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Some observations on amino acid racemization under pyrolytic temperatures and inorganic oxide-catalyzed intermolecular condensation.

The problem of homochirality is of crucial importance for the origins of Life. While most laboratory studies are focused on the search of physical and chemical sources of handedness in the Universe, they reflect only one aspect of the problem: the origin of homochiral biomolecules. At the same time, any space environments where biomolecules are expected to form and where they have to pass through before the first primitive forms of Life emerge, include strong irradiation or/and high temperatures. This automatically implies the possibility of losing the optical activity, i.e. racemization. The simulation experiments performed by our group deal with the following two aspects of amino acid abiotic chemistry: (1) amino acid pyrolysis associated with their extraterrestrial delivery; and (2) peptide formation from amino acids catalyzed by inorganic oxides. According to our observations, the racemization phenomena are very common in the systems considered, not only under pyrolytic temperatures, but in some cases also under rather mild conditions (<100 degrees C). Our results put additional constraints on the environments where the chirality of biomolecules can be efficiently preserved.

Aluminum Oxide↗

Structure of high-molecular carbonaceous compound in carbonaceous chondrites and formation of IR-spectroscopically similar compounds in the laboratory.

Main components of carbonaceous matter in carbonaceous chondrites are high molecular organic matter. Examinations of the compounds using pyrolysis GC/MS and FT-IR indicated the structural resemblance of major part of the molecule for all of the compounds from different types of carbonaceous chondrites (8 Antarctic and 2 none-Antarctic meteorites). A carbonaceous matter derived from graphite on a shock experiment using a rail gun (1g projectile at 7 km/s) showed similar IR spectrum to those of the meteoritic high-molecular organic matter. C-60 fullerene also gave a similar compound (with minor differences in IR spectra) on a shock experiment under the same conditions. A shock experiment using coronene also examined.

Carbon↗

Organic analysis of hydrogen cyanide polymers: prebiotic and extraterrestrial chemistry.

Hydrogen cyanide polymerizes readily to a black solid from which a yellow-brown powder can be extracted by water and further hydrolyzed to alpha-amino acids. These macromolecules could be major components of the dark matter observed on many bodies in the outer solar system, including comets and asteroids. Primitive Earth might therefore have been covered with HCN polymers through bolide bombardment or be terrestrial synthesis. Several instrumental methods were used for the separation and identification of these intriguing polymeric materials, including photoacoustic Fourier transform infrared spectroscopy, supercritical fluid extraction chromatography and pyrolysis mass spectrometry. Our integrated analytical approach revealed fragmentation patterns and chemical functionalities consistent with the presence of polymeric peptide precursors both in HCN polymers and in the Murchison meteorite.

Astronomy↗

Search for life on Mars: evaluation of techniques.

An important question for exobiology is, did life evolve on Mars? To answer this question, experiments must be conducted on the martian surface. Given current mission constraints on mass, power, and volume, these experiments can only be performed using proposed analytical techniques such as: electron microscopy, X-ray fluorescence, X-ray diffraction, alpha-proton backscatter, gamma-ray spectrometry, differential thermal analysis, differential scanning calorimetry, pyrolysis gas chromatography, mass spectrometry, and specific element detectors. Using prepared test samples consisting of 1% organic matter (bovine serum albumin) in palagonite and a mixture of palagonite, clays, iron oxides, and evaporites, it was determined that a combination of X-ray diffraction and differential thermal analysis coupled with gas chromatography provides the best insight into the chemistry, mineralogy, and geological history of the samples.

Aluminum Silicates↗

Formation of mutagens in boiled pork extract.

When boiled pork extract was heated under reflux at 102 degrees C for 4 hr mutagens, which were detected using Salmonella typhimurium strains TA98 and TA1538, were formed. The level of mutagenicity was dependent on the concentration of pork in the extract, the duration of boiling and on pH; the optimum pH for mutagen formation was found to be 9 to 11. Thin-layer chromatographic analysis showed that the mutagens formed in boiled pork extract were chromatographically distinguishable from benzo[a]pyrene and from the primary mutagenic pyrolysis products of tryptophan (3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole and of glutamic acid (2-amino-6-methyldipyrido[1,2-a:3',2'-d]imidazole).

Animals↗

Examples of MAK values and carcinogenicity classification for mixtures.

