Sorbic Alcohol Research Articles

Triplet Photochemistry of Dissolved Black Carbon and Its Effects on the Photochemical Formation of Reactive Oxygen Species.

Dissolved black carbon (DBC) is an important component of dissolved organic matter pool; however, its photochemical properties are not fully understood. In this study, we determined the excited triplet-state quantum yields of DBC (3DBC*) and 1O2 quantum yields (Φ1O2) of six diverse DBCs using sorbic alcohol, 2,4,6-trimethylphenol (TMP), and furfuryl alcohol and compared the results with quantum yields of reference natural organic matters (NOMs). The average Φ1O2 of six DBCs (4.2 ± 1.5%) was greater than that of terrestrial NOM (2.4 ± 0.3%) and comparable to autochthonous NOM (5.3 ± 0.2%). Using TMP as a probe for oxidizing triplets, DBC presented significantly higher apparent quantum yield coefficients for degrading TMP (fTMP) than the reference NOM, reflecting that the fTMP values of low-energy 3DBC* were approximately 12-fold greater than those of low-energy 3NOM*. The differences in the fTMP and Φ1O2 trends among the DBCs indicated that the 3DBC* responsible for these reactions may be from different sources. In addition, DBC was much more effective than NOM, on a carbon-normalized basis, during photodegradation of pharmaceutically active compounds. This result confirms that the presence of DBC can accelerate the photodegradation of contaminants that are susceptible to one-electron oxidation by triplets.

Triplet-State Photochemistry of Dissolved Organic Matter: Triplet-State Energy Distribution and Surface Electric Charge Conditions.

Excited triplet states of chromophoric dissolved organic matter (3CDOM*) are highly reactive species in sunlit surface waters and play a critical role in reactive oxygen species (ROS) formation and pollutant attenuation. In the present study, a series of chemical probes, including sorbic acid, sorbic alcohol, sorbic amine, trimethylphenol, and furfuryl alcohol, were employed to quantitatively determine 3CDOM* and 1O2 in various organic matters. Using a high concentration of sorbic alcohol as high-energy triplet states quencher, 3CDOM* can be first distinguished as high-energy triplet states (>250 kJ mol-1) and low-energy triplet states (<250 kJ mol-1). The terrestrial-origin natural organic matter (NOM) was found to mainly consist of low-energy triplet states, while high-energy triplet states were predominant in autochthonous-origin NOM and effluent/wastewater organic matter (EfOM/WWOM). The 1O2 quantum yields and electron transfer quantum yield coefficients ( fTMP) generated from low-energy triplet states remained constant in all tested organic matters. External phenolic compound showed quenching effects on triplet-state formation and tended to have a higher quenching efficiency for aromatic ketone triplet states, which are the main high-energy triplet states. In comparison with terrestrial-origin NOM, autochthonous-origin NOM and EfOM/WWOM presented lower reaction rate constants for sorbic amines and higher reaction rate constants for sorbic acid, and these differences are likely due to dissimilar surface electric charge conditions. Understanding the triplet-state photochemistry of CDOM is essential for providing useful insights into their photochemical effects in aquatic systems.

Development of Novel Chemical Probes for Examining Triplet Natural Organic Matter under Solar Illumination.

Excited triplet states of chromophoric dissolved organic matter (3CDOM*) are critical transient species in environmental photochemistry. In the present study, sorbic amine (2,4-hexadien-1-amine) and sorbic alcohol were employed as new probe molecules for triplet measurements and compared to the results measured from sorbic acid under identical conditions. Unlike sorbic acid, sorbic amine and sorbic alcohol were not directly photolyzed under solar irradiation. Photosensitized isomerization of the probes with the conjugated diene structure could yield four geometrical isomers. The separation and quantitative determination of the geometrical isomers were accomplished using HPLC and high-resolution NMR analyses. When photoirradiated Suwannee River natural organic matter (SRNOM) was employed as a source of 3CDOM*, significantly different photosensitized isomerization rates were observed for the diverse charged probes. The bimolecular reaction rate constants between 3SRNOM* and the probes were calculated as (0.42 ± 0.1) × 109 M-1 s-1 for sorbic acid, (1.1 ± 0.1) × 109 M-1 s-1 for sorbic alcohol, and (5.2 ± 0.4) × 109 M-1 s-1 for sorbic amine, respectively. The average apparent Φtriplet was (0.96 ± 0.03)% based on an irradiation range of 290 to 400 nm. We developed highly selective and efficient probes for triplet determination and elucidated the different reaction behaviors of these conjugated dienes containing different charged substituents within the photochemical energy transfer process.

