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Extraction of chili, black pepper, and ginger with near-critical CO2, propane, and dimethyl ether: analysis of the extracts by quantitative nuclear magnetic resonance.

Ginger, black pepper, and chili powder were extracted using near-critical carbon dioxide, propane, and dimethyl ether on a laboratory scale to determine the overall yield and extraction efficiency for selected pungent components. The temperature dependency of extraction yield and efficiency was also determined for black pepper and chili using propane and dimethyl ether. The pungency of the extracts was determined by using an NMR technique developed for this work. The volatiles contents of ginger and black pepper extracts were also determined. Extraction of all spice types was carried out with acetone to compare overall yields. Subcritical dimethyl ether was as effective at extracting the pungent principles from the spices as supercritical carbon dioxide, although a substantial amount of water was also extracted. Subcritical propane was the least effective solvent. All solvents quantitatively extracted the gingerols from ginger. The yields of capsaicins obtained by supercritical CO(2) and dimethyl ether were similar and approximately double that extracted by propane. The yield of piperines obtained by propane extraction of black pepper was low at approximately 10% of that achieved with dimethyl ether and CO(2), but improved with increasing extraction temperature.

Capsicum↗

Biodegradation of the gasoline oxygenates methyl tert-butyl ether, ethyl tert-butyl ether, and tert-amyl methyl ether by propane-oxidizing bacteria.

Several propane-oxidizing bacteria were tested for their ability to degrade gasoline oxygenates, including methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). Both a laboratory strain and natural isolates were able to degrade each compound after growth on propane. When propane-grown strain ENV425 was incubated with 20 mg of uniformly labeled [14C]MTBE per liter, the strain converted > 60% of the added MTBE to 14CO2 in < 30 h. The initial oxidation of MTBE and ETBE resulted in the production of nearly stoichiometric amounts of tert-butyl alcohol (TBA), while the initial oxidation of TAME resulted in the production of tert-amyl alcohol. The methoxy methyl group of MTBE was oxidized to formaldehyde and ultimately to CO2. TBA was further oxidized to 2-methyl-2-hydroxy-1-propanol and then 2-hydroxy isobutyric acid; however, neither of these degradation products was an effective growth substrate for the propane oxidizers. Analysis of cell extracts of ENV425 and experiments with enzyme inhibitors implicated a soluble P-450 enzyme in the oxidation of both MTBE and TBA. MTBE was oxidized to TBA by camphor-grown Pseudomonas putida CAM, which produces the well-characterized P-450cam, but not by Rhodococcus rhodochrous 116, which produces two P-450 enzymes. Rates of MTBE degradation by propane-oxidizing strains ranged from 3.9 to 9.2 nmol/min/mg of cell protein at 28 degrees C, whereas TBA was oxidized at a rate of only 1.8 to 2.4 nmol/min/mg of cell protein at the same temperature.

Bacteria↗

Evaluation of various models of propane-powered mosquito traps.

Large cage and field studies were conducted to determine the efficacy of various models of propane-powered mosquito traps. These traps utilized counterflow technology in conjunction with catalytic combustion to produce attractants (carbon dioxide, water vapor, and heat) and a thermoelectric generator that converted excess heat into electricity for stand-alone operation. The cage studies showed that large numbers of Aedes aegypti and Ochlerotatus taeniorhynchus were captured and that each progressive model resulted in increased trapping efficiency. In several field studies against natural populations of mosquitoes two different propane traps were compared against two other trap systems, the professional (PRO) and counterflow geometry (CFG) traps. In these studies the propane traps consistently caught more mosquitoes than the PRO trap and significantly fewer mosquitoes than the CFG traps. The difference in collection size between the CFG and propane traps was due mostly to Anopheles crucians. In spring 1997 the CFG trap captured 3.6X more An. crucians than the Portable Propane (PP) model and in spring 1998 it captured 6.3X more An. crucians than the Mosquito Magnet Beta-1 (MMB-1) trap. Both the PP and MMB-1 captured slightly more Culex spp. than the CFG trap.

