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Fourier transform infrared spectroscopic study of surface acidity by pyridine adsorption on Mo/ZrO2-SiO2(Al2O3) catalysts.

Acidity of the oxidic molybdenum catalysts supported on mixed ZrO2-SiO2 and ZrO2-Al2O3 carriers was investigated by Fourier transform infrared spectroscopy of pyridine adsorption. Deposition of molybdenum on ZrO2-SiO2 and ZrO2-Al2O3 supports leads to formation of surface Brønsted acid sites. The number of the Brønsted and Lewis acid sites in supported-molybdenum catalysts depends on both the ZrO2 content and the type of the support. With increasing ZrO2 content, the Lewis acid sites increase for both series of catalysts. The Brønsted acid sites are higher for Mo/ZrO2-SiO2 samples compared to those for Mo/ZrO2-Al2O3 and also increase with zirconia.

Adsorption↗

Initial characterization of the primary photochemistry of AppA, a blue-light-using flavin adenine dinucleotide-domain containing transcriptional antirepressor protein from Rhodobacter sphaeroides: a key role for reversible intramolecular proton transfer from the flavin adenine dinucleotide chromophore to a conserved tyrosine?

The flavin adenine dinucleotide (FAD)-containing photoreceptor protein AppA (in which the FAD is bound to a novel so-called BLUF domain) from the purple nonsulfur bacterium Rhodobacter sphaeroides was previously shown to be photoactive by the formation of a slightly redshifted long-lived intermediate that is thought to be the signaling state. In this study, we provide further characterization of the primary photochemistry of this photoreceptor protein using UV-Vis and Fourier-transform infrared spectroscopy, pH measurements and site-directed mutagenesis. Available evidence indicates that the FAD chromophore of AppA may be protonated in the receptor state, and that it becomes exposed to solvent in the signaling state. Furthermore, experimental data lead to the suggestion that intramolecular proton transfer (that may involve [anionic] Tyr-17) forms the basis for the stabilization of the signaling state.

Amino Acid Sequence↗

Solvent history dependence of gramicidin-lipid interactions: a Raman and infrared spectroscopic study.

We have investigated the interactions between gramicidin and a model membrane composed of one phospholipid, dimyristoylphosphatidylcholine, as a function of the cosolubilization solvent and incubation time used in the sample preparation. Three organic solvents have been used; trifluoroethanol, a mixture of methanol/chloroform (1:1 v/v), and ethanol. Using Fourier transform infrared spectroscopy, we have demonstrated that the conformation adopted by gramicidin in the membrane is dependent upon the cosolubilization solvent used, and, only with trifluoroethanol, it is possible to incorporate gramicidin entirely as a beta 6.3-helix. Moreover, Raman spectroscopy results indicate that the orientation of the tryptophan side chains in gramicidin and their interaction with the hydrocarbon chains and the carbonyl groups of the lipids are also dependent on the cosolubilization solvent. On the other hand, the effect of the incorporation of gramicidin on the thermotropism of the lipid bilayer was found to be dependent upon the conformation of gramicidin in the lipid bilayers.

Dimyristoylphosphatidylcholine↗

Comparison of epoxides on grafting collagen to polyurethane and their effects on cellular growth.

The current study investigated the effects of vary epoxides on linking capacity of collagen to carboxyl-group-enriched polyurethane (PU) and the consequent effects on the growth of endothelial cells. Epoxides of EX-810, 1,4BDE, DER732, DER331, and DER332 were initially reacted with the carboxyl groups of PU substrates at 110 degrees C for 20 h. Free epoxy rings of epoxide-PU substrates, characterized by Fourier transform infrared spectroscopy and quantified by titration with HCl and NaOH, were available for collagen grafting. The amounts of collagen grafted were in accordance with the amounts of free epoxy rings detected and correlated with the growth of endothelial cells on the substrates. Our results indicated that epoxides with shorter aliphatic intermediate chain can graft more collagen to the epoxide-PU substrates than epoxides with longer intermediate chain or with aromatic groups. Epoxides were also demonstrated to be nontoxic linking agents for biomaterials.

