Volatile Compounds in Pyroligneous Liquids from Karamatsu and Chishima-sasa

Volatile components in pyroligneous liquids obtained from Karamatsu and Chishima-sasa. were extracted, fractionated into neutral/basic and acidic fractions, and identified by gas chromatography-mass spectrometry. In the neutral/basic fraction, 118 components were identified. Cyclic and acyclic ketones, pyridine derivatives, pyrazine derivatives and furan derivatives were important odorous components. Sixty-nine compounds were identified in the acidic fraction. The main groups were carboxylic acids and phenol compounds. The concentrations of alkyl phenols were almost the same between Karamatsu and Chishima-sasa, but there were large differences in the contents of 2-methoxyphenol derivatives and 2,6-dimethoxyphenol derivatives between them.     

Fractionation and Identification of Volatile Compounds in Patis,a Philippine Fish Sauce

Commercial Philippine fish sauce (Patis) was steam-distilled and the distillate was fractionated into four fractions, neutral, basic, acidic and phenolic and each fraction was analyzed using gas chromatography and gas chromatography-mass spectrometry.

As a result of this study, a total of 66 compounds were identified in Patis, 14 of which were only a tentative identification. Out of these 66 identified compounds, 40 identified compounds have not been reported in previous studies on fish sauces. These identified compounds include 19 acids, 14 alcohols, 12 nitrogen containing compounds, 5 esters, 3 sulfur containing compounds, 1 phenol, 3 carbonyls, 7 hydrocarbons and 2 others. In the acidic fraction, 5 acids were considered major constituents which accounted for about 98% of the total acids. n-Butanoic acid was found to be the most abundant accounting for about 50% of the total acids.     

Volatile Flavor Compounds of Boiled Buckwheat Flour

Volatile flavor compounds of boiled buckwheat flour were collected using a Likens and Nickerson apparatus type and were fractionated into acidic, weak acidic, basic and neutral fractions. The neutral fraction was further fractionated by silica gel column chromatography. All fractions were analyzed by gas chromatography and gas chromatography-mass spectrometry.

Two hundred and nine compounds were thus identified. Among them, 168 were newly identified as volatile flavor compounds of buckwheat flour; special note is made of 2-(1′-ethoxyethyl)pyrazine and 2-(1′-ethoxyethyl)-5-methylpyrazine being found which are compounds previously unreported in any literature.     

Bioassay-directed chemical analysis and detection of mutagenicity in ambient air of the coke oven

In the present study, we summarize the results of studies on the mutagenic potential of the main fractions and subfractions of extractable organic material (EOM) in the ambient air at the workplaces of the coke oven. The objective of our experiments was to apply the Bioassay-Directed Chemical Analysis (with the use of the Ames test) for the identification of the differences in the mutagenicity of these fractions, in relationship to the complex mixture of EOM in occupational air. From the evaluation of results, it is possible to deduce the following conclusions: (1) The comparison of the mutagenicity in the main fractions (basic, acidic, neutral) demonstrates the existence of differences in mutagenic potential. Of the total mutagenicity, 20.4% is in the basic fraction, 25.4% in the acidic fraction and 54.2% in the neutral fraction. (2) In general, 90.1% of the mutagenicity found in the basic, acidic and neutral fractions together was associated with the requirement of metabolic activation in vitro (+S9). In the case of the neutral fraction, it was 51.8%. (3) These results also suggest that frameshift mutations are the major component (53.8%) of the total mutagenicity of the main fractions. (4) With regards to the mutagenicity of organic compounds in the neutral fraction it appeared that genotoxicants of its subfractions (slightly and moderately polar and aromatic) play the main role. Carcinogenic aromatic hydrocarbons (PAH) and genotoxic nitrocompounds play an important role as determinants of the mutagenic potential of complex mixtures of harmful compounds in ambient air. This is confirmed first by the results of short-term bacterial tests.     

