Abstract  Supercritical adsorption isotherms were measured for eicosane and 1,2-hexanediol on activated carbon and chromosorb 101 at 324.2K and 11.45 MPa. Adsorption isotherms of both solutes on activated carbon have typical shapes and can be modelled by Langmuir or Freundlich equations. For chromosorb 101 the equilibrium loadings are a linear function of the concentration of the solute in the fluid phase. These results suggest that for chromosorb 101 a partition of the solute between two immiscible phases rather than adsorption occurs. (c) 2005 Elsevier B.V. All rights reserved.

Abstract  In this study, the hydrogels composed of polyvinylpyrrolidone (PVP), kappa-carrageenan (kappa C), and 1,2-hexanediol (HD) were prepared by gamma-ray irradiation. The radiation dose was 25 kGy and the concentration of kappa C was 3 wt%. The physical properties of the hydrogels were investigated as a function of the concentrations of PVP and HD. The gel content and the tensile strength increased with increasing PVP concentration due to the crosslinking between the pyrrolidone molecules and decreased with increasing HD concentration. The degree of swelling was inversely proportional to the gel content because the highly crosslinked hydrogels had a tighter structure, hence reducing their water absorption. The antibacterial tests indicated that the hydrogels containing HD had antibacterial activity.

Abstract  The paper presents the results of viscosity measurements performed on 1,2-hexanediol in water and n-, s- and t-butanol solutions in the whole range of concentrations, at different temperatures. The activation energy for viscous flow of the solutions and the viscosity excess, were determined.

Abstract  Solubilities of 1-hexanol, or 1,2-hexanediol, or 2-hydroxypropanoic acid ethyl ester, or 2-hydroxyhexanoic acid ethyl ester in supercritical CO2 have been measured at T=(311, 318, and 323, or 328)K in the pressure range from 1 MPa to 8 MPa. The measurements have been performed using a flow-type equipment coupled with a novel analytical procedure. An accurate correlation method for the solubility of low volatile substances in supercritical CO2 based on the equilibrium condition for the solute has I,een proposed and successfully applied for the interpolation of our experimental results. (C) 1998 Academic Press.

Abstract  Dilatometric measurements of excess molar volumes. V-E and excess partial molar volumes, (V) over bar (E)(i) have been made for binary mixtures of acetonitrile with 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, and 1,2-hexanediol at 20 degreesC over the entire composition range. V-E for acetonitrile + 1,2-ethanediol and 1,2-propanediol mixtures are negative over the entire range of mole fractions and positive values are obtained for all remaining mixtures. The results are explained in terms of dissociation of the self-associated 1,2-alkanediol molecules and the formation of aggregates between unlike molecules through O-H . . .N-C hydrogen bonding. From the experimental results. VF were calculated and correlated by Redlich-Kister type function in terms of mole fractions. The excess partial molar volumes were extrapolated to zero concentration to obtain the limiting values at infinite dilution, (V) over bar (/E,o)(i).

Abstract  The paper proposes a new method for amino acid determination which can be applied for amino acid profiling in solutions for parenteral nutrition. The MEKC method based on a mixed micellar system was developed for the separation of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatized amino acids. Background electrolyte was based on tris-borate buffer with high alkaline pH. Sodium dodecyl sulfate micelles were modified using 1,2-hexanediol as a co-surfactant. The effect of the modifier on amino acid migration was studied with respect to hydrophobicity of the analytes. The modifier appeared to be suitable to improve the separation of AQC-tagged amino acids without an adverse effect on buffer ionic strength or EOF velocity. The method was successfully validated and applied for amino acid profiling in medicinal preparations for parenteral nutrition. The results obtained were compared with a reference chromatographic method (amino acid analyser).

