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Characterization and comparison of two ligno-cellulosic substrates by (13)C CP/MAS NMR, XPS, conventional pyrolysis and thermochemolysis.

Ligno-cellulosic substrates (LCSs) isolated from wheat straw and bran exhibit high complexing capacities and may have important applications for metal removal from industrial effluents. These two LCSs were examined in the present work by spectroscopic and pyrolytic methods (solid state cross polarization magic angle spinning (CP/MAS) (13)C NMR, XPS, conventional Curie pyrolysis (Cupy)/GC/MS, and TMAH thermochemolysis/GC/MS). This combined study highlighted the limitation of some of the above methods when applied to ligno-cellulosic materials and the resulting biases and the usefulness of TMAH thermochemolysis. A large difference in composition was observed between bran- and straw-LCS due to a much higher contribution of alkyl moieties in the former. These moieties correspond to fatty acids esterified to the ligno-cellulosic macromolecular structure and such carboxylic functions should play an important role for metal complexation.

Journal Article↗

Forensic discrimination of photocopy and printer toners. III. Multivariate statistics applied to scanning electron microscopy and pyrolysis gas chromatography/mass spectrometry.

Copy toner samples were analyzed using scanning electron microscopy with X-ray dispersive analysis (SEM-EDX) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). Principal component and cluster analysis of SEM data for 166 copy toner samples established 13 statistically different subgroups, with the presence or absence of a ferrite base being a major division. When toners were compared for which both SEM and reflection-absorption infrared spectral data were available, 41% of the samples could be assigned to specific manufacturers. Py-GC/MS on poly(styrene:acrylate)-based toners produced eight peaks relevant to toner differentiation. One third of the toners clustered in a small group that contained five statistically different subgroups. Of the 57 toners for which both Py-GC/MS and SEM data were available, 31 could be differentiated using the combined analytical results. The synergy of the complementary information provided by Py-GC/MS and SEM narrows matching possibilities for forensic investigations involving copied or laser printed documents.

Journal Article↗

Degradation efficiency and molecular size alteration during the aerobic microbial treatment of lignite pyrolysis deposit water.

Investigation into aerobic biological degradation were carried out as part of an extensive programme designed to facilitate the cheap remediation of a pyrolysis waste-water deposit. Attention was focused on the processes of carbon conversion by different populations. The susceptibility of a body of lignite-processing deposit water to microbiological degradation was examined in batch investigations in a Sapromat system and in continuous bench-scale fermenter cultivations, with respect to nutrient supply, inoculation culture and molecular size distribution. It was found that degradation best occurs with an adapted mixed culture. The autochthonous culture removes 30% less dissolved organic carbon (DOC) and has a 40% higher specific oxygen demand. A shortage of phosphorus, investigated with a view to avoiding additional eutrophication problems in the open water in the case of in situ remediation, causes reduced DOC degradation and significantly higher specific oxygen demand. The biological process is overlapped by abiotic oxidation. During aerobic treatment, a concentration of colour-giving aromatic substances of between 0.5 kDa and 5 kDa was observed. This phenomenon is caused by the oxidation of low- and high-molecular-mass compounds. The removal of DOC is limited to 65% and mainly occurs in the range below 0.5 kDa (30%) and in the 0.5-1 kDa range (12%); the removal is negligible in the ranges 1-3 kDa (0.8%) and 3-5 kDa (2%) and a little higher in the ranges 5 kDa-0.3 micron (5%) and above 0.3 micron (6%). In the investigations it was discovered that DOC removal causes in the ranges below 0.5 kDa, 0.5-1 kDa and 5 kDa-0.3 micron mainly as a result of degradation, but the range above 0.3 micron is chiefly caused by bioadsorption. Aerobic microbiological treatment is able to remove most low-molecular-mass substances. In order to remove the macromolecular and colour-giving part of the deposit water, an additional treatment stage, e.g. flocculation, is required.

Biodegradation, Environmental↗

Taxonomic discrimination of higher plants by pyrolysis mass spectrometry.

Pyrolysis mass spectrometry (PyMS) is a rapid, simple, high-resolution analytical method based on thermal degradation of complex material in a vacuum and has been widely applied to the discrimination of closely related microbial strains. Leaf samples of six species and one variety of higher plants (Rosa multiflora, R. multiflora var. platyphylla, Sedum kamtschaticum, S. takesimense, S. sarmentosum, Hepatica insularis, and H. asiatica) were subjected to PyMS for spectral fingerprinting. Principal component analysis of PyMS data was not able to discriminate these plants in discrete clusters. However, canonical variate analysis of PyMS data separated these plants from one another. A hierarchical dendrogram based on canonical variate analysis was in agreement with the known taxonomy of the plants at the variety level. These results indicate that PyMS is able to discriminate higher plants based on taxonomic classification at the family, genus, species, and variety level.

