Abstract  The aim of this paper is to develop a new simple, fast and economical method for simultaneous quantitative determination of methylxanthine compounds based on TLC combined with image analysis. To obtain certain results, both extraction and chromatographic separation were optimized. The optimum extraction conditions were maceration in ethanol-water 8:2, v/v. The chromatographic separations were done on the silica gel F(254) TLC plates developed with chloroform-dichloromethane-isopropanol, 4:2:1 v/v/v. Detection was performed under UV lamp at 254 nm and the evaluation of the chromatographic plate was based on digital processing of chromatographic images. The developed TLC method was validated for parameters such as specificity, linearity and range, LOD and LOQ, precision, robustness and accuracy. This method was then applied for determination of caffeine, theobromine and theophylline in different types of tea, commercially available. Moreover, the content of methylxanthines detected and determined in commercial tea samples can be used as chemical marker in quality control.

Abstract  Mononuclear ruthenium(III) complexes of the type [RuX(EPh(3))(2)(L)] (E=P or As; X=Cl or Br; L=dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX(3)(EPh(3))(3)] (where E=P, X=Cl; E=As, X=Cl or Br) and [RuBr(3)(PPh(3))(2)(CH(3)OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh(3))(2)(DHA-PTSC)] (5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

Abstract  Acute severe methemoglobinaemia is an uncommon but life-threatening condition caused by a variety of oxidizing agents commonly used in both health care and industrial settings. Thus, recognition is important as it is readily treatable. The oxygen transport is compromised as a result of abnormal levels of oxidized haemoglobin, and this leads to skin discolouration and a variety of symptoms. Diagnostic confusion occurs as the oxygen saturations (SpO2) on the pulse oximeter are unreliable (Sharma V, Haber A. Acquired methaemoglobinaemia: a case report of benzocaine-induced methaemoglobinaemia and a review of the literature. Clin Pul Med. 2002;9(1):53-8). A case of severe methaemoglobinaemia due to self poisoning with barbicide is presented with a brief discussion of the patho-physiology and an overview of the treatment. A barbicidal overdose has never been reported before.

Abstract  The current study evaluated the Control of Substances Hazardous to Health (COSHH) Essentials model for short-term task-based exposures and full-shift exposures using measured concentrations of three volatile organic chemicals at a small printing plant. A total of 188 exposure measurements of isopropanol and 187 measurements of acetone were collected and each measurement took approximately 60 min. Historically, collected time-weighted average concentrations (seven results) were evaluated for methylene chloride. The COSHH Essentials model recommended general ventilation control for both isopropanol and acetone. There was good agreement between the task-based exposure measurements and the COSHH Essentials predicted exposure range (PER) for cleaning and print preparation with isopropanol and for cleaning with acetone. For the other tasks and for full-shift exposures, agreement between the exposure measurements and the PER was either moderate or poor. However, for both isopropanol and acetone, our findings suggested that the COSHH Essentials model worked reasonably well because the probabilities of short-term exposure measurements exceeding short-term occupational exposure limits (OELs) or full-shift exposures exceeding the corresponding full-shift OELs were <0.05 under the recommended control strategy. For methylene chloride, the COSHH Essentials recommended containment control but a follow-up study was not able to be performed because it had already been replaced with a less hazardous substance (acetone). This was considered a more acceptable alternative to increasing the level of control.

Abstract  Investigation of the freeze-dried dichloromethane: isopropanol extract of the sponge Axinella carteri Dendy, 1889 (Demospongiae: Halichondrida: Axinellidae), collected from Derawan Island, Indonesia, has led to the isolation of a new A-nor sterol with rare D-ring unsaturation, 3beta-(hydroxymethyl)-A-nor-5alpha-cholest-14-en-16-one (1). While the efficacy of the new compound is unknown, moderate cytotoxicity was observed in the fraction from which it was purified. A more polar portion of the extract afforded the known alkaloid dibromoisophakellin (2), previously isolated from an Axinella sp. The purification of the compounds was achieved on silica gel and Sephadex LH-20 supports and the identity of the compounds was established with the aid of 1D and 2D NMR spectroscopic experiments.