Nitrite consumption in ischemic rat heart catalyzed by distinct blood-borne and tissue factors

Nitric oxide (NO) may limit myocardial ischemia-reperfusion injury by slowing the mitochondrial metabolism. We examined whether rat heart contains catalysts potentially capable of reducing nitrite to NO during an episode of regional myocardial ischemia produced by temporary coronary artery occlusion. In intact Sprague-Dawley rats, a 15-min coronary occlusion lowered the nitrite concentration of the myocardial regions exhibiting ischemic glucose metabolism to approximately 50% that of nonischemic regions (185 +/- 223 vs. 420 +/- 203 nmol/l). Nitrite was rapidly repleted during subsequent reperfusion. The heart tissue tested in vitro acquired a substantial ability to consume nitrite when made hypoxic at neutral pH, and this ability was slightly enhanced by simultaneously lowering the pH to 5.5. More than 70% of this activity could be abolished by flushing the coronary circulation with crystalloid to remove trapped erythrocytes. Correspondingly, erythrocytes demonstrated the ability to reduce exogenous nitrite to NO under hypoxic conditions in vitro. In erythrocyte-free heart tissue, the nitrite consumption increased fivefold when the pH was lowered to 5.5. Approximately 40% of this pH-sensitive increase in nitrite consumption could be blocked by the xanthine oxidoreductase inhibitor allopurinol, whereas lowering the Po(2) sufficiently to desaturate myoglobin accelerated it further. We conclude that rat heart contains several factors capable of catalyzing ischemic nitrite reduction; the most potent is contained within erythrocytes and activated by hypoxia, whereas the remainder includes xanthine oxidoreductase and other pH-sensitive factors endogenous to heart tissue, including deoxymyoglobin.     

Nitrite uptake into intact pea chloroplasts : I. Kinetics and relationship with nitrite assimilation

The uptake of nitrite into intact pea chloroplasts was observed and its relationship with internal nitrite reduction was assessed. Net nitrite uptake exhibited saturation kinetics and an alkaline pH preference. This evidence questioned the accepted major role for neutral HNO₂ permeation and its reported influence on photosynthesis. The possible involvement of a nitrite permeation channel or transport protein is discussed. Net nitrite uptake curves were closely comparable with those for nitrite reduction within the chloroplast. Net nitrite uptake into chloroplasts was profoundly influenced by darkness, incubation temperature, and plant nitrate nutrition. Of several inorganic salts tested, sulfite was the only anion to exhibit a distinct inhibition of nitrite uptake. In contrast, nitrite uptake could be stimulated by the presence of certain cations, particularly at acidic pH values. It was concluded that nitrite uptake was closely related to stromal pH, internal nitrite accumulation, and nitrite reduction. The possible dependence of nitrite reduction on nitrite uptake rather than electron transport is discussed. External ATP and NAD(P)H did not significantly affect net nitrite uptake. This suggested that cytoplasmic ATP or reductant could not directly support nitrite uptake and, possibly, nitrite assimilation.     

Nitrite reduction in Veillonella alcalescens.

Nitrite reduction was examined in Veillonella alcalescens C-1, and obligate anaerobe with an ATP-yielding nitrate-reducing system. Hydrogen donors for nitrite reduction included hydrosulfite, hydrogen gas, and pyruvate, but not pyridine nucleotides, in the presnece or absence of flavins. Pyruvate-linked nitrite reduction was not inhibited by 4,4,4-trifluoro-1-(2-thienyl) 1,3-butanedione, dicoumarol, or 2-heptyl-4-hydroxy-quinoline-N-oxide. The noninvolvement of membrane-bound factors was supported by the fact that 100% of pyruvate-linked activity remained in the soluble fraction after fractionation of crude extracts by ultracentrifugation. Using DEAE-cellulose column chromatography, however, the participation of ferredoxin in nitrite reduction was demonstrated. The product of nitrite reduction appeared to be ammonia, as determined from H2-to-NO2- ratios. Nitrite reductase was induced by nitrate or nitrite and was repressed by increased levels of reduced nitrogenous compounds.     

亚硝酸盐影响Lactobacillus brevis 4903发酵的研究

通过研究可知,亚硝酸盐对Lactobacillusbrevis4903发酵有抑制作用,环境中亚硝酸盐一旦分解掉,这种抑制作用就会被解除。分析其原因:①亚硝酸盐抑制了乳酸菌生长,从而抑制了乳酸发酵;②在发酵初期可能因亚硝酸盐还原酶的作用,使亚硝酸盐酶解生成NH3,NH3中和了乳酸菌生成的酸(H ),从而使环境pH值的下降和酸的积累变得缓慢。     

Volatile Flavor Components of Dried Bonito (Katsuobushi) II. From Neutral Fraction

The aqueous extract of dried bonito (Katsuobushi) was distilled under reduced pressure. The resulting distillate with diethyl ether and the extract was separated into acidic, phenolic, basic and neutral fractions. The neutral fraction was further fractionated into ten sub-fractions by silica gel column chromatography. All these sub-fractions were analyzed by gas chromatography and gas chromatography-mass spectrometry.