Hot Temperature↗

Characterization of different decomposition stages of biowaste using FT-IR spectroscopy and pyrolysis-field ionization mass spectrometry.

The decomposition stage and stabilization of organic matter in biowaste (mixture of yard waste and kitchen waste), originating from an open windrow process, were investigated using Fourier transform infrared (FT-IR) spectroscopy and pyrolysis-field ionization mass spectrometry (Py-FIMS). These investigations provided detailed information about chemical constituents and their behavior during the composting process. The chemical compounds were classified by their molecular signals in Py-FIMS. Multivariate statistical analysis revealed, that during the composting process, the group containing lipids, fatty acids and other chemical compounds with aliphatic skeletons changed the most. Corresponding with Py-FIMS findings changes were observed in absorbance bands of infrared spectra that reflect this group of organic compounds: the aliphatic methylene bands at 2925 and 2850 cm(-1), the band of C=O vibrations of carboxylates at 1640 cm(-1) , the O-H in-plane bend of carboxylic acids, the CO2 stretch of carboxylates and the CH2 group of alkanes at around 1430 cm(-1). During decomposition these bands decreased up to a steady level that indicated stabilization. The band at 1260-1240 cm(-1) that can be assigned to the C--O stretch of carboxylic acids or to the C-N stretch of amides and the band of aromatic amines at 1320 cm(-1) disappeared completely. The nitrate band at 1384 cm(-1) appeared at a later stage of the composting process. The relative increase of chemical compounds like moieties of lignin, humic acids and tannins in the composted material contributed to the aromatic C=C band at around 1640 cm(-1).

Biodegradation, Environmental↗

Metabolic activation of Trp-P-2, a tryptophan-pyrolysis mutagen, by isolated rat hepatocytes.

Metabolic activation of a tryptophan-pyrolysis product, 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2), by isolated rat hepatocytes was studied. The substrate (Trp-P-2) disappearance by hepatocytes from untreated rats was slow, but enhanced by 3-methylcholanthrene (MC) pretreatment of rats. The covalent binding of Trp-P-2 to cellular macromolecules was detected in hepatocytes from untreated rats. The amount of covalent binding of Trp-P-2 to protein and RNA was greater than that to DNA. The covalent binding to Trp-P-2 to DNA, RNA and protein in hepatocytes from untreated rats was about 5-10 times less than that in hepatocytes from MC-pretreated rats. 7,8-Benzoflavone strongly inhibited the substrate disappearance and the binding of Trp-P-2 to DNA in hepatocytes from MC-pretreated rats. These results indicate that Trp-P-2 is metabolically activated by the P-448 type of cytochrome P-450 which is induced by MC. Diethylmaleate enhanced by about 50% the binding of Trp-P-2 to DNA in hepatocytes from MC-pretreated rats. On the other hand, cysteine inhibited the binding of Trp-P-2 to DNA with a concomitant reduction in the accumulation of the active metabolite, N-hydroxy-Trp-P-2 (N-OH-Trp-P-2). Sulfhydryl compounds seemed to play important roles in the detoxification of Trp-P-2.

Animals↗

Pyrolysis of inulin, glucose, and fructose.

The pyrolytic behavior of inulin, a (2-->1)-linked fructofuranan, is described. Parallel investigations of the pyrolysis of glucose and of fructose were conducted to supplement the inulin results and to aid comparison with previous results from glucans. Effects of neutral and basic additives are emphasized. As with glucans, the addition of such additives (especially basic) increases the yields of the one-, two-, and three-carbon products (as well as of hexosaccharinolactones), while generally decreasing the yields of anhydro sugar and furan derivatives. The former products include glycolaldehyde, acetol, dihydroxy-acetone, acetic acid, formic acid, and lactic acid. Mechanistic speculations are made regarding the origins of these compounds, as well as of furan derivatives and saccharinic acid lactones. Parallels with alkaline degradation are considered.

Carbohydrate Sequence↗

1,5-Anhydro-beta-L-arabinofuranose from pyrolysis of plant cell wall materials (biomass).

Three types of agricultural waste material having a significant content of L-arabinose have been subjected to mild, vacuum pyrolysis, and yields of 1,5-anhydro-L-arabinofuranose (1) determined. In corn bran, approximately 40% of the L-arabinose is converted into 1, and this conversion is increased to 78% when the bran is subjected to prior acid washing. The inner and outer barks of ponderosa pine give approximately 30% conversion of their L-arabinose content into 1, but orange peel gives only 9% conversion. A mechanism is postulated involving pyrolytic scission of pendant L-arabinofuranose units from polysaccharides, with cyclization to produce 1.