Abstract  A highly sensitive liquid chromatography-tandem mass spectrometric (LC-MS/MS) method has been developed to determine rasagiline in human plasma. The analytical method utilized liquid-liquid extraction of plasma with n-hexane-dichloromethane-isopropanol (20:10:1, v/v/v). Separation of analyte and the internal standard (IS) pseudoephedrine was performed on a Zorbax Extend C(18) column (150 mm x 4.6 mm, 5 microm) with a mobile phase consisting of acetonitrile-5 mM ammonium acetate-acetic acid (40:60:0.05, v/v/v) at a flow rate of 0.5 mL/min. The API 4000 triple quadrupole mass spectrometer was operated in multiple reaction monitoring mode via positive electrospray ionization interface using the transitions m/z 172.1-->m/z (117.1+115.1) for rasagiline, and m/z 166.0-->m/z 148.1 for the internal standard. The method was linear over the concentration range of 0.020-50.0 ng/mL. The intra- and inter-day precisions were less than 11.2% in terms of relative standard deviation (R.S.D.), and the accuracy was within +/-6.4% in terms of relative error (RE). The lower limit of quantification (LLOQ) was identifiable and reproducible at 0.020 ng/mL with acceptable precision and accuracy. The mean extraction-efficiency at three concentrations was 95.6+/-7.0%, 97.9+/-3.0% and 95.3+/-8.3%. The validated method offered increased sensitivity (10 times higher than those reported) and wide linear concentration range. This method was successfully applied for the evaluation of pharmacokinetics of rasagiline after single oral doses of 1, 2 and 5mg rasagiline to 12 Chinese healthy volunteers.

Abstract  Acyclovir, a selective antiherpes virus agent, was loaded in the hollow microspheres to improve bioavailability and patient compliance by prolonging the residence time in the gastrointestinal tract. The hollow microspheres of acyclovir were prepared by solvent evaporation diffusion method using Eudragit S 100 as a controlled polymer. We found that the process conditions that provided the high % yield of the hollow microspheres were the use of 5:8:2 of dichloromethane: ethanol: isopropanol as a solvent system and stirring at 300 rpm for 60 min. The size of the microspheres prepared from different ratios of acyclovir and Eudragit S 100 was 159-218 microm. When the drug-to-polymer ratio was increased, the size and percent drug content increased. The highest percent drug entrapment was obtained at the ratio of 600 mg acyclovir: 1 g Eudragit S 100. The hollow microspheres tended to float over 0.1 M hydrochloric acid containing 0.02% Tween 20 solution for 24 hr. The rate of acyclovir released from the microspheres was generally low in simulated gastric fluid without enzyme due to the low permeability of the polymer. However, in phosphate buffer pH 6.8, the drug release increased as the drug load increased due to the swelling property of the polymer. In simulated intestinal fluids without enzymes, the polymer completely dissolved resulting in instant release of the drug in this medium.

Abstract  The objective of this study was to evaluate the chemical composition CH3OH-CH2Cl2 (1:1) extract and biological activities of various extracts derived from the aerial parts of the brown marine alga Stoechospermum marginatum (C. Agardh). Gas chromatography (GC) and gas chromatography-mass spectroscopy (GC-MS) were used to analyze the composition of the essential oil. Total phenolics assay demonstrated a high value in hexane extract (HE), with a lower value for chloroform extract (CE), and the lowest value for methanol extract (ME). DPPH (2,2-diphenyl-1-picrylhydrazyl) assay showed that extracts of S. marginatum possess radical scavenging activity (RSA). Tests of the antioxidant property of the extracts revealed both electron and hydrogen transfer mechanisms. The antibacterial activity of the ME, CE, and HE as well as an ethanol extract was estimated against seven Gram-positive and Gram-negative bacteria. The ethanol extract showed the highest antibacterial activity, and the HE showed the lowest.

