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Sample records for 5-hydroxymethylfurfural degradation pathways

  1. Degradation of 5-hydroxymethylfurfural in honey.

    Fallico, B; Arena, E; Zappala, M

    2008-11-01

    5-Hydroxymethylfurfural (HMF) is the most important intermediate product of the acid-catalyzed dehydration reaction of hexoses and/or Maillard reaction; furthermore, it is the most used index to evaluate thermal damages or ageing in food products. Usually its degradation reactions, being very slow, are neglected. This study reports the findings concerning the degradation kinetics of HMF, in honeys of different floral origin at a temperature between 25 and 50 degrees C. The results highlighted higher degradation rates (k(HMF) (degradation)) compared to the corresponding formation rates (k(HMF) (formation)) in chestnut and citrus samples. Similar k-values were found in multifloral honey. Moreover, the reaction of HMF degradation was characterized by lower activation energy (E(a)) values compared to E(a) formation values. The final concentration of HMF in honey, during storage at room temperature, should be ascribed to high sugar concentration. The fluctuation of HMF in honeys could depend on the equilibrium between the accumulation and the degradation processes. This can affect the validity of HMF as storage index in some honeys, above all during the analysis of those honeys whose legislation is too restrictive (citrus) or in chestnut honey analysis where it does not accumulate. PMID:19021792

  2. Degradation of 5-hydroxymethylfurfural during yeast fermentation.

    Akıllıoglu, Halise Gül; Mogol, Burçe Ataç; Gökmen, Vural

    2011-12-01

    5-Hydroxymethyl furfural (HMF) may occur in malt in high quantities depending on roasting conditions. However, the HMF content of different types of beers is relatively low, indicating its potential for degradation during fermentation. This study investigates the degradation kinetics of HMF in wort during fermentation by Saccharomyces cerevisiae. The results indicated that HMF decreased exponentially as fermentation progressed. The first-order degradation rate of HMF was 0.693 × 10(-2) and 1.397 × 10(-2)min(-1) for wort and sweet wort, respectively, indicating that sugar enhances the activity of yeasts. In wort, HMF was converted into hydroxymethyl furfuryl alcohol by yeasts with a high yield (79-84% conversion). Glucose and fructose were utilised more rapidly by the yeasts in dark roasted malt than in pale malt (pyeast cells, and presence of sugars in the fermentation medium increases this activity. PMID:22010851

  3. 5-Hydroxymethylfurfural protects against ER stress-induced apoptosis in GalN/TNF-α-injured L02 hepatocytes through regulating the PERK-eIF2α signaling pathway.

    Jiang, Ze-Qun; Ma, Yan-Xia; Li, Mu-Han; Zhan, Xiu-Qin; Zhang, Xu; Wang, Ming-Yan

    2015-12-01

    5-Hydroxymethylfurfural (5-HMF), a water-soluble compound extracted from wine-processed Fructus corni, is a novel hepatic protectant for treating acute liver injury. The present study was designed to investigate the protective effect of 5-HMF in human L02 hepatocytes injured by D-galactosamine (GalN) and tumor necrosis factor-α (TNF-α) in vitro and to explore the underlying mechanisms of action. Our results showed that 5-HMF caused significant increase in the viability of L02 cells injured by GalN/TNF-α, in accordance with a dose-dependent decrease in apoptotic cell death confirmed by morphological and flow cytometric analyses. Based on immunofluorescence and Western blot assays, we found that GalN/TNF-α induced ER stress in the cells, as indicated by the disturbance of intracellular Ca(2+) concentration, the activation of protein kinase RNA (PKR)-like ER kinase (PERK), phosphorylation of eukaryotic initiation factor 2 alpha (eIF2α), and expression of ATF4 and CHOP proteins, which was reversed by 5-HMF pre-treatment in a dose-dependent manner. The anti-apoptotic effect of 5-HMF was further evidenced by balancing the expression of Bcl-2 family members. In addition, the knockdown of PERK suppressed the expression of phospho-PERK, phospho-eIF2α, ATF4, and CHOP, resulting in a significant decrease in cell apoptosis after the treatment with GalN/TNF-α. 5-HMF could enhance the effects of PERK knockdown, protecting the cells against the GalN/TNF-α insult. In conclusion, these findings demonstrate that 5-HMF can effectively protect GalN/TNF-α-injured L02 hepatocytes against ER stress-induced apoptosis through the regulation of the PERK-eIF2α signaling pathway, suggesting that it is a possible candidate for liver disease therapy. PMID:26721708

  4. Dehydration of Different Ketoses and Aldoses to 5-Hydroxymethylfurfural

    van Putten, Robert-Jan; Soetedjo, Jenny N. M.; Pidko, Evgeny A.; van der Waal, Jan C.; Hensen, Emiel J. M.; de Jong, Ed; Heeres, Hero J.

    2013-01-01

    5-Hydroxymethylfurfural (HMF) is considered an important building block for future bio-based chemicals. Here, we present an experimental study using different ketoses (fructose, sorbose, tagatose) and aldoses (glucose, mannose, galactose) under aqueous acidic conditions (65gL(-1) substrate, 100-160

  5. 5-Hydroxymethylfurfural content in foodstuffs determined by micellar electrokinetic chromatography

    Teixidó, Erika; Núñez Burcio, Oscar; Santos Vicente, Francisco Javier; Galcerán Huguet, M. Teresa

    2010-01-01

    Micellar electrokinetic chromatography (MEKC) has been applied for the determination of 5-hydroxymethylfurfural in several foodstuffs. A 75 mM phosphate buffer solution at pH 8.0 containing 100 mM sodium dodecylsulfate was used as background electrolyte (BGE), and the separation was performed by applying +25 kV in a 50 µm I.D. uncoated fused-silica capillary. Good linearity over the range 2.5-250 mg kg-1 (r2 ≥ 0.999) and run-to-run and day-to-day precisions at low and medium concentration lev...

  6. From lignocellulosic biomass to furans via 5-acetoxymethylfurfural as an alternative to 5-hydroxymethylfurfural.

    Kang, Eun-Sil; Hong, Yeon-Woo; Chae, Da Won; Kim, Bora; Kim, Baekjin; Kim, Yong Jin; Cho, Jin Ku; Kim, Young Gyu

    2015-04-13

    A facile pathway to furan derivatives from lignocellulosic biomass via 5-acetoxymethylfurfural (AMF) was developed. AMF possesses advantageous properties due to its less-hydrophilic acetoxymethyl group relative to the hydroxymethyl group of 5-hydroxymethylfurfural (HMF). The hydrophobicity and chemical stability of AMF allowed practical isolation and purification to afford a highly pure product of up to 99.9 %. AMF was produced in good to excellent yields under mild conditions from 5-chloromethylfurfural (CMF) and alkylammonium acetates, both of which could be obtained directly from lignocellulosic biomass. Heterogeneous reactions with polymer-supported alkylammonium acetates were also established; this showed the feasibility of a continuous process for this pathway. AMF could be transformed into various promising furanic compounds, such as 2,5-furandicarboxylic acid (FDCA), 2,5-furandimethanol (FDM), and 5-hydroxymethyl-2-furanoic acid (HFA), in high yields. PMID:25619448

  7. Synthesis of Bis(hydroxylmethylfurfuryl)amine Monomers from 5-Hydroxymethylfurfural.

    Xu, Zhanwei; Yan, Peifang; Liu, Kairui; Wan, Lu; Xu, Wenjuan; Li, Huixiang; Liu, Xiumei; Zhang, Z Conrad

    2016-06-01

    We report the synthesis of bis(hydroxylmethylfurfuryl)amine (BHMFA) from 5-hydroxymethylfurfural (5-HMF) by reacting 5-HMF with primary amines in the presence of homogeneous Ru(II) catalysts having sterically strained ligands. BHMFA is a group of furan-based monomers that offer great potential to form functional biopolymers with tunable properties. A range of primary amines, such as aliphatic and benzyl amines, are readily converted with 5-HMF to form the corresponding BHMFA in good yields. The reaction proceeds through reductive amination of 5-HMF with primary amine to form secondary amine, followed by reductive amination of 5-HMF with in situ generated secondary amine to produce BHMFA. PMID:27151257

  8. Acrylamide and 5-hydroxymethylfurfural formation during baking of biscuits: Part I: Effects of sugar type.

    Nguyen, Ha T; Van der Fels-Klerx, H J Ine; Peters, Ruud J B; Van Boekel, Martinus A J S

    2016-02-01

    This study aimed to investigate the effects of sugar type on the reaction mechanism for formation of acrylamide and 5-hydroxymethylfurfural (HMF) during the baking of biscuits at 200°C using multiresponse modelling. Four types of biscuits were prepared: (1) with sucrose, (2) with glucose and fructose, (3) with fructose only and (4) with glucose only. Experimental data showed that HMF concentration was highest in biscuits with glucose and fructose, whereas acrylamide concentration was highest in biscuits with glucose, also having the highest asparagine concentration. Proposed mechanistic models suggested that HMF is formed via caramelisation and that acrylamide formation follows the specific amino acid route, i.e., reducing sugars react with asparagine to form the Schiff base before decarboxylation, to generate acrylamide without the Amadori rearrangement product and sugar fragmentation. Study results contribute to understanding chemical reaction pathways in real food products. PMID:26304386

  9. Fast quantitation of 5-hydroxymethylfurfural in honey using planar chromatography.

    Chernetsova, Elena S; Revelsky, Igor A; Morlock, Gertrud E

    2011-07-01

    An approach for rapid quantitation of 5-hydroxymethylfurfural (HMF) in honey using planar chromatography is suggested for the first time. In high-performance thin-layer chromatography (HPTLC) the migration time is approximately 5 min. Detection is performed by absorbance measurement at 290 nm. Polynomial calibration in the matrix over a range of 1:80 showed correlation coefficients, r, of  ≥  0.9997 for peak areas and  ≥  0.9996 for peak heights. Repeatability in the matrix confirmed the suitability of HPTLC-UV for quantitation of HMF in honey. The relative standard deviation (RSD, %, n = 6) of HMF at 10 ng/band was 2.9% (peak height) and 5.2% (peak area); it was 0.6% and 1.0%, respectively, at 100 ng/band. Other possible detection modes, for example fluorescence measurement after post-chromatographic derivatization and mass spectrometric detection, were also evaluated and can coupling can be used as an additional tool when it is necessary to confirm the results of prior quantitation by HPTLC-UV. The confirmation is provided by monitoring the HMF sodium adduct [M + Na](+) at m/z 149 followed by quantitation in TIC or SIM mode. Detection limits for HPTLC-UV, HPTLC-MS (TIC), and HPTLC-MS (SIM) were 0.8 ng/band, 4 ng/band, and 0.9 ng/band, respectively. If 12 μL honey solution was applied to an HPTLC plate, the respective detection limits for HMF in honey corresponded to 0.6 mg kg(-1). Thus, the developed method was highly suitable for quantitation of HMF in honey at the strictest regulated level of 15 mg kg(-1). Comparison of HPTLC-UV detection with HPTLC-MS showed findings were comparable, with a mean deviation of 5.1 mg kg(-1) for quantitation in SIM mode and 6.1 mg kg(-1) for quantitation in TIC mode. The mean deviation of the HPTLC method compared with the HPLC method was 0.9 mg kg(-1) HMF in honey. Re-evaluation of the same HPTLC plate after one month showed a deviation of 0.5 mg kg(-1) HMF in honey. It was demonstrated that the proposed

  10. 5-Hydroxymethylfurfural content in foodstuffs determined by micellar electrokinetic chromatography.

    Teixidó, Erika; Núñez, Oscar; Santos, F Javier; Galceran, M Teresa

    2011-06-15

    Micellar electrokinetic chromatography (MEKC) has been applied for the determination of 5-hydroxymethylfurfural in several foodstuffs. A 75mM phosphate buffer solution at pH 8.0 containing 100mM sodium dodecylsulphate was used as background electrolyte (BGE), and the separation was performed by applying +25kV in a 50μm I.D. uncoated fused-silica capillary. Good linearity over the range 2.5-250mgkg(-1) (r(2)⩾0.999) and run-to-run and day-to-day precisions at low and medium concentration levels were obtained. Sample limit of detection (0.7mgkg(-1)) and limit of quantification (2.5mgkg(-1)) were established by preparing the standards in blank matrix. The procedure was validated by comparing the results with those obtained with liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Levels of HMF in 45 different foodstuffs such as breakfast cereals, toasts, honey, orange juice, apple juice, jam, coffee, chocolate and biscuits were determined. PMID:25213975

  11. Protein Engineering of GRE2 from Saccharomyces cerevisiae for Enhanced Detoxification of 5-hydroxymethylfurfural

    Furfural and 5-hydroxymethylfurfural (HMF) are representative inhibitors generated by lignocellulosic biomass pretreatment such as dilute acid hydrolysis that inhibit microbial growth and subsequent fermentation. It is possible to in situ detoxify these inhibitory compounds using tolerant Saccharom...

  12. PRODUCTION OF 5-HYDROXYMETHYLFURFURAL (HMF) VIA FRUCTOSE DEHYDRATION: EFFECT OF SOLVENT AND SALTING-OUT

    F. N. D. C. Gomes; L. R. Pereira; N. F. P. Ribeiro; M. M. V. M. Souza

    2015-01-01

    Abstract 5-Hydroxymethylfurfural (HMF) is a key renewable platform compound for production of fuels and chemical intermediates. The production of 5-hydroxymethylfurfural (HMF) from fructose dehydration was studied using H3PO4 as catalyst, in organic/water system with different solvents (acetone, 2-butanol and ethyl ether). The effect of fructose concentration, temperature and acid concentration was investigated in acetone/water medium. The increase in fructose concentration favors the formati...

  13. 5-Hydroxymethylfurfural from wine-processed Fructus corni inhibits hippocampal neuron apoptosis***

    Hai Gu; Zequn Jiang; Mingyan Wang; Haiying Jiang; Fengming Zhao; Xia Ding; Baochang Cai; Zhen Zhan

    2013-01-01

    Previous studies have shown that 5-hydroxymethylfurfural, a compound extracted from wine- pro-cessed Fructus corni, has a protective effect on hippocampal neurons. The present study was de-signed to explore the related mechanisms. Our study revealed that high and medium doses (10, 1μmol/L) of 5-hydroxymethylfurfural could improve the morphology of H2O2-treated rat hippocampal neurons as revealed by inverted phase-contrast microscopy and transmission electron microscopy. MTT results showed that incubation with high and medium doses of 5-hydroxymethylfurfural caused a significant increase in the viability of neuronal cells injured by H2O2. Flow cytometry assays con-firmed that H2O2 could induce cellapoptosis, while high and medium doses of 5-hydroxymethylfurfural had a visible protective effect on apoptotic rat hippocampal neurons. Re-al-time PCR and western blot analysis showed that high and medium doses of 5-hydroxymethylfurfural prevented H2O2-induced up-regulation of p53, Bax and caspase-3 and antagonized the down-regulation of Bcl-2 induced by H2O2 treatment. These results suggested that 5-hydroxymethylfurfural could inhibit apoptosis of cultured rat hippocampal neurons injured by H2O2 via increase in Bcl-2 levels and decrease in p53, Bax and caspase-3 protein expression lev-els.

  14. One-pot conversion of disaccharide into 5-hydroxymethylfurfural catalyzed by imidazole ionic liquid.

    Qu, Yongshui; Li, Li; Wei, Quanyuan; Huang, Chongpin; Oleskowicz-Popiel, Piotr; Xu, Jian

    2016-01-01

    Conversion of carbohydrate into 5-hydroxymethylfurfural (5- HMF), a versatile, key renewable platform compound is regarded as an important transformation in biomass-derived carbohydrate chemistry. A variety of ILs, not only acidic but also alkaline ILs, were synthesized and used as catalyst in the production of 5-HMF from disaccharide. Several factors including reaction temperature, IL dosage, solvent and reaction time,were found to influence the yield of 5-HMF from cellobiose. Of the ILs tested, hydroxy-functionalized ionic liquid (IL), 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate ([AEMIM]BF4) showed the highest catalytic activity and selectivity. 5-HMF yield of 68.71% from sucrose was obtained after 6 hrs at 160 °C. At the same condition with cellobiose as substrate, 5-HMF yield was 24.73%. In addition, 5-HMF also exhibited good stablity in this reaction system. Moreover, a kinetic analysis was carried out in both acidic and alkaline IL-catalyzed system, suggesting main side reaction in the conversion of fructose catalyzed by acidic and alkaline IL was polymerization of fructose and 5-HMF degradation, respectively. PMID:27181523

  15. Confirmation of patulin and 5-hydroxymethylfurfural in apple juice by gas chromatography/mass spectrometry.

    Rupp, H S; Turnipseed, S B

    2000-01-01

    A gas chromatographic/mass spectrometric (GC/MS) method was developed for the confirmation of patulin and 5-hydroxymethylfurfural (HMF) extracted from apple juice. The extraction is based on the official AOAC method for liquid chromatographic analysis. Juice extracts are quickly and easily derivatized with bis(trimethylsilyl)trifluoracetamide under mild conditions, and the trimethylsilyl ethers of the analytes are stable for at least several hours. The analytes are determined by GC/MS using an electron-impact source and selected ion monitoring of characteristic ions. For both analytes, the interassay differences between base-peak ratios for samples and standards were all <7.1% (absolute). The presence of patulin was confirmed at fortification levels of about 30-400 microg/L and naturally occurring levels of about 80-400 microg/L. The presence of HMF was also confirmed at levels < or = 2 mg/L. The proposed mass spectral fragmentation pathways of the analytes are presented. PMID:10868584

  16. Gold-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Water at Ambient Temperature

    Gorbanev, Yury; Kegnæs, Søren; Woodley, John;

    2009-01-01

    The aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, is examined in water with a titania-supported gold-nanoparticle catalyst at ambient temperature (30 degrees C). The selectivity of the reaction towords 2,5-furandicarboxylic acid and the intermediate oxidation....... product 5-hydroxymethyl-2-furancarboxylic acid is found to depend on the amount of added base and the oxygen pressure, suggesting that the reaction proceeds via initial oxidation of the aldehyde moiety followed by oxidation of the hydroxymethyl group of 5-hydroxymethylfurfural. Under optimized reaction...... conditions, a 71% yield of 2,5-furandicarboxylic acid is obtained at full 5-hydroxymethylfurfural conversion in the presence of excess base....

  17. Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water

    Hansen, Thomas Steen; Mielby, Jerrik Jørgen; Riisager, Anders

    2011-01-01

    Boric acid and salts showed a synergistic effect on the dehydration of concentrated aqueous sugar solutions to yield 5-hydroxymethylfurfural.......Boric acid and salts showed a synergistic effect on the dehydration of concentrated aqueous sugar solutions to yield 5-hydroxymethylfurfural....

  18. Caprolactam from Renewable Resources : Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone

    Buntara, Teddy; Noel, Sebastien; Phua, Pim Huat; Melián-Cabrera, Ignacio; Vries, Johannes G. de; Heeres, Hero J.

    2011-01-01

    Renewable nylon: 5-Hydroxymethylfurfural (HMF), which can be obtained from renewable resources such as D-fructose, was converted into caprolactone with very good overall selectivity in only three steps. The new route involves two hydrogenation steps to obtain 1,6-hexanediol, which was oxidatively cy

  19. Direct conversion of chitin biomass to 5-hydroxymethylfurfural in concentrated ZnCl2 aqueous solution

    Wang, Yingxiong; Pedersen, Christian Marcus; Deng, Tiansheng;

    2013-01-01

    The direct conversion of chitin biomass to 5-hydroxymethylfurfural (5-HMF) in ZnCl2 aqueous solution was studied systemically. D-Glucosamine (GlcNH2) was chosen as the model compound to investigate the reaction, and 5-HMF could be obtained in 21.9% yield with 99% conversion of GlcNH2. Optimization...

  20. Efficient microwave-assisted synthesis of 5-hydroxymethylfurfural from concentrated aqueous fructose

    Søndergaard Hansen, Thomas; Woodley, John; Riisager, Anders

    2009-01-01

    Studies on the HCl-catalysed microwave-assisted dehydration of highly concentrated aqueous fructose (27 wt %) to 5-hydroxymethylfurfural (HMF) revealed a significant increase in the fructose conversion rate over the conventional heated systems. Water, being the most benign solvent and therefore...

  1. PRODUCTION OF 5-HYDROXYMETHYLFURFURAL (HMF VIA FRUCTOSE DEHYDRATION: EFFECT OF SOLVENT AND SALTING-OUT

    F. N. D. C. Gomes

    2015-03-01

    Full Text Available Abstract 5-Hydroxymethylfurfural (HMF is a key renewable platform compound for production of fuels and chemical intermediates. The production of 5-hydroxymethylfurfural (HMF from fructose dehydration was studied using H3PO4 as catalyst, in organic/water system with different solvents (acetone, 2-butanol and ethyl ether. The effect of fructose concentration, temperature and acid concentration was investigated in acetone/water medium. The increase in fructose concentration favors the formation of condensation products and rehydration products are favored at high acid concentration. The solvents exhibited similar performance when the volume ratio of organic to aqueous phase was 1:1, but when this ratio increases to 2:1, the HMF yield obtained with ether was much lower. NaCl addition to the aqueous phase promoted the extraction of HMF to the organic phase, with an HMF yield of 80% in the case of 2:1 acetone/water medium.

  2. Evolution of 5-hydroxymethylfurfural (HMF) and furfural (F) in fortified wines submitted to overheating conditions

    Pereira, V.; Albuquerque, F.M.; Ferreira, A. C.; Cacho, J.; Marques, J. C.

    2011-01-01

    As furfural (F) and 5-hydroxymethylfurfural (HMF) are essentially formed from sugar dehydration, especially in food submitted to heat, they can be found in beverages, as well as fortified sweet wines. In order to assess the impact of temperature on Madeira winemaking, three traditional varieties of Madeira wines (Malvasia, Sercial and Tinta Negra Mole) were studied to evaluate the F and HMF contents. The wines were produced by two vinification processes, following traditional and modern metho...

  3. Acrylamide and 5-hydroxymethylfurfural formation in reconstituted potato chips during frying

    Miao, YuTian; Zhang, HuanJie; Zhang, LuLu; Wu, SiJia; Sun, Yijia; Shan, Yu; Yuan, Yuan

    2013-01-01

    In our present paper, the effect of water activity and processing conditions in reconstituted potato chips was considered as a model to investigate the changes of acrylamide (AA) and 5-hydroxymethylfurfural (HMF). The results suggested that the formation of AA and HMF was highly correlated with frying temperature and time. Water activity could also influence the formation of AA and HMF. Meanwhile, the formation of HMF has significant correlation with the formation of AA in reconstituted potat...

  4. Multiple gene mediated aldehyde reduction is a mechanism of in situ detoxification of furfural and 5-hydroxymethylfurfural by Saccharomyces cerevisiae

    Furfural and HMF (5-hydroxymethylfurfural) are representative inhibitors to ethanologenic yeast generated from biomass pretreatment using dilute acid hydrolysis. Few yeast strains tolerant to inhibitors are available. We have developed tolerant strains of Saccharomyces cerevisiae with enhanced bio...

  5. Effect of Storage on Acrylamide and 5-hydroxymethylfurfural Contents in Selected Processed Plant Products with Long Shelf-life.

    Michalak, Joanna; Gujska, Elżbieta; Czarnowska, Marta; Klepacka, Joanna; Nowak, Fabian

    2016-03-01

    This study investigated the effects of storage and temperature duration on the stability of acrylamide (AA) and 5-hydroxymethylfurfural (HMF) in selected foods with long shelf-life. Products were analysed fresh and stored at temperatures of 4 and 25 °C after 6 and 12 months (with the exception of soft bread samples, which were analysed after 15 and 30 days). The AA and HMF contents were determined with RP-HPLC coupled to a diode array detector (DAD). AA and HMF were not stable in many processed plant products with a long shelf-life. The highest AA reduction and the largest increase in HMF content were observed in the samples stored at a higher temperature (25 °C) for 12 months. It was found that an initial water activity of 0.4 is favourable to HMF formation and that AA reduction may be considerably greater in stored products with a low initial water activity. The kind of product and its composition may also have a significant impact on acrylamide content in stored food. In the final period of storage at 25 °C, acrylamide content in 100% cocoa powder, instant baby foods, 20% cocoa powder and instant coffee was 51, 39, 35 and 33% lower than in products before storage, respectively. It was observed that a large quantity of ε-NH2 and SH groups of amino acids in some products can be assumed as the reason for the significant AA degradation. PMID:26768597

  6. CONVERSION OF FRUCTOSE TO 5-HYDROXYMETHYLFURFURAL WITH A FUNCTIONALIZED IONIC LIQUID

    Hao Ma,

    2011-11-01

    Full Text Available Fructose can be efficiently converted to 5-hydroxymethylfurfural by using the functionalized ionic liquid 3-(2-chloroethyl-1-methylimidazolium chloride as both solvent and catalyst in the presence of water. This work advances the field and is distinct from earlier efforts in the sense that the observed yields of HMF from fructose are rather high and the reaction conditions rather mild and neutral in the complete absence of acidic additives (HMF yield 76% at 100 oC in 40 minutes.

  7. OPTIMIZATION OF PRODUCTION OF 5-HYDROXYMETHYLFURFURAL FROM GLUCOSE IN A WATER: ACETONE BIPHASIC SYSTEM

    A. D. M. Mendonça

    2015-06-01

    Full Text Available Abstract5-Hydroxymethylfurfural (HMF is considered to be an important building block for biorefineries and has a high potential for the production of chemicals and fuels. Production of HMF from glucose was studied using phosphoric acid as catalyst, in a water:acetone system with volume ratio of 1:2 and NaCl. An experimental design was applied to examine the influence of temperature, time and concentration of catalyst on the HMF yield. HMF yields of more than 50 % were obtained when using 200 ºC, 8.4 min and 0.8% of catalyst. The temperature is the main factor influencing the HMF yield.

  8. Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural

    Wang, Guang-Hui; Hilgert, Jakob; Richter, Felix Herrmann; Wang, Feng; Bongard, Hans-Josef; Spliethoff, Bernd; Weidenthaler, Claudia; Schüth, Ferdi

    2014-03-01

    The synthesis of 2,5-dimethylfuran (DMF) from 5-hydroxymethylfurfural (HMF) is a highly attractive route to a renewable fuel. However, achieving high yields in this reaction is a substantial challenge. Here it is described how PtCo bimetallic nanoparticles with diameters of 3.6 ± 0.7 nm can solve this problem. Over PtCo catalysts the conversion of HMF was 100% within 10 min and the yield to DMF reached 98% after 2 h, which substantially exceeds the best results reported in the literature. Moreover, the synthetic method can be generalized to other bimetallic nanoparticles encapsulated in hollow carbon spheres.

  9. Development and validation of an HPLC method to determine metabolites of 5-hydroxymethylfurfural (5-HMF).

    Hardt-Stremayr, Magdalena; Bernaskova, Marketa; Hauser, Stefanie; Kunert, Olaf; Guo, Xinghua; Stephan, Janette; Spreitz, Josef; Lankmayr, Ernst; Schmid, Martin G; Wintersteiger, Reinhold

    2012-10-01

    The food component 5-hydroxymethylfurfural is supposed to have antioxidative properties and is therefore used as an acting agent in a novel anticancer infusion solution, named Karal®, and an oral supplementation. Previous studies showed that after oral and intravenous application, the substance is completely decomposed to its metabolites: 5-hydroxymethylfuroic acid, 2,5-furandicarboxylic acid, and N-(hydroxymethyl)furoyl glycine. The formation of a fourth metabolite, namely 5-sulphoxymethylfurfural, is still not clarified according to literature. Due to commercial unavailability, synthesis of 5-sulphoxymethylfurfural was conducted and a synthesis procedure for N-(hydroxymethyl)furoyl glycine had to be developed. Identification of the synthesised compounds was proven by LC-MS and NMR. An appropriate HPLC method was established to obtain good separation of the four possible metabolic substances and 5-hydroxymethylfurfural within 12 min via a HILIC column (150 × 4.6 mm, 5 μm) using a gradient grade system switching from mobile phase A (ACN/ammonium formate 100 mM, pH 2.35, 95:5, v/v) to mobile phase B (ACN/ammonium formate 100 mM, pH 2.35, 85:15, v/v). The procedure was afterward validated following ICH guidelines in terms of selectivity, linearity, precision, LOD, and LOQ. PMID:22941583

  10. Lysosome: regulator of lipid degradation pathways

    Settembre, Carmine; Ballabio, Andrea

    2014-01-01

    Autophagy is a catabolic pathway that has a fundamental role in the adaptation to fasting and primarily relies on the activity of the endolysosomal system, to which the autophagosome targets substrates for degradation. Recent studies have revealed that the lysosomal–autophagic pathway plays an important part in the early steps of lipid degradation. In this review, we discuss the transcriptional mechanisms underlying co-regulation between lysosome, autophagy, and other steps of lipid catabolis...

  11. An Unexpected Reaction between 5-Hydroxymethylfurfural and Imidazolium-Based Ionic Liquids at High Temperatures

    Zongbao K. Zhao

    2011-10-01

    Full Text Available A new compound was detected during the production of 5-hydroxymethylfurfural (HMF from glucose and cellulose in the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl at high temperatures. Further experiments found that it was derived from the reaction of HMF with [Bmim]Cl. The structure of new compound was established as 1-butyl-2-(5’-methyl-2’-furoylimidazole (BMI based on nuclear magnetic resonance and mass spectrometry analysis, and a possible mechanism for its formation was proposed. Reactions of HMF with other imidazolium-based ionic liquids were performed to check the formation of BMI. Our results provided new insights in terms of side reactions between HMF and imidazolium-based ionic liquids, which should be valuable for designing better processes for the production of furans using biomass and related materials.

  12. Detection and determination of interfering 5-hydroxymethylfurfural in the analysis of caramel-coloured pharmaceutical syrups.

    Hewala, I I; Blaih, S M; Zoweil, A M; Onsi, S M

    1993-02-01

    A comparison between different caramels described for use in the pharmaceutical industry is presented. An interfering substance, 5-hydroxymethylfurfural (5-HMF), was detected in some caramels. Conditions and proofs for the formation of 5-HMF are presented. Interference by 5-HMF during the analysis of the active drugs and the possibility of interaction with the active drugs during the shelf-life of the drug formulation are discussed. A limit test for 5-HMF in caramel was developed. The test depends on measuring the difference in absorbance between two equimolar solutions of caramel, one of which contains sodium borohydride. The test is sensitive and selective for the detection and determination of trace amounts of 5-HMF without interference from the brown products of caramel. PMID:8192718

  13. Simultaneous determination of 5-hydroxymethylfurfural and patulin in apple juice by reversed-phase liquid chromatography.

    Gökmen, V; Acar, J

    1999-06-25

    A rapid, simple and economical method was described for the simultaneous determination of 5-hydroxymethylfurfural (HMF) and patulin in apple juice. The sample was extracted with ethyl acetate and the extract was then cleaned up by extraction with a sodium carbonate solution. Then HMF and patulin were determined by reversed-phase liquid chromatography using a C18 column and a photodiode array detector. HMF and patulin could be completely resolved by using the mixture water-acetonitrile (99:1, v/v) as the mobile phase with a flow rate of 1.0 ml/min. Mean recoveries of HMF ranged from 86% to 100% with an overall mean of 94%, that of patulin ranged from 94% to 125% with an overall mean of 103%, for different spiking levels. The limits of detection for HMF and patulin in apple juice were found to be < 0.01 mg/l and < 5 micrograms/l, respectively. PMID:10431352

  14. Efficient dehydration of fructose to 5-hydroxymethylfurfural catalyzed by a recyclable sulfonated organic heteropolyacid salt.

    Qu, Yongshui; Huang, Chongpin; Zhang, Jie; Chen, Biaohua

    2012-02-01

    The dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) with room temperature ionic liquids (ILs) is a way of producing liquid fuels from renewable resources, but separation of products and IL is energy intensive. In this work, a heteropolyacid salt of an IL-forming cation functionalized with a propanesulfonate group, 1-(3-sulfonicacid)propyl-3-methyl imidazolium phosphotungstate ([MIMPS](3)PW(12)O(40)), was used as a catalyst-rather than as a solvent-in the conversion of fructose to 5-HMF. The maximum yield of 5-HMF was 99.1% at 120°C after 2h using sec-butanol as solvent, and the catalyst was separated from the reaction mixture by a simple process at the end of the reaction and reused six times without loss of activity. PMID:22201545

  15. An RP-HPLC determination of 5-hydroxymethylfurfural in honey The case of strawberry tree honey.

    Spano, Nadia; Casula, Lucia; Panzanelli, Angelo; Pilo, Maria I; Piu, Paola C; Scanu, Roberta; Tapparo, Andrea; Sanna, Gavino

    2006-02-15

    The use of the RP-HPLC official method of the International Honey Commission (IHC) for the determination of 5-hydroxymethylfurfural (HMF) in strawberry tree honey (Arbutus unedo, a typical Sardinian honey) has brought to light a specific and heavy chromatographic interference that prevents accurate quantification. The interference has been identified as homogentisic acid (HA), i.e. the marker of the botanical origin of the honey. For this reason, an alternative RP-HPLC method is proposed. The bias-free method allows a complete separation of HMF from HA to the baseline level and is faster and more precise than the RP-HPLC official method: the detection and quantification limits are 1.9 and 4.0mgkg(-1), respectively, whereas the repeatability is ca. 2% in the HMF concentration range of 5-140mgkg(-1). PMID:18970477

  16. Direct Conversion of Mono- and Polysaccharides into 5-Hydroxymethylfurfural Using Ionic-Liquid Mixtures.

    Siankevich, Sviatlana; Fei, Zhaofu; Scopelliti, Rosario; Jessop, Philip G; Zhang, Jiaguang; Yan, Ning; Dyson, Paul J

    2016-08-23

    Platform chemicals are usually derived from petrochemical feedstocks. A sustainable alternative commences with lignocellulosic biomass, a renewable feedstock, but one that is highly challenging to process. Ionic liquids (ILs) are able to solubilize biomass and, in the presence of catalysts, convert the biomass into useful platform chemicals. Herein, we demonstrate that mixtures of ILs are powerful systems for the selective catalytic transformation of cellulose into 5-hydroxymethylfurfural (HMF). Combining ILs with continuous HMF extraction into methyl-isobutyl ketone or 1,2-dimethoxyethane, which form a biphase with the IL mixture, allows the online separation of HMF in high yield. This one-step process is operated under relatively mild conditions and represents a significant step forward towards sustainable HMF production. PMID:27345462

  17. Efficient Conversion of Carbohydrates to 5-Hydroxymethylfurfural (HMF Using ZrCl4 Catalyst in Nitromethane

    Raju S. Thombal

    2014-09-01

    Full Text Available Solvent nitromethane along with a variety of metal chloride and mineral acids as catalyst were studied for the synthesis of 5-Hydroxymethylfurfural (HMF, a key precursor in the formation of alternative fuel 2,5-dimethylfuran (DMF and other value added chemicals. Reaction time, temperature and catalyst concentration were also systematically studied to achieve highest HMF formation. Among the carbohydrates studied for HMF synthesis, D-fructose and inulin were found particularly most productive yielding >70% and with 100% selectivity using ZrCl4 in nitromethane at 100 oC during 3h. Readily available reagents, solvents, and simple reaction conditions could mark this process promising for HMF formation from biomass.

  18. Recyclable Magnetite Nanoparticle Catalyst for One-Pot Conversion of Cellobiose to 5-Hydroxymethylfurfural in Water

    Anuja Bhalkikar

    2015-01-01

    Full Text Available Environmentally benign and easily recoverable magnetite nanoparticles (Fe3O4 NPs were demonstrated to catalyze the one-pot conversion of cellobiose, a glucose disaccharide, to 5-hydroxymethylfurfural (5-HMF. The conversion was achieved in water under hydrothermal conditions. The catalytic activity of Fe3O4 NPs surpassed those of iron (II and iron (III chlorides in this reaction. Optimized cellobiose conversion reactions catalyzed with Fe3O4 NPs gave the highest 5-HMF yields of 23.4 ± 0.6% at 160°C for 24 hours. After three reuses, the Fe3O4 NP catalyst retained its catalytic activity with similar 5-HMF yields, demonstrating the recyclability of this eco-friendly catalyst in water.

  19. Analysis of 5-hydroxymethylfurfural in foods by gas chromatography-mass spectrometry.

    Teixidó, E; Santos, F J; Puignou, L; Galceran, M T

    2006-11-24

    A new, simple and selective method for the analysis of 5-hydroxymethylfurfural (HMF) in foods by gas chromatography coupled to mass spectrometry (GC-MS) is proposed. Several derivatising procedures based on the formation of an HMF silylated derivative using different reagents were studied. Among the derivatising reagents examined, N,O-bis-trimethylsilyltrifluoroacetamide (BSTFA) provided the best derivatisation yield. Sample clean-up was also optimised, using either liquid-liquid extraction with dichloromethane or solid-phase extraction (SPE) with several commercially available cartridges, and the best results were obtained using ENV+ cartridges. Quality parameters such as day-to-day and run-to-run precision (RSD<10%), linearity (between 25 and 700 ng g(-1)) and detection limit (6 ng g(-1)) were established. This method was successfully applied to the analysis of HMF content in several Spanish food samples from a local market, such as jam, honey, orange juice and bakery products. PMID:17010355

  20. Acrylamide and 5-hydroxymethylfurfural formation in reconstituted potato chips during frying.

    Miao, YuTian; Zhang, HuanJie; Zhang, LuLu; Wu, SiJia; Sun, YiJia; Shan, Yu; Yuan, Yuan

    2014-12-01

    In our present paper, the effect of water activity and processing conditions in reconstituted potato chips was considered as a model to investigate the changes of acrylamide (AA) and 5-hydroxymethylfurfural (HMF). The results suggested that the formation of AA and HMF was highly correlated with frying temperature and time. Water activity could also influence the formation of AA and HMF. Meanwhile, the formation of HMF has significant correlation with the formation of AA in reconstituted potato chips. A typical exponential growth curve was observed by plotting AA levels vs HMF content which were all determined under different heating condition: [Formula: see text]. The model could be used as a tool for estimating the formation of AA when the content of HMF was known. PMID:25477673

  1. Characterisation of viscosity, colour, 5-hydroxymethylfurfural content and diastase activity in raw rape honey (Brassica napus) at different temperatures.

