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Evidence for organic synthesis in high temperature aqueous media--facts and prognosis.

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to >400 degrees C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. Heterocyclic sulfur compounds have been identified in high temperature zones and hydrothermal petroleums of the Guaymas Basin vent systems. They can be interpreted as being synthesized from formaldehyde and sulfur or HS kappa- in the hydrothermal fluids. Other products from potential synthesis reactions have not yet been found in the natural systems but are expected based on known industrial processes and inferences from experimental simulation data. Various industrial processes have been reviewed and are of relevance to hydrothermal synthesis of organic compounds. The reactivity of organic compounds in hot water (200-350 degrees C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to >400 degrees C.

Amino Acids↗

Structural studies on HCN oligomers.

NMR spectral studies on the HCN oligomers suggest the presence of carboxamide and urea groupings. The release of CO2, H2O, HCN, CH3CN, HCONH2 and pyridine on pyrolysis is consistent with the presence of these groupings as well as carboxylic acid groups. No basic primary amine groupings could be detected with fluorescamine. Hydrazinolysis of the HCN oligomers releases 10% of the amino acids normally released by acid hydrolysis. The oligomers give a positive biuret test but this is not due to the presence of peptide bonds. There is no conclusive evidence for the presence of peptide bonds in the HCN oligomers. No diglycine was detected on partial hydrolysis of the HCN oligomers at pH 8.5 suggesting that HCN oligomers were not a source of prebiotic peptides.

Amino Acids↗

The pharmacological effect of fractions obtained by smoking cannabis through a water-pipe. II. A second fractionation step.

The catatonic activity, prolongation of phenobarbital sleeping-time, convulsant action and disruption of nest-building activity was assessed in mice subjected to 4 cannabis pyrolysis products and their tobacco analogues. All but one of the cannabis fractions prolonged the pentobarbital sleeping-time and disrupted the nest-building activity of mice in a way not related to their content in the main cannabinoids. Nest-building activity seems to be the most valid assay we have used so far.

Animals↗

Types of "H2O" in human enamel and in precipitated apatites.

Types of "H2O" in human enamel and in precipitated apatites are characterized using X-ray diffraction, infrared (IR) absorption spectroscopic and thermogravimetric analyses. Changes in lattice parameters (principally in the a-axis dimensions) and in the character of the IR absorption bands are correlated with weight losses at pyrolysis temperatures of 100 degrees to 400 degrees C and with effect of rehydration and reignition of previously ignited samples. This study demonstrated that the loss of "H2O" below 200 degrees C is reversible and causes no significant change in the lattice parameter of these apatites, whereas loss of "H2O" between 200 degrees and 400 degrees C is irreversible and causes a contraction in the a-axis dimension. It is proposed that two general types of "H2O" are present in these apatites: (a) adsorbed H2O--characterized by reversibility, thermal instability below 200 degrees C, and lack of effect on lattice parameters; and (b) lattice H2O--characterized by irreversibility, thermal instability between 200 and 400 degrees C, and induction of expansion in the a-axis dimensions of human enamel and precipitated apatites. Lattice H2O is assumed to be due to H2O-for-OH and/or HPO4-for-PO4 substitutions in these apatites. Loss of adsorbed H2O caused sharpening of the OH absorption bands in the spectra of these apatites. Loss of lattice H2O caused the appearance of P-O-P absorption bands (due to the presence of P2O74- group) in precipitated apatites containing small amounts of CO32-.

Adult↗

[Nutrition and cancer. A meeting report].

A meeting report is given (Annual Symposium on Fundamental Cancer Research, Houston, and International Congress of Nutrition, San Diego) which mainly deals with cancerogenesis: The role of retinoids as inhibitors, and the role of pyrolysis products as promoter of cancerogenesis, both essentially active in the tumor promotion range of cancerogenesis, after previous initiation. In the future, enhanced chances may be foreseen for active prevention and for causal elucidation of cancer formation, which until now seems to be a spontaneous disease.

Carcinogens↗

Analytical studies on illicit heroin. V. Efficacy of volatilization during heroin smoking.

