Abstract  Summary At present, there is an increasing demand for trace gas analytical information, especially in several fields of environmental protection, such as protection of workers from exposure to hazardous substances in work place atmospheres, ambient and indoor air pollution, or gaseous exhalations from polluted soils, waters, or waste deposits. Though the existing powerful trace analytical tools are in principle capable of answering the questions related to these problems, they cannot satisfy the information demand. This is mainly due to the fact that most of these analytical tools are to be used in the course of rather sophisticated multistep procedures which are time consuming and claim high personnel qualification and, thus, are too expensive for large scale application. This difficulty can be overcome by the development of simple one-step procedures based on low price ready-for-use sampling units which can be processed with a minimum of manpower input and, in addition, provide information of the required reliability. One possible way to this goal may be based on the measurement of caloric effects associated with the decomposition of the products resulting during the sampling step from a gas-solid reaction between the traces to be analyzed and suitable solid state reagents. Starting from properly prepared text gas mixtures, the gas-solid reactions of numerous amines, alcohols, aldehydes, ketones, hydrocarbons and halogenated hydrocarbons with several metal complexes and with reagents capable of forming clathrates have been investigated by means of thermoanalytical methods, mainly by means of differential scanning calorimetry (DSC). The results show that in many cases the very simple thermoanalytical evaluation enables both qualitative identification and quantification of the gas traces under concern with satisfying selectivity. These reaction may serve, therefore, as a promising basis for further development of fast, simple and reliable trace gas analysis using thermoanalytical methods.

Abstract  The aim of the current study was to investigate the effect of different co-surfactants on the phase behaviour of the pseudoternary system water:ethyl oleate:nonionic surfactant blend (sorbitan monolaurate/polyoxyethylene 20 sorbitan mono-oleate). Four aliphatic alcohols (1-propanol, 1-butanol, 1-hexanol and 1-octanol) and four 1,2-alkanediols (1,2-propanediol. 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol) were used. The co-surfactant-free system forms two different colloidal structures, a water-in-oil microemulsion (w/o ME) and lamellar liquid crystals (LC) and two coarse dispersions, water-in-oil (w/o EM) and oil-in-water (o/w EM) emulsions. Microemulsion region area (%ME), liquid crystalline region area (%LC), amount of amphiphile blend required to produce a balanced microemulsion (%AMPH) and amount of water solubilised (%W)were used as assessment criteria to evaluate the co-surfactants. Seven calculated physico-chemical descriptors were used to represent the different co-surfactants. 1-butanol, 1,2-hexanediol and 1,2-octanediol produced balanced MEs capable of solubilising a high percentage of both oil and water. A similarity was observed between the descriptors attributed to I-butanol and 1,2-hexanediol. The requirements of a co-surfactant molecule to produce a balanced microemulsion were: HLB Value 7.0-8.0, a carbon backbone of 4-6 atoms, percentage carbon of 60-65%, percentage oxygen of 20-30%, log P value 0.2-0.9 and log 1/S (S: aqueous solubility) close to zero. (C) 2000 Elsevier Science B.V. All rights reserved.

Abstract  Density and isobaric heat capacity per unit volume were determined for aqueous mixtures of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,2-hexanediol over the whole composition range in the temperature interval (283.15-313.15) K at atmospheric pressure. From these data, excess molar volumes and excess isobaric molar heat capacities were obtained. The comparison of experimental data with literature values shows quite good agreement, not only for absolute magnitudes, but also for excess quantities. Excess volumes are negative over the whole composition range and they become more ideal (less negative) as temperature increases. Excess isobaric molar heat capacity is mostly positive, although it is negative for some mixtures at several compositions and temperatures. Moreover, it was found that it presents a maximum at low mole fraction of the alcohol for most systems, as it was previously found for alkanol + water mixtures. As for temperature dependence, excess isobaric molar heat capacity increases with raising temperature in all cases. This increase is more pronounced for concentrated solutions of dialcohol, with the exception of the 1,2-hexanediol system. The obtained results are interpreted in terms of well-known arguments based on definition of excess magnitudes and chemical nature of the compounds. (C) 2013 Elsevier B.V. All rights reserved.

