Distribution by Scientific Domains
Distribution within Chemistry

Kinds of Ortho

  • directed ortho

  • Terms modified by Ortho

  • ortho c
  • ortho lithiation
  • ortho position
  • ortho substituent

  • Selected Abstracts

    Possible mechanisms for the relative efficacies of ortho -phthalaldehyde and glutaraldehyde against glutaraldehyde-resistant Mycobacterium chelonae

    S.E. Walsh
    Aims: This investigation compared glutaraldehyde (GTA)-sensitive and -resistant strains of Mycobacterium chelonae and examined the effects of pretreatment of GTA-sensitive and -resistant strains of Myco. chelonae with chemical agents that interfere with cell wall synthesis. Methods and Results: When exposed to 2% (v/v) GTA at 25°C, GTA-resistant strains of Myco. chelonae dried on to glass carriers were not inactivated to any significant extent. By contrast, GTA-sensitive strains of Myco. chelonae and a strain of Myco. terrae suffered a > 6 log reduction in viability in 5 min. However, ortho -phthalaldehyde (OPA; 0·5% w/v) achieved a corresponding inactivation against two GTA-resistant strains within 5,10 and 10,20 min, respectively. Electron microscopy, using a non-aldehyde fixation process and also negative staining, failed to detect any extensive changes in GTA-sensitive and -resistant cultures exposed to GTA or OPA. Thin-layer chromatography was unsuccessful in detecting differences between GTA-resistant and -sensitive strains of Myco. chelonae. However, pretreatment of GTA-resistant cells with mycobacterial cell wall synthesis inhibitors increased their subsequent susceptibility further to OPA but not to GTA. Conclusions:Ortho -phthalaldehyde is an effective new biocidal agent that, at its in-use concentration, is rapidly bactericidal to non-sporulating bacteria, including GTA-sensitive and -resistant mycobacteria. Significance and Impact of the Study: Pretreatment of GTA-resistant cells with mycobacterial cell wall synthesis inhibitors increased their subsequent susceptibility to OPA but not to GTA. [source]

    Determination of Ortho- and Retronasal Detection Thresholds for 2-Isopropyl-3-Methoxypyrazine in Wine

    G.J. Pickering
    ABSTRACT:, 2-isopropyl-3-methoxypyrazine (IPMP) is a grape-derived component of wine flavor in some wine varieties as well as the causal compound of the off-flavor known as ladybug taint (LBT), which occurs when Harmonia axyridis beetles are incorporated with the grapes during juice and wine processing. The main objective of this study was to obtain robust estimates of the orthonasal (ON) and retronasal (RN) detection thresholds (DTs) for IPMP in wines of differing styles. The ASTM E679 ascending forced choice method of limits was used to determine DTs for 47 individuals in 3 different wines,Chardonnay, Gewürztraminer, and a red wine blend of Baco Noir and Marechel Foch. The group best estimate thresholds (BETs) obtained for IPMP (ng/L) were Chardonnay, ON: 0.32; Gewürztraminer, ON: 1.56, RN: 1.15, and red wine blend, ON: 1.03, RN: 2.29. A large variation in individual DTs was observed. Familiarity with LBT was inversely correlated with DTs for Gewürztraminer, and no difference in thresholds was observed between winemakers and nonwinemakers. We conclude that the human DT for IPMP is extremely low and influenced significantly by wine style and evaluation mode. We recommend against the reporting of single-threshold values for wine flavor compounds, and encourage the determination of consumer rejection thresholds for IPMP in wine. [source]

    Ortho -[18F]Fluoronitrobenzenes by no-carrier-added nucleophilic aromatic substitution with K[18F]F,K222,A comparative study

    M. Karramkam
    Abstract The scope of the nucleophilic aromatic ortho -fluorinations from the corresponding ortho -halonitrobenzene precursors (halo-to-fluoro substitutions) with no-carrier-added [18F]fluoride ion as its activated K[18F]F,K222 complex has been evaluated via the radiosynthesis of ortho -[18F]fluoronitrobenzene, chosen as a model reaction. The parameters studied include the influence of the leaving group in the ortho position of the phenyl ring (,Cl, ,Br, ,l), the quantity of precursor used, the type of activation (conventional heating or microwave irradiations), the solvent, the temperature and the reaction time. The iodo-precursor was completely unreactive and the bromo-precursor gave only low incorporation (<10%) in the optimal conditions used (conventional heating at 145°C or microwave activation, 100 W for 120 s). Only the chloro-precursor was found reactive in the conditions described above and up to 70% yield was observed for the formation of ortho -[18F]fluoronitrobenzene ([18F]- 1). In all the experiments, the unwanted ortho -[18F]fluoro-halobenzenes, potentially resulting from the nitro-to-fluoro substitution, could not be detected. These results will be applied for the radiosynthesis of 5-[18F]fluoro-6-nitroquipazine, a potent radioligand for the imaging of the serotonin transporter with PET. Copyright © 2002 John Wiley & Sons, Ltd. [source]

    The Kinetic Modeling of Strong Diffusion-Limited Reaction with Cyclization for Three Isomers , Diallyl Ortho-, Iso- and Tere - Phthalate in a Bulk

    Iztok Hace
    Abstract Free radical polymerization kinetic in a bulk for three diallyl phthalate isomers , diallyl orthophthalate, diallyl isophthalate and diallyl terephthalate was investigated in a temperature range from 50 to 70,°C initiated with dicyclohexan peroxydicarbonate as initiator at three different initiator concentrations. Conversion points were measured using Fourier Transform Raman measurements. A new kinetic model for polymerization of three diallyl phthalate isomers was developed. It demands the inclusion of only two new kinetic parameters kDegC and kpc which were obtained as a ratio kDegC/kpc from an additional set of experiments conducted. Computed conversions from the proposed kinetic model show good agreement with the conversion and molecular weight measured data for all three investigated diallyl phthalate isomers. [source]

    Ortho Effects in Quantitative Structure Activity Relationships for Lipase Inhibition by Aryl Carbamates