Abstract  UNLABELLED: Preservative agents determining the shelf life of cosmetic products must have effective antimicrobial activity while meeting safety requirements for topical use. In this study, we determined the antimicrobial activity of 1,2-hexanediol against several Gram-positive and Gram-negative bacteria. Antimicrobial susceptibility tests have shown that 1,2-hexanediol exhibits broad-spectrum activity against Gram-positive and Gram-negative bacteria with MICs of 0·5-2% (v/v). The bactericidal concentration of 1,2-hexanediol was ranging from 1 to 2 × MIC as demonstrated by time-kill curve assay. A membrane depolarization assay showed that 1,2-hexanediol disrupted the cytoplasmic membrane potential. A checkerboard assay indicated that the effective concentration of 1,2-hexanediol was reduced up to 0·25-0·5 × MIC when combined with macelignan and octyl gallate against Gram-positive bacteria. However, this combination was not effective against Gram-negative bacteria. A turbidity reduction assay demonstrated that the combination of a high concentration of 1,2-hexanediol with food-grade antimicrobial compounds could trigger lytic activity towards Bacillus cereus cells. The remaining cell turbidity was 24·6 and 22·2% when 2% of 1,2-hexanediol was combined with 8 mg l(-1) octyl gallate or with 32 mg l(-1) macelignan respectively. This study showed that food-grade antimicrobial compounds may be used in combination with 1,2-hexanediol to increase its efficacy as a preservative agent in cosmetics.

SIGNIFICANCE AND IMPACT OF THE STUDY: The antimicrobial activity of 1,2-hexanediol against Gram-positive and Gram-negative bacteria was potentiated with food-grade antimicrobials including xanthorrhizol, macelignan, panduratin A and octyl gallate, which have already been reported to display anti-inflammatory and other beneficial activities related to cosmetics. Therefore, the combination of 1,2-hexanediol and these food-grade antimicrobial agents would have benefits not only for increasing the antimicrobial activity but also in cosmetics use.

Abstract  In this study, we investigated a novel series of micelle modifiers useful to alter selectivity in micellar electrokinetic capillary chromatography (MEKC). These modifiers were alkyl polyalcohols, including 1-octanol, 1,2-octanediol, 1,2,3-octanetriol, 1,2-hexanediol, and 1,2-butanediol, which act as class I organic modifiers in that their effects are on the sodium dodecyl sulfate (SDS) micelle rather than the surrounding aqueous phase. This characteristic allows the alkyl polyols to effect resolution when applied at concentrations as low as 20 mM (0.25% v/v) by altering the selectivity observed with SDS without a modifier. The effects of the alkyl polyols on the critical micelle concentration of SDS, electroosmotic flow, and electrophoretic mobility of the SDS micelle are presented. These modifiers had little impact on the migration time window at the concentrations explored. Changes in selectivity induced by the alkyl polyols for a large set of model compounds are presented. Trends indicate that solutes capable of forming hydrogen bonds tend to decrease their interactions with the micellar phase while nonhydrogen bonding solutes increase their interactions upon addition of the modifiers. The solvation parameter model was used to characterize the induced changes in selectivity. This model suggests that even though the modifiers are structurally similar, each produced a unique set of system constants. It was also demonstrated that the addition of alkyl polyols improved the correlation between the partition coefficients of SDS and water to 1-octanol and water. The usefulness of the alkyl polyols was demonstrated by examining their effects on the separation of 11 priority phenols.

Abstract  The urinary metabolites of 2,5-dimethylhexane (2,5-DMH) in male Fischer 344 rats, administered the hydrocarbon by gavage, included 2,5-dimethyl-1-hexanoic acid, 2,5-dimethyl-1,2-hexanediol, 2,5-dimethyl-1,5-hexanediol, 2,5-dimethyl-2,5-hexanediol and 2,5-dimethyl-5-hydroxy-1-hexanoic acid. Metabolism favored the formation of the diols. The metabolites were identified using gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Histopathologic examination revealed moderate hyaline droplet formation in the renal proximal tubule.

