Abstract  Continuous butanol/isopropanol fermentation with immobilized Clostridium isopropylicum was performed in a downflow column reactor using molasses as the substrate. In order to prevent product inhibition and at the same time obtain high concentration of the products, the column reactor was coupled with a pervaporation module using a supported liquid membrane. The liquid membrane was prepared with oleyl alcohol nontoxic to the microorganism. In comparison with the continuous fermentation without product removal, the specific butanol production rate was 2 times higher. The butanol concentration in the permeate was 230 kg/m(3), which was about 50 times higher than that in the culture broth. A numerical investigation suggested a further increase in the productivity by improving the module construction.

Abstract  HEEP COPYRIGHT: BIOL ABS. Two O2-containing derivatives of unsaturated fatty acids, methyl 12-oxo-trans- 10-octade-cenoate and methyl hydroxyoctadecadienoate, both highly active in the newt test for carcinogenicity, were tested as complete carcinogens and as promoting agents by application to the skin of ST/a mice. Through observation for 2 yr the tumorigenic effect was recorded and compared with that of methyl oleate and adequate positive control substances: 7,12-dimethylbenz(alpha)anthracene and croton oil. Methyl oxoctadecenoate and hydroxyoctadecadienoate showed a significant potency to promote the induction of skin papillomas. The genesis of malignant skin tumors was promoted by methyl oleate and oxoctadecnoate and all 3 methyl esters had weak activity as complete carcinogens to the skin. As a systemic effect all esters promoted the induction of malignant lymphomas, most markedly methyl oxoctadecenoate. Even without preceding initiation this ester and methyl oleate had some activity in lymphoma induction. The various observations show that, when tested by these procedures, methyl oxoctadecenoate is the ester most active in the induction of tumors and the effect is essentially that of a promoter. The relation between molecular configuration and carcinogenicity of fatty acids is discussed.

Abstract  Rosewood tree has high adaptability to environment and tolerance to water stress, and a long history of utilization and plantation in many countries. However, researches on Rosewood were mostly focused on the biomass analyses and utilizations of its wood, and lacked those to analyze the chemical components of extractives of Rosewood leaves, which was very important to recover and utilize the polluting waste Rosewood leaves. Therefore, the chemical components of benzene/ethanol extractives of Rosewood leaves were analyzed by method of GC/MS in order to identify top value-added bioactive components from waste leaves of Rosewood tree. The analytical result showed that the main components of benzene/ethanol extractives of freeze-dried Rosewood leaves by GC/MS analysis were identified 16 constituent (16 peaks) as: Ethanol, 2-butoxy- (40.36%), 2-O-Methyl-D-mannopyranosa (18.22 %), Hydrazine, 1,1-dipropyl- (6.09%), 1-Docosanol (5.59%), 1-Eicosanol (5.28%), Oxirane, hexadecyl- (3.63%), trans-2,4,5-Trimethoxy-center dot beta center dot-methyl- (3.50%), Bicyclo[3.1.1]heptane, 2,6,6-trimethyl- (2.53%), 9,12,15-Octadecatrienoic acid, methyl- (2.43%), Tetratetracontane (2.31%), Hexadecane, 1-(ethenyloxy)- (2.27%), Cholan-24-oic acid, 7,12-bis(acetyloxy)-3-ethoxy-, methyl ester, (3.alpha.,5.beta.)- (2.10%), Hexatriacontane (2.02%), Phytol (1.76%), Octadecane, 1-chloro (1.08%), etc. As the first report here, our result by GC/MS showed that the benzene-methanol extractive of freeze-dried Rosewood leaves can be developed into top value-added materials of medicines, biofuel, and industrial solvents.

Abstract  The rabbit external ear canal was used to define which chemicals caused comedone formation on topical application. Some of the tested ingredients are currently used in topically applied formulations. Certain raw materials have been shown to produce follicular hyperkeratosis in the rabbit ear assay. This study quantifies comedogenic potential of cosmetic materials, including: isopropyl palmitate, isopropyl myristate, butyl stearate, isopropyl isostearate, decyl oleate, isostearyl neopentanoate, isocetyl stearate, myristle myristate, cocoa butter, cetyl alcohol, paraffin, stearyl alcohol sodium lauryl sulfate (SLS), and petrolatum. The first nine were deemed positive. Factors aiding clinical relevance are listed.