Abstract  The incomplete inhibition of platelet function by acetylsalicylic acid (ASA), despite the patients are receiving therapeutic doses of the drug ('aspirin-resistance'), is caused by numbers of risk factors. In this study we verified the idea that plasma homocysteine (Hcy) contributes to 'aspirin-resistance' in patients with coronary artery disease (CAD) and with or without type 2 diabetes mellitus (T2DM). A cross-designed randomized controlled intervention study has been performed (126 CAD pts incl. 26 with T2DM) to determine whether increasing ASA dose from 75mg to 150mg daily may result in the increased antiplatelet effect, in the course of four-week treatment. Platelet response to collagen (coll) or arachidonic acid (AA) was monitored with whole blood aggregometry, plasma thromboxane (Tx), and Hcy levels were determined immunochemically. The ASA-mediated reductions in platelet response to coll (by 12±3%) or AA (by 10±3%) and in plasma Tx (by 20±9%; p<0.02 or less) were significantly greater for higher ASA dose and significantly correlated with plasma Hcy, which was significantly lower in "good" ASA responders compared to "poor" responders (p<0.001). Higher plasma Hcy appeared a significant risk factor for blood platelet refractoriness to low ASA dose (OR=1.11; ±95%CI: 1.02-1.20, p<0.02, adjusted to age, sex and CAD risk factors). Hcy diminished in vitro antiplatelet effect of low ASA concentration and augmented platelet aggregation (by up to 62% (p<0.005) for coll and up to 15% (p<0.005) for AA), whereas its acetyl derivative acted oppositely. Otherwise, Hcy intensified antiplatelet action of high ASA. Hyperhomocysteinaemia may be a novel risk factor for the suppressed blood platelet response to ASA, and homocysteine may act as a specific sensitizer of blood platelets to some agonists. While homocysteine per se acts as a proaggregatory agent to blood platelets, its acetylated form is able to reverse this effect. Thus, these findings reveal a possibly new challenging potential of the acetylating properties of ASA therapy.

Abstract  Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand-binding energies of [Ag(L)(n)](+) (L=SO(2), CH(2)Cl(2); n=1, 2) and solid-state enthalpies obtained from Born-Fajans-Haber cycles by using the volume-based thermodynamics (VBT) approach. Bonding analysis (VB, NBO, MO) of [Ag(L)(n)](+) suggests that these complexes are almost completely stabilized by electrostatic interaction, that is, monopole-dipole interaction, with almost no covalent contribution by electron donation from the ligand orbitals into the vacant 5s orbital of Ag(+). All experimental findings and theoretical considerations demonstrate that SO(2) is less covalently bound to Ag(+) than CH(2)Cl(2) and support the thesis that SO(2) is a polar but non-coordinating solvent towards Ag(+).

Abstract  Chloroform (CF, CHCl(3)) is a recalcitrant and toxic environmental pollutant. In this communication we report for the first time a microbial community capable of complete CF dechlorination by metabolic processes. Cultures derived from subsurface soil (3.5 m) could sustain complete dechlorination of CF at levels of least 360 µM at a rate of 40 µM per day. Scrutiny of CF dechlorination revealed two metabolic processes at work. First, CF was respired to dichloromethane (DCM, CH(2) Cl(2)), which was then fermented to acetate, hydrogen and carbon dioxide. Elevated hydrogen partial pressures were found to inhibit the fermentation process. Interspecies hydrogen transfer was observed in the form of methanogenesis and acetogenesis. This suggests that the dechlorination process required syntrophic partners to maintain low hydrogen partial pressures. (13)C-labelled DCM was employed to help elucidate the chemistry of the process and identify bacterial community members involved. CF respiring cultures, where emulsified vegetable oil was supplied as the electron donor and DCM fermenting cultures, where DCM was supplied as the sole organic carbon source were studied separately. Pyrosequencing of these cultures revealed Dehalobacter lineages as a predominant community member in both. Subsequent growth experiments confirmed that the proliferation of Dehalobacter was linked directly to both the dehalorespiration and dehalofermentation processes.