The recovery of heroin in fumes was investigated. In the Netherlands the common mode of heroin smoking is the 'chasing the dragon' procedure: heroin is heated on an aluminium foil by a lighter and the fumes are inhaled. The efficiency of the volatilization of heroin using this procedure was studied under laboratory conditions using thin layer chromatography, gas chromatography and high pressure liquid chromatography. A considerable influence of the form (salt or base) of the heroin was found as well as strong influences of other substances that may be present in illicit heroin samples as diluents. The danger of the inhalation of fumes containing unknown pyrolysis products is mentioned and a hypothesis is given for the phenomenon of 'heroin'-leucoencephalopathy that was observed in heroin smokers in Amsterdam in 1981. The types of heroin encountered in the Netherlands are discussed with regard to their suitability for smoking.

Barbital↗

[Nutrition and the etiology of colon cancer: from descriptive epidemiology to dietary prevention].

Colon cancer is one of the most frequent forms of cancer in the Federal Republic of Germany and in most Western countries, but is, however, generally rare in Africa, Asia, and Latin America. Based on epidemiological investigations, differing dietary practices are considered to be main reason for these differences. A high fat and protein consumption was identified as a risk factor, while a high fibre content of the diet was found to be protective. Existing hypotheses of the etiology of colon cancer, which are based on the two-stage initiation-promotion model, regard interactions between initiators, promotors, and inhibitors as decisive for the final outcome of colon cancer. Possible initiators are pyrolysis products of protein-rich food (meat or fish), generated by heating, and products of metabolism of intestinal bacteria (e.g. faecal mutagens, N-nitroso compounds, transformation products of bile acids). Fats probably exert their influence only at the promotional stage. The diet-dependent bacterial formation of deoxycholic and lithocholic acids is a possible mechanism which has been experimentally substantiated. The protective effect of a diet rich in fibre seems to be mediated in particular by dilution and adsorption of harmful compounds. Further protective factors in human diet may be calcium, selenium, vitamin A and beta-carotene. In this paper, evidence, both supporting and refuting the existing hypotheses, is discussed, as well as the possibilities of dietary prevention of colon cancer.

Colonic Neoplasms↗

Mycobacterial taxonomy.

The minimal standards for including a species in the genus Mycobacterium are i) acid-alcohol fastness, ii) the presence of mycolic acids containing 60-90 carbon atoms which are cleaved to C22 to C26 fatty acid methyl esters by pyrolysis, and iii) a guanine + cytosine content of the DNA of 61 to 71 mol %. Currently, there are 71 recognized or proposed species of Mycobacterium which can be divided into two main groups based on growth rate. The slowly growing species require > 7 days to form visible colonies on solid media while the rapidly growing species require < 7 days. Slowly growing species are often pathogenic for humans or animals while rapidly growing species are usually considered nonpathogenic for humans, although important exceptions exist. The taxonomic and diagnostic characteristics of medically important species and of newly described species of the Mycobacterium genus are reviewed.

Animals↗

X-ray diffraction of the calcified tissues in Polypterus.

Pyrolyzed scales, fin spines, and bone from the ray-finned bony fish Polypterus (Actinopterygii) showed two mineral phases on X-ray diffraction: hydroxyapatite (HA), Ca5(PO4)3OH, and whitlockite, Ca3(PO4)2. The ratio of HA/whitlockite varied with the structure (scale, spine, bone) within each individual fish. The relative proportions of HA to whitlockite in pyrolyzed samples reflected the Ca/P ratio of the sample. Whitlockite appears after pyrolysis when the Ca/P is lower than 1.67. Among the five fish investigated, for each structure a general trend was noted. The proportion of HA relative to whitlockite increased with size (age) of the fish. Thus the smallest fish, a juvenile, exhibited a low Ca/P mineral in its calcified tissues, whereas the larger fish had progressively more HA and less whitlockite.

Animals↗

Reaction of ergosteryl acetate with maleic anhydride and preparation of 5,7-ergostadien-3beta-ol1,2.

An improved, large scale synthesis of the ergosteryl acetate-maleic anhydride Diels-Alder adduct and its pyrolysis are described. The complex mixture obtained by reaction of the two constituents was refluxed with methanol to convert the succinic anhydride derivatives, formed by the "ene" reaction, to soluble half esters, leaving the insoluble Diels-Alder adduct largely unchanged. The latter was hydrogenated and pyrolyzed in vacuo to yield 5,7-ergostadienyl acetate together with lesser quantities of the acetates of 7,9(11)-ergostadien-3beta-ol, 6,8(9)-ergostadien-3beta-ol, and 8,14-ergostadien-3beta-ol. These components were separated and purified by argentation column chromatography and crystallization.

