduction,collision and slab breakoff,extrusion of tectonic fragments that make up the Southern Steep Belt of the Central Alps. Copyright © 2000 John Wiley & Sons, Ltd. [source] Kinetics of adsorption of 2-CEES and HD on impregnated silica nanoparticles under static conditionsAICHE JOURNAL, Issue 5 2009Amit Saxena Abstract Silica nanoparticles of high surface area (887.3 m2/g) were synthesized using aerogel route and, thereafter, impregnated with those reactive chemicals, which have already been proven to be effective against sulfur mustard (HD). Thus, developed adsorbents were tested for their potential by conducting studies on kinetics of adsorption of 2-chloroethylethyl sulfide (2-CEES) and HD under static conditions. Kinetics of adsorption was studied using linear driving force model and Fickian diffusion model. The kinetic parameters such as equilibration constant, equilibration capacity, diffusional exponent, and adsorbate-adsorbent interaction constant were also determined. Trichloroisocyanuric acid impregnated silica nanoparticles (10% w/w) showed the maximum uptake of 2-CEES (1824 mg/g) and HD (1208 mg/g). Values of diffusional exponent indicated the mechanisms to be Fickian and anomalous. Chemical interaction seemed to be another mechanism involved in the toxicant uptake rate. Hydrolysis, dehydrochlorination, and oxidation reactions were found to be the route of degradation of toxicants. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Photochromic Properties of a Spirooxazine and a Spiropyran in Alcoholic Solutions of Zirconium and Aluminium Alkoxides: Influence of the Ethyl Acetoacetate Chelating Agent on the Optical PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2003Aurélie Lafuma Abstract The photochromism of two spiro compounds, a spiropyran and a spirooxazine, dissolved in alcoholic solutions of metal alkoxides M(OR)n (M = Zr, Al) has been studied. In the case of the aluminium alkoxide Al(OsBu)3, special photochromic behaviour is observed characteristic of complexation between the coloured form of the dyes and the aluminium. This chemical interaction induces a considerable shift in the absorption spectra and a significant retardation rate in the dark. Addition of ethyl acetoacetate, a bidentate chelate of aluminium, leads to the disappearance of this particular photochromic behaviour. (© Wiley-VCH Verlag GmbH & Co KGaA, 69451 Weinheim, Germany, 2003) [source] Four-year water degradation of a resin-modified glass-ionomer adhesive bonded to dentinEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 1 2004Jan De Munck Glass-ionomers are auto-adhesive to tooth tissue through combined micro-mechanical and chemical bonding. How much each of the two bonding components contributes to the actual bonding effectiveness is, however, not known and there is not much information available on long-term stability. The objective of this study was to assess the bonding effectiveness of a resin-modified glass-ionomer adhesive to dentin after 4 yr of water storage. Fuji Bond LC (GC) was applied without (i) and with pretreatment using (ii) a polyalkenoic acid conditioner and (iii) a 37.5% phosphoric acid etchant. The etchant was used to exclude any chemical interaction with hydroxyapatite. The micro-tensile bond strength (µTBS) to dentin decreased significantly over the 4 yr period in all three experimental groups. After 24 h and 4 yr, the lowest µTBS was recorded when dentin was not pretreated. The highest µTBS was obtained following polyalkenoic acid pretreatment, although this was not significantly different from specimens that were pretreated using phosphoric acid. Pretreating dentin with phosphoric acid intensified micromechanical interlocking at the expense of chemical bonding potential to hydroxyapatite. Nevertheless, correlating the µTBS data with failure analysis through scanning electron microscopy and transmission electron microscopy indicated that combined micro-mechanical and chemical bonding involving pretreatment with the polyalkenoic acid conditioner yielded the most durable bond. [source] A Simple and Innovative Route to Prepare a Novel Carbon Nanotube/Prussian Blue Electrode and its Utilization as a Highly Sensitive H2O2 Amperometric SensorADVANCED FUNCTIONAL MATERIALS, Issue 24 2009Edson Nossol Abstract The utilization of iron-based species (mainly metallic iron, hematite and magnetite) encapsulated into multi-walled carbon nanotubes (CNTs) as reactants in an electrochemical synthesis is reported for the first time in this work. Prussian blue (PB) is electrosynthesized in a heterogeneous reaction between ferricyanide ions in aqueous solution and the iron-species encapsulated into CNTs, resulting in novel CNT/PB paste electrodes. This innovative preparation route produces an intimate contact between the PB and the CNTs, which improves the stability and redox properties of PB. The PB formation and the chemical interaction between the PB and the CNTs are confirmed by Raman spectroscopy. The electrode is employed as a hydrogen peroxide