The German Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area (MAK Commission) generally sets MAK values for single pure substances. MAK values for mixtures are only established after specific toxicological evaluation of the particular mixture. In practice, there are a few cases in which a common MAK value for the sum of all components was set, such as for mixtures of isomers (e.g. xylenes) or mixtures of related compounds (e.g. Kathon), in which the components of the mixture show comparable toxicological effects. For mixtures of isomers with different toxicological potentials, different MAK values for the single isomers are usually established. The only exception is for the isomer mixture of alpha- and beta-hexachlorocyclohexane, for which a mathematically calculated MAK value was proposed. A safe threshold cannot be established for mixtures containing substances with a genotoxic and carcinogenic potential. These mixtures are categorized either according to the proven carcinogenicity of the mixture, such as alpha-chlorinated toluenes, or according to the carcinogenic substances included, as for pyrolysis products such as coal tars.

Animals↗

Fractionation of a mutagenic principle from broiled fish by high-pressure liquid chromatography.

A mutagenic principle present in the basic fraction of broiled sardines cooked in the ordinary way was fractionated by high-pressure liquid chromatography using a reversed-phase column. Results indicated that the major mutagenic principle is not identical with any of the mutagens previously isolated from amino acid pyrolysis products, and that a new, unidentified mutagen exists in broiled sardines.

Amino Acids↗

Activation of heterocyclic amines by combinations of prostaglandin H synthase-1 and -2 with N-acetyltransferase 1 and 2.

Cooking of meats produces several heterocyclic amines which are mutagenic and potentially carcinogenic. We found that metabolic activation of one of these heterocyclic amines, the quinoline derivative 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), can be catalyzed by prostaglandin H synthase (PHS) as well as by CYP1A2. N-Acetyltransferase (NAT) increased IQ-DNA adduct formation by either of these pathways. In sonicate from transiently transfected COS cells, NAT1 increased CYP1A2 catalyzed adduct formation 4-fold while NAT2 increased adduct formation 12-fold. Both expressed human and purified ovine PHS-1 and PHS-2 catalyzed IQ-DNA adduct formation. The presence of NAT1 and NAT2 increased PHS-1 catalyzed adduct formation 2.5- and 4-fold, respectively. PHS-2 catalyzed IQ adduct formation was also enhanced by either NAT. The pyridine derivative, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine, also produced by protein pyrolysis, did not form detectable DNA adducts during incubation with PHS. These results indicate that IQ is a substrate for both PHS-1 and PHS-2 and that NAT increases the ability of the resulting IQ metabolites to cause DNA damage. PHS activity, constitutive and induced, as well as NAT polymorphisms should be considered as factors in environmental carcinogenesis.

Acetyltransferases↗

Role of well-done, grilled red meat, heterocyclic amines (HCAs) in the etiology of human cancer.

High-temperature cooking techniques and doneness level of red meat are linked to cancer of various sites, particularly colorectal cancer. In a colorectal adenoma study, we found an elevated risk for red meat consumption that was mainly due to an association with well-done/very well-done red meat. High-temperature cooking methods (i.e. grilling) were also associated with increased risk. We are currently using an HCA database linked to this questionnaire to estimate MeIQx, DiMeIQx and PhIP consumption and determine their association with risk of colorectal adenoma. Similar results on red meat doneness and fried meat were found in a case-control study of lung cancer. Thus, initial positive findings are stimulating the development of a more refined questionnaire instrument and its validation using food diaries, 24-h recalls, biomarkers of internal dose and direct food measurements. Furthermore, the use of these exposure assessment approaches are being used in large prospective studies world wide and should help clarify the role of doneness, cooking practices and pyrolysis products in the etiology of human cancer.

Carcinogens↗

Thermodynamic driving forces for PAH isomerization and growth during thermal treatment of polluted soils.