Animals↗

Probe molecule chemisorption-low energy ion scattering study of surface active sites present in the orthorhombic Mo-V-(Te-Nb)-O catalysts for propane (amm)oxidation.

Methanol and allyl alcohol chemisorption and surface reaction in combination with low energy ion scattering (LEIS) were employed to determine the outermost surface compositions and chemical nature of active surface sites present on the orthorhombic (M1) Mo-V-O and Mo-V-Te-Nb-O phases. These orthorhombic phases exhibited vastly different behavior in propane (amm)oxidation reactions and, therefore, represented highly promising model systems for the study of the surface active sites. The LEIS data for the Mo-V-Te-Nb-O catalyst indicated surface depletion for V (-23%) and Mo (-27%), and enrichments for Nb (+55%) and Te (+165%) with respect to its bulk composition. Only minor changes in the topmost surface composition were observed for this catalyst under the conditions of the LEIS experiments at 400 degrees C, which is a typical temperature employed in these propane transformation reactions. These findings strongly suggested that the bulk orthorhombic Mo-V-Te-Nb-O structure may function as a support for the unique active and selective surface monolayer in propane (amm)oxidation. Moreover, direct evidence was obtained that the topmost surface VO(x) sites in the orthorhombic Mo-V-Te-Nb-O catalyst were preferentially covered by chemisorbed allyloxy species, whereas methanol was a significantly less discriminating probe molecule. The surface TeO(x) and NbO(x) sites on the Mo-V-Te-Nb-O catalyst were unable to chemisorb these probe molecules to the same extent as the VO(x) and MoO(x) sites. Our findings suggested that different surface locations for V(5+) ions in the orthorhombic Mo-V-O and Mo-V-Te-Nb-O catalysts may be primarily responsible for vastly different catalytic behavior exhibited by the Mo-V-O and Mo-V-Te-Nb-O phases. Although the proposed isolated V(5+) pentagonal bipyramidal sites in the orthorhombic Mo-V-O phase may be capable of converting propane to propylene with modest selectivity, the selective 8-electron transformation of propane to acrylic acid and acrylonitrile may require the presence of several surface VO(x) redox sites lining the entrances to the hexagonal and heptagonal channels of the orthorhombic Mo-V-Te-Nb-O phase. The study of allyl alcohol oxidation over the Mo-V-O and Mo-V-Te-Nb-O catalysts further suggested that water plays a critical role during the oxidation of acrolein intermediate to acrylic acid over the orthorhombic (M1 phase) Mo-V-Te-Nb-O catalysts. Finally, the present study strongly indicated that chemical probe chemisorption combined with low energy ion scattering (LEIS) is a novel and highly promising surface characterization technique for the investigation of the active surface sites present in the bulk mixed metal oxides.

Journal Article↗

Bacterial community composition determined by culture-independent and -dependent methods during propane-stimulated bioremediation in trichloroethene-contaminated groundwater.

An in situ co-metabolic air sparging (CAS) study was carried out at McClellan Air Force Base (MAFB), Sacramento, CA, USA, in a trichloroethene- (TCE) and cis-dichloroethene (cis-DCE)-contaminated aquifer where one test zone received 2% propane in air and the other served as a control and received only air. As part of that study, bacterial population shifts were evaluated by length heterogeneity polymerase chain reaction (LH-PCR). The results showed that an organism(s) that had a fragment size of 385 bp was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled from the propane-sparged groundwater included clones of a TM7 division bacterium that had a 385 bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385 bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. Extinction culturing in natural unamended groundwater medium was used to assess the bacterial diversity of the culturable fraction of microorganisms in both CAS and air-sparged groundwater and to bring novel species into culture for further study. The dominant cultures acquired from the CAS groundwater were from the Herbaspirillum/Oxalobacter clade. The dominant cultures from the air-sparged groundwater were from a novel beta-Proteobacterial clade, which we named after isolate HTCC333.

