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At least 1,207 records · Page 67Linked to original sources
PubMed2001

Enzyme-induced biodegradation of polycarbonate-polyurethanes: dependence on hard-segment chemistry.

Polycarbonate urethanes (PCNUs) have been used as a replacement for traditional biomedical polyether-urethanes due to their reported resistance to oxidative biodegradation. However, relatively little is known about their hydrolytic stability in the presence of inflammatory derived enzymes. This has in part motivated the current study relating to the effect of hard segment chemistry and the microdomain structures generated by such chemistry, on the cholesterol esterase (CE) catalyzed hydrolysis of PCNUs. The bulk structures of the studied materials were characterized using gel permeation chromatography (GPC), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR) for their bulk structures, and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) for their subsurface structures. 14C-labeled PCNUs were incubated with CE (400 units/mL), for a period of 10 weeks (pH 7.0 at 37 degrees C), and radiolabel release was used to monitor the degradation. The results showed that all of the polymers synthesized in this study were susceptible to CE-catalyzed hydrolytic degradation, and that the extent of degradation was highly dependent on the nature of hard segment interactions within the polymer and at the surface. More specifically, the degree of phase separation and soft segment crystallinity were found to be less important in comparison to the hydrogen bonding among the carbonate and urethane linkages. The rank of the different chemical groups' susceptibility to hydrolysis was as follows: nonhydrogen bonded carbonate > nonhydrogen bonded urethane > hydrogen bonded carbonate > hydrogen bonded urethane. The findings suggest that the degree of hydrogen bonding, when processed into a polyurethane material could be an important parameter to consider in the design of new biostable polyurethane products.

Biocompatible Materials↗
PubMedDate not supplied

Use of multivariate analysis of MIR spectra to study bread staling.

Different kinds of bread, stored at constant temperature and at controlled humidity conditions for a week since their manufacturing date, were analysed by Attenuated Total Reflectance-Fourier Transform InfraRed (ATR-FTIR) spectroscopy. The collected spectra were processed by Principal Component Analysis (PCA), in order to evaluate the changes occurring during bread ageing. For the sake of comparison, the 1060-950 cm spectral window has been also investigated by curve-fitting methods. It was observed that the first PC increases monotonically with ageing of samples. Furthermore, the more influential variables on PC1 correspond to spectral regions where are located stretching and bending bands, which are mainly attributed to typical starch bonds vibrations.

Bread↗
PubMed2002

Expanding phenotype of XNP mutations: mild to moderate mental retardation.

Mutations in the XNP gene have been reported in alpha thalassemia/mental retardation (MR) syndrome (ATR-X) and other severe X-linked MR conditions with facial dysmorphisms. In this report, we describe a missense mutation in exon 18 in a family with borderline to moderate MR. Like other disorders associated with an XNP mutation, skewed X-inactivation was found in all carrier females in this family. Only retrospective examination revealed childhood facial hypotonia and HbH inclusions in some of the affected males. These results expand the spectrum of clinical phenotypes known to be due to mutations in the XNP gene, and indicate that XNP mutation analysis should not be restricted to patients with severe MR and characteristic facial features.

Adult↗
PubMed2001

Angelman syndrome: mimicking conditions and phenotypes.

The diagnosis of Angelman syndrome (AS) can be confirmed by genetic laboratory in about 80% of cases. In 20%, the diagnosis remains clinical, but often there is uncertainty about the correctness of the clinical diagnosis and alternative diagnoses may be investigated. In evaluating individuals for AS in our center since 1989, we have encountered several mimicking conditions, and additional ones have been reported in the literature. Mimicking conditions can be grouped into the areas of chromosome, single gene, and symptom complex anomalies. Microdeletions or microduplications include chromosome regions 2,4,17, 22, and 15. Single gene conditions include methylene tetrahydrofolate reductase deficiency (MTHFR), Rett syndrome, alpha-thalassemia retardation syndrome (ATR-X), and Gurrieri syndrome. Symptom complexes include cerebral palsy, static encephalopathy, Lennox-Gastaut syndrome, autism spectrum disorder, pervasive developmental delay (PDD), and mitochondrial disorders. We present a review of these mimicking disorders to increase the awareness about conditions that can lead to an incorrect clinical diagnosis of AS.

