Low-molecular-weight components of olive oil mill wastewaters

A new lignan 1-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-6-(3-acetyl-4-hydroxy-5-methoxyphenyl)-3,7-dioxabicyclo[ 3.3.0]octane, the secoiridoid 2H-pyran-4-acetic acid,3-hydroxymethyl-2,3-dihydro-5-(methoxycarbonyl)-2- methyl-, methyl ester, the phenylglycoside 4-[β -D-xylopyranosyl-(1→6)]-β -D-glucopyranosyl-1,4-dihydroxy-2- methoxybenzene and the lactone 3-[1-(hydroxymethyl)-1-propenyl] δ -glutarolactone were isolated and identified on the basis of spectroscopic data including two-dimensional NMR, as components of olive oil mill waste-waters. The known aromatic compounds catechol, 4-hydroxybenzoic acid, protocatechuic acid, vanillic acid, 4-hydroxy- 3,5-dimethoxybenzoic acid, 4-hydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, tyrosol, hydroxytyrosol, 2-(4-hydroxy-3-methoxy)phenylethanol, 2-(3,4-dihydroxy)phenyl-1,2-ethandiol, p-coumaric acid, caffeic acid, ferulic acid, sinapic acid, 1-O-[2-(3,4-dihydroxy)phenylethyl]-(3,4-dihydroxy)phenyl-1,2-ethandiol, 1-O-[2-(4- hydroxy)phenylethyl]-(3,4-dihydroxy)phenyl-1,2-ethandiol, D(+)-erythro-1-(4-hydroxy-3-methoxy)-phenyl-1,2,3- propantriol, p-hydroxyphenethyl-β-D-glucopyranoside, 2(3,4-dihydroxyphenyl)ethanol 3β-D-glucopyranoside, and 2(3,4-dihydroxyphenyl)ethanol 4β-D-glucopyranoside were also confirmed as constituents of the waste-waters

Preparation of highly fluorinated diols containing ether linkages.

Hydroxy-terminated perfluoroethers and polyurethane resins derived from ethers have outstanding chemical resistance and good thermal properties. They can be used as potting compounds, coatings, and seals. The hydroxy-terminated ethers serve as intermediates in the synthesis of highly fluorinated elastomers and adhesives

A novel synthesis of 2'-hydroxy-1',3'-xylyl crown ethers

Six novel 2' - hydroxy - 1',3' - xylyl crown ethers (8a–e and 13)1 have been synthesized utilizing the allyl group to protect the OH function during the cyclization reaction. The macrocycles 6a-e were formed in yields of 26 to 52%, by intermolecular reaction of 4 - chloro - 2,6 - bis(bromomethyl) - 1 - (2 - propenyloxy)benzene (5) with polyethylene glycols; 6a was also obtained by an intramolecular cyclization reaction of monotosylate 14.\ud A 30-membered ring with a 2' - hydroxy - 1',3' - xylyl sub-unit was obtained in 87% yield by reaction of ditosylate 9 with bis [2 - (o - hydroxyphenoxy)ethyl]ether (11) in the presence of cesium fluoride. The synthesis of crown ethers with a 2' - hydroxy - 1',3' - xylyl sub-unit (1c–e, H for CH3) by demethylation of the corresponding 2'-methoxy crown ethers 1c–e with lithium iodide were unsuccessful; it would appear that the demethylation reaction is restricted to 15- and 18-membered rings. One of the 2' - hydroxy - 1',3' - xylyl crown ethers 8d forms a crystalline 1:1-complex with water

Characterization of the human omega-oxidation pathway for omega-hydroxy-very-long-chain fatty acids

Very-long-chain fatty acids (VLCFAs) have long been known to be degraded exclusively in peroxisomes via beta-oxidation. A defect in peroxisomal beta-oxidation results in elevated levels of VLCFAs and is associated with the most frequent inherited disorder of the central nervous system white matter, X-linked adrenoleukodystrophy. Recently, we demonstrated that VLCFAs can also undergo omega-oxidation, which may provide an alternative route for the breakdown of VLCFAs. The omega-oxidation of VLCFA is initiated by CYP4F2 and CYP4F3B, which produce omega-hydroxy-VLCFAs. In this article, we characterized the enzymes involved in the formation of very-long-chain dicarboxylic acids from omega-hydroxy-VLCFAs. We demonstrate that very-long-chain dicarboxylic acids are produced via two independent pathways. The first is mediated by an as yet unidentified, microsomal NAD(+)-dependent alcohol dehydrogenase and fatty aldehyde dehydrogenase, which is encoded by the ALDH3A2 gene and is deficient in patients with Sjogren-Larsson syndrome. The second pathway involves the NADPH-dependent hydroxylation of omega-hydroxy-VLCFAs by CYP4F2, CYP4F3B, or CYP4F3A. Enzyme kinetic studies show that oxidation of omega-hydroxy-VLCFAs occurs predominantly via the NAD(+)-dependent route. Overall, our data demonstrate that in humans all enzymes are present for the complete conversion of VLCFAs to their corresponding very-long-chain dicarboxylic acids

Steroid substrate-induced epimerase mechanism in the active site of the human 11β-hydroxysteroid dehydrogenase type 1