Abstract  Dichloro or chloro ruthenium(III) complexes with polyaminopolycarboxylato ligands were synthesized (ligands: ethylenediaminetetraacetate (edta), N,N-dimethylethylenediamine-N,N'-diacetate (N,N'-Me(2)edda), and nitrilotriacetate (nta)). Magnetic moments of these ruthenium(III) complexes are about 2. So they are low spin complexes. The oxidation of olefines (cyclohexene, styrene or 1-hexene) catalyzed by these ruthenium(III) complexes in the presence of hydrogen peroxide has been studied: catalyst, polyaminopolycarboxylatoruthenium(III) complex (1.0 x 10(-3) mol dm(-3)); substrate, olefin (0.2 mol dm(-3)); co-oxidizing reagent, hydrogen peroxide (0.75 mol dm(-3)); solvent, 1,4-dioxane-water (1:1 (v/v)). The chloro Hedta ruthenium complex ([RuCl(Hedta)](-)) was the most effective catalyst for the oxidation under these conditions. The main product of this reaction was diol (yield:48%, 1,2-cyclohexanediol; 68%, 1-phenyl-1,2-ethanediol; 6.5%, 1,2-hexanediol). Since UV/visible spectrum of the edta complex in the presence of hydrogen peroxide shows the formation of the oxoruthenium(V) complex, the oxoruthenium(V) species is supposed to be the active species.

Abstract  A correct description of the aerosol's phases is required to determine its gas/particle partitioning, its reactivity and its water uptake and release. In this study, we investigate organic/electrolyte interactions of ammonium sulfate, nitrate and sodium chloride with substances containing carboxylic acids (COOH) and hydroxyl (OH) functional groups. As organic model compounds, we chose polyols with different OH/CHn (n = 0-3) ratios-namely, glycerol, 1,4-butanediol, and 1,2-hexanediol-as well as PEG 400 and a mixture of dicarboxylic acids consisting of malic, malonic, maleic, glutaric, and methylsuccinic acid. Bulk solubility and water activity measurements of these model systems together with a survey of literature data showed that NaCl is a salting-out agent for alcohols and organic acids whereas ammonium nitrate and sulfate exhibited salting-in and salting-out tendencies depending on the nature and number of functional groups as well as on the concentration of the solution. All investigated salts induce a liquid-liquid phase separation in the 1,2-hexanediol/water system. Considering the composition of the tropospheric aerosol, such phase separations might indeed occur frequently when particles in the atmosphere are exposed to varying relative humidity. To complement the bulk experiments, we investigated single particles consisting of ammonium sulfate and dicarboxylic acids as well as of ammonium sulfate and PEG 400 in an electrodynamic balance. Whereas the relative humidities of total deliquescence as well as the water uptake and release of the fully deliquesced particles are in good agreement with the bulk results and represent thermodynamic equilibrium, the water uptake before full deliquescence shows significant deviations. These deviations may be caused by morphological effects.

Abstract  Dilatometric measurements of excess molar volumes and excess partial molar volumes have been made for binary mixtures of N, N-dimethylformamide with 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, and 1,2-hexanediol at 20 degrees C over the entire composition range. The results are explained in terms of dissociation of the self-associated 1,2-alkanediol molecules and the formation of aggregates between unlike molecules through C = O ... 3H-O hydrogen bonding. Further, the effects of difference in chain lengths and steric factors on molecular interactions are also examined. From the experimental results, excess molar volumes were calculated and correlated by a Redlich-Kister type function in terms of mole fractions.

Abstract  The substrate scope of the flavoprotein alditol oxidase (AldO) from Streptomyces coelicolor A3(2), recombinantly produced in Escherichia coli, was explored. While it has been established that AldO efficiently oxidizes alditols to D-aldoses. this study revealed that the enzyme is also active with a broad range of aliphatic and aromatic alcohols. Alcohols containing hydroxy groups at the C-1 and C-2 positions like 1,2,4-butanetriol (K(m) =170 mM, k(cat) = 4.4 s(-1)), 1,2-pentanediol (K(m) = 52 mM, k(cat) = 0.85 s(-1)) and 1,2-hexanediol (K(m) = 97 mM, k(cat) = 2.0 s(-1)) were readily accepted by AIM Furthermore, the enzyme was highly enantioselective for the oxidation of 1,2-diols [e.g.. for 1-phenyl-1,2-ethanediol the (R)-enantiomer was preferred with all E-value of 74]. For several diols the oxidation products were determined by GC-MS and NMR. Interestingly. for all tested 1,2-diols the products were found to be the alpha-hydroxy acids instead of the expected alpha-hydroxy aldehydes. Incubation of (R)-1-phenyl-1,2-ethanediol with (18)O-labelled water (H(2)(18)O) revealed that a second enzymatic oxidation step occurs via the hydrate product intermediate. The relaxed Substrate specificity. excellent enantioselectivity, and independence of coenzymes make AldO an attractive enzyme for the preparation of optically pure 1,2-diols and alpha-hydroxy acids.

