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Free-volume viscosity model for fluids in the dense and gaseous states.

A free-volume and friction viscosity model is presented versus pressure and temperature, valid for both gaseous and dense fluids. This model involves only three adjustable parameters for each pure compound. It is able to represent the gas-liquid transition and the behavior in the supercritical conditions. The model has been successfully applied to methane (885 data points for 0.01< or =P< or =200 MPa and 90.7< or =T< or =600 K) and to propane (1085 data points for 0.01< or =P< or =200 MPa and 90< or =T< or =600 K) in the gaseous and dense states (average absolute deviation is 2.59% for methane and 2.50% for propane, with maximum deviation of 14.8% for methane and 9.19% for propane). It has also been applied to hexane, octane, dodecane, benzene, trans-decaline, and 2,2-dimethylpropane (903 data points) in a large pressure range (up to 505.5 MPa). Considering these compounds the maximum deviation is 19.5% (for octane) and the average deviation is 3.51% in the worst case (dodecane, which has data points up to 501.6 MPa).

Journal Article↗

Multiple bridging modes in a novel trinuclear titanium 1,3-dioxypropane compound, Ti3(methyliminodiethanolate)2(1,3-propanediolate)4.

The title compound, bis(2,2'-methyliminodiethanolato)-1kappa(3)O,N,O';3kappa(3)O,N,O'-di-micro(3)-propane-1,3-diolato-1:2:3kappa(8)O:O,O':O'-micro-propane-1,3-diolato-1:3kappa(2)O:O'-propane-1,3-diolato-2kappa(2)O,O'-trititanium(IV), [Ti(3)(C(5)H(11)NO(2))(2)(C(3)H(6)O(2))(4)], has four 1,3-propanediolate ligands binding in three different modes. Two ligands chelate adjacent Ti atoms with normal micro(3)-O bridges, giving typical edge-sharing of the Ti distorted octahedra, one chelating to the central Ti atom with no micro-bridging, and the other spanning the cluster, binding only to the outermost Ti atoms. The two methyliminodiethanolate ligands each coordinate to the outer Ti atoms via their N and two O atoms. The Ti-O bond lengths range, in a self-consistent fashion, from 1.816 (2) to 2.082 (2) A, while the average Ti-N distance is 2.391 (3) A.

Journal Article↗

The action of hydrocarbons and carbon tetrachloride on the sodium current of the squid giant axon.

The effects of the n-alkanes propane to hexane, cyclopropane, cyclopentane and cyclohexane and carbon tetrachloride on the ionic currents and electrical capacity of the squid giant axon membrane have been examined. Both the peak inward and steady-state outward currents were reduced reversibly by each substance, though propane at 1 atm had very little effect. The membrane capacity at 100 kHz was reduced by all substances except propane at 1 atm. Na currents were recorded in intracellularly perfused axons before and during exposure to the hydrocarbons and the records were fitted with equations similar to those proposed by Hodgkin & Huxley (1952). Shifts in the curves of the steady-state activation and inactivation parameters (m infinity and h infinity) against membrane potential, changes in the peak heights of the activation and inactivation time constants (tau m and tau h) and reductions in the maximum Na conductance (gNa) have been tabulated. The effects of the various hydrocarbons and carbon tetrachloride on the parameters of the Hodgkin-Huxley equations suggest that the suppression of the Na current by these substances originates from several different phenomena. The underlying physico-chemical events are considered in the light of the observed capacity changes and of information on artificial pore-containing membranes.

Action Potentials↗

Characterization of an extracellular lignin peroxidase of the lignocellulolytic actinomycete Streptomyces viridosporus.