Abstract  The objective of this study was to predict the inhalation toxicokinetics of chemicals in mixtures using an integrated QSAR-PBPK modelling approach. The approach involved: (1) the determination of partition coefficients as well as V(max) and K(m) based solely on chemical structure for 53 volatile organic compounds, according to the group contribution approach; and (2) using the QSAR-driven coefficients as input in interaction-based PBPK models in the rat to predict the pharmacokinetics of chemicals in mixtures of up to 10 components (benzene, toluene, m-xylene, o-xylene, p-xylene, ethylbenzene, dichloromethane, trichloroethylene, tetrachloroethylene, and styrene). QSAR-estimated values of V(max) varied compared with experimental results by a factor of three for 43 out of 53 studied volatile organic compounds (VOCs). K(m) values were within a factor of three compared with experimental values for 43 out of 53 VOCs. Cross-validation performed as a ratio of predicted residual sum of squares and sum of squares of the response value indicates a value of 0.108 for V(max) and 0.208 for K(m). The integration of QSARs for partition coefficients, V(max) and K(m), as well as setting the K(m) equal to K(i) (metabolic inhibition constant) within the mixture PBPK model allowed to generate simulations of the inhalation pharmacokinetics of benzene, toluene, m-xylene, o-xylene, p-xylene, ethylbenzene, dichloromethane, trichloroethylene, tetrachloroethylene and styrene in various mixtures. Overall, the present study indicates the potential usefulness of the QSAR-PBPK modelling approach to provide first-cut evaluations of the kinetics of chemicals in mixtures of increasing complexity, on the basis of chemical structure.

Abstract  Toxicity and exposure evaluations remain the two of the key components of human health assessment. While improvement in exposure assessment relies on a better understanding of human behavior patterns, toxicity assessment still relies to a great extent on animal toxicity testing and human epidemiological studies. Recent advances in computer modeling of the dose-response relationship and distribution of xenobiotics in humans to important target tissues have advanced our abilities to assess toxicity. In particular, physiologically based pharmacokinetic (PBPK) models are among the tools than can enhance toxicity assessment accuracy. Many PBPK models are available to the health assessor, but most are so difficult to use that health assessors rarely use them. To encourage their use these models need to have transparent and user-friendly formats. To this end the Agency for Toxic Substances and Disease Registry (ATSDR) is using translational research to increase PBPK model accessibility, understandability, and use in the site-specific health assessment arena. The agency has initiated development of a human PBPK tool-kit for certain high priority pollutants. The tool kit comprises a series of suitable models. The models are recoded in a single computer simulation language and evaluated for use by health assessors. While not necessarily being state-of-the-art code for each chemical, the models will be sufficiently accurate to use for screening purposes. This article presents a generic, seven-compartment PBPK model for six priority volatile organic compounds (VOCs): benzene (BEN), carbon tetrachloride (CCl(4)), dichloromethane (DCM), perchloroethylene (PCE), trichloroethylene (TCE), and vinyl chloride (VC). Limited comparisons of the generic and original model predictions to published kinetic data were conducted. A goodness of fit was determined by calculating the means of the sum of the squared differences (MSSDs) for simulation vs. experimental kinetic data using the generic and original models. Using simplified solvent exposure assumptions for oral ingestion and inhalation, steady-state blood concentrations of each solvent were simulated for exposures equivalent to the ATSDR Minimal Risk Levels (MRLs). The predicted blood levels were then compared to those reported in the National Health and Nutrition Examination Survey (NHANES). With the notable exception of BEN, simulations of combined oral and inhalation MRLs using our generic VOC model yielded blood concentrations well above those reported for the 95th percentile blood concentrations for the U.S. populations, suggesting no health concerns. When the PBPK tool kit is fully developed, risk assessors will have a readily accessible tool for evaluating human exposure to a variety of environmental pollutants.