Angelman Syndrome↗
PubMed2003

A gene for nonsyndromic X-linked mental retardation (MRX77) maps to Xq12-Xq21.33.

Nonsyndromic X-linked mental retardation (MRX) is a highly heterogeneous condition in which mental retardation appears to be the only consistent manifestation. According to the most recent data, 77 MRX families with a lod score of >2 have been mapped and eight genes have been cloned. We hereby report on a linkage analysis performed on a Greek family with apparently nonsyndromic MRX. The affected males have moderate to severe mental retardation, severe speech problems, and aggressive behavior. Two-point linkage analysis with 26 polymorphic markers spanning the entire X chromosome was carried out. We could assign the causative gene to a 27 Mb interval in Xq12-Xq21.33. The maximum LOD score was found for markers DXS1225, DXS8114, and DXS990 at 2.36, 2.06, 2.06, respectively at theta = 0.00. Recombination was observed for DXS983 at the proximal side and DXS6799 at the distal side. Nineteen other MRX families have been described with a partial overlapping disease gene interval in proximal Xq. No mutations were found in the MRX77 family for three known or candidate MRX genes, from this region OPHN1, RSK4, and ATR-X. These data indicate that the Xq12-Xq21.33 interval contains at least one additional MRX gene.

Chromosome Mapping↗
PubMed2004

Effects of dopamine receptor D4 variation on alcohol and tobacco use and on novelty seeking: multivariate linkage and association analysis.

The dopamine D4 receptor gene contains a polymorphic sequence consisting of a variable number of 48-base-pair (bp) repeats, and there have been a number of reports that this polymorphism is associated with variation in novelty seeking or in substance abuse and addictive behaviors. In this study we have assessed the linkage and association of DRD4 genotype with novelty seeking, alcohol use, and smoking in a sample of 377 dizygotic twin pairs and 15 single twins recruited from the Australian Twin Registry (ATR). We found no evidence of linkage or association of the DRD4 locus with any of the phenotypes. We made use of repeated measures for some phenotypes to increase power by multivariate genetic analysis, but allelic effects were still non-significant. Specifically, it has been suggested that the DRD4 7-repeat allele is associated with increased novelty seeking in males but we found no evidence for this, despite considerable power to do so. We conclude that DRD4 variation does not have an effect on use of alcohol and the problems that arise from it, on smoking, or on novelty seeking behavior.

Australia↗
PubMed2005

Vibrational spectroscopic studies to acquire a quality control method of Eucalyptus essential oils.

This article presents a novel and original approach to analyze in situ the main components of Eucalyptus oil by means of Raman spectroscopy. The obtained two-dimensional Raman maps demonstrate a unique possibility to study the essential oil distribution in the intact plant tissue. Additionally, Fourier Transform (FT)-Raman and attenuated total reflection (ATR)-IR spectra of essential oils isolated from several Eucalyptus species by hydrodistillation are presented. Density Functional Theory (DFT) calculations were performed in order to interpret the spectra of the essential oils of the Eucalyptus species. It is shown that the main components of the essential oils can be recognized by both vibrational spectroscopic techniques using the spectral information of the pure terpenoids. Spectroscopic analysis is based on the key bands of the individual volatile substances and therefore allows one to discriminate different essential oil profiles of several Eucalyptus species. It has been found that the presented spectroscopic data correlate very well with those obtained by gas chromatography (GC) analysis. All these investigations are helpful tools to generate a fast and easy method to control the quality of the essential oils with vibrational spectroscopic techniques in combination with DFT calculations.

Eucalyptus↗
PubMed2005

Analysis of human tear fluid by Fourier transform infrared spectroscopy.