Cell Division↗

Chitosan-alginate-CaCl(2) system for membrane coat application.

Water-based formulations are preferred for membrane coat application because they do not require the use of noxious solvents. A novel aqueous chitosan-alginate-CaCl(2) system was evaluated as a potential formulation to produce water-insoluble membranes of biodegradable polymers. Chitosan-alginate coacervates were prepared by controlled reaction of chitosan (0.25% w/v) and sodium alginate (0.25% w/v) solutions. Coherent membranes were obtained by casting and drying the coacervates suspended in aqueous CaCl(2) solutions (0.05-0.07% w/v). Increasing the calcium content did not modify membrane thickness (25-26 microm), but reduced the water vapor transmission rate from 658 to 566 g/m(2)/day, and improved the tensile strength of the membranes from 9.33 to 17.13 MPa. Differential scanning calorimetry, Fourier transform infrared spectroscopy, and elemental analyses of the chitosan-alginate coacervates indicated they were stable for up to 4 weeks of storage in distilled water at ambient temperature. Membranes of the stored coacervates required less calcium to attain maximum mechanical strength. They also had higher water vapor transmission rates than corresponding films prepared from fresh coacervates. On the basis of the properties of the cast film and its storage stability, the chitosan-alginate-CaCl(2) system can be considered for potential membrane coat application.

Alginates↗

Effects of sodium tetraborate and boric acid on nonisothermal mannitol crystallization in frozen solutions and freeze-dried solids.

The purpose of the present study was to elucidate the effects of sodium tetraborate (borax) and boric acid on the crystallization of mannitol in frozen aqueous solutions and freeze-dried solids. Thermal analysis of frozen solutions showed that sodium tetraborate inhibits mannitol crystallization at sodium tetraborate/mannitol molar concentration ratios of approximately 0.05, which is much lower than the other co-solutes studied (boric acid, sucrose, sodium phosphate buffer). Inhibition of the mannitol crystallization in frozen solutions resulted in highly amorphous mannitol in the freeze-dried solids. Mannitol remained in an amorphous state in some of the combination freeze-dried solids, even at elevated temperatures. Changes in the thermal transition temperatures (glass transition temperature of maximally freeze-concentrated solute ( T'g) and glass transition temperature of freeze-dried solid (Tg)) suggested reduced mannitol molecular mobility with increases in the sodium tetraborate ratio. Fourier-transform infrared spectroscopy (FT-IR) analysis of the bovine serum albumin secondary structure showed apparent protein structure-stabilizing effects of the amorphous mannitol and sodium tetraborate combination during the freeze-drying process. The mannitol and sodium tetraborate combination also protected lactate dehydrogenase (LDH) from inactivation during freeze-drying. We conclude that the complex formation and the accompanying reduction in molecular mobility make sodium tetraborate an effective mannitol crystallization inhibitor in frozen solutions and freeze-dried solids.

Animals↗

Observation of CO(2) in Fourier transform infrared spectral measurements of living Acholeplasma laidlawii cells.

In monitoring the time course of conformational disorder by Fourier transform infrared spectroscopy for intact Acholeplasma laidlawii cells grown at 37 degrees C on binary fatty acid mixtures containing oleic acid and for cells grown on pure palmitic acid, an absorption band at 2343 cm(-1) was observed. The band intensity was found to increase with time. This band was not observed in the spectra for isolated membranes. It is suggested that the 2343 cm(-1) band is due to CO(2) dissolved in water, most likely produced at the final point of fermentation of amino acid by this microorganism.

Acholeplasma laidlawii↗

Functional properties of oat globulin modified by a calcium-independent microbial transglutaminase.