Abstract  Using biomass-derived ethylene glycol (bio-EG) to synthesize poly(ethylene terephthalate) (PET) is of notable significance for alleviating the dependence on fossil energy resources. Bio-EG readily contains a small amount of miscellaneous diols, which derive from the side reactions in the catalytic conversion of biomass. To disclose the effects of miscellaneous diols on the synthesis and properties of PET, EG feedstock containing four 1,2-diols, i.e., 1,2-propylene glycol, 1,2-butanediol, 1,2-pentanediol, and 1,2-hexanediol at 0-10% concentrations was used for the synthesis of PET. The molecular weights, intrinsic viscosities, and thermal and mechanical properties of obtained PET materials were measured. It was found that when the overall content of miscellaneous diols in EG was lower than 5%, the molecular weights and thermal properties of the prepared PET materials were very similar to that of PET synthesized from pure EG. The miscellaneous diols were less likely to be incorporated into PET resin because of the steric hindrance of the alkyl group in diols to the esterification and polycondensation reactions. Instead, they preferred to undergo dehydration reactions to form low-boiling-point aldehydes and hemiacetals, which could be removed from the reaction system during the reactions. Three bio-EG samples at purities of 99.9, 98.5, and 95.8 wt % were used for the bio-PET synthesis. Transparent and colorless bio-PET samples were obtained, demonstrating that the presence of miscellaneous diols does not have negative effects on the color quality of PET. The physical properties of bio-PET prepared with bio-EG at a purity of higher than 98 wt % were nearly the same as those of PET derived from pure EG. At a lower bio-EG purity of 95.8 wt %, the tensile strength of the obtained bio-PET sample was slightly decreased. The comprehensive results of property characterization show that bio-PET materials prepared with bio-EG at purity higher than 95 wt % could be used as widely as the conventional petro-PET resin without notable deterioration in their performance.

Abstract  To study the potential for delayed Type IV dermal sensitivity of a new preservative system containing 1,2-hexanediol and caprylyl glycol, 200-subject repeat insult patch tests were performed with a 15% mixture of 1,2-hexanediol and caprylyl glycol (equal parts of the 2 ingredients) in carbomer gel and a cosmetic formulation at an actual use concentration. No delayed Type IV hypersensitivity reactions were observed.

Abstract  Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead, they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR (Fourier transform infrared) spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance and, therefore, particles prepared in this study should mimic atmospheric mixed-phase aerosol particles. Some results of this study tend to be in agreement with previous microscopy experiments, but others, such as phase separation properties of 1,2,6-hexanetriol, do not agree with previous work. Because the particles studied in this experiment are of a smaller size than those used in microscopy studies, the discrepancies found could be a size-related effect.

Abstract  The micelle formation process for a typical anionic surfactant. sodium dodecyl sulfate, and a typical cationic surfactant, dodecyltrimethylammonium bromide, has been investigated in a series of mixed solvents consisting of different concentrations of isomeric hexanediols (1,2-hexanediol and 1,6-hexanediol) in water. The critical micelle concentrations and the degrees of counterion dissociation of the mixed micelles were obtained from conductance experiments. Luminescence probing experiments have been used to determine the concentration of micelles in solution and, hence, the micellar aggregation numbers of the surfactants in the mixed solvent systems. The alcohol aggregation numbers were determined by combining the partition coefficients (obtained using NMR paramagnetic relaxation enhancement experiments) with the micellar concentrations from the luminescence probing experiments. All these results are interpreted in terms of the difference in the interaction of the isomeric hexanediols with the surfactant as a function of the position of the hydroxyl groups on the six-carbon chain of the alcohol.