amperometric sensor, resulting in a very low limit of detection (1.94,×,10,8,mol L,1) and very high sensitivity (15.3,A cm,2M,1). [source] A comparative in situ Rietveld refinement study: thermal decomposition and transformation of CoAl and CoZnAl layered double hydroxidesJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 6 2008Rune E. Johnsen Rietveld refinement based on in situ X-ray powder diffraction (XRPD) data was combined with thermogravimetric analysis (TGA) and mass spectrometry (MS) to study and compare the phase transformations, thermal stability, microstructural and structural changes of two cobalt-containing nitrate-based layered double hydroxides (LDHs) upon heating in a controlled inert atmosphere of nitrogen. The XRPD data were collected, using synchrotron X-ray radiation, with a time resolution of 107,s, which made it possible to carry out detailed structural studies of the initial layered double hydroxides as well as their decomposition products: spinel for a CoAl,NO3 LDH and spinel/zincite for a CoZnAl,NO3 LDH. Correlating these data with those from the TGA,MS analyses gives us information about the transformation mechanisms. Rietveld refinements of the two spinel phases reveal remarkable differences. The a axis of the spinel formed by decomposition of the CoAl,NO3 LDH increases almost linearly from approximately 598 to 1163,K, mainly due to the dominating thermal expansion, whereas the a axis of the spinel formed by decomposition of the CoZnAl,NO3 shows a more complex temperature dependency. Between approximately 698 and 1073,K, the a axis is almost constant due to pronounced chemical interaction with an additional amorphous phase and the zincite phase, whereas from 1073 up to 1163,K it increases linearly. Calculations, based on the results of the Rietveld refinements, of the size of the octahedral and tetrahedral coordination polyhedra in the spinel show that the octahedra shrink and the tetrahedra expand with increasing temperature. The unusual thermal behaviour of the octahedra is discussed and attributed to the low formation temperature of the cobalt aluminium spinel phase. Finally, the intensity of a low-angle scattering (LAS) signal observed in the XRPD patterns was correlated with the decomposition of the LDH, and determination of the specific surface areas gave the temperature-dependent BET surface areas. [source] Compatible blends of ethylene-vinyl acetate copolymer and hydrogenated nitrile rubberADVANCES IN POLYMER TECHNOLOGY, Issue 1 2004P. Thavamani Abstract The miscibility and some physico-mechanical characteristics of ethylene vinyl acetate (EVA) copolymer and hydrogenated nitrile rubber (HNBR) have been investigated using differential scanning calorimetry, dynamic mechanical and thermal analysis, and electrical conductivity. EVA was found to be miscible with HNBR at all properties. Infrared spectroscopic studies revealed that there is some chemical interaction between the constituent polymers. Scanning electron microscopic observations on the morphology of preferential solvent extracted samples indicated that in the blend the major constituent forms a continuous matrix in which the minor one is dispersed. At equal proportions, both EVA and HNBR exist as discontinuous phase. Variation of strength properties with blend composition is also discussed. © 2004 Wiley Periodicals, Inc. Adv Polym Techn 23: 5,17, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.10066 [source] Polyacrylate/(carboxymethylcellulose modified montmorillonite) superabsorbent nanocomposite: Preparation and water absorbencyJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Haixia Qiu Abstract Montmorillonite (MMT) was modified with carboxymethylcellulose (CMC). The X-ray diffraction (XRD) and FTIR analyses showed that the CMC chains had intercalated into the MMT sheets, and the strong chemical interaction between the ether bonds from CMC and SiO bonds from MMT was the driving force for intercalation. Polyacrylate (PAA)/modified MMT superabsorbent nanocomposites were fabricated by effectively dispersing the modified MMT in acrylic acid solution and polymerizing the acid. The superabsorbent composites were characterized by XRD, TEM, and FTIR. The influence of modified MMT, weight ratio of CMC to MMT, and modified MMT content in the nanocomposites on the water absorbency was investigated. Results showed that the introduction of pure MMT could decrease the water absorbency of the gel, but adding modified MMT could not only effectively increase the water absorbency of the gel, but also improve its water retention ability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Synthesis and characterization of conducting polyaniline-activated carbon nanocompositesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2007Mohammad Rezaul Karim Abstract Conducting polyaniline (PAni)/activated carbon (AC) nanocomposites were synthesized by the in situ chemical polymerization method. The resultant shell,core PAni,AC nanocomposites were characterized by elemental analysis, Fourier transform infrared, scanning electron microscopy, thermal gravimetric analysis, X-ray diffraction, and transmission electron microscopy. We did not observe any significant chemical interaction between the PAni and AC, only core,shell coupling between the AC and the tightly coated polymer chain was revealed. Measurement of the physical properties showed that the incorporation of conducting PAni on to AC particles during chemical synthesis increased electrical conductivity and thermal stability by several orders of magnitude to that of the pristine PAni powders. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1973,1977, 2007 [source] Glutaraldehyde-crosslinked chitosan beads for controlled release of diclofenac sodiumJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007V. H. Kulkarni Abstract An inexpensive and simple method was adopted for the preparation of chitosan beads, crosslinked with glutaraldehyde (GA), for the controlled release of diclofenac sodium (DS). The beads were prepared by varying the experimental conditions such as pH, temperature, and extent of crosslinking. The absence of any chemical interaction among drug, polymer, and the crosslinking agent was confirmed by FTIR and thermal analysis. The beads were characterized by microscopy, which indicated that the particles were in the size range of 500,700 ,m and SEM studies revealed smooth surface and spherical shape of beads. The beads produced at higher temperature and extended exposure to GA exhibited lower drug content, whereas increased drug loading resulted in enhanced drug release. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 211,217, 2007 [source] Polymeric systems for amorphous ,9 -tetrahydrocannabinol produced by a hot-melt method.JOURNAL OF PHARMACEUTICAL SCIENCES, Issue 11 2006Part II: Effect of oxidation mechanisms, chemical interactions on stability Abstract The objectives of the present research investigations were to (i) elucidate the mechanism for the oxidative degradation of ,9 -tetrahydrocannabinol (THC) in polymer matrix systems prepared by a hot-melt fabrication procedure, and (ii) study the potential for controlling these mechanisms to reduce the degradation of THC in solid dosage formulations. Various factors considered and applied included drug-excipient compatibility, use of antioxidants, cross-linking in polymeric matrices, microenvironment pH, and moisture effect. Instability of THC in polyethylene oxide (PEO)-vitamin E succinate (VES) patches was determined to be due to chemical interaction between the drug and the vitamin as well as with the atmospheric oxygen. Of the different classes and mechanisms of antioxidants studied, quenching of oxygen by reducing agents, namely, ascorbic acid was the most effective in stabilizing THC in PEO-VES matrices. Only 5.8% of the drug degraded in the ascorbic acid-containing patch as compared to the control (31.6%) after 2 months of storage at 40°C. This coupled with the cross-linking extent and adjustment of the pH microenvironment, which seemed to have an impact on the THC degradation, might be effectively utilized towards stabilization of the drug in these polymeric matrices and other pharmaceutical dosage forms. These studies are relevant to the development of a stable transmucosal matrix system for the therapeutic delivery of amorphous THC. © 2006 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 95:2473,2485, 2006 [source] Surface-enhanced resonance Raman spectroscopy of rifamycins on silver nanoparticles: insight into their adsorption mechanismsJOURNAL OF RAMAN SPECTROSCOPY, Issue 9 2006Barry D. Howes Abstract Three widely used antibiotics from the rifamycin family, rifamycin SV sodium salt, rifampicin and rifaximin, have been characterized by resonance Raman (RR) and surface-enhanced resonance Raman spectroscopy (SERRS). SERRS spectra were recorded using aqueous silver colloidal dispersions prepared with two reducing agents, sodium borohydride and hydroxylamine hydrochloride, for a range of pH values to identify the SERRS-active substrate surface most suitable for each of the three antibiotics. Rifampicin was found to give intense SERRS signals only for the borohydride-reduced colloid and only at pH < 7.7, whereas the hydroxylamine HCl-reduced colloid was the best substrate for rifaximin, giving considerably more intense SERRS spectra than the borohydride colloid. SERRS spectra of rifaximin were observed only at pH < 7.0. It is proposed that the marked pH dependence of the SERRS enhancement results from a transition from an anionic to a neutral zwitterionic state. SERRS spectra of rifamycin SV were not observed for any experimental conditions. The antibiotics display remarkably contrasting SERRS behaviour, reflecting differences in the nature of the substituent groups on the chromophore ring. A vibrational assignment of the RR spectra and detailed comparison between the RR and SERRS data have given insight into the mechanism of adsorption of the antibiotics onto the Ag surface. Rifampicin