    Gialih Lin
    Abstract Ortho -substituted phenyl- N -butyl carbamates (1,11) are synthesized and evaluated for their inhibition effects on Pseudomonas species lipase. Carbamates 1,11 are characterized as pseudo-substrate inhibitors of the enzyme. The logarithms of dissociation constant (Ki), carbamylation constant (k2), and bimolecular inhibition constant (ki) multiply linearly correlate with Hammett substituent constant (,), Taft-Kutter-Hansch ortho steric constant (ES), and Swan-Lupton field constant (F). For ,logKi -, logk2 -, and logki -correlations, values of ,, ,, f, ,XR are 0.2, ,0.06, ,1.7, 0.8; 0.0, 0.0, 1.0, ,0.07; and ,1.8, 7, 0.6, 5; respectively. The enzyme inhibition mechanism is composed of four steps: 1) the first step which is protonation of carbamates 1,11, 2) the second step (Ki1) which involves in the proton 1,3-shift of protonated carbamates 1,11 then the pseudo- trans to cis conformational change, 3) the third step (Ki2) which is formation of a negative charged enzyme-inhibitor tetrahedral intermediate, and 4) the fourth step (k2) which is the carbamylation step. The former three steps are likely composed of the Ki step. There is little ortho steric enhancement effect in the Ki step. From cross-interaction correlations, distance between carbamate and phenyl substituents in transition state for the Ki step is relatively short due to a large ,XR value of 7. The k2 step is insensitive to ortho steric effect. The k2 step involves in departure of leaving group, substituted phenol in which is protonated from the proton 1,3-shift but not from the active site histidine of the enzyme. From cross-interaction correlations, the distance between carbamate and phenyl substituents in transition state for the k2 step is relatively long due to a small ,XR value of 0.6. [source]

    DHTP Ligands for the Highly Ortho -Selective, Palladium-Catalyzed Cross-Coupling of Dihaloarenes with Grignard Reagents: A Conformational Approach for Catalyst Improvement,

    ANGEWANDTE CHEMIE, Issue 4 2010
    Shunpei Ishikawa Dr.
    Palladiumkatalysatoren mit Dihydroxyterphenylphosphan-Liganden (wie 1) eignen sich für die ortho -selektive Kreuzkupplung von Grignard-Reagentien mit Dihalogenarenen. Die zweite Hydroxygruppe des Terphenylphosphan-Liganden erhöhte die katalytische Effizienz drastisch und erweiterte den Anwendungsbereich der Reaktion. [source]

    In vivo effects of amorphous calcium phosphate-containing orthodontic composite on enamel demineralization around orthodontic brackets

    T Uysal
    Abstract Background:, The aim of this study was to evaluate the in vivo effects of an amorphous calcium phosphate-containing orthodontic composite in reducing enamel demineralization around orthodontic brackets, and to compare it with the control. Methods:, Fourteen orthodontic patients were divided into two equal groups. They received brackets fitted to all first premolars, bonded with either Aegis Ortho® (The Bosworth Co.), an ACP-containing orthodontic composite (experimental group), or Concise® (3M Dental Products), a resin-based orthodontic composite (control group). After 30 days, the teeth were extracted and longitudinally sectioned, and evaluated by superficial-microhardness analysis. The determinations were made at the bracket edge cementing limits and at occlusal and cervical points 100 and 200 ,m away from the edge. In all of these positions, indentations were made at depths of 10, 20, 30, 50, 70, and 90 ,m from the enamel surface. Analysis of variance (ANOVA) and Tukey post hoc test was used. The statistical significance level was set at p <0.05. Results:, The ANOVA showed statistically significant differences for position, material, depth, and their interactions (p <0.001). The multiple comparison test showed that the ACP-containing orthodontic composite was significantly more efficient than the control composite, reducing enamel demineralization in almost all evaluations (p <0.001). Conclusions:, Present results indicated that ACP-containing orthodontic composite for bonding orthodontic brackets successfully inhibited demineralization in vivo. This effect was localized to the area around the brackets and was statistically significant after 30 days. [source]

    Ototoxicity in Rats Exposed to Ortho-, Meta- and Para-Xylene Vapours for 13 Weeks

    François Gagnaire
    Brainstem auditory-evoked responses were used to determine auditory thresholds at different frequencies. Among the three isomers studied, only para-xylene produced moderate to severe ototoxicity in rats exposed at 900 and 1800 p.p.m. Increased auditory thresholds were observed at 2, 4, 8 and 16 kHz in rats exposed to 1800 p.p.m. para-xylene. The auditory threshold shifts (35 to 38 dB) did not reverse after 8 weeks of recovery. Moderate and severe losses of outer hair cells of the organ of Corti occurred in animals exposed to 900 and 1800 p.p.m. para-xylene respectively. Thus, the no observed effect level of para-xylene was 450 p.p.m. based on the loss of outer hair cells observed by light and electron microscopy. [source]

    Effects of in utero exposure to 2,2,,4,4,,5,5,-hexachlorobiphenyl (PCB 153) on somatic growth and endocrine status in rat offspring

    Kenichi Kobayashi
    ABSTRACT Exposure to polychlorobiphenyl (PCB) mixtures at an early stage of development has been reported to affect endocrine glands; however, little is known about the precise toxicological properties of individual PCB. The present study was undertaken to determine whether prenatal exposure to 2,2,,4,4,,5,5,-hexachlorobiphenyl (PCB 153), a di- ortho -substituted non-coplanar congener, affects postnatal development in rat offspring. Pregnant Sprague-Dawley rats (Crj: CD (SD) IGS) were given PCB 153 (0, 16, or 64 mg/kg/day) orally from gestational day (GD) 10 through GD 16, and developmental parameters in the male and female offspring were examined. We found no dose-dependent changes in body weight, body length (nose,anus length), tail length, or the weights of kidneys, testes, ovaries and uterus in offspring at 1 or 3 weeks of age. Liver weights were increased in the PCB 153,treated groups, although we observed a significant difference only in males. Anogenital distance was unaffected in the PCB 153,treated groups. We observed a significant dose-dependent decrease in the plasma concentrations of thyroxine and tri-iodothyronine, whereas those of thyroid-stimulating hormone were not significantly changed. In addition, there were no dose-dependent changes in plasma concentrations of growth hormone and insulin-like growth factor-I in any dose group. These findings suggest that prenatal exposure to PCB 153 (GD 10,16, 16,64 mg/kg/day) may alter the thyroid status in rat offspring to some extent without affecting somatic growth or its related hormonal parameters. [source]