Oat globulin was modified by a calcium-independent microbial transglutaminase (TG). The TG-polymerized protein had higher solubility than the control at acidic pH and had improved water- and fat-binding properties. Incubation of 10% (w/v) oat globulin dispersions in the presence of TG at 37 degrees C led to the formation of a well-developed viscoelastic gel network with a microstructure characterized by thick strands and large clusters. The TG-induced gels had higher modulus values, lower loss tangent values, and lower frequency dependency than the heat-induced gels. The TG-induced gel system has the characteristics of classical polymer gel with permanent "chemical" cross-links, whereas the heat-denatured system has the characteristics of a temporary "physical" gel with breakable cross-links. Fourier transform infrared spectroscopy showed marked shift and intensity changes in several major bands, suggesting pronounced changes in protein conformation during TG-induced gelation. Aggregation of protein molecules was also indicated by the progressive increases in two infrared bands (1679-1682 and 1622-1625 cm(-)(1)) associated with the formation of intermolecular beta-sheets and strands. Results suggest that new food polymers with unique functionality can be produced from oat globulin treated with TG and that elastic gels can be formed near neutral pH, instead of the alkaline pH required for thermally induced oat globulin gels.

Avena↗

Incipient caries lesions on cementum by mono- and co-culture oral bacteria.

OBJECTIVES: There is increasing prevalence of root caries. We hypothesized different biofilms will cause varying demineralization in cementum. This study investigated the extent of demineralization of cementum by oral biofilm formed from three major cariogenic microorganisms: Streptococcus mutans, Lactobacillus acidophilus, and Actinomyces israelii. Sound cementum tooth blocks were incubated with mono-, bi-, and tri-species combinations of the bacteria under investigation. MATERIALS AND METHODS: The matrix (amide I) and phosphate content of the lesions was analyzed by Fourier-transform infrared spectroscopy (FTIR), and calcium and phosphorus levels were analyzed by scanning electron microscopy and energy-dispersive spectroscopy (SEM-EDX). RESULTS: The log[amide I:HPO(4)(2-) absorbance] values showed that A. israelii mono-culture caused significantly more demineralization than the other bacterial cultures. log[Ca:P] showed that all carious lesions were confined to the cementum. CONCLUSIONS: Oral biofilm arising from bacterial species A. israelii alone was the most cariogenic of those tested and produced the most demineralization in incipient carious lesions in cementum.

Actinomyces↗

Histological and microscopy FT-IR imaging study on the proliferative activity and angiogenesis in head and neck tumours.

Micro Fourier transform infrared spectroscopy enables one to study small samples because of the high quality spectra that can be obtained. Biochemical and morphological changes between control and pathological tissues of head and neck tumours have been monitored drawing three-dimensional chemical maps of the main vibrational modes in the regions of interest. Comparison between spectral and histological data shows a satisfactory degree of accordance. Among all, proliferating and regressive states of the tumours can be identified.

Antigens, CD34↗

Preparation and characterization of novel hybrid of chitosan-g-lactic acid and montmorillonite.

The utilization of biopolymers and the development of organic-inorganic hybrids are ever increasing interest of material science researchers around the globe for various applications. The present attempt is intended to prepare nanocomposites of lactic acid grafted chitosan and layered silicates. Nanocomposites were prepared by dissolving chitosan and dispersing sodium montmorillonite in aqueous solution of L-lactic acid with subsequent heating and film casting. They were characterized by conventional techniques such as Fourier transform infrared spectroscopy, X-ray diffractometry, thermogravimetric analysis, energy dispersive X-ray spectroscopy, and elemental analysis. The results from polar optical and transmission electron microscopic measurements are also discussed. Sorption behavior of samples has been followed by measuring swelling degree and contact angle. The films have shown enhanced hydrophilicity when compared with polylactic acid (PLA). Issues on the interactions of polycationic chitosan with clay are also discussed. It is observed that nanocomposites are exhibiting better thermal and physical properties than neat chitosan-g-LA and PLA.

Bentonite↗

In vitro response of osteoblast-like and odontoblast-like cells to unsubstituted and substituted apatites.