Abstract  Structure-activity relationships between acute toxicities of 95 alcohols to rat and mouse (oral LD50) and four special substructure factors, hydroxyl number, carbon atom number were examined by means of expert system method. The results showed that the expert system based QSAR model was excellent for classification for miscellaneous alcohols (only 9 of them were wrong classified). It was also used to predict the toxicity of other 25 alcohols, and the false prediction rate was only 12%.

Abstract  Scanning tunneling microscopy (STM) images of 1-docosanol, 1-docosanethiol, didocosyl disulfide, and 1-chlorooctadecane on graphite are compared. The images of the 1-docosanethiol and didocosyl disulfide show bright spots which are attributed to the positions of the S-H and S-S functional groups. The STM images of the 1-docosanol and 1- chlorooctadecane do not show such bright spots. The fact that both the S-H and S-S groups appear bright in the STM images indicates that the presence of an S atom on graphite results in a higher tunneling current when the tip scans over it compared to the tunneling current over a C, O, or Cl atom. The different behavior of the S atoms compared to the O, C, and Cl atoms is discussed in terms of the interactions between these atoms and the underlying graphite substrate. The persistent brightness of S atoms in the images of molecular adsorbates suggests that sulfur may serve as a useful ''chromophore'' for molecules imaged by STM.

Abstract  Emulsion copolymerization of vinyl chloride with vinyl acetate comonomer was performed. Potassium persulfate, a mixture of stearyl alcohol and sodium lauryl sulfate, was used and reactions were performed at 55 degrees C in a pressurized reactor. By sampling during the reaction in different intervals copolymer composition was investigated using FTIR and NMR spectroscopy. The results showed that the partitioning of vinyl acetate in the copolymerization in general follows the Mayo-Lewis copolymerization equation with some discrepancy. This was attributed to the gaseous nature of vinyl chloride monomer and the differences between polymerization in heterogeneous and homogeneous systems. Both FT - IR and NMR spectroscopy showed two peaks in vinyl acetate content of copolymer beyond 65% conversion which was attributed to the elimination of vinyl chloride droplets in the media and replacing them with vinyl acetate monomer. The first increase is related to the consumption of vinyl chloride droplets and the second is related to the consumption of gaseous vinyl chloride; in both instances vinyl acetate governs the polymerization.

Abstract  A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Abstract  Experiments concerning the effect of shear flow on the turbidity of a colloidal dispersion close to its gas-liquid critical point are described. Theory predicts that in the mean-field region, the turbidity of the sheared syst em relative to that of the quiescent dispersion is a function of a single dimensionless group lambda that is proportional to gamma xi(-4) (gamma is the shear rate and xi(-1) is the correlation length of the quiescent dispersion at the given temperature). Experiments are found to be in accordance with this scaling behavior. Moreover, the experiments confirm the theoretically predicted lambda dependence. As a model colloidal system, we used spherical silica particles coated with stearyl alcohol. When dissolved in benzene, these colloidal particles attract each other, due to the fact that benzene is a marginal solvent for the stearyl coating. These attractions give rise to a gas-liquid critical point.

Abstract  OBJECTIVE: To study the chemical constituents of Wikstroemia indica.

METHODS: The constituents were isolated and purified by silica gel chromatography repeatedly, and the structures were determined by spectral data and chemical envidance.

RESULTS: Six compounds were isolated from its petroleum ether, dichloromethane, acetone and methanol extracts and identified as: daphnoretin-7-O-beta-D-glucoside (1), aloe-emodin (2), kaempferol (3), 29-nonacosanolide (4), 1-octadecanol (5), beta-sitosterol (6).

CONCLUSION: Compounds 2, 4, 5 are isolated from this plant for the first time.

Abstract  Systematically synthetic zinc 3-hydroxymethyl-131-oxo-chlorins esterified by different linear alcohols (methanol, 1-propanol, 1-hexanol, 1-dodecanol and 1-octadecanol) at the 17-propionate were self-assembled in the presence of cetyltrimethylammonium bromide in an aqueous solution. These zinc chlorins exhibited red-shifted Qy absorption bands and circular dichroism (CD) signals in the corresponding Qy region after incubation for 17h, indicating that the zinc chlorins formed self-aggregates like those in natural chlorosomes of green photosynthetic bacteria. Visible absorption and CD spectra of self-aggregates of the zinc chlorins depended on the length of their esterifying alcohols. Zinc chlorins esterified by shorter alcohols gave larger changes in their visible absorption and CD spectra after incubation above 40 degrees C, whereas zinc chlorins esterified by longer alcohols afforded smaller changes. These results indicate that hydrophobic interaction among esterifying chains of chlorin molecules as well as that between the esterifying chains and peripheral surfactants or lipids play an important role in the stability of chlorosomal self-aggregates.