    Field-amplified sample injection-micellar electrokinetic capillary chromatography for the analysis of bisphenol A, bisphenol F, and their diglycidyl ethers and derivatives in canned soft drinks

    ELECTROPHORESIS, Issue 9 2010
    Héctor Gallart-Ayala
    Abstract Conditions were established for the separation and analysis of bisphenol A, bisphenol F, and their diglycidyl ethers by micellar electrokinetic capillary chromatography (MECC). Good resolution was obtained for all compounds, although in order to achieve the separation of ortho,ortho, ortho,para, and para,para isomers of bisphenol F diglycidyl ether (BFDGE), BFDGE·2H2O and BFDGE·2HCl, it was necessary to use a 25,,m id fused silica capillary. To increase sensitivity, a field-amplified sample injection (FASI)-MECC method was developed using 10,mM SDS solution as injection matrix and a 75,,m id fused silica capillary. Instrumental quality parameters such as LODs (<55,,g/L with standards), linearity (r2>0.999), and run-to-run and day-to-day precisions (RSD values lower than 12.5%) were determined. Finally, the suitability of the FASI-MECC method for the analysis of bisphenol A, bisphenol F, and their diglycidyl ethers in canned soft drinks was evaluated. Quantitation was performed by matrix-matched calibration using a plastic-bottled isotonic drink as matrix. The results showed that FASI-MECC is an economic method for the screening and quantitation of these kinds of compounds in soft drink beverages, with no loss of reproducibility, and effective at concentrations lower than the specific migration level values established by the European Union. [source]

    Compositional effects on electrophoretic and chromatographic figures of merit in electrokinetic chromatography with cetyltrimethylammonium bromide/sodium octyl sulfate vesicles as the pseudostationary phase.

    ELECTROPHORESIS, Issue 5 2008
    Part 1: Effect of the phase ratio
    Abstract The effect of the phase ratio on the electrophoretic and chromatographic properties of unilamellar vesicles comprised of cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) was investigated in EKC. The surfactant concentration of the vesicles was 0.9, 1.2, 1.5, and 1.8% w/v, with a mole ratio of 1:3.66 (CTAB/SOS). Results were compared to those obtained using SDS micelles at concentrations of 1.0% (w/v, 35,mM) and 1.5% (52,mM). The CTAB/SOS vesicles (0.9,1.8% w/v) provided a significantly larger elution range (5.7,,,tves/t0,,,8.7) and greater hydrophobic (methylene) selectivity (2.8,,,,CH2,,,3.1) than SDS micelles (3.1,,,tmc/t0,,,3.3; ,CH2,=,2.2). Whereas the larger elution range can be attributed to the 25% reduction in EOF due to the interaction of unaggregated CTAB cations and the negatively charged capillary wall, the higher methylene selectivity is likely due to the lower concentration of water expected in the CTAB/SOS vesicle bilayer compared to the Palisades layer of SDS micelles. For a given phase ratio, CTAB/SOS vesicles are somewhat less retentive than SDS micelles, although retention factors comparable to those observed in 1.0,1.5% SDS can be obtained with 1.5,1.8% CTAB/SOS. A linear relationship was observed between phase ratio and retention factor, confirming the validity of the phase ratio model for these vesicles. Unique polar group selectivities and positional isomer shape selectivities were obtained with CTAB/SOS vesicles, with both types of selectivities being nearly independent of the phase ratio. For four sets of positional isomers, the elution order was always para < ortho < meta. Finally, the thermodynamics of solute retention was qualitatively similar to that reported for other surfactant aggregates (micelles and microemulsions); the enthalpic contribution to retention was consistently favorable for all compounds, whereas the entropic contribution was favorable only to hydrophobic solutes. [source]

    Analysis of sub-ppb levels of Fe(II), Co(II), and Ni(II) by electrokinetic supercharging preconcentration, CZE separation, and in-capillary derivatization

    ELECTROPHORESIS, Issue 20 2007
    Marek Urbanek
    Abstract The analysis of sub-ppb levels of Fe(II), Co(II), and Ni(II) in heat exchanger fluids of nuclear power plants is needed to monitor corrosion. A method involving preconcentration with electrokinetic supercharging (electrokinetic injection with transient ITP), CZE separation, and in-capillary derivatization with ortho -phenanthroline (o -Phe) for direct UV detection was thus developed. First, a multizone BGE was loaded into the capillary by successive hydrodynamic introduction of zones of (i) o -Phe-containing BGE, (ii) BGE for the zonal separation, and (iii) ammonium-based leading electrolyte. Metal cations were electrokinetically injected and stacked at the capillary inlet behind this last leading zone. Finally, a terminating electrolyte zone was hydrodynamically introduced. When a constant voltage was applied, metal ions kept on concentrating isotachophoretically, then separated in CZE mode, were complexed by migrating through an o -Phe zone, and finally detected by direct absorbance. To detect extremely thin peaks, it was attempted for the first time to focus the derivatization reagent by inducing a second transient ITP, before labeling analytes, already separated in CZE mode. With this arrangement, LODs were about 30,ppt in pure water. In heat exchanger fluid matrices containing 1000,ppm bore and 2,ppm lithium, only Fe(II) cation was detected among the three cations of interest at the 1,ppb level using the present method, and its LOD was about ten times higher, due to the lower loading rate during electrokinetic injection. [source]