Previously we reported production of an extracellular lignin-inducible peroxidase by Streptomyces viridosporus (M. Ramachandra, D.L. Crawford, and A.L. Pometto III, Appl. Environ. Microbiol. 53:2754-2760, 1987). This peroxidase was shown to oxidize 3,4-dihydroxyphenylalanine, 2,4-dichlorophenol, homoprotocatechuic acid, caffeic acid, and N,N,N',N'-tetramethylphenylenediamine and was found in higher than normal levels in strains enhanced for lignocellulose degradation. In the present study, we used a pure extracellular enzyme preparation with high peroxidase isoform P3 activity to oxidize lignin substructure model compounds of both the 1,2-diaryl propane and arylglycerol-beta-aryl ether types and containing C alpha-carbonyl and C alpha-hydroxyl groups. The reactions were monitored by gas chromatography-mass spectrometry and high-pressure liquid chromatography techniques. In the presence, but not the absence, of hydrogen peroxide, the enzyme preparation catalyzed C alpha-C beta bond cleavage in the side chains of the diaryl ethers 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (I) and 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propan-1-one (II) and the diaryl ethane 1-(4-methoxyphenyl)-2-(phenyl)ethan-1-one (III). Rapid hydrogen peroxide consumption was observed when the enzyme preparation was added to either milled corn lignin or lignocellulose. Additional characterizations showed that this enzyme is a heme protein (Soret band, 408 nm) and a major component of the ligninolytic system of S. viridosporus T7A. This is the first report of a lignin peroxidase in a bacterium. We have designated this new lignin peroxidase as ALiP-P3.

Biodegradation, Environmental↗

Biodegradation of trichloroethylene in continuous-recycle expanded-bed bioreactors.

Experimental bioreactors operated as recirculated closed systems were inoculated with bacterial cultures that utilized methane, propane, and tryptone-yeast extract as aerobic carbon and energy sources and degraded trichloroethylene (TCE). Up to 95% removal of TCE was observed after 5 days of incubation. Uninoculated bioreactors inhibited with 0.5% Formalin and 0.2% sodium azide retained greater than 95% of their TCE after 20 days. Each bioreactor consisted of an expanded-bed column through which the liquid phase was recirculated and a gas recharge column which allowed direct headspace sampling. Pulses of TCE (20 mg/liter) were added to bioreactors, and gas chromatography was used to monitor TCE, propane, methane, and carbon dioxide. Pulsed feeding of methane and propane with air resulted in 1 mol of TCE degraded per 55 mol of substrate utilized. Perturbation studies revealed that pH shifts from 7.2 to 7.5 decreased TCE degradation by 85%. The bioreactors recovered to baseline activities within 1 day after the pH returned to neutrality.

Journal Article↗

Aerobic mineralization of trichloroethylene, vinyl chloride, and aromatic compounds by rhodococcus species.

Two Rhodococcus strains which were isolated from a trichloroethylene (TCE)-degrading bacterial mixture and Rhodococcus rhodochrous ATCC 21197 mineralized vinyl chloride (VC) and TCE. Greater than 99.9% of a 1-mg/liter concentration of VC was degraded by cell suspensions. [1,2-C]VC was degraded by cell suspensions, with the production of greater than 66% CO(2) and 20% C-aqueous phase products and incorporation of 10% of the C into the biomass. Cultures that utilized propane as a substrate were able to mineralize greater than 28% of [1,2-C]TCE to CO(2), with approximately 40% appearing in C-aqueous phase products and another 10% of C incorporated into the biomass. VC degradation was oxygen dependent and occurred at a pH range of 5 to 10 and temperatures of 4 to 35 degrees C. Cell suspensions degraded up to 5 mg of TCE per liter and up to 40 mg of VC per liter. Propane competitively inhibited TCE degradation. Resting cell suspensions also degraded other chlorinated aliphatic hydrocarbons, such as chloroform, 1,1-dichloroethylene, and 1,1,1-trichloroethane. The isolates degraded a mixture of aromatic and chlorinated aliphatic solvents and utilized benzene, toluene, sodium benzoate, naphthalene, biphenyl, and n-alkanes ranging in size from propane to hexadecane as carbon and energy sources. The environmental isolates appeared more catabolically versatile than R. rhodochrous ATCC 21197. The data report that environmental isolates of Rhodococcus species and R. rhodochrous ATCC 21197 have the potential to degrade TCE and VC in addition to a variety of aromatic and chlorinated aliphatic compounds either individually or in mixtures.

