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Terms modified by C8 Selected AbstractsSynthesis and crystal structure determination of 6,7-dihydro-2-methoxy-4-(substituted)-5H -benzo[6,7]cyclohepta[1,2- b ]pyridine-3-carbonitrileCRYSTAL RESEARCH AND TECHNOLOGY, Issue 4 2007A. M. Moustafa Abstract The compounds 6,7-dihydro-2-methoxy-4-(4-methylphenyl)-5H -benzo[6.7]cyclohepta[1,2 -b ]pyridine-3-carbonitrile (compound IIIa) and 4-(4-chlorophenyl)-6,7-dihydro-2-methoxy-5H -benzo[6,7]cyclohepta[1,2- b ]pyridine-3-carbonitrile (compound IIIb) were synthesized and their structures have been determined from three dimensional X-ray data using direct method and refined by full matrix least squares with anisotropic thermal parameters for non-hydrogen atoms to conventional R(gt) of 0.036 and 0.038 for the two compounds respectively. For compound (IIIa) the crystals are monoclinic, space group Cc, with a=11.2909 (5) Å, b=17.7755(8) Å, c=9.1437(4) Å and ,=95.428(3)°, while the crystals of the second compound (IIIb) are triclinic, space group P1, with a=8.7465(3)Å, b=10.3958(3)Å, c=10.9011(4)Å, ,= 108.3870(10)°, ,=101.3741(12)°, ,=97.9594(12)°. The molecular structure of the two compounds have nearly the same configuration, where the cyclohepta ring takes the boat shape and the methoxy and the carbonitrile groups are attached at the same position C2 and C8. The difference occurs only at the position C4, where the substituent is methylphenyl for compound (IIIa) and chlorophenyl for the other. The bond lengths, valency angles and the hydrogen bonding were calculated and fully discussed. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Long-term follow-up of children with obstetric brachial plexus palsy II: neurophysiological aspectsDEVELOPMENTAL MEDICINE & CHILD NEUROLOGY, Issue 3 2007Christina Strömbeck MD The aim of this study was to examine long-term neurophysiological outcomes and sensory function in patients with obstetric brachial plexus palsy (OBPP). The same 70 children/adolescents examined in part I: functional aspects (35 males, 35 females; age range 7-20y, mean 13y 6mo [SD 4y 3mo], median 13y) were examined with neurophysiological methods at 3 to 7 months and at 7 to 20 years of age. Thirteen of the 70 participants underwent nerve reconstruction before 1 year of age. Electromyography (EMG) was performed on deltoid and first interossei muscles; Quantitative Sensory Test was used for C6 and C8 dermatomes. Tests for functional sensibility and 2-point discrimination for C6 and C8 were performed. This study shows that considerable EMG changes can be observed in OBBP, even in those fully recovered. EMG changes in the deltoid were shown to deteriorate over time, and sensibility is considerably less affected than motor function. [source] On-line preconcentration and enantioseparation of thalidomide racemates by CEC with the hyphenation of octyl and norvancomycin monolithsELECTROPHORESIS, Issue 4 2009An-Na Tang Abstract A method was developed for simultaneous preconcentration and chiral separation of thalidomide enantiomers in human urine by CEC in combination with self-concentration and solvent gradient effects. A 4,cm long octyl (C8) monolithic column was hyphenated with a 15,cm long norvancomycin (NVC)-bonded monolithic column via a fluorinated ethylene,propylene interface. Sample solution was injected into the C8 monolithic column, the two thalidomide enantiomers were first preconcentrated on the C8 monolithic column, and then separated with a further concentration on the NVC-bonded monolithic column by CEC. Injection of 34.8,mm plug of sample solution gave 278- and 298-fold enhancement in sensitivity, and detection limits of 90 and 94,,g/L for the two thalidomide enantiomers. Peak areas of the two isomers were linear in a range of 0.5,50,mg/L. The precision for five replicate injections of 10,mg/L were 0.8,0.9 and 1.1,2.3% for the migration time and peak height, respectively. The developed method was applied to the determination of racemic thalidomide in spiked human urine samples. [source] Capillary electrophoresis of amphipathic ,-helical peptide diastereomersELECTROPHORESIS, Issue 1 2004Traian V. Popa Abstract We have made a rigorous assessment of the ability of capillary electrophoresis to resolve peptide diastereomers through its application to the separation of a series of synthetic 18-residue, amphipathic ,-helical monomeric peptide analogues, where a single site in the centre of the hydrophobic face of the ,-helix is substituted by 19 L - or D -amino acids. Such L - and D -peptide pairs have the same mass-to-charge ratio, amino acid sequence and intrinsic hydrophobicity, varying only in the stereochemistry of one residue. CE approaches assessed in their ability to separate diastereomeric peptide pairs included capillary zone electrophoresis (uncoated capillary), micellar electrokinetic chromatography (uncoated capillary in the presence of 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate, CHAPS), open-tubular capillary electrochromatography (C8 -coated capillary in the presence of 25% 2,2,2-trifluoroethanol (TFE) or 25% ethanol). Overall, the OT-CEC methods were the most effective at separating the most peptide pairs, particularly for those containing hydrophilic side chains. However, the MEKC approach proved most effective for separation of peptide pairs containing hydrophobic or aromatic side chains. [source] Autoinducers extracted from microbial mats reveal a surprising diversity of N -acylhomoserine lactones (AHLs) and abundance changes that may relate to diel pHENVIRONMENTAL MICROBIOLOGY, Issue 2 2009Alan W. Decho Summary Microbial mats are highly structured and diverse communities, and one of the earliest-known life assemblages. Mat bacteria interact within an environment marked by strong geochemical gradients and fluctuations. We examined