    On-line sample preconcentration with chemical derivatization of bacterial biomarkers by capillary electrophoresis: A dual strategy for integrating sample pretreatment with chemical analysis

    ELECTROPHORESIS, Issue 21 2005
    Adam S. Ptolemy
    Abstract Simple, selective yet sensitive methods to quantify low-abundance bacterial biomarkers derived from complex samples are required in clinical, biological, and environmental applications. In this report, a new strategy to integrate sample pretreatment with chemical analysis is investigated using on-line preconcentration with chemical derivatization by CE and UV detection. Single-step enantioselective analysis of muramic acid (MA) and diaminopimelic acid (DAP) was achieved by CE via sample enrichment by dynamic pH junction with ortho -phthalaldehyde/N -acetyl- L -cysteine labeling directly in-capillary. The optimized method resulted in up to a 100-fold enhancement in concentration sensitivity compared to conventional off-line derivatization procedures. The method was also applied toward the detection of micromolar levels of MA and DAP excreted in the extracellular medium of Escherichia coli bacterial cell cultures. On-line preconcentration with chemical derivatization by CE represents a unique approach for conducting rapid, sensitive, and high-throughput analyses of other classes of amino acid and amino sugar metabolites with reduced sample handling, where the capillary functions simultaneously as a concentrator, microreactor, and chiral selector. [source]

    Polybrominated diphenyl ethers, toxaphenes, and other halogenated organic pollutants in great blue heron eggs

    Louise Champoux
    Abstract The great blue heron (Ardea herodias) has been used as a bioindicator of the state of the St. Lawrence River (Québec, Canada) since 1996. At 5-year intervals, selected breeding colonies along the River and its estuary are visited to estimate reproductive success and determine levels of contamination. Brominated flame retardants are found in many ecosystems and are increasing in concentration in the Great Lakes, which is the source of much of the water for the St. Lawrence River. In 2001 and 2002, in addition to polychlorinated biphenyls (PCBs) and chlorinated pesticides, the levels of polybrominated diphenyl ethers (PBDEs), polychlorinated bornanes (toxaphene) congeners and non- ortho -substituted PCBs were measured for the first time in pools of great blue heron eggs. The PBDE levels in great blue heron eggs (70,1,377,ng/g wet wt) were comparable to those measured in herring gull (Larus argentatus) eggs from the Great Lakes. Toxaphene was detected in great blue heron eggs at levels comparable to those of other major chlorinated pesticides. Major toxaphene congeners were octachlorobornane P44 and the nonachlorobornane P50. Environ. Toxicol. Chem. 2010;29:243,249. © 2009 SETAC [source]

    Oxidative transformation of tetrachlorophenols and trichlorophenols by manganese dioxide

    Ling Zhao
    Abstract This study examined the transformation kinetics of three tetrachlorophenols (TeCPs) and three trichlorophenols (TCPs) in the presence of MnO2 under different solution chemistry conditions. The reaction rate measured for each CP decreased as a function of solution pH, and under the same solution chemistry conditions, the measured rates may depend primarily on both the adsorbability at the MnO2 surfaces and the isomeric structures of the CPs. Isomeric effects indicated that chloro substituent on ortho or para positions exhibited faster rates of transformation than on meta positions. Gas chromatography-mass spectrometry analysis with a derivatization method showed that dimers including polychlorinated phenoxyphenols and chlorinated polyhydroxybi-phenyl were among the major products for all CPs. Monomeric products were among the major products of 2,4,6-TCP, 2,3,4-TCP, and 2,3,4,6-TeCP, whereas trimeric products also were among the major products of 2,3,4-TCP and 2,4,5-TCP. It appeared that hydroxylation of CPs and formation of dimeric or trimeric products via oxidative coupling were the major reaction mechanisms involved in the oxidation of CPs by MnO2. [source]

    Bioaccumulation and trophic transfer of polychlorinated biphenyls by aquatic and terrestrial insects to tree swallows (Tachycineta bicolor)

    Jonathan D. Maul
    Abstract Insectivorous passerines often bioaccumulate polychlorinated biphenyls (PCBs) via trophic transfer processes. Tree swallows (Tachycineta bicolor) frequently are used for estimating PCB bioaccumulation, yet the focus on specific trophic links between contaminated sediment and bird has been limited. Bioaccumulation of PCBs from sediment to tree swallows was examined with focus on trophic pathways by simultaneously examining PCBs in emergent aquatic and terrestrial insects and gut contents of nestlings. Total PCB concentrations increased from sediment (123.65 ± 15.93 ,g/kg) to tree swallow nestlings (2,827.76 ± 505.67 ,g/kg), with emergent aquatic insects, terrestrial insects, and gut content samples having intermediate concentrations. Biota-sediment accumulation factors (BSAFs) varied among congeners for tree swallow nestlings and for male and female Chironomus spp. For nestlings, the highest BSAF was for the mono- ortho -substituted congener 118. Nestling biomagnification values were similar for gut contents and female Chironomus spp., suggesting this diet item may be the main contributor to the overall PCB transfer to nestlings. However, gut content samples were highly variable and, on a PCB congener pattern basis, may have been influenced by other taxa, such as terrestrial insects. Considering dietary plasticity of many insectivorous birds, the present study suggests that a variety of potential food items should be considered when examining PCB accumulation in insectivorous passerines. [source]

    Induction of cytochrome P4501A in African brown house snake (Lamprophis fuliginosus) primary hepatocytes