Journal Article↗

Fractionation of membrane components from tachyzoite forms of Toxoplasma gondii: differential recognition by immunoglobulin M (IgM) and IgG present in sera from patients with acute or chronic toxoplasmosis.

Tachyzoite forms of Toxoplasma gondii were subjected to a sequential organic solvent extraction, which allows fractionation of membrane components according to their degrees of hydrophobicity, yielding three fractions named F1 (most hydrophobic) to F3 (least hydrophobic). Fractions F2 (80.85% specificity and 86.95% sensitivity) and F3 (89.36% specificity and 93.61% sensitivity) gave the best results, being preferentially recognized by immunoglobulin M (IgM) and IgG in sera from patients with acute and chronic toxoplasmosis, respectively. Improved scores of specificity (100%) and sensitivity (100%) were achieved when a secondary antibody against human IgG1 instead of total IgG was employed to measure the reactivity of IgG antibodies with the F3 fraction. To purify tachyzoite antigens recognized by human IgM or IgG antibodies, the F2 or F3 fraction was loaded onto an octyl-Sepharose column and eluted with a propan-1-ol gradient. The main antigen(s) recognized by IgM or IgG eluted in a single peak from the octyl-Sepharose resin loaded with either F2 (30 to 50% propan-1-ol) or F3 (15 to 35% propan-1-ol), respectively. These semipurified fractions gave improved scores when used to detect T. gondii-specific IgM (95.7% specificity and 81.8% sensitivity) or IgG (100% specificity and 93. 75% sensitivity) in an enzyme-linked immunosorbent assay. Further biochemical and immunological analyses of antigens partially purified from F2 and F3 indicate that glycoinositolphospholipids are preferentially recognized by IgM, whereas proteins of approximately 30 to 40 kDa are recognized by IgG, elicited during T. gondii infection in humans.

Acute Disease↗

Metabolic O-demethylation of 3,4-dimethoxyamphetamine in vivo in dog and monkey.

1. The disposition of the hallucinogen 3,4-dimethoxyamphetamine in vivo was examined in dogs and monkeys. 2. O-Demethylation is important since 3-O-methyl-alpha-methyldopamine (3-methoxy-alpha-methyltyramine) was found in the urine of both species, and traces of alpha-methyldopamine were found in the urine of dogs. 3. Also found in the urine of dogs were 1-(3,4-dihydroxyphenyl)propan-2-one and 3,4-dihydroxybenzoic acid, which are side-chain modified metabolites of alpha-methyldopamine. 4. 1-(3-Methoxy-4-hydroxyphenyl)propan-2-one, a side-chain modified metabolite of 3-O-methyl-alpha-methyldopamine, was present in the urine of both dogs and monkeys. 5. The 3-O-demethylated isomers 4-O-methyldopamine and 1-(3-hydroxy-4-methoxyphenyl)propan-2-one were not detected.

Amphetamines↗

The metabolism of eugenol in man.