and rifaximin adsorb adopting an approximately similar vertical orientation of the chromophore ring with respect to the surface; however, rifampicin adsorbs by direct chemical interaction with the Ag whereas rifaximin does not form a direct bond with the Ag surface. Copyright © 2006 John Wiley & Sons, Ltd. [source] Molten Salt Synthesis and Characterization of Potassium Polytitanate Ceramic Precursors with Varied TiO2/K2O Molar RatiosJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 9 2008Tomas Sanchez-Monjaras Semi-crystalline potassium titanates, useful as precursors to produce composite materials and coatings, were synthesized by thermal treatment of powdered TiO2 in molten mixtures of KNO3 and KOH at 450°,550°C. The products obtained had similar structures of laminar crystals, aggregated in particles of about 3 ,m of n=TiO2/K2O molar ratio in the range 2.8,6.0. The value of n could be regulated by the temperature of synthesis, the weight ratio of [KOH]/[KNO3] in the molten salt mixture, and the number of water washing operations. The reduction of the TiO2/K2O molar ratio increased the contents of H2O in the composition of potassium polytitanate, from 5.3 to 11.4 and from 0.2 to 8.6 (wt%) in the adsorbed and structural forms. The thermal treatment of the potassium polytitanate precursors obtained resulted in dehydration and chemical interaction with unreacted TiO2 at 500°,750°C, amorphization at 750°,850°C, crystallization of K2Ti4O9 (in some cases K3Ti8O17) at 850°,1090°C, and crystallization of K2Ti6O13 at temperatures >1090°C. The mechanisms of the structural transformation and phase evolution were considered as a function of the TiO2/K2O molar ratio in the potassium polytitanate. [source] Nucleation of Hydroxyapatite Crystal through Chemical Interaction with CollagenJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 11 2000Sang-Hoon Rhee The nucleation of hydroxyapatite (HAp) crystal through chemical interaction with collagen was investigated. A collagen membrane was soaked in a supersaturated simulated body fluid (1.5 SBF) solution with ion concentrations at 1.5 times that of normal simulated body fluid (1.0 SBF). A few carbonate-containing HAp crystals were formed mostly on the edge-side of the collagen membrane after 4 weeks. In the Fourier-transform infrared spectometry (FTIR) results, the carboxylate band of the collagen membrane showed red chemical shifts after the formation of HAp crystals, which coincided well with the decrease of the calculated bond orders of the carboxylate group when chelated with a calcium ion, which emulated the first-step nucleation of HAp crystal on the carboxylate group of collagen. The result implies that the binding of a calcium ion to the carboxylate group of collagen is one of the key factors for the nucleation of HAp crystals in a 1.5 SBF solution. [source] Alignment of the energy levels and charge injection barriers at interfaces for spin injection: La0.7Sr0.3MnO3 in contact with organic semiconductorsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 5 2008M. Grobosch Abstract For determination of the energy-level alignment at inter- faces between La0.7Sr0.3MnO3 films and two typical organic semiconductors, copper-phthalocyanine (CuPc) and ,-sexithiophene (,-6T) we have performed a combined X-ray and ultraviolet photoemission study. La0.7Sr0.3MnO3 thin films were grown by using the pulsed laser deposition (PLD) technique and subsequently ex-situ cleaned before the organic materials were thermally evaporated. We show that under these conditions the interfaces are free from chemical interaction and are characterized by a short-range interface dipole and large injection barriers. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Effect of hybrid network formation on adhesion properties of polycyanurate/polyurethane semi-interpenetrating polymer networksPOLYMER ENGINEERING & SCIENCE, Issue 12 2002O. Grigoryeva The adhesion characteristics of modified polycyanurates based on the principle of semi-interpenetrating polymer networks (semi-IPNs) have been studied. It has been shown that the formation of a polycyanurate network in the presence of linear polyurethane (LPU) leads to increasing adhesion strength to aluminum and titanium. The peculiarities of polycyanurate network (PCN) formation in the presence of different amounts of LPU are discussed. It has been found that chemical incorporation of LPU into PCN occurs during network formation owing to chemical interaction of urethane groups with cyanate groups of growing PCN. At LPU content in the initial composition up to around 20 wt% only a hybrid network is formed. The maximal values of adhesive strength to aluminum and titanium are achieved at LPU content of 20,25%, corresponding to formation of a hybrid network. The further increase of LPU content leads to the presence of non-incorporated LPU (semi-IPN formation) in the adhesive layer and to reduction of the adhesive strength. [source] Thermal, mechanical and morphological analysis of