    Kędzierska-Matysek, Monika; Florek, Mariusz; Wolanciuk, Anna; Skałecki, Piotr; Litwińczuk, Anna

    2016-04-01

    The effect of heating at various temperatures (30, 40, 50, 60, 70 and 80 °C) on dynamic viscosity, colour, 5-hydroxymethylfurfural (5-HMF) concentration and diastase activity of raw rape honey were assessed. In fresh honey, moisture, ash, free acidity, pH and electrical conductivity averaged 185.3 g kg(-1), 1.2 g kg(-1), 18.71 mEq kg(-1), 4.2 and 0.25 mS cm(-1), respectively. Heating significantly (p ≤ 0.05) increased lightness (L*), yellowness (b*), chroma (C*), hue (h°) values, but decreased redness (a*). The viscosity at 20 °C (33.6 Pa s) differed significantly (p ≤ 0.01) with those at 30, 40 and 50 °C (8.2, 2.5, and 1.6 Pa s, respectively). Diastase activity decreased concomitant with heating at higher temperatures. Honey heated at 80 °C for 15 min showed the maximum increase of 5-HMF content, with an average of 1.9 mg kg(-1) (62 %), compared to unheated samples. Heating for 15 min between 50 °C and 80 °C did not significantly degrade the quality of the honey, but, slightly enhanced formation of 5-HMF and reduced the diastase activity. PMID:27413239

  2. Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Solid catalyst systems comprised of ruthenium hydroxide supported on magnesium-based carrier materials (spinel, magnesium oxide and hydrotalcite) were investigated for the selective, aqueous aerobic oxidation of the biomass-derived chemical 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid...

  3. Acrylamide and 5-hydroxymethylfurfural formation during baking of biscuits: NaCl and temperature-time profile effects and kinetics

    Fels, van der H.J.; Capuano, E.; Nguyen, H.T.; Mogol, B.A.; Kocadagli, T.; Goncuoglu Tas, N.; Hamzalioglu, A.; Boekel, van M.A.J.S.; Gokmen, V.

    2014-01-01

    The present study aimed to investigate the effect of recipe and temperature–time on the formation of acrylamide and 5-hydroxymethylfurfural (HMF) during biscuit baking. Baking experiments were performed with biscuits of two different recipes, with and without NaCl, at 180 °C, 190 °C and 200 °C. Acry

  4. Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran

    Sádaba, Irantzu; Gorbanev, Yury; Kegnæs, Søren;

    2013-01-01

    The catalytic performance of zeolite-supported vanadia catalysts was examined for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) in organic solvents such as N,N-dimethylformamide (DMF), methyl isobutyl ketone, toluene, trifluorotoluene and DMSO. Catalysts based on...

  5. Kinetic mechanism of an aldehyde reductase of Saccharomyces cerevisiae that relieves toxicity of furfural and 5-hydroxymethylfurfural

    An effective means of relieving the toxicity of furan aldehydes, furfural (FFA) and 5-hydroxymethylfurfural (HMF), on fermenting organisms is essential for achieving efficient fermentation of lignocellulosic biomass to ethanol and other products. Ari1p, an aldehyde reductase from Saccharomyces cerev...

  6. Inoculum pre-treatment affects the fermentative activity of hydrogen-producing communities in the presence of 5-hydroxymethylfurfural.

    Bellucci, Micol; Botticella, Giuseppe; Francavilla, Matteo; Beneduce, Luciano

    2016-01-01

    To enhance the productivity of mixed microbial cultures for fermentative bio-hydrogen production, chemical-physical pre-treatments of the original seed are needed to suppress the activity of hydrogen (H2)-consuming microbes. This approach might influence negatively the composition and diversity of the hydrogen-producing community with consequences on the functional stability of the H2-producing systems in case of perturbations. In this study, we aimed at investigating the effect of different types of pre-treatment on the performance of hydrogen production systems in the presence of an inhibitor, such as 5-hydroxymethylfurfural (HMF). The efficiency and the microbial community structure of batch reactors amended with HMF and inoculated with non-pretreated and pretreated (acid, heat shock, and aeration) anaerobic sludge were evaluated and compared with control systems. The type of pre-treatments influenced the microbial community assembly and activity in inhibited systems, with significant effect on the performance. Cumulative H2 production tests showed that the pre-aerated systems (control and HMF inhibited) were the most efficient, while the difference of the lag phase of the pre-acidified control and HMF-added test was negligible. Analyses of the structure of the enriched microbial community in the systems through PCR-denaturing gradient gel electrophoresis (DGGE) followed by band sequencing revealed that the differences in performance were mostly related to shifts in the metabolic pathways rather than in the predominant species. In conclusion, the findings suggest that the use of specific inoculum pre-treatment could contribute to regulate the metabolic activity of the fermentative H2-producing bacteria in order to enhance the bio-energy production. PMID:26428244

  7. Catalytic conversion of inulin and fructose into 5-hydroxymethylfurfural by lignosulfonic acid in ionic liquids.

    Xie, Haibo; Zhao, Zongbao K; Wang, Qian

    2012-05-01

    In this work, we found that lignosulfonic acid (LS), which is a waste byproduct from the paper industry, in ionic liquids (ILs) can catalyze the dehydration of fructose and inulin into 5-hydroxymethylfurfural (HMF) efficiently, which is a promising potential substitute for petroleum-based building blocks. The effects of reaction time, temperature, catalyst loading, and reusability of the catalytic system were studied. It was found that a 94.3% yield of HMF could be achieved in only 10 min at 100 °C under mild conditions. The reusability study of the LS-IL catalytic system after removal of HMF by ethyl acetate extraction demonstrated that the catalytic activity decreased from 77.4 to 62.9% after five cycles and the catalytic activity could be recovered after simply removing the accumulated humins by filtration after adding ethanol to the LS-ILs. The integrated utilization of a biorenewable feedstock, catalyst, and ILs is an example of an ideal green chemical process. PMID:22517537

  8. Simultaneous determination of melamine and 5-hydroxymethylfurfural in milk by capillary electrophoresis with diode array detection.

    Chen, Zhijun; Yan, Xiaomei

    2009-10-14

    This article describes the development of a simple analytical approach for the simultaneous determination of melamine and 5-hydroxymethylfurfural (HMF) in milk samples using capillary electrophoresis (CE) with diode array detection (DAD) for the first time. Ultraviolet absorption at wavelengths of 214 and 280 nm was applied for the detection of melamine and HMF, respectively. Milk samples were extracted with 1% trichloroacetic acid using a high-speed blender and ultrasonication. After centrifugation and filtration, the extract was analyzed by CE-DAD directly. Micellar electrokinetic capillary chromatography was employed as the separation mode by adding sodium dodecyl sulfate (SDS) to the electrolyte. Under optimal separation conditions, melamine, HMF, and interferents were well resolved. The linear dynamic ranges were 0.05-100 microg/mL for melamine (R(2) = 0.9996) and 0.1-100 microg/mL for HMF (R(2) = 0.9997). The assay detection limits were 0.047 microg/mL and 0.067 microg/mL for melamine and HMF, respectively. Satisfactory results were obtained for the assay recovery rate and repeatability. The proposed method was successfully applied for the analysis of melamine and HMF in real milk samples, and the results of melamine were comparable to those obtained using HPLC-UV reference method. PMID:19761188

  9. Bifunctional polyacrylonitrile fiber-mediated conversion of sucrose to 5-hydroxymethylfurfural in mixed-aqueous systems.

    Shi, Xian-Lei; Zhang, Min; Lin, Huikun; Tao, Minli; Li, Yongdan; Zhang, Wenqin

    2015-03-01

    A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF-PA[BnBr]) and a metal chloride was employed to produce 5-hydroxymethylfurfural (HMF) from sucrose in mixed-aqueous systems. The promoter of PANF-PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8%) of HMF, superior recyclability (6 cycles) of the process, and effective scale-up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix-bed reactor. PMID:25573698

  10. Rapid determination of 5-hydroxymethylfurfural by DART ionization with time-of-flight mass spectrometry.

    Rajchl, Aleš; Drgová, Ladislava; Grégrová, Adéla; Cížková, Helena; Sevčík, Rudolf; Voldřich, Michal

    2013-05-01

    DART (direct analysis in real time), a novel technique with wide potential for rapid screening analysis, coupled with high-resolution time-of-flight mass spectrometry (TOF-MS) has been used for quantitative analysis of 5-hydroxymethylfurfural (5-HMF), a typical temperature marker of food. The DART/TOF-MS method was optimised and validated. Quantification of 5-HMF was achieved by use of a stable isotope-labelled 5-HMF standard prepared from glucose. Formation of 5-HMF from saccharides, a potential source of overestimation of results, was evaluated. Forty-four real samples (honey and caramelised condensed sweetened milk) and 50 model samples of heated honey were analysed. The possibility of using DART for analysis of heated samples of honey was confirmed. HPLC and DART/TOF-MS methods for determination of 5-HMF were compared. The correlation equation between these methods was DART = 1.0287HPLC + 0.21340, R(2) = 0.9557. The DART/TOF-MS method has been proved to enable efficient and rapid determination of 5-HMF in a variety of food matrices, for example honey and caramel. PMID:23503749

  11. Direct conversion of chitin biomass to 5-hydroxymethylfurfural in concentrated ZnCl2 aqueous solution.

    Wang, Yingxiong; Pedersen, Christian Marcus; Deng, Tiansheng; Qiao, Yan; Hou, Xianglin

    2013-09-01

    The direct conversion of chitin biomass to 5-hydroxymethylfurfural (5-HMF) in ZnCl2 aqueous solution was studied systemically. D-Glucosamine (GlcNH2) was chosen as the model compound to investigate the reaction, and 5-HMF could be obtained in 21.9% yield with 99% conversion of GlcNH2. Optimization of the reaction parameters including the screening of 8 co-catalysts was carried out. Among them, AlCl3 and B(OH)3 improved 5-HMF yield, whereas CdCl2, CuCl2 and NH4Cl had no effect. CrCl3, SnCl4 and SnCl2 showed negative effects, i.e. lower yields. Consequently, the optimal reaction conditions were found to be 67 wt.% ZnCl2 aqueous solution, at 120 °C without co-catalyst. The reactions were further studied by in situ NMR, and no intermediate or other byproducts, except humins, were observed. Finally, the substrate scope was expanded from GlcNH2 to N-acetyl-D-glucosamine and various chitosan polymers with different molecular weights, 5-HMF yield from polymers were generally lower than that from GlcNH2. PMID:23819974

  12. High 5-hydroxymethylfurfural concentrations are found in Malaysian honey samples stored for more than one year.

    Khalil, M I; Sulaiman, S A; Gan, S H

    2010-01-01

    5-Hydroxymethylfurfural (HMF) content is an indicator of the purity of honey. High concentrations of HMF in honey indicate overheating, poor storage conditions and old honey. This study investigated the HMF content of nine Malaysian honey samples, as well as the correlation of HMF formation with physicochemical properties of honey. Based on the recommendation by the International Honey Commission, three methods for the determination of HMF were used: (1) high performance liquid chromatography (HPLC), (2) White spectrophotometry and (3) Winkler spectrophotometry methods. HPLC and White spectrophotometric results yielded almost similar values, whereas the Winkler method showed higher readings. The physicochemical properties of honey (pH, free acids, lactones and total acids) showed significant correlation with HMF content and may provide parameters that could be used to make quick assessments of honey quality. The HMF content of fresh Malaysian honey samples stored for 3-6 months (at 2.80-24.87 mg/kg) was within the internationally recommended value (80 mg/kg for tropical honeys), while honey samples stored for longer periods (12-24 months) contained much higher HMF concentrations (128.19-1131.76 mg/kg). Therefore, it is recommended that honey should generally be consumed within one year, regardless of the type. PMID:20595027

  13. Glucose transformation to 5-hydroxymethylfurfural in acidic ionic liquid: A quantum mechanical study.

    Arifin; Puripat, Maneeporn; Yokogawa, Daisuke; Parasuk, Vudhichai; Irle, Stephan

    2016-01-30

    Isomerization and transformation of glucose and fructose to 5-hydroxymethylfurfural (HMF) in both ionic liquids (ILs) and water has been studied by the reference interaction site model self-consistent field spatial electron density distribution (RISM-SCF-SEDD) method coupled with ab initio electronic structure theory, namely coupled cluster single, double, and perturbative triple excitation (CCSD(T)). Glucose isomerization to fructose has been investigated via cyclic and open chain mechanisms. In water, the calculations support the cyclic mechanism of glucose isomerization; with the predicted activation free energy is 23.8 kcal mol(-1) at experimental condition. Conversely, open ring mechanism is more favorable in ILs with the energy barrier is 32.4 kcal mol(-1) . Moreover, the transformation of fructose into HMF via cyclic mechanism is reasonable; the calculated activation barriers are 16.0 and 21.5 kcal mol(-1) in aqueous and ILs solutions, respectively. The solvent effects of ILs could be explained by the decomposition of free energies and radial distribution functions of solute-solvent that are produced by RISM-SCF-SEDD. PMID:26453901

  14. Catalytic conversion of carbohydrates to 5-hydroxymethylfurfural from the waste liquid of acid hydrolysis NCC.

    Sun, Yonghui; Liu, Pengtao; Liu, Zhong

    2016-05-20

    The principal goal of this work was to reuse the carbohydrates and recycle sulfuric acid in the waste liquid of acid hydrolysis nanocrystalline cellulose (NCC). Therefore, in this work, the optimizations of further hydrolysis of waste liquid of acid hydrolysis NCC and catalytic conversion of L4 to 5-hydroxymethylfurfural (5-HMF) were studied. Sulfuric acid was separated by spiral wound diffusion dialysis (SWDD). The results revealed that cellulose can be hydrolyze to glucose absolutely under the condition of temperature 35 °C, 3 h, and sulfuric acid's concentration 62 wt%. And 78.3% sulfuric acid was recovered by SWDD. The yield of 5-HMF was highest in aqueous solution under the optimal condition was as follows, temperature 160 °C, 3 h, and sulfuric acid's concentration 12 wt%. Then the effect of biphasic solvent systems catalytic conversion and inorganic salt as additives were still examined. The results showed that both of them contributed to prepare 5-HMF. The yield and selectivity of 5-HMF was up to 21.0% and 31.4%, respectively. PMID:26917388

  15. Sulfonic acid heterogeneous catalysts for dehydration of C6-monosaccharides to 5-hydroxymethylfurfural in dimethyl sulfoxide

    Gabriel Morales; Juan A.Melero; Marta Paniagua; Jose Iglesias; Blanca Hernández; María Sanz

    2014-01-01

    Sulfonic acid-functionalized heterogeneous catalysts have been evaluated in the catalytic dehydra-tion of C6 monosaccharides into 5-hydroxymethylfurfural (HMF) using dimethyl sulfoxide (DMSO) as solvent. Sulfonic commercial resin Amberlyst-70 was the most active catalyst, which was as-cribed to its higher concentration of sulfonic acid sites as compared with the other catalysts, and it gave 93 mol%yield of HMF from fructose in 1 h. With glucose as the starting material, which is a much more difficult reaction, the reaction conditions (time, temperature, and catalyst loading) were optimized for Amberlyst-70 by a response surface methodology, which gave a maximum HMF yield of 33 mol%at 147°C with 23 wt%catalyst loading based on glucose and 24 h reaction time. DMSO promotes the dehydration of glucose into anhydroglucose, which acts as a reservoir of the substrate to facilitate the production of HMF by reducing side reactions. Catalyst reuse without a regeneration treatment showed a gradual but not very significant decay in catalytic activity.

  16. Influence of Salts on the Partitioning of 5-Hydroxymethylfurfural in Water/MIBK.

    Mohammad, Sultan; Held, Christoph; Altuntepe, Emrah; Köse, Tülay; Sadowski, Gabriele

    2016-04-28

    This study investigates the influence of electrolytes on the performance of extracting 5-hydroxymethylfurfural (HMF) from aqueous media using methyl isobutyl ketone (MIBK). For that purpose, liquid-liquid phase equilibria (LLE) of quaternary systems containing HMF, water, MIBK and salts were measured at atmospheric pressure and 298.15 K. The salts under investigation were composed of one of the anions NO(3-), SO4(2-), Cl(-), or CH3COO(-) and of one of the alkali cations Li(+), Na(+), or K(+). On the basis of these LLE data, the partition coefficient of HMF between the aqueous and the MIBK phase KHMF was determined. It could be shown that KHMF significantly depends on the kind and concentration of the added salt. Weak electrolytes (e.g., sulfates, acetates) caused salting-out, whereas nitrates caused salting-in of HMF to the aqueous phase. Unexpectedly, LiCl caused salting-out at low LiCl concentrations and salting-in at LiCl concentrations higher than 3 mol/kgH2O. The model electrolyte perturbed-chain SAFT (ePC-SAFT) was used to predict the salt influence on the LLE in the quaternary systems water/MIBK/HMF/salt in good agreement with the experimental data. On the basis of ePC-SAFT, it could be concluded that the different salting-out/salting-in behavior of the various salts is mainly caused by their different tendency to form ion pairs in aqueous solutions. PMID:27027570

  17. Dehydration of Carbohydrates to 5-Hydroxymethylfurfural in Ionic Liquids Catalyzed by Hexachlorotriphosphazene

    宋金良; 张斌斌; 史敬华; 马珺; 杨冠英; 韩布兴

    2012-01-01

    Development of efficient catalysts for the dehydration of carbohydrates to produce 5-hydroxymethylfurfural (HMF) is a very attractive topic. In this work, dehydration of fructose catalyzed by three organic molecules, includ- ing hexachlorotriphosphazene (N3P3CI6), trichloromelamine (C3N6H3CI3) and N-bromosuccinimide (NBS), was studied in ionic liquids. It was discovered that the three organic molecules had high activity in accelerating the de- hydration of fructose and N3P3C16 was the most efficient catalyst among them. The effects of amount of catalysts, temperature, solvents, reaction time, and substrate/solvent weight ratio on the reaction were investigated using N3P3C16 as the catalyst and 1-butyl-3-methylimidazolium chloride ([Bmim]C1) as the solvent. It was demonstrated that the N3P3C16/[Bmim]CI catalytic system was very effective for catalyzing the reaction. The yield of HMF could reach 92.8% in 20 rain at the optimized conditions and the N3P3C16/[Bmim]C1 system could be reused. Further study indicated that the N3P3C16/[Bmim]CI system was also effective for the dehydration of sucrose and inulin and satisfactory yield could be obtained at suitable conditions.

  18. Catalytic hydrolysis of lignocellulosic biomass into 5-hydroxymethylfurfural in ionic liquid.

    Wang, Pan; Yu, Hongbing; Zhan, Sihui; Wang, Shengqiang

    2011-03-01

    Production of 5-hydroxymethylfurfural (HMF) from cellulose catalyzed by solid acids and metal chlorides was studied in the 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) under microwave irradiation. Among the applied catalysts, the use of CrCl(3)/LiCl resulted in the highest yield of HMF. The effects of catalyst dosage (mole ratio of catalyst to glucose units in the feedstock) and reaction temperature on HMF yields were investigated to obtain optimal process conditions. With the 1:1 mol ratio of catalyst to glucose unit, the HMF yield reached 62.3% at 160°C for 10 min. Untreated wheat straw was also investigated as feedstock to produce HMF for the practical use of raw biomass, in which the HMF yield was comparable to that from pure cellulose. After the extraction of HMF, [BMIM]Cl and CrCl(3)/LiCl could be reused and exhibited no activity loss after three successive runs. PMID:21232942

  19. Glucose dehydration to 5-hydroxymethylfurfural in a biphasic system over solid acid foams.

    Ordomsky, Vitaly V; van der Schaaf, John; Schouten, Jaap C; Nijhuis, T Alexander

    2013-09-01

    A solid acid foam-structured catalyst based on a binderless zirconium phosphate (ZrPO) coating on aluminum foam was prepared. The catalyst layer was obtained by performing a multiple washcoating procedure of ZrPO slurry on the anodized aluminum foam. The effect of the pretreatment of ZrPO, the concentration of the slurry, and the amount of coating on the properties of the foam was studied. The catalytic properties of the prepared foams have been evaluated in the dehydration of glucose to 5-hydroxymethylfurfural (HMF) in a biphasic reactor. The catalytic behavior of ZrPO foam-based catalysts was studied in a rotating foam reactor and compared with that of bulk ZrPO. The effect of a silylation procedure on the selectivity of the process was shown over bulk and foam catalysts. This treatment resulted in a higher selectivity due to the deactivation of unselective Lewis acid sites. Addition of methylisobutylketone leads to extraction of HMF from the aqueous phase and stabilization of the selectivity to HMF over bulk ZrPO. A more intensive contact of the foam with the aqueous and organic phases leads to an increase in the selectivity and resistance to deactivation of the foam in comparison with a bulk catalyst. PMID:23616489

  20. Over-expression of NADH-dependent oxidoreductase (fucO) for increasing furfural or 5-hydroxymethylfurfural tolerance

    Miller, Elliot N.; Zhang, Xueli; Yomano, Lorraine P.; Wang, Xuan; Shanmugam, Keelnatham T.; Ingram, Lonnie O'Neal

    2015-10-13

    The subject invention pertains to the discovery that the NADH-dependent propanediol oxidoreductase (FucO) can reduce furfural. This allows for a new approach to improve furfural tolerance in bacterial and/or yeast cells used to produce desired products. Thus, novel biocatalysts (bacterial, fungal or yeast cells) exhibiting increased tolerance to furfural and 5-hydroxymethylfurfural (5-HMF) are provided as are methods of making and using such biocatalysts for the production of a desired product.

  1. Bioactivation of food genotoxicants 5-hydroxymethylfurfural and furfuryl alcohol by sulfotransferases from human, mouse and rat: a comparative study.

    Sachse, Benjamin; Meinl, Walter; Sommer, Yasmin; Glatt, Hansruedi; Seidel, Albrecht; Monien, Bernhard H

    2016-01-01

    5-Hydroxymethylfurfural (HMF) and furfuryl alcohol (FFA) are moderately potent rodent carcinogens that are present in thermally processed foodstuffs. The carcinogenic effects were hypothesized to originate from sulfotransferase (SULT)-mediated bioactivation yielding DNA-reactive and mutagenic sulfate esters, a confirmed metabolic pathway of HMF and FFA in mice. It is known that orthologous SULT forms substantially differ in substrate specificity and tissue distribution. This could influence HMF- and FFA-induced carcinogenic effects. Here, we studied HMF and FFA sulfoconjugation by 30 individual SULT forms of humans, mice and rats. The catalytic efficiencies (k cat/K M) of HMF sulfoconjugation of human SULT1A1 (13.7 s(-1) M(-1)), mouse Sult1a1 (15.8 s(-1) M(-1)) and 1d1 (4.8 s(-1) M(-1)) and rat Sult1a1 (5.3 s(-1) M(-1)) were considerably higher than those of all other SULT forms investigated (≤0.73 s(-1 )M(-1)). FFA sulfoconjugation was monitored using adenosine as a nucleophilic scavenger for the reactive 2-sulfoxymethylfuran (t 1/2 = 20 s at 37 °C). The resulting adduct N (6)-((furan-2-yl)methyl)-adenosine (N (6)-MF-A) was quantified by isotope-dilution UPLC-MS/MS. The rates of N (6)-MF-A formation showed that hSULT1A1 and its orthologues in mice and rats were also the most important contributors to FFA sulfoconjugation in each of the species. Taken together, the catalytic capacity of hSULT1A1 is comparable to that of mSult1a1 in mice, the species in which carcinogenic effects of HMF and FFA were detected. This is of primary concern due to the expression of hSULT1A1 in many different tissues. PMID:25370010

  2. Organocatalyzed One-Step Synthesis of Functionalized N-Alkyl-Pyridinium Salts from Biomass Derived 5-Hydroxymethylfurfural.

    Sowmiah, Subbiah; Veiros, Luís F; Esperança, José M S S; Rebelo, Luís P N; Afonso, Carlos A M

    2015-11-01

    An efficient and scalable method has been developed for the synthesis of N-alkylpyridinium salts from biomass derived 5-hydroxymethylfurfural and alkyl amines using a catalytic amount of formic acid. This protocol is also extended to various diamines providing the exclusive formation of mono-N-alkylpyridinium salts. In addition, the mechanism for the formation of pyridinium salts was studied by DFT and using H2(18)O isotope labeled experiments showing no incorporation of (18)O in the product. PMID:26493742

  3. Separation of galactose, 5-hydroxymethylfurfural and levulinic acid in acid hydrolysate of agarose by nanofiltration and electrodialysis.

    Kim, Jae Hyung; Na, Jeong-Geol; Yang, Ji-Won; Chang, Yong Keun

    2013-07-01

    A two-stage membrane process for the separation of galactose, 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) has been proposed. The first step of nanofiltration (NF) is to remove 5-HMF and LA from galactose solution obtained by the hydrolysis of agarose, the main component of red algal galactan for the reduction of its microbial toxicity. 5-HMF and LA are inhibitory to fermentation but at the same time useful compounds themselves with many applications. The second step of electrodialysis (ED) is to separate 5-HMF and LA in the permeate from NF. More than 91% of 5-HMF and up to 62% of LA could be removed from agarose hydrolysate, while galactose was almost completely retained by NF. Further removal of LA was expected to be possible with no loss of galactose by operating the NF process in a diafiltration mode. 5-HMF and LA could be effectively separated from each other by ED. PMID:23672940

  4. Base-Free Aqueous-Phase Oxidation of 5-Hydroxymethylfurfural over Ruthenium Catalysts Supported on Covalent Triazine Frameworks.

    Artz, Jens; Palkovits, Regina

    2015-11-01

    The base-free aqueous-phase oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxilic acid (FDCA) was performed at 140 °C and 20 bar of synthetic air as the oxidant. Ru clusters supported on covalent triazine frameworks (CTFs) enabled superior conversion (99.9%) and FDCA yields in comparison to other support materials such as activated carbon and γ-Al2O3 after only 1 h. The properties of the CTFs such as pore volume, specific surface area, and polarity could be tuned by using different monomers. These material properties influence the catalytic activity of Ru/CTF significantly as mesoporous CTFs showed superior activity compared to microporous materials, whereas high polarities provide further beneficial effects. The recyclability of the prepared Ru/CTF catalysts was comparable to that of Ru/C at high conversions and product yields. Nevertheless, minor deactivation in five successive recycling experiments was observed. PMID:26482331

  5. Chlorogenic acid increased 5-hydroxymethylfurfural formation when heating fructose alone or with aspartic acid at two pH levels.

    Zhang, Zhenhua; Zou, Yueyu; Wu, Taigang; Huang, Caihuan; Pei, Kehan; Zhang, Guangwen; Lin, Xiaohua; Bai, Weibin; Ou, Shiyi

    2016-01-01

    Chlorogenic acid (CGA) is a phenolic acid that ubiquitously exists in fruits. This work aims to investigate whether and how CGA influences HMF formation during heating fructose alone, or with an amino acid. The results showed that that CGA increased 5-hydroxymethylfurfural (HMF) formation. At pH 5.5 and 7.0, the addition of 5.0 μmol/ml CGA increased HMF formation by 49.4% and 25.2%, respectively when heating fructose alone, and by 9.0% and 16.7%, respectively when heating fructose with aspartic acid. CGA significantly increased HMF formation by promoting 3-deoxosone formation, and its conversion to HMF by inhibiting HMF elimination, especially in the Maillard reaction system. A comparison of the catalytic capacity of CGA with its six analogous compounds showed that both its di-hydroxyphenyl and carboxyl groups function in increasing HMF formation. PMID:26213045

  6. Critical Influence of 5-Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass Conversion in Organic Synthesis.

    Galkin, Konstantin I; Krivodaeva, Elena A; Romashov, Leonid V; Zalesskiy, Sergey S; Kachala, Vadim V; Burykina, Julia V; Ananikov, Valentine P

    2016-07-11

    Spectral studies revealed the presence of a specific arrangement of 5-hydroxymethylfurfural (5-HMF) molecules in solution as a result of a hydrogen-bonding network, and this arrangement readily facilitates the aging of 5-HMF. Deterioration of the quality of this platform chemical limits its practical applications, especially in synthesis/pharma areas. The model drug Ranitidine (Zantac®) was synthesized with only 15 % yield starting from 5-HMF which was isolated and stored as an oil after a biomass conversion process. In contrast, a much higher yield of 65 % was obtained by using 5-HMF isolated in crystalline state from an optimized biomass conversion process. The molecular mechanisms responsible for 5-HMF decomposition in solution were established by NMR and ESI-MS studies. A highly selective synthesis of a 5-HMF derivative from glucose was achieved using a protecting group at O(6) position. PMID:27271823

  7. Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

    Hansen, Thomas S.; Sádaba, Irantzu; Garcia, Eduardo;

    2013-01-01

    The renewable chemical building block 5-hydroxymethylfurfural (HMF) was oxidized to 2,5-diformylfuran by an oxidation system consisting of the radical 2,2,6,6-tetramethyl-piperidin-1-oxyl (TEMPO) and CuCl. The system was optimized by exploring several reaction conditions and by employing nitrogen...

  8. From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors : Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol

    Buntara, Teddy; Noel, Sébastien; Phua, Pim Huat; Melián-Cabrera, Ignacio; Vries, Johannes G. de; Heeres, Hero J.

    2012-01-01

    1,6-hexanediol (1) is an important polymer precursor for the polyester industry. In this paper, exploratory catalyst screening studies on the synthesis of 1 from 1,2,6-hexanetriol (2) are described via two different routes. The latter is available by a two-step procedure from 5-hydroxymethylfurfural

  9. Microbial PAH-Degradation in Soil: Degradation Pathways and Contributing Factors

    ZHANG Xu-Xiang; CHENG Shu-Pei; ZHU Cheng-Jun; SUN Shi-Lei

    2006-01-01

    Adverse effects on the environment and high persistence in the microbial degradation and environmental fate of polycyclic aromatic hydrocarbons (PAHs) are motivating interest. Many soil microorganisms can degrade PAHs and use various metabolic pathways to do so. However, both the physio-chemical characteristics of compounds as well as the physical, chemical, and biological properties of soils can drastically influence the degradation capacity of naturally occurring microorganisms for field bioremediation. Modern biological techniques have been widely used to promote the efficiency of microbial PAH-degradation and make the biodegradation metabolic pathways more clear. In this review microbial degradation of PAHs in soil is discussed, with emphasis placed on the main degradation pathways and the environmental factors affecting biodegradation.

  10. A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2006-01-01

    Levulinic acid (LA), accessible by the acid catalyzed degradation of biomass, is potentially a very versatile green intermediate chemical for the synthesis of various (bulk) chemicals for applications like fuel additives, polymers, and resin precursors. We report here a kinetic study on one of the k

  11. Enzymatic description of the anhydrofructose pathway of glycogen degradation. I

    Yu, Shukun; Refdahl, Charlotte; Lundt, Inge

    2004-01-01

    The anhydrofructose pathway describes the degradation of glycogen and starch to metabolites via 1,5-anhydro-D-fructose (1,5AnFru). The enzyme catalyzing the first reaction step of this pathway, i.e., a-1,4-glucan lyase (EC 4.2.1.13), has been purified, cloned and characterized from fungi and red ...

  12. Metabolic pathway engineering of the toluene degradation pathway

    Regan, L.

    1995-01-01

    This thesis addresses the problem of how to examine a metabolic pathway and identify what are the key elements, specifically with respect to rate-limitation. The aim is to be able to analyze a pathway, identify the bottlenecks and implement genetic modifications to remove these bottlenecks. This is done by defining the system of interest and developing a predictive model using kinetic data. The model predictions can then be verified using fermentation data and genetic technique...

  13. Phenanthrene-degrading pathway of Agrobacterium sp. Phx1

    ZHANG Lei; YUAN Hongli; WANG Shuangqing; HUANG Huaizeng

    2005-01-01

    The metabolic pathway of phenanthrene-degrading strain Agrobacterium sp. Phx1 was investigated. Phx1 almost was able to transform 100 υg/mL of phenanthrene completely in 1 day in broth media of beef extract-peptone (BP), Luria-Bertani (LB) and mineral salts media (MS), and LB and BP could promote the growth and degradation efficiency of Phx1. The GC-MS was employed to analyze the metabolites of the 1st, 3rd, 7th days of phenanthrene degradation in MS. As a result, the 1-Hydroxy-2-naphthoic acid (1H2N) and 1-naphthol (NOL) were detected in the metabolites of the 1st day. Only NOL was observed on the 3rd day and it disappeared on the 7th day. The accumulated NOL did not pertain to the defined pathway of phenanthrene degradation by bacteria. The further HPLC study confirmed the finding in GC-MS analysis and found the production of catechol (CAT) from o-phthalic acid (OPA) in the phenanthrene metabolizing, which has never been reported in the defined degrading pathways. This production was also evidenced by the production of CAT using OPA as substrate. All of our results showed that the Agrobacterium sp. Phx1 had a novel phenanthrene-degrading pathway.

  14. Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems

    This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (–COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and 13C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed

  15. Removal and recovery of furfural, 5-hydroxymethylfurfural, and acetic acid from aqueous solutions using a soluble polyelectrolyte.

    Carter, Brian; Gilcrease, Patrick C; Menkhaus, Todd J

    2011-09-01

    In the cellulosic ethanol process, furfural, 5-hydroxymethylfurfural (HMF), and acetic acid are formed during the high temperature acidic pretreatment step needed to convert biomass into fermentable sugars. These compounds can inhibit cellulase enzymes and fermentation organisms at relatively low concentrations (≥ 1 g/L). Effective removal of these inhibitory compounds would allow the use of more severe pretreatment conditions to improve sugar yields and lead to more efficient fermentations; if recovered and purified, they could also be sold as valuable by-products. This study investigated the separation of aldhehydes (furfural and HMF) and organic acid (acetic acid) inhibitory compounds from simple aqueous solutions by using polyethyleneimene (PEI), a soluble cationic polyelectrolyte. PEI added to simple solutions of each inhibitor at a ratio of 1 mol of functional group to 1 mol inhibitor removed up to 89.1, 58.6, and 81.5 wt% of acetic acid, HMF, and furfural, respectively. Furfural and HMF were recovered after removal by washing the polyelectrolyte/inhibitor complex with dilute sulfuric acid solution. Recoveries up to 81.0 and 97.0 wt% were achieved for furfural and HMF, respectively. The interaction between PEI and acetic acid was easily disrupted by the addition of chloride ions, sulfate ions, or hydroxide ions. The use of soluble polymers for the removal and recovery of inhibitory compounds from biomass slurries is a promising approach to enhance the efficiency and economics of an envisioned biorefinery. PMID:21455937

  16. Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems

    Dutta, Saikat; Wu, Kevin C.-W., E-mail: hmkao@cc.ncu.edu.tw, E-mail: kevinwu@ntu.edu.tw [Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan (China); Kao, Hsien-Ming, E-mail: hmkao@cc.ncu.edu.tw, E-mail: kevinwu@ntu.edu.tw [Department of Chemistry, National Central University, Chung-Li 32054, Taiwan (China)

    2014-11-01

    This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (–COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and {sup 13}C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

  17. Direct Production of 5-Hydroxymethylfurfural via Catalytic Conversion of Simple and Complex Sugars over Phosphated TiO2.

    Atanda, Luqman; Shrotri, Abhijit; Mukundan, Swathi; Ma, Qing; Konarova, Muxina; Beltramini, Jorge

    2015-09-01

    A water-THF biphasic system containing N-methyl-2-pyrrolidone (NMP) was found to enable the efficient synthesis of 5-hydroxymethylfurfural (HMF) from a variety of sugars (simple to complex) using phosphated TiO2 as a catalyst. Fructose and glucose were selectively converted to HMF resulting in 98 % and 90 % yield, respectively, at 175 °C. Cellobiose and sucrose also gave rise to high HMF yields of 94 % and 98 %, respectively, at 180 °C. Other sugar variants such as starch (potato and rice) and cellulose were also investigated. The yields of HMF from starch (80-85 %) were high, whereas cellulose resulted in a modest yield of 33 %. Direct transformation of cellulose to HMF in significant yield (86 %) was assisted by mechanocatalytic depolymerization-ball milling of acid-impregnated cellulose. This effectively reduced cellulose crystallinity and particle size, forming soluble cello-oligomers; this is responsible for the enhanced substrate-catalytic sites contact and subsequent rate of HMF formation. During catalyst recyclability, P-TiO2 was observed to be reusable for four cycles without any loss in activity. We also investigated the conversion of the cello-oligomers to HMF in a continuous flow reactor. Good HMF yield (53 %) was achieved using a water-methyl isobutyl ketone+NMP biphasic system. PMID:26238933

  18. Dietary exposure to 5-hydroxymethylfurfural from Norwegian food and correlations with urine metabolites of short-term exposure.