Cytochrome P4507B1 7[alpha]-hydroxylates dehydroepiandrosterone (DHEA), epiandrosterone (EpiA) and 5[alpha]-androstane-3[beta],17[beta]-diol (Adiol). 11[beta]-Hydroxysteroid dehydrogenase type 1 (11[beta]-HSD1) interconverts 7[alpha]- and 7[beta]- forms. Whether the inter-conversion proceeds through oxido-reductive steps or epimerase activity is investigated. Experiments using ^3^H-labeled 7[beta]-hydroxy-DHEA, 7[beta]-hydroxy-EpiA and 7[beta]-hydroxy-Adiol show the ^3^H-label to accumulate in 7-oxo-DHEA trap but neither in 7-oxo-EpiA nor 7-oxo-Adiol traps. Computed models of 7-oxygenated steroids dock in the active site of 11[beta]-HSD1 either in a flipped or turned form relative to cortisone and cortisol. 7-Oxo-steroid reduction in 7[alpha]- or 7[beta]-hydroxylated derivatives results from either turned or flipped forms. 11[beta]-HSD1 incubation in H~2~^18^O medium with each 7-hydroxysteroid did not incorporate ^18^O in 7-hydroxylated derivatives of EpiA and Adiol independently of the cofactor used. Thus oxido-reductive steps apply for the interconversion of 7[alpha]- and 7[beta]-hydroxy-DHEA through 7-oxo-DHEA. Epimerisation may proceed on the 7-hydroxylated derivatives of EpiA and Adiol through a mechanism involving the cofactor and Ser170

Efficient routes to epimerically-pure side-chain derivatives of lanosterol

A technically simple route is described to individual epimers of side-chain derivatives of lanosterol (3-hydroxy-5-lanosta-8,24-diene). Epimerically pure 24,25-epoxy-, 24,25-dihydroxy- and 24-bromo-25-hydroxy-lanosterol have been prepared in good yield from commercial (50-60%) lanosterol. Hypophosphorous acid was used as a catalyst for the cohalogenation of the 24(25) bond and also for the efficient conversion of 24,25-epoxy- and 24-bromo-25-hydroxylanosterol to epimerically pure 24(R) or 24(S)-24,25-dihydroxylanosterols

Micellar electrokinetic capillary chromatography—Synchronous monitoring of substrate and products in the myrosinase catalysed hydrolysis of glucosinolates

A micellar electrokinetic capillary chromatography (MECC) method has been developed for monitoring the myrosinase catalysed hydrolysis of 2-hydroxy substituted glucosinolates and the simultaneous formation of the corresponding degradation products (oxazolidine-2-thiones (OZTs) and nitriles). Glucosibarin ((2R)-2-hydroxy-2-phenylethylglucosinolate) was chosen as the model glucosinolate owing to the difficulties in determining hydrolysis rates of this type of substrates in traditional UV-assays. The method was afterwards validated with glucobarbarin ((2S)-2-hydroxy-2-phenylethylglucosinolate) and progoitrin ((2R)-2-hydroxybut-3-enylglucosinolate). Aromatic glucosinolates without a 2-hydroxy group in their side chains, such as glucotropaeolin (benzylglucosinolate) and gluconasturtiin (phenethylglucosinolate) were also tested. Formation of the glucosinolate hydrolysis products was monitored simultaneously at 206 nm and 230 nm. This allowed estimation of the extinction coefficient of the OZT derived from glucosibarin, which was found to be 18,000M−1 cm−1 and 12,000M−1 cm−1 at 206 nm and 230 nm, respectively. The developed method has limit of detection of 0.04mM and 0.06mM and limit of quantification of 0.2mM and 0.3mM for the glucosibarin derived OZT and nitrile, respectively. Linearity of the glucosinolate concentration was examined at six concentration levels from 2.5mMto 100mMand at 206 nm a straight line (R2 = 0.9996) was obtained. The number of theoretical plates (N) at the optimal system conditions was 245,000 for the intact glucosibarin, 264,000 for the OZT and 252,000 for the nitrile

Computational Study of the Electronic Structure of Various Cobalt (Hydroxy) Oxides in Electrolysis Reactions

In their electrolysis reaction to produce H 2 fuel, the Solar Thermal Decoupled Electrolysis group at Valparaiso University observed increased reaction rate as time goes on and proposed that the deposited products on the Ni anode might be conductive and acting as a new electrode surface. It is of great interest to gain a better understanding of the underlying mechanism. In this study, the structure and stability of various cobalt (hydroxy)oxide species on a Ni (111) surface were determined from first-principles calculations to see if the observations made by the Solar Thermal Decoupled Electrolysis group are consistent with theoretical results and what could be responsible for the extended conductive electrode. From the known bulk crystal structures of various cobalt (hydroxy)oxide species, mono-layers of each of these materials were constructed. These monolayers were then placed on a Ni (111) metal support and optimal configurations of the combined systems were determined. The electronic structure of the cobalt (hydroxy) oxide monolayers and bulks will be reported

Hydroxy terminated perfluoro ethers Patent

Chemical synthesis of hydroxy terminated perfluoro ethers as intermediates for highly fluorinated polyurethane resin

Fluorohydroxy ethers

The preparation of poly(polyfluoroalkylene-glycol) mono (hydroxy polyfluoroalkylene) ethers from fluoroalkylene oxides is described