poly(,-caprolactone), cellulose acetate and their blendsPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10 2003F. C. Bragança Abstract Poly(,-caprolactone) (PCL), cellulose acetate (CA) and their blends were characterized by their tensile strength, differential scanning calorimetry (DSC) and optical microscopy (OM). The compatibility of the blends was investigated and the OM results showed that CA tended to disperse as discrete particles in PCL. Thermal analysis showed the characteristic melting temperature peaks for PCL and CA in all blends, indicating that the compounds were immiscible. The addition of CA to PCL increased slightly the crystallinity of PCL, decreased the elongation at yield and the tensile strength up to 40/60 PCL/CA (w/w), which suggested incompatibility between the polymers. Together, these results indicate the absence of a strong chemical interaction between the two polymers. In agreement with this, the addition of CA to blends with PCL increased Young's modulus. Copyright © 2003 John Wiley & Sons, Ltd. [source] Color and Toxicity Removal following Tyrosinase-Catalyzed Oxidation of PhenolsBIOTECHNOLOGY PROGRESS, Issue 4 2000Keisuke Ikehata The products of phenol oxidation catalyzed by mushroom tyrosinase (polyphenol oxidase, EC 1.14.18.1) were assessed in terms of their residual color and toxicity. The addition of aluminum sulfate had little effect on the removal of colored products from phenol solutions treated with tyrosinase. Although chitosan was used successfully to remove the color when added before the reaction initiation or after the reaction completion, the required dose of chitosan was lower when it was added after the reaction. In this case, the minimum doses of chitosan required to achieve 90% color removal were proportional to the logarithm of the initial concentration of phenol. The color removal induced by chitosan addition appeared to be the result of chemical interaction followed by a coagulation mechanism. All treated solutions of phenol and chlorophenols, except 2,4-dichlorophenol, had substantially lower toxicities than their corresponding initial toxicities, as measured using the Microtox assay. Chitosan addition significantly enhanced the reduction in toxicity. The toxicities of the phenol solutions treated with tyrosinase were markedly lower than previously reported toxicities of solutions treated with peroxidase enzymes. [source] Unexpected Deformations Induced by Surface Interaction and Chiral Self-Assembly of CoII -Tetraphenylporphyrin (Co-TPP) Adsorbed on Cu(110): A Combined STM and Periodic DFT StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 38 2010Philip Donovan Abstract In a combined scanning tunnelling microscopy (STM) and periodic density functional theory (DFT) study, we present the first comprehensive picture of the energy costs and gains that drive the adsorption and chiral self-assembly of highly distorted CoII -tetraphenylporphyrin (Co-TPP) conformers on the Cu(110) surface. Periodic, semi-local DFT calculations reveal a strong energetic preference for Co-TPP molecules to adsorb at the short-bridge site when organised within a domain. At this adsorption site, a substantial chemical interaction between the molecular core and the surface causes the porphyrin macrocycle to accommodate close to the surface and in a flat geometry, which induces considerable tilting distortions in the phenyl groups. Experimental STM images can be explained in terms of these conformational changes and adsorption-induced electronic effects. For the ordered structure we unambiguously show that the substantial energy gain from the molecule,surface interaction recuperates the high cost of the induced molecular and surface deformations as compared with gas phase molecules. Conversely, singly adsorbed molecules prefer a long-bridge adsorption site and adopt a non-planar, saddle-shape conformation. By using a van der Waals density functional correction scheme, we found that the intermolecular ,,, interactions make the distorted conformer more stable than the saddle conformer within the organic assembly. These interactions drive supramolecular assembly and also generate chiral expression in the system, pinning individual molecules in a propeller-like conformation and directing their assembly along non-symmetric directions that lead to the coexistence of mirror-image chiral domains. Our observations reveal that a strong macrocycle,surface interaction can trigger and stabilise highly unexpected deformations of the molecular structure and thus substantially extend the range of chemistries possible within these systems. [source] Effects of salinity on copper accumulation in the common killifish (Fundulus heteroclitus)ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2005Jonathan Blanchard Abstract Results of laboratory and field studies have demonstrated that salinity influences the accumulation of copper. The present study is, to our knowledge, the first to examine the effect of salinity on copper accumulation in a teleost fish across