One hundred and sixty-five compounds were identified and 12 compounds were tentatively identified from the neutral fraction. Among them, 111 compounds were newly identified as flavor components of Katsuobushi.     

Possible role of hydrogen cyanide in chemical evolution investigation of the proposed direct synthesis of peptides from hydrogen cyanide

The compounds formed upon oligomerization of cyanide in aqueous solution have been separated into acidic, basic, amphoteric and neutral fractions. Urea is the major constituent of the neutral fraction and oxalic acid is present in the acidic fraction. The oligomerization mixtures isolated in the acid, basic and amphoteric fractions consist of low molecular weight substances which yield amino acids on acid hydrolysis. Citrulline has been identified as a major amino acid released on acid hydrolysis of the product mixture. No amino acids are released from the oligomerization mixture by pronase or carboxypeptidase A. This catalyzed hydrolysis demonstrates that this system does not contain compounds with peptide links. The oligomerization products are susceptible to oxidizing agents but are affected little by reducing agents.     

Collection and Identification of Allelopathic Compounds from the Undisturbed Root System of Bigalta Limpograss (Hemarthria altissima)

Collection of allelopathic chemicals from the undisturbed plant root system is difficult because of their low concentrations and the high level of contaminants in growth media such as soil. A new approach for the continuous trapping of quantities of extracellular chemicals from donor plants is described. Bigalta limpograss (Hemarthria altissima), a tropical forage with allelopathic activities, was established in sand culture. Nutrient solution was circulated continuously through the root system and a column containing XAD-4 resin. Extracellular hydrophobic metabolites were selectively adsorbed by the resin, while inorganic nutrients were recycled to sustain plant growth. Columns were eluted with methanol and the eluate separated into neutral, acidic, and basic fractions. Bioassays of trapped root exudates using lettuce seed combined with paper and thin layer chromatography showed that the inhibitors were mainly phenolic compounds. The active neutral fraction was methylated and analyzed by gas chromatography-mass spectrometry. Twelve compounds were identified, with two additional compounds tentatively identified. 3-Hydroxyhydrocinnamic, benzoic, phenylacetic, and hydrocinnamic acids were the major rhizospheric compounds with known growth regulatory activities.     

Chemical composition of acid–base fractions separated from biooil derived by fast pyrolysis of chicken manure

Our earlier investigations on the chemical composition of biooils derived by the fast pyrolysis of chicken manure revealed the presence of more than 500 compounds. In order to simplify this heterogeneous and complex chemical system, we produced four biooil fractions namely strongly acidic fraction A, weakly acidic fraction B, basic fraction C and neutral fraction D on the basis of their solubilities in aqueous solutions at different pHs. The yield (wt/wt.%) for fraction A was 3%, for fraction B 21.3%, for fraction C 2.4% and for fraction D 32.4%, respectively. The four fractions were analyzed by elemental analyses, Fourier Transform infrared spectrophotometry (FTIR), ¹H and ¹³C nuclear magnetic spectroscopy (NMR), and electrospray ionization mass spectrometry (ESI-MS). The major components of the four fractions were saturated and unsaturated fatty acids, N-heterocyclics, phenols, sterols, diols and alkylbenzenes. The pH separation system produced fractions of enhanced chemical homogeneity.     

Nitrate Reduction to Nitrite, a Possible Source of Nitrite for Growth of Nitrite-Oxidizing Bacteria

Growth yields and other parameters characterizing the kinetics of growth of nitrite-oxidizing bacteria are presented. These parameters were measured during laboratory enrichments of soil samples with added nitrite. They were then used to reanalyze data for nitrite oxidizer growth in a previously reported field study (M. G. Volz, L. W. Belser, M. S. Ardakani, and A. D. McLaren, J. Environ. Qual. 4:179-182, 1975), where nitrate, but not nitrite or ammonium, was added. In that report, analysis of the field data indicated that in unsaturated soils, the reduction of nitrate to nitrite may be a significant source of nitrite for the growth of nitrite oxidizers. A yield of 1.23 × 10⁴ cells per μg of N was determined to be most appropriate for application to the field. It was determined that if nitrite came only from mineralized organic nitrogen via ammonium oxidation, 35 to 90% of the organic nitrogen would have had to have been mineralized to produce the growth observed. However, it is estimated that only about 2% of the organic nitrogen could have been mineralized during the growth period. Thus, it appears that another source of nitrite is required, the most likely being the reduction of nitrate to nitrite coupled to the oxidation of organic matter.     