Bacteria↗

Epoxidation of short-chain alkenes by resting-cell suspensions of propane-grown bacteria.

Sixteen new cultures of propane-utilizing bacteria were isolated from lake water from Warinanco Park, Linden, N.J. and from lake and soil samples from Bayway Refinery, Linden, N.J. In addition, 19 known cultures obtained from culture collections were also found to be able to grow on propane as the sole carbon and energy source. In addition to their ability to oxidize n-alkanes, resting-cell suspensions of both new cultures and known cultures grown on propane oxidize short-chain alkenes to their corresponding 1,2-epoxides. Among the substrate alkenes, propylene was oxidized at the highest rate. In contrast to the case with methylotrophic bacteria, the product epoxides are further metabolized. Propane and other gaseous n-alkanes inhibit the epoxidation of propylene. The optimum conditions for in vivo epoxidation are described. Results from inhibition studies indicate that a propane monooxygenase system catalyzes both the epoxidation and hydroxylation reactions. Experiments with cell-free extracts show that both hydroxylation and epoxidation activities are located in the soluble fraction obtained after 80,000 x g centrifugation.

Journal Article↗

Divergent metabolic pathways for propane and propionate utilization by a soil isolate.

The metabolism of propane and propionate by a soil isolate (Brevibacterium sp. strain JOB5) was investigated. The presence of isocitrate lyase in cells grown on isopropanol, acetate, or propane and the absence of this inducible enzyme in n-propanol- and propionate-grown cells suggested that propane is not metabolized via C-terminal oxidation. Methylmalonyl coenzyme A mutase and malate synthase are constitutive in this organism. The incorporation of (14)CO(2) into pyruvate accumulated during propionate utilization suggests that propionate is metabolized via the methyl-malonyl-succinate pathway. These results were further substantiated by radiorespirometric studies with propionate-1-(14)C, -2-(14)C, and -3-(14)C as substrate. Propane -2-(14)C was shown, by unlabeled competitor experiments, to be oxidized to acetone; acetone and isopropanol are oxidized in this organism to acetol. Cleavage of acetol to acetate and CO(2) would yield the inducer for the isocitrate lyase present in propane-grown cells.

Alkanes↗

Quantity of remaining double bonds of propanal-containing resins.

Improved mechanical properties of resin composites have been reported to be a consequence of the addition of aldehyde to the resins. The objective of the present study was to examine whether this improvement could be attributed to an increased degree of conversion of double bonds. For this purpose, propanal was added to monomer mixtures, which were then made light-curing. The monomer mixtures were varied with respect to monomer composition and content of propanal. The quantity of remaining double bonds was determined by means of transmission infrared spectra of the resins recorded before and after wet or dry storage for one week. The addition of propanal resulted in a decrease in the quantity of remaining double bonds by as much as 89% as compared with the mixtures without propanal. Negative correlations of statistical significance were found between the content of propanal and quantity of remaining double bonds in BISGMA:TEGDMA-based as well as in UEDMA:HEMA-based resins for both modes of storage. Significant negative correlations were found between the quantity of remaining double bonds and the previously determined mechanical properties.

Aldehydes↗

Gene structure and regulation of alkane monooxygenases in propane-utilizing Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7.

Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7 were isolated from soil samples as propane-utilizing bacteria and were found to be able to utilize various gaseous and liquid n-alkanes as carbon and energy sources. One gene cluster, M-prmABCD, and two gene clusters, P-prm1ABCD and P-prm2ABCD, were cloned from the genomes of Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7, respectively. These gene clusters are homologous to the gene cluster encoding the multicomponent propane monooxygenase (prmABCD) of Gordonia sp. TY-5. The expression of prm gene clusters in Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7 was shown to be induced by gaseous n-alkanes (C2-C4) except methane, suggesting that the products of these genes are involved in gaseous n-alkane oxidation. Homologous genes for an alkane hydroxylase system (alk system) involved in liquid n-alkane oxidation were also cloned from the genomic DNA of Mycobacterium sp. TY-6. The alk gene cluster was transcribed in response to liquid n-alkanes (C11-C15). These results indicate that Mycobacterium sp. TY-6 has two distinct gene clusters for multicomponent monooxygenases involved in alkane oxidation. Whole-cell reactions revealed that propane is oxidized to 1-propanol through terminal oxidation in Mycobacterium sp. TY-6 and that propane is oxidized to 1-propanol and 2-propanol through both terminal and subterminal oxidations in Pseudonocardia sp. TY-7. This study reveals the diversity of propane metabolism present in microorganisms.

Actinomycetales↗

Retention of propanal and diacetyl in experimental resins.

The degree of evaporation from experimental resins containing 0.40 mol% propanal or diacetyl was determined over a 6-month period at 60 degrees C. From the results the maximum evaporation possible, M infinity was calculated for each resin and was found to vary between 0.28% and 7.51% by weight. At low contents of propanal or diacetyl, M infinity 1 remained unchanged as compared with the control resins without additive. At higher contents of additive, M infinity increased significantly. In resins based on BisGMA and TEGDMA, propanal was retained to a lesser extent than diacetyl. In resins based on UEDMA and HEMA, propanal was retained to a greater extent than diacetyl. This study confirms that propanal and diacetyl become bound in the polymer structure, and theories as to the reaction mechanisms are presented.

Acrylic Resins↗

The carcinogenic response in mice to the topical application of propane sultone to the skin.

The carcinogenic effects of limited and repeated skin applications of propane sultone were investigated in three strains of mice, CF1, C3H and CBah (a hairless strain). Propane sultone was shown to be carcinogenic when given as a single application of a 25% w/v solution in toluene and also following twice weekly application of a 2.5% w/v solution for up to 58 weeks. More limited exposure to 2.5% w/v solutions of propane sultone resulted in a few skin tumours, although the incidences were not statistically significant. Most neoplasms were papillomas or carcinomas, although a small number of mesenchymal tumours of dermal origin also developed. No skin neoplasms were found in any control mice. The skin application of propane sultone was associated with a statistically significant increase in the incidence of systematic neoplasia in CFl and C3H mice. The exposed CFl mice had a higher incidence of neoplasms of lymphoreticular and lung origin, while female C3H mice showed a higher incidence of mammary gland and uterine tumours. In mice exposed to beta-propiolactone as a positive control, neoplasms developed at the site of application but, there was no evidence of increased systemic neoplasis in contrast to the findings with ptopane sultone.

Animals↗

Quantification of propane in biological materials by head-space GC.

Propane was measured in specimens taken from two persons who died from a LPG explosion in an apartment using head-space-GC/FID. Because of the variation of instrument performance and sample injection, the internal standard pentane was used. Calibration standards were prepared by injecting each calculated volume of pure propane gas into capped vials containing 2 ml of blood and 5 microl of internal standard. The calibration curve revealed good linearity from 0.09 microg/ml to at least 90 microg/ml. The method validation data also included repeatability and recovery. The propane quantities in blood, fat and brain tissue were between 0.27 and 71 microg/ml (microg/g) with the highest concentration observed in fat. The confirmation of propane was conducted by the means of solid phase micro-extraction and mass spectrometry.

Adipose Tissue↗

Propane and butane emission sources to ambient air of Mexico City metropolitan area.