a comprehensive range of salinity from freshwater to seawater. This was done in an effort to identify potential target tissues and differences in chemical interactions across salinities that will aid in the development of a seawater biotic ligand model (BLM) for copper. Killifish (Fundulus heteroclitus) were acclimated to five salinities (0, 5, 11, 22, and 28 ppt) and exposed to three copper concentrations (0 [nominal], 30, and 150 ,g L,1), yielding 15 treatment groups. Fish from each group were sampled for tissue copper analysis at 0, 4, 12, and 30 d postexposure. Whole-body and liver accumulations were highest at lower salinities. The liver accounted for 57 to 86% of the whole-body copper even though it accounted for less than 4% of the body mass. Similarly, the gill accumulated more copper at lower salinities, whereas the intestine generally accumulated more copper at higher salinities. Speciation calculations indicate that CuCO3 likely accounts for much of the accumulation, possibly with some contributions from CuOH+ and Cu(OH)2. The free ion, Cu2+, does not appear to be associated with copper accumulation. However, the differences in physiology and in the concentrations of competing cations across salinities suggest that speciation alone cannot explain accumulation. The present findings may have implications for future development of a BLM for saline environments by identifying potential target tissues. [source] Gravel-Corrected Kd ValuesGROUND WATER, Issue 6 2000Daniel I. Kaplan Standard measurements of solute sorption to sediments are typically made on the <2 mm sediment fraction. This fraction is used by researchers to standardize the method and to ease experimental protocol so that large labware is not required to accommodate the gravel fraction (>2 mm particles). Since sorption is a phenomenon directly related to surface area, sorption measurements based on the <2 mm fraction would be expected to overestimate actual whole-sediment values for sediments containing gravel. This inaccuracy is a problem for ground water contaminant transport modelers who use laboratory-derived sorption values, typically expressed as a distribution coefficients (Kd), to calculate the retardation factor (Rf), a parameter that accounts for solute-sediment chemical interactions. The objectives of this laboratory study were to quantify the effect of gravel on strontium Kd and Rf values and to develop an empirical method to calculate gravel-corrected Kdgc values for the study site (Hanford Site in Richland, Washington). Three gravel corrections, Kd values, were evaluated: a correction based on the assumption that the gravel simply diluted the Kd<2mm and had no sorption capacity (Kdgc,g=0), a correction based on the assumption that the Kd of the intact sediment (Kdtot was a composite of the Kd<2mm and the Kd>2mm (Kdgc,g = x), and a correction based on surface area (Kdgc,surf). On average, Kd<2mm tended to overestimate Kdtot by 28% to 47%; Kdgc,g = x overestimated Kdtot by only 3% to 5%; and Kdgc,g = 0 and Kdgc,surf underestimated Kdtot by 10% to 39%. Kdgc,g = x provided the best estimate of actual values (Kdtot); however, Kdgc,g = 0 was appreciably easier to acquire. Although other contaminants will likely have different gravel-correction values, these results have important implications regarding the traditional approach to modeling contaminant transport which uses Kd<2mm values. Such calculations may overestimate the tendency of gravel-containing sediments to retard contaminant migration. [source] Bioaccessibility studies of ferro-chromium alloy particles for a simulated inhalation scenario: A comparative study with the pure metals and stainless steelINTEGRATED ENVIRONMENTAL ASSESSMENT AND MANAGEMENT, Issue 3 2010Klara Midander Abstract The European product safety legislation, REACH, requires that companies that manufacture, import, or use chemicals demonstrate safe use and high level of protection of their products placed on the market from a human health and environmental perspective. This process involves detailed assessment of potential hazards for various toxicity endpoints induced by the use of chemicals with a minimum use of animal testing. Such an assessment requires thorough understanding of relevant exposure scenarios including material characteristics and intrinsic properties and how, for instance, physical and chemical properties change from the manufacturing phase, throughout use, to final disposal. Temporary or permanent adverse health effects induced by particles depend either on their shape or physical characteristics, and/or on chemical interactions with the particle surface upon human exposure. Potential adverse effects caused by the exposure of metal particles through the gastrointestinal system, the pulmonary system, or the skin, and their subsequent potential for particle dissolution and metal release in contact with biological media, show significant gaps of knowledge. In vitro bioaccessibility testing at conditions of relevance for different exposure