The purpose of this research is to find some useful spectroscopic factors in human tear fluid contents to monitor diurnal changes of the physicochemical ocular conditions noninvasively. All tear fluid samples were collected with glass microcapillary tubes from both eyes of three donors and analyzed by Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR). We measured the peak intensities at 2852, 1735, 1546, and 1242 cm(-1), and the peak intensity ratios among those peaks in the second derivative spectra. We found significant diurnal and individual variations in those peak intensities for tear fluid obtained from right and left eyes. Among these variations, we observed significant changes in tear samples between right and left eyes. In this case the peak intensity ratio between 1242 (phosphate ester) and 2852 cm(-1) (fatty acid methylene) of right eye tear fluid was increased in the afternoon (1600 to 1900 h), while that of left eye tear fluid did not change significantly. In the ratio between 1242 (phosphate ester) and 1546 cm(-1) (amide II), the difference was not observed between both eyes. We conclude that the difference in diurnal variations of biochemical constituents between right and left eye tear fluids could be monitored noninvasively and nondestructively by FTIR technique and this method could be useful in the future for tear diagnoses.

Circadian Rhythm↗
PubMed2006

Effect of membrane mimicking environment on the conformation of a pore-forming (xSxG)6 peptide.

The mechanism of membrane interaction by beta-sheet peptides is important to understand fundamental principles of folding of beta-barrel proteins and various beta-amyloid proteins. Here, we examined the conformational characteristics of a porin-like channel forming (xSxG)(6) peptide in solution and membrane-mimicking environments (CD and ATR-IR) to understand the structural changes of the peptide during membrane association and channel formation. A comparison of the peptide conformations in different microenvironments showed that beta-sheet formation is enhanced in membrane-mimicking liposomes and SDS-micelles. The lipid-induced beta-sheet formation was confirmed by the formation of a characteristic beta-sheet structure on mixing a methanolic solution of the peptide (partially folded) with preformed liposomes. The amphipathicity of the peptide; increased hydrogen bonding, hydrophilicity, and reduction in dimensionality of the membrane surface; membrane-peptide interaction-forces; and presence of flexible glycines might facilitate beta-sheet formation in membranes. Though the CD spectra of both the peptide-bound and peptide-incorporated lipids are reminiscent of a beta-sheet structure, a significant variation in the peak positions of the two beta-sheet structures was noticed. The channel characteristics of (xSxG)(6) in the presence of low ionic strength solutions of NEt(3)BzCl and glucosammonium chloride are comparable to those reported under high ionic strength solutions. Altogether the data suggest that the channel formation by (xSxG)(6) proceeds via beta-sheet aggregate formation at the membrane surface, beta-sheet insertion, and rearrangement into a beta-barrel-like structure. The beta-barrel-like channel formation most likely arises from a sequence similarity to beta-barrel porins whereas the lipid-induced beta-sheet formation is governed by the above-mentioned factors.

2-Propanol↗
PubMed2004

Self-assembled monolayers of dendritic polyglycerol derivatives on gold that resist the adsorption of proteins.

Highly protein-resistant, self-assembled monolayers (SAMs) of dendritic polyglycerols (PGs) on gold can easily be obtained by simple chemical modification of these readily available polymers with a surface-active disulfide linker group. Several disulfide-functionalized PGs were synthesized by N,N'-dicyclohexylcarbodiimide-mediated ester coupling of thioctic acid. Monolayers of the disulfide-functionalized PG derivatives spontaneously form on a semitransparent gold surface and effectively prevent the adsorption of proteins, as demonstrated by surface plasmon resonance (SPR) kinetic measurements. A structure-activity relationship relating the polymer architecture to its ability to effectuate protein resistance has been derived from results of different surface characterization techniques (SPR, attenuated total reflectance infrared (ATR-IR), and contact-angle measurements). Dendritic PGs combine the characteristic structural features of several highly protein-resistant surfaces: a highly flexible aliphatic polyether, hydrophilic surface groups, and a highly branched architecture. PG monolayers are as protein resistant as poly(ethylene glycol) (PEG) SAMs and are significantly better than dextran-coated surfaces, which are currently used as the background for SPR spectroscopy. Due to the higher thermal and oxidative stability of the bulk PG as compared to the PEG and the easy accessibility of these materials, dendritic polyglycerols are novel and promising candidates as surface coatings for biomedical applications.

Adsorption↗
PubMed2003

Multisite catalysis: a mechanistic study of beta-lactone synthesis from epoxides and CO--insights into a difficult case of homogeneous catalysis.