Abstract  The nematode Caenorhabditis elegans arrests development at the first larval stage if food is not present upon hatching. Larvae in this stage provide an excellent model for studying stress responses during development. We found that supplementing starved larvae with ethanol markedly extends their lifespan within this L1 diapause. The effects of ethanol-induced lifespan extension can be observed when the ethanol is added to the medium at any time between 0 and 10 days after hatching. The lowest ethanol concentration that extended lifespan was 1 mM (0.005%); higher concentrations to 68 mM (0.4%) did not result in increased survival. In spite of their extended survival, larvae did not progress to the L2 stage. Supplementing starved cultures with n-propanol and n-butanol also extended lifespan, but methanol and isopropanol had no measurable effect. Mass spectrometry analysis of nematode fatty acids and amino acids revealed that L1 larvae can incorporate atoms from ethanol into both types of molecules. Based on these data, we suggest that ethanol supplementation may extend the lifespan of L1 larvae by either serving as a carbon and energy source and/or by inducing a stress response.

Abstract  Primary alcohols, from methanol to eicosanol, were applied to water for control of larval stage mosquitoes. By applying the alkanols as soluble solutions rather than as insoluble monolayers, and by trapping larvae under glass in assays that isolated them from the surface phenomena believed to be responsible for death by suffocation, we have shown that the action of alkanols against mosquito larvae is biochemical in nature, not just physical. Primary alcohols are known to act as general anesthetics, with increasing potency correlated to increasing chain length until a point of cutoff is reached, usually at dodecanol (C12), after which activity disappears entirely. In mosquitoes, we found that activity levels off after undecanol (C11) but does not disappear until after pentadecanol (C15), that it is reversible, and that chain length plays a role not only in potency, but also in the time needed to manifest toxic effects. We used sonication, a surfactant, temperature, and the introduction of double bonds to manipulate activity around the cutoff, suggesting that it is at least partially a function of solubility. Mosquitoes appear to be the first animal for which cutoff has been demonstrated to occur at a chain length beyond C12, offering new insights into the molecular basis of anesthetic cutoff and suggesting the possibility that alkanols might be used for selective pest control. Alkanols are stable, colorless, inexpensive, biodegradable and essentially non-toxic to humans, making them promising candidates for pest management programs.

Abstract  In the present work some stability studies on Supported Liquid Membranes (SLMs) to be used for chiral separations were realized. In particular, primary aim was to determine how a modification of the support surface influences the SLM stability. First, the procedure for support modification was optimised, making a screening of various compounds (sulphuric acid, nitric acid, chromic acid, sodium dodecyl sulphate (SDS), glycerol, oleic alcohol, propylene glycol (PPG), bovine serum albumin (BSA)) and testing their performance by means of contact angle measurements. Next, a second screening was realized by permeation tests in a stirred cell. Finally, to compare the stability of modified with unmodified support in a process of interest for chemical and/or biochemical industries, some permeation tests for resolution of DNB-DL-Leucine were realized in a re-circulation system. Results showed a better surface hydrophilization of chemically modified support and better stability of the sulphonated support. However, in operating conditions a little high stability of the unmodified support was obtained.

Abstract  49 substances permitted for use in food in the United States was tested for mutagenicity in the Ames Salmonella typhimurium assay and in Escherichia coli strain WP2. Four of these substances caused increases in revertant counts in S. typhimurium. Two of these four (papain and pepsin) were found to contain histidine, and therefore the results of the tests on these two substances could not be taken as demonstrating mutagenicity. The other two substances causing increases in revertant counts (hydrogen peroxide and potassium nitrite) were mutagenic. The results on one chemical, beta-carotene, were evaluated as inconclusive or questionable. The remaining 44 substances were nonmutagenic in the test systems used. It is concluded that, for those generally physiologically innocuous chemicals tested, there are very few 'false positives' in the bacterial test systems used.