    Markus Hecker
    Abstract Ahough there have been numerous sudies involving fish, birds, and mammals, little is known about the response of the cytochrome P4501A system of snakes to halogenated aromatic hydrocarbons (HAHs). The present study describes the induction of ethoxyresorufin- O -deethylase (EROD) in primary hepatocytes of the African brown house snake (Lamprophis fuliginosus). Hepatocytes were exposed in multiwell plates to 2,3,7,8-tetrachlorodibenzo- p -dioxin (TCDD) and four different non- ortho -substi-tuted coplanar polychlorinated biphenyls (PCBs 77, 81, 126, and 169). Exposure to TCDD and PCB 126 resulted in a dose-dependent increase in EROD activity, with maximum inducible EROD activities of 177 ± 56 (mean ± SEM) and 101.1 ± 55 pmol/min/mg protein for TCDD and PCB 126, respectively. None of the other PCBs caused a measurable induction of EROD, which suggests reduced inducibility of snake hepatocytes compared to some vertebrate taxa. Median effective concentrations (EC50s) were 0.16 ± 0.03 nM for TCDD and 8.25 ± 4.14 nM for PCB 126. The relative potency (REP20,80) range for PCB 126 was 0.044 to 0.046. Compared to results from in vitro systems using other vertebrate species, both the maximum inducibility and the REPs estimated for L. fuliginosus were within the same range as those reported for mammals and the more sensitive bird species but were greater than the values reported for most fish species. In conclusion, induction of EROD activity in primary hepatocytes appears to be a useful approach for evaluating the dioxin-like potencies of aryl hydrocarbon,receptor agonists in snakes. The test system offers a method for rapid screening of reptilian responsiveness to these compounds using smaller numbers of organisms than with in vivo studies, an important consideration for many declining reptile species. [source]

    New organochlorine contaminants and metabolites in plasma and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian Arctic

    Jonathan Verreault
    Abstract The present study investigated new or lesser-studied and legacy organochlorine (OC) contaminants and metabolites in plasma and eggs of glaucous gulls (Larus hyperboreus) collected from major breeding colonies on Bear Island in the Norwegian Arctic. Hexachlorobutadiene was below the method limit of detection (<0.07 ng/g lipid wt) in all samples. The sum (sum) of 20 chlorobornane congener concentrations ranged between 294 and 986 ng/g lipid weight and 104 and 1,121 ng/g lipid weight in plasma and eggs, respectively, whereas those of ,20polychlorinated naphthalene ranged between 1.34 and 126 ng/g lipid weight in plasma and 1.82 and 162 ng/g lipid weight in eggs. Bis(4-chlorophenyl) sulfone concentrations ranged between 5.24 and 143 ng/g lipid weight plasma, which is the first report of this contaminant in arctic biota north of Sweden. Based on 2,3,7,8-tetrachlorodibenzo- p -dioxin toxic equivalents (TEQs), partial dioxin-like toxicity varied between 3.04 and 20.8 ng TEQ/g lipid weight in plasma and 0.94 and 46.5 ng TEQ/g lipid weight in eggs, and largely was due to concentrations of non- ortho polychlorinated biphenyls (PCBs), with a very minor contribution from mono- ortho PCBs and polychlorinated naphthalenes. The major aryl sulfone metabolite in plasma was an unidentified hexachlorinated MeSO2 -PCB congener (range: 13.5,551 ng/g lipid wt), whereas the pentachlorinated congeners 3,- and 4,-MeSO2 -CB101 (range: 4.49,38.1 ng/g lipid wt) dominated in eggs. The predominant halogenated phenolic compound (HPC) in plasma was consistently the PCB metabolite 4-OH-CB187 (range: 0.29,17.5 ng/g wet wt), whereas in eggs, detectable HPCs were at very low and transient concentrations. As part of a complex profile of contaminant exposure, these chemical classes and metabolites may be contributing factors to enhance physiological stress in breeding glaucous gulls. [source]

    Hepatic microsomal cytochrome P450 enzyme activity in relation to in vitro metabolism/inhibition of polychlorinated biphenyls and testosterone in Baltic grey seal (Halichoerus grypus)

    Hongxia Li
    Abstract Among other factors, cytochrome P450 (CYP) enzyme activity determines polychlorinated biphenyl (PCB) bioaccu-mulation, biotransformation, and toxicity in exposed species. We measured the oxidative metabolism in vitro of 12 PCB congeners, representing structural groups based on the number and position of the chlorine atoms, by the hepatic microsomes of one Baltic grey seal (Halichoerus grypus). Microsomal metabolism was observed for several PCBs with vicinal H atoms exclusively in the ortho and meta positions and without any ortho -Cl substituents (CB-15 [4,4,-Cl2] and CB-77 [3,3,,4,4,-Cl4]), vicinal meta and para -H atoms (CB-52 [2,2,,5,5,-Cl4], and ,101 [2,2,,4,5,5,-Cl5]) or with both characteristics in combination with either only one ortho -Cl (CB-26 [2,3,,5-Cl3], CB-31 [2,4,,5-Cl3]) or two ortho -Cl substituents (CB-44 [2,2,,3,5,-Cl4]). To allocate PCB biotransformation to specific CYPs, the inhibitive effect of compounds with known CYP-specific inhibition properties was assessed on in vitro PCB metabolism and on regio- and stereospecific testosterone hydroxylase activities. Metabolic inhibition was considered relevant at concentrations ,1.0 ,M because these inhibitors became decreasingly selective at higher concentrations. At <1.0 ,M, ellipticine (CYP1A1/2 inhibitor) selectively inhibited CB-15, ,26, ,31, and ,77 metabolism, with no significant inhibition of CB-44, ,52, and ,101 metabolism. Inhibition of CB-52 and ,101 metabolism by chloramphenicol (CYP2B inhibitor) started at 1.0 ,M and maximized at about 100% at 10 ,M. Ketoconazole (CYP3A inhibitor) appeared to selectively inhibit CB-26, ,31, and ,44 metabolism relative to CB-15, ,77, and ,52 at concentrations ,1.0 ,M. Major testosterone metabolites formed in vitro were 2,-(CYP3A), 6,- (CYP3A, CYP1A), and 16,- (CYP2B) hydroxytestosterone and androstenedione (CYP2B, CYP2C11). The CYP forms indicated are associated with the specific metabolism of testosterone in laboratory animals. Inhibition of 2,- and 6,-hydroxytestosterone formation at ellipticine and ketoconazole concentrations ,1.0,M suggested that both inhibitors were good substrates of CYP3A-like enzymes in grey seal. Chloramphenicol (model for CYP2B) is apparently not a good inhibitor of CYP1A and CYP3A activities in grey seal because the chemical did not inhibit any metabolic route of testosterone at concentrations from 0.1 to 10 ,M. Our findings demonstrated that at least CYP1A- and CYP3A-like enzymes in the liver of grey seals are capable of metabolizing PCBs with ortho - meta and/or meta - para vicinal hydrogens. A CYP2B form might also be involved, but this could not be proven by the results of our experiments. Defining the profiles of CYP enzymes that are responsible for PCB biotransformation is necessary to fully understand the bioaccumulation, toxicokinetics, and risk of PCB exposure in seals and other free-ranging marine mammals. [source]