natural mat systems for the presence of autoinducers involved in quorum sensing, a form of cell,cell communication. Our results revealed that a diverse array of N -acylhomoserine lactones (AHLs) including C4 - to C14 -AHLs, were identified from mat extracts using mass spectrometry (MS), with further confirmation by MS/MS-collision-induced dissociation (CID), and additions of external standards. Microelectrode measurements showed that mats exhibited diel pH fluctuations, ranging from alkaline (pH 9.4) during daytime (net photosynthesis) to acidic (pH 6.8) during darkness (net respiration/fermentation). Under laboratory conditions, AHLs having shorter acyl-chains were degraded within the time frame that daily alkaline pH (> 8.2) conditions exist in mats. Intensive sampling of mats after full day- or night-time incubations revealed that accumulations of extractable shorter-chain AHLs (e.g. C8 - and C10 -AHLs) were significantly (P < 0.001) diminished during daytime. Our study offers evidence that stabilities of AHLs under natural conditions may be influenced by the proximal extracellular environment. We further propose that the ancient periodicity of photosynthesis/respiration in mats may potentially drive a mechanism for diel differences in activities of certain autoinducers, and hence bacterial activities mediated through quorum sensing. [source] Cadmium-regulated gene fusions in Pseudomonas fluorescensENVIRONMENTAL MICROBIOLOGY, Issue 4 2000Silvia Rossbach To study the mechanisms soil bacteria use to cope with elevated concentrations of heavy metals in the environment, a mutagenesis with the lacZ -based reporter gene transposon Tn5 -B20 was performed. Random gene fusions in the genome of the common soil bacterium Pseudomonas fluorescens strain ATCC 13525 were used to create a bank of 5000 P. fluorescens mutants. This mutant bank was screened for differential gene expression in the presence of the toxic metal cadmium. Fourteen mutants were identified that responded with increased or reduced gene expression to the presence of cadmium. The mutants were characterized with respect to their metal-dependent gene expression and their metal tolerance. Half the identified mutants reacted with differential gene expression specifically to the metal cadmium, whereas some of the other mutants also responded to elevated concentrations of copper and zinc ions. One of the mutants, strain C8, also showed increased gene expression in the presence of the solvent ethanol, but otherwise no overlap between cadmium-induced gene expression and general stress response was detected. Molecular analysis of the corresponding genetic loci was performed using arbitrary polymerase chain reaction (PCR), DNA sequencing and comparison of the deduced protein products with sequences deposited in genetic databases. Some of the genetic loci targeted by the transposon did not show any similarities to any known genes; thus, they may represent ,novel' loci. The hypothesis that genes that are differentially expressed in the presence of heavy metals play a role in metal tolerance was verified for one of the mutants. This mutant, strain C11, was hypersensitive to cadmium and zinc ions. In mutant C11, the transposon had inserted into a genetic region displaying similarity to genes encoding the sensor/regulator protein pairs of two-component systems that regulate gene expression in metal-resistant bacteria, including czcRS of Ralstonia eutropha, czrRS of Pseudomonas aeruginosa and copRS of Pseudomonas syringae. Although the P. fluorescens strain used in this study had not been isolated from a metal-rich environment, it nevertheless contained at least one genetic region enabling it to cope with elevated concentrations of heavy metals. [source] Anaerobic transformation of compounds of technical toxaphene.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2003Abstract Technical toxaphene (Melipax) and the single compounds of technical toxaphene (CTTs) 2,2,5- endo, 6- exo, 8,8,9,10- octachlorobornane (B8-806), 2,2,5- endo, 6- exo, 8,9,9,10-octachlorobornane (B8-809), 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9- 1025), 2- endo, 3- exo, 5- endo, 6- exo, 8,8,9,10,10-nonochlorobornane (B9-1679), 2- endo, 3- exo, 5- endo, 6- exo, 8,9,10,10-octachlorobornane (B8-1414), 2- endo, 3- exo, 5- endo, 6- exo, 8,8,9,10-octachlorobornane (B8-1412), and 2- exo, 3- endo, 5- exo, 9,9,10,10-heptachlorobornane (B7-1453) were treated with suspensions of the anaerobic bacterium Dehalospirillum multivorans. After 7 d, more than 50% of technical toxaphene was transformed, and the relative amount of early eluting CTTs increased. After 16 d, only 2- exo, 3- endo, 6- exo, 8,9,10-hexachlorobornane (B6-923), 2- endo, 3- exo, 5- endo, 6- exo, 8,9,10-heptachlorobornane (B7-1001), and a few minor penta- and hexachloro-CTTs were detected in the samples. The result of the transformation was comparable with observations in naturally contaminated sediments and soil. However, the performance with D. multivorans was more simple and reproducible, as well as faster, than use of soil, sediment, or anaerobic sewage sludge. In agreement with reports in the literature, reductive dechlorination at geminal chlorine atoms (gem -Cls) was found to be the major CTT transformation pathway. Experiments conducted with CTTs and gem -Cls at both primary and secondary carbons clarified that the initial Cl -> H substitution takes place at the secondary carbon C2. Furthermore, the 2- endo -Cl position was preferably substituted with hydrogen. In the case of B8-806, the dechlorination at the secondary carbon C2 was approximately 20-fold faster than the subsequent, slow reduction at the primary carbon C8. The three different formerly unknown heptachloro-CTTs, 2- exo, 3- endo, 6- exo, 8,9,9,10-heptachlorobornane (B7-1473), 2- exo, 3- endo, 6- endo, 