    Husøy, T; Haugen, M; Murkovic, M; Jöbstl, D; Stølen, L H; Bjellaas, T; Rønningborg, C; Glatt, H; Alexander, J

    2008-12-01

    5-Hydroxymethylfurfural (HMF) is formed in carbohydrate-rich food during acid-catalysed dehydration and in the Maillard reaction from reducing sugars. HMF is found in mg quantities per kg in various foods. HMF is mainly metabolised to 5-hydroxymethyl-2-furoic acid (HMFA), but unknown quantities of the mutagenic 5-sulphoxymethylfurfural (SMF) may also be formed, making HMF potentially hazardous to humans. We determined the HMF content in Norwegian food items and estimated the dietary intake of HMF in 53 volunteers by means of 24h dietary recall. The estimated intakes of HMF were correlated with urinary excretion of HMFA. Coffee, prunes, dark beer, canned peaches and raisins had the highest levels of HMF. The 95th percentile of the estimated daily dietary intake of HMF and the 24h urinary excretion of HMFA were 27.6 and 28.6mg, respectively. Coffee, dried fruit, honey and alcohol were identified as independent determinants of urinary HMFA excretion. Most participants had lower estimated HMF intake than the amount of HMFA excreted in urine. In spite of this there was a significant correlation (r=0.57, PHMF intake and urinary HMFA. Further studies are needed to reveal alternative sources for HMF exposure. PMID:18929614

  19. Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems

    Dutta, Saikat; Kao, Hsien-Ming; Wu, Kevin C.-W.

    2014-11-01

    This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (-COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and 13C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

  20. Rapid Method for the Determination of 5-Hydroxymethylfurfural and Levulinic Acid Using a Double-Wavelength UV Spectroscopy

    Junhua Zhang

    2013-01-01

    Full Text Available This study reports on a rapid method for the determination of levulinic acid (LA and 5-hydroxymethylfurfural (HMF in acid hydrolyze system of glucose based on UV spectroscopy. It was found that HMF and LA have a maximum absorption at the wavelengths of 284 nm and 266 nm, respectively, in a water medium, and the absorptions of HMF and LA at 284 nm and 266 nm follow Beer’s law very well. However, it was found that a major spectral interference species will arise in the quantification of HMF and LA; nonetheless, this interference can be eliminated through the absorption treatment of charcoal. Therefore, both HMF and LA can be quantified with a double-wavelength technique. The repeatability of the method had a relative standard deviation of less than 4.47% for HMF and 2.25% for LA; the limit of quantification (LOQ was 0.017 mmol/L for HMF and 4.68 mmol/L for LA, and the recovery ranged from 88% to 116% for HMF and from 94% to 105% for LA. The present method is simple, rapid, and accurate. It is suitable to use in the research of the preparation of HMF and LA in biorefinery area.

  1. Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts.

    Bohre, Ashish; Saha, Basudeb; Abu-Omar, Mahdi M

    2015-12-01

    Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3 )x ), which gave 92 % C9 -aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3 )x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3 )x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-β catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. PMID:26549016

  2. Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems

    Saikat Dutta

    2014-11-01

    Full Text Available This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs functionalized with carboxylic acid (–COOH group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and 13C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

  3. Experimental and Modeling Studies on the Conversion of Inulin to 5-Hydroxymethylfurfural Using Metal Salts in Water

    Boy Arief Fachri

    2015-12-01

    Full Text Available Inulin, a plant polysaccharide consisting of mainly d-fructose units, is considered an interesting feed for 5-hydroxymethylfurfural (HMF, a top 12 bio-based chemical. We here report an exploratory experimental study on the use of a wide range of homogeneous metal salts as catalysts for the conversion of inulin to HMF in water. Best results were obtained using CuCl2. Activity-pH relations indicate that the catalyst activity of CuCl2 is likely related to Lewis acidity and not to Brönsted acidity. The effects of process conditions on HMF yield for CuCl2 were systematically investigated and quantified using a central composite design (160–180 °C, an inulin loading between 0.05 and 0.15 g/mL, CuCl2 concentration in range of 0.005–0.015 M, and a reaction time between 10 and 120 min. The highest experimental HMF yield in the process window was 30.3 wt. % (39 mol %, 180 °C, 0.05 g/mL inulin, 0.005 M CuCl2 and a reaction time of 10 min. The HMF yields were modelled using non-linear, multi variable regression and good agreement between experimental data and model were obtained.

  4. Determination of 5-hydroxymethylfurfural using derivatization combined with polymer monolith microextraction by high-performance liquid chromatography.

    Wu, Jian-Yuan; Shi, Zhi-Guo; Feng, Yu-Qi

    2009-05-27

    A simple and sensitive method for the determination of 5-hydroxymethylfurfural (HMF) in coffee, honey, beer, Coke, and urine by high-performance liquid chromatography (HPLC) is presented. This method is based on the formation of the 2,4-dinitrophenylhydrazone of HMF and subsequent polymer monolith microextraction (PMME) of this derivative. A poly(methacrylic acid-co-ethylene glycol dimethacrylate) (MAA-co-EGDMA) monolithic capillary column was selected as the extraction medium. Several parameters affecting the derivatization of HMF with 2,4-dinitrophenylhydrazine (DNPH) followed by extraction of the derivative were optimized. The procedure is simple and offers high sensitivity and specificity since the derivative of HMF is well preconcentrated by PMME with poly(MAA-co-EGDMA) monolith and well separated from the other components of the samples under examination. The recoveries in coffee, honey, beer, Coke, and urine samples were in the range of 83.9-110.8% spiked at different levels with HMF. The inter- and intraday precisions were less than 10%. The LOD (S/N = 3) and LOQ (S/N = 10) for HMF were 1.0 ng/mL and 3.4 ng/mL, respectively. PMID:19397264

  5. Simultaneous quantitative determination of alpha-ketoglutaric acid and 5-hydroxymethylfurfural in human plasma by gas chromatography-mass spectrometry.

    Wagner, Bernhard M; Donnarumma, Fabrizio; Wintersteiger, Reinhold; Windischhofer, Werner; Leis, Hans J

    2010-04-01

    Alpha-ketoglutaric acid (alpha-KG) and 5-hydroxymethylfurfural (5-HMF) are currently under investigation as promising cancer cell damaging agents. A method for the simultaneous quantitative determination of alpha-KG and 5-HMF in human plasma was established for screening these compounds in human plasma. Plasma samples were directly treated with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride to form the corresponding oximes, thus facilitating subsequent liquid-liquid extraction. After formation of the trimethylsilyl ethers, samples were analyzed by gas chromatography with electron ionization mass spectrometry. Stable isotope labeled standards were used, the preparation of (13)C(6)-5-HMF is described. Limits of quantitation were set to 0.938 microg/mL for alpha-KG and 0.156 microg/mL for 5-HMF. Inter-day accuracy was < or = 93.7% (alpha-KG) and < or = 92.8% (5-HMF). Inter-day precision was < or = 6.0% (alpha-KG) and < or = 4.6% (5-HMF). The method has been successfully applied to pharmacokinetic profiling of the compounds after intravenous application. PMID:20155414

  6. One pot production of 5-hydroxymethylfurfural with high yield from cellulose by a Brønsted-Lewis-surfactant-combined heteropolyacid catalyst.

    Zhao, Shun; Cheng, Mingxing; Li, Junzi; Tian, Juan; Wang, Xiaohong

    2011-02-21

    A Brønsted-Lewis-surfactant-combined heteropolyacid (HPA) Cr[(DS)H(2)PW(12)O(40)](3) has been synthesized, and is used as a heterogeneous catalyst for the conversion of cellulose to 5-hydroxymethylfurfural in one pot within 2 h at 150 °C with 77.1% conversion and 52.7% yield. This micellar HPA catalyst shows stability and can be recycled by simple separation process. PMID:21203610

  7. Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical

    Su, Yu; Brown, Heather M.; Huang, Xiwen; Zhou, Xiao Dong; Amonette, James E.; Zhang, Z. Conrad

    2009-06-20

    The ability to use cellulosic biomass as feedstock for the production of fuels and chemicals currently derived from petroleum depends critically on the development of effective low-temperature processes. While HMF, as a versatile platform chemical suitable for use in polymer synthesis or production of liquid biofuels, can currently be made from fructose and glucose, synthesis of HMF directly from raw natural cellulose represents the last major barrier toward the development of a sustainable HMF platform. Here we report an unprecedented single-step pathway that depolymerizes cellulose rapidly under mild conditions and converts the resulting glucose to hydroxymethylfurfural (HMF). A pair of metal chlorides (CuCl2 and CrCl2) dissolved in 1-ethyl-3-methylimidazolium chloride at temperatures of 80-120°C catalyzes cellulose depolymerization and the subsequent glucose conversion to HMF with 95% selectivity among recoverable products (at 56% HMF yield). Cellulose depolymerization, which can also be catalyzed by other metalchloride pairs such as CuCl2 paired with PdCl2, CrCl3, or FeCl3, occurs at a rate that is more than one order of magnitude faster than conventional acid-catalyzed hydrolysis. In contrast, single-metal chlorides at the same total loading showed low activity under similar conditions. Mechanistic studies suggest that the C2 hydrogen of the imidazolium ring is activated by the paired metal-chloride catalysts.

  8. Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid%Rapid conversion of cellulose to5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

    Hussein Abou-Yousef; El Barbary Hassan; Philip Steele

    2013-01-01

    Direct conversion of cellulose into 5-hydroxymethylfurfural (HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride ([EMIM] Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone (FHMK),and furfural (FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives (HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF (35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeC13/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF (39.9%) with total yield (63.8%) of fttrans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals (5 ~ 20 min).

  9. 蔗糖脱水制备5-羟甲基糠醛的研究%Preparation of 5-Hydroxymethylfurfural by Dehydration of Sucrose

    孔珊珊; 刘仕伟; 李露; 于世涛

    2014-01-01

    研究了BrÖnsted-Lewis复合催化体系催化蔗糖脱水制备5-羟甲基糠醛,考察了反应条件对5-羟甲基糠醛收率的影响,最佳反应条件为:蔗糖2.0 g,复合催化体系HCl-CrCl3(质量比5:1)0.8 g,二甲基亚砜20 mL,反应时间30 min,反应温度200℃。在上述较佳反应条件下,蔗糖转化率为100%,5-羟甲基糠醛的收率达72.7%。此外,CrCl3对产物5-羟甲基糠醛具有良好的稳定性,在一定程度上可避免产物继续发生水合/脱羧反应而生成甲酸和乙酰丙酸。%The preparation of 5-hydroxymethylfurfural ( HMF ) from sucrose was studied in the presence of Br nsted-Lewis composite catalytic system. The effects of reaction conditions on the yield of 5-hydroxymethylfurfural were examined. The optimal reaction conditions were obtained as follows: sucrose 2. 0 g, composite catalytic system HCl-CrCl3(mass ratio 5:1) 0. 8 g , dimethyl sulfoxide 20 mL, reaction time 30 min and reaction temperature 200 ℃. Under the above conditions, the conversion of sucrose was 100 %, and the yield of 5-hydroxymethylfurfural reached 72. 7 %. Moreover, CrCl3 had a good stability on the product 5-hydroxymethylfurfural. It could avoid 5-hydroxymethylfurfural over-reacting to form formic acid and levulinic acid by the hydration/decarboxylation reaction to a certain extent.

  10. Simultaneous determination of furfural, acetic acid, and 5-hydroxymethylfurfural in corncob hydrolysates using liquid chromatography with ultraviolet detection.

    Dong, Bo-Yu; Chen, Ye-Fu; Zhao, Chang-Chun; Zhang, Shi-Jie; Guo, Xue-Wu; Xiao, Dong-Guang

    2013-01-01

    A single-laboratory validation study was conducted using HPLC for detecting and quantifying acetic acid, furfural, and 5-hydroxymethylfurfural (HMF) in corncob hydrolysates. A pretreatment procedure using dilute sulfuric acid was optimized for corncob hydrolysis. The final hydrolysates were analyzed by HPLC using a C18 RP column with aqueous 0.01% (v/v) H2SO4-CH3OH (95 + 5) as the mobile phase at a flow rate of 1 mL/min. The wavelengths for detecting the three compounds were changed to their optimal UV detection wavelengths at the time of elution. The wavelength detection adjustments were as follow: 205 nm (0 to 4 min); 284 nm (4 to 7 min); and 276 nm (7 to 10 min). Separation was achieved with a chromatographic run time of 10 min. The calibration curves for the three compounds had correlation coefficients (r2) > or = 99.8%. The analytical range, as defined by the calibration curves, was 0.5-10 mg/L for acetic acid, 0.4-22 mg/L for furfural, and 0.1-18 mg/L for HMF. The LODs for acetic acid, furfural, and HMF were estimated to be 0.05, 0.03, and 0.02 mg/L, respectively; the LOQs were 0.196, 0.135, and 0.074 mg/L, respectively. The RSD values for the intraday precision study ranged from 0.31 to 2.22%, and from 0.57 to 2.43% for the interday study. The mean recovery rates in all compounds were between 100.08 and 101.49%. PMID:24645500

  11. Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural.

    Pacheco, Joshua J; Davis, Mark E

    2014-06-10

    Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleum-derived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve Diels-Alder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190 °C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder dehydration product is observed. PMID:24912153

  12. Comparison of an HPTLC method with the Reflectoquant assay for rapid determination of 5-hydroxymethylfurfural in honey.

    Hošťálková, Anna; Klingelhöfer, Ines; Morlock, Gertrud E

    2013-11-01

    5-Hydroxymethylfurfural (HMF) was analyzed in 17 botanical varieties of honey from 12 countries. A recently developed high-performance thin-layer chromatographic (HPTLC) method was limited because of increased matrix effects at higher honey sample loading. Therefore, the method was modified to achieve higher sensitivity and eliminate matrix interference by use of rectangular application combined with a focusing step. The HPTLC results were compared with results from the new spectrophotometric Reflectoquant hydroxymethylfurfural assay. Both methods had quantification limits of 4 mg kg(-1) and were suitable for rapid quantification of HMF in honey at the strictest regulated level of 15 mg kg(-1). Comparable results were obtained for the 17 honey samples, with a mean deviation of 2.9 mg kg(-1) (15%). The optimized HPTLC method was proved to be highly matrix-robust and was validated for the 17 different honey matrices (correlation coefficients ≥0.9994 (n = 6), mean intra-day precision 3.2% (n = 3 within a plate; n = 2 repeated within a day), mean inter-day precision 3.7% (n = 3), mean reproducibility over the whole procedure including sample preparation 4.1% (n = 2), and mean recovery 106.9% (n = 5 different concentrations; n = 4 different honey matrices). Recovery for a range of different application volumes, and thus for different honey matrix loading, differed by only ≤4.2%. HMF results when calculated by use of external calibration and by use of the standard addition method varied by 8.8%. Both revealed that any matrix effect was minor and that the original matrix interference problem was successfully solved. PMID:24091734

  13. Trichloroethylene degradation by two independent aromatic-degrading pathways in Alcaligenes eutrophus JMP134.

    Harker, A R; Kim, Y.

    1990-01-01

    The bacterium Alcaligenes eutrophus JMP134(pJP4) degrades trichloroethylene (TCE) by a chromosomal phenol-dependent pathway and by the plasmid-encoded 2,4-dichlorophenoxyacetic acid pathway. The two pathways were independent and exhibited different rates of removal and capacities for quantity of TCE removed. The phenol-dependent pathway was more rapid (0.2 versus 0.06 nmol of TCE removed per min per mg of protein) and consumed all detectable TCE. The 2,4-dichlorophenoxyacetic acid-dependent p...

  14. Preparation of 5-hydroxymethylfurfural from cellulose catalyzed by composite catalyst%复合催化剂降解纤维素制备5-羟甲基糠醛

    袁玉国; 王景芸; 王强; 付霓虹; 周明东; 臧树良

    2016-01-01

    The degradation of microcrystalline cellulose(MCC) to 5-hydroxymethylfurfural in ionic liquid 1-allyl-3-methylimidazolium chloride([Amim]Cl) was studied with sulfoacid type cation exchange resin and CrCl3·6H2O as composite catalyst and microwave-assisted heating. The effects of catalyst dosage,reaction temperature,time and water dosage on the degradation were investigated. The results indicated that,MCC could be completely converted with the total reducing sugar yield of 75.2% and the highest 5-hydroxymethylfurfural yield of 53.0% under the conditions of sulfoacid type cation exchange resin and CrCl3·6H2O as the composite catalyst,ionic liquid[Amim]Cl as the solvent 2 g,MCC 0.1 g,m(resin):m(MCC) 1:1,n(CrCl3·6H2O):n(MCC) 1:10,reaction temperature 160℃ by microwave-assisted heating and reaction time 30 min.%以离子液体1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)为溶剂,以磺酸型阳离子交换树脂和CrCl3·6H2O为复合催化剂,在微波辅助加热条件下采用一锅法降解微晶纤维素制备5-羟甲基糠醛,考察了催化剂加入量、反应温度、反应时间、加水量等反应条件对微晶纤维素降解反应的影响.实验结果表明,当[Amim]Cl用量为2 g、微晶纤维素质量为0.1 g、m(磺酸型阳离子交换树脂):m(微晶纤维素)=1:1、n(CrCl3·6H2O):n(微晶纤维素)=1:10、反应温度为160℃、反应时间为30 min、加水量为50 μL时,微晶纤维素可完全转化,同时总还原糖收率为75.2%,5-羟甲基糠醛收率最高可达53.0%.

  15. Autophagy: a pathway that contributes to connexin degradation

    Lichtenstein, Alexandra; Minogue, Peter J.; Beyer, Eric C.; Berthoud, Viviana M.

    2011-01-01

    The function of connexins, which form gap junctions, can be rapidly modulated by degradation, because they have half-lives of only a few hours. Autophagy is a degradation pathway that has been implicated in several diseases and can be induced by cellular stresses such as starvation. We investigated the involvement of autophagy in proteolysis of the wild-type connexins CX50 and CX43, and a cataract-associated connexin mutant, CX50P88S, which forms cytoplasmic accumulations. We observed that cy...

  16. Vacuole import and degradation pathway:Insights into a specialized autophagy pathway

    Abbas; A; Alibhoy; Hui-Ling; Chiang

    2011-01-01

    Glucose deprivation induces the synthesis of pivotagluconeogenic enzymes such as fructose-1,6-bisphos-phatase, malate dehydrogenase, phosphoenolpyruvatecarboxykinase and isocitrate lyase in Saccharomycescerevisiae. However, following glucose replenishment,these gluconeogenic enzymes are inactivated and de-graded. Studies have characterized the mechanismsby which these enzymes are inactivated in response toglucose. The site of degradation of these proteins hasalso been ascertained to be dependent on the dura-tion of starvation. Glucose replenishment of short-termstarved cells results in these proteins being degradedin the proteasome. In contrast, addition of glucose tocells starved for a prolonged period results in theseproteins being degraded in the vacuole. In the vacuoledependent pathway, these proteins are sequestered inspecialized vesicles termed vacuole import and degra-dation (Vid). These vesicles converge with the endo-cytic pathway and deliver their cargo to the vacuolefor degradation. Recent studies have identified thatinternalization, as mediated by actin polymerization, isessential for delivery of cargo proteins to the vacuolefor degradation. In addition, components of the targetof rapamycin complex 1 interact with cargo proteins during glucose starvation. Furthermore, Tor1p dissoci-ates from cargo proteins following glucose replenish-ment. Future studies will be needed to elaborate on the importance of internalization at the plasma membrane and the subsequent import of cargo proteins into Vid vesicles in the vacuole dependent degradation pathway.

  17. Enzymatic description of the anhydrofructose pathway of glycogen degradation. I

    Yu, Shukun; Refdahl, Charlotte; Lundt, Inge

    2004-01-01

    The anhydrofructose pathway describes the degradation of glycogen and starch to metabolites via 1,5-anhydro-D-fructose (1,5AnFru). The enzyme catalyzing the first reaction step of this pathway, i.e., a-1,4-glucan lyase (EC 4.2.1.13), has been purified, cloned and characterized from fungi and red...... algae in our laboratory earlier. In the present study, two 1,5AnFru metabolizing enzymes were discovered in the fungus Anthracobia melaloma for the formation of ascopyrone P (APP), a fungal secondary metabolite exhibiting antibacterial and antioxidant activity. These are 1,5AnFru dehydratase (AFDH) and...

  18. Kinetic mechanism of an aldehyde reductase of Saccharomyces cerevisiae that relieves toxicity of furfural and 5-hydroxymethylfurfural.

    Jordan, Douglas B; Braker, Jay D; Bowman, Michael J; Vermillion, Karl E; Moon, Jaewoong; Liu, Z Lewis

    2011-12-01

    An effective means of relieving the toxicity of furan aldehydes, furfural (FFA) and 5-hydroxymethylfurfural (HMF), on fermenting organisms is essential for achieving efficient fermentation of lignocellulosic biomass to ethanol and other products. Ari1p, an aldehyde reductase from Saccharomyces cerevisiae, has been shown to mitigate the toxicity of FFA and HMF by catalyzing the NADPH-dependent conversion to corresponding alcohols, furfuryl alcohol (FFOH) and 5-hydroxymethylfurfuryl alcohol (HMFOH). At pH 7.0 and 25°C, purified Ari1p catalyzes the NADPH-dependent reduction of substrates with the following values (k(cat) (s(-1)), k(cat)/K(m) (s(-1)mM(-1)), K(m) (mM)): FFA (23.3, 1.82, 12.8), HMF (4.08, 0.173, 23.6), and dl-glyceraldehyde (2.40, 0.0650, 37.0). When acting on HMF and dl-glyceraldehyde, the enzyme operates through an equilibrium ordered kinetic mechanism. In the physiological direction of the reaction, NADPH binds first and NADP(+) dissociates from the enzyme last, demonstrated by k(cat) of HMF and dl-glyceraldehyde that are independent of [NADPH] and (K(ia)(NADPH)/k(cat)) that extrapolate to zero at saturating HMF or dl-glyceraldehyde concentration. Microscopic kinetic parameters were determined for the HMF reaction (HMF+NADPH↔HMFOH+NADP(+)), by applying steady-state, presteady-state, kinetic isotope effects, and dynamic modeling methods. Release of products, HMFOH and NADP(+), is 84% rate limiting to k(cat) in the forward direction. Equilibrium constants, [NADP(+)][FFOH]/[NADPH][FFA][H(+)]=5600×10(7)M(-1) and [NADP(+)][HMFOH]/[NADPH][HMF][H(+)]=4200×10(7)M(-1), favor the physiological direction mirrored by the slowness of hydride transfer in the non-physiological direction, NADP(+)-dependent oxidation of alcohols (k(cat) (s(-1)), k(cat)/K(m) (s(-1)mM(-1)), K(m) (mM)): FFOH (0.221, 0.00158, 140) and HMFOH (0.0105, 0.000104, 101). PMID:21890004

  19. Kynurenine pathway in psychosis: evidence of increased tryptophan degradation.

    Barry, Sandra

    2009-05-01

    The kynurenine pathway of tryptophan degradation may serve to integrate disparate abnormalities heretofore identified in research aiming to elucidate the complex aetiopathogenesis of psychotic disorders. Post-mortem brain tissue studies have reported elevated kynurenine and kynurenic acid in the frontal cortex and upregulation of the first step of the pathway in the anterior cingulate cortex of individuals with schizophrenia. In this study, we examined kynurenine pathway activity by measuring tryptophan breakdown, a number of pathway metabolites and interferon gamma (IFN-gamma), which is the preferential activator of the first-step enzyme, indoleamine dioxygenase (IDO), in the plasma of patients with major psychotic disorder. Plasma tryptophan, kynurenine pathway metabolites were measured using high-performance liquid chromatography (HPLC) in 34 patients with a diagnosis on the psychotic spectrum (schizophrenia or schizoaffective disorder) and in 36 healthy control subjects. IFN-gamma was measured using enzyme-linked immunosorbent assay (ELISA). The mean tryptophan breakdown index (kynurenine\\/tryptophan) was significantly higher in the patient group compared with controls (P < 0.05). IFN-gamma measures did not differ between groups (P = 0.23). No relationship was found between measures of psychopathology, symptom severity and activity in the first step in the pathway. A modest correlation was established between the tryptophan breakdown index and illness duration. These results provide evidence for kynurenine pathway upregulation, specifically involving the first enzymatic step, in patients with major psychotic disorder. Increased tryptophan degradation in psychoses may have potential consequences for the treatment of these disorders by informing the development of novel therapeutic compounds.

  20. 5-Hydroxymethylfurfural (5-HMF) Production from Hexoses: Limits of Heterogeneous Catalysis in Hydrothermal Conditions and Potential of Concentrated Aqueous Organic Acids as Reactive Solvent System

    Nadine Essayem; Franck Rataboul; Rodrigo Lopes de Souza; Hao Yu

    2012-01-01

    5-Hydroxymethylfurfural (5-HMF) is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose. The treatment at 150–250 °C of glucose or fructose in pure water and batch conditions, with catalytic amounts of most of the usual acid-basic solid catalysts, gave limited yields in 5-HMF, due mainly to the fast formation of soluble oligomers. Niobic acid, which possesses both Lewis and Brønsted acid sites, gave the highest 5-HMF yield, 28%, when high catalyst/gluco...

  1. Preparation of 5-hydroxymethylfurfural by dehydration of glucose%葡萄糖脱水制备5-羟甲基糠醛的研究

    孔珊珊; 刘仕伟; 李露; 于世涛

    2013-01-01

    研究了Br(o)nsted-Lewis复合催化体系催化葡萄糖脱水制备5-羟甲基糠醛,详细考察了溶剂种类和用量、催化体系种类和用量、反应时间和反应温度等因素对5-羟甲基糠醛收率的影响,得到最佳工艺条件:葡萄糖2.0g,复合催化体系HCl-CrCl3[m(HCl)∶m(CrCl3·6H2O)=5∶1]0.6 g,正丁醇20 mL,反应时间15 min,反应温度200℃.在该反应条件下,5-羟甲基糠醛的收率达42.5%.结果表明,同单酸型的催化剂相比,复合催化体系更有利于葡萄糖脱水制备5-羟甲基糠醛.%The preparation of 5-hydroxymethylfurfural from glucose was studied in the presence of Br(o)nsted-Lewis composite catalytic system.The effects of reaction conditions,such as solvents,catalysts,reaction time and reaction temperature,on the yield of 5-hydroxymethylfurfural were examined.The optimum reaction conditions were obtained as follow:glucose 2.0 g,composite catalytic system HC1-CrCl3 (mass ratio 5 ∶ 1) 0.6 g,n-butyl alcohol 20 mL,reaction time 15 min and reaction temperature 200 ℃.Under above optimum conditions,the conversion of glucose was 90.4 %,and the yield of 5-hydroxymethylfurfural reached 42.5 %.The results indicated that,composite catalytic system is more conducible to preparation of 5-hydroxymethylfurfural by dehydration of glucose compared with the single-acid catalyst.

  2. Iodinated contrast media electro-degradation: Process performance and degradation pathways

    The electrochemical degradation of six of the most widely used iodinated contrast media was investigated. Batch experiments were performed under constant current conditions using two DSA® electrodes (titanium coated with a proprietary and patented mixed metal oxide solution of precious metals such as iridium, ruthenium, platinum, rhodium and tantalum). The degradation removal never fell below 85% (at a current density of 64 mA/cm2 with a reaction time of 150 min) when perchlorate was used as the supporting electrolyte; however, when sulphate was used, the degradation performance was above 80% (at a current density of 64 mA/cm2 with a reaction time of 150 min) for all of the compounds studied. Three main degradation pathways were identified, namely, the reductive de-iodination of the aromatic ring, the reduction of alkyl aromatic amides to simple amides and the de-acylation of N-aromatic amides to produce aromatic amines. However, as amidotrizoate is an aromatic carboxylate, this is added via the decarboxylation reaction. The investigation did not reveal toxicity except for the lower current density used, which has shown a modest toxicity, most likely for some reaction intermediates that are not further degraded. In order to obtain total removal of the contrast media, it was necessary to employ a current intensity between 118 and 182 mA/cm2 with energy consumption higher than 370 kWh/m3. Overall, the electrochemical degradation was revealed to be a reliable process for the treatment of iodinated contrast media that can be found in contaminated waters such as hospital wastewater or pharmaceutical waste-contaminated streams. - Highlights: • The electrochemical degradation of six iodinated contrast media were investigated. • Treatment feasibility as well as reaction by-products and toxicity were investigated. • In all the investigated cases, the removal efficiency was higher than 80%. • Two main degradation pathways were identified

  3. Iodinated contrast media electro-degradation: Process performance and degradation pathways

    Del Moro, Guido; Pastore, Carlo; Di Iaconi, Claudio; Mascolo, Giuseppe, E-mail: giuseppe.mascolo@ba.irsa.cnr.it

    2015-02-15

    The electrochemical degradation of six of the most widely used iodinated contrast media was investigated. Batch experiments were performed under constant current conditions using two DSA® electrodes (titanium coated with a proprietary and patented mixed metal oxide solution of precious metals such as iridium, ruthenium, platinum, rhodium and tantalum). The degradation removal never fell below 85% (at a current density of 64 mA/cm{sup 2} with a reaction time of 150 min) when perchlorate was used as the supporting electrolyte; however, when sulphate was used, the degradation performance was above 80% (at a current density of 64 mA/cm{sup 2} with a reaction time of 150 min) for all of the compounds studied. Three main degradation pathways were identified, namely, the reductive de-iodination of the aromatic ring, the reduction of alkyl aromatic amides to simple amides and the de-acylation of N-aromatic amides to produce aromatic amines. However, as amidotrizoate is an aromatic carboxylate, this is added via the decarboxylation reaction. The investigation did not reveal toxicity except for the lower current density used, which has shown a modest toxicity, most likely for some reaction intermediates that are not further degraded. In order to obtain total removal of the contrast media, it was necessary to employ a current intensity between 118 and 182 mA/cm{sup 2} with energy consumption higher than 370 kWh/m{sup 3}. Overall, the electrochemical degradation was revealed to be a reliable process for the treatment of iodinated contrast media that can be found in contaminated waters such as hospital wastewater or pharmaceutical waste-contaminated streams. - Highlights: • The electrochemical degradation of six iodinated contrast media were investigated. • Treatment feasibility as well as reaction by-products and toxicity were investigated. • In all the investigated cases, the removal efficiency was higher than 80%. • Two main degradation pathways were identified.

  4. E1AF degradation by a ubiquitin-proteasome pathway

    E1AF is a member of the ETS family of transcription factors. In mammary tumors, overexpression of E1AF is associated with tumorigenesis, but E1AF protein has hardly been detected and its degradation mechanism is not yet clear. Here we show that E1AF protein is stabilized by treatment with the 26S protease inhibitor MG132. We found that E1AF was modified by ubiquitin through the C-terminal region and ubiquitinated E1AF aggregated in nuclear dots, and that the inhibition of proteasome-activated transcription from E1AF target promoters. These results suggest that E1AF is degraded via the ubiquitin-proteasome pathway, which has some effect on E1AF function

  5. Photo-fenton degradation of diclofenac: identification of main intermediates and degradation pathway.

    Pérez-Estrada, Leónidas A; Malato, Sixto; Gernjak, Wolfgang; Agüera, Ana; Thurman, E Michael; Ferrer, Imma; Fernández-Alba, Amadeo R

    2005-11-01

    In recent years, the presence of pharmaceuticals in the aquatic environment has been of growing interest. These new contaminants are important because many of them are not degraded under the typical biological treatments applied in the wastewater treatment plants and represent a continuous input into the environment. Thus, compounds such as diclofenac are present in surface waters in all Europe and a crucial need for more enhanced technologies that can reduce its presence in the environment has become evident. In this sense, advanced oxidation processes (AOPs) represent a good choice for the treatment of hazardous nonbiodegradable pollutants. This work deals with the solar photodegradation of diclofenac, an antiinflammatory drug, in aqueous solutions by photo-Fenton reaction. A pilot-scale facility using a compound parabolic collector (CPC) reactor was used for this study. Results obtained show rapid and complete oxidation of diclofenac after 60 min, and total mineralization (disappearance of dissolved organic carbon, DOC) after 100 min of exposure to sunlight. Although diclofenac precipitates during the process at low pH, its degradation takes place in the homogeneous phase governed by a precipitation-redissolution-degradation process. Establishment of the reaction pathway was made possible by a thorough analysis of the reaction mixture identifying the main intermediate products generated. Gas chromatography-mass spectrometry (GC/ MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) were used to identify 18 intermediates, in two tentative degradation routes. The main one was based on the initial hydroxylation of the phenylacetic acid moiety in the C-4 position and subsequent formation of a quinone imine derivative that was the starting point for further multistep degradation involving hydroxylation, decarboxylation, and oxidation reactions. An alternative route was based on the transient preservation of the biphenyl amino moiety

  6. Proteogenomic Characterization of Monocyclic Aromatic Hydrocarbon Degradation Pathways in the Aniline-Degrading Bacterium Burkholderia sp. K24

    Yun, Sung Ho; Choi, Chi-Won; Yi, Yoon-Sun; Kim, Jonghyun; Chung, Young-Ho; Park, Edmond Changkyun; Kim, Seung Il

    2016-01-01

    Burkholderia sp. K24, formerly known as Acinetobacter lwoffii K24, is a soil bacterium capable of utilizing aniline as its sole carbon and nitrogen source. Genomic sequence analysis revealed that this bacterium possesses putative gene clusters for biodegradation of various monocyclic aromatic hydrocarbons (MAHs), including benzene, toluene, and xylene (BTX), as well as aniline. We verified the proposed MAH biodegradation pathways by dioxygenase activity assays, RT-PCR, and LC/MS-based quantitative proteomic analyses. This proteogenomic approach revealed four independent degradation pathways, all converging into the citric acid cycle. Aniline and p-hydroxybenzoate degradation pathways converged into the β-ketoadipate pathway. Benzoate and toluene were degraded through the benzoyl-CoA degradation pathway. The xylene isomers, i.e., o-, m-, and p-xylene, were degraded via the extradiol cleavage pathways. Salicylate was degraded through the gentisate degradation pathway. Our results show that Burkholderia sp. K24 possesses versatile biodegradation pathways, which may be employed for efficient bioremediation of aniline and BTX. PMID:27124467

  7. Iodinated contrast media electro-degradation: process performance and degradation pathways.

    Del Moro, Guido; Pastore, Carlo; Di Iaconi, Claudio; Mascolo, Giuseppe

    2015-02-15

    The electrochemical degradation of six of the most widely used iodinated contrast media was investigated. Batch experiments were performed under constant current conditions using two DSA® electrodes (titanium coated with a proprietary and patented mixed metal oxide solution of precious metals such as iridium, ruthenium, platinum, rhodium and tantalum). The degradation removal never fell below 85% (at a current density of 64 mA/cm(2) with a reaction time of 150 min) when perchlorate was used as the supporting electrolyte; however, when sulphate was used, the degradation performance was above 80% (at a current density of 64 mA/cm(2) with a reaction time of 150 min) for all of the compounds studied. Three main degradation pathways were identified, namely, the reductive de-iodination of the aromatic ring, the reduction of alkyl aromatic amides to simple amides and the de-acylation of N-aromatic amides to produce aromatic amines. However, as amidotrizoate is an aromatic carboxylate, this is added via the decarboxylation reaction. The investigation did not reveal toxicity except for the lower current density used, which has shown a modest toxicity, most likely for some reaction intermediates that are not further degraded. In order to obtain total removal of the contrast media, it was necessary to employ a current intensity between 118 and 182 mA/cm(2) with energy consumption higher than 370 kWh/m(3). Overall, the electrochemical degradation was revealed to be a reliable process for the treatment of iodinated contrast media that can be found in contaminated waters such as hospital wastewater or pharmaceutical waste-contaminated streams. PMID:25433384

  8. Characterization of a novel oxyfluorfen-degrading bacterial strain Chryseobacterium aquifrigidense and its biochemical degradation pathway.

    Zhao, Huanhuan; Xu, Jun; Dong, Fengshou; Liu, Xingang; Wu, Yanbing; Wu, Xiaohu; Zheng, Yongquan

    2016-08-01

    Persistent use of the diphenyl ether herbicides oxyfluorfen may seriously increase the health risks and ecological safety problems. A newly bacterium R-21 isolated from active soil was able to degrade and utilize oxyfluorfen as the sole carbon source. R-21 was identified as Chryseobacterium aquifrigidense by morphology, physiobiochemical characteristics, and genetic analysis. Under the optimum cultural conditions (pH 6.9, temperature 33.4 °C, and inoculum size 0.2 g L(-1)), R-21 could degrade 92.1 % of oxyfluorfen at 50 mg L(-1) within 5 days. During oxyfluorfen degradation, six metabolites were detected and identified by atmospheric pressure gas chromatography coupled to quadrupole-time of flight mass spectrometry and ultra-performance liquid chromatography coupled to quadrupole-time of flight mass spectrometry, and a plausible degradation pathway was deduced. Strain R-21 is a promising potential in bioremediation of oxyfluorfen-contaminated environments. PMID:27079576

  9. Research Progress on Production of 5-Hydroxymethylfurfural from Carbohydrates%碳水化合物制备5-羟甲基糠醛研究进展

    罗家凤; 吴剑; 张钰萍; 杨松

    2012-01-01

    5-羟甲基糠醛(5-HMF)是一种基于生物质的重要平台小分子,综述了近几年从葡萄糖或者纤维素等制备5-HMF的方法及研究进展,阐述了5-HMF制备收率的影响因素.最后展望了固体酸催化葡萄糖或者纤维素制备5-HMF的发展趋势.%5-Hydroxylmethylfurfural (5-HMF) is a key intermediate in the biomass chemistry and petrochemical industry. The research progress on the conversion of cellulose or glucose to 5-HMF is reviewed, and the effects of different parameters are also discussed. Finally, the development tendency of solid acid catalyzed production of 5-hydroxymethylfurfural is proposed.