    Application of sewage sludge to arable land,soil concentrations of polybrominated diphenyl ethers and polychorinated dibenzo- p -dioxins, dibenzofurans, and biphenyls, and their accumulation in earthworms

    Nadja Matscheko
    Abstract Soils from five agricultural sites, three research sites, and two privately owned farms were analyzed for polychlorinated dibenzo- p -dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and polybronimated diphenylethers (PBDEs). In soils that had not been treated with sludge (reference soils), the international toxic equivalents (I-TEQs) were 0.6 to 1.5 pg/g dry matter (DM) for the PCDD/Fs, which are low compared to generally reported background soil levels in Europe. The concentrations of sum of six penta- and hexa-PCBs were 450 to 1,400 pg/g DM. The PBDEs 47 and 99 dominated among the tri- to hepta-PBDEs analyzed (8,80 pg/g DM). The impact of adding 1 to 3 tonnes of sludge (DM) per hectare per year on the concentrations was studied at the three research sites by calculating ratios of the compounds in sludge-treated soil to reference soil (S/R ratio). The concentrations of I-TEQs did not increase in the sludge-treated soil, whereas the S/R ratios for PBDEs were greater than one. Also, although the PCB contents were higher in the sludge-treated soils, the background sources were more important for the concentrations of PCBs than of PBDEs. The largest increase in the S/R ratios was found at a private farm where large amounts of sludge had been used in the past. Accumulation of the compounds in earthworms from the sites also was investigated. The biota-soil accumulation factors (BSAFs) of the tested compounds declined in the following order: ortho -PCBs , PBDEs > non-ortho -PCBs > 2,3,7,8-substituted PCDD/Fs. The average BSAF for ortho -PCBs was five (organic matter/lipids), and the lowest BSAFs (0.1,0.8) found were for octachlorodibenzo- p -dioxin. To our knowledge, accumulation of PBDEs in earthworms has not been published previously. [source]

    Biological activity associated with noncoplanar polychlorinated biphenyls after microbial dechlorination of aroclor 1242® and aroclor 1254®

    Patricia E. Ganey
    Abstract Bioremediation of polychlorinated biphenyls (PCBs) byanaerobic microbial dechlorination occurring naturally in the subsurface and in engineered systems results in mixtures of lower-chlorinated, primarily ortho-substituted biphenyls. The purpose of this study was to determine whether this process of bacterial dechlorination results in a mixture that differs in biological activity from that of the parent PCB mixture. Two biological assays sensitive to the action of ortho-substituted PCBs were employed: insulin release by RINm5F cells, and superoxide anion (O2) production by rat neutrophils. The PCB mixtures Aroclor 1242® and Aroclor 1254® were incubated for nine months with microbes from PCB-contaminated sites (Silver Lake, MA, USA, or River Raisin, MI, USA), and the products of dechlorination were then extracted. Exposure of RINm5F cells to dechlorinated Aroclor 1242 or 1254 product mixtures caused an increase in insulin release similar to the hormone release from cells exposed to non-dechlorinated Aroclors. When tested alone, several of the major products identified in the dechlorination mixture (i.e., 2,2,,4,4,-tetrachlorobiphenyl, 2,2,,4-trichlorobiphenyl [TCB], 2,3,,4-TCB, 2,3,,5-TCB, and 2,2,-dichlorobiphenyl) caused an increase in insulin release. In studies using neutrophils isolated from rat peritoneum, the amount of O2 produced on exposure to product mixtures resulting from dechlorination of Aroclor 1242 was not different from the amount produced in nondechlorinated controls. The product mixture resulting from Aroclor 1254 dechlorination by organisms from River Raisin increased generation of O2, relative to the parent Aroclor. Taken together, these results suggest that anaerobic dechlorination of Aroclor mixtures of PCBs does not reduce the biological activities associated with lightly chlorinated and ortho -substituted PCBs. This observation has implications for the usefulness of PCB bioremediation efforts that involve only anaerobic dechlorination. [source]

    Synthesis and Electrochemical Study of an Original Copper(II)-Capped Salen,Cyclodextrin Complex

    Elise Deunf
    Abstract A new metallocapped cyclodextrin (CD) was synthesized by the regioselective debenzylation, induced by diisobutylaluminium hydride (DIBAL-H), of perbenzylated cyclodextrins. This reaction allowed for the efficient preparation of an unprecedented CD,salen type copper(II) complex. The electrochemical behavior of both the bound and unbound CD,salen compounds was investigated by cyclic voltammetry. Notably, it was shown that the presence of tert -butyl groups at the ortho - and para -positions of the salen aromatic rings stabilized the copper(II) phenoxyl radical species that was generated upon the one-electron oxidation of the starting compound. Importantly, this stabilization remained effective when the salen-type ligand was covalently attached to the CD. This allowed for investigations of the reactivity of the copper(II) phenoxyl radical complex towards a primary alcohol to be performed by cyclic voltammetry. This reaction can be considered as mimicking the behavior of galactose oxidase. However, under these conditions, no reactivity was observed in the presence of benzyl alcohol. This may be due to distortion, either of the initially square planar salen ligand after its grafting to the CD primary face, and/or of the CD itself. On the other hand, the electrochemical reduction of the un-grafted copper(II) salen-type ligand led to a transient anionic species that exhibited significant stability on the time-scale of the slow cyclic voltammetry measurement in the absence of the CD, but was unstable in the presence of the CD. In the latter case, it was demonstrated that the anionic species was protonated by the CD. Importantly, this protonation was not fast enough to prevent catalytic activation of iodomethane by the electro-generated copper(I)-capped salen CD complex. [source]