Abstract  Synthesis and characterization of dithiolene complexes of arsenic and antimony in trivalent state have been reported. A four coordinated structural motif results in a ladder like arrangement in the arsenic complex due to the inter-anionic As-S interaction which is replaced by Sb-π interaction with the counter cation in the solid state structure of the similar antimony complex. Electronic structure calculations on ground state geometries and the time-dependent density functional theoretical calculations were performed in order to characterize the absorption spectra incorporating solvent effects. Notably, both the complexes display intense second order optical non-linearity as has been determined using hyper-Rayleigh scattering technique in dichloromethane solution and the results are corroborated by DFT calculations.

Abstract  The complex cis-[Ru(phpy)(phen)(CH3CN)2](+) (phpy=2-phenylpyridine, phen=1,10-phenanthroline) was investigated as a potential photodynamic therapy (PDT) agent. This complex presents desirable photochemical characteristics including a low energy absorption tail extending into the PDT window (600-850nm) and photoinduced exchange of the CH3CN ligands, generating a species analogous to the chemotherapy drug cisplatin. Furthermore, photochemical reactivity can be controlled through selective irradiation into the Ru-phen singlet metal-to-ligand charge transfer ((1)MLCT) band (λirr=500 nm) of [Ru(phpy)(phen)(CH3CN)2](+) in the presence of excess t-butylammonium chloride (TBACl) resulting in efficient photoinduced production of [Ru(phpy)(phen)(CH3CN)Cl] (Φ=0.25). This lower energy irradiation resulted in greater quantum yield of photosubstitution when compared to direct irradiation into the Ru-phpy (1)MLCT peak (λirr=450 nm; Φ=0.08) in CH2Cl2. It was found that the lower quantum yield observed for irradiation into the Ru→phpy(-)(1)MLCT band results from significant orbital mixing of the phpy(-) ligand with the t2g-type filled set in the metal, giving this state significant ligand-centered character. Lastly, this complex produced a decrease in the mobility of linearized ds-DNA when irradiated with λirr≥420nm, indicative of covalent binding by the transition metal complex similar to that observed for cisplatin. No change in mobility was found for the same samples kept in the dark indicating, unlike cisplatin, DNA binding of cis-[Ru(phpy)(phen)(CH3CN)2](+) only occurs with the activation of light. These observations support the use of cis-[Ru(phpy)(phen)(CH3CN)2](+) as a potential PDT agent by the photoinduced generation of a cisplatin analog.

Abstract  COX-2 (Cyclooxygenase-2) and iNOS ( inducible nitric oxide synthase) are involved in various pathophysiological processes such as inflammation. In a search for inhibitors of COX-2 and iNOS, we found that extracts of Dictyota dichotoma inhibit Nitric oxide ( NO) and PGE(2) generation in LPS-stimulated RAW 264.7 macrophage cells, as well as levels of iNOS and COX-2 mRNA and protein. D. dichotoma were extracted with 80% EtOH. The extract was then partitioned with hexane, CH2Cl2, EtOAc, BuOH, and water, successively. The results indicate that the CH2Cl2 fraction of D. dichotoma extract is an effective inhibitor of LPS-induced NO and PGE(2) production in RAW 264.7 cells. These inhibitory effects of the CH2Cl2 fraction of D. dichotoma were accompanied by decreases in the expression of iNOS and COX-2 proteins and iNOS and COX-2 mRNA in dose-dependent pattern. To test the inhibition effects of D. dichotoma fractions on other cytokines, we also performed RT-PCR on TNF-alpha, IL-1 beta, and IL-6 in LPS-stimulated RAW 264.7 macrophage cells. In these assays, the CH2Cl2 fraction of D. dichotoma also showed decreases in the expression of TNF-alpha, IL-1 beta, and IL-6 mRNA. Based on these results, we suggest that D. dichotoma extracts may be considered possible anti-inflammatory candidates for human health.