Abstract  The polyol dehydrogenase PDH-11300 from Deinococcus geothermalis was cloned, functionally expressed in Escherichia coli and biochemically characterized. The enzyme showed the highest activity in the oxidation of xylitol and 1,2-hexanediol and had an optimum temperature of 45 °C. The enzyme exhibited a T⁶⁰₅₀-value of 48.3 °C. The T⁶⁰₅₀ is the temperature where 50% of the initial activity remains after incubation for 1h. In order to elucidate the structural reasons contributing to thermostability, the substrate-binding loop of PDH-11300 was substituted by the loop-region of a homolog enzyme, the galactitol dehydrogenase from Rhodobacter sphaeroides (PDH-158), resulting in a chimeric enzyme (PDH-loop). The substrate scope of this chimera basically represented the average of both wild-type enzymes, but surprisingly the T⁶⁰₅₀ was noticeably increased by 7 °C up to 55.3 °C. Further mutations in the active site led to identification of residues crucial for enzyme activity. The cofactor specificity was successfully altered from NADH to NADPH by an Asp55Asn mutation, which is located at the NAD⁺ binding cleft, without influencing the catalytic properties of the dehydrogenase.

Abstract  From the Rhodobacter sphaeroides mutant D a galactitol dehydrogenase (GDH) was isolated and characterized in an earlier investigation (1). The enzyme expressed activity with a wide spread substrate spectrum, like sugars, sugar alcohols, secondary alcohols or the corresponding ketones and it can be used for the production of the rare sugar L-tagatose by regioselective oxidation of galactitol (2). This study focuses on the preparation of optically pure aliphatic diols by oxidation of one enantiomer or stereospecific reduction of keto-alcohols and diketones. The oxidation of 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol and 1,2-hexanediol occurred highly specific with the S-enantiomer leaving the R-enantiomer of the diols in the reaction vessel. Also (S)-1,2,6-hexanetriol was oxidized by GDH to 1,6-dihydroxy-2-hexanone. The Km values of these reactions decreased with increasing length of the carbon chain. Reduction of hydroxyacetone or 1-hydroxy-2-butanone resulted in an excess of 93% (S)-1,2-propanediol and more than 98% of (S)-1,2-butanediol, respectively. The diketone 2,3-hexanedione was only reduced to (2R,3S)-2,3-hexanediol, one of the possible four configurations. The wide substrate spectrum on one hand and the selectivity in the reaction on the other hand make GDH a very interesting enzyme for the production of optically pure building blocks in the chemical synthesis of bioactive compounds.

Abstract  Galactitol dehydrogenase (GatDH) from Rhodobacter sphaeroides is a multifunctional enzyme that catalyzes in the presence of oxidized beta-nicotinamide adenine dinucleotide (NAD(+)) the interconversion of various multivalent aliphatic alcohols to the corresponding ketones. The recombinant GatDH was provided with an N-terminal His(6)-tag to which distally up to three cysteine residues were attached. This protein construct maintained nearly full enzymatic activity, and it could be covalently immobilized via thiol bonds onto the surface of a gold electrode. Binding of GatDH onto the gold electrode was verified by SPR measurements, and residual enzyme activity was measured by cyclic voltammetry using 1,2-hexanediol as substrate, the cofactor NAD(+) and the redox mediator CTFM (4-carboxy-2,5,7-trinitrofluorenyliden-malonnitrile) in solute form. The results demonstrate the possibility of a directed functional immobilization of proteins on gold surfaces, which represents a proof-of-concept for the development of reactors for electrochemical synthon preparation using dehydrogenases.