Abstract  Eight phthalate esters, with alcohol chain lengths of 1-11 carbon atoms and with various degrees of branching, were tested in vitro in the L5178Y mouse lymphoma mammalian cell mutation assay and in the Balb/3T3 cell transformation assay. The tests were performed as part of a voluntary testing agreement between the Chemical Manufacturers Association's Phthalate Esters Panel and the United States Environmental Protection Agency (US EPA). The esters tested were: dimethyl phthalate (DMP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), di- inverted question markn-hexyl, n-octyl, n-decyl inverted question mark phthalate (610P), di-isononyl phthalate (DINP), di- inverted question markheptyl, nonyl, undecyl inverted question mark phthalate (711P), di-isodecyl phthalate (DIDP) and di-undecyl phthalate (DUP). Both DMP and DBP were found to produce significant increases in the mutant frequency in the mouse lymphoma assay in the presence but not in the absence of an Aroclor-induced rat liver activation system (S-9). Ester 610P gave equivocal results in the mouse lymphoma assay in the presence and absence of rat liver S-9. There was no indication of mutagenic potential for any of the other test materials in the mouse lymphoma assay, and none of the test materials increased transformation frequency in the Balb/3T3 cell transformation assay. Aldehyde metabolites of the de-esterified alcohols are postulated to play a role in the positive results for DMP and DBP.

Abstract  BACKGROUND: The volatile composition of alcaparras stoned table olives produced from five of the most representative olive cultivars (cv. Cobrançosa, Madural, Negrinha de Freixo, Santulhana and Verdeal Transmontana) from the Trás-os-Montes region (north-east of Portugal) was analytically characterised using headspace-solid phase microextraction/gas chromatography-ion trap-mass spectrometry.

RESULTS: Overall, 42 volatile compounds were identified, belonging to distinct chemical classes: 15 aldehydes, seven esters, five alcohols, five sesquiterpenes, four norisoprenoids derivates, three monoterpenes, o ne ketone and two alkenes. Aldehydes were the major chemical class identified in all olive cultivars studied (more than 74% of all the volatile compounds identified). Hexanal, phenylacetaldehyde and (E,E)-2,4-heptadienal were the major volatile compounds identified.

CONCLUSIONS: It was possible to discriminate the results obtained from the volatile profile of the five olive cultivars by using principal component analysis. Both qualitative and quantitative fractions of alcaparras table olives were influenced by olive cultivar, which confers a single aroma. This fact certainly influences consumer preference and acceptability towards a specific olive cultivar.

Abstract  Breflate is a water soluble prodrug developed to facilitate parenteral administration of the investigational antineoplastic agent brefeldin A (BFA). Previously, using analytical methods based upon reversed-phase high performance liquid chromatography (HPLC) with low wavelength UV detection or gas chromatography (GC) with electron capture detection following derivatization with heptafluorobutyrylimidazole, it was demonstrated that breflate undergoes rapid and efficient conversion to BFA following bolus i.v. injection in mice and dogs. However, plasma concentrations of the drug and prodrug achieved during the administration of nontoxic doses of breflate to beagle dogs as a 72 h continuous i.v. infusion were undetectable (< 0.1 microgram ml-1) by these methods. The sensitivity and specificity required for therapeutic drug level monitoring were achieved by GC with selected-ion mass spectrometry (MS) detection. Breflate, BFA and 1-eicosanol, the latter added to the sample as an internal standard (IS), were extracted from plasma into tert-butyl methyl ether (TBME) and esterified with trifluoroacetic anhydride. Methanol was added to the reaction mixture to effect the convenient removal of excess reagent as the volatile methyl ester during evaporation of the solvent. The residual material was analyzed directly upon reconstitution by capillary GC with automated splitless injection. Electron-ionization (70 eV) MS detection was performed by sequentially scanning ions at m/z 58, 202 and 325. The lowest concentration of either analyte quantified with acceptable reproducibility, as defined by an inter-day R.S.D. of about 20%, was near 10 ng ml-1 in plasma using a sample volume of 100 microliters. The assay has proven to be sufficiently sensitive, specific and reproducible for the routine analysis of pharmacokinetic specimens acquired during IND (investigational new drug)-directed toxicology studies in dogs.

Abstract  Structural analogues of phospholipidic platelet activating factor, (2-acetoxy-3-octadecyloxy)propyl-1-phosphonocholine and (2-methoxy-3-octadecyloxy)propyl-1-phosphonocholine, were synthesized. High efficiency of the polymer-bound dibenzo-18-crown-6-ether as the 0-alkylation catalyst was demonstrated. Reaction of allyl-octadecyl ether with methanol and iodine in the presence of zinc oxide was shown to give a mixture of 1-iodo-2-methoxy- and 1-methoxy-2-iodoprop-3-yl ethers of octadecanol in the 3 : 1 ratio.