Anhydrides↗

Determination of selenium in the human brain by graphite furnace atomic absorption spectrometry.

For the investigation of neurological disorders, a development of simple and accessible methods for determining selenium in human brain samples is required. We devised a method of determining selenium using graphite furnace atomic absorption spectrometry (GFAAS). An electrodeless discharge lamp provided the sufficient sensitivity to determine brain selenium. The matrix interferences were avoided by using high temperature, a prolonged pyrolysis step, and a palladium matrix modifier. The technique of standard addition was used to evaluate the sample concentrations. The accuracy of the method was confirmed by a bovine liver reference material. The detection limit of selenium was 0.04 ng. The determined selenium concentrations of human brain cortex and white matter were higher than those of putamen (115-155 and 206-222 ng/g wet wt, respectively). These GFAAS values agreed with those obtained by fluorometric analysis (r = 0.91, n = 10). Moreover, the GFAAS values were compatible to those reported by other researchers (99-274 ng/g wet wt), in which selenium concentrations in putamen also tended to be higher than the other two regions. We conclude that GFAAS is useful for selenium analysis in brain samples.

Brain↗

Indirect methods of determination of activity of root-nodule bacteria.

Significant correlations exist between the ability of root-nodule bacteria to fix molecular nitrogen and some of their properties (accumulation of riboflavin, cobalamine, ATP, cell pyrolysis, effect on plant vegetation characteristics) which can be used for quickly assessing the activity of the process in individual strains of rhizobia.

Adenosine Triphosphate↗

[Laser-resistance of a new jet ventilation catheter (LaserJet) under simulated clinical conditions].

BACKGROUND: Laser surgery within the airway is often performed with the patient under general anaesthesia and with infraglottic jet ventilation via a specially designed catheter which should not be inflammable. We investigated the laser-resistance of a recently introduced jet ventilation catheter (LaserJet) made of polytetrafluoroethylene. METHODS: For the simulation of gas accumulation in the hypopharynx a cylindric steel chamber with an open and a closed end was used to simulate the operative setting according to the European standard ISO-11990. In a series of 12 tests the disposable laser jet catheter was attached to the proximal end of the oxygen supply tubing, and the distal end was introduced 10 cm into the steel chamber. The catheter was repeatedly exposed to the beam of a CO(2)-laser device with energies varying from 2-15 W and with an impact angle of 75 degrees. The changes in the catheter were assessed with and without an oxygen flow of 6 l/min. Time of exposure varied from 1 to 10 s. Size and nature of the changes in the catheter were documented. RESULTS: We found damage to the catheter that occurred in the following order: simple (front wall) and double perforation (front and back wall), smoke emission as evidence for pyrolysis, discolouration, deformation and rupture. The extent of damage to the catheter shaft under direct laser beam exposition was dependent on the laser intensity. When there was no oxygen flow, a beam of 2 W needed 40 s to perforate the catheter shaft, while with an oxygen flow of 6 l/min, a laser intensity of 4 W needed 20 s to cause perforation. Rupture of the catheter occurred in less than 10 s with a laser intensity of 8 W or more. CONCLUSIONS: We could demonstrate that the LaserJet catheter is not inflammable and also does not sustain fire. However, it is not laser-resistant as to maintaining its texture and shape while under direct exposure to a continuous laser beam, as applied under clinical conditions. Polytetrafluoroethylene deforms and melts at temperatures above 327 degrees C which is usually exceeded by the CO(2)-laser.

Biocompatible Materials↗

Identification of QTLs influencing wood property traits in loblolly pine ( Pinus taeda L.). II. Chemical wood properties.