  10. 5-Hydroxymethylfurfural modified rhodamine B dual-function derivative: Highly sensitive and selective optical detection of pH and Cu2+

    Wang, Enze; Zhou, Yanmei; Huang, Qi; Pang, Lanfang; Qiao, Han; Yu, Fang; Gao, Bin; Zhang, Junli; Min, Yinghao; Ma, Tongsen

    2016-01-01

    A dual-function optical chemosensor (RBF) was designed and easily synthesized by condensation reaction of 5-Hydroxymethylfurfural and rhodamine B hydrazide. RBF exhibited highly sensitive, highly selective and quick response to acidic pH. The fluorescence intensity of RBF exhibited a more than 41-fold increase within the pH range from 7.50 to 3.73 with a pKa value of 5.02, which could be successfully applied to monitor intracellular pH in living PC12 cells and HeLa cells. Additionally, the spectroscopy of UV-Vis and EDTA-adding experiments indicated that RBF was a highly selective and reversible colorimetric chemosensor for Cu2+ in Tris-HCl (10 mM, pH = 7.2) aqueous buffer solution as well as other metal ions had no obvious interference. Moreover, RBF has been successfully applied to detect Cu2+ in real water samples.

  11. 5-Hydroxymethylfurfural modified rhodamine B dual-function derivative: Highly sensitive and selective optical detection of pH and Cu(2+).

    Wang, Enze; Zhou, Yanmei; Huang, Qi; Pang, Lanfang; Qiao, Han; Yu, Fang; Gao, Bin; Zhang, Junli; Min, Yinghao; Ma, Tongsen

    2016-01-01

    A dual-function optical chemosensor (RBF) was designed and easily synthesized by condensation reaction of 5-Hydroxymethylfurfural and rhodamine B hydrazide. RBF exhibited highly sensitive, highly selective and quick response to acidic pH. The fluorescence intensity of RBF exhibited a more than 41-fold increase within the pH range from 7.50 to 3.73 with a pKa value of 5.02, which could be successfully applied to monitor intracellular pH in living PC12 cells and HeLa cells. Additionally, the spectroscopy of UV-Vis and EDTA-adding experiments indicated that RBF was a highly selective and reversible colorimetric chemosensor for Cu(2+) in Tris-HCl (10mM, pH=7.2) aqueous buffer solution as well as other metal ions had no obvious interference. Moreover, RBF has been successfully applied to detect Cu(2+) in real water samples. PMID:26232576

  12. Aqueous photodegradation of antibiotic florfenicol: kinetics and degradation pathway studies.

    Zhang, Ya; Li, Jianhua; Zhou, Lei; Wang, Guoqing; Feng, Yanhong; Wang, Zunyao; Yang, Xi

    2016-04-01

    The occurrence of antibacterial agents in natural environment was of scientific concern in recent years. As endocrine disrupting chemicals, they had potential risk on ecology system and human beings. In the present study, the photodegradation kinetics and pathways of florfenicol were investigated under solar and xenon lamp irradiation in aquatic systems. Direct photolysis half-lives of florfenicol were determined as 187.29 h under solar irradiation and 22.43 h under xenon lamp irradiation, respectively. Reactive oxygen species (ROS), such as hydroxyl radical (·OH) and singlet oxygen ((1)O2) were found to play an important role in indirect photolysis process. The presence of nitrate and dissolved organic matters (DOMs) could affect photolysis of florfenicol in solutions through light screening effect, quenching effect, and photoinduced oxidization process. Photoproducts of florfenicol in DOMs solutions were identified by solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) analysis techniques, and degradation pathways were proposed, including photoinduced hydrolysis, oxidation by (1)O2 and ·OH, dechlorination, and cleavage of the side chain. PMID:26705756

  13. Tetracycline degradation by ozonation in the aqueous phase: Proposed degradation intermediates and pathway

    During the ozonation of tetracycline (TC) in aqueous media at pHs 2.2 and 7.0, the effects of pH variations, protonation and dissociation of functional groups and variation in free radical exposure were investigated to elucidate the transformation pathway. Liquid chromatography-triple quadrupole mass spectrometry detected around 15 ozonation products, and uncovered their production and subsequent degradation patterns. During ozonation at pH 2.2, the TC degradation pathway was proposed on the basis of the structure, ozonation chemistry and mass spectrometry data of TC. Ozonation of TC at the C11a-C12 and C2-C3 double bonds, aromatic ring and amino group generated products of m/z 461, 477, 509 and 416, respectively. Further ozonation at the above mentioned sites gave products of m/z 432, 480, 448, 525 and 496. The removal of TOC reached a maximum of ∼40% after 2 h of ozonation, while TC was completely removed within 4-6 min at both pHs. The low TOC removal efficiency might be due to the generation of recalcitrant products and the low ozone supply for high TC concentration. Ozonation decreased the acute toxicity of TC faster at pH 7.0 than pH 2.2, but the maximum decrease was only about 40% at both pHs after 2 h of ozonation. In this study, attempts were made to understand the correlation between the transformation products, pathway, acute toxicity and quantity of residual organics in solution. Overall, ozonation was found to be a promising process for removing TC and the products initially generated.

  14. Tetracycline degradation by ozonation in the aqueous phase: Proposed degradation intermediates and pathway

    Khan, M. Hammad; Bae, Hyokwan [Water Environment Center, Korea Institute of Science and Technology, 39-1 Hawolgok-Dong, Seongbuk-Gu, Seoul 136-791 (Korea, Republic of); Jung, Jin-Young, E-mail: jinjung@ynu.ac.kr [Department of Environmental Engineering, Yeungnam University, 214-1 Dae-Dong, Gyeongsan-Si, Gyeongsangbuk-Do 712-749 (Korea, Republic of)

    2010-09-15

    During the ozonation of tetracycline (TC) in aqueous media at pHs 2.2 and 7.0, the effects of pH variations, protonation and dissociation of functional groups and variation in free radical exposure were investigated to elucidate the transformation pathway. Liquid chromatography-triple quadrupole mass spectrometry detected around 15 ozonation products, and uncovered their production and subsequent degradation patterns. During ozonation at pH 2.2, the TC degradation pathway was proposed on the basis of the structure, ozonation chemistry and mass spectrometry data of TC. Ozonation of TC at the C11a-C12 and C2-C3 double bonds, aromatic ring and amino group generated products of m/z 461, 477, 509 and 416, respectively. Further ozonation at the above mentioned sites gave products of m/z 432, 480, 448, 525 and 496. The removal of TOC reached a maximum of {approx}40% after 2 h of ozonation, while TC was completely removed within 4-6 min at both pHs. The low TOC removal efficiency might be due to the generation of recalcitrant products and the low ozone supply for high TC concentration. Ozonation decreased the acute toxicity of TC faster at pH 7.0 than pH 2.2, but the maximum decrease was only about 40% at both pHs after 2 h of ozonation. In this study, attempts were made to understand the correlation between the transformation products, pathway, acute toxicity and quantity of residual organics in solution. Overall, ozonation was found to be a promising process for removing TC and the products initially generated.

  15. A rapid gas chromatographic injection-port derivatization method for the tandem mass spectrometric determination of patulin and 5-hydroxymethylfurfural in fruit juices.

    Marsol-Vall, Alexis; Balcells, Mercè; Eras, Jordi; Canela-Garayoa, Ramon

    2016-07-01

    A novel method consisting of injection-port derivatization coupled to gas chromatography-tandem mass spectrometry is described. The method allows the rapid assessment of 5-hydroxymethylfurfural (HMF) and patulin content in apple and pear derivatives. The chromatographic separation of the compounds was achieved in a short chromatographic run (12.2min) suitable for routine controls of these compounds in the fruit juice industry. The optimal conditions for the injection-port derivatization were at 270°C, 0.5min purge-off, and a 1:2 sample:derivatization reagent ratio (v/v). These conditions represent an important saving in terms of derivatization reagent consumption and sample preparation time. Quality parameters were assessed for the target compounds, giving LOD of 0.7 and 1.6μg/kg and LOQ of 2 and 5μg/kg for patulin and HMF, respectively. These values are below the maximum patulin concentration in food products intended for infants and young children. Repeatability (%RSD n=5) was below 12% for both compounds. In addition, the method linearity ranged between 25 and 1000μg/kg and between 5 and 192μg/kg for HMF and patulin, respectively. Finally, the method was applied to study HMF and patulin content in various fruit juice samples. PMID:27240947

  16. Separation and determination of 4-methylimidazole, 2-methylimidazole and 5-hydroxymethylfurfural in beverages by amino trap column coupled with pulsed amperometric detection.

    Xu, Xian-Bing; Liu, Ding-Bo; Yu, Shu-Juan; Yu, Pei; Zhao, Zhen-Gang

    2015-02-15

    A method for simultaneous determination of 4-methylimidazole (4-MeI), 2-methylimidazole (2-MeI) and 5-hydroxymethylfurfural (HMF) in beverages was developed using solid-phase extraction (SPE) and amino trap column coupled with pulsed amperometric detection (AMTC-PAD). A single amino trap column (P/N: 046122) was first applied to separate the targeted analytes in samples after SPE pretreatment. This method demonstrated low limit of quantification (0.030mg/L for methylimidazoles and 0.300mg/L for HMF) and excellent linearity with correlation of determination (R(2)=0.999 for 2-MeI, 0.997 for 4-MeI and 0.998 for HMF). Nearly no 2-MeI was found in all soft drinks. However, 4-MeI could be detected in cola drinks and soft drinks containing caramel colour (ranging from 0.13 to 0.34mg/L), whereas HMF were only found in cola drinks (ranging from 1.07 to 4.47mg/L). Thus, AMTC-PAD technique would be a valid and inexpensive alternative to analysis of 4-MeI, 2-MeI and HMF. PMID:25236220

  17. An improved method for the determination of 5-hydroxymethylfurfural in Shenfu injection by direct analysis in real time-quadrupole time-of-flight mass spectrometry.

    Gao, Wen; Qi, Lian-Wen; Liu, Charles C; Wang, Rui; Li, Ping; Yang, Hua

    2016-07-01

    The emergence of direct analysis in real time (DART) ion source provides the great possibility for rapid analysis of hazardous substance in drugs. DART mass spectrometry (DART-MS) enabled the conducting of a fast and non-contact analysis of various samples, including solid or liquid ones, without complex sample preparation or chromatographic separation. In this study, a modified DART-quadrupole time-of-flight mass spectrometry (DART-QTOF-MS) method was developed for identification and determination of 5-hydroxymethylfurfural (5-HMF) in Shenfu (SF) injection. The quantitative transfer of sample solution was introduced to the glass tips of DIP-it sampler at a fixed volume, which significantly increases the repeatability and accuracy of analytical results. The protonated ion of dibutyl phthalate in the atmosphere was used as the reference mass for TOF-MS recalibration during the data acquisition for constant high accuracy mass measurements. Finally, the developed DART-MS method was used to determine 5-HMF in seven batches of SF injection, and the contents of 5-HMF were not higher than 100 µg/mL. The results obtained were further confirmed by an ultra-high performance liquid chromatography combined with triple quadrupole mass spectrometer (UHPLC-QQQ-MS). The overall results demonstrated that the DART-QTOF-MS method could be applied as an alternative technique for rapid monitoring 5-HMF in herbal medicine injection. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26197974

  18. Simultaneous determination of pesticides and 5-hydroxymethylfurfural in honey by the modified QuEChERS method and liquid chromatography coupled to tandem mass spectrometry.

    Tomasini, Débora; Sampaio, Maicon R F; Caldas, Sergiane S; Buffon, Jaqueline G; Duarte, Fábio A; Primel, Ednei G

    2012-09-15

    Nowadays, bee products are being produced in an environment polluted by different sources of contamination, such as pesticides, which can be transported by honey bees to the hive and incorporated into honey. In addition, the increasing consumption of honey has demanded efficient quality control for this product. In this study, the determination of the pesticides fipronil, imidacloprid, thiamethoxam, dimethoate, carbendazin, tebuconazole, amitraz, τ-fluvalinate and 5-hydroxymethylfurfural (HMF) which are used as indicators of honey quality, was carried out simultaneously. For the sample preparation, the optimized QuEChERS method was used and the determinations were done by LC-APCI-MS/MS. The LOQs of the method ranged between 0.005 and 1.0 mg kg(-1). For the recovery calculations and method evaluation a working curve was drawn. All the analytical curves showed r values higher than 0.99. The recoveries ranged between 70% and 112%, with RSD lower than 20% for all compounds. The matrix effect was evaluated, and most of the compounds showed signal enrichment. The applicability of the method for honey from different flowers was verified, and the method showed robustness and recoveries in the range 70-120% established for all compounds in samples belonging to different blossoms. HMF was detected in all samples, with concentrations ranging between 4.6 and 51.7 mg kg(-1); it was below the maximum concentration allowed by the legislation. PMID:22967568

  19. 5-Hydroxymethylfurfural (5-HMF Production from Hexoses: Limits of Heterogeneous Catalysis in Hydrothermal Conditions and Potential of Concentrated Aqueous Organic Acids as Reactive Solvent System

    Nadine Essayem

    2012-09-01

    Full Text Available 5-Hydroxymethylfurfural (5-HMF is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose. The treatment at 150–250 °C of glucose or fructose in pure water and batch conditions, with catalytic amounts of most of the usual acid-basic solid catalysts, gave limited yields in 5-HMF, due mainly to the fast formation of soluble oligomers. Niobic acid, which possesses both Lewis and Brønsted acid sites, gave the highest 5-HMF yield, 28%, when high catalyst/glucose ratio is used. By contrast, we disclose in this work that the reaction of fructose in concentrated aqueous solutions of carboxylic acids, formic, acetic or lactic acids, used as reactive solvent media, leads to the selective dehydration of fructose in 5-HMF with yields up to 64% after 2 hours at 150 °C. This shows the potential of such solvent systems for the clean and easy production of 5-HMF from carbohydrates. The influence of adding solid catalysts to the carboxylic acid media was also reported, starting from glucose.

  20. 食品中5-羟甲基糠醛的形成与控制%Formation and mitigation of 5-hydroxymethylfurfural in foods

    裴珂晗; 欧仕益

    2016-01-01

    5-羟甲基糠醛(5-hydroxymethylfurfural,HMF)是食品热加工和贮藏过程中产生的内源性污染物,主要通过美拉德反应和己糖在酸性条件下脱水产生,其形成过程受反应底物种类、加热温度、反应体系pH、水分活度及金属离子等影响.HMF具有一定神经毒性、遗传毒性;摄入后在磺基转移酶作用下可转化为具有致癌毒性的羟甲基糠醛次硫酸,因而近年来HMF受到了国内外的广泛关注.本文综述了HMF形成的途径、影响因素和控制措施.

  1. Short-term supplementation with alpha-ketoglutaric acid and 5-hydroxymethylfurfural does not prevent the hypoxia induced decrease of exercise performance despite attenuation of oxidative stress.

    Gatterer, H; Greilberger, J; Philippe, M; Faulhaber, M; Djukic, R; Burtscher, M

    2013-01-01

    Reactive oxygen species are thought to partly be responsible for the hypoxia induced performance decrease. The present study evaluated the effects of a broad based antioxidant supplementation or the combined intake of alpha-ketoglutaric acid (α-KG) and 5-hydroxymethylfurfural (5-HMF) on the performance decrease at altitude. 18 healthy, well-trained males (age: 25±3 years; height: 179±6 cm; weight: 76.4±6.8 kg) were randomly assigned in a double-blind fashion to a placebo group (PL), a α-KG and 5-HMF supplementation group (AO1) or a broad based antioxidant supplementation group (AO2). Participants performed 2 incremental exercise tests to exhaustion on a cycle ergometer; the first test under normoxia and the second under hypoxia conditions (simulated altitude, FiO2=13% ~ 4 300 m). Supplementation started 48 h before the hypoxia test. Maximal oxygen uptake, maximal power output, power output at the ventilatory and lactate threshold and the tissue oxygenation index (NIRS) were measured under both conditions. Oxidative stress markers were measured before the supplementation and after the hypoxia test. Under hypoxia conditions all performance parameters decreased in the range of 19-39% with no differences between groups. A significant change from normoxia to hypoxia (pextraction, as indicated by the tissue oxygenation index, might indicate that mitochondrial functioning was actually influenced by the supplementation. PMID:22893323

  2. Theoretical Elucidation of Glucose Dehydration to 5-Hydroxymethylfurfural Catalyzed by a SO3H-Functionalized Ionic Liquid.

    Li, Jingjing; Li, Jinghua; Zhang, Dongju; Liu, Chengbu

    2015-10-22

    While the catalytic conversion of glucose to 5-hydroxymethyl furfural (HMF) catalyzed by SO3H-functioned ionic liquids (ILs) has been achieved successfully, the relevant molecular mechanism is still not understood well. Choosing 1-butyl-3-methylimidazolium chloride [C4SO3HmimCl] as a representative of SO3H-functioned IL, this work presents a density functional theory (DFT) study on the catalytic mechanism for conversion of glucose into HMF. It is found that the conversion may proceed via two potential pathways and that throughout most of elementary steps, the cation of the IL plays a substantial role, functioning as a proton shuttle to promote the reaction. The chloride anion interacts with the substrate and the acidic proton in the imidazolium ring via H-bonding, as well as provides a polar environment together with the imidazolium cation to stabilize intermediates and transition states. The calculated overall barriers of the catalytic conversion along two potential pathways are 32.9 and 31.0 kcal/mol, respectively, which are compatible with the observed catalytic performance of the IL under mild conditions (100 °C). The present results provide help for rationalizing the effective conversion of glucose to HMF catalyzed by SO3H-functionalized ILs and for designing IL catalysts used in biomass conversion chemistry. PMID:26434955

  3. Conversion of the common food constituent 5-hydroxymethylfurfural into a mutagenic and carcinogenic sulfuric acid ester in the mouse in vivo.

    Monien, Bernhard H; Frank, Heinz; Seidel, Albrecht; Glatt, Hansruedi

    2009-06-01

    5-Hydroxymethylfurfural (HMF), formed by acid-catalyzed dehydration and in the Maillard reaction from reducing sugars, is found at high levels in numerous foods. It was shown to initiate colon aberrant crypt foci in rats and skin papillomas and hepatocellular adenomas in mice. HMF is inactive in in vitro genotoxicity tests using standard activating systems but is activated to a mutagen by sulfotransferases. The product, 5-sulfoxymethylfurfural (SMF), is a stronger carcinogen than HMF. SMF has not been detected in the biotransfomation experiments conducted on HMF in humans and animals in vivo up to date. Here, we report pharmacokinetic properties of HMF and SMF in FVB/N mice. Sensitive assays for the quantification of HMF and SMF by LC-MS/MS multiple reaction monitoring were devised. SMF, intravenously injected (4.4 micromol/kg body mass), showed first-order elimination kinetics in blood plasma (t(1/2) = 7.9 min). HMF, injected intravenously (793 micromol/kg body mass), demonstrated biphasic kinetics in plasma (t(1/2) = 1.7 and 28 min for the initial and terminal elimination phases, respectively); the volume of distribution of the central compartment corresponded approximately to the total body water. The maximum SMF plasma level was observed at the first sampling time, 2.5 min after HMF administration. On the basis of these kinetic data, it was estimated that between 452 and 551 ppm of the initial HMF dose was converted to SMF and reached the circulation. It is likely that additional SMF reacted with cellular structures at the site of generation and thus is ignored in this balance. Our work supports the hypothesis that HMF-related carcinogenicity may be mediated by its reactive metabolite SMF. PMID:19382817

  4. HPLC法检测乳品中5-羟甲基糠醛和糠醛%Detection of 5-Hydroxymethylfurfural and Furfural in Dairy Products by HPLC

    赵贞; 李翠枝; 岳虹; 万鹏; 吕海燕; 邵建波

    2015-01-01

    A method for detecting of 5-Hydroxymethylfurfural (5-HMF) and furfural in dairy products by HPLC is described. The samples were precipitated and filtered at first, then separated on a C18 column with the mobile phase (water-methanol solution), and detected with UV detector at 280 nm. The result showed that 5-HMF and furfural were completely separated. The method has good linearity relationship in the range of(0.03~100) mg/kg, and high recovery rate at (83.3~113.3)%. This method is simple, accurate and good reproducibility for detecting of 5-HMF and furfural in dairy products.%建立了乳制品中5-羟甲基糠醛和糠醛的高效液相色谱分析方法。样品用沉淀剂沉淀过滤后,以水-甲醇溶液为流动相,C18反相色谱柱分离,紫外检测器280nm检测。结果表明,5-羟甲基糠醛和糠醛可以完全分离。在0.03~100.00mg/kg范围内,该方法呈良好的线性关系,回收率为83.3%~113.3%。本方法用于乳制品中5-羟甲基糠醛和糠醛的测定,操作简单、定量准确、重复性好。

  5. Conversion of Suspected Food Carcinogen 5-Hydroxymethylfurfural by Sulfotransferases and Aldehyde Dehydrogenases in Postmitochondrial Tissue Preparations of Humans, Mice, and Rats.

    Sachse, Benjamin; Meinl, Walter; Glatt, Hansruedi; Monien, Bernhard H

    2016-01-01

    The food contaminant 5-hydroxymethylfurfural (HMF) is formed by heat- and acid-catalyzed reactions from carbohydrates. More than 80% of HMF is metabolized by oxidation of the aldehyde group in mice and rats. Sulfo conjugation yields mutagenic 5-sulfoxymethylfurfural, the probable cause for the neoplastic effects observed in HMF-treated rodents. Considerable metabolic differences between species hinder assessing the tumorigenic risk associated with human dietary HMF uptake. Here, we assayed HMF turnover catalyzed by sulfotransferases or by aldehyde dehydrogenases (ALDHs) in postmitochondrial preparations from liver, kidney, colon, and lung of humans, mice, and rats. The tissues-specific clearance capacities of HMF sulfo conjugation (CL(SC)) and ALDH-catalyzed oxidation (CL(OX)) were concentrated to the liver. The hepatic clearance CL(SC) in mice (males: 487 µl/min/kg bw, females: 2520 µl/min/kg bw) and rats (males: 430 µl/min/kg bw, females: 198 µl/min/kg bw) were considerably higher than those in humans (males: 21.2 µl/min/kg bw, females: 32.2 µl/min/kg bw). The ALDH-related clearance rates CLOX in mice (males: 3400 ml/min/kg bw, females: 1410 ml/min/kg bw) were higher than those of humans (males: 436 ml/min/kg bw, females: 646 ml/min/kg bw) and rats (males: 627 ml/min/kg bw, females: 679 ml/min/kg bw). The ratio of CL(OX) to CL(SC) was lowest in female mice. This finding indicated that HMF sulfo conjugation was most substantial in the liver of female mice, a target tissue for HMF-induced neoplastic effects, and that humans may be less sensitive regarding HMF sulfo conjugation compared with the rodent models. PMID:26454887

  6. 葡萄糖脱水制备5-羟甲基糠醛的研究进展%Advances in production of 5-hydroxymethylfurfural from glucose

    胡磊; 孙勇; 林鹿

    2011-01-01

    5-羟甲基糠醛(5-HMF)是一种重要的平台化合物,具有非常广泛的应用价值和市场前景。葡萄糖的选择性脱水是制备5-HMF的主要方法之一,也是碳水化合物降解研究中的重点和难点,现在已经受到了人们越来越广泛的重视。本文综述了近年来葡萄糖制备5-HMF的研究成果,着重介绍了5-HMF的形成机理以及制备5-HMF的催化体系与溶剂体系,并对葡萄糖制备5-HMF的研究前景进行了展望,以期为5-HMF的进一步研究提供思路和参考。%5-Hydroxymethylfurfural(5-HMF)is a kind of important platform chemical compound and possesses wide application value and market prospect.Selective dehydration of glucose is one of main synthesis methods for 5-hydroxymethylfurfural and has attracted increasingly more attention.In this paper,the recent research achievements in the dehydration of glucose for preparation of 5-HMF are summarized,including formation mechanisms,catalyst systems and solvent systems,and the future research trends of 5-HMF from dehydration of glucose are prospected.

  7. Determination of 5-Hydroxymethylfurfural in Liuweidihuang Pills by HPLC%HPLC测定六味地黄浓缩丸中5-HMF的含量

    蔡银燕; 石婷婷; 黄巧玲

    2012-01-01

    OBJECTIVE To establish an HPLC method for the determination of 5-hydroxymethylfurfural(5-HMF) in Liuweidihuang pills. METHODS The HPLC method was performed on an Agilent Zorbax C18column(250 mm×4.6 mm, 5 urn) with 284 nm as the detection wavelength, and methanol-water(20 : 80) was used as mobile phase. The column temperature was 30 ℃, and the flow rate was 1.0 mL·min‐1. RESULTS The regression results which was based on weighted least square method showed a good linearity within the range of 0.026 2-2.62 mg·nL‐1, and the average recovery was 99.7% with R.SD of 0.57%. CONCLUSION The HPLC method was accurate, sensitive and suitable for determining the content of 5-HMF in Liuweidihuang pills.%目的 建立六味地黄浓缩丸中5-羟甲基糠醛(5-HMF)的含量测定方法.方法 采用Agilent Zorbax C18色谱柱(250 mm×4.6 mm,5 μm);流动相为甲醇-水(20∶80);流速:1.0 mL·min-1;检测波长:280 nm;柱温:30℃.结果 5-HMF在0.026 2~2.62 mg·mL-1内线性关系良好,平均回收率为99.7%,RSD为0.57%.结论 该方法简便、快速、准确度好,可有效控制该制剂中5-羟甲基糠醛含量.

  8. A second pathway to degrade pyrimidine nucleic acid precursors in eukaryotes

    Andersen, Gorm; Bjornberg, Olof; Polakova, Silvia;

    2008-01-01

    Pyrimidine bases are the central precursors for RNA and DNA, and their intracellular pools are determined by de novo, salvage and catabolic pathways. In eukaryotes, degradation of uracil has been believed to proceed only via the reduction to dihydrouracil. Using a yeast model, Saccharomyces kluyv...... of the eukaryotic or prokaryotic genes involved in pyrimidine degradation described to date....

  9. ORGANOPHOSPHORUS PESTICIDE DEGRADATION PATHWAYS DURING DRINKING WATER TREATMENT

    The objective of this work was to investigate organophosphorus (OP) pesticide transformation pathways as a class in the presence of aqueous chlorine. Seven priority OP pesticides were examined for their reactivity with aqueous chlorine: chlorpyrifos (CP), parathion (PA), diazino...

  10. 3'-5' RNA degradation pathways in human cells

    Lubas, Michal Szymon

    revealed the interaction network of the main 3'-5' RNA degradation machinery – the RNA exosome complex. One of the key findings was the identification and characterisation of the Nuclear Exosome Targeting (NEXT) complex, important for nuclear functions of the exosome. Michal Lubas also studied the role...

  11. Tissue factor pathway inhibitor relates to fibrin degradation in patients with acute deep venous thrombosis

    Sidelmann, Johannes J; Bladbjerg, Else-Marie; Gram, Jørgen;

    2008-01-01

    studied the association between inflammation, endothelial cell perturbation, fibrin degradation and the concentration of tissue factor pathway inhibitor in patients suspected for acute deep venous thrombosis. We determined the tissue factor pathway inhibitor -33T/C polymorphism, free and total tissue....... The significant relationship is not associated with the -33T/C polymorphism, inflammation or endothelial cell perturbation, but is most likely related to release of tissue factor pathway inhibitor from fibrin deposits....

  12. HPLC determination of 5-hydroxymethylfurfural in Shengqifuzheng injection and preliminary study on the generation approach of 5-hydroxymethylfurfural%HPLC法测定参芪扶正注射液中5-羟甲基糠醛的含量及其来源的初步探讨

    刘潇潇; 杨立伟; 于江泳; 林锦锋

    2012-01-01

    目的:建立己糖降解产物5-羟甲基糠醛的含量测定方法,对参芪扶正注射液中的5-羟甲基糠醛进行测定,并对其来源进行初步探讨.方法:采用Diamonsil C18(250 mm ×4.6 mm,5μmm,)色谱柱,以乙腈-0.5%醋酸溶液(3∶97)为流动相,检测波长284 nm,流速1.0 mL·min-1,柱温30℃.结果:5-羟甲基糠醛在浓度为0.94~18.8 μg· mL-1范围内与峰面积具有良好的线性关系(r =0.9999),精密度和重复性的RSD分别为0.7%和2.2%.在模拟高温灭菌的过程中发现仅有果糖受热后转化生成5-羟甲基糠醛及其相关物质.结论:该方法操作简便,结果准确可靠,可用于参芪扶正注射液中5-羟甲基糠醛的含量测定,为进一步评价中药注射液的安全性提供参考.%Objective:To establish a method for the detenninantion of 5 - hydroxymethylfurfural in Shengqifuzheng injection. Methods;The HPLC separation was performed on a Diamonsil C18 reversed -phase column with the mobile phase of acetonitrile -0.5% acetic acid(3:97) ,and the determination wavelength was 284 run. The column temperature was kept at 30℃,and the mobile phase flow rate was 1.0mL·min-1. Results:The calibration curves showed good linear regression (r =0.9999) within 0. 94 and 18. 8 μg o mL-1. Precisions and repeatabilities of the methods were 0. 7% and 2. 2% .respectively. Otherwise,only fructose generated 5 - hydroxymethylfurfural after high -temperature sterilization. Conclusion:The method was simple,reliable and suitable for the quality control of the products, supplying helpful information to the further study on the safety evaluation of traditional Chinese medicine injection.

  13. PHOSPHOLIPIDS OF FIVE PSEUDOMONAD ARCHETYPES FOR DIFFERENT TOLUENE DEGRADATION PATHWAYS

    Liquid chromatography/electrospray ionization/mass spectrometry (LC/ESI/MS) was used to determine phospholipid profiles for five reference pseudomonad strains harboring distinct toluene catabolic pathways: Pseudomonas putida mt-2, Pseudomonas putida F1, Burkholderia cepacia G4, B...

  14. Characterization of the novel dimethyl sulfide-degrading bacterium Alcaligenes sp. SY1 and its biochemical degradation pathway.

    Sun, Yiming; Qiu, Jiguo; Chen, Dongzhi; Ye, Jiexu; Chen, Jianmeng

    2016-03-01

    Recently, the biodegradation of volatile organic sulfur compounds (VOSCs) has become a burgeoning field, with a growing focus on the reduction of VOSCs. The reduction of VOSCs encompasses both organic emission control and odor control. Herein, Alcaligenes sp. SY1 was isolated from active sludge and found to utilize dimethyl sulfide (DMS) as a growth substrate in a mineral salt medium. Response surface methodology (RSM) analysis was applied to optimize the incubation conditions. The following conditions for optimal degradation were identified: temperature 27.03°C; pH 7.80; inoculum salinity 0.84%; and initial DMS concentration 1585.39 μM. Under these conditions, approximately 99% of the DMS was degraded within 30 h of incubation. Two metabolic compounds were detected and identified by gas chromatography-mass spectrometry (GC-MS): dimethyl disulfide (DMDS) and dimethyl trisulfide (DMTS). The DMS degradation kinetics for different concentrations were evaluated using the Haldane-Andrews model and the pseudo first-order model. The maximum specific growth rate and degradation rate of Alcaligenes sp. SY1 were 0.17 h(-1) and 0.63 gs gx(-1)h(-1). A possible degradation pathway is proposed, and the results suggest that Alcaligenes sp. SY1 has the potential to control odor emissions under aerobic conditions. PMID:26623933

  15. Metabolic pathway for degradation of 2-chloro-4-aminophenol by Arthrobacter sp. SPG

    Arora, Pankaj Kumar; Mohanta, Tapan Kumar; Srivastava, Alok; Bae, Hanhong; Singh, Vijay Pal

    2014-01-01

    A degradation pathway of 2-chloro-4-aminophenol (2C4AP) was studied in an Arthrobacter sp. SPG that utilized 2C4AP as its sole source of carbon and energy. The 2C4AP degradation was initiated by a 2C4AP-deaminase that catalyzed the conversion of 2C4AP into chlorohydroquinone (CHQ) with removal of ammonium ion. In the next step, a CHQ-dehalogenase dehalogenated CHQ to hydroquinone (HQ) that cleaved into γ-hydroxymuconic semialdehyde by a HQ-dioxygenase. The 2C4AP degradation was also investiga...

  16. Photocatalytic degradation of triazophos in aqueous titanium dioxide suspension: Identification of intermediates and degradation pathways

    The photocatalytic degradation of triazophos in aqueous TiO2 suspension has been studied in a photoreactor operating with simulated solar radiation. The decrease in triazophos concentration followed first-order kinetics with a half-life of 4.76 ± 0.42 h at a TiO2 suspension concentration of 10 mg/L. Seventeen degradation products were identified using HPLC-UV, HPLC/MS/MS, GC/MS/MS and IC, and by comparing retention times and spectra with commercially available authentic standards. On the basis of the observed transformation products, two routes were proposed, one based on the initial oxidative cleavage of P = S bond to P = O bond, and the other on initial cleavage of the ester P-O bonds. Photocatalysis holds promise for the solar treatment of pesticide-contaminated waters

  17. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC. PMID:26452660

  18. Nuclear mRNA degradation pathway(s are implicated in Xist regulation and X chromosome inactivation.

    Constance Ciaudo

    2006-06-01

    Full Text Available A critical step in X-chromosome inactivation (XCI, which results in the dosage compensation of X-linked gene expression in mammals, is the coating of the presumptive inactive X chromosome by the large noncoding Xist RNA, which then leads to the recruitment of other factors essential for the heterochromatinisation of the inactive X and its transcriptional silencing. In an approach aimed at identifying genes implicated in the X-inactivation process by comparative transcriptional profiling of female and male mouse gastrula, we identified the Eif1 gene involved in translation initiation and RNA degradation. We show here that female embryonic stem cell lines, silenced by RNA interference for the Eif1 gene, are unable to form Xist RNA domains upon differentiation and fail to undergo X-inactivation. To probe further an effect involving RNA degradation pathways, the inhibition by RNA interference of Rent1, a factor essential for nonsense-mediated decay and Exosc10, a specific nuclear component of the exosome, was analysed and shown to similarly impair Xist upregulation and XCI. In Eif1-, Rent1-, and Exosc10-interfered clones, Xist spliced form(s are strongly downregulated, while the levels of unspliced form(s of Xist and the stability of Xist RNA remain comparable to that of the control cell lines. Our data suggests a role for mRNA nuclear degradation pathways in the critical regulation of spliced Xist mRNA levels and the onset of the X-inactivation process.