For a limiting case of thermodynamic equilibrium, the importance of two classes of thermal chemical reactions that modify the structure and bioactivity of polycyclic aromatic hydrocarbons (PAH) was assessed computationally. These reactions are molecular weight (MW) growth by acetylene addition, and intramolecular rearrangement (isomerization). Temperatures (300-1100 degrees C), and the chemical environment (C(2)H(2)/H(2) molar ratios) were selected for relevancy to thermal treatment of PAH-contaminated soils under oxygen-free conditions. Molecular mechanics methods [MM3(92)] were used to compute thermochemical properties for calculation of equilibrium constants, i.e., heats of formation, standard entropies, and heat capacities for 30 PAH with empirical formulae C(14)H(10), C(16)H(10), C(18)H(10), C(18)H(12), C(20)H(10), and C(20)H(12). Included were 11 PAH containing only six-membered rings and 19 PAH containing both five- and six-membered rings. For each of these PAH the calculations predict that with increasing temperature, isomerization increases the "complexity" of the PAH mixture, i.e., the relative abundance of each PAH isomer in the mixture other than the most stable isomer, increases. Isomerization also partially transforms non-mutagens to mutagens, e.g., pyrene and benzo[e]pyrene to fluoranthene and benzo[a]pyrene, respectively, and partially converts cyclopenta[c, d]pyrene (CPEP) and chrysene, both human cell mutagens, to one and three additional human cell mutagens, respectively. Acetylene addition transforms the non-mutagens phenanthrene and pyrene to the mutagens triphenylene and CPEP, respectively. Some of the predicted PAH have been observed elsewhere among the products of aromatics pyrolysis. This study elucidates PAH reactivity for comparison with measurements, and identifies PAH reactions to be monitored and avoided in soil thermal decontamination and other waste remediation processes.

Models, Theoretical↗

Thermal treatment of soils contaminated with gas oil: influence of soil composition and treatment temperature.

Samples of two soils containing different organic matter contents, neat or contaminated with gas oil (diesel fuel oil) at 2.5 wt.% were heated from room temperature to different final temperatures (200-900 degrees C). The experiments, performed in an anaerobic media, simulate conditions pertinent to ex situ thermal desorptive and thermal destructive treatments. The products generated during the heating were collected and light gases were analyzed by gas chromatography. The results indicate that the chemical composition of the soil is a key factor since it strongly influences the quantity and composition of the off-gases. According to the liquid and light gas yields, the gas oil does not affect appreciably the generation of pyrolysis products of the own soil constituents and the gas oil does not suffer significant chemical transformations even at high operating temperatures (e.g. 900 degrees C). With surface areas of 16000 cm(2)/g (Soil A) and 85000 cm(2)/g (Soil B) based on the monolayer adsorbed model, 4 and 20%, respectively, of the original gas oil can be adsorbed. These values are in good agreement with experimental data. Even for high temperatures, the employed thermal treatment is capable to practically remove the gas oil from the soil bed without changing appreciably the original chemical composition of the contaminant.

Carcinogens, Environmental↗

Effects of hot electron emission on a low-conductivity tetracyanoethylene polymer layer including studies of the corrugation of the film surface.

The effect of strong field electron emission (FEE) on a tetracyanoethylene (TCNE) polymer layer was studied by Field Ion Microscopy (FIM) using TCNE and Ne as the imaging gases. The TCNE polymer was formed on each tungsten tip by radical polymerisation before FEE. The FIM images show field emission spots all over the surface of the tip. The FEM images show a random distribution of several field emission areas at the onset of FEE. After sometime at a current of about microA, there is a transition to higher currents at the same voltage, in which the electron emission pattern changes to have only one emitting area. After this transition, two different types of FIM images were observed, depending on the imaging gas that was used. Neon FIM images at low tip voltages show spots in the areas where the electron emission current was greatest, and at much higher voltages these images show emission from other areas with lower surface corrugation. However, the FIM images with TCNE as the imaging gas do not show any differences between the areas with and without electron emission. The FIM images remain as before FEE, which can be explained by the formation of a new polymer by the reaction of the surface layer with the imaging gas. It is assumed that chemically reactive fragments at the polymer/vacuum interface, which are needed for the polymerisation reaction, are formed by pyrolysis and sputtering processes during FEE.

Journal Article↗

Simple method for the determination of choline and acetylcholine by prolysis gas chromatography.

An improved purification procedure is described for the simultaneous assay of endogenous choline and acetylcholine by pyrolysis gas chromatography, particularly for providing a simple and effective method for propionylation of choline in the presence of acetylcholine. The reaction was carried out in acetonitrile solution prepared by dissolving the evaporated residue of the supernatant of brain homogenate. Thus samples for propionylation were prepared without the use of ion-exchange chromatography.

Acetylcholine↗

Chromatographic separations of aromatic carboxylic acids.