Different types of calcium phosphate compounds [calcium-deficient apatite (CDA); beta-tricalcium phosphate (beta-TCP); biphasic calcium phosphate (BCP)] are commercially available for medical and dental applications as bone substitute materials. Most of the reported in vitro studies on cell-material interactions have used osteoblast-like cells. The purpose of this study was to investigate the in vitro response of osteoblast-like (MC3T3-E1) and odontoblast-like (MDPC23) cells on unsubstituted (HA) and substituted (F-substituted) apatites. MC3T3-E1 and MDPC23 were cultured in alpha-modified medium containing 10% fetal bovine serum, ascorbic acid (50 microg/mL) and beta-glycerophosphate (2 mM). The cells were seeded on pellets made from HA, and FAp (with low, medium, and high F concentrations). Cell morphology was observed after 7 and 14 days using scanning electron microscopy (SEM). Cell attachment and differentiation were determined from the DNA content, alkaline phosphatase (ALP) activity, and total collagen content. Pellet surface composition was characterized by using Fourier Transform infrared spectroscopy. MC3T3-E1 and MDPC23 cells on HA were normal in shape and in fusion but not on FAp. Results of this study showed that the pattern of cell proliferation of osteoblast-like cells was different from that of the odontoblast-like cells. This study suggests that cell morphology, fusion, and proliferation on biomaterial surfaces depend on cell type (osteoblast-like vs odontoblast-like cell) and biomaterial composition (unsubstituted vs substituted F-apatites).

Alkaline Phosphatase↗

A kinetic model for Xylella fastidiosa adhesion, biofilm formation, and virulence.

Xylella fastidiosa is the causal agent of citrus variegated chlorosis and Pierce's disease which are the major threat to the citrus and wine industries. The most accepted hypothesis for Xf diseases affirms that it is a vascular occlusion caused by bacterial biofilm, embedded in an extracellular translucent matrix that was deduced to be the exopolysaccharide fastidian. Fourier transform infrared spectroscopy analysis demonstrated that virulent cells which form biofilm on glass have low fastidian content similar to the weak virulent ones. This indicates that high amounts of fastidian are not necessary for adhesion. In this paper we propose a kinetic model for X. fastidiosa adhesion, biofilm formation, and virulence based on electrostatic attraction between bacterial surface proteins and xylem walls. Fastidian is involved in final biofilm formation and cation sequestration in dilute sap.

Bacterial Adhesion↗

Poly(fumaric-co-sebacic anhydride). A degradation study as evaluated by FTIR, DSC, GPC and X-ray diffraction.

The degradation of three poly(fumaric-co-sebacic anhydride) [P(FA:SA)] copolymers is examined in a composition of microspheres made by the hot melt encapsulation process. The emergence of low molecular weight oligomers occurs during degradation of the copolymer microspheres, as evidenced by a variety of characterization methods. Characterization was conducted to determine the extent of degradation of the polyanhydride microspheres using Fourier-transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and X-ray diffraction. It is demonstrated that degradation of P(FA:SA) is greatly accelerated at basic pH, yet there is little difference between degradation in neutral and acidic buffers. A good correlation exists between the results of each characterization method, which allows a better understanding of the degradation process and the resulting formation of low molecular weight oligomers in poly(fumaric-co-sebacic anhydride).

Anhydrides↗

Electron transfer from Shewanella algae BrY to hydrous ferric oxide is mediated by cell-associated melanin.

Shewanella algae BrY uses insoluble mineral oxides as terminal electron acceptors, but the mechanism of electron transfer from cell surface to mineral surface is not well understood. We tested the hypothesis that cell-associated melanin produced by S. algae BrY serves as an electron conduit for bacterial-mineral reduction. Results from Fourier transform infrared spectroscopy and cell surface hydrophobicity assays indicated that extracellular melanin was associated with the cell surface. With H(2) as electron donor, washed cell suspensions of melanin-coated S. algae BrY reduced hydrous ferric oxide (HFO) 10 times faster than cells without melanin. The addition of melanin (20 microg ml(-1)) to these melanin-free cells increased their HFO reduction rate two-fold. These results suggest that cell-associated melanin acts as an electron conduit for iron mineral reduction by S. algae BrY.

Electron Transport↗

Evaluation of controlled-release polar lipid microparticles.