    Novel Enantioselective Synthesis of Functionalized Pyridylarsanes by a Chiral Palladium Template Promoted Asymmetric Hydroarsanation Reaction

    Fengli Liu
    Abstract The asymmetric hydroarsanation reactions between diphenylarsane and (E)-1-phenyl-3-(pyridin-2-yl)-2-propenone and (E)-1-methyl-3-(pyridin-2-yl)-2-propenoate have been achieved by use of the organopalladium complex containing ortho -metalated (R)-[1-(dimethylamino)ethyl]naphthalene as the chiral reaction template in high regio- and stereoselectivities under mild conditions. Hydroarsanation of (E)-1-phenyl-3-(pyridin-2-yl)-2-propenone with diphenylarsane generated two stereoisomeric products in the ratio of 3:1 as five-membered As,N bidentate chelates on the chiral naphthylamine palladium template. Using the same chiral metal template, the corresponding hydroarsanation reaction with (E)-1-methyl-3-(pyridin-2-yl)-2-propenoate gave only one product as a six-membered As,N bidentate chelate. The naphthylamine auxiliary could be removed chemoselectively by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes. Subsequent ligands displacement from the palladium using aqueous potassium cyanide generated the optically pure keto- and ester-functionalized chiral pyridylarsane ligands. The absolute configuration and the coordination properties of the pyridylarsanes have been established by single-crystal X-ray analysis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

    Syntheses, Characterization, and Luminescent Properties of Monoethylzinc Complexes with Anilido,Imine Ligands

    Qing Su
    Abstract The syntheses of three anilido,imine ligands of the general formula ortho -C6H4(NHAr,)(CH=NAr, [Ar, = 7-(2,4-Me2)C9H4N, Ar, = 2,6-Me2C6H3 (2a); Ar, = 7-(2,4-Me2)C9H4N, Ar,= 2,6-Et2C6H3 (2b); Ar, = 7-(2,4-Me2)C9H4N, Ar,= 2,6- iPr2C6H3 (2c)] and four zinc(II) complexes of the general formula [ortho -C6H4(NHAr,)(CH=NAr,)]ZnEt [Ar, = 7-(2,4-Me2)C9H4N, Ar,= 2,6-Me2C6H3 (3a); Ar, = 7-(2,4-Me2)C9H4N, Ar,= 2,6-Et2C6H3 (3b); Ar, = 7-(2,4-Me2)C9H4N, Ar, = 2,6- iPr2C6H3 (3c); Ar, = 2,6-Me2C6H3, Ar, = 2,6- iPr2C6H3 (3d)] are described. The complexes were synthesized from the reaction of ZnEt2 with corresponding ligands 2 by alkane elimination. All compounds were characterized by elemental analysis and 1H and 13C NMR spectroscopy. The molecular structures of compounds 2a, 2b, 3b, and 3c were determined by single-crystal X-ray crystallography. The X-ray analysis reveals that complexes 3b and 3c exist in the dimeric form with the N atom in the quinolyl ring coordinating to the other Zn atom to make the Zn atoms four coordinate. Luminescent properties of ligands 2a,2d and complexes 3a,3d in both solution and the solid state were studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

    Diastereopure Cationic NCN-Pincer Palladium Complexes with Square Planar ,4 - N,C,N,O Coordination

    Silvia Gosiewska
    Abstract Neutral NCN-pincer palladium bromide complex 2 containing the monoanionic, enantiopure pincer ligand 2,6-bis{[(S)-2-hydroxymethyl-1-pyrrolidinyl]methyl}phenyl bromide (1) with bis- ortho -(S)-prolinol substituents was synthesized and isolated as a mixture of three stereoisomers [(SN,SN,SC,SC), (RN,SN,SC,SC), and (RN,RN,SC,SC)] in a 1:1:1 ratio. Upon abstraction of the bromide ion from the unresolved mixture of 2, single diastereoisomers of the cationic complexes [3]BF4 and [3]PF6, respectively, were formed with a unique,4 - N,C,N,O coordination mode of ligand 1. X-ray crystal structure determination established the intramolecular,4 - N,C,N,O coordination of 1 to palladium where the typical mer -,3 - N,C,N pincer coordination is accompanied by coordination of one of the hydroxy groups of the (S)-prolinol moieties. The water molecule that was cocrystallized in the crystal structure of [3]PF6 does not coordinate to palladium, but instead is involved in a hydrogen bonding network. The catalytic potential of both cationic complexes, [3]BF4 and [3]PF6, was tested in an aldol reaction of aldehydes with methyl isocyanoacetate to yield the oxazoline products as racemic mixtures.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

    A Crystalline Phase Transition and Optical Properties in a CoIICuII Oxamato-Bridged Ferrimagnetic Chain

    Cynthia L. M. Pereira
    Abstract The compound [CoCu(opba)(DMSO)3] (1) [opba = ortho -phenylenebis(oxamato)] has been synthesized and characterized. Its crystal structure has been analyzed by X-ray diffraction techniques at 100 and 298 K. A structural phase-transition has been detected at around 150 K. An orthorhombic crystalline system is found at both temperatures, with very similar unit-cell dimensions. At room temperature 1 crystallizes in the Pnam space group (, -1 phase), with a = 7.6712(2), b = 14.8003(3), c = 21.0028(5) Å, and Z = 4, whereas at low temperature it crystallizes in the Pna21 space group (, -1 phase), with a = 7.3530(2), b = 14.5928(4), c = 21.0510(7) Å, and Z = 4. Both crystalline phases consist of linearly ordered bimetallic chains with the [Cu(opba)]2, units tied by CoII ions to form a one-dimensional system. The DMSO molecules in , -1, which are coordinated to either CuII or CoII, are disordered. At low temperature, a small reorganization of the CuII and CoII environments is observed. The origin of this phase transition, which is completely reversible, is the modification of the crystalline packing with the temperature. Linear birefringence measurements were done on single crystals in the 100,300 K temperature range. Around 150 K, the linear birefringence curve shows an inflexion that is interpreted as being related to the conversion of ,-1 into , -1. Both dc and ac magnetic measurements were performed on the polycrystalline sample. The results reveal a one-dimensional ferrimagnetic behavior. Single crystal optical characterization at room temperature shows that 1 presents a very strong dichroism superposed on the linear birefringence. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