Abstract  In a previous study, a synergistic retardation effect of 1,4-cyclohexanediol and 1,2-hexanediol on percutaneous absorption and penetration of metronidazole (MTZ) was discovered. A complex formation between 1,4-cyclohexanediol and 1,2-hexanediol was proposed to be responsible for the observed effect. The objective of this study was to investigate the necessity of hydroxyl group and the ring structure in 1,4-cyclohexanediol on percutaneous absorption and penetration of MTZ. Eleven formulations were studied in an in vitro porcine skin model using glass vertical Frans Diffusion Cell. 1,4-Cyclohexanediol was changed into 1,4-cyclohexanedicarboxylic acid, trans (and cis)-1,2-cyclohexanediol and 1,6-hexanediol, respectively, to study if H-bonding or ring structure would influence the retardation effect. MTZ was applied at infinite dose (100 mg), which corresponded to 750 μg of MTZ. Based on modifier ratios (MR) calculated by the flux values, the retardation effect on percutaneous absorption and penetration of MTZ was found in the formulations containing 1,4-cyclohexanedicarboxylic acid or cis-1,2-cyclohexanediol (MR values were 0.47 for which only contains 1,4-cyclohexanedicarboxylic acid, 0.74 for the formulation containing both 1,4-cyclohexanedicarboxylic acid and 1,2-hexanediol, and 0.90 for the formulation containing cis-1,2-cyclohexanediol and 1,2-hexanediol, respectively). The results showed that the hydroxyl group and structure of 1,4-cyclohexanediol played a significant role in retardation effects and provided valuable insight on the mechanisms of retardation effect through structure-activity relationships.

Abstract  The ruthenium aqua complexes [Ru(H(2)O)(2)(bipy)(2)](OTf)(2), [cis-Ru(6,6'-Cl(2)-bipy)(2)(OH(2))(2)](OTf)(2), [Ru(H(2)O)(2)(phen)(2)](OTf)(2), [Ru(H(2)O)(3)(2,2':6',2''-terpy)](OTf)(2) and [Ru(H(2)O)(3)(Phterpy)](OTf)(2) (bipy = 2,2'-bipyridine; OTf(-) = triflate; phen = phenanthroline; terpy = terpyridine; Phterpy = 4'-phenyl-2,2':6',2''-terpyridine) are water- and acid-stable catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOS(O)(2)CF(3) (triflic acid) as a dehydration co-catalyst they directly convert 1,2-hexanediol to n-hexanol and hexane. The terpyridine complexes are stable and active as catalysts at temperatures > or = 250 degrees C and in either aqueous sulfolane solution or pure water convert glycerol into n-propanol and ultimately propane as the final reaction product in up to quantitative yield. For the terpy complexes the active catalyst is postulated to be a carbonyl species [(4'-R-2,2':6',2''-terpy)Ru(CO)(H(2)O)(2)](OTf)(2) (R = H, Ph) formed by the decarbonylation of aldehydes (hexanal for 1,2-hexanediol and 3-hydroxypropanal for glycerol) generated in the reaction mixture through acid-catalyzed dehydration. The structure of the dimeric complex [{(4'-phenyl-2,2':6',2''-terpy)Ru(CO)}(2)(mu-OCH(3))(2)](OTf)(2) has been determined by single crystal X-ray crystallography (Space group P1 (a = 8.2532(17); b = 12.858(3); c = 14.363(3) A; alpha = 64.38(3); beta = 77.26(3); gamma = 87.12(3) degrees, R = 4.36 %).

Abstract  OBJECTIVE: This study was to investigate the topical skin targeting effects and mechanism of combination penetration modifiers of 1,2-hexanediol (or 1,2-heptanediol) and 1,4-cyclohexanediol on transdermal absorption of metronidazole (MTZ) in different skin models.