1. The metabolism of eugenol (4-hydroxy-3-methoxy-allylbenzene) was investigated in male and female healthy volunteers. It was rapidly absorbed and metabolized after oral administration and was almost completely excreted in the urine within 24 h. Unmetabolized eugenol excreted in urine amounted to less than 0.1% of the dose. 2. The urine contained conjugates of eugenol and of nine metabolites. The structures of these metabolites, elucidated using g.l.c.-mass spectrometry, and by comparison with synthetic reference compounds, were identified as: eugenol, 4-hydroxy-3-methoxyphenyl-propane, cis- and trans-isoeugenol, 3-(4-hydroxy-3-methoxyphenyl)-propylene-1,2-oxide, 3-(4-hydroxy-3-methoxyphenyl)-propane-1,2-diol, and 3-(4-hydroxy-3-methoxyphenyl)-propionic acid. 3. The structures of the following metabolites were tentatively deduced from mass spectra only, as reference compounds were not available: 3-hydroxy-3-(4-hydroxy-3-methoxyphenyl)-allylbenzene, 3-(6?-mercapto-4-hydroxy-3-methoxyphenyl)-propane, and 2-hydroxy-3-(4-hydroxy-3-methoxyphenyl)-propionic acid. 4. The amounts of the individual metabolites excreted were determined by g.l.c. Some 95% of the dose was recovered in the urine, most of which (greater than 99%) consisted of phenolic conjugates; 50% of the conjugated metabolites were eugenol-glucuronide and sulphate. Other metabolic routes observed were the epoxide-diol pathway, synthesis of a thiophenol and of a substituted propionic acid, allylic oxidation, and migration of the double bond.

Adult↗

Studies on cryopreservation of luc gene transfected bluegill sunfish fibroblast cell line.

The effect of cryopreservation on the survival of luc gene transfected bluegill sunfish fibroblast (BF-2) cells was investigated. Propane-1,2-diol was found to be the least toxic cryoprotectant when compared with DMSO and methanol. Both propane-1,2-diol and DMSO are effective in protecting cells from freezing damage. Whilst there were no significant differences in cell survival between cryoprotectant concentration (10 or 15%) and culture age used in this study, 7-day old culture appeared to be more resistant to freezing without cryoprotectant when compared with 3- and 14-day old culture. The highest cell survival values obtained with propane-1,2-diol (10%) and DMSO (10%) protection were 96.2 1.2% and 94.0 3.1% respectively. Initial subsequent cell growth after cryopreservation was slower than their non-frozen controls. The survival of transfected BF-2 cells (BF-2/luc1) after cryopreservation were very similar to those obtained with wild type cells being: 94.0 3.1% and 95.2 1.5% respectively with 10% DMSO protection. These results suggested that genetically modified fish cell lines may be equally amenable to cryopreservation as the wild type.

Animals↗

[Study on the phase II metabolites of phenoprolamine hydrochloride in rat bile by LC/DAD/MSD].

AIM: To study the phase II metabolites of phenoprolamine hydrochloride (DDPH) in rat bile. METHODS: DDPH was administered by i.p. to bile duct-cannulated rats. Bile samples were collected before drug administration and up to 12 h after drug administration. After being purified and enriched with C-18 SPE columns the rat bile samples were analyzed by LC/DAD/MSD to identify the peaks of phase II metabolites. The fractions of phase II metabolites were prepared by HPLC and treated with beta-glucuronidase, and then were purified and enriched with C-18 SPE columns and analyzed by LC/DAD/MSD. The corresponding reference standards of DDPH phase I metabolites were analyzed by LC/DAD/MSD under identical conditions. RESULTS: The peaks M7, M8 and M9 in the chromatograms of rat bile samples were the phase II metabolites of DDPH and the enzymatic hydrolysates of M7, M8 and M9 were 1-(2, 6-dimethyl-4-hydroxyphenoxy)-2-(3, 4-methoxyphenylethylamino)-propane (M3), 1-(2, 6-dimethyl-3-hydroxyphenoxy)-2-(3, 4-methoxyphenylethylamino)-propane (M2) and 1-(2,6-dimethylphenoxy)-2-(3-methoxy-4-hydroxyphenylethyl-amino)-propane (M1) respectively. CONCLUSION: beta-1-O-[3,5-dimethyl-4-[-2-methyl-2-(3,4-dimethoxy-phenylethylamino)- ethoxy]-phenyl]-glucuronic acid (M7, glucuronide of M3), beta-1-O-[2, 4-dimethyl-3-[2-methyl-2-(3, 4-dimethoxy-phenylethylamino)-ethoxy]-phenyl]-glucuronic acid (M8, glucuronide of M2) and beta-1-O-[2-methoxy-4-[1-methyl-2-(2, 6-dimethylphenoxy)-ethylamino-ethyl]-phenyl]-glucuronic acid (M9, glucuronide of M1) were the phase II metabolites of DDPH in rat bile.