Abstract  Long chain aliphatic 1,2-diols like 1,2-hexanediol and 1,2-octanediol can be converted to the corresponding alpha-hydroxy-alkanoates with total chemoselectivity, in an oxidation catalyzed by an aqueous gold sol under O-2 atmosphere. The sol is stabilized with poly(vinylalcohol), and the reaction is performed in alcohol solvents. Two methods are proposed for the efficient recycling of the colloidal Au catalyst. Firstly a solvent-resistant membrane filtration can be applied. As the membrane material, poly(dimethylsiloxane) is chosen. Secondly, in appropriate conditions, the reaction proceeds in the liquid biphasic mode, and the aqueous Au sol can be recycled by phase separation. Using either of both approaches, the colloidal stability and catalytic activity can be preserved over several recycles.

Abstract  Background: Traditional preservation systems currently used in cosmetic and skin care products are safe and effective. New ingredients with similar efficacy are continually being introduced to fulfill this function. Objective: To study the potential for delayed type IV allergic hypersensitivity and irritation of a new preservative system containing 1,2-hexanediol and caprylyl glycol. Methods: A 200-subject repeat insult patch test (RIPT) was performed. A 15% mixture of 1,2-hexanediol and caprylyl glycol (equal parts of the two ingredients) in carbomer gel was placed under a series of 9 continuous occlusive induction patches, each 48 hours in duration. Three induction patches were applied each week, for a total of 3 weeks. Following a 10-day rest period during which no patches were applied, a single challenge application using the same mixture was applied and left on for 48 hours and read at 48 and 72 hours postapplication. A cosmetic formulation containing this same preservation system at an actual use concentration was tested by the same RIPT protocol. Results: Two hundred and twelve subjects completed the study. One hundred and sixty-eight were female and 44 were male ranging in age from 18 to 70 years. No reactions were seen during the induction or challenge phases. An additional 212 subjects were enrolled in a separate RIPT that evaluated the cosmetic formulation containing the same preservation system. No delayed type IV allergic hypersensitivity or irritation reactions were observed. Conclusion: A new preservative system utilizing 1,2-hexanediol and caprylyl glycol did not induce delayed type IV allergic hypersensitivity or irritation in human subjects.

Abstract  A study has been made of the acetoxylation of 1-hexene and cyclohexene in the presence of PdCl42- and a nitrate-iodate reoxidative system ensuring high yields of the corresponding acetoxyalkanes. It has been established that a binuclear pi-olefinic bridge-type palladium complex is a catalytically active particle. It is assumed that the mechanisms of formation of 1,2-hexanediol monoacetate and diacetoxycyclohexane differ at the final stage of transformation of the acetoxonium ion. Acetoxylation is retarded by the reaction products, which screen the coordination sphere of palladium.

Abstract  Aqueous dilute solutions of 2-butoxyethanol, 1,2-hexanediol, tert-butanol, 1-pentylamine and 1-butylamine are analized through the dynamic light scattering technique. The mutual diffusion coefficient is determined against amphiphile composition, showing, in all cases, clear minima in the dilute region. Using the Stokes-Einstein relation, the mean size of the aggregates is also obtained as a function of mole fraction. For enough concentrated solutions, structures in the range 2-20 angstrom are observed. It is found that both their size and the minimum amphiphile mole fraction for which aggregation is observed are strongly correlated with the hydrophobic character of the amphiphile. (C) 2017 Elsevier B.V. All rights reserved.

Abstract  We report the use of the ionic liquid tetrabutylphosphonium bromide as a solvent and catalyst for dehydration of diols to conjugated dienes. This system combines stability, high reaction rates, and easy product separation. A reaction mechanism for the model compound 1,2-hexanediol is proposed and experimentally corroborated. This particular mechanism allows for the selective formation of conjugated dienes, in contrast with purely acidic catalysis. Next, the reaction is also performed on various other diols. As a first application, we assessed the biobased production of 1,3-butadiene. With 1,4-butanediol as the starting material, a 94% yield of butadiene was reached at 100% conversion.