Oxidation of Microcystin-LR by Ferrate(VI): Kinetics, Degradation Pathways, and Toxicity Assessments

The presence of the potent cyanotoxin, microcystin-LR (MC-LR), in drinking water sources poses a serious risk to public health. The kinetics of the reactivity of ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) with MC-LR and model compounds (sorbic acid, sorbic alcohol, and glycine anhydride) are reported over a range of solution pH. The degradation of MC-LR followed second-order kinetics with the bimolecular rate constant (kMCLR+Fe(VI)) decreasing from 1.3 ± 0.1 × 10(2) M(-1) s(-1) at pH 7.5 to 8.1 ± 0.08 M(-1) s(-1) at pH 10.0. The specific rate constants for the individual ferrate species were determined and compared with a number of common chemical oxidants employed for water treatment. Detailed product studies using liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) indicated the oxidized products (OPs) were primarily the result of hydroxylation of the aromatic ring, double bond of the methyldehydroalanine (Mdha) amino acid residue, and diene functionality. Products studies also indicate fragmentation of the cyclic MC-LR structure occurs under the reaction conditions. The analysis of protein phosphatase (PP1) activity suggested that the degradation byproducts of MC-LR did not possess significant biological toxicity. Fe(VI) was effective for the degradation MC-LR in water containing carbonate ions and fulvic acid (FA) and in lake water samples, but higher Fe(VI) dosages would be needed to completely remove MC-LR in lake water compared to deionized water.

How to Select the Fire-Resistant Calculation Model for the Completed Steel Structure

Finite element model of the three-dimension steel frame of sorbic alcohol warehouse is built to study the response of the steel structure on fire. The material nonlinearity and geometrical nonlinearity being aroused by high-temperature are taken into account adequately during this computation. Shell elements are used to model the concrete floor slab，beams as well as columns. The rigid connection and flexible connection between the beams and column are considered respectively. In order to reduce the computing amount, the effects of the completed structure and the neighboring span have been explored under the local fire. It turns out that it has more effects on stresses and deflections in the neighboring span than that in others when the whole structure is under local fire. It has greater deflections when using the rigid connection than using flexible connection between the components. Meanwhile, according to the rules of the stresses and the deflections of the structure, the method of selecting the effective and reasonable simulating areas under the local fire is concluded. The conclusions are important for building the reasonable simulating areas on fire and for further studying the mechanical behaviors of the steel structure, also significant for providing references for the fire-resistant calculation of the completed steel structure.

Synthesis of all-cis 2,5-imino-2,5-dideoxy-fucitol and its evaluation as a potent fucosidase and galactosidase inhibitor

We here describe a simple and efficient synthetic method for a non-hydrolysable precursor of a GDP-fucose analogue: The synthesis of the racemic aminofuranofucitol 3 from sorbic alcohol by nitroso-Diels-Alder reaction. This 'all-cis-pyrrolidine', with all substituents occupying a cis position, has been determined as a potent inhibitor of α-L-fucosidase and a moderate inhibitor of α- and β-D-galactosidase. The good recognition of this fucose moiety analogue by specific enzymes is thus confirmed. The C-anomeric bond in this particular structure is in the β-position and makes this compound an interesting candidate for further chemical modifications. Influence of the methyl and hydroxymethyl groups on the inhibition potency is discussed.

The acyl nitroso Diels–Alder (ANDA) reaction of sorbate derivatives: an X-ray and 15N NMR study with an application to amino-acid synthesis

We present a study of the acyl nitroso Diels-Alder (ANDA) reaction of sorbate esters and sorbic alcohol derivatives, using alkoxycarbonyl nitroso dienophiles. An optimisation of the reaction conditions for ethyl sorbate is first presented, and the product is used in an efficient synthesis of 5-methylornithine. Structure-reactivity trends in sorbic alcohol (E,E-2,4-hexadien-1-ol) and its acylated analogues are then discussed. We present single-crystal X-ray structural proof for key adducts in both series and present in detail a novel HMBC/HSQC ((1)H-(15)N) criterion for ready distinction of regioisomers arising from such ANDA reactions.