8,9,9,10-hepatchlorobornane (B7-1461), and 2- exo, 3- endo, 6- exo, 8,8,9,10-heptachlorobornane (B7-1470) were found as intermediates of the B8-806/809 transformation. Treatment of B9-1679 with D. multivorans indicated that gem -Cls on the bridge (C8 and C9) are dechlorinated faster than gem -Cls on the bridgehead (C10). [source] ,, ,-Unsaturated sulfophenylcarboxylates as degradation intermediates of linear alkylbenzenesulfonates: Evidence for ,-oxygenation followed by ,-oxidations by liquid chromatography-mass spectrometryENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2002Peter Eichhorn Abstract Liquid chromatography with an electrospray interface to a mass spectrometer (LC-ES-MS) and LC-ES coupled to a tandem MS (LC-ES-MS/MS) were used to detect and identify intermediates excreted transiently during the aerobic degradation of linear alkylbenzenesulfonates (LAS) in fixed-bed bioreactors (FBBR). The inoculum for the FBBR was the microflora of the River Rhine, Germany. Two major phenomena were observed on the addition of 100 mg/L LAS to the system, sorption and then biodegradation. Disappearance due to sorption was followed in an inhibited FBBR. Biodegradation of LAS started on day 7 and was accompanied by the transient excretion of intermediates, which were later largely degraded. We detected not only the sulfophenylcarboxylates (SPCs) observed previously but also the ,, ,-unsaturated SPCs (SPC-2H), which have not been reported before. Experiments with the (4-sulfophenyl)dodecanes (C12-LAS), which had minor contaminants of C11-LAS, showed C12-, C10-, C8-, C6-, and C4-SPCs when LAS was degraded as well as traces of C9-, C7-, and C5-SPCs. Signals from the SPC-2H species were usually some 10% of those from the corresponding SPCs. Samples from these experiments were also examined by gas chromatography-mass spectrometry (GC-MS), but no desulfonated intermediates were detected. We interpret the data to mean that the only attack on LAS was by ,-oxygenation; there was no visible initial desulfonation. The products of ,-oxygenation were oxidized to the corresponding SPC and subject to ,-oxidation, as evidenced not only by the pattern of C-2 units in the excreted SPCs but also in the corresponding series of SPC-2H, representing the intermediates in ,-oxidation. [source] Effects of Valproate on Acylcarnitines in Children with Epilepsy Using ESI-MS/MSEPILEPSIA, Issue 1 2007Tamara Werner Summary:,Purpose: To determine the influence of valproate (VPA) treatment on acylcarnitines in children with epilepsy. Methods: Determination of acylcarnitines (including free carnitine and acylcarnitines from C2 to C18) in dried blood spot specimens using tandem-mass spectrometry. Longitudinal study of changes in acylcarnitines in children under VPA treatment without pretreatment (group 1) or with pretreatment with other antiepileptic drugs (group 2) before the start of VPA treatment at an early and a late treatment interval (12,66, 90,260 days after the beginning of treatment, respectively). Cross-sectional comparison of these two VPA groups and of a group receiving carbamazepine monotherapy (group 3) with controls. Results: Acylcarnitines in epileptic patients before VPA therapy did not differ from control values. In group 1, decreases of C0 (,26%), C2 (,12%), C16 (,31%), C18 (,41%), Ctotal (,10%), increases of C5OH (+31%), C8 (+33%) in the early treatment interval, and decreases of C16 (,21%), C18 (,42%), and increases of C2 (+26%), C5OH (+44%) in the late treatment interval were significant. In group 2, both in the longitudinal and the cross-sectional study, only a decrease of C18 (,41%, ,43%, respectively) in the late treatment interval was found. In group 3, no significant changes have been observed. Conclusions: We could prove changes in acylcarnitine subspecies, which were associated with VPA treatment in children with epilepsy. The treatment interval with the most marked changes coincides with the interval of highest risk for VPA-induced hepatotoxicity. The observed specific acylcarnitine pattern might point to the impaired intermediary metabolism that is responsible for VPA-induced hepatotoxicity. [source] DAP kinase activity is critical for C2 -ceramide-induced apoptosis in PC12 cellsFEBS JOURNAL, Issue 1 2002Mutsuya Yamamoto Exposure of PC12 cells to C2 -ceramide results in dose-dependent apoptosis. Here, we investigate the involvement of death-associated protein (DAP) kinase, initially identified as a positive mediator of the interferon-,-induced apoptosis of HeLa cells, in the C2 -ceramide-induced apoptosis of PC12 cells. DAP kinase is endogenously expressed in these cells. On exposure of PC12 cells to 30 µm C2 -ceramide, both the total (assayed in the presence of Ca2+/calmodulin) and Ca2+/calmodulin-independent (assayed in the presence of EGTA) DAP kinase activities were transiently increased 5.0- and 12.2-fold, respectively, at 10 min, and then decreased to 1.7- and 3.4-fold at 90 min. After 10 min exposure to 30 µm C2 -ceramide, the Ca2+/calmodulin independent activity/ total activity ratio increased from 0.22 to 0.60. These effects were dependent on the C2 -ceramide concentration. C8 -ceramide, another active ceramide analog, also induced apoptosis and activated DAP kinase, while C2 -dihydroceramide, an inactive ceramide analog, failed to induce apoptosis and increase DAP kinase activity. Furthermore, transfection studies revealed that overexpression of wild-type DAP kinase enhanced the sensitivity to C2 - and C8 -ceramide, while a catalytically inactive DAP kinase mutant and a construct containing the death domain and C-terminal tail of DAP kinase, which act in a dominant-negative manner, rescued cells from C2 -, and C8 -ceramide-induced apoptosis. These findings demonstrate that DAP kinase is an important component of the apoptotic machinery involved in ceramide-induced