Carbonylation of epoxides with a combination of Lewis acids and cobalt carbonyls was studied by both theoretical and experimental methods. Only multisite catalysis opens a low-energy pathway for trans opening of oxirane rings. This ring-opening reaction is not easily achieved with a single-site metal catalyst due to structural and thermodynamic constraints. The overall reaction pathway includes epoxide ring opening, which requires both a Lewis acid and a tetracarbonylcobaltate nucleophile, yielding a cobalt alkyl-alkoxy-Lewis acid moiety. After CO insertion into the Co-C(alkyl) bond, lactone formation results from a nucleophilic attack of the alkoxy Lewis acid entity on the acylium carbon atom. A theoretical study indicates a marked influence of the Lewis acid on both ring-opening and lactone-formation steps, but not on carbonylation. Strong Lewis acids induce fast ring opening, but slow lactone formation, and visa versa: a good balance of Lewis acidity would give the fastest catalytic cycle as all steps have low barriers. Experimentally, carbonylation of propylene oxide to beta-butyrolactone was monitored by online ATR-IR techniques with a mixture of tetracarbonylcobaltate and Lewis acids, namely BF(3), Me(3)Al, Et(2)Al(+).diglyme, and a combination of Me(3)Al/dicobaltoctacarbonyl. We found that the last two mixtures are extremely active in lactone formation.

Journal Article↗
PubMed2003

Characterization of the 310-helix in model peptides by HRMAS NMR spectroscopy.

A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis.

Nuclear Magnetic Resonance, Biomolecular↗
PubMed2005

Maleimido-terminated self-assembled monolayers.

Four approaches have been explored for the preparation of maleimido-functionalized self-assembled monolayers (SAMs) on silicon. SAMs prepared by self-assembly of maleimido-functionalized alkyltrichlorosilanes (11-maleimido-undecyl-trichlorosilane) on oxide-covered silicon yield higher signals from maleimido functionalities in ATR-IR (attenuated total reflection IR) spectroscopy and XPS (X-ray photoelectron spectroscopy) than the other three methods. The surface composition of maleimido groups was tailored further by the formation of mixed monolayers with nonfunctionalized alkyltrichlorosilanes (decyltrichlorosilane). The order of the alkyl chains within the monolayers only slightly depends on the composition of the mixed monolayers. We utilized the maleimido-terminated SAMs to bind various nucleophilic compounds, alkylamines, alkylthiols, and thiol-tagged DNA oligonucleotides by means of conjugate addition.

Journal Article↗
PubMed2005

Lamellar bridged silsesquioxanes: self-assembly through a combination of hydrogen bonding and hydrophobic interactions.

The synthesis of four bis(trialkoxysilylated) organic molecules capable of self-assembly--(EtO)3Si(CH2)3NHCONH-(CH2)n-NHCONH(CH2)3Si(OEt)3 (n = 9-12)--associating urea functional groups and alkylidene chains of variable length is described. These compounds behave as organogelators, forming supramolecular assemblies thanks to the intermolecular hydrogen bonding of urea groups. Whereas fluoride ion-catalysed hydrolysis in ethanol in the presence of a stoichiometric amount of water produced amorphous hybrids, acid-catalysed hydrolysis in an excess of water gave rise to the formation of crystalline lamellar hybrid materials through a self-organisation process. The structural features of these nanostructured organic/inorganic hybrids were analysed by several techniques: attenuated Fourier transformed infrared (ATR-FTIR), solid-state NMR spectroscopy (13C and 29Si), scanning and transmission electron microscopy (SEM and TEM) and powder X-ray diffraction (PXRD). The reaction conditions, the hydrophobic properties of the long alkylidene chains and the hydrogen-bonding properties of the urea groups are determining factors in the formation of these self-assembled nanostructured hybrid silicas.

Journal Article↗
PubMed2005

Mechanistic aspects of the metal catalyzed alternating copolymerization of epoxides and carbon monoxide.

The cobalt-catalyzed alternating copolymerization of epoxides and CO is a novel, direct approach to aliphatic polyesters, such as poly(hydroxybutyrate) (PHB). This reaction was found to be catalyzed by Ph3Si[Co(CO)4] (4) and pyridine affording in a first step the stable mono-insertion product Ph3Si-O-CH(CH3)-CH2-CO-Co(CO)4 (5). However, a profound mechanistic understanding, especially of the role of pyridine as the key component for the polymerization reaction was missing. ATR-IR online monitoring under catalytic conditions and DFT calculations were used to show that an acylpyridinium cation is formed by cleavage of the cobalt-acyl bond of 5 in the presence of pyridine. The Lewis acid thus generated activates the next incoming epoxide monomer for ring opening through [Co(CO)4]-. The catalytic cycle is completed by a subsequent CO insertion in the new cobalt-alkyl bond. The calculations are used to explore the energetic hypersurface of the polymerization reaction and are complemented by extended experimental investigations that also support the mechanistic hypotheses.