Abstract  Sorbitol can be selectively transformed into liquid alkanes over a bifunctional catalytic system Pt/ZrO2 + TiO2-WOx. In this paper, we investigated the reaction mechanism by carefully analyzing the numerous products issued from sorbitol and by studying the reactivity of some identified intermediates (1-hexanol 2-hexanol, 2-hexanone, 2,5-dimethyltetrahydrofuran, 1,2-hexanediol and 1,2,6-hexanetriol). This led us to propose that C-C cleavage reactions occur on terminal C-C bonds and mainly consist of dehydrogenation-decarbonylation reactions. The limiting steps of the sorbitol transformation are the isosorbide and mono-oxygenated intermediate transformations, especially the hydrogenation of ketones. It is also assessed that diols or triols with n carbon atoms are mainly converted in compounds with n - 1 carbon atoms. Short compounds (1 to 3 carbon atoms) are obtained via a dehydrogenation-retro-aldol reaction pathway and not from isosorbide conversion. (C) 2014 Elsevier Inc. All rights reserved.

Abstract  Parabens are used as antimicrobial preservatives in consumer products. Exposure to methylparaben (MP) has been associated with adverse health outcomes, therefore, an alternative compound, 1,2-hexanediol (1,2-H), has been applied for cosmetics. In the present study, the phototoxicity of MP and 1,2-H, as well as the toxic effect caused by chronic exposure, were investigated using Daphnia magna. The 48 h acute toxicity tests with D. magna were conducted under indoor or ultraviolet (UV) light irradiation conditions, i.e., exposure to 4 h/d sunlight. Changes in the transcription of genes related to oxidative stress were determined in D. magna juveniles, to investigate the underlying mechanism of phototoxicity. The 21 d chronic toxicity tests of MP and 1,2-H were performed under indoor light irradiation. Exposure to MP under environmental level of UV light was more detrimental to D. magna. Transcripts of catalase and glutathione-S-transferase genes in D. magna was significantly increased by co-exposure to MP and UV light. After 21 d of chronic exposure to MP and 1,2-H, the reproduction no-observed effect concentrations for D. magna were 1 and >10 mg/L, respectively. The present study showed that exposure to UV could magnify the toxicity of MP on daphnids. Although acute and chronic toxicities of 1,2-H were generally lower than those of MP, its effects on other aquatic organisms should not be ignored. Further studies are needed to identify other mechanisms of MP phototoxicity.

Abstract  Caprylyl glycol and related 1,2-glycols are used mostly as skin and hair conditioning agents and viscosity agents in cosmetic products, and caprylyl glycol and pentylene glycol also function as cosmetic preservatives. The Cosmetic Ingredient Review (CIR) Expert Panel noted that, while these ingredients are dermally absorbed, modeling data predicted decreased skin penetration of longer chain 1,2-glycols. Because the negative oral toxicity data on shorter chain 1,2-glycols and genotoxicity data support the safety of the 1,2-glycols reviewed in this safety assessment, the Panel concluded that these ingredients are safe in the present practices of use and concentration described in this safety assessment.