Samples of volatile organic compounds (VOCs) were collected in a smog chamber in order to determine whether automotive exhausts or LP Gas emissions play a greater role in the source of propane and butane, which affect ozone formation and other pollutants in the ambient air of the Mexico City metropolitan area (MCMA). These samples were collected in April 1995 during mornings and evenings. The testing methodology used for measuring exhaust emission were FTP or EPA-74 tests, and SHED type tests were also conducted in order to evaluate evaporative emissions. The finding from analysis of the VOCs collected in the morning demonstrate that in the atmosphere, propane concentrations are higher than that of butane but the reverse in evaporative and exhaust emissions, with the concentration of propane lower than that of butane. Our conclusion is that most of C3 and C4 in the ambient air comes from LP gas and not vehicle exhaust or evaporative emission, due to the higher levels of propane than butane in its formulation. The analysis of VOCs also indicates that although the conversion (in the smog chamber) of alkanes is low during the day, due to the high initial concentration, their contribution in the reaction mechanism to produce ozone can be appreciable.

Butanes↗

Toxicological evaluation of propane expanded tobacco.

A tiered testing strategy has been developed to evaluate the potential for tobacco processes, ingredients, and other technological developments to increase or decrease the biological activity resulting from burning tobacco. The strategy is based on comparative chemical and biological testing. Propane expanded tobacco is an example of a processed tobacco used in the modern manufacture of cigarettes. Test cigarettes containing propane expanded tobacco were compared to control cigarettes containing tobacco expanded with a traditional expansion agent (Freon-11). The toxicological evaluation included chemistry studies using mainstream cigarette smoke (determination of selected constituent yields), in vitro studies using cigarette smoke condensate (Ames study in Salmonella typhimurium and sister chromatid exchange study in Chinese hamster ovary cells) and in vivo studies (13-week inhalation study of mainstream cigarette smoke in Sprague-Dawley rats and 30-week dermal tumor promotion study of cigarette smoke condensate in SENCAR mice). Although statistically significant differences in several smoke constituents were observed, most constituents from cigarettes containing 100% propane expanded tobacco were within market survey ranges. Furthermore, biological tests indicated that the cigarettes containing propane or Freon-11 expanded tobacco were not significantly different.

Administration, Inhalation↗

Supercritical CO(2) and subcritical propane extraction of pungent paprika and quantification of carotenoids, tocopherols, and capsaicinoids.

Ground paprika (Capsicum annuum L.) was extracted with supercritical carbon dioxide (SC-CO(2)) and subcritical propane at different conditions of pressure and temperature to estimate the yield and variation in carotenoid, tocopherol, and capsaicinoid contents and composition. The yield of paprika extract was found to be affected by the extraction conditions with SC-CO(2) but fairly constant at different conditions with subcritical propane. The maximum yields of oleoresin were 7.9 and 8.1% of ground paprika by SC-CO(2) and subcritical propane, respectively. The quantitative distribution of carotenoids, tocopherols, and capsaicinoids between paprika extract and powder was influenced by extraction conditions. SC-CO(2) was inefficient in the extraction of diesters of xanthophylls even at 400 bar and 55 degrees C, whereas tocopherols and capsaicinoids were easy to extract at these conditions. Under mild conditions subcritical propane was superior to SC-CO(2) in the extraction of carotenoids and tocopherols but less efficient in the extraction of capsaicinoids.

Capsicum↗

Studies of site selective hydrogen atom abstractions by Cl atoms from isobutane and propane by laser flash photolysis/IR diode laser spectroscopy.