    Regiospecific Cyclometalation of Diphenyl(2-substituted phenyl)phosphane with Methyltetrakis(trimethylphosphane)cobalt(I)

    Hans-Friedrich Klein
    Abstract The pre-chelate molecules 2-(diphenylphosphanyl)- N,N -dimethylaniline, [2-(diphenylphosphanyl)benzyl]dimethylamine, 1-(diphenylphosphanyl)-2-ethylbenzene, 1-(diphenylphosphanyl)-2-isopropylbenzene, and 2-(diphenylphosphanyl)benzonitrile, in a reaction with [CoMe(PMe3)4], eliminate methane to afford the selectively 6- ortho -metalated complexes 1,5 that contain four-membered metallacycles. The molecular structure of 3 shows a tbp-coordinated cobalt atom, with axial C and PMe3 donor groups. Metalation in the aliphatic side-chain occurs with 2-(diphenylphosphanyl)toluene, giving complex 6 that contains a five-membered metallacycle. Benzyldiphenylphosphane is selectively ortho -metalated in the benzyl group, affording 7. As shown by the molecular structures, complex 7 is a true ligand isomer of 6. Substitution of a trimethylphosphane group in compounds 4 and 6 by ethene gives the pentacoordinate complexes 8 and 9, respectively. The ethene ligand is ,-coordinated in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, complex 6 forms monocarbonyl complex 10. Carbonylation of complexes 3 and 4 proceeds by insertion of CO into the Co,C bond under ring expansion, affording the aroylcobalt complexes 11 and 12, respectively. Complex 6 reacts with iodomethane in an oxidative substitution reaction yielding a structurally characterized octahedral complex mer - 13, which eliminates a methyl group in THF at 20 °C to form a pentacoordinate cobalt(II) complex 14. Complex 3 oxidatively adds iodomethane in a stereoselective cis addition to give the cobalt(III) complex mer - 15, which retains its four-membered metallacycle and the CoCH3 group. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

    Investigations on 1-Metallaindanes

    Marcel Schreuder Goedheijt
    Abstract 1-Mercuraindane (6) was prepared in three steps from 1-bromo-2-(2-bromoethyl)benzene (3) and converted into 1-magnesaindane (1) by reaction with magnesium. In solution, 6 was observed to occur in a remarkable dimer/trimer equilibrium, whereas 1 forms a dimer. From 1 and dichlorozirconocene, the 1-zirconaindane 2 was obtained, which reacted with B(C6F5)3 to form the adduct 13. According to spectroscopic data, 13 is formed by attack of the ,-methylene carbon atom at the boron atom and has a zwitterionic structure with weak interactions between the zirconium ion and one of the ortho -fluorine atoms. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

    Benzene-di- N -substituted carbamates as conformationally constrained analogs of Pseudomonas lipase substrates

    Ming-Cheng Lin
    Abstract Benzene-1,2-, -1,3-, and -1,4-di- N -substituted carbamates (1,15) are synthesized as the constrained analogs of gauche, eclipsed, and anti conformations of diesters of ethylene glycol, respectively. Carbamates 1,15 are characterized as the pseudo-substrate inhibitors of Pseudomonas species lipase. Long-chain carbamates are more potent inhibitors than short-chain ones. Different geometries of benzene-di-substituted carbamates, such as benzene-1,2-di- N -octylcarbamate (3) (ortho compound), benzene-1,3-di- N -octylcarbamate (8) (meta compound), and benzene-1,4-di- N -octylcarbamate (13) (para compound), show similar inhibitory potencies for the enzyme. In other words, kinetic data suggest that the enzyme does not discriminate ortho, meta, and para geometries of these constrained analogs. [source]

    Inhibition of lipid peroxidation by anthocyanins, anthocyanidins and their phenolic degradation products

    Jonathan E. Brown
    Abstract Food components that delay or prevent biomolecule oxidation may be relevant in shelf life extension as well as disease prevention. Anthocyanins are a potentially important group of compounds, but they are prone to degradation both in vitro and in vivo, producing simple phenols. In this study, eight structurally related (poly)phenols [anthocyan(id)ins and phenolic acids] were examined for their ability to inhibit lipid oxidation at physiologically relevant concentrations (100,1000,nM) using the Cu2+ -mediated low-density lipoprotein oxidation model. Interaction between each (poly)phenol and Cu2+ ions was also investigated. (Poly)phenols with an ortho -dihydroxy group arrangement, i.e. cyanidin-3-glucoside, cyanidin and protocatechuic acid, were the most effective within their class, extending the lag phase to oxidation by 137, 255 and 402%, respectively (at 1000,nM). At the same concentration, trihydroxy-substituted compounds (delphinidin and gallic acid) were of intermediate efficacy, extending the lag phase by 175 and 38%, respectively. Compounds with the 4'-hydroxy-3',5'-methoxy arrangement (i.e. malvidin-3-glucoside and malvidin) were the least effective (3 and 58% extension, respectively), while syringic acid (4-hydroxy-3,5-dihydroxy benzoic acid) was pro-oxidant (lag phase shortened by 31%). (Poly)phenols with the ortho -dihydroxy arrangement chelated Cu2+ ions, which in part explains their greater efficacy over the other (poly)phenols in this model oxidation system. However, differences in their hydrogen-donating properties and their partitioning between lipid and hydrophilic phases are also relevant in explaining these structure-activity relationships. [source]