Agriculture↗

Characterisation of polysaccharides by in-source pyrolysis positive- and negative-ion direct chemical ionisation-mass spectrometry.

Series of oligosaccharide ions have been generated from a range of polysaccharides by the application of in-source pyrolysis mass spectrometry, using both ammonia positive-ion chemical ionisation and negative-ion chlorine-nucleophilic-addition ionisation. Glucans with alpha-(1----6), beta-(1----6), alpha-(1----4), beta-(1----4), beta-(1----3), and beta-(1----2) linkages were studied, together with pentosans, xyloglucans, and an arabinogalactan. The series of ions correspond to intact, desorbed oligosaccharides with a terminal anhydro-sugar unit, and to similar oligosaccharides with attached sugar ring-cleavage fragments. The ions generated are dependent on the position of the linkage and ring size, and retain significant information on the structure of the original polysaccharide.

Carbohydrate Sequence↗

Di-D-fructose dianhydrides from the pyrolysis of inulin.

Inulin was pyrolyzed in air to produce di-D-fructose dianhydrides (DFDAs) in approximately 26% yield, three of which were identified by MS, NMR, and comparison with literature data. The mass spectra of the per-O-trimethylsilyl derivatives of the DFDAs are discussed. A mechanism is proposed for the formation of DFDAs from inulin during pyrolysis.

Disaccharides↗

Metabolic activation of glutamic acid pyrolysis products, 2-amino-6-methyldipyrido[1,2-a:3',2'-d]imidazole and 2-amino-dipyrido[1,2-a:3',2'-d]imidazole, by purified cytochrome P-450.

Metabolic activation by cytochrome P-450 of glutamic acid pyrolysis products, 2-amino-6-methyldipyrido(1,2-a:3',2'-d)imidazole (Glu-P-1) and 2-amino-dipyrido(1,2,-a:3',2'-d)imidazole (Glu-P-2), to mutagenic metabolites was studied using Salmonella typhimurium TA98 as a tester strain. Cytochrome P-450, NADPH-cytochrome P-450 reductase and NADPH were essential requirements for the activation of these compounds. Of the four forms of cytochrome P-450 examined, polychlorinated biphenyls (PCB) P-448 and 3-methylcholanthrene (MC) P-448 purified from liver microsomes of rats treated with a PCB mixture and MC, respectively, showed high activity in the activation of both Glu-P-1 and Glu-P-2. The presence of three metabolites from Glu-P-1 or Glu-P-2 was demonstrated by high performance liquid chromatographic (HPLC) analysis. Among the metabolites of Glu-P-1, two metabolites were mutagenic without any further enzymatic activation. In accordance with the results of a mutation assay, PCB P-448 also exhibited higher activity to form the major mutagenic metabolite of Glu-P-1. The major active metabolite of Glu-P-1 was characterized as N-hydroxy-Glu-P-1 by chemical analysis using oxidizing and reducing reagents and by mass spectrometry.

Animals↗

Simultaneous measurement of acetylcholine and choline in brain by pyrolysis-gas chromatography-mass spectrometry.

Pyrolysis-gas chromatography and chemical ionization mass fragmentography were combined to develop a specific, simple and rapid method for simultaneously measuring endogenous and stable isotopic variants of acetylcholine and choline with a detection limit of approximately 10(-12) mol. The recovery and reproducibility of the method are excellent, and the method is suitable for measuring acetylcholine and choline in discrete regions of rat brain and to measure incorporation of choline into acetylcholine, both of which uses are demonstrated. This method affords easy analysis of 40 samples in a working day. The new technique used to extract compounds from tissues and the modified gas flow arrangement may be useful to measure other compounds as well.

Acetylcholine↗

Synthesis of novel tellurium containing analogues of choline and acetylcholine and their quantitation by pyrolysis-gas chromatography-mass spectrometry.

Methods for the synthesis and quantitation of the novel choline analogues, telluronium choline and acetyltelluronium choline, are described. An assay procedure utilizing pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) with cold trapping was developed with [2H4]telluronium choline and [2H4]acetyltelluronium choline as internal standards. The telluronium compounds were ion-pair extracted from tissue with dipicrylamine, washed with 2-butanone, and pyrolyzed prior to GC-MS analysis. The compounds were monitored using selected ion monitoring at m/z 232 and m/z 190 for acetyltelluronium and telluronium choline, respectively, and at m/z 236 and m/z 194 for the analogous deuterated internal standards. The assay was linear over a range of 20 pmol-20 nmol of compound taken through the assay.

Gas Chromatography-Mass Spectrometry↗

Detection of Trp-P-1 and Trp-P-2, carcinogenic tryptophan pyrolysis products, in dialysis fluid of patients with uremia.