  19. Combination of degradation pathways for naphthalene utilization in Rhodococcus sp. strain TFB.

    Tomás-Gallardo, Laura; Gómez-Álvarez, Helena; Santero, Eduardo; Floriano, Belén

    2014-03-01

    Rhodococcus sp. strain TFB is a metabolic versatile bacterium able to grow on naphthalene as the only carbon and energy source. Applying proteomic, genetic and biochemical approaches, we propose in this paper that, at least, three coordinated but independently regulated set of genes are combined to degrade naphthalene in TFB. First, proteins involved in tetralin degradation are also induced by naphthalene and may carry out its conversion to salicylaldehyde. This is the only part of the naphthalene degradation pathway showing glucose catabolite repression. Second, a salicylaldehyde dehydrogenase activity that converts salicylaldehyde to salicylate is detected in naphthalene-grown cells but not in tetralin- or salicylate-grown cells. Finally, we describe the chromosomally located nag genes, encoding the gentisate pathway for salicylate conversion into fumarate and pyruvate, which are only induced by salicylate and not by naphthalene. This work shows how biodegradation pathways in Rhodococcus sp. strain TFB could be assembled using elements from different pathways mainly because of the laxity of the regulatory systems and the broad specificity of the catabolic enzymes. PMID:24325207

  20. Differential impact of diverse anticancer chemotherapeutics on the Cdc25A-degradation checkpoint pathway

    When exposed to DNA-damaging insults such as ionizing radiation (IR) or ultraviolet light (UV), mammalian cells activate checkpoint pathways to halt cell cycle progression or induce cell death. Here we examined the ability of five commonly used anticancer drugs with different mechanisms of action to activate the Chk1/Chk2-Cdc25A-CDK2/cyclin E cell cycle checkpoint pathway, previously shown to be induced by IR or UV. Whereas exposure of human cells to topoisomerase inhibitors camptothecin, etoposide, or adriamycin resulted in rapid (within 1 h) activation of the pathway including degradation of the Cdc25A phosphatase and inhibition of cyclin E/CDK2 kinase activity, taxol failed to activate this checkpoint even after a prolonged treatment. Unexpectedly, although the alkylating agent cisplatin also induced degradation of Cdc25A (albeit delayed, after 8-12 h), cyclin E/CDK2 activity was elevated and DNA synthesis continued, a phenomena that correlated with increased E2F1 protein levels and consequently enhanced expression of cyclin E. These results reveal a differential impact of various classes of anticancer chemotherapeutics on the Cdc25A-degradation pathway, and indicate that the kinetics of checkpoint induction, and the relative balance of key components within the DNA damage response network may dictate whether the treated cells arrest their cell cycle progression

  1. Catalytic thermolysis in treating Cibacron Blue in aqueous solution: Kinetics and degradation pathway.

    Su, Claire Xin-Hui; Teng, Tjoon-Tow; Wong, Yee-Shian; Morad, Norhashimah; Rafatullah, Mohd

    2016-03-01

    A thermal degradation pathway of the decolourisation of Reactive Cibacron Blue F3GA (RCB) in aqueous solution through catalytic thermolysis is established. Catalytic thermolysis is suitable for the removal of dyes from wastewater as it breaks down the complex dye molecules instead of only transferring them into another phase. RCB is a reactive dye that consists of three main groups, namely anthraquinone, benzene and triazine groups. Through catalytic thermolysis, the bonds that hold the three groups together were effectively broken and at the same time, the complex molecules degraded to form simple molecules of lower molecular weight. The degradation pathway and products were characterized and determined through UV-Vis, FT-IR and GCMS analysis. RCB dye molecule was successfully broken down into simpler molecules, namely, benzene derivatives, amines and triazine. The addition of copper sulphate, CuSO4, as a catalyst, hastens the thermal degradation of RCB by aiding in the breakdown of large, complex molecules. At pH 2 and catalyst mass loading of 5 g/L, an optimum colour removal of 66.14% was observed. The degradation rate of RCB is well explained by first order kinetics model. PMID:26741557

  2. Determination of 5-Hydroxymethylfurfural in Yangyin Qingfei Pills by HPLC%HPLC法测定养阴清肺丸中5-羟甲基糠醛的含量

    康强; 孔令峰

    2013-01-01

    目的:建立养阴清肺丸中5-羟甲基糠醛含量的测定方法,考察不同企业养阴清肺丸中5-羟甲基糠醛的含量差异.方法:采用高效液相色谱法.色谱柱为Agilent C18 (250 mm×4.6 mm,5μm)柱,柱温为30℃,流动相为甲醇-水(10∶90),流速0.8 ml· min-1,检测波长:284 nm,进样量为10μl.结果:5-羟甲基糠醛进样量在0.020 2 ~0.404 0 μg范围内与峰面积积分值呈良好的线性关系(r=1.000 0);平均加样回收率为101.52%,RSD=2.7%(n=6).结论:该方法简便、准确、灵敏度高、重复性好,可用于养阴清肺丸中5-羟甲基糠醛的含量测定.%Objective:To establish a method for the content determination of 5-hydroxymethylfurfural in Yangyin Qingfei pills,and study the content difference in Yangyin Qingfei pills from different enterprises.Method:The determination was performed on an Agilent C18 (250 mm × 4.6 mm,5μm) column at 30℃ with the mobile phase consisted of methanol-water (10∶ 90) at the flow rate of 0.8ml · min-1.The detection wavelength was set at 284nm and the injection volume was 10 μl.Result:The linear range of 5-hydroxymethylfurfural was 0.020 2-0.404 0 μg (r =1.000 0) with the average recovery of 101.52% (RSD =2.7%,n =6).Conclusion:The method is simple,accurate,sensitive and reproducible in the content determination of 5-hydroxymethylfurfural in Yangyin Qingfei pills.

  3. New metabolic pathway for degradation of 2-nitrobenzoate by Arthrobacter sp. SPG

    Pankaj Kumar Arora

    2015-06-01

    Full Text Available Arthrobacter sp. SPG utilized 2-nitrobenzoate as its sole source of carbon and energy and degraded it with accumulation of stoichiometric amounts of nitrite ions. Salicylate and catechol were detected as metabolites of the 2-nitrobenzoate degradation using high performance liquid chromatography and gas chromatography-mass spectrometry. Enzyme activities for 2-nitrobenzoate-2-monooxygenase, salicylate hydroxylase, and catechol-1,2-dioxygenase were detected in the crude extracts of the 2-nitrobenzoate-induced cells of strain SPG. The 2-nitrobenzoate-monooxygenase activity resulted in formation of salicylate and nitrite from 2-nitrobenzoate whereas salicylate hydroxylase catalyzed the conversion of salicylate to catechol. The ring-cleaving enzyme, catechol-1,2-dioxygenase cleaved catechol to cis, cis-muconic acid. Cells of strain SPG were able to degrade 2-nitrobenzoate in sterile as well as non-sterile soil microcosms. The results of microcosm studies showed that strain SPG degraded more than 90% of 2-nitrobenzoate within 10-12 days. This study clearly shows that Arthrobacter sp. SPG degraded 2-nitrobenzoate via a new pathway with formation of salicylate and catechol as metabolites. Arthrobacter sp. SPG may be used for bioremediation of 2-nitrobenzoate-contaminated sites due to its ability to degrade 2-nitrobenzoate in soil.

  4. Sodium persulfate-assisted mechanochemical degradation of tetrabromobisphenol A: Efficacy, products and pathway.

    Liu, Xitao; Zhang, Xiaohui; Zhang, Kunlun; Qi, Chengdu

    2016-05-01

    In recent years, activated persulfate (PS) oxidation has been developed as a new advanced oxidation process for the degradation of organic pollutants. On the other hand, the mechanochemical method has exhibited a unique advantage in dealing with chemical wastes. The degradation of tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant (BFR), in wastes has attracted considerable attention. In this study, the efficacy of a CaO-mechanochemical (CaO-MC) treatment system assisted by the addition of PS for the degradation of TBBPA was investigated. Under the optimum reaction conditions with a mole ratio of PS:CaO = 1:4 and less than 12.5% of TBBPA by mass, the degradation and debromination of TBBPA were completed within 2 h, while the mineralization was completed within 4 h. Characterization of the milled sample by XRD revealed that CaSO4 crystallization occurred. The TG results illustrate that there was little organic matter left after 4 h of milling. Raman and FT-IR spectra exhibited the TBBPA destruction process and disappearance of the organic groups. Through analysis by LC/MS/MS, seventeen intermediates were identified. The mechanism of TBBPA degradation by the PS-assisted CaO-MC treatment system was explained from two aspects, the course of crystallization and the degradation of TBBPA by activated PS, and two parallel initiation pathways were proposed. PMID:26359264

  5. A novel denitrifying bacterial isolate that degrades trimethylamine both aerobically and anaerobically via two different pathways.

    Kim, S G; Bae, H S; Lee, S T

    2001-10-01

    The aerobic and anaerobic degradation of trimethylamine by a newly isolated denitrifying bacterium from an enrichment culture with trimethylamine inoculated with activated sludge was studied. Based on 16S rDNA analysis, this strain was identified as a Paracoccus sp. The isolate, strain T231, aerobically degraded trimethylamine, dimethylamine and methylamine and released a stoichiometric amount of ammonium ion into the culture fluid as a metabolic product, indicating that these methylated amines were completely degraded to formaldehyde and ammonia. The strain degraded trimethylamine also under denitrifying conditions and consumed a stoichiometric amount of nitrate, demonstrating that complete degradation of trimethylamine was coupled with nitrate reduction. Cell-free extract prepared from cells grown aerobically on trimethylamine exhibited activities of trimethylamine mono-oxygenase, trimethylamine N-oxide demethylase, dimethylamine mono-oxygenase, and methylamine mono-oxygenase. Cell-free extract from cells grown anaerobically on trimethylamine and nitrate exhibited activities of trimethylamine dehydrogenase and dimethylamine dehydrogenase. These results indicate that strain T231 had two different pathways for aerobic and anaerobic degradation of trimethylamine. This is a new feature for trimethylamine metabolism in denitrifying bacteria. PMID:11685371

  6. Molecular and biochemical characterization of the tetralin degradation pathway in Rhodococcus sp. strain TFB

    Tomás‐Gallardo, Laura; Santero, Eduardo; Camafeita, Emilio; Calvo, Enrique; Schlömann, Michael; Floriano, Belén

    2009-01-01

    Summary The tetralin biodegradation pathway in Rhodococcus sp. strain TFB, a Gram‐positive bacterium resistant to genetic manipulation, was characterized using a proteomic approach. Relative protein expression in cell free extracts from tetralin‐ and glucose‐grown cells was compared using the 2D‐DIGE technique. Identification of proteins specifically expressed in tetralin‐grown cells was used to characterize a complete set of genes involved in tetralin degradation by reverse genetics. We prop...

  7. Metabolic pathway of 3,6-anhydro-D-galactose in carrageenan-degrading microorganisms.

    Lee, Sun Bok; Kim, Jeong Ah; Lim, Hyun Seung

    2016-05-01

    Complete hydrolysis of κ-carrageenan produces two sugars, D-galactose and 3,6-anhydro-D-galactose (D-AnG). At present, however, we do not know how carrageenan-degrading microorganisms metabolize D-AnG. In this study, we investigated the metabolic pathway of D-AnG degradation by comparative genomic analysis of Cellulophaga lytica LIM-21, Pseudoalteromonas atlantica T6c, and Epulopiscium sp. N.t. morphotype B, which represent the classes Flavobacteria, Gammaproteobacteria, and Clostridia, respectively. In this bioinformatic analysis, we found candidate common genes that were believed to be involved in D-AnG metabolism. We then experimentally confirmed the enzymatic function of each gene product in the D-AnG cluster. In all three microorganisms, D-AnG metabolizing genes were clustered and organized in operon-like arrangements, which we named as the dan operon (3,6-d-anhydro-galactose). Combining bioinformatic analysis and experimental data, we showed that D-AnG is metabolized to pyruvate and D-glyceraldehyde-3-phosphate via four enzyme-catalyzed reactions in the following route: 3,6-anhydro-D-galactose → 3,6-anhydro-D-galactonate → 2-keto-3-deoxy-D-galactonate (D-KDGal) → 2-keto-3-deoxy-6-phospho-D-galactonate → pyruvate + D-glyceraldehyde-3-phosphate. The pathway of D-AnG degradation is composed of two parts: transformation of D-AnG to D-KDGal using two D-AnG specific enzymes and breakdown of D-KDGal to two glycolysis intermediates using two DeLey-Doudoroff pathway enzymes. To our knowledge, this is the first report on the metabolic pathway of D-AnG degradation. PMID:26875872

  8. Entner-Doudoroff pathway for sulfoquinovose degradation in Pseudomonas putida SQ1.

    Felux, Ann-Katrin; Spiteller, Dieter; Klebensberger, Janosch; Schleheck, David

    2015-08-01

    Sulfoquinovose (SQ; 6-deoxy-6-sulfoglucose) is the polar head group of the plant sulfolipid SQ-diacylglycerol, and SQ comprises a major proportion of the organosulfur in nature, where it is degraded by bacteria. A first degradation pathway for SQ has been demonstrated recently, a "sulfoglycolytic" pathway, in addition to the classical glycolytic (Embden-Meyerhof) pathway in Escherichia coli K-12; half of the carbon of SQ is abstracted as dihydroxyacetonephosphate (DHAP) and used for growth, whereas a C3-organosulfonate, 2,3-dihydroxypropane sulfonate (DHPS), is excreted. The environmental isolate Pseudomonas putida SQ1 is also able to use SQ for growth, and excretes a different C3-organosulfonate, 3-sulfolactate (SL). In this study, we revealed the catabolic pathway for SQ in P. putida SQ1 through differential proteomics and transcriptional analyses, by in vitro reconstitution of the complete pathway by five heterologously produced enzymes, and by identification of all four organosulfonate intermediates. The pathway follows a reaction sequence analogous to the Entner-Doudoroff pathway for glucose-6-phosphate: It involves an NAD(+)-dependent SQ dehydrogenase, 6-deoxy-6-sulfogluconolactone (SGL) lactonase, 6-deoxy-6-sulfogluconate (SG) dehydratase, and 2-keto-3,6-dideoxy-6-sulfogluconate (KDSG) aldolase. The aldolase reaction yields pyruvate, which supports growth of P. putida, and 3-sulfolactaldehyde (SLA), which is oxidized to SL by an NAD(P)(+)-dependent SLA dehydrogenase. All five enzymes are encoded in a single gene cluster that includes, for example, genes for transport and regulation. Homologous gene clusters were found in genomes of other P. putida strains, in other gamma-Proteobacteria, and in beta- and alpha-Proteobacteria, for example, in genomes of Enterobacteria, Vibrio, and Halomonas species, and in typical soil bacteria, such as Burkholderia, Herbaspirillum, and Rhizobium. PMID:26195800

  9. Novel degradation pathway and kinetic analysis for buprofezin removal by newly isolated Bacillus sp.

    Wang, Guangli; Xu, Dayong; Xiong, Minghua; Zhang, Hui; Li, Feng; Liu, Yuan

    2016-09-15

    Given the intensive and widespread application of the pesticide, buprofezin, its environmental residues potentially pose a problem; yet little is known about buprofezin's kinetic and metabolic behaviors. In this study, a novel gram-positive strain, designated BF-5, isolated from aerobic activated sludge, was found to be capable of metabolizing buprofezin as its sole energy, carbon, and nitrogen source. Based on its physiological and biochemical characteristics, other aspects of its phenotype, and a phylogenetic analysis, strain BF-5 was identified as Bacillus sp. This study investigated the effect of culture conditions on bacterial growth and substrate degradation, such as pH, temperature, initial concentration, different nitrogen source, and additional nitrogen sources as co-substrates. The degradation rate parameters, qmax, Ks, Ki and Sm were determined to be 0.6918 h(-1), 105.4 mg L(-1), 210.5 mg L(-1), and 148.95 mg L(-1) respectively. The capture of unpublished potential metabolites by gas chromatography-mass spectrometry (GC-MS) analysis has led to the proposal of a novel degradation pathway. Taken together, our results clarify buprofezin's biodegradation pathway(s) and highlight the promising potential of strain BF-5 in bioremediation of buprofezin-contaminated environments. PMID:27208995

  10. Cadmium interferes with the degradation of ATF5 via a post-ubiquitination step of the proteasome degradation pathway

    ATF5 is a member of the CREB/ATF family of transcription factors. In the current study, using a transient transfection system to express FLAG epitope fusion proteins of ATF5, we have shown that CdCl2 or NaAsO3 increases the protein levels of ATF5 in cells, and that cadmium stabilizes the ATF5 protein. Proteasome inhibitors had a similar effect to cadmium on the cellular accumulation of ATF5. Proteasome inhibition led to an increase in ubiquitinated ATF5, while cadmium did not appear to reduce the extent of ATF5 ubiquitination. ATF5 contains a putative nuclear export signal within its N-terminus. We demonstrated that whereas deletion of N-terminal region resulted in a increase of ATF5 levels, this region does not appear to be involved in the ubiquitination of ATF5. These results indicate that ATF5 is targeted for degradation by the ubiquitin-proteasome pathway, and that cadmium slows the rate of ATF5 degradation via a post-ubiquitination mechanism.

  11. Enhanced degradation in soil of the herbicide EPTC and determination of its degradative pathway by an isolated soil microorganism

    A series of experiments was conducted to examine the ability of Ohio soils to develop enhanced degradation of the herbicide EPTC (s-ethyl N,N-dipropyl carbamothiaote) and to determine its metabolism by an isolated soil microorganism. Three soils selected to obtain an range in pH, texture, and organic carbon were treated with EPTC for 4 consecutive applications (6 weeks between applications). EPTC concentrations as measured by gas chromatography, decreased 80% or more one week after the second application in all three soils. Metabolism of unlabelled and labelled EPTC by an isolated soil microbe was followed by GC/MS and TLC/LSC analysis, respectively. Rapid decrease in 14-C activity in the organic fraction corresponded with rapid 14CO2 evolution and transient increase in 14-C activity in the aqueous fraction. Four metabolites were observed in the TLC analysis. Two were identified as EPTC-sulfoxide and N-depropyl EPTC with N-depropyl EPTC being confirmed by GC/MS analysis. The availability of different pathways for EPTC metabolism by soil microbes after repeated applications to the soil results in its very rapid degradation and loss of efficacy

  12. From ether to acid: A plausible degradation pathway of glycerol dialkyl glycerol tetraethers

    Liu, Xiao-Lei; Birgel, Daniel; Elling, Felix J.; Sutton, Paul A.; Lipp, Julius S.; Zhu, Rong; Zhang, Chuanlun; Könneke, Martin; Peckmann, Jörn; Rowland, Steven J.; Summons, Roger E.; Hinrichs, Kai-Uwe

    2016-06-01

    Glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous microbial lipids with extensive demonstrated and potential roles as paleoenvironmental proxies. Despite the great attention they receive, comparatively little is known regarding their diagenetic fate. Putative degradation products of GDGTs, identified as hydroxyl and carboxyl derivatives, were detected in lipid extracts of marine sediment, seep carbonate, hot spring sediment and cells of the marine thaumarchaeon Nitrosopumilus maritimus. The distribution of GDGT degradation products in environmental samples suggests that both biotic and abiotic processes act as sinks for GDGTs. More than a hundred newly recognized degradation products afford a view of the stepwise degradation of GDGT via (1) ether bond hydrolysis yielding hydroxyl isoprenoids, namely, GDGTol (glycerol dialkyl glycerol triether alcohol), GMGD (glycerol monobiphytanyl glycerol diether), GDD (glycerol dibiphytanol diether), GMM (glycerol monobiphytanol monoether) and bpdiol (biphytanic diol); (2) oxidation of isoprenoidal alcohols into corresponding carboxyl derivatives and (3) chain shortening to yield C39 and smaller isoprenoids. This plausible GDGT degradation pathway from glycerol ethers to isoprenoidal fatty acids provides the link to commonly detected head-to-head linked long chain isoprenoidal hydrocarbons in petroleum and sediment samples. The problematic C80 to C82 tetraacids that cause naphthenate deposits in some oil production facilities can be generated from H-shaped glycerol monoalkyl glycerol tetraethers (GMGTs) following the same process, as indicated by the distribution of related derivatives in hydrothermally influenced sediments.

  13. Metabolic pathway for degradation of 2-chloro-4-aminophenol by Arthrobacter sp. SPG.

    Arora, Pankaj Kumar; Mohanta, Tapan Kumar; Srivastava, Alok; Bae, Hanhong; Singh, Vijay Pal

    2014-01-01

    A degradation pathway of 2-chloro-4-aminophenol (2C4AP) was studied in an Arthrobacter sp. SPG that utilized 2C4AP as its sole source of carbon and energy. The 2C4AP degradation was initiated by a 2C4AP-deaminase that catalyzed the conversion of 2C4AP into chlorohydroquinone (CHQ) with removal of ammonium ion. In the next step, a CHQ-dehalogenase dehalogenated CHQ to hydroquinone (HQ) that cleaved into γ-hydroxymuconic semialdehyde by a HQ-dioxygenase. The 2C4AP degradation was also investigated in sterile and non-sterile soil microcosms using strain SPG. The results show that the SPG cells degraded 2C4AP more rapidly in sterile soil than non-sterile soil. Our studies showed that strain SPG may be used for bioremediation of 2C4AP-contaminated sites. This is the first report of the 2C4AP degradation by any bacteria. PMID:25427856

  14. Oxidative degradation of N-Nitrosopyrrolidine by the ozone/UV process: Kinetics and pathways.

    Chen, Zhi; Fang, Jingyun; Fan, Chihhao; Shang, Chii

    2016-05-01

    N-Nitrosopyrrolidine (NPYR) is an emerging contaminant in drinking water and wastewater. The degradation kinetics and mechanisms of NPYR degradation by the O3/UV process were investigated and compared with those of UV direct photolysis and ozonation. A synergistic effect of ozone and UV was observed in the degradation of NPYR due to the accelerated production of OH• by ozone photolysis. This effect was more pronounced at higher ozone dosages. The second-order rate constants of NPYR reacting with OH• and ozone was determined to be 1.38 (± 0.05) × 10(9) M(-1) s(-1) and 0.31 (± 0.02) M(-1) s(-1), respectively. The quantum yield by direct UV photolysis was 0.3 (± 0.01). An empirical model using Rct (the ratio of the exposure of OH• to that of ozone) was established for NPYR degradation in treated drinking water and showed that the contributions of direct UV photolysis and OH• oxidation on NPYR degradation were both significant. As the reaction proceeded, the contribution by OH• became less important due to the exhausting of ozone. Nitrate was the major product in the O3/UV process by two possible pathways. One is through the cleavage of nitroso group to form NO• followed by hydrolysis, and the other is the oxidation of the intermediates of amines by ozonation. PMID:26733013

  15. Effects of reforesting degraded grassland on hydrological flow pathways on Leyte, the Philippines

    van Meerveld, Ilja; Zhang, Jun; Bruijnzeel, Sampurno

    2014-05-01

    Reforestation of degraded land in the tropics is promoted for a wide range of expected benefits, including carbon sequestration and streamflow regulation. However, how reforestation of degraded land affects runoff generation mechanisms and catchment water yield is still poorly understood as most experimental work pertains to non-degraded terrain. We set out to study the differences in hydrological functioning of a small degraded grassland catchment and a similar catchment that was reforested 15 years ago. Both catchments are located near Tacloban, Leyte, the Philippines. Stream stage, EC and temperature are measured continuously since June 2013. Precipitation, soil moisture content, and groundwater levels are monitored as well. Samples are taken from streamflow, precipitation, groundwater, and soil water prior to and during rainfall events for geochemical and stable isotope analysis to elucidate source contributions to storm runoff. Streamflow and event water contributions increase rapidly during almost every rainfall event in the grassland. In the reforested catchment, event water contributions to streamflow are much smaller and only increase during large events. These tracer results suggest that overland flow occurs much less frequently and is much less widespread in the reforested catchment compared to the grassland catchment. Our results thus indicate that the dominant flow pathways have changed as a result of reforestation and suggest that reforestation can largely restore the hydrological functioning of degraded sites if the forest is allowed to develop over a sufficiently long period without subsequent disturbance.

  16. Identification of the degradation pathways of alkanolamines with TiO{sub 2} photocatalysis

    Lu, Chung-Shin, E-mail: cslu6@ntcnc.edu.tw [Department of General Education, National Taichung Nursing College, Taichung 403, Taiwan (China); Chen, Chiing-Chang [Department of Science Application and Dissemination, National Taichung University, Taichung 403, Taiwan (China); Mai, Fu-Der [Department of Biochemistry, School of Medicine, Taipei Medical University, Taipei 110, Taiwan (China); Li, Hua-Kuang [Department of General Education, National Taichung Nursing College, Taichung 403, Taiwan (China)

    2009-06-15

    The present study deals with the photocatalytic degradation of the alkanolamine, 2-dimethylamino-2-methyl-1-propanol (DMAMP), in the presence of TiO{sub 2} particles and UV-A ({lambda} = 365 nm) radiation. The obtained results show complete oxidation of DMAMP after 20 h, and a little over 90% of DMAMP was mineralization after 64-h of treatment. The effects of the solution pH, catalyst loading, and anions on the photocatalytic degradation of DMAMP were investigated, as well as the reaction intermediates that were formed during treatment. To the best of our knowledge, this is the first time that reports the degradation pathways of DMAMP. A number of intermediates were identified by GC/MS techniques during the treatment of DMAMP, following three tentative degradation routes. The first one is based on the oxidation of the primary alcohol group leading to the formation of corresponding aldehyde and carboxylic acid. The second route is based on the rupture of the N-C bond to form 2-methylpropanal and acetone. The last degradation route is based on the cyclization of the {beta}-amino alcohol group to form the oxazolidine derivatives.

  17. Identification of the degradation pathways of alkanolamines with TiO2 photocatalysis

    The present study deals with the photocatalytic degradation of the alkanolamine, 2-dimethylamino-2-methyl-1-propanol (DMAMP), in the presence of TiO2 particles and UV-A (λ = 365 nm) radiation. The obtained results show complete oxidation of DMAMP after 20 h, and a little over 90% of DMAMP was mineralization after 64-h of treatment. The effects of the solution pH, catalyst loading, and anions on the photocatalytic degradation of DMAMP were investigated, as well as the reaction intermediates that were formed during treatment. To the best of our knowledge, this is the first time that reports the degradation pathways of DMAMP. A number of intermediates were identified by GC/MS techniques during the treatment of DMAMP, following three tentative degradation routes. The first one is based on the oxidation of the primary alcohol group leading to the formation of corresponding aldehyde and carboxylic acid. The second route is based on the rupture of the N-C bond to form 2-methylpropanal and acetone. The last degradation route is based on the cyclization of the β-amino alcohol group to form the oxazolidine derivatives.

  18. 食品中糠醛和5-羟甲基糠醛的产生机理、含量检测及安全性评价研究进展%A Review on Formation Mechanism, Determination and Safety Assessment of Furfural and 5-Hydroxymethylfurfural (HMF) in Foods

    张玉玉; 宋弋; 李全宏

    2012-01-01

    Sugar-rich foods could generate large amounts of furfural and 5-hydroxymethylfurfural during thermal processing. During these different processes, the contents of furfural and 5-hydroxymethylfurfural were also different in foods. When the contents of furfural and 5-hydroxymethylfurfural exceeded a certain limit, it would harm human health. In this paper, the mechanisms, determination methods and safety of furfural and 5-hydroxymethylfurfural have been reviewed.%含糖丰富的食品在热加工过程中会产生大量的糠醛和5-羟甲基糠醛(HMF),不同食品加工后所产生的糠醛及HMF的含量有所差异,但当含量超过标准时就会对人体产生危害。因此,本文对食品中糠醛和HMF的产生机理、含量检测分析及安全性评价进行综述。

  19. KCTD1 suppresses canonical Wnt signaling pathway by enhancing β-catenin degradation.

    Xinxin Li

    Full Text Available The canonical Wnt signaling pathway controls normal embryonic development, cellular proliferation and growth, and its aberrant activity results in human carcinogenesis. The core component in regulation of this pathway is β-catenin, but molecular regulation mechanisms of β-catenin stability are not completely known. Here, our recent studies have shown that KCTD1 strongly inhibits TCF/LEF reporter activity. Moreover, KCTD1 interacted with β-catenin both in vivo by co-immunoprecipitation as well as in vitro through GST pull-down assays. We further mapped the interaction regions to the 1-9 armadillo repeats of β-catenin and the BTB domain of KCTD1, especially Position Ala-30 and His-33. Immunofluorescence analysis indicated that KCTD1 promotes the cytoplasmic accumulation of β-catenin. Furthermore, protein stability assays revealed that KCTD1 enhances the ubiquitination/degradation of β-catenin in a concentration-dependent manner in HeLa cells. And the degradation of β-catenin mediated by KCTD1 was alleviated by the proteasome inhibitor, MG132. In addition, KCTD1-mediated β-catenin degradation was dependent on casein kinase 1 (CK1- and glycogen synthase kinase-3β (GSK-3β-mediated phosphorylation and enhanced by the E3 ubiquitin ligase β-transducin repeat-containing protein (β-TrCP. Moreover, KCTD1 suppressed the expression of endogenous Wnt downstream genes and transcription factor AP-2α. Finally, we found that Wnt pathway member APC and tumor suppressor p53 influence KCTD1-mediated downregulation of β-catenin. These results suggest that KCTD1 functions as a novel inhibitor of Wnt signaling pathway.

  20. Degradation of retinoid X receptor α by TPA through proteasome pathway in gastric cancer cells

    Xiao-Feng Ye; Su Liu; Qiao Wu; Xiao-Feng Lin; Bing Zhang; Jia-Fa Wu; Ming-Qing Zhang; Wen-Jin Su

    2003-01-01

    AIM: To investigate and determine the mechanism and signal pathway of tetradecanoylphorbol-1, 3-acetate (TPA) in degradation of RXRα.METHODS: Gastric cancer cell line, BGC-823 was used in the experiments. The expression level of R XRα protein was detected by Western blot. Nuclear and cytoplasmic protein fractions were prepared through lysis of cell and centrifugation.Localization and translocation of RXRα were observed under laser-scanning confocal microscope through labeling specific anti-RXRα antibody and corresponding immunofiuorescent antibody as secondary antibody. Different inhibitors were used as required.RESULTS: In BGC-823 cells, RXRα was expressed in the nucleus. When cells were treated with TPA, expression of RXRα was repressed in a time-dependent and TPAconcentration-dependent manner. Meanwhile, translocation of RXR from the nucleus to the cytoplasm occurred, also in a time-dependent manner. When cells were pre-incubated with proteasome inhibitor MG132 for 3 hrs, followed by TPA for another 12 hrs, TPA-induced RXRα degradation was inhibited. Further observation of RXRα translocation in the presence of MG132 showed that MG-132 could block TPAinduced RXRα redistribution. Conversely, when RXRαtranslocation was inhibited by LMB, an inhibitor for blocking protein export from the nucleus, TPA could not repress expression of RXRα.CONCLUSION: TPA could induce the degradation of RXRα protein in BGC-823 cells, and this degradation is time-and TPA-concentration-dependent. Furthermore, the degradation of RXRα by TPA is via a proteasome pathway and associated with RXRα translocation from the nucleus to the cytoplasm.

  1. It's all about talking: two-way communication between proteasomal and lysosomal degradation pathways via ubiquitin.

    Liebl, Martina P; Hoppe, Thorsten

    2016-08-01

    Selective degradation of proteins requires a fine-tuned coordination of the two major proteolytic pathways, the ubiquitin-proteasome system (UPS) and autophagy. Substrate selection and proteolytic activity are defined by a plethora of regulatory cofactors influencing each other. Both proteolytic pathways are initiated by ubiquitylation to mark substrate proteins for degradation, although the size and/or topology of the modification are different. In this context E3 ubiquitin ligases, ensuring the covalent attachment of activated ubiquitin to the substrate, are of special importance. The regulation of E3 ligase activity, competition between different E3 ligases for binding E2 conjugation enzymes and substrates, as well as their interplay with deubiquitylating enzymes (DUBs) represent key events in the cross talk between the UPS and autophagy. The coordination between both degradation routes is further influenced by heat shock factors and ubiquitin-binding proteins (UBPs) such as p97, p62, or optineurin. Mutations in enzymes and ubiquitin-binding proteins or a general decline of both proteolytic systems during aging result in accumulation of damaged and aggregated proteins. Thus further mechanistic understanding of how UPS and autophagy communicate might allow therapeutic intervention especially against age-related diseases. PMID:27225656

  2. Blue Light Induces a Distinct Starch Degradation Pathway in Guard Cells for Stomatal Opening.

    Horrer, Daniel; Flütsch, Sabrina; Pazmino, Diana; Matthews, Jack S A; Thalmann, Matthias; Nigro, Arianna; Leonhardt, Nathalie; Lawson, Tracy; Santelia, Diana

    2016-02-01

    Stomatal pores form a crucial interface between the leaf mesophyll and the atmosphere, controlling water and carbon balance in plants [1]. Major advances have been made in understanding the regulatory networks and ion fluxes in the guard cells surrounding the stomatal pore [2]. However, our knowledge on the role of carbon metabolism in these cells is still fragmentary [3-5]. In particular, the contribution of starch in stomatal opening remains elusive [6]. Here, we used Arabidopsis thaliana as a model plant to provide the first quantitative analysis of starch turnover in guard cells of intact leaves during the diurnal cycle. Starch is present in guard cells at the end of night, unlike in the rest of the leaf, but is rapidly degraded within 30 min of light. This process is critical for the rapidity of stomatal opening and biomass production. We exploited Arabidopsis molecular genetics to define the mechanism and regulation of guard cell starch metabolism, showing it to be mediated by a previously uncharacterized pathway. This involves the synergistic action of β-amylase 1 (BAM1) and α-amylase 3 (AMY3)-enzymes that are normally not required for nighttime starch degradation in other leaf tissues. This pathway is under the control of the phototropin-dependent blue-light signaling cascade and correlated with the activity of the plasma membrane H(+)-ATPase. Our results show that guard cell starch degradation has an important role in plant growth by driving stomatal responses to light. PMID:26774787

  3. Genetic immunization based on the ubiquitin-fusion degradation pathway against Trypanosoma cruzi

    Chou, Bin [Department of Microbiology and Immunology, Faculty of Medicine, Fukuoka University, 7-45-1 Nanakuma, Jonan-ku, Fukuoka 814-0180 (Japan); Department of Parasitology, Graduate School of Medical Science, Kyushu University, Fukuoka 812-8582 (Japan); Hiromatsu, Kenji, E-mail: khiromatsu@fukuoka-u.ac.jp [Department of Microbiology and Immunology, Faculty of Medicine, Fukuoka University, 7-45-1 Nanakuma, Jonan-ku, Fukuoka 814-0180 (Japan); Hisaeda, Hajime; Duan, Xuefeng; Imai, Takashi [Department of Parasitology, Graduate School of Medical Science, Kyushu University, Fukuoka 812-8582 (Japan); Murata, Shigeo; Tanaka, Keiji [Department of Molecular Oncology, The Tokyo Metropolitan Institute of Medical Science, Tokyo 113-8613 (Japan); Himeno, Kunisuke [Department of Parasitology, Graduate School of Medical Science, Kyushu University, Fukuoka 812-8582 (Japan)

    2010-02-12

    Cytotoxic CD8{sup +} T cells are particularly important to the development of protective immunity against the intracellular protozoan parasite, Trypanosoma cruzi, the etiological agent of Chagas disease. We have developed a new effective strategy of genetic immunization by activating CD8{sup +} T cells through the ubiquitin-fusion degradation (UFD) pathway. We constructed expression plasmids encoding the amastigote surface protein-2 (ASP-2) of T. cruzi. To induce the UFD pathway, a chimeric gene encoding ubiquitin fused to ASP-2 (pUB-ASP-2) was constructed. Mice immunized with pUB-ASP-2 presented lower parasitemia and longer survival period, compared with mice immunized with pASP-2 alone. Depletion of CD8{sup +} T cells abolished protection against T. cruzi in mice immunized with pUB-ASP-2 while depletion of CD4{sup +} T cells did not influence the effective immunity. Mice deficient in LMP2 or LMP7, subunits of immunoproteasomes, were not able to develop protective immunity induced. These results suggest that ubiquitin-fused antigens expressed in antigen-presenting cells were effectively degraded via the UFD pathway, and subsequently activated CD8{sup +} T cells. Consequently, immunization with pUB-ASP-2 was able to induce potent protective immunity against infection of T. cruzi.

  4. Organelle interactions and possible degradation pathways visualized in high-pressure frozen algal cells.

    Aichinger, N; Lütz-Meindl, U

    2005-08-01

    Summary Organelle interactions, although essential for both anabolic and catabolic pathways in plant cells have not been examined in detail so far. In the present study the structure of different organelle-organelle, organelle-vesicle and organelle-membrane interactions were investigated in growing and nongrowing cells of the green alga Micrasterias denticulata by use of high pressure freeze fixation and energy filtering transmission electron microscopy. It became clear that contacts between mitochondria always occur by formation of a cone-shaped protuberance of one of the mitochondria which penetrates into its fusion partner. In the same way, structural interactions between mitochondria and mucilage vesicles and between microbodies and mucilage vesicles are achieved. Lytic compartments contact mitochondria or mucilage vesicles again by forming protuberances and by extending their contents into the respective compartment. Detached portions of mitochondria are found inside lytic compartments as a consequence of such interactions. Mitochondria found in contact with the plasma membrane reveal structural disintegration. Our study shows that interactions of organelles and vesicles are frequent events in Micrasterias cells of different ages. The interactive contacts between lytic compartments and organelles or vesicles suggest a degradation pathway different from autophagy processes described in the literature. Both the interactions between vesicles and organelles and the degradation pathways occur independently from cytoskeleton function as demonstrated by use of cytochalasin D and the microtubule inhibitor amiprophos-methyl. PMID:16159344

  5. Genetic immunization based on the ubiquitin-fusion degradation pathway against Trypanosoma cruzi

    Cytotoxic CD8+ T cells are particularly important to the development of protective immunity against the intracellular protozoan parasite, Trypanosoma cruzi, the etiological agent of Chagas disease. We have developed a new effective strategy of genetic immunization by activating CD8+ T cells through the ubiquitin-fusion degradation (UFD) pathway. We constructed expression plasmids encoding the amastigote surface protein-2 (ASP-2) of T. cruzi. To induce the UFD pathway, a chimeric gene encoding ubiquitin fused to ASP-2 (pUB-ASP-2) was constructed. Mice immunized with pUB-ASP-2 presented lower parasitemia and longer survival period, compared with mice immunized with pASP-2 alone. Depletion of CD8+ T cells abolished protection against T. cruzi in mice immunized with pUB-ASP-2 while depletion of CD4+ T cells did not influence the effective immunity. Mice deficient in LMP2 or LMP7, subunits of immunoproteasomes, were not able to develop protective immunity induced. These results suggest that ubiquitin-fused antigens expressed in antigen-presenting cells were effectively degraded via the UFD pathway, and subsequently activated CD8+ T cells. Consequently, immunization with pUB-ASP-2 was able to induce potent protective immunity against infection of T. cruzi.