Notes on selectivity aspects in sorbic acid and sorbic alcohol hydrogenation

Sorbic acid and sorbic alcohol hydrogenations to the cis-hex-3-enoic acid or cis-hex-3-en-1-ol were carried out at the same conditions in three different systems—homogeneous, two-phase and heterogeneous. The complex [Cp*Ru(sorbic acid)]CF3SO3 was used as a catalyst. Selectivity and reactivity of both the compounds varied significantly. Using sorbic acid as a hydrogenation substrate by-products were the other izomers of hexenoic acid and hexanoic acid, with sorbic alcohol as a hydrogenation substrate by-products were aldehydes and hemiacetals.

Sorbic alcohol hydrogenation

Hydrogenation of sorbic alcohol was carried out in homogeneous, two-phase and heterogeneous arrangements. The effects of the reaction conditions on the reaction rate and the selectivity were studied. The highest selectivity was reached using ethylene glycol as the solvent and in two-phase arrangement, in which ethylene glycol was used as the catalyst phase.

Effect of Sorbic Alcohol on the Radiolysis of Aromatic Compounds in Aqueous Solution

Sorbic alcohol (CH3CHCHCHCHCH2OH) and 2-phenylethanol (C6H5CH2CH2OH) or phenylacetic acid/phenylacetate (C6H5CH2COOH/C6H5CH2COO-) have been studied as a model for the conjugated double bond (C−CC−C...

ChemInform Abstract: Stereoselective Catalytic Hydrogenation of Sorbic Acid and Sorbic Alcohol with New Cp*Ru Complexes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Stereoselective catalytic hydrogenation of sorbic acid and sorbic alcohol with new Cp*Ru complexes

The new Cp*Ru complexes [Cp*Ru(η4-MeCHCHCHCHCO2H)]+ X− (X− = CF3SO3− or [B{C6H3(CF3)2-3,5} 4]−) are very effective catalysts for the hydrogenation of sorbic acid to cis-hex-3-enoic acid and of sorbic alcohol to cis-hex-3-en-1-ol (leaf alcohol) under mild conditions in liquid two-phase systems.

Purification and properties of methanol dehydrogenase from Methylosinus sp. WI 14.

Similarly to the recently described methanol dehydrogenase (MDH) from Methylocystis sp. GB 25 (Grosse et al. 1997) MDH from Methylosinus sp. WI 14 is able to catalyse the oxidation of methanol to formate directly. The enzyme was purified about 9-fold to electrophoretic homogeneity and is localised in the soluble fraction. The relative molecular mass of the native enzyme has been determined to be 140 kDa. It is composed of two identical subunits of relative molecular mass 70 kDa. The amino terminal sequence shows a strong similarity (a match of 80% over the first 20 amino acids) to the MDH from Methylocystis sp. GB 25. PQQ could be detected as the prosthetic group of MDH in the purified enzyme fraction by using the apoenzyme of a membrane-bound glucose dehydrogenase from Pseudomonas aeruginosa. A PQQ ratio of 1.3 per mole MDH was estimated. The purified enzyme has an optimum activity at pH 9.0 and at 57 degrees C. MDH from Methylosinus sp. WI 14 oxidises only primary alcohols up to octanol and several aldehydes. The estimated K(m)-values vary between 0.18 mM for the sorbic alcohol and 6.3 mM for butanol and show no dependence upon the chain length.

Photoreaction of Valerophenone in Aqueous Solution

Kinetics and products of the photoreaction of the phenyl ketone valerophenone were investigated as a function of temperature, pH, and wavelength in aqueous solution. Under these conditions (<10-4 M), the photoreactions are pseudo-first-order with respect to valerophenone concentration. Type II quantum yields for photoreaction were close to unity throughout the 290−330 nm spectral region and in the temperature range from 10 to 40 °C. The quantum yields for the photoproducts were 0.65 ± 0.04 for cleavage to acetophenone and propene and an overall yield of 0.32 ± 0.03 for cyclization to two cyclobutanols at 20 °C. A small amount of 1-phenylcyclopentanol (∼2% yield) also was formed. These photoreactions were quenchable by additions of the triplet quenchers sorbic alcohol or sorbic acid, and Stern−Volmer plots were linear up to at least 80% quenching of the photoreactions. On the basis of quenching studies with steady-state irradiations, the triplet lifetime of valerophenone at 20 °C was estimated to be 52 ns,...