METHODS: Six formulations were applied to pig abdominal skin and pig ear skin models, respectively, and the results were compared with the previous data on hairless mouse skin worked out by our laboratory. Four parameters (flux, Tlag, Q24 and targeting ratio) were used to evaluate permeability and targeting effect in skin.

RESULTS: The combined penetration modifiers played a general role on decreasing permeability without reducing skin retention. The most significant skin permeability decrement to MTZ was pig abdominal skin (permeability decrement was ∼20% for hairless mouse skin, 60% for pig abdominal skin and 40% for pig ear skin, respectively) while the strongest skin targeting effect appeared in hairless mouse skin (targeting ratios were 1.79 for hairless mouse skin, 1.24 for pig abdominal skin and 1.05 for pig ear skin, respectively) under the role of penetration modifiers.

CONCLUSIONS: Thickness of stratum corneum (SC) was the major factor impact on skin targeting effect. Selection criteria of skin models also have been discussed in this study.

Abstract  The lipase from Candida cylindracea catalyzes the enantioselective esterification of 2-hydroxy acids in nearly anhydrous organic solvents with primary alcohols as nucleophiles. The nature of the 2-hydroxy acid and organic reaction medium affects the efficiency of catalysis and the enantioselectivity. Straight-chain 2-hydroxy acids are highly reactive and give nearly 100% enantioselectivities in esterification reactions with 1-butanol. Slight branching with a methyl group adjacent to the 2-hydroxy moiety in toluene causes a substantial loss (up to 200-fold) in the lipase's catalytic efficiency with a concomitant loss in enantioselectivity. Losses in catalytic efficiency and enantioselectivity are also observed when the lipase is employed in hydrophilic organic media such as dioxane or tetrahydrofuran as compared to hydrophobic solvents such as toluene. With straight-chain substrates, the lipase is over 100-fold more active in toluene than in tetrahydrofuran or dioxane, while optimal enantioselectivity is observed in toluene. The loss in enantioselectivity in hydrophilic solvents is mainly due to a drop in the catalytic efficiencies of the S isomers, as the R isomers' catalytic efficiencies remain largely unchanged. In highly apolar solvents, such as cyclohexane, enantioselective relaxation occurs due to an increase in the reactivity of the R isomers relative to that of their S counterparts. These findings enabled a rational selection of substrates and solvents for a two-step, chemoenzymatic synthesis of optically active 1,2-diols to be carried out, the first step being the aforementioned enantioselective esterification of 2-hydroxy acids followed by reduction with LiAl(OCH3)3H to give the optically active 1,2-diol. Diols such as (S)-(+)-1,2-propanediol, (S)-(-)1,2-butanediol, (S)-(-)-1,2-hexanediol, and (S)-(-)-4-methyl-1,2-pentanediol were produced in high optical purities (at least 98% enantiomeric excess (ee)).

Abstract  In this work, density and viscosity have been determined for (polyethylene glycol dimethyl ether 250 + 1,2-propanediol, or 1,2-butanediol, or 1,2-pentanediol, or 1,2-hexanediol) binary systems over the whole concentration range at temperatures of (293.15, 303.15, 313.15, 323.15) K and atmospheric pressure. Experimental data of mixtures were used to calculate the excess molar volumes V(E), and viscosity deviations Delta(eta). These results were fitted by the Redlich-Kister polynomial relation to obtain the coefficients and standard deviations. (C) 2008 Elsevier Ltd. All rights reserved.

Abstract  The results of positron annihilation experiments in aqueous solutions of 1,2- and 1,6-hexanediols were compared to those of ultrasonic velocity. For the former, the positron annihilation measurement shows strong hydrophobic interactions and formation of clathrate-like hydrates in solution, although their stoichiometries as well as architecture are untypical. Ultrasonic data for this system seem to be strongly influenced by a relaxation process and do not allow to conclude about formation of open-work structures in this system. For the system water + 1,6-hexanediol both the ultrasonic and annihilation methods suggest formation of labile, water-rich hydrates. They are very weak compared to those existing in the water + 1,2-hexanediol, what results from the hydrophilic hydration competing the hydrophobic one.