The kinetics of chlorine atom abstractions from normal and selectively deuterated propane and isobutane have been measured at room temperature and 195 K using a laser flash photolysis system, and following the course of the reaction via IR diode laser absorption measurements of HCl product. In conjunction with the kinetic measurements, a comparison of the HCl signal heights from pairs of measurements on normal and selectively deuterated systems has allowed the determination of the branching fractions of the reactions at the primary, secondary (propane) and tertiary (isobutane) positions. The kinetic data (all in units of cm(3) molecule(-1) s(-1)) for the reaction of Cl atoms with propane ((1.22 +/- 0.02) x10(-10), 195 K; (1.22 +/- 0.03) x10(-10) 298 K) and isobutane ((1.52 +/- 0.02) x10(-10), 195 K; (1.25 +/- 0.04) x10(-10), 298 K) are generally in good agreement with literature data. No data are available for comparison with our measurements for the reactions of Cl atoms with CH(3)CD(2)CH(3) ((1.02 +/- 0.03) x10(-10), 195 K; (1.09 +/- 0.02) x10(-10), 298 K) or (CH(3))(3)CD ((1.32 +/- 0.03) x10(-10), 195 K; (1.12 +/- 0.04) x10(-10), 298 K). Rate coefficients at 195 K for the reactions of Cl atoms with ethane ((5.04 +/- 0.08) x10(-11) and n-butane ((2.19 +/- 0.03) x10(-10)) were also measured. The branching fractions for abstraction at the primary position increased with temperature for both propane ((40 +/- 3)% at 195 K to (48 +/- 3)% at 298 K) and isobutane ((49 +/- 4)% at 195 K to (62 +/- 5)% at 298 K). The direct measurements from this study are in good agreement with most calculations based on structure activity relationships.

Butanes↗

Effect of varying the combustion parameters on the emissions of carbon monoxide and nitrogen oxides in the exhaust gases from propane-fueled vehicles.

Propane-fueled forklifts are one source of carbon monoxide (CO) contamination of workplace air. The previous study carried out by the Quebec Occupational Health and Safety Research Institute dealt with worker exposure to CO during forklift use in buildings. It recommends that exhaust gas emissions be kept below a 1 percent concentration. However, this control has not produced a significant reduction in worker exposure to CO, when factors (ventilation, type of work tasks, and management of vehicle fleet) specific to companies are taken into account. Consequently, a reduction in CO emissions below the threshold of 0.3 percent should be considered. The experience acquired with propane-fueled ice resurfacers can be used to determine the effect of combustion parameters on exhaust gas emissions. It is known that a reduction in CO emissions from ice resurfacers resulted in the appearance of nitrogen oxides (NOx) and eventually in nitrogen dioxide (NO2) poisoning. Few publications present NOx results in relation to the CO measured in the exhaust gases of propane-fueled vehicles. The objective of this study is to define the level to which CO emissions can be reduced without increasing NOx concentrations. This real-situation study quantified the CO, NO, and NOx in the exhaust gases of a fleet of propane-fueled forklifts in relation to the mixture ratio. The results show the impact of the motor speed and mixture ratio on the CO, NO, and NO2 concentrations. They confirm an increase in NOx concentrations when CO concentrations are reduced. They also show that proper maintenance of forklifts combined with optimal adjustments can reduce CO and NOx emissions. The study proposes a compromise between CO and NOx emissions by taking into account worker health and safety as well as vehicle performance. Monitoring must be done to control air quality in work areas and worker exposure to CO and NO2. A forklift preventive maintenance program and general building ventilation are the favored and recommended means of control.

Air Pollution, Indoor↗

Clusters of ionisation in nanometre targets for propane-experiments with a Jet Counter.

Further evidence on the reliability of the device called the Jet Counter (JC) for studying the formation of ionisation clusters at the nanometre level are presented. The new experimental data on the distributions of ionisation cluster size originating from a 2-10 nm size target in propane irradiated by 3.8 MeV alpha particles are described. The JC consists of a pulse-operated valve that injects an expanding jet of propane into an interaction chamber, where a sensitive volume in the form of a cylinder is created. The sensitive volume was irradiated by 3.8 MeV alpha particles. The resulting distribution of ion clusters, ranging from 2 to 10 nm in unit density gas, has been measured. A method of determining the efficiency of registration of single propane ions using an ion detector is described. A method of deconvolution of the measured to true cluster size distributions is also given. Finally, the measured cluster size distributions are compared with modelled distributions based on Monte Carlo calculations. The results for propane together with previous ones for nitrogen indicate the JC to be an efficient tool for the investigation of radiation quality at the nanometre level.

Algorithms↗