Abstract  Inducible nitric oxide synthase (iNOS) and cyclooxygenase (COX)-2 have been used as tools for the screening of anti-inflammatory agents. In a search for inhibitors of COX-2 and iNOS, we found that extracts of Enteromorpha prolifera inhibit the production of nitric oxide (NO) and prostaglandin (PG)E-2 in LPS-stimulated RAW 264.7 macrophage cells. We first extracted E. prolifera with 80% ethanol and the extract was partitioned with hexane, dichloromethane, ethyl acetate, butanol, and water, successively. The results indicate that the hexane and ethyl acetate fractions effective inhibited LPS-induced NO and PGE(2) production in RAW 264.7 cells. To test the inhibition effects of the E. prolifera fractions on other cytokines, we also performed an ELISA assay on tumor necrosis factor (TNF)-alpha, IL-1 beta, and IL-6 in LPS-stimulated RAW 264.7 macrophage cells. The expression of TNF-alpha, IL-1 beta, and IL-6 was also decreased following treatment with the hexane and ethyl acetate fractions. To test the potential application of the E. prolifera extract as a cosmetic material, we also performed MTT assays on keratinocyte HaCaT cells as well as primary skin irritation tests. In these assays, the E. prolifera extracts did not induce any adverse reactions. Based on these results, we suggest that E. prolifera extracts may be considered potential anti- inflammatory candidates for skin health.

Abstract  A series of mononuclear iron(III) complexes of the type [Fe(L)Cl(3)], where L is a systematically modified N(2)O or N(3)O ligand with a methoxyethyl/tetrahydrofuryl ether oxygen donor atom, have been isolated and studied as models for catechol dioxygenases. The X-ray crystal structures of [Fe(L2)Cl(3)] 2, [Fe(L6)Cl(3)] 6, [Fe(L5)(TCC)Cl] 5a, where H(2)TCC = tetrachlorocatechol, [Fe(L6)(TCC)Br] 6a, and the μ-oxo dimer [{Fe(L6)Cl}(2)O](ClO(4))(2) 6b have been successfully determined. In [Fe(L2)Cl(3)] 2 the N(2)O ligand is facially coordinated to iron(III) through the pyridine and secondary amine nitrogen atoms and the tetrahydrofuryl oxygen atom. In [Fe(L6)Cl(3)] 6, [Fe(L5)(TCC)Cl] 5a and [Fe(L6)(TCC)Br] 6a the N(3)O donor ligands L5 and L6 act as a tridentate N3 donor ligand coordinated through two pyridine and one secondary amine nitrogen atoms, whereas the ether oxygen is not coordinated. The spectral and electrochemical properties of the adducts [Fe(L)(DBC)Cl] of 1-8, where H(2)DBC = 3,5-di-tert-butylcatechol, in DMF and their solvated adduct species [Fe(L)(DBC)(Sol)](+), where Sol = DMF/H(2)O, generated in situ in dichloromethane, respectively, have been investigated. The product analysis demonstrates that the adducts [Fe(L)(DBC)Cl] effect cleavage of catechol in the presence of O(2) in DMF to give mainly the intradiol (I) product with a small amount of the extradiol (E) product (E/I, 0.2:1-0.7:1). Interestingly, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 1-4 cleave H(2)DBC to provide mainly the extradiol cleavage products with lower amounts of intradiol products (E/I, 2.3:1-4.3:1) in dichloromethane. In contrast, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 5-8 cleave H(2)DBC to provide both extradiol and intradiol products (E/I, 0.6:1-2.3:1) due to the involvement of the ether oxygen donor of the methoxyethyl/tetrahydrofuryl arm in the coordination to iron(III) upon removal of a chloride ion.

Abstract  Compound specific isotope analysis (CSIA) has been applied to monitor bioremediation of groundwater contaminants and provide insight into mechanisms of transformation of chlorinated ethanes. To date there is little information on its applicability for chlorinated methanes. Moreover, published enrichment factors (ε) observed during the biotic and abiotic degradation of chlorinated alkanes, such as carbon tetrachloride (CT); 1,1,1-trichloroethane (1,1,1-TCA); and 1,1-dichloroethane (1,1-DCA), range from -26.5‰ to -1.8‰ and illustrate a system where similar C-Cl bonds are cleaved but significantly different isotope enrichment factors are observed. In the current study, biotic degradation of chloroform (CF) to dichloromethane (DCM) was carried out by the Dehalobacter containing culture DHB-CF/MEL also shown to degrade 1,1,1-TCA and 1,1-DCA. The carbon isotope enrichment factor (ε) measured during biodegradation of CF was -27.5‰ ± 0.9‰, consistent with the theoretical maximum kinetic isotope effect for C-Cl bond cleavage. Unlike 1,1,1-TCA and 1,1-DCA, reductive dechlorination of CF by the Dehalobacter-containing culture shows no evidence of suppression of the intrinsic maximum kinetic isotope effect. Such a large fractionation effect, comparable to those published for cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) suggests CSIA has significant potential to identify and monitor biodegradation of CF, as well as important implications for recent efforts to fingerprint natural versus anthropogenic sources of CF in soils and groundwater.