The purpose of this review is to present methods of chromatographic analysis of aromatic carboxylic acids. The separation, identification and quantitative analysis of aromatic carboxylic acids are necessary because of their importance as non-steroid antiphlogistic drugs, semi-products of biosynthesis of aromatic amino-acids in plants (phenolic acids), metabolites of numerous toxic substances, drugs and catecholamines. HPLC separation of ionic samples tends to be more complicated than separation of non-ionic compounds. The review describes the dependence of the retention of ionic solutes on pH and solvent composition as well as on the ionic strength of a mobile phase. The application of the ion-suppressing RP-HPLC method using organic modifiers (aqueous buffer solutions) as eluents in aromatic carboxylic acid analysis is also presented. In more difficult cases of analysis the addition of an ion-pairing reagent, such as the quaternary alkylammonium ion, is necessary to obtain satisfactory separations. Hypotheses of ion-pair formation in reversed-phase systems as well as the influence of various agents on the separation of ionic solutes in IP-RP systems are explained. Examples of the application of ion-pair liquid chromatography to the analysis of aromatic carboxylic acids have also been reviewed. The principles and application of ion-exchange chromatography to the purification, isolation and less frequently, to chromatographic analysis are discussed. Polar adsorbents and polar bonded stationary phases are also widely used in carboxylic acid separation in normal-phase systems, mainly by TLC, often coupled with densitometry. The review also shows examples of separation of chiral benzoic acids and their derivatives in LC systems. The possibilities of application of gas chromatography preceded by derivatisation or pyrolysis of acidic compounds and applications of GC-MS and Py-GC-MS coupled methods in identification and quantitation of aromatic carboxylic acids is also reviewed.

Carboxylic Acids↗

Use of porous pyrolytic carbon for analytical and microscale high-performance liquid chromatographic bioseparations.

Porous carbonaceous adsorbent was prepared by carbonization of saccharose in silica gel pores followed by leeching out of the silica matrix. The product of pyrolysis was then deactivated by hydrogenation. The resulting adsorbent shows intermediate sorption properties between those of the highly polar pyrolytic glassy carbon and the hydrophobic graphitized carbon. The microparticulate mesoporous carbon was examined for its use in capillary HPLC separations. The separation of selected stereoisomers in a 320 microm I.D. capillary column packed with the porous carbon particles is described and discussed. Additionally, the porous carbon filled with dextran gel was tested as a material for direct HPLC analysis of drugs in human serum.

Adsorption↗

Gas chromatographic-mass spectrometric detection of anhydroecgonine methyl ester (methylecgonidine) in human serum as evidence of recent smoking of crack.

The discrimination between smoking of crack and other routes of cocaine application has forensic implications. The pyrolysis product anhydroecgonine methyl ester (AEME, methylecgonidine) has been found to be a marker for smoked cocaine. An improved method for the determination of AEME in serum was developed, consisting of mixed phase solid-phase extraction and GC-MS. Special care was taken for the volatility of AEME and tert.-butyldimethylsilylation was used for derivatization. Thus AEME could be determined for the first time in 13 serum samples from living subjects. The concentrations found were in a range of 3 to 34 ng/ml, a correlation with the storage time of the samples or with benzoylecgonine concentrations could not be found.

Acetamides↗

Micro-thermal analysis: scanning thermal microscopy and localised thermal analysis.

Micro-thermal analysis combines the imaging capabilities of atomic force microscopy with the ability to characterise, with high spatial resolution, the thermal behaviour of materials. The conventional AFM tip is replaced by a miniature heater/thermometer which enables a surface to be visualised according to its response to the input of heat (in addition to measuring its topography). Areas of interest may then be selected and localised thermal analysis (modulated temperature calorimetry and thermomechanical analysis) carried out. Localised dynamic mechanical measurements are also possible. Spatially resolved chemical analysis can be performed using the same basic apparatus by means of pyrolysis gas chromatography-mass spectrometry or high-resolution photothermal infrared spectrometry.

Acetaminophen↗

A protocol for the forensic analysis of condom and personal lubricants found in sexual assault cases.

In sexual assault cases, lubricant trace evidence may supplement biological evidence, or may be the primary physical evidence where biological evidence is unavailable. This study considered a total of 50 lubricants from condoms and personal lubricant products available in Australia. Differentiation of the samples was attempted using fluorescence examination, Fourier transform infrared spectroscopy (DRIFTS), gas chromatography-mass spectrometry, liquid chromatography-tandem mass spectrometry, and pyrolysis gas chromatography-mass spectrometry. Eleven of the samples were uniquely identified by the analysis scheme, while the remainder of the samples were separated into nine groups. As a result of this study, a recommended protocol for the detection and analysis of an "unknown" biological swab was produced.

Australia↗