apoptosis, and that the intrinsic DAP kinase activity is critical for ceramide-induced apoptosis. [source] N -acyl-homoserine lactone-mediated quorum-sensing in Azospirillum: an exception rather than a ruleFEMS MICROBIOLOGY ECOLOGY, Issue 2 2006Ludovic Vial Abstract Forty Azospirillum strains were tested for their ability to synthesize N -acyl-homoserine lactones (AHLs). AHL production was detected for four strains belonging to the lipoferum species and isolated from a rice rhizosphere. AHL molecules were structurally identified for two strains: Azospirillum lipoferum TVV3 produces 3O,C8 -HSL (N -3-oxo-octanoyl-homoserine-lactone), C8 -HSL (N -3-octanoyl-homoserine-lactone), 3O,C10 -HSL (N -3-oxo-decanoyl-homoserine-lactone), 3OH,C10 -HSL (N -3-hydroxy-decanoyl-homoserine-lactone) and C10 -HSL (N -3-decanoyl-homoserine-lactone), whereas A. lipoferum B518 produced 3O,C6 -HSL (N -3-oxo-hexanoyl-homoserine-lactone), C6 -HSL (N -3-hexanoyl-homoserine-lactone), 3O,C8 -HSL, 3OH,C8 -HSL and C8 -HSL. Genes involved in AHL production were characterized for A. lipoferum TVV3 by generating a genomic library and complementing an AHL-deficient strain with sensor capabilities. Those genes, designated alpI and alpR, were found to belong to the luxI and luxR families, respectively. When cloned in a suitable heterologous host, alpI and alpR could direct the synthesis of the five cognate AHLs present in A. lipoferum TVV3. These two adjacent genes were found to be located on a 85kb plasmid. Southern hybridization experiments with probes alpI/R indicated that genes involved in AHL production in the three other AHL-producing strains were not closely related to alpI and alpR. This study demonstrates that AHL-based quorum-sensing is not widespread among the genus Azospirillum and could be found only in some A. lipoferum strains. [source] On the existence of non-supersymmetric black hole attractors for two-parameter Calabi-Yau's and attractor equationsFORTSCHRITTE DER PHYSIK/PROGRESS OF PHYSICS, Issue 12 2006P. Kaura We look for possible nonsupersymmetric black hole attractor solutions for type II compactification on (the mirror of) CY3(2,128) expressed as a degree-12 hypersurface in WCP4[1,1,2,2,6]. In the process, (a) for points away from the conifold locus, we show that the existence of a non-supersymmetric attractor along with a consistent choice of fluxes and extremum values of the complex structure moduli, could be connected to the existence of an elliptic curve fibered over C8 which may also be "arithmetic" (in some cases, it is possible to interpret the extremization conditions for the black-hole superpotential as an endomorphism involving complex multiplication of an arithmetic elliptic curve), and (b) for points near the conifold locus, we show that existence of non-supersymmetric black-hole attractors corresponds to a version of A1 -singularity in the space Image(Z6,R2/Z2 (,R3)) fibered over the complex structure moduli space. The (derivatives of the) effective black hole potential can be thought of as a real (integer) projection in a suitable coordinate patch of the Veronese map: CP5,CP20, fibered over the complex structure moduli space. We also discuss application of Kallosh's attractor equations (which are equivalent to the extremization of the effective black-hole potential) for nonsupersymmetric attractors and show that (a) for points away from the conifold locus, the attractor equations demand that the attractor solutions be independent of one of the two complex structure moduli, and (b) for points near the conifold locus, the attractor equations imply switching off of one of the six components of the fluxes. Both these features are more obvious using the attractor equations than the extremization of the black hole potential. [source] A Facile Synthesis Approach to C8 -Functionalized Magnetic Carbonaceous Polysaccharide Microspheres for the Highly Efficient and Rapid Enrichment of Peptides and Direct MALDI-TOF-MS AnalysisADVANCED MATERIALS, Issue 21 2009Hemei Chen Biocompatible C8 -functionalized magnetic carbonaceous polysaccharide microspheres are synthesized via a facile, low-cost, and large-scale route, and their use for the enrichment of peptides from protein digest mixtures is presented. The process of enrichment is very simple, quick, and efficient. Peptides loaded onto the C8 -functionalized magnetic carbonaceous polysaccharide microspheres can be directly analyzed by MALDI-TOF-MS without prior elution from the microspheres. [source] Quantum chemical study of leaving group activation in T. vivax nucleoside hydrolaseINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2006Stefan Loverix Abstract General acid catalysis is a powerful and widely used strategy in enzymatic nucleophilic displacement reactions. However, in the nucleoside hydrolase of the parasite Trypanosoma vivax, crystallographic and mutagenesis studies failed to identify a general acid. The only groups in the vicinity of the leaving group that contribute to catalysis are (i) the indole side chain of Trp260, and (ii) the 5,-group of the substrate's ribose moiety. The x-ray structure of the slow Asp10Ala mutant of nucleoside hydrolase with the substrate inosine bound in the active site displays a face-to-face aromatic stacking interaction between Trp260 and the purine base of the substrate, as well as a peculiar C4,-endo ribose pucker that allows the 5,-OH group to accept an intramolecular hydrogen bond from the C8 of the purine. The first interaction (aromatic stacking) has been shown to raise the pKa of the leaving purine. Here, we present a DFT study showing that the 5,-OH group of ribose fulfills a similar role, rather than stabilizing the oxocarbenium-like transition state. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Approaching risk assessment of complex disease development in horse chestnut trees: a chemical ecologist's perspectiveJOURNAL OF APPLIED ENTOMOLOGY, Issue 5 2008A. B. Johne Abstract The chemo-ecological predispositions were investigated for the development of a complex disease on the basis of an insect,fungus mutualism using the system of horse chestnuts (Aesculus hippocastanum and Aesculus x carnea), the horse chestnut leaf miner (Cameraria ohridella) and the biotrophic powdery mildew (Erysiphe flexuosa). Both C. ohridella and E. flexuosa can appear on the same horse chestnut leaf tissue simultaneously. The olfactory detection of fungal infection by the insect, its ability to discriminate the potentially mutualistic fungus from other fungi and the impact of fungal infection on insect oviposition were examined. Gas chromatography coupled with mass spectroscopic and electroantennographic detection by C. ohridella (GC-MS/EAD) was used to assess the olfactory detection of fungal-infected A. hippocastanum and A. x carnea leaves by C. ohridella. Infection-related compounds, such as benzyl alcohol, dodecane, tridecane and methyl salicylate as well as fungus-related C8 compounds, are perceived by C. ohridella. The discrimination of E. flexuosa from another phytopathogenic fungus, such as Guignardia aesculi, is based primarily on the differing pattern of C8 compounds of these fungi. Oviposition on fungal-infected leaves of A. hippocastanum and leaves treated with fungal-related compounds showed that C. ohridella is able to respond to the modifications in the leaf volatile profiles of horse chestnuts caused by the different fungal infections. Thus, from the perception point of view, the necessary predispositions for the development of a close insect,fungus relation between the biotrophic fungus E. flexuosa and the leaf-mining insect C. ohridella are fulfilled. However, decreased oviposition on infected leaves does not enhance the selective contact between the species. As a consequence, an important predisposition for forming an insect,fungus mutualism is not fulfilled by these two species and, according to this approach, the risk of forming a complex disease can be assessed as low. [source] Effectiveness test of alginate-derived polymeric surfactantsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 2 2002Hyun-Ah Kang Abstract A series of alginate-derived polymeric surfactants (APSs) with a linear alkyl group (C8, C12, C16) was synthesized by oxidation followed by reductive amination of 2,3-dialdehydic alginate. The products were characterized by measuring IR spectra, NMR spectra, surface tension and critical micelle concentration (cmc). They were also tested for the solubilization of azobenzene and adsorption of heavy metal. In the case of 40% CHO-C8 APSs, the lowest interfacial tension value (31.5,m Nm,1) was obtained at the cmc value of 1.35,g,dm,3. The dissolving capacity of 40% CHO-C8 APS towards azobenzene was 27 times greater than that of alginate. The overall cobalt (Co2+) removal efficiency by adsorption using APSs was high compared with that of sodium alginate at pH 3, 5 and 7. Equilibrium aspects of cobalt adsorption onto 10% CHO-APSs were studied, and the results show that APSs had high equilibrium capacities for cobalt uptake, 115.5,mgg,1. © 2002 Society of Chemical Industry [source] Analyses of Glycolipids in Clove, Red Pepper, and Nutmeg by High-Performance Liquid ChromatographyJOURNAL OF FOOD SCIENCE, Issue 6 2000H. Suzuki ABSTRACT: To determine the existence of glycolipids (neutral glycosphingolipid and glycoglycerolipid) in clove, red pepper, and nutmeg, we performed silica gel chromatography and high-performance liquid chromatography (HPLC) using an Aquasil-SS column and a C8 -reversed-phase silica gel column. HPLC (Aquasil-SS column) with a UV absorption detector was used to analyze neutral glycosphingolipid. These chromatograms showed two typical peaks in clove lipids. UV-HPLC (C8 -reversed phase silica gel column) was also used to analyze glycoglycerolipid. The chromatograms indicated a small peak in clove lipids. Moreover, we observed the same two peaks in the glycolipid fraction of clove lipid when we used HPLC (Aquasil-SS column) with a differential refractometer detector. These results suggest that clove may contain new and plural neutral glycosphingolipids. [source] 4-Chloro-3,-methylsulfinyl-5(6 or 8)-nitro-3,4,-diquinolinyl sulfides,JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 4 2000Maria J. Ma, lankiewicz Reaction of 4-chloro-3,-methylthio-3,4,-diquinolinyl sulfides 3, 9b, 9c with a nitrating mixture proceeds via the 3,-methylthio group monooxidation and yields 3,-methylsulfinyl diquinolinyl sulfides 4, 5b, 5c, respectively. Further treatment of 4 with a nitrating mixture followed as C5 - and C8 -nitration and gives mixture of 5a and 5c. Treatment of 3,-methylsulfinyl quinolines 6 and 7 with hydrochloric acid/potassium iodide system causes reduction of the sulfoxide group in 6 and 7 to the sulfide group yielding 8, in case of 4-methoxyquinolines 6, hydrolysis of the 4-methoxyquinoline moiety to the 4-quinolinone moiety takes place simultaneously. The proton and carbon chemical shifts of 4 and 5a were completely assigned following COSY, HETCOR and INEPT or COLOC studies. [source] Ticlopidine quantification in human plasma by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 12 2004Application to bioequivalence study Abstract A rapid, sensitive and specific method to quantify ticlopidine in human plasma using clopidogrel as the internal standard (IS) is described. The analyte and the IS were extracted from acidified plasma by liquid,liquid extraction using diethyl ether,hexane (80 : 20, v/v). The extracts were analyzed by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry (HPLC/MS/MS). Chromatography was performed isocratically on a Jones Genesis C8 4 µm analytical column (150 × 4.1 mm i.d.). The