Animals↗

[In vitro reactivation of acetylcholinesterase inhibition by O-isopropylmethylfluorophosphonate using the bisquarternary oxime, HS-6].

The ability of the oxime HS-6 [1-(4-hydroxyiminomethylpyridinium)-3-(4-carbamoylpyridinium)-2-oxa-propane dichloride] to reactive in vitro the enzyme acetylcholinesterase inhibited by the nerve agent sarin [O-isopropylmethylfluorophosphonate] was evaluated. The reactivators 2-PAM [2-hydroxyiminomethyl-1-methylpyridinium chloride], toxogonin [1,3-bis(4-hydroxyiminomethylpyridinium)-2-oxa-propane dichloride] and H-oxime HI-6 [1-(2-hydroxyiminomethylpyridinium)-3-(4-carbamoylpyridinium)-2-oxa-propane dichloride] were chosen for comparison. The oxime HS-6 was an effective reactivator of sarin-inhibited AChE. It is not as effective as the H-oxime HI-6, but it is better than 2-PAM and obidoxime.

Acetylcholinesterase↗

Study of the liquid chromatography retention of some fibrate-type antihyperlipidemic drugs on C18 and CN columns: application for quantitation in pharmaceutical formulations.

The 6 antihyperlipidemic agents-bezafibrate, ciprofibrate, clofibrate, clofibric acid, fenofibrate, and gemfibrozil-were separated on octadecyl (C18) and cyano (CN) chemically bonded columns using mobile phases containing phosphate buffer and different amounts of acetonitrile, dioxane, propan-2-ol, methanol, and tetrahydrofuran. Relationships between log k values and mobile phase composition have been examined for these systems. Analysis was performed on a Waters LC system with Merck LichroCART C18 and CN 125 mm columns using a flow rate of 1 mL/min and 227 nm detection. More than one-half of the results fitted Snyder-Soczewinski equations with r >0.995. Separation of all drugs was achieved on the C18 column with a mobile phase containing 45% propan-2-ol in phosphate buffer (pH = 2.145) and on a CN column with 20% acetonitrile in the same buffer. The best mobile phase, containing 45% propan-2-ol, was used to quantitate bezafibrate, ciprofibrate, fenofibrate, and gemfibrozil in pharmaceutical formulations. The active substances were extracted with methanol. The calibration curve was constructed in the 0.1-0.8 mg/mL range for all drugs and provided satisfactory linearity (Lack-of-Fit test and Mandel's test). The recovery function was sufficiently linear in all cases, with an insignificant intercept and slope very close to 1. Accuracy was tested by quantitating 3 fortified samples (50, 100, and 150%), which gave results without significant differences. None of the excipients interfered in the analysis. The recovery was 99.85% for bezafibrate, 99.02% for ciprofibrate, 99.53% for fenofibrate, and 99.92% for gemfibrozil, with relative standard deviation values of 0.63, 1.61, 1.84, and 0.88%, respectively.

Calibration↗

Ultra-rapid freezing of thin biological samples.

Miniature thermocouples are used to follow the time course of cooling within test samples plunged into liquid coolants. Variations in the temperature and type of coolant (propane, Freon 22, sub-cooled liquid nitrogen), in the velocity and depth of plunge, and in the size and shape of samples were investigated. Coolants have their optimum cooling properties at their lowest liquid temperatures but show different dependencies on temperature. The optimum velocity of plunge depends on the shape of the sample. The strongest influence on cooling rate comes from the size and shape of the sample. Spherical samples about 1 mm3 show rates < 500 decrees C/s while samples 0.001 mm3 show rates > 50,000 degrees C/s for freezing in liquid propane under identical conditions. Thin samples of equivalent volume can be more rapidly frozen. Cooling rates of about 11,900 degrees C/s (0 degrees C to -100 degrees C) are recorded for thin samples (0.1 mm3 and 20 micrometers thick) sandwiched between copper strips and rapidly plunged into liquid propane (-190 degrees C). An apparatus is described for using these holders in freeze-fracture studies. Thin samples thus frozen show no evidence of ice crystal growth in either low-temperature x-ray diffraction patterns or in freeze-fracture electron micrographs.