Abstract  GC-MS fingerprints of unifloral sour cherry (Prunus cerasus L.) honey were investigated for the first time by GC-FID and GC-MS {after headspace solid phase microextraction (HS-SPME) and ultrasonic solvent extraction (USE)}. Additionally, other physico- chemical characteristics of the samples were determined (total phenolic content, antioxidant activity and CIE L*a*b*C*h chromatic coordinates). The principal volatile components of the honey headspace were lilac aldehydes (46.0; 50.6%) along with benzaldehyde (18.0; 19.4%). The dominant component of the dichloromethane USE extract was vomifoliol (39.6; 44.9%). The abundant identified compounds may only serve as non-specific markers of the honey's botanical origin since they also occur in other honey types. The honey contained low-moderate amount of polyphenols (209.0 - 309.5 mg GAE/kg) and exhibited moderate antioxidant activity (0.4 - 0.6 mmol TEAC/kg; 1.6 - 1.9 mmol Fe2+/kg).

Abstract  The influence of chemical cleaning agents on the bond strength between resin cement and glass-fiber posts was investigated. The treatments included 10% hydrofluoric acid, 35% phosphoric acid, 50% hydrogen peroxide, acetone, dichloromethane, ethanol, isopropanol, and tetrahydrofuran. Flat glass-fiber epoxy substrates were exposed to the cleaners for 60 s. Resin cement cylinders were formed on the surfaces and tested in shear. All treatments provided increased bond strength compared to untreated control specimens. All failures were interfacial. Although all agents improved the bond strength, dichloromethane and isopropanol were particularly effective.

Abstract  The feasibility of the enhanced immunization with diphtheria toxoid-loaded bioerodible microspheres was examined by investigating the serum antibody levels and lethal test in vivo. PLGA polymer was selected based on the properties such as degradability, tissue compatibility, and ease of particulate preparation. The double emulsion solvent extraction method was employed for the fabrication of microspheres to control the release of diphtheria toxoid. Dichloromethane or ethyl acetate was applied as an organic phase and poly (vinyl alcohol) as a secondary emulsion stabilizer during fabrication procedure. Diphtheria toxoid can be microencapsulated using PLGA copolymer without a loss of its immunogenicity. The results from the in vivo study with bioerodible microsphere indicated that immunogenic response, expressed as ELISA IgG titers, was significantly higher than the conventional antigen for 8 weeks after single injection. Consequently, these microspheres could provide the controlled release of antigens for developing enhanced vaccine formulations as a parenteral carrier system.

Abstract  The synthesis and physical properties of the ternary complex 3(2+), prepared by reaction of a naphthalene diimide dicarboxylate 2 with the binucleating dinickel(II) cavitand 1, are discussed. The complex 3(2+) is characterised by cyclic voltammetry which shows a wealth of metal-centred and diimide-based processes at -1.62, -1.04 and 0.15 V vs Fc/Fc+. Absorption and fluorescence spectroscopy of 3(2+) in CH2Cl2 compared to the components 4+ and 5, respectively, are used to characterise the complex further. In particular there is a substantial quenching (approximately 95%) of the diimide fluorescence upon complexation. X-Ray crystallography has been used to characterise complex 3(2+) in the solid state. Of particular interest is the supramolecular structure in which the naphthalene diimide is included between the two metallocavitand hemispheres.