The aim of the present study was to prepare controlled-release tablets of poorly-soluble drug, felodipine, and various erodable lipophilic excipients. Spray chilling was used to formulate the drug and the excipients into solid dispersion microparticles, which were then compressed. The microparticles were characterised by Fourier transform infrared spectroscopy, hot-stage microscopy, scanning electron microscopy, and image analysis. The amine and the carbonyl groups of felodipine formed hydrogen bonds with the carriers. The shape of the particles was spherical with the median particle diameter ranging from 25 to 35 microm. Surprisingly, the degree of crystallinity in felodipine and the ease of tablet disintegration played a more significant role on the felodipine dissolution rate than the matrix lipophilicity. Felodipine release rate was slowest from the least lipophilic tablets.

Antihypertensive Agents↗

A comparative study of the activation of protein kinase C alpha by different diacylglycerol isomers.

The lipid activation of protein kinase C alpha (PKC alpha) has been studied by comparing the activation capacity of different 1, 2-diacylglycerols and 1,3-diacylglycerols incorporated into mixed micelles or vesicles. Unsaturated 1,2-diacylglycerols were, in general, more potent activators than saturated ones when 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoserine (POPS)/Triton X-100 mixed micelles and pure POPS vesicles were used. In contrast, these differences were not observed when 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/POPS (4:1, molar ratio) vesicles were used. Diacylglycerols bearing short fatty acyl chains showed a very high activation capacity, however, the capacity was less in mixed micelles. Furthermore, 1, 2-diacylglycerols had a considerably higher activating capacity than 1,3-diacylglycerols in POPS/Triton X-100 mixed micelles and in POPC/POPS vesicles. However, the differences between the two types of diacylglycerols were smaller when pure POPS vesicles were used. Differential scanning calorimetry (DSC) showed that POPC/POPS membrane samples containing diacylglycerols had endothermic transitions in the presence of 200 microM Ca2+ and 5 mM Mg2+. Transitions were not detected when using pure POPS vesicles due to the formation of dehydrated phases as demonstrated by FTIR (Fourier-transform infrared) spectroscopy. PKC alpha binding studies, performed by differential centrifugation in the presence of 200 microM Ca2+ and 5 mM Mg2+, showed that 1,2-sn-dioleoylglycerol (1, 2-DOG) was more effective than 1,3-dioleoylglycerol (1,3-DOG) in promoting binding to POPC/POPS vesicles. However, when pure POPS vesicles were used, PKC alpha was able to bind to membranes containing either 1,2-DOG or 1,3-DOG to the same extent.

Calcium↗

Silver-particle-based surface-enhanced Raman scattering spectroscopy for biomolecular sensing and recognition.

In this study, we demonstrate that 2-microm-sized Ag (microAg) powders can be used as a core material for constructing molecular sensing/recognition units operating via surface-enhanced Raman scattering (SERS). This is possible because microAg powders are very efficient substrates for both the infrared and Raman-spectroscopic characterization of molecular adsorbates prepared in a similar manner on silver surfaces; we can obtain an infrared spectrum of organic molecules adsorbed on microAg particles with a very high signal-to-noise ratio by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and the Raman spectrum of organic monolayers on powdered silver is an SERS spectrum. The agglomeration of microAg particles in a highly concentrated buffer solution could be prevented by the layer-by-layer deposition of cationic and anionic polyelectrolytes such as poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA). In fact, prior to depositing PAA and PAH, 4-aminobenzenethiol (4-ABT) was assembled on the surfaces of the microAg particles as SERS markers. Because of the presence of amine groups of 4-ABT, PAA could be readily deposited on the microAg particles. On the other hand, the outermost PAA layer could also be derivatized with biotin-derivatized poly(L-lysine). The nonspecific interaction of poly(L-lysine) with proteins could be suppressed by grafting poly(ethylene glycol) into the biotin-derivatized poly(L-lysine) molecules. On the basis of the nature of the SERS peaks of 4-ABT, it was confirmed that these biotinylated microAg powders were effective in selectively recognizing the streptavidin arrays. Because a number of different molecules can be used as SERS-marker molecules, such as probable 4-ABT, commercially available microAg powders must be a prospective material in molecular sensing/recognition, particularly via SERS.

Acrylic Resins↗