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Sample records for 5-hydroxymethyl furfural hmf

  1. Biotransformation of furfural and 5-hydroxymethyl furfural (HMF) by Clostridium acetobutylicum ATCC 824 during butanol fermentation.

    PubMed

    Zhang, Yan; Han, Bei; Ezeji, Thaddeus Chukwuemeka

    2012-02-15

    The ability of fermenting microorganisms to tolerate furan aldehyde inhibitors (furfural and 5-hydroxymethyl furfural (HMF)) will enhance efficient bioconversion of lignocellulosic biomass hydrolysates to fuels and chemicals. The effect of furfural and HMF on butanol production by Clostridium acetobutylicum 824 was investigated. Whereas specific growth rates, μ, of C. acetobutylicum in the presence of furfural and HMF were in the range of 15-85% and 23-78%, respectively, of the uninhibited Control, μ increased by 8-15% and 23-38% following exhaustion of furfural and HMF in the bioreactor. Using high performance liquid chromatography and spectrophotometric assays, batch fermentations revealed that furfural and HMF were converted to furfuryl alcohol and 2,5-bis-hydroxymethylfuran, respectively, with specific conversion rates of 2.13g furfural and 0.50g HMF per g (biomass) per hour, by exponentially growing C. acetobutylicum. Biotransformation of these furans to lesser inhibitory compounds by C. acetobutylicum will probably enhance overall fermentation of lignocellulosic hydrolysates to butanol. PMID:21925629

  2. Ameliorative Effects of 5-Hydroxymethyl-2-furfural (5-HMF) from Schisandra chinensis on Alcoholic Liver Oxidative Injury in Mice

    PubMed Central

    Li, Wei; Qu, Xin-Nan; Han, Ye; Zheng, Si-Wen; Wang, Jia; Wang, Ying-Ping

    2015-01-01

    The aim of this paper is to evaluate the protective effect of 5-hydroxymethyl-2-furfural (5-HMF) on acute alcohol-induced liver oxidative injury in mice. 5-HMF, a maillard reaction product, was isolated from the fruits of Schisandra chinensis for animal experiments. Experimental ICR mice were pretreated with different doses of 5-HMF (7.5, 15, and 30 mg/kg) for seven days by gavage feeding. Biochemical markers and enzymatic antioxidants from serum and liver tissue were examined. Our results showed that the activities of ALT (alanine aminotransferase), AST (aspartate transaminase), TC (total cholesterol), TG (triglyceride), L-DLC (low density lipoprotein) in serum and the levels of MDA (malondialdehyde) in liver tissue, decreased significantly (p < 0.05) in the 5-HMF-treated group compared with the alcohol group. On the contrary, enzymatic antioxidants CAT (catalase), GSH-Px (glutathione peroxidase), and GSH SOD (superoxide dismutase) were markedly elevated in liver tissue treated with 5-HMF (p < 0.05). Furthermore, the hepatic levels of pro-inflammatory response marker tumor necrosis factor-alpha (TNF-α) and interleukin-1β (IL-1β) were significantly suppressed (p < 0.05). Histopathological examination revealed that 5-HMF (30 mg/kg) pretreatment noticeably prevented alcohol-induced hepatocyte apoptosis and fatty degeneration. It is suggested that the hepatoprotective effects exhibited by 5-HMF on alcohol-induced liver oxidative injury may be due to its potent antioxidant properties. PMID:25622257

  3. IDENTIFICATION AND URINARY EXCRETION OF METABOLITES OF 5-(HYDROXYMETHYL)-2-FURFURAL (HMF) IN HUMAN SUBJECTS FOLLOWING CONSUMPTION OF DRIED PLUMS OR DRIED PLUM JUICE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    5-(hydroxymethyl)-2-Furfural (HMF) is a major breakdown product occurring in solutions with high concentrations of fructose and glucose and is present in many fruit juices, in heat-sterilized parental solutions, and in baby cereals. The objective of this study was to characterize and identify for th...

  4. Method to convert biomass to 5-(hydroxymethyl)-furfural (HMF) and furfural using lactones, furans, and pyrans as solvents

    DOEpatents

    Dumesic, James A.; Ribeiro Gallo, Jean Marcel; Alonso, David

    2014-07-08

    Described is a process to produce hydroxymethyl furfural (HMF) from biomass-derived sugars. The process includes the steps of reacting a C5 and/or C6 sugar-containing reactant derived from biomass in a monophasic or biphasic reaction solution comprising water and a co-solvent. The co-solvent can be beta-, gamma-, and/or delta-lactones derived from biomass, tetrahydrofuran (THF) derived from biomass, and/or methyltetrahydrofuran (MTHF) derived from biomass. The reaction takes place in the presence of an acid catalyst and a dehydration catalyst for a time and under conditions such that at least a portion of glucose or fructose present in the reactant is converted to HMF.