Abstract  The antimicrobial activity of the n-hexane, chloroform, ethyl acetate and ethanol extracts of the aerial parts of C. drabifolia S.M. subsp. cappadocica (DC.) Wagenitz (Asteraceae) was evaluated against microorganisms including multi-antibiotic resistant bacteria using the paper disc diffusion method. The chemical composition of the chloroform extract of this plant was determined by gas chromatography and gas chromatography-mass spectrometry. The chloroform extract exhibited significant antibacterial activity against all the bacteria tested, except Stenotrophomonas maltophilia MU63. The major compounds of the chloroform extract were spathulenol (14.1%), caryophyllene oxide (12.5%), octadecanol (10.2%), ethyl palmitate (7.7%), [Z,Z]-10,12-hexadecadienal (6.0%), 3-hydroxy p-anisaldehyde (5.9%) and pentacosane (5.8%).

Abstract  In an ongoing study of the fate of petroleum hydrocarbons in fish, petroleum derived metabolites which concentrate in the gall bladder bile of rainbow trout (Salmo gairdneri) have been examined. The metabolism of three structural isomers of butylbenzene, n-butylbenzene, sec-butylbenzene and tert-butylbenzene, in rainbow trout is reported. These compounds were chosen because several isomers of C-4 benzene were detected in analysis of No. 2 fuel oil. Groups of 10 to 12 trout were intubed through the mouth with 0.5 ml of a 5% solution of one of the butylbenzenes in olive oil; 0.5% and 0.1% sec-butylbenzene solutions were also utilized. After 120 hours the fish were killed and their gall bladder bile analyzed for the type of glucuronides formed. Three alcohols were identified. The major sec-butylbenzene and n-butyl metabolites were identified as the tertiary alcohol, 2-phenyl-2-butanol and 1-phenyl-1-butanol, respectively. When the concentration of the solution of sec-butylbenzene in olive oil was reduced from 5 to 0.5% (by a factor of ten), the concentration of the metabolites was reduced by about a factor of four. When trout were exposed to tert-butyl benzene, five new peaks were detected by gas-liquid chromatography. The major metabolite was a monohydroxylated derivative of tert-butyl benzene. Results indicate that upon exposure of trout to three aromatic hydrocarbons of the same molecular weight, ring structure, and with a single side chain, oxidation of the side chain will take place preferentially to that of the ring.

Abstract  Aerobic oxidation of a thin film of octadecanol at 105 degrees C and ambient pressures to its corresponding carbonyl derivatives (a mixture of aldehyde and carboxylic acid) was for the first time performed over a flat-model (i.e. two-dimensional), silicon wafer-supported metallic silver catalyst. The experimental set-up was extraordinary simple. An open-to-the-atmosphere glass beaker was used as reactor. Just enough octadecanol was placed on the silicon-supported catalytic surface to cover it with a thin film when melted. Reaction progress was monitored by ATR-FTIR analyses to identify the appearance of octadecanal and octadecanoic acid carbonyl stretching peaks at 1730 and 1710 cm(-1) respectively. The successful demonstration of this simple approach in studying catalysed small-molecule condensed organic reactions opens a new avenue towards simplified catalytic mechanistic studies of such processes. The catalyst was prepared by spin coating silver nitrate on a flat silicon wafer with (100) surface orientation, pretreated to have 4-5 silanol (-Si-OH) groups per nm(2). Reduction by hydrogen at 350 degrees C afforded metallic silver particles on the two-dimensional support at a nominal surface concentration of ca. 21-23 silver atoms/nm(2). XPS differentiation between the catalyst precursor, AgNO3. and the metallic silver catalytic surface required use of the Auger MNN kinetic energies. TEM studies of the active catalyst showed no serious aggregation of metallic Ag particles occurred during reduction. (C) 2012 Elsevier B.V. All rights reserved.

Abstract  Synopsis Transparent formulations of a liposoluble sunscreen in an aqueous medium were studied, taking into account the different chemicals of a selected system situated in the vertices of a regular tetrahedron: sunscreen agent, co-solvent, (surfactants +/- mineral oil) mixture (in the tetrahedron base) and water as the fourth component. Several compositions were selected at optimized component ratios after which water was added progressively. Clear gel and liquid compositions were obtained yielding a sunscreen agent that it suitable for conventional use. The physico-chemical properties of some compositions were assessed in terms of water/sunscreen agent content.