method had a chromatographic run time of 3.0 min and a linear calibration curve over the range 1.0,1000 ng ml,1 (r2 > 0.999427). The limit of quantification was 1.0 ng ml,1. This HPLC/MS/MS procedure was used to assess the bioequivalence of two ticlopidine 250 mg tablet formulations (ticlopidine test formulation from Apotex do Brasil, Brazil, and Ticlid from Sanofi-Synthelabo, standard reference formulation). A single 250 mg dose of each formulation was administered to healthy volunteers. The study was conducted using an open, randomized, two-period crossover design with a 2 week washout interval. Since the 90% confidence interval for Cmax and area under the curve ratios were all inside the 80,125% interval proposed by the US Food and Drug Administration, it was concluded that ticlopidine formulation from Apotex do Brasil is bioequivalent to Ticlid formulation with respect to both the rate and the extent of absorption. Copyright © 2004 John Wiley & Sons, Ltd. [source] Influence of the intermediate digestion phases of common formulation lipids on the absorption of a poorly water-soluble drugJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 3 2005Greg A. Kossena Abstract The influence of different model intestinal phases (modelled on those likely to be produced in vivo after the digestion of commonly used formulation lipids) on the absorption profile of cinnarizine has been studied. Combinations of C8, C12, or C18:1 fatty acid and monoglyceride and simulated endogenous intestinal fluid were formulated to provide examples of liquid (L1), lamellar (L,), and cubic (C) liquid crystalline phases. Phases containing cinnarizine were dosed intraduodenally and absorption was assessed in an anesthetized rat model. Bile duct ligation was performed to inhibit the effects of digestion/dilution on the phase structure. Absorption from the L, phases (C8 and C12 lipids) was statistically higher (p,<,0.05) than a cinnarizine suspension: however, a statistically significant difference was not observed from the L1 and C phases. The rigid C18:1 C phase showed evidence of providing for sustained drug absorption. Experiments in bile intact rats with the C8 L, and C18:1 C phase highlighted that the absorption-modifying properties of these phases were influenced by dilution in the endogenous bile milieu, with absorption from L, phase reducing (possibly through precipitation of solubilized drug) and increasing in the case of the C18:1 C phase, possibly through the coexistence of L1 and C upon dilution permitting more efficient transfer of solubilized drug. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 94:481,492, 2005 [source] Cotinine as a biomarker of tobacco exposure: Development of a HPLC method and comparison of matricesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 4-5 2010Guilherme Oliveira Petersen Abstract Tobacco dependence reaches one-third of the world population, and is the second leading cause of death around the world. Cotinine, a major metabolite of nicotine, is the most appropriate parameter to evaluate tobacco exposure and smoking status due to its higher stability and half-life when compared to nicotine. The procedure involves liquid,liquid extraction, separation on a RP column (Zorbax® XDB C8), isocratic pump (0.5,mL/min of water,methanol,sodium acetate (0.1,M),ACN (50:15:25:10, v/v/v/v), 1.0,mL of citric acid (0.034,M) and 5.0,mL of triethylamine for each liter) and HPLC-UV detection (261,nm). The analytical procedure proved to be sensitive, selective, precise, accurate and linear (r>0.99) in the range of 5,500.0,ng/mL for cotinine. 2-Phenylimidazole was used as the internal standard. The LOD was 0.18,ng/mL and the LOQ was 5.0,ng/mL. All samples from smoking volunteers were collected simultaneously to establish a comparison between serum, plasma, and urine. The urinary cotinine levels were normalized by the creatinine and urine density. A significant correlation was found (p<0.01) between all matrices. Results indicate that the urine normalization by creatinine or density is unnecessary. This method is considered reliable for determining cotinine in serum and plasma of smokers and in environmental tobacco smoke exposure. [source] Enrichment of peptides from plasma for peptidome analysis using multiwalled carbon nanotubesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 6 2007Xin Li Abstract Human plasma contains a complex matrix of proteolytically derived peptides (plasma peptidome) that may provide a correlate of biological events occurring in the entire organism. Analyzing these peptides from a small amount of serum/plasma is difficult due to the complexity of the sample and the low levels of these peptides. Here, we describe a novel peptidome analysis approach using multiwalled carbon nanotubes (MWCNTs) as an alternative adsorbent to capture endogenous peptides from human plasma. Harvested peptides were analyzed by using liquid chromatography-mass spectrometry as a means of detecting and assessing the adsorbed molecules. The improved sensitivity and resolution obtained by using liquid chromatography-mass spectrometry allowed detection of 2521 peptide features (m/z 300,1800 range) in about 50 ,L of plasma. 