  6. Titanium dioxide-mediated heterogeneous photocatalytic degradation of terbufos: Parameter study and reaction pathways

    Wu, R.-J. [Department of Applied Chemistry, Providence University, Taichung 433, Taiwan (China); Chen, C.-C. [Department of General Education, National Taichung Nursing College, Taichung 403, Taiwan (China); Chen, M.-H. [Department of Applied Chemistry, Providence University, Taichung 433, Taiwan (China); Lu, C.-S. [Department of General Education, National Taichung Nursing College, Taichung 403, Taiwan (China)], E-mail: cslu6@ntcnc.edu.tw

    2009-03-15

    The photocatalytic degradation of terbufos in aqueous suspensions was investigated by using titanium dioxide (TiO{sub 2}) as a photocatalyst. About 99% of terbufos was degraded after UV irradiation for 90 min. Factors such as pH of the system, TiO{sub 2} dosage, and presence of anions were found to influence the degradation rate. Photodegradation of terbufos by TiO{sub 2}/UV exhibited pseudo-first-order reaction kinetics, and a reaction quantum yield of 0.289. The electrical energy consumption per order of magnitude for photocatalytic degradation of terbufos was calculated and showed that a moderated efficiency (E{sub EO} = 71 kWh/(m{sup 3} order)) was obtained in TiO{sub 2}/UV process. To obtain a better understanding of the mechanistic details of this TiO{sub 2}-assisted photodegradation of terbufos with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. The probable photodegradation pathways were proposed and discussed.

  7. Titanium dioxide-mediated heterogeneous photocatalytic degradation of terbufos: Parameter study and reaction pathways

    The photocatalytic degradation of terbufos in aqueous suspensions was investigated by using titanium dioxide (TiO2) as a photocatalyst. About 99% of terbufos was degraded after UV irradiation for 90 min. Factors such as pH of the system, TiO2 dosage, and presence of anions were found to influence the degradation rate. Photodegradation of terbufos by TiO2/UV exhibited pseudo-first-order reaction kinetics, and a reaction quantum yield of 0.289. The electrical energy consumption per order of magnitude for photocatalytic degradation of terbufos was calculated and showed that a moderated efficiency (EEO = 71 kWh/(m3 order)) was obtained in TiO2/UV process. To obtain a better understanding of the mechanistic details of this TiO2-assisted photodegradation of terbufos with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. The probable photodegradation pathways were proposed and discussed

  8. Dysfunction of two lysosome degradation pathways of α-synuclein in Parkinson's disease: potential therapeutic targets?

    Tian-Fang Jiang; Sheng-Di Chen

    2012-01-01

    Parkinson's disease (PD) is pathologically characterized by the presence of α-synuclein (α-syn)-positive intracytoplasmic inclusions named Lewy bodies in the dopaminergic neurons of the substantia nigra.A series of morbid consequences are caused by pathologically high amounts or mutant forms of α-syn,such as defects of membrane trafficking and lipid metabolism.In this review,we consider evidence that both point mutation and overexpression of α-syn result in aberrant degradation in neurons and microglia,and this is associated with the autophagy-lysosome pathway and endosomelysosome system,leading directly to pathological intracellular aggregation,abnormal externalization and re-internalization cycling (and,in turn,internalization and re-externalization),and exocytosis.Based on these pathological changes,an increasing number of researchers have focused on these new therapeutic targets,aiming at alleviating the pathological accumulation of α-syn and re-establishing normal degradation.

  9. Tyrosol degradation via the homogentisic acid pathway in a newly isolated Halomonas strain from olive processing effluents

    Liebgott, Pierre-Pol; Labat, Marc; Amouric, Agnès; Tholozan, Jean-Luc; LORQUIN, Jean

    2008-01-01

    To isolate a new Halomonas sp. strain capable of degrading tyrosol, a toxic compound present in olive mill wastewater, through the homogentisic acid (HGA) pathway. A moderately halophilic Gram-negative bacterium belonging to the Halomonas genus and designated strain TYRC17 was isolated from olive processing effluents. This strain was able to completely degrade tyrosol (2-(p-hydroxyphenyl)-ethanol), a toxic compound found in such effluent. Tyrosol degradation begins by an oxidation to 4-hydrox...

  10. Insulin-degrading enzyme is exported via an unconventional protein secretion pathway

    Leissring Malcolm A

    2009-01-01

    Full Text Available Abstract Insulin-degrading enzyme (IDE is a ubiquitously expressed zinc-metalloprotease that degrades several pathophysiologically significant extracellular substrates, including insulin and the amyloid β-protein (Aβ, and accumulating evidence suggests that IDE dysfunction may be operative in both type 2 diabetes mellitus and Alzheimer disease (AD. Although IDE is well known to be secreted by a variety of cell types, the underlying trafficking pathway(s remain poorly understood. To address this topic, we investigated the effects of known inhibitors or stimulators of protein secretion on the secretion of IDE from murine hepatocytes and HeLa cells. IDE secretion was found to be unaffected by the classical secretion inhibitors brefeldin A (BFA, monensin, or nocodazole, treatments that readily inhibited the secretion of α1-antitrypsin (AAT overexpressed in the same cells. Using a novel cell-based Aβ-degradation assay, we show further that IDE secretion was similarly unaffected by multiple stimulators of protein secretion, including glyburide and 3'-O-(4-benzoylbenzoyl-ATP (Bz-ATP. The calcium ionophore, A23187, increased extracellular IDE activity, but only under conditions that also elicited cytotoxicity. Our results provide the first biochemical evidence that IDE export is not dependent upon the classical secretion pathway, thereby identifying IDE as a novel member of the select class of unconventionally secreted proteins. Further elucidation of the mechanisms underlying IDE secretion, which would be facilitated by the assays described herein, promises to uncover processes that might be defective in disease or manipulated for therapeutic benefit.

  11. Cystic fibrosis transmembrane conductance regulator degradation: cross-talk between the ubiquitylation and SUMOylation pathways.

    Ahner, Annette; Gong, Xiaoyan; Frizzell, Raymond A

    2013-09-01

    Defining the significant checkpoints in cystic fibrosis transmembrane conductance regulator (CFTR) biogenesis should identify targets for therapeutic intervention with CFTR folding mutants such as F508del. Although the role of ubiquitylation and the ubiquitin proteasome system is well established in the degradation of this common CFTR mutant, the part played by SUMOylation is a novel aspect of CFTR biogenesis/quality control. We identified this post-translational modification of CFTR as resulting from its interaction with small heat shock proteins (Hsps), which were found to selectively facilitate the degradation of F508del through a physical interaction with the SUMO (small ubiquitin-like modifier) E2 enzyme, Ubc9. Hsp27 promoted the SUMOylation of mutant CFTR by the SUMO-2 paralogue, which can form poly-chains. Poly-SUMO chains are then recognized by the SUMO-targeted ubiquitin ligase, RNF4, which elicited F508del degradation in a Hsp27-dependent manner. This work identifies a sequential connection between the SUMO and ubiquitin modifications of the CFTR mutant: Hsp27-mediated SUMO-2 modification, followed by ubiquitylation via RNF4 and degradation of the mutant via the proteasome. Other examples of the intricate cross-talk between the SUMO and ubiquitin pathways are discussed with reference to other substrates; many of these are competitive and lead to different outcomes. It is reasonable to anticipate that further research on SUMO-ubiquitin pathway interactions will identify additional layers of complexity in the process of CFTR biogenesis and quality control. PMID:23809253

  12. Ubiquitin initiates sorting of Golgi and plasma membrane proteins into the vacuolar degradation pathway

    Scheuring David

    2012-09-01

    Full Text Available Abstract Background In yeast and mammals, many plasma membrane (PM proteins destined for degradation are tagged with ubiquitin. These ubiquitinated proteins are internalized into clathrin-coated vesicles and are transported to early endosomal compartments. There, ubiquitinated proteins are sorted by the endosomal sorting complex required for transport (ESCRT machinery into the intraluminal vesicles of multivesicular endosomes. Degradation of these proteins occurs after endosomes fuse with lysosomes/lytic vacuoles to release their content into the lumen. In plants, some PM proteins, which cycle between the PM and endosomal compartments, have been found to be ubiquitinated, but it is unclear whether ubiquitin is sufficient to mediate internalization and thus acts as a primary sorting signal for the endocytic pathway. To test whether plants use ubiquitin as a signal for the degradation of membrane proteins, we have translationally fused ubiquitin to different fluorescent reporters for the plasma membrane and analyzed their transport. Results Ubiquitin-tagged PM reporters localized to endosomes and to the lumen of the lytic vacuole in tobacco mesophyll protoplasts and in tobacco epidermal cells. The internalization of these reporters was significantly reduced if clathrin-mediated endocytosis was inhibited by the coexpression of a mutant of the clathrin heavy chain, the clathrin hub. Surprisingly, a ubiquitin-tagged reporter for the Golgi was also transported into the lumen of the vacuole. Vacuolar delivery of the reporters was abolished upon inhibition of the ESCRT machinery, indicating that the vacuolar delivery of these reporters occurs via the endocytic transport route. Conclusions Ubiquitin acts as a sorting signal at different compartments in the endomembrane system to target membrane proteins into the vacuolar degradation pathway: If displayed at the PM, ubiquitin triggers internalization of PM reporters into the endocytic transport route

  13. Electrochemical treatment of trypan blue synthetic wastewater and its degradation pathway

    ANANTHA N. SUBBA RAO

    2013-11-01

    Full Text Available The trypan blue (TB dye synthetic wastewater was treated in presence of chloride ions by electrochemical method. The effect of current density, pH, initial concentration of dye and supporting electrolyte on color and COD removal were investigated. The UV-Vis ab­sorption intensity, chemical oxygen demand (COD, cyclic voltammetry (CV, Fourier transform- infrared spectroscopy (FT-IR, gas chromatography – mass spectrometry (GC-MS analysis were conducted to investigate the kinetics and degradation pathway of TB dye.

  14. Elimination of paternal mitochondria through the lysosomal degradation pathway in C. elegans.

    Zhou, Qinghua; Li, Haimin; Xue, Ding

    2011-12-01

    In mammals, the inheritance of mitochondrion and its DNA (mtDNA) is strictly maternal, despite the fact that a sperm can inject up to 100 functional mitochondria into the oocyte during fertilization. The mechanisms responsible for the elimination of the paternal mitochondria remain largely unknown. We report here that this paternal mitochondrial elimination process is conserved in Caenorhabditis elegans, and that the lysosomal pathway actively participates in this process. Molecular and cell biological analyses indicate that in wild-type animals paternal mitochondria and mtDNA are destroyed within two hours after fertilization. In animals with compromised lysosomes, paternal mitochondria persist until late embryonic stages. Therefore, the lysosomal pathway plays an important role in degrading paternal mitochondria introduced into the oocyte during fertilization. Our study indicates that C. elegans is an excellent animal model for understanding and dissecting this conserved biological process critical for animal development and reproduction. PMID:22105480

  15. Elimination of paternal mitochondria through the lysosomal degradation pathway in C.elegans

    Qinghua Zhou; Haimin Li; Ding Xue

    2011-01-01

    In mammals,the inheritance of mitochondrion and its DNA (mtDNA) is strictly maternal,despite the fact that a sperm can inject up to 100 functional mitochondria into the oocyte during fertilization.The mechanisms responsible for the elimination of the paternal mitochondria remain largely unknown.We report here that this paternal mitochondrial elimination process is conserved in Caenorhabditis elegans,and that the lysosomal pathway actively participates in this process.Molecular and cell biological analyses indicate that in wild-type animals paternal mitoehondria and mtDNA are destroyed within two hours after fertilization.In animals with compromised lysosomes,paternal mitochondria persist until late embryonic stages.Therefore,the lysosomal pathway plays an important role in degrading paternal mitochondria introduced into the oocyte during fertilization.Our study indicates that C.elegans is an excellent animal model for understanding and dissecting this conserved biological process critical for animal development and reproduction.

  16. Def defines a conserved nucleolar pathway that leads p53 to proteasome-independent degradation

    Ting Tao; Hui Shi; Yihong Guan; Delai Huang; Ye Chen; David P Lane; Jun Chen

    2013-01-01

    p53 protein turnover through the ubiquitination pathway is a vital mechanism in the regulation of its transcriptional activity; however,little is known about p53 turnover through proteasome-independent pathway(s).The digestive organ expansion factor (Def) protein is essential for the development of digestive organs.In zebrafish,loss of function of defselectively upregulates the expression of p53 response genes,which raises a question as to what is the relationship between Def and p53.We report here that Def is a nucleolar protein and that loss of function of defleads to the upregulation of p53 protein,which surprisingly accumulates in the nucleoli.Our extensive studies have demonstrated that Def can mediate the degradation of p53 protein and that this process is independent of the proteasome pathway,but dependent on the activity of Calpain3,a cysteine protease.Our findings define a novel nucleolar pathway that regulates the turnover function of p53,which will advance our understanding of p53's role in organogenesis and tumorigenesis.

  17. Pathways and Determinants of Early Spontaneous Vegetation Succession in Degraded Lowland of South China

    Wen-Jun Duan; Hai Ran; Sheng-Lei Fu; Qin-Feng Guo; Jun Wang

    2008-01-01

    Continuous and prolonged human disturbances have caused severe degradation of a large portion of lowland in South China, and how to restore such degraded ecosystems becomes an increasing concern. The process and mechanisms of spontaneous succession, which plays an important role in vegetation restoration, have not been adequately examined. To identify the pathways of early spontaneous vegetation succession, 41 plots representing plant communities abandoned over different times were established and Investigated. The communities and indicator species of the vegetation were classified by analyzing the important values of plant species using multivariate analyses. The reaults indicated that the plant species could be classified into nine plant communities repreaenting six succession staages. The pathway and species composition alao changed in the process of succession. We also meaeurad 13 environmental variables of microtopography, soil structure and soil nutrition in each plot to examine the driving forces of auccession and the vegetation-environment relationships. Our resulta ahowed that the environmental variables changed in diverse directions, and that aoil bulk density, soil water capacity and soU acidity were the most important factors.

  18. Preparation of 5-Hydroxymethylfurfural with Sucrose Catalyzed by In-situ Iodine%原位合成碘催化蔗糖制备5-羟甲基糠醛

    胡宁播; 董喜恩; 罗根祥; 刘春生; 韩春玉

    2011-01-01

    着重研究以原位合成碘(即三氯化铬和碘化钠发生氧化还原反应产生的碘)为催化剂,蔗糖为原料制备羟甲基糠醛.考察了反应时间、反应温度、催化剂用量(以三氯化铬和碘化钠质量计)、蔗糖质量百分数对羟甲基糠醛收率的影响.得到以原位合成碘为催化剂的优化条件:时间45min、温度130℃、催化剂用量0.25g、蔗糖质量百分数8%.在此优化条件下,用单质碘做催化剂制备羟甲基糠醛,把两者的结果相比较.以原位合成碘为催化剂,收率达到79.5%(根据果糖部分计算);以碘为催化剂,收率达到51.1%.产物经紫外可见分光光度计检测.%The preparation of 5-hydroxymethylfurfural was studied which used in-situ iodine as catalyst (in-situ iodine was generated by redox reaction of chromium trichloride and sodium iodide) and sucrose as raw materials.The effects of reaction time, temperature, the catalyst amount, the sucrose mass percentage on the yield of 5-hydroxymethyffurfural were investigated.The most suitable condition for the reaction were as follows: the reaction time was 45 min, temperature was 130℃, the catalyst amount was 0.25g, the sucrose mass percentage was 8%.Under these conditions, the yield of 5-hydroxymethylfurfural was 79.5% and 51.1% respectively which used in-situ iodine and iodine as catalyst respectively.The products were examined with UV-Vis spectrophotometer.

  19. Degradation pathway of quinolines in a biofilm system under denitrifying conditions

    Johansen, S.S.; Arvin, E.; Mosbaek, H. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Environmental Science and Engineering; Hansen, A.B. [National Environmental Research Inst., Roskilde (Denmark). Dept. of Environmental Chemistry

    1997-09-01

    This article reports for the first time the degradation pathways of quinoline, isoquinoline, and methylquinolines by a mixed culture in a biofilm under nitrate-reducing conditions. A simple reverse-phase high-performance liquid chromatography method using ultraviolet detection at 223 nm for determination of seven quinoline analogues and 15 metabolites was developed, and gas chromatography--mass spectrometry and thin-layer chromatography analyses were used for identification. The inhibition of nitrification by the parent compounds and their degradation products was assessed by a nitrification toxicity test called MINNTOX. Quinoline and 3-, 4-, 6-, and 8-methylquinoline were all transformed by hydroxylation into their 2-hydroxyquinoline analogues (2-quinolinones), and isoquinoline was transformed into 1-hydroxyisoquinoline. 2-Methylquinoline was not transformed by this microcosm, likely due to the blockage at position 2 by the methyl group. The hydroxylated metabolites of isoquinoline and quinolines methylated at the heterocyclic ring were not transformed further, whereas metabolites of quinoline and quinolines methylated at the homocyclic ring were hydrogenated at position 3 and 4, and the resulting 3,4-dihydro-2-quinolinone analogues accumulated. Of these metabolites, only 3,4-dihydro-2-quinolinone from the degradation of quinoline was further transformed into unidentified products. All quinolines and their metabolites had inhibiting effects on the nitrifying bacteria at the same level (ppm) in the applied bioassay, indicating that the inhibition of the compounds was not influenced by the initial transformation reactions.

  20. Aqueous photodegradation of 4-tert-butylphenol: By-products, degradation pathway and theoretical calculation assessment.

    Wu, Yanlin; Shi, Jin; Chen, Hongche; Zhao, Jianfu; Dong, Wenbo

    2016-10-01

    4-tert-butylphenol (4-t-BP), an endocrine disrupting chemical, is widely distributed in natural bodies of water but is difficult to biodegrade. In this study, we focused on the transformation of 4-t-BP in photo-initiated degradation processes. The steady-state photolysis and laser flash photolysis (LFP) experiments were conducted in order to elucidate its degradation mechanism. Identification of products was performed using the GC-MS, LC-MS and theoretical calculation techniques. The oxidation pathway of 4-t-BP by hydroxyl radical (HO) was also studied and H2O2 was added to produce HO. 4-tert-butylcatechol and 4-tert-butylphenol dimer were produced in 4-t-BP direct photolysis. 4-tert-butylcatechol and hydroquinone were produced by the oxidation of HO. But the formation mechanism of 4-tert-butylcatechol in the two processes was different. The benzene ring was fractured in 4-t-BP oxidation process and 29% of TOC was degraded after 16h irradiation. PMID:27213674

  1. Unfolded protein response and activated degradative pathways regulation in GNE myopathy.

    Honghao Li

    Full Text Available Although intracellular beta amyloid (Aβ accumulation is known as an early upstream event in the degenerative course of UDP-N-acetylglucosamine 2-epimerase/N-acetylmannosamine kinase (GNE myopathy, the process by which Aβdeposits initiate various degradative pathways, and their relationship have not been fully clarified. We studied the possible secondary responses after amyloid beta precursor protein (AβPP deposition including unfolded protein response (UPR, ubiquitin proteasome system (UPS activation and its correlation with autophagy system. Eight GNE myopathy patients and five individuals with normal muscle morphology were included in this study. We performed immunofluorescence and immunoblotting to investigate the expression of AβPP, phosphorylated tau (p-tau and endoplasmic reticulum molecular chaperones. Proteasome activities were measured by cleavage of fluorogenic substrates. The expression of proteasome subunits and linkers between proteasomal and autophagy systems were also evaluated by immunoblotting and relative quantitative real-time RT-PCR. Four molecular chaperones, glucose-regulated protein 94 (GRP94, glucose-regulated protein 78 (GRP78, calreticulin and calnexin and valosin containing protein (VCP were highly expressed in GNE myopathy. 20S proteasome subunits, three main proteasome proteolytic activities, and the factors linking UPS and autophagy system were also increased. Our study suggests that AβPP deposition results in endoplasmic reticulum stress (ERS and highly expressed VCP deliver unfolded proteins from endoplasmic reticulum to proteosomal system which is activated in endoplasmic reticulum associated degradation (ERAD in GNE myopathy. Excessive ubiquitinated unfolded proteins are exported by proteins that connect UPS and autophagy to autophagy system, which is activated as an alternative pathway for degradation.

  2. Identification of Genes and Pathways Related to Phenol Degradation in Metagenomic Libraries from Petroleum Refinery Wastewater

    Silva, Cynthia C.; Hayden, Helen; Sawbridge, Tim; Mele, Pauline; De Paula, Sérgio O.; Silva, Lívia C. F.; Vidigal, Pedro M. P.; Vicentini, Renato; Sousa, Maíra P.; Torres, Ana Paula R.; Santiago, Vânia M. J.; Oliveira, Valéria M.

    2013-01-01

    Two fosmid libraries, totaling 13,200 clones, were obtained from bioreactor sludge of petroleum refinery wastewater treatment system. The library screening based on PCR and biological activity assays revealed more than 400 positive clones for phenol degradation. From these, 100 clones were randomly selected for pyrosequencing in order to evaluate the genetic potential of the microorganisms present in wastewater treatment plant for biodegradation, focusing mainly on novel genes and pathways of phenol and aromatic compound degradation. The sequence analysis of selected clones yielded 129,635 reads at an estimated 17-fold coverage. The phylogenetic analysis showed Burkholderiales and Rhodocyclales as the most abundant orders among the selected fosmid clones. The MG-RAST analysis revealed a broad metabolic profile with important functions for wastewater treatment, including metabolism of aromatic compounds, nitrogen, sulphur and phosphorus. The predicted 2,276 proteins included phenol hydroxylases and cathecol 2,3- dioxygenases, involved in the catabolism of aromatic compounds, such as phenol, byphenol, benzoate and phenylpropanoid. The sequencing of one fosmid insert of 33 kb unraveled the gene that permitted the host, Escherichia coli EPI300, to grow in the presence of aromatic compounds. Additionally, the comparison of the whole fosmid sequence against bacterial genomes deposited in GenBank showed that about 90% of sequence showed no identity to known sequences of Proteobacteria deposited in the NCBI database. This study surveyed the functional potential of fosmid clones for aromatic compound degradation and contributed to our knowledge of the biodegradative capacity and pathways of microbial assemblages present in refinery wastewater treatment system. PMID:23637911

  3. Physiology of deletion mutants in the anaerobic β-myrcene degradation pathway in Castellaniella defragrans

    Lüddeke Frauke

    2012-09-01

    Full Text Available Abstract Background Monoterpenes present a large and versatile group of unsaturated hydrocarbons of plant origin with widespread use in the fragrance as well as food industry. The anaerobic β-myrcene degradation pathway in Castellaniella defragrans strain 65Phen differs from well known aerobic, monooxygenase-containing pathways. The initial enzyme linalool dehydratase-isomerase ldi/LDI catalyzes the hydration of β-myrcene to (S-(+-linalool and its isomerization to geraniol. A high-affinity geraniol dehydrogenase geoA/GeDH and a geranial dehydrogenase geoB/GaDH contribute to the formation of geranic acid. A genetic system was for the first time applied for the betaproteobacterium to prove in vivo the relevance of the linalool dehydratase-isomerase and the geraniol dehydrogenase. In-frame deletion cassettes were introduced by conjugation and two homologous recombination events. Results Polar effects were absent in the in-frame deletion mutants C. defragrans Δldi and C. defragrans ΔgeoA. The physiological characterization of the strains demonstrated a requirement of the linalool dehydratase-isomerase for growth on acyclic monoterpenes, but not on cyclic monoterpenes. The deletion of geoA resulted in a phenotype with hampered growth rate on monoterpenes as sole carbon and energy source as well as reduced biomass yields. Enzyme assays revealed the presence of a second geraniol dehydrogenase. The deletion mutants were in trans complemented with the broad-host range expression vector pBBR1MCS-4ldi and pBBR1MCS-2geoA, restoring in both cases the wild type phenotype. Conclusions In-frame deletion mutants of genes in the anaerobic β-myrcene degradation revealed novel insights in the in vivo function. The deletion of a high-affinity geraniol dehydrogenase hampered, but did not preclude growth on monoterpenes. A second geraniol dehydrogenase activity was present that contributes to the β-myrcene degradation pathway. Growth on cyclic monoterpenes

  4. Removal and Degradation Pathways of Sulfamethoxazole Present in Synthetic Municipal Wastewater via an Anaerobic Membrane Bioreactor

    Sanchez Huerta, Claudia

    2016-05-01

    The current global water crisis in addition to continues contamination of natural water bodies with harmful organic micropollutants (OMPs) have driven the development of new water treatment technologies that allow the efficient removal of such compounds. Among a long list of OMPs, antibiotics are considered as top priority pollutants to be treated due to their great resistance to biological treatments and their potential to develop bacterial resistance. Different approaches, such as membrane-based and advance oxidation processes have been proposed to alleviate or minimize antibiotics discharge into aquatic environments. However most of these processes are costly and generate either matrices with high concentration of OMPs or intermediate products with potentially greater toxicity or persistence. Therefore, this thesis proposes the study of an anaerobic membrane bioreactor (AnMBR) for the treatment of synthetic municipal wastewater containing sulfamethoxazole (SMX), a world widely used antibiotic. Besides the general evaluation of AnMBR performance in the COD removal and biogas production, this research mainly focuses on the SMX removal and its degradation pathway. Thus 5 SMX quantification was performed through solid phase extraction-liquid chromatography/mass spectrometry and the identification of its transformation products (TPs) was assessed by gas chromatography/mass spectrometry technique. The results achieved showed that, working under optimal conditions (35°C, pH 7 and ORP around -380 to -420 mV) and after a biomass adaptation period (maintaining 0.85 VSS/TSS ratio), the AnMBR process provided over 95% COD removal and 95-98% SMX removal, while allowing stable biogas composition and methane production (≈130 mL CH4/g CODremoved). Kinetic analysis through a batch test showed that after 24 h of biological reaction, AnMBR process achieved around 94% SMX removal, indicating a first order kinetic reaction with K= 0.119, which highlights the high degradation

  5. 5-羟甲基糠醛在 F-55果葡糖浆贮存过程中的变化研究%Research changes of 5-hydroxymethylfurfural in F55-fructose syrup storage

    李惠安; 伍伯良; 许永苗; 叶晓蕾; 黄智钧

    2014-01-01

    5-羟甲基糠醛(HMF)作为影响果葡糖浆风味的异味化合物之一,在贮存过程中的变化很可能直接影响到果葡糖浆制成品口感的好坏。研究了 HMF 在 F-55果葡糖浆贮存过程中的变化情况,结果表明温度升高会导致 HMF 含量在40 d 后达到最高峰。果葡糖浆在低温条件下贮存,且贮存期控制在40 d 内,可减少 HMF 对糖浆质量的影响。%5-hydroxymethylfurfural is one of the off-odor compounds that influence the flavor of high fructose syrup. Its changes in storage can influence the taste of fructose syrup. The changing situations in storage of F-55 fructose syrup were researched. Results showed when temperature raised and the storage time reached 40 days, the F-55 content increased to the peak; when temperature was controlled low and the storage time was within 40 days, the F-55 quality was less influ-enced by HMF.

  6. CrCl3催化果糖制备5-羟甲基糠醛的研究%CrCl3 Catalyzed Preparation of 5-Hydroxymethylfurfural from Fructose

    李向阳; 郑志锋; 宁静; 郑云武

    2012-01-01

    以CrCl3 · 6H2O为催化剂,考察溶剂种类、反应温度、反应时间、催化剂用量等条件对果糖制备5-羟甲基糠醛(HMF)产率的影响.结果表明,二甲基亚砜(DMSO)是果糖制备HMF的优良溶剂;以DMSO为溶剂,当反应温度为180℃、反应时间140 min、CrCl3·6H2O催化剂用量为果糖质量5%时,果糖制备HMF的产率可达49.2%.%Taking CrCl3 · 6H2O as catalyst, the effect of the solvent type, reaction temperature, reaction time and the amount of catalyst on the yield of 5 - hydroxymethylfurfural( HMF) from fructose was studied. The results showed that dimethyl sulfoxide (DMSO) was an ideal solvent to prepare HMF with fructose. The yield of HMF could be up to 49. 2% under the conditions of using DMSO as the solvent, taking 5% of CrCl3 · 6H2O as catalyst based on the weight of fructose to react for 140 min at 180℃

  7. Determination of 5- hydroxymethylfurfural (5-HMF) in over mature vinegar by HPLC%高效液相色谱法测定老陈醋中的5-羟甲基糠醛

    周婷婷; 杨瑞学; 宋弋; 张玉玉; 吕茜; 倪元颖; 李全宏

    2012-01-01

    利用高效液相色谱法测定老陈醋中5-羟甲基糠醛(5-HMF)的含量,以5%甲醇水溶液为流动相,采用C18色谱柱,在284nm波长条件下检测样品中的5-HMF。结果表明,该方法快速、准确,在0.0143~0.1001μg范围内线性相关系数为R2=0.9994,平均回收率88.27%~96.69%,相对标准偏差为2.09%~4.70%。%A method for the determination of 5-hydroxymethylfurfural by high-performance liquid chromatography in old mature vinegar was developed.Samples were analyzed on a Cls column at 284nm using a mixture of methanol and water(5:95, v/v)as the mobile phase.Within the linear range of 0.0143 - 0.1001μg , the method was accurate with the range of average recoveries rate and relative standard deviation of 88.27%-96.69% and 2.09% 4.70%, respectively.

  8. 离子液体中葡萄糖催化转化为5-羟甲基糠醛%Preparation of 5-hydroxymethylfurfural from glucose in ionic liquid

    徐英钊; 漆新华; 郭海心; 李陆杨

    2011-01-01

    以绿色溶剂离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)作为溶剂,六水合氯化铬(CrCl3.6H2O)为催化剂,研究了最重要的生物质衍生糖类葡萄糖向平台化合物5-羟甲基糠醛(HMF)的转化.该催化反应体系十分有效,在130℃下反应20min,HMF的产率可达到70%以上.并且该催化体系可以循环使用,经过5次的重复使用后仍保持稳定的活性.%An efficient process for preparation of 5-hydroxymethylfurfural ( HMF ) from glucose was developed with ionic liquid 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl])as solvent and CrCl3 as catalyst. A HMF yield of above 70% could be obtained at 130 ℃ in 20 min. Recycle of the ionic liquid and CrCl3 demonstrated constant activity after 5 cycles of use.

  9. Excretion pathways and ruminal disappearance of glyphosate and its degradation product aminomethylphosphonic acid in dairy cows.

    von Soosten, D; Meyer, U; Hüther, L; Dänicke, S; Lahrssen-Wiederholt, M; Schafft, H; Spolders, M; Breves, G

    2016-07-01

    From 6 balance experiments with total collection of feces and urine, samples were obtained to investigate the excretion pathways of glyphosate (GLY) in lactating dairy cows. Each experiment lasted for 26d. The first 21d served for adaptation to the diet, and during the remaining 5d collection of total feces and urine was conducted. Dry matter intake and milk yield were recorded daily and milk and feed samples were taken during the sampling periods. In 2 of the 6 experiments, at the sampling period for feces and urine, duodenal contents were collected for 5d. Cows were equipped with cannulas at the dorsal sac of the rumen and the proximal duodenum. Duodenal contents were collected every 2h over 5 consecutive days. The daily duodenal dry matter flow was measured by using chromium oxide as a volume marker. All samples (feed, feces, urine, milk and duodenal contents were analyzed for GLY and aminomethylphosphonic acid (AMPA). Overall, across the 6 experiments (n=32) the range of GLY intake was 0.08 to 6.67mg/d. The main proportion (61±11%; ±SD) of consumed GLY was excreted with feces; whereas excretion by urine was 8±3% of GLY intake. Elimination via milk was negligible. The GLY concentrations above the limit of quantification were not detected in any of the milk samples. A potential ruminal degradation of GLY to AMPA was derived from daily duodenal GLY flow. The apparent ruminal disappearance of GLY intake was 36 and 6%. In conclusion, the results of the present study indicate that the gastrointestinal absorption of GLY is of minor importance and fecal excretion represents the major excretion pathway. A degradation of GLY to AMPA by rumen microbes or a possible retention in the body has to be taken into account. PMID:27108173

  10. Photocatalytic degradation of metoprolol tartrate in suspensions of two TiO{sub 2}-based photocatalysts with different surface area. Identification of intermediates and proposal of degradation pathways

    Abramovic, Biljana, E-mail: biljana.abramovic@dh.uns.ac.rs [Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg D. Obradovica 3, 21000 Novi Sad (Serbia); Kler, Sanja, E-mail: sanja.kler@dh.uns.ac.rs [Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg D. Obradovica 3, 21000 Novi Sad (Serbia); Sojic, Daniela, E-mail: daniela.sojic@dh.uns.ac.rs [Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg D. Obradovica 3, 21000 Novi Sad (Serbia); Lausevic, Mila, E-mail: milal@tmf.bg.ac.rs [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Radovic, Tanja, E-mail: tradovic@tmf.bg.ac.rs [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Vione, Davide, E-mail: davide.vione@unito.it [Dipartimento di Chimica Analitica, Universita di Torino, Via Pietro Giuria 5, 10125 Torino (Italy)

    2011-12-30

    Highlights: Black-Right-Pointing-Pointer Kinetics and efficiency of photocatalytic degradation of the {beta}{sub 1}-blocker metoprolol tartrate (MET). Black-Right-Pointing-Pointer Two TiO{sub 2} specimens employed. Black-Right-Pointing-Pointer Faster degradation of MET, but slower mineralization, obtained with the TiO{sub 2} specimen having lower surface area. Black-Right-Pointing-Pointer Photocatalytic transformation pathways of MET including mineralization. - Abstract: This study investigates the efficiency of the photocatalytic degradation of metoprolol tartrate (MET), a widely used {beta}{sub 1}-blocker, in TiO{sub 2} suspensions of Wackherr's 'Oxyde de titane standard' and Degussa P25. The study encompasses transformation kinetics and efficiency, identification of intermediates and reaction pathways. In the investigated range of initial concentrations (0.01-0.1 mM), the photocatalytic degradation of MET in the first stage of the reaction followed approximately a pseudo-first order kinetics. The TiO{sub 2} Wackherr induced a significantly faster MET degradation compared to TiO{sub 2} Degussa P25 when relatively high substrate concentrations were used. By examining the effect of ethanol as a scavenger of hydroxyl radicals ({center_dot}OH), it was shown that the reaction with {center_dot}OH played the main role in the photocatalytic degradation of MET. After 240 min of irradiation the reaction intermediates were almost completely mineralized to CO{sub 2} and H{sub 2}O, while the nitrogen was predominantly present as NH{sub 4}{sup +}. Reaction intermediates were studied in detail and a number of them were identified using LC-MS/MS (ESI+), which allowed the proposal of a tentative pathway for the photocatalytic transformation of MET as a function of the TiO{sub 2} specimen.

  11. Photocatalytic degradation of metoprolol tartrate in suspensions of two TiO2-based photocatalysts with different surface area. Identification of intermediates and proposal of degradation pathways

    Highlights: ► Kinetics and efficiency of photocatalytic degradation of the β1-blocker metoprolol tartrate (MET). ► Two TiO2 specimens employed. ► Faster degradation of MET, but slower mineralization, obtained with the TiO2 specimen having lower surface area. ► Photocatalytic transformation pathways of MET including mineralization. - Abstract: This study investigates the efficiency of the photocatalytic degradation of metoprolol tartrate (MET), a widely used β1-blocker, in TiO2 suspensions of Wackherr's “Oxyde de titane standard” and Degussa P25. The study encompasses transformation kinetics and efficiency, identification of intermediates and reaction pathways. In the investigated range of initial concentrations (0.01–0.1 mM), the photocatalytic degradation of MET in the first stage of the reaction followed approximately a pseudo-first order kinetics. The TiO2 Wackherr induced a significantly faster MET degradation compared to TiO2 Degussa P25 when relatively high substrate concentrations were used. By examining the effect of ethanol as a scavenger of hydroxyl radicals (·OH), it was shown that the reaction with ·OH played the main role in the photocatalytic degradation of MET. After 240 min of irradiation the reaction intermediates were almost completely mineralized to CO2 and H2O, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied in detail and a number of them were identified using LC–MS/MS (ESI+), which allowed the proposal of a tentative pathway for the photocatalytic transformation of MET as a function of the TiO2 specimen.

  12. The histamine degradative uptake pathway in human vascular endothelial cells and skin fibroblasts is dependent on extracellular Na+ and Cl-

    We have previously reported that human vascular endothelial cells and skin fibroblasts carry out degradation of [3H]histamine by a mechanism involving two successive enzymatic steps: imidazole ring tele-methylation by the cells' endogenous methyltransferase and subsequent amine oxidation by an exogenous diamine oxidase. Both histamine and the exogenous second enzyme in the pathway associate with the cells via separate binding sites or receptors. The enzymatic degradation process results in cellular accumulation of the proximal and distal metabolites tele-methylhistamine and 1-methyl-4-imidazoleacetic acid (MIAA). We have now demonstrated that this two-stage histamine degradative pathway is dependent on Na+ and Cl- in the extracellular environment. Accumulation of [3H] histamine-derived products is partially inhibited under conditions of Na+ deprivation and more substantially when Cl- is also withdrawn. The individual tele-methylation and amine oxidation enzymatic reactions themselves are unaffected or actually facilitated under these conditions. This indicates that it is the cellular mechanism for uptake coupled to the degradative pathway which reflects the cation and anion dependency. Restoration of degradative uptake displays a biphasic Na+ concentration curve, suggesting that the uptake process may be driven by multiple components. These findings indicate a role for both inward Na+ and Cl- ion movement in this cellular degradative uptake mechanism

  13. Characteristics of the Thermal Degradation of Glucose and Maltose Solutions

    Woo, Koan Sik; Kim, Hyun Young; Hwang, In Guk; Lee, Sang Hoon; Jeong, Heon Sang

    2015-01-01

    In order to investigate the thermal degradation of glucose and maltose solutions after high temperature and high pressure (HTHP) treatment, the samples were treated at temperatures of 110, 120, 130, 140, and 150°C for 1, 2, 3, 4, and 5 h in an apparatus for HTHP treatment. Glucose and maltose solutions (20% w/w) were prepared by weighing glucose and maltose and adding distilled water in the desired proportion. Chromaticity, pH, organic acids, 5-hydroxymethylfurfural (HMF), free sugar contents...