Sources and Sinks for Ammonia and Nitrite on the Early Earth and the Reaction of Nitrite with Ammonia

An analysis of sources and sinks for ammonia and nitrite on the early Earth was conducted. Rates of formation and destruction, and steady state concentrations of both species were determined by steady state kinetics. The importance of the reaction of nitrite with ammonia on the feasibility of ammonia formation from nitrite was evaluated. The analysis considered conditions such as temperature, ferrous iron concentration, and pH. For sinks we considered the reduction of nitrite to ammonia, reaction between nitrite and ammonia, photochemical destruction of both species, and destruction at hydrothermal vents. Under most environmental conditions, the primary sink for nitrite is reduction to ammonia. The reaction between ammonia and nitrite is not an important sink for either nitrite or ammonia. Destruction at hydrothermal vents is important at acidic pH's and at low ferrous iron concentrations. Photochemical destruction, even in a worst case scenario, is unimportant under many conditions except possibly under acidic, low iron concentration, or low temperature conditions. The primary sink for ammonia is photochemical destruction in the atmosphere. Under acidic conditions, more of the ammonia is tied up as ammonium (reducing its vapor pressure and keeping it in solution) and hydrothermal destruction becomes more important.     

Genotoxicity and PAC analysis of particulate and vapour phases of environmental tobacco smoke

Samples of indoor air were collected from an office room (88 m3) both before smoking and during experimental smoking of 96 cigarettes by 10 persons within 6 h. The particulates were collected on glass-fibre filters and the vapour-phase compounds on XAD-2 resin. The samples were extracted with acetone and analysed quantitatively for polycyclic aromatic compounds and qualitatively with GC-MS. The extracts of filters and XAD-2 resins were fractionated into neutral/acidic and 2 basic (strong and weak bases) fractions; all these fractions were tested with the sister-chromatid exchange (SCE) assay in Chinese hamster ovary (CHO) cells and with the Salmonella/microsome test (strain TA98). Total concentrations of PAC were 205 ng/m3 in the background sample and 1207 ng/m3 after contamination by cigarette smoking. The total PAC concentrations were 4-6 times higher in the vapour phase than in the particulate phase. The fractions of the particulate samples collected before smoking showed mainly marginal genotoxic activity, whereas after smoking their genotoxicity increased dramatically. The fractions of the vapour phase samples were not genotoxic before smoking, but after smoking the neutral/acidic and strong basic fractions induced responses in both assays. The SCE assay was more sensitive towards the vapour-phase mutagens of environmental tobacco smoke (ETS). The relative responses of the two basic fractions, whereas the fraction containing neutral and acidic compounds was the most potent in the SCE assay. In the Salmonella test, the mutagenic activity was mainly detected with metabolic activation, while the induction of SCE in CHO cells was also seen without an exogenous metabolic activation system.     

Ethanol extraction of free amino acids from soil

Summary A technique was developed for extracting and analyzing the free amino acid fraction of soil. Ethanol was used as an extracting agent. Ethanolextraction curves showed 20 per cent ethanol was the optimum percentage for extraction. Extraction-time curves indicated 18 to 20 hours of extraction with 20 per cent ethanol produced satisfactory results.The free amino acid fraction of soil was characterized and the limitations of the technique were determined. The naturally occurring amino acids extracted with 20 per cent ethanol were limited to acidic and neutral amino acids; basic amino acids were not extracted in sufficient quantities to permit detection. Based on the percent recovery of amino acids incorporated into soil and extracted with 20 per cent ethanol 90 to 95 per cent of the acidic, 80 to 85 per cent of the neutral and 1 to 5 per cent of the basic amino acids used were recovered with the technique.     