374 unique peptides were identified with high confidence by two-dimensional liquid chromatography system coupled to a nano-spray ionization linear ion trap-mass spectrometer. High recovery of BSA digest peptides enriched with MWCNTs, in both standard buffer and high abundance protein solution, was observed. Comparative studies showed that MWCNTs were superior to C18 and C8 for the capture of the smaller peptides. This approach could hold promise of routine plasma peptidome analysis. [source] Reduced-bore monolithic silica column modified with C8 -TEOS for reversed-phase electrochromatographyJOURNAL OF SEPARATION SCIENCE, JSS, Issue 9 2004Qishu Qu Abstract Monolithic silica columns of 2.7 mm ID were prepared and derivatized with C8 -TEOS and TEOS by on-column sol-gel reaction. These C8 large diameter monolithic silica columns gave 21 000 theoretical plates for aromatic hydrocarbons in 60% acetonitrile and 40% Tris-HCl buffer. The surface areas as well as the separation reproducibility were improved on coating by the sol-gel approach. Joule heating was greatly reduced by using monolithic columns to which fine quartz sand had been added during column preparation. Since this is a preliminary investigation on a monolithic column with such a large inner diameter, the separation efficiency was not so high as that presently achieved in normal capillary electrochromatography (CEC). However, use of the columns improved sample loadability and concentration detectability of electrochromatography, and semi-preparative separations could be performed. [source] Carbon-13 chemical shift anisotropy in DNA bases from field dependence of solution NMR relaxation rates,MAGNETIC RESONANCE IN CHEMISTRY, Issue 3 2006Jinfa Ying Abstract Knowledge of 13C chemical shift anisotropy (CSA) in nucleotide bases is important for the interpretation of solution-state NMR relaxation data in terms of local dynamic properties of DNA and RNA. Accurate knowledge of the CSA becomes particularly important at high magnetic fields, prerequisite for adequate spectral resolution in larger oligonucleotides. Measurement of 13C relaxation rates of protonated carbons in the bases of the so-called Dickerson dodecamer, d(CGCGAATTCGCG)2, at 500 and 800 MHz 1H frequency, together with the previously characterized structure and diffusion tensor yields CSA values for C5 in C, C6 in C and T, C8 in A and G, and C2 in A that are closest to values previously reported on the basis of solid-state FIREMAT NMR measurements, and mostly larger than values obtained by in vacuo DFT calculations. Owing to the noncollinearity of dipolar and CSA interactions, interpretation of the NMR relaxation rates is particularly sensitive to anisotropy of rotational diffusion, and use of isotropic diffusion models can result in considerable errors. Copyright © 2006 John Wiley & Sons, Ltd. [source] Total obstetric brachial plexus palsy: Results and strategy of microsurgical reconstructionMICROSURGERY, Issue 3 2010Tarek A. El-gammal M.D. From 2000 to 2006, 35 infants with total obstetric brachial plexus palsy underwent brachial plexus exploration and reconstruction. The mean age at surgery was 10.8 months (range 3,60 months), and the median age was 8 months. All infants were followed for at least 2.5 years (range 2.5,7.3 years) with an average follow-up of 4.2 years. Assessment was performed using the Toronto Active Movement scale. Surgical procedures included neurolysis, neuroma excision and interposition nerve grafting and neurotization, using spinal accessory nerve, intercostals and contralateral C7 root. Satisfactory recovery was obtained in 37.1% of cases for shoulder abduction; 54.3% for shoulder external rotation; 75.1% for elbow flexion; 77.1% for elbow extension; 61.1% for finger flexion, 31.4% for wrist extension and 45.8% for fingers extension. Using the Raimondi score, 18 cases (53%) achieved a score of three or more (functional hand). The mean Raimondi score significantly improved postoperatively as compared to the preoperative mean: 2.73 versus 1, and showed negative significant correlation with age at surgery. In total, obstetrical brachial plexus palsy, early intervention is recommended. Intercostal neurotization is preferred for restoration of elbow flexion. Tendon transfer may be required to improve external rotation in selected cases. Apparently, intact C8 and T1 roots should be left alone if the patient has partial hand recovery, no Horner syndrome, and was operated early (3- or 4-months old). Apparently, intact nonfunctioning lower roots with no response to electrical stimulation, especially in the presence of Horner syndrome, should be neurotized with the best available intraplexal donor. © 2010 Wiley-Liss, Inc. Microsurgery, 2010. [source] Histopathological basis of Horner's syndrome in obstetric brachial plexus palsy differs from that in adult brachial plexus injuryMUSCLE AND NERVE, Issue 5 2008Yi-Gang Huang MD Abstract Although Horner's syndrome is usually taken as an absolute indicator of avulsions of the C8 and T1 ventral roots in adult brachial plexus injury, its pathological basis in obstetric brachial plexus palsy (OBPP) is unclear. We therefore examined the morphological mechanism for the presence of Horner's syndrome in brachial plexus injury in infants and adults. Some axons of sympathetic preganglionic neurons in T1 innervate the superior cervical ganglion via the C7 ventral root in infants but not in adults. Therefore, the presence of Horner's syndrome may relate in part to avulsion of the C7 root in OBPP. These findings suggest that Horner's syndrome in OBPP is not necessarily indicative of avulsions of the C8 and T1 roots, as it can occur with avulsion of the C7 root. Muscle Nerve, 2008 [source] Metal/Fluorocarbon Pyrolants: V. Theoretical Evaluation of the Combustion Performance of Metal/Fluorocarbon Pyrolants based on Strained FluorocarbonsPROPELLANTS, EXPLOSIVES, PYROTECHNICS, Issue 1 2004Ernst-Christian Koch Abstract The potential of strained fluorocarbons, which can act as oxidizers in metal-based pyrolant systems, is investigated. The oxidizing performance of fluorocarbons is evaluated by the enthalpy of combustion ,cH(298K) and the fractional electron transfer ,N. ,cH(298K) can be related to hybridisation, molar C/F ratio and strain of the parent carbon skeleton of the fluorocarbon. Considered fluorocarbons are tetrafluorotetrahedrane (CF)4 (3), tetrakis(trifluoromethyl)tetrahedrane C4(CF3)4 (4), hexafluoro[3]prismane (CF)6 (5), hexakis(trifluoromethyl)[3]prismane C6(CF3)6 (6), octafluorocubane (CF)8 (7), octakis(trifluoromethyl)cubane C8(CF3)8 (8), eicosafluorododecahedrane (CF)20 (9), eicosakis(trifluoromethyl)dodecahedrane C20(CF3)20 (10), C60F48 (11) and perfluorofullerane (CF)60 (12). Powerful oxidisers in terms of exothermicity are those possessing both tertiary CF-units and strained carbon skeletons. Nevertheless the reactivity, which is estimated on basis of ,N, the fraction of electrons transferred according to Pearson, has been found to be high with the corresponding perfluoromethyl derivatives and maximum with the fluorofulleranes. For part IV see Ref. 17. [source] Facile synthesis of C8 -functionalized magnetic silica microspheres for enrichment of low-concentration peptides for direct MALDI-TOF MS analysisPROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 14 2008Hemei Chen Abstract In this study, novel C8 -functionalized magnetic polymer microspheres were prepared by coating single submicron-sized magnetite particle with silica and subsequent modification with chloro (dimethyl) octylsilane. The resulting C8 -functionalized magnetic silica (C8 -f-M-S) microspheres exhibit well-defined magnetite-core-silica-shell structure and possess high content of magnetite, which endow them with high dispersibility and strong magnetic response. With their magnetic property, the synthesized C8 -f-M-S microspheres provide a convenient and efficient way for enrichment of low-abundance peptides from tryptic protein digest and human serum. The enriched peptides/proteins were subjected for MALDI-TOF MS analysis and the enrichment efficiency was documented. In a word, the facile synthesis and efficient enrichment process of the novel C8 -f-M-S microspheres make them promising candidates for isolation of peptides even in complex biological samples such as serum, plasma, and urine. [source] Simultaneous determination of mercapturic acids derived from ethylene oxide (HEMA), propylene oxide (2-HPMA), acrolein (3-HPMA), acrylamide (AAMA) and N,N -dimethylformamide (AMCC) in human urine using liquid chromatography/tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2008Thomas Schettgen Mercapturic acids are highly important and specific biomarkers of exposure to carcinogenic substances in occupational and environmental medicine. We have developed and validated a reliable, specific and very sensitive method for the simultaneous determination of five mercapturic acids derived from several high-production chemicals used in industry, namely ethylene oxide, propylene oxide, acrylamide, acrolein and N,N -dimethylformamide. Analytes are enriched and cleaned up from urinary matrix by offline solid-phase extraction. The mercapturic acids are subsequently separated by means of high-performance liquid chromatography on a Luna C8 (2) column and specifically quantified by tandem mass spectrometric detection using isotopically labelled analytes as internal standards. The limits of detection (LODs) for N -acetyl- S -2-carbamoylethylcysteine (AAMA) and N -acetyl- S -2-hydroxyethylcysteine (HEMA) were 2.5,µg/L and 0.5,µg/L urine, while for N -acetyl- S -3-hydroxypropylcysteine (3-HPMA), N -acetyl- S -2-hydroxypropylcysteine (2-HPMA) and N -acetyl- S -(N -methylcarbamoyl)cysteine (AMCC) it was 5,µg/L. These LODs were sufficient to detect the background exposure of the general population. We applied the method on spot urine samples of 28 subjects of the general population with no known occupational exposure to these substances. Median levels for AAMA, HEMA, 3-HPMA, 2-HPMA and AMCC in non-smokers (n,=,14) were 52.6, 2.0, 155, 7.1 and 113.6,µg/L, respectively. In smokers (n,=,14), median levels for AAMA, HEMA, 3-HPMA, 2-HPMA and AMCC were 243, 5.3, 1681, 41.7 and 822,µg/L, respectively. Due to the simultaneous quantification of these mercapturic acids, our method is well suited for the screening of workers with multiple chemical exposures as well as the determination of the background excretion of the general population. Copyright © 2008 John Wiley & Sons, Ltd. [source] Serum biomarker profiling by solid-phase extraction with particle-embedded micro tips and matrix-assisted laser desorption/ionization mass spectrometry,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 7 2008Arti Navare One of the main challenges in high-throughput serum profiling by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is the development of proteome fractionation approaches that allow the acquisition of reproducible profiles with a maximum number of spectral features and minimum interferences from biological matrices. This study evaluates a new class of solid-phase extraction (SPE) pipette tips embedded with different chromatographic media for fractionation of model protein digests and serum samples. The materials embedded include strong anion exchange (SAX), weak cation exchange (WCX), C18, C8, C4, immobilized metal affinity chromatography (IMAC) and zirconium dioxide particles. Simple and rapid serum proteome profiling protocols based on these SPE micro tips are described and tested using a variety of MALDI matrices. We show that different types of particle-embedded SPE micro tips provide complementary information in terms of the spectral features detected for , -casein digests and control human serum samples. The effect of different sample pretreatments, such as serum dilution and ultrafiltration using molecular weight cut-off membranes, and the reproducibility observed for replicate experiments, are also evaluated. The results demonstrate the usefulness of these simple SPE tips combined with offline MALDI-TOF MS for obtaining information-rich serum profiles, resulting in a robust, versatile and reproducible open-source platform for serum biomarker discovery. Copyright © 2008 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||||||||