A CONVENIENT ROUTE TO 1-ALKOXYMETHYLVINYLPHOSPHONATES.A NOVEL REACTION OF DIETHYLPHOSPHONOACETIC ACID

Abstract 1-Alkoxymethylvinylphosphonates 3a-e have been synthesized by piperidine catalyzed condensation of diethylphosphonoacetic acid 1 with paraformaldehyde in the presence of various primary and secondary alcohols. Similar reaction of the acid 1 with paraformaldehyde and sorbic alcohol 3f afforded a mixture of three bicyclic compounds 7, 9 and 11 in a ratio 2:1:1, respectively. The latter results strongly evidence the intermediacy of phosphonoacrylic acid 4 in the condensation. Under analogous conditions the olefin 14 was obtained from the acid (E,Z)-13.

ChemInform Abstract: Synthesis of Leaf Alcohol from Methyl Sorbate.

AbstractReduction of methyl sorbate (I) with lithium aluminum hydride gives sorbic alcohol (II) which is subsequently hydrogenated in the presence of chromium hexacarbonyl, producing leaf alcohol (III).

Production by Lactic Acid Bacteria of Sorbic Alcohol, the Precursor of the Geranium Odor Compound

Twenty-eight strains of <i>Leuconostoc, Lactobacillus</i>, and <i>Pediococcus</i> species were grown in media containing sorbate. All 19 of the leuconostocs produced sorbic alcohol, the precursor of the compound responsible for the so-called geranium odor, while none of the other types did so. Although no sorbic aldehyde was detected, it was postulated that the strains capable of degrading sorbic acid possessed an aldehyde dehydrogenase that the others lacked. However, the ability to reduce sorbic aldehyde was not the deciding reaction. Results indicated that this latter reaction was carried out by all of the strains of lactic acid bacteria tested as well as by commercial alcohol dehydrogenase from yeast.

Photosolvolysis of 3,4-dichloroaniline in water : Evidence for an aryl cation intermediate

Irradiation of 3,4-dichloroaniline in water (λ > 290nm) gave 2-chloro-5-aminophenol with a conversion of 78±5%. The photolysis quantum yield at 313 nm of 0.052±0.003 was unaffected by cyanide (0.35 M) or pH changes between 4 and 12. A MO calculation indicated a large excited singlet state shift in electron density to the carbon undergoing substitution. The reaction is suggested to proceed through an aryl cation intermediate produced by heterolytic cleavage of the meta carbon-chlorine bond. Reaction from the triplet state is not considered likely since neither oxygen nor sorbic alcohol affected the quantum yield.

Fungal metabolism of .ALPHA.,.BETA.-unsaturated carboxylic acids. II. Fungal metabolism of sorbic acid.

The metabolism of sorbic acid (S A) by 11 species of Mucor and 14 other fungi in addition to Mucor sp. A–73 were studied. All species of Mucor metabolized SA to trans-4-hexenol (4–HEL) without exception. The metabolic pathway was investigated precisely by using the resting cells of Mucor sp. A–73. The reduction of SA to 4–HEL by the fungus demanded glucose. The reduction of SA to sorbic alcohol (SAL) was catalyzed by the inducible enzymic system and that of SAL to 4–HEL by the constitutive enzyme. In the phosphate buffer, a part of 4–HEL produced from SA was further transformed into mono-trans-4-hexenyl phosphate by Mucor sp. A–73.The reductive action of the fungus upon several trans-2-alkenoic acids was also examined.

Fungal reduction of C6 .ALPHA.,.BETA.-unsaturated carboxylic acids.

The metabolism of sorbic acid (trans-2,trans-4-hexadienoic acid) and its related compounds by Mucor sp. A-73 was investigated. Sorbic acid was reduced by this fungus to trans-4-hexenol (more than 90% yield). In a series of hexamonoenoic acids, carboxyl groups and α,β-double bond were reduced, but β,γand γ,δ double bonds were hardly reduced. The reduction of cis-2-hexenoic acid was slower than that of the corresponding trans isomer. Sorbic alcohol, one of α,β-unsaturated alcohols, was converted well to trans-4-hexenol by the fungus. These results showed that this fungus could carry out two independent reductions: (i) carboxyl group→alcohol, (ii) α,β-unsaturated alcohol→αβ-saturated one. Furthermore, α,β-unsaturated alcohols were temporarily detected in the course of fungal reductions of some α,β-unsaturated acids. The fact suggested that the reduction of α,β-unsaturated acids to α,β-saturated alcohols was initiated by the reaction (i) and followed by (ii). The biological hydrogenation of α,β-unsaturated al...