Differential decomposition of humic acids by marine and estuarine bacterial communities at varying salinities

Humic substances (HS) constitute 50–80% of total dissolved organic matter (DOM) in freshwaters but in the open ocean <3%, indicating that large fractions of DOM and HS are removed in the estuarine and coastal zone. In order to assess the role of bacteria in this removal, we conducted experiments in flow-through cultures to examine the decomposition of peat bog-born humic acids (HA) by marine (salinity 30, Exp1) and estuarine (salinity 10, Exp2) bacterial communities. After ~70 days 40–>60% of the HA were decomposed. Highest fractions were decomposed in treatments in which the bacterial communities were fed by HA media of a foreign salinity, e.g., of 14 in Exp1 and of 28 in Exp2. Some of the HA material was not decomposed but broken down to smaller moieties entering the fulvic acid (FA) fraction. The analysis of the HA media and their residuals after bacterial decomposition by pyrolysis GC/MS showed that individual organic compounds were decomposed. In Exp1, 32 aliphatic and aromatic compounds, including lignin biomarkers, were detected in the HA medium of which mainly aliphatic compounds were decomposed. In Exp2, 49 compounds were detected of which ~40–60% were not detected any more after bacterial decomposition in the HA fraction but still in the FA fraction. The results show that estuarine and marine bacterial communities can decompose large amounts of HA and that this process is important in reducing the amount of terrestrial HS and DOM entering the estuarine and coastal region.     

Nitrite utilization by excised Zea mays L. roots under anaerobic conditions

Under both aerobic and anaerobic conditions exogenously supplied nitrite was utilized by sterile excised Zea mays L. root. A slightly greater quantity of nitrite was used under aerobic conditions than under anaerobiosis. The uncoupler of oxidative phosphorylation, pentachlorophenol (PCP), diminished the utilization of nitrite under aerobic and anaerobic conditions resulting in a net accumulation of nitrite rather than a net disappearance of nitrite. Nitrite supplied together with nitrite resulted in a slight reduction in the level of nitrite utilized. Supply of exogenous nitrite had no effect on nitrate reduction under aerobic or anaerobic conditions. A net accumulation of nitrite occurs only when roots are supplied with nitrate in the absence of added nitrite. However, the level of nitrite accumulated under anaerobiosis, when roots were supplied with nitrate only, was found to be a fraction of the quantity of nitrite utilized when roots were supplied with nitrite under anaerobiosis. Nitrate utilization far exceeded the level of nitrite accumulated under anaerobiosis when roots were supplied with nitrate only.     

Nitrite and nitrosyl compounds in food preservation.

Nitrite is consumed in the diet, through vegetables and drinking water. It is also added to meat products as a preservative. The potential risks of this practice are balanced against the unique protective effect against toxin-forming bacteria such as Clostridium botulinum. The chemistry of nitrite, and compounds derived from it, in food systems and bacterial cells are complex. It is known that the bactericidal species is not nitrite itself, but a compound or compounds derived from it during food preparation. Of a range of nitrosyl compounds tested, the anion of Roussin's black salt [Fe4S3(NO)7]- was the most inhibitory to C. sporogenes. This compound is active against both anaerobic and aerobic food-spoilage bacteria, while some other compounds are selective, indicating multiple sites of action. There are numerous possible targets for inhibition in the bacterial cells, including respiratory chains, iron-sulfur proteins and other metalloproteins, membranes and the genetic apparatus.     

Acid-mediated mutagenicity of tobacco snuff: its possible mechanism

Polar solvent extracts of tobacco snuff under acidic conditions were mutagenic in Salmonella typhimurium. Using the Griess reagent test, nitrite ranging from approximately 1.8 to 5.4 mg/g of snuff was found in the polar fraction of extracts. After acid treatment, nitroso compounds in the amount corresponding to the nitrite concentration were detected. The mutagenic potency of the acid-treated extracts was consistent with the content of nitroso compounds generated. Formation of nitroso compounds and the mutagenic activity under acidic conditions was inhibited by ascorbic acid. The results indicate that a nitrosation process was involved in snuff extracts during acid treatment. Studies related to the source of nitrite in tobacco snuff demonstrated that snuff contained bacteria which were able to reduce nitrate to nitrite and that the amount of nitrite in snuff extracts could be further increased by incubation of the extracts with the bacteria. Since snuff contains a considerable amount of nitrate, it seems that reduction of nitrate in snuff to nitrite by bacteria, and nitrosation of certain constituents in snuff by nitrite under acidic conditions to form mutagenic nitroso compounds are possible mechanisms responsible for the acid-mediated mutagenicity of snuff extracts.