Journal Article↗
PubMed2006

Induction and inhibition of preferential enrichment by controlling the mode of the polymorphic transition with seed crystals.

Both induction and inhibition of "preferential enrichment", an unusual symmetry-breaking enantiomeric-resolution phenomenon observed upon simple recrystallization of a certain kind of racemic crystals from organic solvents, have been successfully achieved by controlling the mode of the polymorphic transition during crystallization with appropriate seed crystals. Such control of the polymorphic transition can be interpreted in terms of a novel phenomenon consisting of 1) the adsorption of prenucleation aggregates, 2) the heterogeneous nucleation and crystal growth of a metastable crystalline form, and 3) the subsequent polymorphic transition into the more stable form; these three processes occur on the same surface of a seed crystal. We refer to this phenomenon as an "epitaxial transition", which has been confirmed by means of in situ attenuated total reflection (ATR) FTIR spectroscopy in solution and the solid state, differential scanning calorimetry (DSC) measurements of the deposited crystals, and X-ray crystallographic analysis of the single crystals or the direct-space approach employing the Monte Carlo method with the Rietveld refinement for the structure solution from the powder X-ray diffraction data.

Journal Article↗
PubMed2006

Selective oxidation of alkanes with molecular oxygen and acetaldehyde in compressed (supercritical) carbon dioxide as reaction medium.

The oxidation of cycloalkanes or alkylarenes with molecular oxygen and acetaldehyde as sacrificial co-reductant occurs efficiently in compressed (supercritical) carbon dioxide (scCO2) under mild multiphase conditions. No catalyst is required and high-pressure ATR-FTIR online measurements show that a radical reaction pathway is heterogeneously initiated by the stainless steel of the reactor walls. For secondary carbon atoms, high ketone to alcohol ratios are observed (3.5-7.9), most probably due to fast consecutive oxidation of alcoholic intermediates. Since C--C scission reactions are detected only to a very small extent, tertiary carbon atoms are transformed into the corresponding alcohols with high selectivity. Detailed analysis of the product distributions and other mechanistic evidence suggest that acetaldehyde acts not only as the sacrificial oxygen acceptor, but also as an efficient H-atom donor for peroxo and oxo radicals and as a crucial reductant for hydroperoxo intermediates. In comparison to other inert gases such as compressed N2 or Ar, the use of carbon dioxide was shown to increase the yields of alkane oxygenates under identical reaction conditions.

Journal Article↗
PubMed2007

Reversible immobilization and direct electron transfer of cytochrome c on a pH-sensitive polymer interface.

A pH-sensitive polymer interface has been used as a matrix for reversible immobilization of cytochrome c (Cyt c) on an Au surface through a dip-coating process. The pH-sensitive behavior of the polymer brush interface has been demonstrated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The reversible immobilization and electron-transfer properties of Cyt c have been investigated by in situ UV/Vis spectrophotometry and CV. The results have shown that the poly(acrylic acid) (PAA) brush acted as an excellent adsorption matrix and a good accelerant for the direct electron transfer of Cyt c, which gave redox peaks with a formal potential of 40 mV versus Ag/AgCl in pH 7.6 phosphate buffer solution. The average surface coverage of Cyt c on the PAA film was about 1.7 x 10(-10) mol cm(-2), indicating a multilayer of Cyt c. The electron-transfer rate constant was calculated to be around 0.19 s(-1) according to the CV experiments. The interface was subjected to in situ attenuated total internal reflection Fourier-transform infrared (ATR-FTIR) spectroscopic analysis, in order to further confirm the immobilization of Cyt c on the surface. This polymer-protein system may have potential applications in the design of biosensors, protein separation, interfacial engineering, biomimetics, and so on.

Acrylic Resins↗