In order to estimate the exposure levels of mutagenic and carcinogenic heterocyclic amines in humans, we developed a high-performance liquid chromatography method to detect 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1) and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2) in dialysis fluid of patients with uremia. Using this methods, dialysis fluid of 12 patients who had received hemodialysis treatment or continuous ambulatory peritoneal dialysis was examined. Trp-P-1 was detected in dialysate of all uremic patients (727 +/- 282 pmoles, n = 12). In patients who had been treated with continuous ambulatory peritoneal dialysis, the average amount of Trp-P-1 found in whole dialysate (6 l) per day was 710 +/- 203 pmoles (mean +/- S.D., n = 8). Moreover, Trp-P-2 could be detected in 5 out of 12 patients (206 +/- 85 pmoles, n = 5). These results indicate that patients with uremia are actually exposed to carcinogenic tryptophan pyrolysis products. The average exposure level of Trp-P-1 in uremic patients apparently exceeded 710 pmoles (150 ng) per day.

Carbolines↗

Exposure level monitor of a carcinogenic glutamic acid pyrolysis product in rabbits.

In order to determine a suitable indicator for estimating the exposure levels of the dietary carcinogen 2-amino-6-methyldipyrido[1,2-a:3',2'-d]imidazole (Glu-P-1), a carcinogenic glutamic acid pyrolysis product, the levels of Glu-P-1 bound to blood components were monitored for 8 weeks by a high-performance liquid chromatography method after the dietary carcinogen was administered as single oral doses (0.2-50 mg) to rabbits. In all rabbits dosed with Glu-P-1, Glu-P-1 in erythrocytes was detectable even on day 42 after administration. Glu-P-1 in plasma disappeared faster than did Glu-P-1 in erythrocytes. Glu-P-1 levels in rabbit hemoglobin were linearly related to administered doses at all points of time investigated. The results suggest that Glu-P-1 covalently bound to hemoglobin is very suitable for monitoring long-term exposure levels.

Administration, Oral↗

Pyrolysis mass spectrometry of Listeria monocytogenes isolates from sheep.

Forty-eight isolates of Listeria monocytogenes from sheep and silage, involved in five small outbreaks of listeriosis, were compared by pyrolysis mass spectrometry (PyMS). The method clustered isolates from single animals, and showed that epidemiologically associated isolates were closely related to each other. PyMS is a simple technique capable of analysing large numbers of samples daily, and its application in veterinary studies should help to elucidate the epidemiology of listeriosis.

Animals↗

Differentiation between mycobacteria of the Mycobacterium tuberculosis complex by pyrolysis mass spectrometry.

32 isolates belonging to the Mycobacterium tuberculosis complex were examined by pyrolysis mass spectrometry (PyMS). This technique demonstrated that recent clinical isolates of M. africanum were indistinguishable from those of M. bovis and together formed a homogeneous group distinct from M. tuberculosis. Isolates of BCG were heterogeneous and more closely related to laboratory-adapted strains of M. tuberculosis than to recent isolates of either M. tuberculosis or M. bovis. PyMS is a simple and inexpensive technique which gives interesting information on the relationships between members of the M. tuberculosis complex and can make the clinically important distinction between strains of M. bovis and M. tuberculosis accurately and much more rapidly than conventional techniques.

Mass Spectrometry↗

Interaction between phencyclidine and its pyrolysis product, 1-phenylcyclohexene.

The interaction between phencyclidine (PCP) and its pyrolysis product, 1-phenylcyclohexene (PC), at metabolic level was evaluated in Swiss male mice (21-24 g). PC (1.1, 2.2 and 4.4 mmol/kg/day for 4 days, IP, in corn oil) treatment to mice induced the in vitro metabolism (p less than 0.05) of amidopyrine (17%), aniline (12%), phenacetin (62-100%), pentobarbital (20-26%), PCP (25-80%) and benzo[a]pyrene (81-147%) in the 9000 g liver fraction and the hepatic microsomal contents of cytochrome P-450 (18-42%). The induction of the mixed function oxygenase (MFO) system was consistent with the decreases in the concentrations of IP administered pentobarbital (0.27 mmol/kg, in saline) and PCP (16.4, 32.8 and 65.6 mumol/kg, in saline) in the serum, brain, liver and kidneys of PC pretreated mice. At 1 hr after the above doses of PC, the in vitro metabolism of amidopyrine, aniline, or phenacetin was not inhibited. However, the biotransformation of benzo[a]pyrene was inhibited by 33 to 45%. Though PC after a single dose did not alter the tissue concentrations of PCP, it increased the pentobarbital concentrations in the tissues studied (p less than 0.05). These results indicate that PC has a potential to induce the MFO system after the 4-day treatment. This property of PC plays an important role in the reduction of the action of PCP by enhancing its metabolism, thereby decreasing its tissue levels.

Aminopyrine N-Demethylase↗