Chemical wood property traits were analyzed for the presence of quantitative trait loci (QTLs) in a three-generation outbred pedigree of loblolly pine ( Pinus taeda L.). These traits were assayed using pyrolysis molecular beam mass spectrometry and include mass spectrum peak intensities associated with carbohydrates, alpha-cellulose and hemicellulose sugars, and lignin. Models for projection to latent structures (PLS) were used to also estimate the chemical composition of cell walls (i.e., alpha-cellulose, galactan and lignin) from mass spectrum data using multivariate regression. Both earlywood and latewood fractions from the fifth annual ring were analyzed for each trait. An interval mapping approach designed for an outbred pedigree was used to estimate the number of QTLs, the magnitude of QTL effects, and their genomic position. Eight unique QTLs influencing cell wall chemistry were detected from multiple peak intensities and/or PLS estimates using the one- and two-QTL models. Significant differences in chemical contents were observed among the populations from North Carolina vs Oklahoma, and results from QTLxenvironment analyses suggest that QTLs interact with environmental location. QTLs should be verified in larger experiments and in different genetic and environmental backgrounds. QTL mapping will help towards eventually identifying genes having a major effect on chemical wood properties.

Journal Article↗

Chemical modifiers for direct determination of cobalt in coal combustion residues by ultrasonic slurry-sampling-ETAAS.

Five modifiers were tested for the direct determination of cobalt in coal fly ash and slag by ultrasonic slurry-sampling electrothermal atomic absorption spectrometry (USS-ETAAS). The furnace temperature programs and the appropriate amount for each modifier were optimized to get the highest signal and the best separation between the atomic and background signals. Nitric acid (0.5% v/v) was the most adequate chemical modifier for cobalt determination, selecting 1,450 degrees C and 2,100 degrees C as pyrolysis and atomization temperatures, respectively. This modifier also acts as liquid medium for the slurry simplifying the procedure. The remaining modifiers enhanced the background signal, totally overlapped with cobalt peak. The method optimized gave a limit of detection of 0.36 microg g(-1), a characteristic mass of 13 +/- 1 pg and an overall-method precision which is highly satisfactory (<7%, RSD). The method was validated by analyzing two certified coal fly ash materials, and satisfactory recoveries were obtained (83-90%) and no statistical differences were observed between the experimental and the certified cobalt concentrations. Additionally, certified sediment, soil and urban particulate matter were assayed; again good results were obtained. The developed methodology was used to determine cobalt in several coal combustion residues from five Spanish power plants.

Calibration↗

Performance of permanent iridium modifier in the presence of corrosive matrix in graphite furnace atomic absorption spectrometry.

The influence of up to 16% HNO3, 28% HCl, and the mixture of both acids in aqua regia on the analytical performance of electrodeposited modifiers (Ir or Ir+Pd) was evaluated and discussed. Cadmium was used as an example of volatile elements often determined by graphite furnace atomic absorption spectrometry (GF AAS). In the presence of HCl, the maximum pyrolysis temperature that could be applied was found to be 600 degrees C. In the presence of HNO3 and aqua regia, both modifiers stabilized cadmium up to 800 degrees C. The long-term performance of electrodeposited Ir or Ir+Pd was not influenced by mineral acids; moreover the tube lifetime was significantly prolonged compared with a non-modified tube.

Journal Article↗

Determination of Cd and Pb in food slurries by GFAAS using cryogenic grinding for sample preparation.

A simple method combining slurry sampling after cryogenic grinding and the use of a permanent modification of the integrated platform inside the transversely heated graphite atomizer (THGA) was proposed for the determination of Cd and Pb in foods. Potentialities of the cryogenic grinding were evaluated for grinding different materials of difficult homogenization such as high fat and high fiber tissues. Animal and vegetal samples were cut into small pieces and ground in liquid nitrogen for 2 min. Slurries were prepared directly in the autosampler cup after cryogenic grinding by transferring an exact amount of homogeneous powdered material (5-20 mg) to the cup, followed by 1.00 mL of 0.2% (v/v) HNO3 containing 0.04% (v/v) Triton X-100 and sonication for 30 s, before transferring into the platform previously coated with 250 microg W and 200 microg Rh. Use of a tungsten carbide-rhodium permanent modifier combined with NH4H2PO4 conventional modifier improves tube lifetime and increases the pyrolysis temperature for Cd. Homogeneity tests, carried out by comparing the between- and within-batch precision for each kind of sample, showed no significant differences at the 95% confidence level, indicating good homogeneity for 5-20 mg masses. Detection limits were 3.3 ng g(-1) Cd and 75 ng g(-1) Pb for 1% m/v slurries. Results for determination of Cd and Pb in foods slurries were in agreement with those obtained with digested samples, since no statistical differences were found by the paired t-test at the 95% level.

Cadmium↗