  14. 磷钨酸盐催化果糖水解制备5-羟甲基糠醛%Conversion of fructose to 5-hydroxymethylfurfural catalyzed by heteropolyacid salts

    曲永水; 黄崇品; 宋彦磊; 张傑; 陈标华

    2012-01-01

    The dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) catalyzed by a variety of heteropolyacid salts has been studied. The highest 5-HMF yield was 99. 2% , obtained using a CePW12O40 catalyst in DMSO with 5% (mass fraction) of catalyst at 160℃ with reaction time 8 h. Furthermore, the conversion of fructose to 5-HMF catalyzed by heteropolyacid salts was conducted under microwave conditions. Compared with the conventional heating method, microwave heating showed a remarkable ability to both accelerate the reaction rate and improve the yield of 5-HMF. Moreover, the catalyst could be separated from the reaction mixture by a simple process at the end of the reaction and the catalyst could be reused six times without loss of activity.%以磷钨酸盐为催化剂,研究了其对果糖水解过程的影响,考察了反应时间、温度、催化剂种类及用量等因素 对5-羟甲基糠醛(5-HMF)收率的影响.实验结果表明:160℃时在二甲基亚砜(DMSO)中,以CePW12O40为催化剂,反应8h,5-HMF的收率最高为99.2%;该催化剂循环使用6次,仍能保持较高活性,5-HMF的收率仍能保持90.5%.与传统加热方法相比,微波加热可明显加快反应速率,缩短反应时间.

  15. Catalytic conversion of glucose to 5-hydroxymethylfurfural by metal halides%金属氯化物催化葡萄糖制备5-羟甲基糠醛

    朱萍; 范文元; 陈慧

    2015-01-01

    Using metal halides as catalyst and alkali metal halides as co-catalyst catalyzed glucose to dehydrate to make 5-hydroxymethylfurfural(5-HMF).Under the condition that the mass ratio of the material and catalyst is 10∶1 and the mass ratio of the material and co-catalyst is 1∶1,the following observations and studies were made on the influence of the metal halides、co-catalyst、solvent、temperature and time on the yield of 5-HMF.The results showed that,when NaI was used as co-catalyst for the AlCl3-catalyzed conversion of glucose at 130℃for 15 min in N,N-Dimethylacetamide (DMAC) the yield of 5-HMF is up to 30.6%.%用金属氯化物做催化剂,碱金属卤化物做助剂,催化葡萄糖脱水制备5-羟甲基糠醛(5-HMF).在原料与催化剂的质量比为10∶1,原料与助催化剂的质量比为1∶1的情况下,考察金属氯化物、助剂、溶剂、温度、时间对5-HMF收率的影响.结果显示:AlCl3做催化剂、NaI做助剂、溶剂为N,N-二甲基乙酰胺(DMAC)、反应温度为130℃、反应时间为15 min时5-HMF收率可达30.6%.

  16. Determination of 5-hydroxymethylfurfural in Zhenjiang Vinegar by HPLC%高效液相色谱法测定镇江香醋中5-羟甲基糠醛的含量

    张玉玉; 宋弋; 周婷婷; 吕茜; 杨瑞学; 李全宏

    2012-01-01

    A method for determination of 5-hydroxymethylfurfural by high-performance liquid chromatography in Zhenjiang vinegar was developed.Samples were analyzed on a Venusil XBP-C18 column with oven temperature of 30 ℃,using a mixture of methanol and water(5∶95,v/v) as the mobile phase with the flow rate of 1.0 mL/min,and detected at 284 nm.Within the linear range of 0.014 3~0.085 8 μg,the correlation coefficient was 0.999 9.The method was accurate with the average recoveries rate and relative standard deviation of 98.66% and 5.53%,respectively.%采用高效液相色谱法,对镇江香醋中5-羟甲基糠醛进行了定量分析.样品中的HMF含量的测定条件为:以甲醇-水溶液(体积比为5∶95)为流动相,流速为1.0 mL/min,采用Venusil XBP-C18色谱柱分离,柱温为30℃,UV检测器的检测波长为284 nm.定量分析结果表明,镇江香醋中HMF的含量为8.01 mg/kg.高效液相色谱法分析镇江香醋中HMF含量的方法测定准确,稳定性高,HMF在0.014 3~0.085 8μg的进样范围内线性相关系数为R2=0.999 9,平均回收率98.66%,相对标准偏差为5.53%.

  17. Study on the Generation of 5-Hydroxymethylfurfural in Chinese Medicine Injection%中药注射液中5-羟甲基糠醛来源探讨

    杨立伟; 刘潇潇; 李泳雪

    2012-01-01

    目的:通过对中药注射液中的5-羟甲基糠醛(5-HMF,5-Hydroxymethylfurfural)来源的初步探讨,为提高中药注射液的质量控制水平提供参考依据.方法:利用HPLC方法对注射液、中间体中的5-HMF和寡糖(葡萄糖、果糖及蔗糖)分别进行含量测定,确定5-HMF的来源;通过模拟生产过程考察不同寡糖的受热不稳定情况,来探讨5-HMF的生成机制.结果:只有在含有果糖的中间体中含有5 -HMF.模拟高温灭菌过程发现仅有果糖受热后转化生成5-羟甲基糠醛及其相关物质,而葡萄糖和蔗糖均没有转化.结论:并不是所有的寡糖在高温下都易转化5-HMF.在常见的三种糖中,只有果糖在高温下易转化生成5-HMF,而葡萄糖和蔗糖不易转化.建议对含果糖的中药注射液进行5-HMF的限度检查,而含葡萄糖和蔗糖的可以不控制该项目.

  18. 棉秆水热法制备5-羟甲基糠醛的动力学研究%Dynamics of 5-Hydroxymethylfurfural Preparation From Cotton Stalk with Hydrothermal Method

    周涛; 廖孝艳; 蒋崇文; 周礼超

    2013-01-01

    为了提高生物质中纤维素的降解率和5-羟甲基糠醛(5-hydroxymethylfurfural,5-HMF)的产率,对棉杆水热法降解生成5-HMF的过程进行了研究.通过分析各因素对纤维素降解和5-HMF合成的影响,确定最佳操作工艺条件;在催化剂SO42-/ZrO2存在与不存在时,对棉秆水热法制备5-HMF的过程进行了动力学分析.研究结果表明,催化剂SO42-/ZrO2添加质量分数为20%,在230℃下反应90 min时,纤维素降解率可达94.43%,5-HMF产率可达25.3%,相同条件下较无催化剂可提高79.4%.动力学研究表明催化剂SO42-/ZrO2对纤维素降解和5-HMF合成都具有正向催化效果.加入催化剂后,纤维素降解反应活化能由106.0 kJ·mol-1降低至96.7 kJ·mol-1,5-HMF合成反应活化能由119.4 kJ·mol-1降低至84.2 kJ·mol-1.

  19. Advances in Selective Hydrogenation of 5-Hydroxymethylfurfural into 2,5-Dimethylfuran%5-羟甲基糠醛选择性加氢制备2,5-二甲基呋喃的研究进展

    胡磊; 吴真; 许家兴; 孙勇; 林鹿; 徐宁; 戴本林

    2015-01-01

    The renewable liquid fuel,2,5-dimethylfuran (DMF),which can be produced by the selective hydrogenation of 5-hydroxymethylfurfural ( HMF ) with high energy density, high boiling point, high octane number, and water insolubility, has attracted more attention all over the world. According to its excellent physicochemical properties, the momentous application values, and the broad market prospects, the various catalytic systems and the latest research progress for the selective hydrogenation of HMF into DMF from the point of the diversity of hydrogen donors such as molecular hydrogen, formic acid, alcohols,and water are systematically summarized. The future research trends are prospected to offer the valuable ideas and advices for the selective hydrogenation of HMF and provide the theoretical references and technical supports for the industrial production and practical application of DMF.%鉴于2,5-二甲基呋喃(DMF)优良的理化性质、重要的应用价值和广阔的市场前景,着重从氢气、甲酸、醇类和水等不同氢供体的角度入手,系统归纳和总结了自2007年以来5-羟甲基糠醛(HMF)选择性加氢制备DMF 的催化反应体系及其最新的研究进展,并对今后HMF 选择性加氢制备DMF 的研究前景进行了展望。

  20. Catalytic Dehydration of Fructose to 5-hydroxymethylfurfural by Lanthanum Salt in Ethanol%乙醇中镧盐催化果糖脱水制备5-羟甲基糠醛的研究

    李秉正; 吴学众

    2011-01-01

    A preliminary study of catalytic dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) was carried out by using ethanol as solvent and lanthanum salt as catalyst. A comparison study indicated that the yields of 5-HMF in ethanol was much larger than those in water. LaCl3 had higher catalytic activity than La(NO3)3. Increasing the catalyst concentration can accelerate the reaction of dehydration of fructose to 5-HMF, but had little effect on increasing the maximum yield of 5-HMF. The yield of 5-HMF,as well as the reaction rate of dehydration of fructose to 5-HMF,increased along with the increase in temperature. The yield of 5-HMF up to 41.6 % was achieved after 20 min at 140℃.%以乙醇为反应溶剂,镧盐为催化剂催化果糖制备5-羟甲基糠醛(5-HMF)进行了初步研究.乙醇作为反应溶剂时,5-HMF产率远高于以水作为反应溶剂.氯化镧与硝酸镧相比具有更好的催化活性.提高催化剂浓度可以增大果糖转化为5-HMF的速率,但是对5-HMF的最大产率影响较小.随着反应温度的提高,果糖转化为5-HMF的速率增大,5-HMF的产率也明显提高.当反应温度为140℃时,反应20 min产率即可达到41.6%.

  1. Preparation of 5-Hydroxymethylfurfural From Glucose With Mesoporus Aluminophosphate as Catalyst%介孔磷酸铝催化葡萄糖制备5-羟甲基糠醛

    陈浩凤; 刘军; 刘春霞

    2015-01-01

    AlPO catalyst was synthesized from Al(NO3)3 and H3PO4 in the presence of citric acid. The samples were characterized by BET, XRD, FT-IR. The AlPO catalyst was evaluated for synthesis of 5-hydroxymethylfurfural from glucose. The effect of n(P)/n(Al), reaction temperature, reaction time, catalyst dosage and glucose quality on the synthesis was investigated. The results show that,under the condition of 10%(wt) catalyst, n(P)/n(Al)=1:1 and 10 mL DMSO as solvent, temperature 150 ℃,time 5 h,HMF yield can reach to 35%.%以硝酸铝和磷酸为原料,采用柠檬酸法制备了介孔磷酸铝材料 AlPO,利用 BET、XRD 和 FT-IR等分析方法对材料的物化性能进行了表征。通过催化葡萄糖转化制备5-羟甲基糠醛(HMF)的反应研究了其催化活性。对材料 P/Al 物质的量比,反应温度,反应时间,催化剂用量和反应底物浓度的考察表明,当n(P)/n(Al)=1:1时,10%(wt)的催化剂用量,在150℃条件下催化葡萄糖反应5 h 后,HMF 的收率可达35%。

  2. 酸性离子液体催化蔗糖转化合成5-羟甲基糠醛%Synthesis of 5-hydroxymethylfurfural from sucrose with acidic ionic liquids as the catalysts

    仝新利; 李梦然

    2011-01-01

    研究了离子液体催化蔗糖合成5-羟甲基糠醛的反应过程.合成并表征了N-甲基吡咯烷酮甲磺酸盐和N-甲基吡咯烷酮硫氢酸盐两种离子液体,并考察了两种离子液体在N,N-二甲基甲酰胺-溴化锂(DMF-LiBr)溶剂体系中催化蔗糖合成5-羟甲基糠醛的反应情况.结果表明,N-甲基吡咯烷酮甲磺酸盐催化效果较好,氮气保护下,在反应温度85℃、反应时间60 min和加入催化剂N-甲基吡咯烷酮甲磺酸盐占蔗糖物质的量的10.0%条件下,蔗糖脱水生成5-羟甲基糠醛的收率可达48.2%.%The synthesis of 5-hydroxymethylfurfural was studied using sucrose as mw material and ionic liquids as the catalysts. The ionic liquids including N-methyl-2-pyrrolidonium methyl sulfonate and N-methyl-2-pyrrolidonium hydrogen suffate was synthesized and characterized, and the catalytic dehydration of sucrose by these ionic liquids was investigated. The results indicated that N-methyl-2-pyrrolidonium methyl sulfonate exhibited better catalytic properties and 5-hydroxymethyffuffural yield of 48.2% was obtained under the condition as follows: reaction time 60 rain, reaction temperature 85 ℃, N2 atmosphere,N-methyl-2-pyrrolidonium methyl sulfonate dosage 10.0% (mole fraction) of sucrose and N, N-dimethylformamide-lithium bromide (DMF-LiBr) as the solvent.

  3. 蜜环菌发酵液中5-羟甲基糠醛提取工艺优化%Optimization of Extracting Process of 5-Hydroxymethylfurfural from Armillaria mellea Fermentation Broth

    陈楠; 焦连庆; 郑毅男; 于敏; 刘晓杰

    2012-01-01

    以蜜环菌发酵液为原料,通过正交试验优选5-羟甲基糠醛的提取工艺.超声提取蜜环菌发酵液中5-羟甲基糠醛,运用高效液相色谱法测定其含量,并用L9(33)正交试验设计,考察提取溶剂量(mLg)、提取时间、提取次数对提取率的影响.蜜环菌发酵液中5-羟甲基糠醛的最佳提取条件为:提取溶剂量6倍量、提取时间20min、提取次数2次.在最佳提取条件下,5-羟甲基糠醛提取率为6.12%.%The orthogonal experimental design method was used to optimize the extracting process of 5-Hydroxymethylfurfural (5-HMF) in the sample of A rmillaria mellea fermentation broth. 5-HMF was extracted by supersonic wave from Armillaria mellea fermentation broth. Then the content of 5-HMF was determined by high performance liquid chromatography. The L, (3s) orthogonal experimental design was used to study the influence of different dosage of extraction solvent (mL: g), extraction time, and the number of extraction on the extraction rate of 5-HMF. The optimum extraction condition: the dosage of extraction solvent was 6 times, extraction time was 20 min, and the number of extraction times was 2. 5-HMF's extraction rate was 6.12% in the best extraction conditions.

  4. Connecting Lignin-Degradation Pathway with Pre-Treatment Inhibitor Sensitivity of Cupriavidus necator

    Wang, W. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Yang, S. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Hunsinger, G. B. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pienkos, P. T. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Johnson, D. K. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2014-05-27

    In order to produce lignocellulosic biofuels economically, the complete release of monomers from the plant cell wall components, cellulose, hemicellulose, and lignin, through pre-treatment and hydrolysis (both enzymatic and chemical), and the efficient utilization of these monomers as carbon sources, is crucial. In addition, the identification and development of robust microbial biofuel production strains that can tolerate the toxic compounds generated during pre-treatment and hydrolysis is also essential. In this work, Cupriavidus necator was selected due to its capabilities for utilizing lignin monomers and producing polyhydroxylbutyrate (PHB), a bioplastic as well as an advanced biofuel intermediate. We characterized the growth kinetics of C. necator in pre-treated corn stover slurry as well as individually in the pre-sence of 11 potentially toxic compounds in the saccharified slurry. We found that C. necator was sensitive to the saccharified slurry produced from dilute acid pre-treated corn stover. Five out of 11 compounds within the slurry were characterized as toxic to C. necator, namely ammonium acetate, furfural, hydroxymethylfurfural (HMF), benzoic acid, and p-coumaric acid. Aldehydes (e.g., furfural and HMF) were more toxic than the acetate and the lignin degradation products benzoic acid and p-coumaric acid; furfural was identified as the most toxic compound. Although toxic to C. necator at high concentration, ammonium acetate, benzoic acid, and p-coumaric acid could be utilized by C. necator with a stimulating effect on C. necator growth. Consequently, the lignin degradation pathway of C. necator was reconstructed based on genomic information and literature. The efficient conversion of intermediate catechol to downstream products of cis,cis-muconate or 2-hydroxymuconate-6-semialdehyde may help improve the robustness of C. necator to benzoic acid and p-coumaric acid as well as improve PHB productivity.

  5. Connecting lignin-degradation pathway with pretreatment inhibitor sensitivity of Cupriavidus necator

    Wei eWang

    2014-05-01

    Full Text Available To produce lignocellulosic biofuels economically, the complete release of monomers from the plant cell wall components, cellulose, hemicellulose and lignin, through pretreatment and hydrolysis (both enzymatic and chemical, and the efficient utilization of these monomers as carbon sources, is crucial. In addition, the identification and development of robust microbial biofuel production strains that can tolerate the toxic compounds generated during pretreatment and hydrolysis is also essential. In this work, Cupriavidus necator was selected due to its capabilities for utilizing lignin monomers and producing polyhydroxylbutyrate (PHB, a bioplastic as well as an advanced biofuel intermediate. We characterized the growth kinetics of C. necator in pretreated corn stover slurry as well as individually in the presence of 11 potentially toxic compounds in the saccharified slurry. We found that C. necator was sensitive to the saccharified slurry produced from dilute acid pretreated corn stover. Five out of 11 compounds within the slurry were characterized as toxic to C. necator, namely ammonium acetate, furfural, hydroxymethylfurfural (HMF, benzoic acid, and p-coumaric acid. Aldehydes (e.g., furfural and HMF were more toxic than the acetate and the lignin degradation products benzoic acid and p-coumaric acid; furfural was identified as the most toxic compound. Although toxic to C. necator at high concentration, ammonium acetate, benzoic acid, and p-coumaric acid could be utilized by C. necator with a stimulating effect on C. necator growth. Consequently, the lignin degradation pathway of C. necator was reconstructed based on genomic information and literature. The efficient conversion of intermediate catechol to downstream products of cis,cis-muconate or 2-hydroxymuconate-6-semialdehyde may help improve the robustness of C. necator to benzoic acid and p-coumaric acid as well as improve PHB productivity.

  6. The Whole Genome Sequence of Sphingobium chlorophenolicum L-1: Insights into the Evolution of the Pentachlorophenol Degradation Pathway

    Copley, Shelley D. [University of Colorado; Rokicki, Joseph [University of Colorado; Turner, Pernilla [University of Colorado; Daligault, Hajnalka E. [Los Alamos National Laboratory (LANL); Nolan, Matt [U.S. Department of Energy, Joint Genome Institute; Land, Miriam L [ORNL

    2012-01-01

    Sphingobium chlorophenolicum Strain L-1 can mineralize the toxic pesticide pentachlorophenol (PCP). We have sequenced the genome of S. chlorophenolicum Strain L-1. The genome consists of a primary chromosome that encodes most of the genes for core processes, a secondary chromosome that encodes primarily genes that appear to be involved in environmental adaptation, and a small plasmid. The genes responsible for degradation of PCP are found on chromosome 2. We have compared the genomes of S. chlorophenolicum Strain L-1 and Sphingobium japonicum, a closely related Sphingomonad that degrades lindane. Our analysis suggests that the genes encoding the first three enzymes in the PCP degradation pathway were acquired via two different horizontal gene transfer events, and the genes encoding the final two enzymes in the pathway were acquired from the most recent common ancestor of these two bacteria.

  7. Insights from 14C into C loss pathways in degraded peatlands

    Evans, Martin; Evans, Chris; Allott, Tim; Stimson, Andrew; Goulsbra, Claire

    2016-04-01

    Peatlands are important global stores of terrestrial carbon. Lowered water tables due to changing climate and direct or indirect human intervention produce a deeper aerobic zone and have the potential to enhance loss of stored carbon from the peat profile. The quasi continuous accumulation of organic matter in active peatlands means that the age of fluvial dissolved organic carbon exported from peatland systems is related to the source depth in the peat profile. Consequently 14C analysis of DOC in waters draining peatlands has the potential not only to tell us about the source of fluvial carbon and the stability of the peatland but also about the dominant hydrological pathways in the peatland system. This paper will present new radiocarbon determinations from peatland streams draining the heavily eroded peatlands of the southern Pennine uplands in the UK. These blanket peatland systems are highly degraded, with extensive bare peat and gully erosion resulting from air pollution during the industrial revolution, overgrazing, wildfire and climatic changes. Deep and extensive gullying has significantly modified the hydrology of these systems leading to local and more widespread drawdown of water table. 14C data from DOC in drainage waters are presented from two catchments; one with extensive gully erosion and the other with a combination of gully erosion and sheet erosion of the peat. At the gully eroded site DOC in drainage waters is as old as 160 BP but at the site with extensive sheet erosion dates of up to 1069 BP are amongst the oldest recorded from blanket peatland globally These data indicate significant degradation of stored carbon from the eroding peatlands. Initial comparisons of the 14C data with modelled water table for the catchments and depth-age curves for catchment peats suggests that erosion of the peat surface, allowing decomposition of exposed older organic material is a potential mechanism producing aged carbon from the eroded catchment. This

  8. REGγ regulates ERα degradation via ubiquitin–proteasome pathway in breast cancer

    Chai, Fan; Liang, Yan [Breast Disease Center, Southwest Hospital, Third Military Medical University, Chongqing 400038 (China); Bi, Jiong [Laboratory of General Surgery, First Affiliated Hospital, Sun Yet-sen University, Guangzhou 510080 (China); Chen, Li; Zhang, Fan [Breast Disease Center, Southwest Hospital, Third Military Medical University, Chongqing 400038 (China); Cui, Youhong [Institute of Pathology and Southwest Cancer Center, Southwest Hospital, Third Military Medical University, Chongqing 400038 (China); Jiang, Jun, E-mail: jcbd@medmail.com.cn [Breast Disease Center, Southwest Hospital, Third Military Medical University, Chongqing 400038 (China)

    2015-01-02

    Highlights: • High expression of REGγ is correlated with ERα status and poor clinical features. • Cell growth, mobility and invasion are significantly impaired by REGγ knockdown. • REGγ indirectly regulates ERα protein expression. - Abstract: REGγ is a proteasome coactivator which regulates proteolytic activity in eukaryotic cells. Abundant lines of evidence have showed that REGγ is over expressed in a number of human carcinomas. However, its precise role in the pathogenesis of cancer is still unclear. In this study, by examining 200 human breast cancer specimens, we demonstrated that REGγ was highly expressed in breast cancers, and the expression of REGγ was positively correlated with breast cancer patient estrogen receptor alpha (ERα) status. Moreover, the expression of REGγ was found positively associated with poor clinical features and low survival rates in ERα positive breast cancer patients. Further cell culture studies using MCF7 and BT474 breast cancer cell lines showed that cell proliferation, motility, and invasion capacities were decreased significantly by REGγ knockdown. Lastly, we demonstrated that REGγ indirectly regulates the degradation of ERα protein via ubiquitin–proteasome pathway. In conclusion, our findings provide the evidence that REGγ expression was positively correlated with ERα status and poor clinical prognosis in ERα positive breast cancer patients. As well, we disclose a new connection between the two molecules that are both highly expressed in most breast cancer cases.

  9. Chemotaxis and degradation of organophosphate compound by a novel moderately thermo-halo tolerant Pseudomonas sp. strain BUR11: evidence for possible existence of two pathways for degradation.

    Pailan, Santanu; Saha, Pradipta

    2015-01-01

    An organophosphate (OP) degrading chemotactic bacterial strain BUR11 isolated from an agricultural field was identified as a member of Pseudomonas genus on the basis of its 16S rRNA gene sequence. The strain could utilize parathion, chlorpyrifos and their major hydrolytic intermediates as sole source of carbon for its growth and exhibited positive chemotactic response towards most of them. Optimum concentration of parathion for its growth was recorded to be 200 ppm and 62% of which was degraded within 96 h at 37 °C. Growth studies indicated the strain to be moderately thermo-halo tolerant in nature. Investigation based on identification of intermediates of parathion degradation by thin layer chromatography (TLC), high performance liquid chromatography (HPLC), gas chromatography (GC) and liquid chromatography mass spectrometry (LC-MS/MS) provided evidence for possible existence of two pathways. The first pathway proceeds via 4-nitrophenol (4-NP) while the second proceeds through formation of 4-aminoparathion (4-APar), 4-aminophenol (4-AP) and parabenzoquinone (PBQ). This is the first report of chemotaxis towards organophosphate compound by a thermo-halo tolerant bacterium. PMID:26587344

  10. Degradative intracellular transport of antisecretory component in cultured hepatocytes. An alternate pathway for the immunoglobulin A receptor

    The liver efficiently transports dimeric immunoglobulin A (dIgA) from blood to bile in a direct, nonlysosomal pathway involving smooth-surfaced vesicles. Secretory component (SC), the plasma membrane receptor for dIgA, is released into bile still bound to its ligand by disulfide bridges. Rabbit IgG antirat SC binds specifically to plasma membrane SC, yet the biliary secretion of anti-SC is markedly lower than that of dIgA, suggesting that the IgG antibodies utilize an alternate transhepatocellular pathway. Uptake of commercially available antihuman SC conjugated to horseradish peroxidase was examined by quantitative electron microscopic immunocytochemistry using primary rat hepatocyte monolayer cultures. Coincubation with human polymeric IgA, rabbit antiserum to rat SC, free human SC, human secretory IgA, and rat bile, all significantly suppressed uptake of anti-SC-horseradish peroxidase, thus demonstrating the specificity of the labeled antibody. Coated vesicles accounted for greater than 70% of the total uptake of either the anti-SC-horseradish peroxidase preparation or colloidal gold-labeled IgG antirat SC. Both compounds could also be observed in other structures associated with the degradative pathway, i.e., multivesicular bodies and lysosomes. Moreover, the extent to which 125I-anti-SC was degraded was significantly greater than that of 125I-dIgA. These data demonstrate that dIgA and anti-SC utilize different intracellular pathways, with anti-SC undergoing lysosomal degradation

  11. Androgens upregulate Cdc25C protein by inhibiting its proteasomal and lysosomal degradation pathways.

    Yu-Wei Chou

    Full Text Available Cdc25C is a cell cycle protein of the dual specificity phosphatase family essential for activating the cdk1/Cyclin B1 complex in cells entering into mitosis. Since altered cell cycle is a hallmark of human cancers, we investigated androgen regulation of Cdc25C protein in human prostate cancer (PCa cells, including androgen-sensitive (AS LNCaP C-33 cells and androgen-independent (AI LNCaP C-81 as well as PC-3 cells. In the regular culture condition containing fetal bovine serum (FBS, Cdc25C protein levels were similar in these PCa cells. In a steroid-reduced condition, Cdc25C protein was greatly decreased in AS C-33 cells but not AI C-81 or PC-3 cells. In androgen-treated C-33 cells, the Cdc25C protein level was greatly elevated, following a dose- and a time-dependent manner, correlating with increased cell proliferation. This androgen effect was blocked by Casodex, an androgen receptor blocker. Nevertheless, epidermal growth factor (EGF, a growth stimulator of PCa cells, could only increase Cdc25C protein level by about 1.5-fold. Altered expression of Cdc25C in C-33 cells and PC-3 cells by cDNA and/or shRNA transfection is associated with the corresponding changes of cell growth and Cyclin B1 protein level. Actinomycin D and cycloheximide could only partially block androgen-induced Cdc25C protein level. Treatments with both proteasomal and lysosomal inhibitors resulted in elevated Cdc25C protein levels. Immunoprecipitation revealed that androgens reduced the ubiquitination of Cdc25C proteins. These results show for the first time that Cdc25C protein plays a role in regulating PCa cell growth, and androgen treatments, but not EGF, greatly increase Cdc25C protein levels in AS PCa cells, which is in part by decreasing its degradation. These results can lead to advanced PCa therapy via up-regulating the degradation pathways of Cdc25C protein.

  12. Porcine arterivirus activates the NF-κB pathway through IκB degradation

    Nuclear factor-kappaB (NF-κB) is a critical regulator of innate and adaptive immune function as well as cell proliferation and survival. The present study demonstrated for the first time that a virus belonging to the Arteriviridae family activates NF-κB in MARC-145 cells and alveolar macrophages. In porcine reproductive and respiratory syndrome virus (PRRSV)-infected cells, NF-κB activation was characterized by translocation of NF-κB from the cytoplasm to the nucleus, increased DNA binding activity, and NF-κB-regulated gene expression. NF-κB activation was increased as PRRSV infection progressed and in a viral dose-dependent manner. UV-inactivation of PRRSV significantly reduced the level of NF-κB activation. Degradation of IκB protein was detected late in PRRSV infection, and overexpression of the dominant negative form of IκBα (IκBαDN) significantly suppressed NF-κB activation induced by PRRSV. However, IκBαDN did not affect viral replication and viral cytopathic effect. PRRSV infection induced oxidative stress in cells by generating reactive oxygen species (ROS), and antioxidants inhibited NF-κB DNA binding activity in PRRSV-infected cells, suggesting ROS as a mechanism by which NF-κB was activated by PRRSV infection. Moreover, NF-κB-dependent expression of matrix metalloproteinase (MMP)-2 and MMP-9 was observed in PRRSV-infected cells, an observation which implies that NF-κB activation is a biologically significant aspect of PRRSV pathogenesis. The results presented here provide a basis for understanding molecular pathways of pathology and immune evasion associated with disease caused by PRRSV

  13. Determination of 5-hydroxymethylfurfural in fruit juice concentrate and fruit fructose by HPLC%高效液相色谱法测定浓缩果汁及水果果糖中5-羟甲基糠醛

    孔祥虹; 李小军; 何强; 高军刚; 吴双民

    2012-01-01

    A HPLC method was established for the determination of 5-hydroxymethylfurfural(5-HMF)in fruit juice concentrate and fruit fructose.The sample was diluted with water, separated by using Inetrsil ODS-3 C18 (250mm × 4.6mm,5μm) chromatographic column.The method showed that a good linearity within the range of 1.0-25.0mg/L( r = 9998).The LOD of 5-HMF was 0.2mg/kg, the average recoveries from 82.2% to 103.3%, the relative standard deviation(RSD) from 0.62% to 1.25%.The HPLC method is quick, accurate, sensitive and suitable for determining the content of 5-HMF in fruit juice concentrate.%建立了浓缩苹果汁、浓缩梨汁和水果果糖中的5-羟甲基糠醛的高效液相色谱(HPLC)检测方法。样品用甲醇溶解后,经水稀释,Inetrsil ODS-3 C18(250mm×4.6mm,5μm)色谱柱分离,紫外检测器在282nm处进行检测;5-羟甲基糠醛在1.0-25.0mg/L范围内线性关系良好,相关系数为0.9998,回收率为82.2%~103.3%,精密度(RSD)为0.62%-1.25%,方法的检出限(LOD)为0.2mg/kg。本方法具有快速、简单、灵敏度高、适用范围广等特点,可以满足果汁中5-羟甲基糠醛的分析要求。

  14. Study on antioxidation capability of fructose-oligosaccharide and 5- hydroxymethylfurfural%低聚蔗果糖及其5-羟甲基糠醛抗氧化能力研究

    宋玉蓉; 刘云; 乐国伟; 张蓉; 施用晖

    2010-01-01

    目的:研究微渡辅助合成低聚蔗果糖(W-FOS)及其在合成过程中产生的5-HMF(5-hydroxymethylfurfural)抗氧化能力.方法:测定W-FOS及5-HMF清除DPPH、ABTS~+能力;清洁级昆明小鼠60只,随机分6组:对照组、高脂组(脂肪含量20%)、高脂+0.5%E-FOS(酶法合成低聚果糖)组、高脂+0.5%W-FOS+5-HMF组(5-HMF含量分别为0.20%、0.02%、0.0%).饲喂5w后测定机体抗氧化指标水平.结果:W-FOS具有清除DPPH、ABTS~+能力,且5-HMF能提高其清除力;E-FOS、W-FOS+5-HMF组能使高脂日粮小鼠血脂水平得到显著恢复(P<0.05);W-FOS+5-HMF组能使高脂日粮小鼠血脂水平显著降低(P<0.05);添加含中低、高水平5-HMF的W-FOS分别能显著恢复高脂日粮小鼠血浆T-AOC、CAT、MDA、ROS和CAT、ROS水平;含中低水平5-HMF的W-FOS对高脂日粮小鼠肝脏GSH-Px、MDA、ROS的保护作用优于高水平5-HMF的W-FOS.结论:W-FOS和5-HMF都具有清除DPPH、ABTS~+的能力;0.5%W-FOS及其5-HMF水平为0.00%~0.02%对,对高脂日粮小鼠的血脂水平、血浆、肝脏的抗氧化能力均具有良好的保护作用.

  15. Determination of the Contents of 5-hydroxymethylfurfural in DangShen by HPLC%HPLC法测定党参中5-羟甲基糠醛的含量

    王宇; 张玉兰

    2014-01-01

    目的:建立党参中己糖降解产物5-羟甲基糠醛(5-HMF)的含量测定方法,对党参药材中的5-羟甲基糠醛进行含量测定。方法:采用Agilent Extend-C18(250 mm×4.6 mm,5μm)色谱柱,以乙腈-0.3%醋酸溶液(3∶97)为流动相,检测波长284 nm,流速1.0 mL/min,柱温30℃。结果:5-羟甲基糠醛在浓度为2.538~63.45μg/mL范围内与峰面积具有良好的线性关系(r=0.9998),精密度和重复性的RSD分别为0.8%和2.5%。结论:该方法操作简便,结果准确可靠,可用于党参中5-羟甲基糠醛的含量测定,为进一步评价党参的安全性提供参考。%Objective:To establish the determination method for 5-hydroxymethylfurfural (5-HMF) in Dang-Shen (Radix Codonopsis Pilosulae) and determine its contents. Methods:Agilent Extend-C18 (250 mm×4.6 mm, 5μm) chromatographic column was adopted with the mobile phase of acetonitrile-0.3% acetum (3:97), detection wave-length was 284nm, flow rate was 1.0mL/min, column temperature was 30℃. Results:It showed better linear rela-tionship in the range between 2.538 and 63.45μg/mL and peak area (r=0.999 8), accuracy and repeatability RSD were 0.8%and 2.5%respectively. Conclusion:The method, simple and reliable, could be used to the determination of 5-HMF contained in DangShen, which could provide reference for further assessment of the safety of DangShen.

  16. Different pathways of degradation of SP-A and saturated phosphatidylcholine by alveolar macrophages.

    Baritussio, A; Alberti, A; Armanini, D; Meloni, F; Bruttomesso, D

    2000-07-01

    Alveolar macrophages degrade surfactant protein (SP) A and saturated phosphatidycholine [dipalmitoylphosphatidylcholine (DPPC)]. To clarify this process, using rabbit alveolar macrophages, we analyzed the effect of drugs known to affect phagocytosis, pinocytosis, clathrin-mediated uptake, caveolae, the cytoskeleton, lysosomal pH, protein kinase C, and phosphatidylinositol 3-kinase (PI3K) on the degradation of SP-A and DPPC. We found the following: 1) SP-A binds to the plasma membrane, is rapidly internalized, and then moves toward degradative compartments. Uptake could be clathrin mediated, whereas phagocytosis, pinocytosis, or the use of caveolae are less likely. An intact cytoskeleton and an acidic milieu are necessary for the degradation of SP-A. 2) Stimulation of protein kinase C increases the degradation of SP-A. 3) PI3K influences the degradation of SP-A by regulating both the speed of internalization and subsequent intracellular steps, but its inhibition does not prevent SP-A from reaching the lysosomal compartment. 4) The degradation of DPPC is unaffected by most of the treatments able to influence the degradation of SP-A. Thus it appears that DPPC is degraded by alveolar macrophages through mechanisms very different from those utilized for the degradation of SP-A. PMID:10893207

  17. Regulation of enzymes of the 3,5-xylenol-degradative pathway in Pseudomonas putida: evidence for a plasmid.

    Hopper, D. J.; Kemp, P D

    1980-01-01

    Constitutive synthesis of enzymes responsible for methyl group oxidation in 3,5-xylenol degradation and an associated p-cresol methylhydroxylase in Pseudomonas putida NCIB 9869 was shown by their retention at high specific activities in cells transferred from 3,5-xylenol medium to glutamate medium. The specific activities of other enzymes of the 3,5-xylenol pathway declined upon removal of aromatic substrate, consistent with their inducible control. Specific activities of the methyl-oxidizing...

  18. Microbial oil-degradation under mild hydrostatic pressure (10 MPa): which pathways are impacted in piezosensitive hydrocarbonoclastic bacteria?