scenarios, combined with the generation of a detailed understanding of intrinsic material properties and surface characteristics, are in this context a useful approach to address aspects of relevance for accurate risk and hazard assessment of chemicals, including metals and alloys and to avoid the use of in vivo testing. Alloys are essential engineering materials in all kinds of applications in society, but their potential adverse effects on human health and the environment are very seldom assessed. Alloys are treated in REACH as mixtures of their constituent elements, an approach highly inappropriate because intrinsic properties of alloys generally are totally different compared with their pure metal components. A large research effort was therefore conducted to generate quantitative bioaccessibility data for particles of ferro-chromium alloys compared with particles of the pure metals and stainless steel exposed at in vitro conditions in synthetic biological media of relevance for particle inhalation and ingestion. All results are presented combining bioaccessibility data with aspects of particle characteristics, surface composition, and barrier properties of surface oxides. Iron and chromium were the main elements released from ferro-chromium alloys upon exposure in synthetic biological media. Both elements revealed time-dependent release processes. One week exposures resulted in very small released particle fractions being less than 0.3% of the particle mass at acidic conditions and less than 0.001% in near pH-neutral media. The extent of Fe released from ferro-chromium alloy particles was significantly lower compared with particles of pure Fe, whereas Cr was released to a very low and similar extent as from particles of pure Cr and stainless steel. Low release rates are a result of a surface oxide with passive properties predominantly composed of chromium(III)-rich oxides and silica and, to a lesser extent, of iron(II,III)oxides. Neither the relative bulk alloy composition nor the surface composition can be used to predict or assess the extent of metals released in different synthetic biological media. Ferro-chromium alloys cannot be assessed from the behavior of their pure metal constituents. Integr Environ Assess Manag 2010;6:441,455. © 2009 SETAC [source] Chemical Interactions at Metal/Molecule Interfaces in Molecular Junctions,A Pathway Towards Molecular Recognition,ADVANCED MATERIALS, Issue 3 2009Mila Manolova A 4-aminothiophenol self-assembled monolayer (see image) is prepared on top of a Au(111) crystal, which is subsequently metallized by a nearly closed Pd overlayer of monoatomic height. Analysis of its structural setup and electronic properties reveals that the monolayer consists of a minimum of two molecular layers, and strong chemical interactions between the metal overlayer and the amino groups are found to play a decisive role in determining the overall electronic, and thus the transport properties, of the layer/metal contact. [source] Microencapsulation of doxycycline into poly(lactide- co -glycolide) by spray drying technique: Effect of polymer molecular weight on process parametersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Pradip Patel Abstract Poly(lactide- co -glycolide) (PLGA) polymers with three different molecular weights were prepared, and microparticles were produced by spray drying and water-in-oil-water (w/o/w) double emulsion techniques to encapsulate 86% of doxycycline (DXY), an antibiotic drug, for the use of periodontitis. Placebo and drug-loaded microspheres and pristine DXY were analyzed by Fourier transform infrared spectroscopy, which indicated no chemical interactions between DXY and PLGA. X-ray diffraction of drug-loaded microspheres confirmed the molecular level dispersion of DXY in PLGA. Scanning electron microscopy confirmed spherical nature and smooth surfaces of the microspheres. Mean particle size as measured by laser light scattering technique ranged between 10 and 25 ,m. In vitro release of DXY performed in 7.4 pH media continued up to 72 h and depended on molecular weight of PLGA and extent of DXY loading. Antimicrobial studies performed on one formulation and placebo microspheres suggested that drug concentrations during in vitro release are above the minimum inhibitory concentration (MIC) for Staphylococcus aureus growth. Overall, the release studies depended on the molecular weight of PLGA, extent of drug loading, and the method used to prepare microspheres. Statistical analyses of release data performed using the analysis of variance (ANOVA) method agreed well with experimental observations. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Novel Poly(vinyl alcohol)-tetraethoxysilane hybrid matrix membranes as oxygen barriers,JOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Mallikarjunagouda B. Patil Abstract Novel type of membranes based on poly(vinyl alcohol) crosslinked with tetraethoxysilane have been prepared by solution casting and solvent-evaporation method. The membranes thus formed were characterized by Fourier transform infrared spectroscopy (FTIR) to study the chemical interactions, X-ray diffraction (XRD), and thermogravimetry (TGA) to investigate morphological and thermal properties. Membranes were prepared in two different thicknesses (30 and 55 ,m) and used for measuring the oxygen permeability under varying feed pressures (maintaining the desired pressure differential across the membrane) in the range from 1 to 50 kg/cm2 pressure. Oxygen permeability of the membranes ranged from 0.0091 to 1.6165 Barrer for 30 ,m and 0.0305 to 0.1409 Barrer for 55-,m thick membranes by increasing the feed pressures on the feed side. Except at 50 kg/cm2 pressure, the observed oxygen permeability values are almost close to total permeability. Membranes of this study could be useful as oxygen barriers for applications in food packaging industries. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 273,278, 2007 [source] The effect of water on particle size, porosity and the rate of drug release from implanted titania reservoirsJOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2010Tessy Lopez Abstract The implantation of controlled drug release devices represents a new strategy in the treatment of neurodegenerative disorders. Sol,gel titania implants filled with valproic acid, have been used for this purpose to treat induced epilepsy in rats. The kinetics of the drug release depend on: (a) porosity, (b) chemical interactions between valproic acid and surface hydroxyl groups of titania, (c) particle size, and (d) particle size agglomerates. The concentration of water used in the hydrolysis reaction is an important variable in the degree of porosity, hydroxylation, and structural defects of the nanostructured titanium oxide reservoir. The titanium n -butoxide/water ratio was systematically varied during the sol,gel synthesis, while maintaining the amount of valproic acid constant. Characterization studies were performed using DTA-TGA, FTIR, Raman, TEM, SEM, BET, and in vitro release kinetic measurements. The particle agglomerate size and porosity were found to depend on the amount of water used in the sol,gel reaction. © 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2010 [source] Improved physical stability of amorphous state through acid base interactionsJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 6 2009Chitra Telang Abstract To investigate role of specific interactions in aiding formation and stabilization of amorphous state in ternary and binary dispersions of a weakly acidic drug. Indomethacin (IMC), meglumine (MU), and polyvinyl pyrollidone (PVP) were the model drug, base, and polymer, respectively. Dispersions were prepared using solvent evaporation. Physical mixtures were cryogenically coground. XRPD, PLM, DSC, TGA, and FTIR were used for characterization. MU has a high crystallization tendency and is characterized by a low Tg (17°C). IMC crystallization was inhibited in ternary dispersion with MU compared to IMC/PVP alone. An amorphous state formed readily even in coground mixtures. Spectroscopic data are indicative of an IMC,MU amorphous salt and supports solid-state proton transfer. IMC,MU salt displays a low Tg,,,50°C, but is more physically stable than IMC, which in molecular mixtures with MU, resisted crystallization even when present in stoichiometric excess of base. This is likely due to a disrupted local structure of amorphous IMC due to specific interactions. IMC showed improved physical stability on incorporating MU in polymer, in spite of low Tg of the base indicating that chemical interactions play a dominant role in physical stabilization. Salt formation could be induced thermally and mechanically. © 2008 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 98:2149,2159, 2009 [source] Raman spectroscopy and molecular simulation investigations of adsorption on the surface of single-walled carbon nanotubes and nanospheresJOURNAL OF RAMAN SPECTROSCOPY, Issue 6 2007Maher S. Amer Abstract Raman spectroscopy has, for long, been utilized to investigate material systems on the micro and mesoscales. Recently, the technique has proven its ability in exploring systems on the nanoscale. In this paper, we review our recent work on the Raman investigation of molecular adsorption from liquid mixtures on surfaces of single-walled carbon nanotubes and fullerene nanospheres, emphasizing the following major research findings: the development of a Raman-based technique capable of sensing local chemical interactions on the surface of carbon nanotubes and spheres; the molecular simulation results supporting the Raman investigation; the possibility of creating mesostructures based upon mixtures of carbon nanotubes and nanospheres that are crucial for selective adsorption. The current findings represent a major new thrust for the development of new nanostructured materials with superior adsorption capabilities and unique applications. Copyright © 2007 John Wiley & Sons, Ltd. [source] | |||||||||||||||||||||||||||||||||||||