Freeze Fracturing↗

[Alkyl nitrosoureidodioxans and alkyl nitrosoureidopropane diols -- new groups of antitumor compounds].

1,3-dioxan- and 1,3-propane diol derivatives of alkyl nitrosourea have been synthesized and studied. Like other 2/chloroethylnitrosoureas, they exerted pronounced influence on a wide range of transplantable tumors, including those transplanted intracranially. Antitumor effect was found to depend on C5 and C2 atom substituent in the 1,3-dioxan cycle and 1,3-propane diol, respectively. The therapeutic effect and toxicity of 1,3-propane diol derivatives were higher than those of 1,3-dioxan. The substances lost all antitumor properties if a methyl group was substituted for the 2-chloroethyl one, even though a nitroso group was retained in their structure.

Animals↗

Catabolism of 2,4,6-trinitrotoluene by Mycobacterium vaccae.

Mycobacterium vaccae strain JOB-5 cometabolized 2,4,6-trinitrotoluene (TNT) in the presence of propane as a carbon and energy source. Two novel oxidized metabolites, as well as several known reduced products, were generated during catabolism of TNT by M. vaccae. During the cometabolic process, there was transient production of a brown chromophore. This compound was identified as 4-amino-2,6-dinitrobenzoic acid. When M. vaccae was incubated with [14C]TNT and propane, 50% of the added radiolabel was incorporated into the cellular lipid fraction. These results suggest that ring cleavage occurred prior to the incorporation of radiolabelled carbon into phosphatidyl-L-serine, phosphatidylethanolamine, cardiolipin, and other polar lipids.

Biotransformation↗

Identification of 1-furan-2-yl-3-pyridin-2-yl-propenone, an antiinflammatory agent, and its metabolites in rat liver subcellular fractions.

1-Furan-2-yl-3-pyridin-2-yl-propenone (FPP-3) has been characterized to have an anti-inflammatory activity through the inhibition of the production of nitric oxide and tumor necrosis factor-alpha. In the present studies, the phase 1 metabolism of FPP-3 was investigated in rat liver microsomes and cytosols. When FPP-3 was incubated with rat liver microsomes and cytosols in the presence of NADPH, 2 major peaks were detected on a liquid chromatography/electrospray ionization-mass spectrometry. Two metabolites (i.e., M1 and M2) were characterized as reduced forms on propenone: M1 (1-furan-2-yl-3-pyridin-2-yl-propan-1-one) was the initial metabolite and M2 (1-furan-2-yl-3-pyridin-2-yl-propan-l-ol) was a secondary alcohol believed to be formed from M1.

Animals↗

Generation of volatile hydrocarbons from amino acids and proteins by an iron/ascorbate/GSH system.

Incubation of free, but not of peptide-bound methionine in an iron/ascorbate system resulted in ethylene generation, which was inhibited by glutathione. Leucine and isoleucine, however, when incubated in an iron/ascorbate/GSH system, released small amounts of propane and ethane, respectively. Peptide-bound leucine additionally yielded butane, as did bovine serum albumin or casein. Hydrocarbon generation from amino acids was inhibited by hydroxyl radical scavengers, but catalase and superoxide dismutase were more efficient. Additionally, ethane and propane generation in this system was optimal at pH 6.2 suggesting the involvement of protonated superoxide besides OH-radicals which attack the side chains of Leu and Ile and very probably produce carbon-centered radicals, which should abstract a hydrogen atom from the thiol group of GSH resulting in the formation of saturated hydrocarbons.

Amino Acids↗