Abstract  The objective of the present study is to investigate the effect of hydrocarbon chain length in 1,2-alkanediols on percutaneous absorption of metronidazole (MTZ). Twelve formulations (1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol in 4% concentration, 1,2-hexanediol, and 1,2-heptanediol in 1% concentration, in the absence and presence of 1,4-cyclohexanediol, respectively) were studied in an in vitro hairless mouse skin model using Franz diffusion cell. Based on the flux values and retardation ratios (RR), a penetration retardation effect on percutaneous absorption of MTZ was observed for the formulations containing 1,2-diols having six- to seven-carbon chain in the presence of 1,4-cyclohexanediol (1,2-hexanediol with chain length of six hydrocarbons, RRs are 0.69 and 0.76 in the concentration of 4% and 1%, respectively; 1,2-heptanediol with chain length of seven hydrocarbons, RR is 0.78 in the concentration of 1%). On the other hand, no retardation effect was observed in formulations containing short alkyl chains (RRs of 1,2-propanediol, 1,2-butanediol, and 1,2-pentanediol are 0.99, 1.61, and 0.96, respectively). Instead, a penetration enhancement effect was observed for 1,2-diols having four and five carbons. In other words, effect of 1,2-alkanediols on percutaneous absorption of MTZ can be systematically modulated by simply varying number of -CH2 groups in the hydrocarbon chain-from being a penetration enhancer to retardant. These observations shed light on mechanism of the penetration enhancement and retardation effect and provide insight into rational design of penetration enhancers and retardants. Furthermore, the combination of 1,2-alkanediols and 1,4-cyclohexanediol could become a general vehicle for controlled release of pharmaceutical and cosmetic active ingredients.

Abstract  The ruthenium aqua complexes [cp*Ru(OH2)(N-N)](OTf) (cp* = [small eta]5-pentamethylcyclopentadienyl, N-N = 2,2[prime or minute]-bipyridine, phen = 1,10-phenanthroline, OTf- = trifluoromethanesulfonate) and the acetonitrile complex [cpRu(CH3CN)(bipy)](OTf) (cp = [small eta]5-cyclopentadienyl) are water-, acid-, and thermally stable (200 [degree]C) catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOTf as a co-catalyst, they effect the deoxygenation of 1,2-hexanediol to 1-hexanol and hexane. Glycerol is deoxygenated to 1-propanol in up to 18% yield and under more forcing conditions completely deoxygenated to propene. The structure of the acetonitrile pro-catalyst [cpRu(CH3CN)(bipy)](OTf) has been determined by X-ray crystallography (space group P[1 with combining macron] (a = 9.3778(10) A; b = 10.7852(10) A; c = 11.1818(13) A; [small alpha] = 101.718(5)[degree]; [small beta] = 114.717(4)[degree]; [gamma] = 102.712(5)[degree]; R = 3.95%).

Abstract  Two tests for biodegradability, the modified OECD test and the modified Sturm test, were compared by application to 5 organic compounds (aniline, monoethanolamine, pentaerythritol, 1,6-dihydroxyhexane, and 2,4,6-trichlorophenol), using activated sludge from a full scale sewage works as inoculum. In both tests, there was 70 per cent reduction in dissolved organic carbon for all the test compounds. In the modified Sturm test, however, when biodegradability was assessed on the bases of carbon dioxide production, it appeared to be much lower. The discrepancy between the results was attributed to carbon assimilation and was most obvious when a preconditioned innoculum was used. The implication for standardization of tests on biodegradability are indicated.

Abstract  Silicon nanowire possesses great potential as the material for renewable energy harvesting and conversion. The significantly reduced spectral reflectivity of silicon nanowire to visible light makes it even more attractive in solar energy applications. However, the benefit of its use for solar thermal energy harvesting remains to be investigated and has so far not been clearly reported. The purpose of this study is to provide practical information and insight into the performance of silicon nanowires in solar thermal energy conversion systems. Spectral hemispherical reflectivity and transmissivity of the black silicon nanowire array on silicon wafer substrate were measured. It was observed that the reflectivity is lower in the visible range but higher in the infrared range compared to the plain silicon wafer. A drying experiment and a theoretical calculation were carried out to directly evaluate the effects of the trade-off between scattering properties at different wavelengths. It is clearly seen that silicon nanowires can improve the solar thermal energy harnessing. The results showed that a 17.8 % increase in the harvest and utilization of solar thermal energy could be achieved using a silicon nanowire array on silicon substrate as compared to that obtained with a plain silicon wafer.