    Alberto Scoma; Marta Barbato; Emma Hernandez-Sanabria; Francesca Mapelli; Daniele Daffonchio; Sara Borin; Nico Boon

    2016-01-01

    Oil spills represent an overwhelming carbon input to the marine environment that immediately impacts the sea surface ecosystem. Microbial communities degrading the oil fraction that eventually sinks to the seafloor must also deal with hydrostatic pressure, which linearly increases with depth. Piezosensitive hydrocarbonoclastic bacteria are ideal candidates to elucidate impaired pathways following oil spills at low depth. In the present paper, we tested two strains of the ubiquitous Alcanivora...

  19. New pathway for degradation of sulfonated azo dyes by microbial peroxidases of Phanerochaete chrysosporium and Streptomyces chromofuscus.

    Goszczynski, S; Paszczynski, A; Pasti-Grigsby, M B; Crawford, R L; Crawford, D. L.

    1994-01-01

    Pathways for the degradation of 3,5-dimethyl-4-hydroxy-azobenzene-4'-sulfonic acid (I) and 3-methoxy-4-hydroxyazobenzene-4'-sulfonamide (II) by the manganese peroxidase and ligninase of Phanerochaete chrysosporium and by the peroxidase of Streptomyces chromofuscus have been proposed. Twelve metabolic products were found, and their mechanisms of formation were explained. Preliminary oxidative activation of the dyes resulted in the formation of cationic species, making the molecules vulnerable ...

  20. TRIM22 Inhibits the TRAF6-stimulated NF-κB Pathway by Targeting TAB2 for Degradation

    Hui Qiu; Fang Huang; Han Xiao; Binlian Sun; Rongge Yang

    2013-01-01

    Tripartite motif containing 22 (TRIM22),a member of the TRIM/RBCC family,has been reported to activate the nuclear factor-kappa B (NF-κB) pathway in unstimulated macrophage cell lines,but the detailed mechanisms governing this activation remains unclear.We investigated this mechanism in HEK293T cells.We found that overexpression of TRIM22 could activate the NF-κB pathway and conversely,could inhibit the tumor necrosis factor receptor-associated factor 6 (TRAF6)-stimulated NF-κB pathway in HEK293T cells.Further experiments showed that TRIM22 could decrease the self-ubiquitination of TRAF6,and interact with and degrade transforming growth factor-β activated kinase 1 binding protein 2 (TAB2),and that these effects could be partially rescued by a TRIM22 RING domain deletion mutant.Collectively,our data indicate that overexpression of TRIM22 may negatively regulate the TRAF6-stimulated NF-κB pathway by interacting with and degrading TAB2.

  1. Adsorption and Photocatalytic Decomposition of the β-Blocker Metoprolol in Aqueous Titanium Dioxide Suspensions: Kinetics, Intermediates, and Degradation Pathways

    Violette Romero

    2013-01-01

    Full Text Available This study reports the photocatalytic degradation of the β-blocker metoprolol (MET using TiO2 suspended as catalyst. A series of photoexperiments were carried out by a UV lamp, emitting in the 250–400 nm range, providing information about the absorption of radiation in the photoreactor wall. The influence of the radiation wavelength on the MET photooxidation rate was investigated using a filter cutting out wavelengths shorter than 280 nm. Effects of photolysis and adsorption at different initial pH were studied to evaluate noncatalytic degradation for this pharmaceutical. MET adsorption onto titania was fitted to two-parameter Langmuir isotherm. From adsorption results it appears that the photocatalytic degradation can occur mainly on the surface of TiO2. MET removed by photocatalysis was 100% conditions within 300 min, while only 26% was achieved by photolysis at the same time. TiO2 photocatalysis degradation of MET in the first stage of the reaction followed approximately a pseudo-first-order model. The major reaction intermediates were identified by LC/MS analysis such as 3-(propan-2-ylaminopropane-1,2-diol or 3-aminoprop-1-en-2-ol. Based on the identified intermediates, a photocatalytic degradation pathway was proposed, including the cleavage of side chain and the hydroxylation addition to the parent compounds.

  2. Metabolism of 2-Chloro-4-Nitroaniline via Novel Aerobic Degradation Pathway by Rhodococcus sp. Strain MB-P1

    Khan, Fazlurrahman; Pal, Deepika; Vikram, Surendra; Cameotra, Swaranjit Singh

    2013-01-01

    2-chloro-4-nitroaniline (2-C-4-NA) is used as an intermediate in the manufacture of dyes, pharmaceuticals, corrosion inhibitor and also used in the synthesis of niclosamide, a molluscicide. It is marked as a black-listed substance due to its poor biodegradability. We report biodegradation of 2-C-4-NA and its pathway characterization by Rhodococcus sp. strain MB-P1 under aerobic conditions. The strain MB-P1 utilizes 2-C-4-NA as the sole carbon, nitrogen, and energy source. In the growth medium, the degradation of 2-C-4-NA occurs with the release of nitrite ions, chloride ions, and ammonia. During the resting cell studies, the 2-C-4-NA-induced cells of strain MB-P1 transformed 2-C-4-NA stoichiometrically to 4-amino-3-chlorophenol (4-A-3-CP), which subsequently gets transformed to 6-chlorohydroxyquinol (6-CHQ) metabolite. Enzyme assays by cell-free lysates prepared from 2-C-4-NA-induced MB-P1 cells, demonstrated that the first enzyme in the 2-C-4-NA degradation pathway is a flavin-dependent monooxygenase that catalyzes the stoichiometric removal of nitro group and production of 4-A-3-CP. Oxygen uptake studies on 4-A-3-CP and related anilines by 2-C-4-NA-induced MB-P1 cells demonstrated the involvement of aniline dioxygenase in the second step of 2-C-4-NA degradation. This is the first report showing 2-C-4-NA degradation and elucidation of corresponding metabolic pathway by an aerobic bacterium. PMID:23614030

  3. Metabolism of 2-chloro-4-nitroaniline via novel aerobic degradation pathway by Rhodococcus sp. strain MB-P1.

    Fazlurrahman Khan

    Full Text Available 2-chloro-4-nitroaniline (2-C-4-NA is used as an intermediate in the manufacture of dyes, pharmaceuticals, corrosion inhibitor and also used in the synthesis of niclosamide, a molluscicide. It is marked as a black-listed substance due to its poor biodegradability. We report biodegradation of 2-C-4-NA and its pathway characterization by Rhodococcus sp. strain MB-P1 under aerobic conditions. The strain MB-P1 utilizes 2-C-4-NA as the sole carbon, nitrogen, and energy source. In the growth medium, the degradation of 2-C-4-NA occurs with the release of nitrite ions, chloride ions, and ammonia. During the resting cell studies, the 2-C-4-NA-induced cells of strain MB-P1 transformed 2-C-4-NA stoichiometrically to 4-amino-3-chlorophenol (4-A-3-CP, which subsequently gets transformed to 6-chlorohydroxyquinol (6-CHQ metabolite. Enzyme assays by cell-free lysates prepared from 2-C-4-NA-induced MB-P1 cells, demonstrated that the first enzyme in the 2-C-4-NA degradation pathway is a flavin-dependent monooxygenase that catalyzes the stoichiometric removal of nitro group and production of 4-A-3-CP. Oxygen uptake studies on 4-A-3-CP and related anilines by 2-C-4-NA-induced MB-P1 cells demonstrated the involvement of aniline dioxygenase in the second step of 2-C-4-NA degradation. This is the first report showing 2-C-4-NA degradation and elucidation of corresponding metabolic pathway by an aerobic bacterium.

  4. Metabolism of 2-chloro-4-nitroaniline via novel aerobic degradation pathway by Rhodococcus sp. strain MB-P1.

    Khan, Fazlurrahman; Pal, Deepika; Vikram, Surendra; Cameotra, Swaranjit Singh

    2013-01-01

    2-chloro-4-nitroaniline (2-C-4-NA) is used as an intermediate in the manufacture of dyes, pharmaceuticals, corrosion inhibitor and also used in the synthesis of niclosamide, a molluscicide. It is marked as a black-listed substance due to its poor biodegradability. We report biodegradation of 2-C-4-NA and its pathway characterization by Rhodococcus sp. strain MB-P1 under aerobic conditions. The strain MB-P1 utilizes 2-C-4-NA as the sole carbon, nitrogen, and energy source. In the growth medium, the degradation of 2-C-4-NA occurs with the release of nitrite ions, chloride ions, and ammonia. During the resting cell studies, the 2-C-4-NA-induced cells of strain MB-P1 transformed 2-C-4-NA stoichiometrically to 4-amino-3-chlorophenol (4-A-3-CP), which subsequently gets transformed to 6-chlorohydroxyquinol (6-CHQ) metabolite. Enzyme assays by cell-free lysates prepared from 2-C-4-NA-induced MB-P1 cells, demonstrated that the first enzyme in the 2-C-4-NA degradation pathway is a flavin-dependent monooxygenase that catalyzes the stoichiometric removal of nitro group and production of 4-A-3-CP. Oxygen uptake studies on 4-A-3-CP and related anilines by 2-C-4-NA-induced MB-P1 cells demonstrated the involvement of aniline dioxygenase in the second step of 2-C-4-NA degradation. This is the first report showing 2-C-4-NA degradation and elucidation of corresponding metabolic pathway by an aerobic bacterium. PMID:23614030

  5. Characterization of a new degradation product of nifedipine formed on catalysis by atenolol: A typical case of alteration of degradation pathway of one drug by another.

    Handa, Tarun; Singh, Saranjit; Singh, Inder Pal

    2014-02-01

    An increasing interest is being shown throughout the world on the use of fixed-dose combinations of drugs in the therapy of select diseases, like cardiovascular diseases, due to their multiple advantages. Though the main criterion for combining drugs in a single dosage form is the rationale, but consideration like stability of formulation is equally important, due to an added aspect of drug-drug interaction. The objective of this study was to evaluate interaction among the drugs in an antihypertensive combination of nifedipine and atenolol. Nifedipine is a known light sensitive drug, which degrades via intra-molecular mechanisms to nitro- and nitroso-pyridine analogs, along with a few minor secondary products that are formed through inter-molecular interactions amongst primary degradation products and their intermediates. Atenolol is reasonably stable weakly basic drug that is mainly hydrolyzed at acetamide terminal amide moiety to its corresponding carboxylic acid. To the best of our knowledge, there is no known information on chemical compatibility among the two drugs. The present study involved subjecting of nifedipine, atenolol and their combination to a variety of accelerated and stress conditions. HPLC studies revealed formation of a new product in the mixture of two drugs (∼2%), which was also generated from nifedipine alone, but at trace levels (<0.1%). The product was isolated by preparative chromatography and subjected to indepth studies for its characterization. Ultra-violet, FT-IR, mass spectrometric and nuclear magnetic resonance spectroscopic studies highlighted that the principal photo-degradation pathway of nifedipine was modified and diverted in the presence of atenolol. To verify the same, a study was conducted employing two other β-blockers with similar structures to atenolol, and the same product was formed in relatively higher quantity therein also. The new product is postulated to be produced as a result of rearrangement of hydroxylamine

  6. Def defines a conserved nucleolar pathway that leads p53 to proteasome-independent degradation

    Tao, Ting; Hui SHI; Guan, Yihong; Huang, Delai; Chen, Ye; Lane, David P; Chen, Jun; Peng, Jinrong

    2013-01-01

    p53 protein turnover through the ubiquitination pathway is a vital mechanism in the regulation of its transcriptional activity; however, little is known about p53 turnover through proteasome-independent pathway(s). The digestive organ expansion factor (Def) protein is essential for the development of digestive organs. In zebrafish, loss of function of def selectively upregulates the expression of p53 response genes, which raises a question as to what is the relationship between Def and p53. W...

  7. The Rtr1p CTD phosphatase autoregulates its mRNA through a degradation pathway involving the REX exonucleases

    Hodko, Domagoj; Ward, Taylor; Chanfreau, Guillaume

    2016-01-01

    Rtr1p is a phosphatase that impacts gene expression by modulating the phosphorylation status of the C-terminal domain of the large subunit of RNA polymerase II. Here, we show that Rtr1p is a component of a novel mRNA degradation pathway that promotes its autoregulation through turnover of its own mRNA. We show that the 3′UTR of the RTR1 mRNA contains a cis element that destabilizes this mRNA. RTR1 mRNA turnover is achieved through binding of Rtr1p to the RTR1 mRNP in a manner that is dependent on this cis element. Genetic evidence shows that Rtr1p-mediated decay of the RTR1 mRNA involves the 5′-3′ DExD/H-box RNA helicase Dhh1p and the 3′-5′ exonucleases Rex2p and Rex3p. Rtr1p and Rex3p are found associated with Dhh1p, suggesting a model for recruiting the REX exonucleases to the RTR1 mRNA for degradation. Rtr1p-mediated decay potentially impacts additional transcripts, including the unspliced BMH2 pre-mRNA. We propose that Rtr1p may imprint its RNA targets cotranscriptionally and determine their downstream degradation mechanism by directing these transcripts to a novel turnover pathway that involves Rtr1p, Dhh1p, and the REX family of exonucleases. PMID:26843527

  8. The regulatory role of reversible phosphorylation in the chlorophyll degradation pathway

    Senescence represents the final stage of plant development and is characterized by several processes including the systematic degradation of the photosynthetic apparatus and chlorophyll molecules inside chloroplasts. Normally, chlorophyll is catabolized to colorless compounds through a series of enz...

  9. Liver mitochondria contain an ATP-dependent, vanadate-sensitive pathway for the degradation of proteins.

    Desautels, M; Goldberg, A L

    1982-01-01

    A large fraction (30-50%) of the various proteins synthesized within isolated rat liver mitochondria were degraded to amino acids within 60 min after synthesis. Incomplete mitochondrial polypeptides resulting from the incorporation of puromycin were degraded even more extensively (80% per hr). Protein breakdown was measured by the appearance of acid-soluble radioactivity and by the disappearance of labeled polypeptides detected on NaDodSO4/polyacrylamide gel electrophoresis. The amino acids g...

  10. Combination of degradation pathways for naphthalene utilization in Rhodococcus sp. strain TFB

    Tomás-Gallardo, Laura; Gómez-Álvarez, Helena; Santero, Eduardo; Floriano, Belén

    2013-01-01

    R hodococcus sp. strain TFB is a metabolic versatile bacterium able to grow on naphthalene as the only carbon and energy source. Applying proteomic, genetic and biochemical approaches, we propose in this paper that, at least, three coordinated but independently regulated set of genes are combined to degrade naphthalene in TFB. First, proteins involved in tetralin degradation are also induced by naphthalene and may carry out its conversion to salicylaldehyde. This is the only part of the napht...

  11. Regulation of protein degradation pathways by amino acids and insulin in skeletal muscle of neonatal pigs

    Suryawan, Agus; Davis, Teresa A.

    2014-01-01

    Background The rapid gain in lean mass in neonates requires greater rates of protein synthesis than degradation. We previously delineated the molecular mechanisms by which insulin and amino acids, especially leucine, modulate skeletal muscle protein synthesis and how this changes with development. In the current study, we identified mechanisms involved in protein degradation regulation. In experiment 1, 6- and 26-d-old pigs were studied during 1) euinsulinemic-euglycemic-euaminoacidemic, 2) e...

  12. Alteration of Dynein Function Affects α-Synuclein Degradation via the Autophagosome-Lysosome Pathway

    Da Li; Ji-Jun Shi; Cheng-Jie Mao; Sha Liu; Jian-Da Wang; Jing Chen; Fen Wang; Ya-Ping Yang; Wei-Dong Hu; Li-Fang Hu; Chun-Feng Liu

    2013-01-01

    Growing evidence suggests that dynein dysfunction may be implicated in the pathogenesis of neurodegeneration. It plays a central role in aggresome formation, the delivery of autophagosome to lysosome for fusion and degradation, which is a pro-survival mechanism essential for the bulk degradation of misfolded proteins and damaged organells. Previous studies reported that dynein dysfuntion was associated with aberrant aggregation of α-synuclein, which is a major component of inclusion bodies in...

  13. Novel Pathway of Salicylate Degradation by Streptomyces sp. Strain WA46

    Ishiyama, Daisuke; Vujaklija, Dusica; Davies, Julian

    2004-01-01

    A novel salicylate-degrading Streptomyces sp., strain WA46, was identified by UV fluorescence on solid minimal medium containing salicylate; trace amounts of gentisate were detected by high-pressure liquid chromatography when strain WA46 was grown with salicylate. PCR amplification of WA46 DNA with degenerate primers for gentisate 1,2-dioxygenase (GDO) genes produced an amplicon of the expected size. Sequential PCR with nested GDO primers was then used to identify a salicylate degradation gen...

  14. A novel role for ATM in regulating proteasome-mediated protein degradation through suppression of the ISG15 conjugation pathway.

    Laurence M Wood

    Full Text Available Ataxia Telangiectasia (A-T is an inherited immunodeficiency disorder wherein mutation of the ATM kinase is responsible for the A-T pathogenesis. Although the precise role of ATM in A-T pathogenesis is still unclear, its function in responding to DNA damage has been well established. Here we demonstrate that in addition to its role in DNA repair, ATM also regulates proteasome-mediated protein turnover through suppression of the ISG15 pathway. This conclusion is based on three major pieces of evidence: First, we demonstrate that proteasome-mediated protein degradation is impaired in A-T cells. Second, we show that the reduced protein turnover is causally linked to the elevated expression of the ubiquitin-like protein ISG15 in A-T cells. Third, we show that expression of the ISG15 is elevated in A-T cells derived from various A-T patients, as well as in brain tissues derived from the ATM knockout mice and A-T patients, suggesting that ATM negatively regulates the ISG15 pathway. Our current findings suggest for the first time that proteasome-mediated protein degradation is impaired in A-T cells due to elevated expression of the ISG15 conjugation pathway, which could contribute to progressive neurodegeneration in A-T patients.

  15. Mechanism and Reaction Pathways for Microcystin-LR Degradation through UV/H2O2 Treatment

    Liu, Yafeng; Ren, Jing; Wang, Xiangrong; Fan, Zhengqiu

    2016-01-01

    Microcystin-LR (MCLR) is the most common cyanotoxin in contaminated aquatic systems. MCLR inhibits protein phosphatases 1 and 2A, leading to liver damage and tumor formation. MCLR is relatively stable owing to its cyclic structures. The combined UV/H2O2 technology can degrade MCLR efficiently. The second-order rate constant of the reaction between MCLR and hydroxyl radical (·OH) is 2.79(±0.23)×1010 M−1 s−1 based on the competition kinetics model using nitrobenzene as reference compound. The probable degradation pathway was analyzed through liquid chromatography mass spectrometry. Results suggested that the major destruction pathways of MCLR were initiated by ·OH attack on the benzene ring and diene of the Adda side chain. The corresponding aldehyde or ketone peptide residues were formed through further oxidation. Another minor destruction pathway involved ·OH attack on the methoxy group of the Adda side chain, followed by complete removal of the methoxy group. The combined UV/H2O2 system is a promising technology for MCLR removal in contaminated aquatic systems. PMID:27281173

  16. 不同热作用条件下牛乳中5-HMF生成量的变化研究%Study on the Quantities Change of the 5-Hydroxymethylfurfural in Milk under the Different Heat Treatments

    高萌; 葛武鹏; 张小军; 崔璐璐; 秦立虎

    2012-01-01

    : To discuss the 5-HMF as the milk heat degree validation of target sensitivity and direct the scientific of determine the different heat treatment processes. A high performance liquid chromatographic (HPLC) method was developed for the quantities change of 5-Hydroxymethylfurfural (5-HMF) in milk under the different heating temperature and time, revealed its regularity changes. The results showed that: First, with increasing the heating temperature and heating time, the 5-HMF quantities in pasteurizing milk and instantaneous ultra high temperature sterilizing (UHT) milk all had changed. The higher the heating temperature and the longer the heating time the UHT was, the higher quantities of 5-HMF had. Second, Using this method could rapid determined the rule in quantities of 5-HMF and existed a well linear relationship between peak area and content, the determination results had high accuracy and reproducibility, and the recovery percent of 5-HMF was 90.63%-96.23%. The conclusion was that: 5-HMF as mark was scientific and feasible, based on this, establishment of the liquid milk for process parameters was: the pasteurization dairy temperature should be controlled at ( 85±2 ) ℃, the time for 15 s; the UHT dairy temperature should be controlled at ( 137±2 ) ℃, the time for 4 s.%旨在探讨5-羟甲基糠醛(5-HMF)作为牛乳中热作用程度标示物的可行性并指导不同热处理工艺参数确定的科学性。采用高效液相色谱(HPLC)法对不同温度和时间处理条件下牛乳中的5-HMF生成量变化进行分析比较,揭示其规律性变化。结果表明:(1)随着加热温度的升高和时间的延长,巴杀乳和超高温瞬时灭菌(UHT)乳中5-HMF的生成量均有相应变化,且加热温度越高,时间越长,5-HMF的生成量越高,表明5-HMF作为牛乳受热作用程度标示物可行。(2)可以快速测定牛乳中5-HMF生成量变化,结果具有

  17. Researching in different activated carbon for absorption of 5-hydroxymethylfurfural and decolorization of fructose syrup%不同活性炭对果葡糖浆脱色性能及5-羟甲基糠醛吸附力的比较

    伍伯良; 许永苗; 叶晓蕾; 黄智钧; 杨曦宇

    2014-01-01

    5-羟甲基糠醛是影响果葡糖浆风味的异味物质之一,在果葡糖浆的生产工艺上无法完全去除,需要通过调节工艺参数得以控制。通过分析活性炭对5-羟甲基糠醛的吸附力及对糖浆的脱色效果,得出了不同工艺制造的粉状活性炭的优劣性,为果葡糖浆生产厂家活性炭的选择及添加比例提供参考。%5-hydroxymethylfurfural is one of the off-odor compounds that influence the flavor of high fructose syrup, it can't be completely wiped up in fructose production process and can be controlled by adjusting experimental operating parameters. By analyzing the effects of activated carbon for absorption of 5-hydroxymethylfurfural by and decolorization of fructose syrup, the advantages and disadvantages of different activated carbon were found out. This result is available for the reference to choose and use activated carbon in producing fructose syrup.

  18. Gamma radiolytic eradication of methoxychlor in aqueous media. The degradation pathways using HPLC and SPME-GC-MS

    The gamma radiation-induced degradation of environmental pollutant methoxychlor in water was investigated. A 60Co gamma radiation source with a dose rate of 372 Gy h-1 was used for gamma irradiation of 1 mg L-1 and 10 mg L-1 methoxychlor in water with a varied absorbed dose of 1-5 kGy. A single step clean up and pre-concentration procedure based on solid phase micro-extraction was optimized. The extent of radiolytic degradation was monitored by reversed phase HPLC-UV and GC-ECD. The trace and ultra trace level degradation products were identified using GC-MS-SPME by comparing their mass spectra with the NIST 98 m mass spectral library. Most of the generated products for 4 kGy dose are substituted chlorophenols. The reaction pathways of these substituted chlorophenols and benzophenone formation are also proposed. However, generated chlorophenols disappeared along with methoxychlor for an absorbed dose of 5 kGy. The attained degradation of methoxychlor is ∝ 95% that reflects the potential use of ionization radiation for wastewater treatment. (orig.)

  19. Gamma radiolytic eradication of methoxychlor in aqueous media. The degradation pathways using HPLC and SPME-GC-MS

    Butt, S.B.; Zafar, A. [PINSTECH, Nilore, Islamabad (Pakistan). Central Analytical Facility Div.; Riaz, M. [PINSTECH, Nilore, Islamabad (Pakistan). Chemistry Div.

    2013-08-01

    The gamma radiation-induced degradation of environmental pollutant methoxychlor in water was investigated. A {sup 60}Co gamma radiation source with a dose rate of 372 Gy h{sup -1} was used for gamma irradiation of 1 mg L{sup -1} and 10 mg L{sup -1} methoxychlor in water with a varied absorbed dose of 1-5 kGy. A single step clean up and pre-concentration procedure based on solid phase micro-extraction was optimized. The extent of radiolytic degradation was monitored by reversed phase HPLC-UV and GC-ECD. The trace and ultra trace level degradation products were identified using GC-MS-SPME by comparing their mass spectra with the NIST 98 m mass spectral library. Most of the generated products for 4 kGy dose are substituted chlorophenols. The reaction pathways of these substituted chlorophenols and benzophenone formation are also proposed. However, generated chlorophenols disappeared along with methoxychlor for an absorbed dose of 5 kGy. The attained degradation of methoxychlor is {proportional_to} 95% that reflects the potential use of ionization radiation for wastewater treatment. (orig.)

  20. Bis(2-chloroethoxy)methane degradation by TiO2 photocatalysis: Parameter and reaction pathway investigations

    Haloethers are widely used in industry, and the release of these species into the environment is of great concern because of their toxicity and carcinogenicity. The present study deals with the photocatalytic degradation of the haloether, bis(2-chloroethoxy)methane (BCEXM), in the presence of TiO2 particles and UV-A (λ = 365 nm) radiation. About 99.5% of BCEXM was degraded after UV irradiation for 16 h. Factors such as solution pH, TiO2 dosage, and the presence of anions were found to influence the degradation rate. To obtain a better understanding of the mechanistic details of this TiO2-assisted photodegradation of BCEXM with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. To the best of our knowledge, this is the first report on the degradation pathways of BCEXM. The first step in the destruction of BCEXM is thought to be abstraction of a hydrogen by ·OH to form a carbon-centered radical which then reacts with O2 to form a peroxyl radical. Peroxyl radicals react with one another and produce an alkoxy radical. The β-bond fragmentation of the alkoxy radical produces different intermediates.

  1. Bis(2-chloroethoxy)methane degradation by TiO{sub 2} photocatalysis: Parameter and reaction pathway investigations

    Chen, Chiing-Chang [Department of Science Application and Dissemination, National Taichung University, Taichung 403, Taiwan (China); Wu, Ren-Jang; Yao, I.-Chun [Department of Applied Chemistry, Providence University, Taichung 433, Taiwan (China); Lu, Chung-Shin, E-mail: cslu6@ntcnc.edu.tw [Department of General Education, National Taichung Nursing College, No. 193, Sec. 1, San-Min Road, Taichung 403, Taiwan (China)

    2009-12-30

    Haloethers are widely used in industry, and the release of these species into the environment is of great concern because of their toxicity and carcinogenicity. The present study deals with the photocatalytic degradation of the haloether, bis(2-chloroethoxy)methane (BCEXM), in the presence of TiO{sub 2} particles and UV-A ({lambda} = 365 nm) radiation. About 99.5% of BCEXM was degraded after UV irradiation for 16 h. Factors such as solution pH, TiO{sub 2} dosage, and the presence of anions were found to influence the degradation rate. To obtain a better understanding of the mechanistic details of this TiO{sub 2}-assisted photodegradation of BCEXM with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. To the best of our knowledge, this is the first report on the degradation pathways of BCEXM. The first step in the destruction of BCEXM is thought to be abstraction of a hydrogen by {sup {center_dot}}OH to form a carbon-centered radical which then reacts with O{sub 2} to form a peroxyl radical. Peroxyl radicals react with one another and produce an alkoxy radical. The {beta}-bond fragmentation of the alkoxy radical produces different intermediates.

  2. SIAH-1 interacts with alpha-tubulin and degrades the kinesin Kid by the proteasome pathway during mitosis.

    Germani, A; Bruzzoni-Giovanelli, H; Fellous, A; Gisselbrecht, S; Varin-Blank, N; Calvo, F

    2000-12-01

    SIAH-1, a human homologue of the Drosophila seven in absentia (Sina), has been implicated in ubiquitin-mediated proteolysis of different target proteins through its N-terminal RING finger domain. SIAH-1 is also induced during p53-mediated apoptosis. Furthermore, SIAH-1-transfected breast cancer cell line MCF-7 exhibits an altered mitotic process resulting in multinucleated giant cells. Now, using the two-hybrid system, we identified two new SIAH interacting proteins: Kid (kinesin like DNA binding protein) and alpha-tubulin. We demonstrate that SIAH is involved in the degradation of Kid via the ubiquitin-proteasome pathway. Our results suggest that SIAH-1 but not its N-terminal deletion mutant, affects the mitosis by an enhanced reduction of kinesin levels. Our results imply, for the first time, SIAH-1 in regulating the degradation of proteins directly implicated in the mitotic process. PMID:11146551

  3. 乙酸、糠醛和5-羟甲基糠醛对产酸克雷伯氏菌发酵生产2,3-丁二醇的影响%Effect of acetic acid, furfural and 5-hydroxymethylfurfural on production of 2,3-butanediol by Klebsiella oxytoca

    吴晶; 程可可; 李文英; 冯杰; 张建安

    2013-01-01

    To get the tolerability and consumption of Klebsiella oxytoca on major inhibitors in lignocelluloses hydrolysate, we studied the effect of acetic acid, furfural and 5-hydroxymethylfurfural on production of 2,3-butanediol by Klebsiella oxytoca. The metabolites of furfural and 5-hydroxymethylfurfural were measured. The results show that when acetic acid, furfural and 5-hydroxymethylfurfural was individually added, tolerance threshold for Klebsiella oxytoca was 30 g/L, 4 g/L and 5 g/L, respectively. Acetic acid was likely used as substrate to produce 2,3-butanediol. The yield of 2,3-butanediol increased when acetic acid concentration was lower than 30 g/L. In the fermentation, more than 70% 5-hydroxymethylfurfural was converted to 2,5-furandimethanol. All furfural and the rest of 5-hydroxymethylfurfural were metabolized by Klebsiella oxytoca. It showed that in the detoxification process of 2,3-butanediol production using lignocelluloses hydrolysate, furfural should be given priority to remove and a certain concentration of acetic acid is not need to removal.%为了解产酸克雷伯氏菌对木质纤维素水解液中主要抑制物的耐受和代谢,考察了产酸克雷伯氏菌发酵生产2,3-丁二醇(2,3-butanediol,2,3-BDO)过程中对3种发酵抑制物乙酸、糠醛和5-羟甲基糠醛(5-hydroxymethylfurfural HMF)的耐受以及抑制物浓度的变化,检测了糠醛和HMF的代谢产物.结果表明:产酸克雷伯氏菌对乙酸、糠醛和HMF的耐受浓度分别为30 g/L、4 g/L和5 g/L.并且部分乙酸可作为生产2,3-丁二醇的底物,在0~30 g/L浓度范围内可提高2,3-丁二醇的产量.发酵过程中产酸克雷伯氏菌可将HMF和糠醛全部转化,其中约70%HMF被转化为2,5-呋喃二甲醇,30%HMF和全部糠醛被菌体代谢.研究表明在木质纤维素水解液生产2,3-丁二醇的脱毒过程中可优先考虑脱除糠醛,一定浓度的乙酸可以不用脱除.

  4. Abiotic degradation of methyl parathion by manganese dioxide: Kinetics and transformation pathway.

    Liao, Xiaoping; Zhang, Caixiang; Liu, Yuan; Luo, Yinwen; Wu, Sisi; Yuan, Songhu; Zhu, Zhenli

    2016-05-01

    Methyl parathion, a widely used insecticide around the world, has aroused gradually extensive concern of researchers due to its degradation product such as methyl paraoxon, with higher toxicity for mammals and more recalcitrant. Given the ubiquity of manganese dioxide (MnO2) in soils and aquatic sediments, the abiotic degradation of methyl parathion by α-MnO2 was investigated in batch experiments. It was found that methyl parathion was decomposed up to 90% by α-MnO2 in 30 h and the removal efficiency of methyl parathion depended strongly on the loading of α-MnO2 and pH value in the solution where the reactions followed pseudo-first-order model well. The coexisting metal ions (such as Ca(2+), Mg(2+) and Mn(2+)) weakened markedly the degradation of methyl parathion by α-MnO2. However, the effect of dissolved organic matter (HA-Na) on reaction rates presented two sides: to improve hydrolysis rate but deteriorate oxidation rate of methyl parathion. Based on the degradation products identified by gas chromatography-mass spectrometer (GC/MS) and liquid chromatography high-resolution mass spectrometer (LC/HRMS), both hydrolysis and oxidation processes were proposed to be two predominant reaction mechanisms contributing to methyl parathion degradation by α-MnO2. This study provided meaningful information to elucidate the abiotic dissipation of methyl parathion by manganese oxide minerals in the environment. PMID:26891361

  5. Elucidating the Pseudomonas aeruginosa Fatty Acid Degradation Pathway: Identification of Additional Fatty Acyl-CoA Synthetase Homologues

    Zarzycki-Siek, Jan; Norris, Michael H.; Kang, Yun (Kenneth); Sun, Zhenxin; Bluhm, Andrew P.; McMillan, Ian A.; Hoang, Tung T.

    2013-01-01

    The fatty acid (FA) degradation pathway of Pseudomonas aeruginosa, an opportunistic pathogen, was recently shown to be involved in nutrient acquisition during BALB/c mouse lung infection model. The source of FA in the lung is believed to be phosphatidylcholine, the major component of lung surfactant. Previous research indicated that P. aeruginosa has more than two fatty acyl-CoA synthetase genes (fadD; PA3299 and PA3300), which are responsible for activation of FAs using ATP and coenzyme A. T...

  6. Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

    This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil. - BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid

  7. (13)C Tracers for Glucose Degrading Pathway Discrimination in Gluconobacter oxydans 621H.

    Ostermann, Steffen; Richhardt, Janine; Bringer, Stephanie; Bott, Michael; Wiechert, Wolfgang; Oldiges, Marco

    2015-01-01

    Gluconobacter oxydans 621H is used as an industrial production organism due to its exceptional ability to incompletely oxidize a great variety of carbohydrates in the periplasm. With glucose as the carbon source, up to 90% of the initial concentration is oxidized periplasmatically to gluconate and ketogluconates. Growth on glucose is biphasic and intracellular sugar catabolism proceeds via the Entner-Doudoroff pathway (EDP) and the pentose phosphate pathway (PPP). Here we studied the in vivo contributions of the two pathways to glucose catabolism on a microtiter scale. In our approach we applied specifically (13)C labeled glucose, whereby a labeling pattern in alanine was generated intracellularly. This method revealed a dynamic growth phase-dependent pathway activity with increased activity of EDP in the first and PPP in the second growth phase, respectively. Evidence for a growth phase-independent decarboxylation-carboxylation cycle around the pyruvate node was obtained from (13)C fragmentation patterns of alanine. For the first time, down-scaled microtiter plate cultivation together with (13)C-labeled substrate was applied for G. oxydans to elucidate pathway operation, exhibiting reasonable labeling costs and allowing for sufficient replicate experiments. PMID:26404385

  8. 13C Tracers for Glucose Degrading Pathway Discrimination in Gluconobacter oxydans 621H

    Steffen Ostermann

    2015-09-01

    Full Text Available Gluconobacter oxydans 621H is used as an industrial production organism due to its exceptional ability to incompletely oxidize a great variety of carbohydrates in the periplasm. With glucose as the carbon source, up to 90% of the initial concentration is oxidized periplasmatically to gluconate and ketogluconates. Growth on glucose is biphasic and intracellular sugar catabolism proceeds via the Entner–Doudoroff pathway (EDP and the pentose phosphate pathway (PPP. Here we studied the in vivo contributions of the two pathways to glucose catabolism on a microtiter scale. In our approach we applied specifically 13C labeled glucose, whereby a labeling pattern in alanine was generated intracellularly. This method revealed a dynamic growth phase-dependent pathway activity with increased activity of EDP in the first and PPP in the second growth phase, respectively. Evidence for a growth phase-independent decarboxylation-carboxylation cycle around the pyruvate node was obtained from 13C fragmentation patterns of alanine. For the first time, down-scaled microtiter plate cultivation together with 13C-labeled substrate was applied for G. oxydans to elucidate pathway operation, exhibiting reasonable labeling costs and allowing for sufficient replicate experiments.

  9. Pathways of nitrobenzene degradation in horizontal subsurface flow constructed wetlands: Effect of intermittent aeration and glucose addition.

    Kirui, Wesley K; Wu, Shubiao; Kizito, Simon; Carvalho, Pedro N; Dong, Renjie

    2016-01-15

    Intermittent aeration and addition of glucose were applied to horizontal subsurface flow constructed wetlands in order to investigate the effect on pathways of nitrobenzene (NB) degradation and interactions with microbial nitrogen and sulphur transformations. The experiment was carried out in three phases A, B and C consisting of different NB loading and glucose dosing. For each phase, the effect of aeration was assessed by intermittently aerating one wetland and leaving one unaerated. Regardless of whether or not the wetland was aerated, at an influent NB concentration of 140 mg/L, both wetlands significantly reduced NB to less than 2 mg/L, a reduction efficiency of 98%. However, once the influent NB concentration was increased to 280 mg/L, the aerated wetland had a higher removal performance 82% compared to that of the unaerated wetland 71%. Addition of glucose further intensified the NB removal to 95% in the aerated wetlands and 92% in the unaerated. Aeration of wetlands enhanced NB degradation, but also resulted in higher NB volatilization of 6 mg m(-2) d(-1). The detected high concentration of sulphide 20-60 mg/L in the unaerated wetland gave a strong indication that NB may act as an electron donor to sulphate-reducing bacteria, but this should be further investigated. Aeration positively improved NB removal in constructed wetlands, but resulted in higher NB volatilization. Glucose addition induced co-metabolism to enhance NB degradation. PMID:26468606

  10. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); Stolte, Stefan [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); UFT-Centre of Environmental Research and Sustainable Technology, University of Bremen, Leobener Straße UFT, D-28359 Bremen (Germany); Siedlecka, Ewa Maria, E-mail: ewa.siedlecka@ug.edu.pl [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland)

    2014-09-15

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na{sub 2}SO{sub 4}. The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test.