  5. Enhanced Hypoxia-Inducible Factor (HIF)-1α Stability Induced by 5-Hydroxymethyl-2-Furfural (5-HMF) Contributes to Protection against Hypoxia

    PubMed Central

    He, Yun-Ling; Li, Ming-Ming; Wu, Li-Ying; Zhao, Tong; Di, Yao; Huang, Xin; Ding, Xue-Feng; Wu, Kui-Wu; Fan, Ming; Zhu, Ling-Ling

    2014-01-01

    We first reported the role of 5-hydroxymethyl-2-furfural (5-HMF) against hypoxia. Here, we studied the mechanism by using oxygen-dependent degradation domain (ODD)-Luc mice, which are a useful model to probe the stabilization of hypoxia-inducible factor 1α (HIF-1α). Compared with three other compounds that have been reported to have a role in stabilizing HIF-1α, 5-HMF caused stronger bioluminescence, which is indicative of HIF-1α stability in the brain and kidney of ODD-Luc mice. We further demonstrated that the HIF-1α protein accumulated in response to 5-HMF in the brains and kidneys of these mice, as well as in PC12 cells. Additionally, 5-HMF promoted the nuclear translocation of HIF-1α and the transcriptional activity of HIF-1, which was evaluated by detecting vascular endothelial growth factor (VEGF ) mRNA expression. These results suggest that 5-HMF stabilized HIF-1α and increased its activity. Considering the role of proline hydroxylases (PHDs) in negatively regulating HIF-1α stability, we explored whether 5-HMF interacts with the substrates and cofactors of PHDs, such as 2-oxoglutarate (2-OG), Fe2+ and vitamin C (VC), which affects the activity of PHDs. The result revealed that 5-HMF did not interact with Fe2+ or 2-OG but interacted with VC. This interaction was confirmed by subsequent experiments, in which 5-HMF entered into cells and reduced the VC content. The enhanced stability of HIF-1α by 5-HMF was reversed by VC supplementation, and the improved survival of mice caused by 5-HMF under hypoxia was abrogated by VC supplementation. Thus, we demonstrated for the first time that 5-HMF increases HIF-1α stability by reducing the VC content, which mediates the protection against hypoxia. PMID:25333920

  6. Enhanced hypoxia-inducible factor (HIF)-1α stability induced by 5-hydroxymethyl-2-furfural (5-HMF) contributes to protection against hypoxia.

    PubMed

    He, Yun-Ling; Li, Ming-Ming; Wu, Li-Ying; Zhao, Tong; Di, Yao; Huang, Xin; Ding, Xue-Feng; Wu, Kui-Wu; Fan, Ming; Zhu, Ling-Ling

    2014-01-01

    We first reported the role of 5-hydroxymethyl-2-furfural (5-HMF) against hypoxia. Here, we studied the mechanism by using oxygen-dependent degradation domain (ODD)-Luc mice, which are a useful model to probe the stabilization of hypoxia-inducible factor 1α (HIF-1α). Compared with three other compounds that have been reported to have a role in stabilizing HIF-1α, 5-HMF caused stronger bioluminescence, which is indicative of HIF-1α stability in the brain and kidney of ODD-Luc mice. We further demonstrated that the HIF-1α protein accumulated in response to 5-HMF in the brains and kidneys of these mice, as well as in PC12 cells. Additionally, 5-HMF promoted the nuclear translocation of HIF-1α and the transcriptional activity of HIF-1, which was evaluated by detecting vascular endothelial growth factor (VEGF ) mRNA expression. These results suggest that 5-HMF stabilized HIF-1α and increased its activity. Considering the role of proline hydroxylases (PHDs) in negatively regulating HIF-1α stability, we explored whether 5-HMF interacts with the substrates and cofactors of PHDs, such as 2-oxoglutarate (2-OG), Fe(2+) and vitamin C (VC), which affects the activity of PHDs. The result revealed that 5-HMF did not interact with Fe(2+) or 2-OG but interacted with VC. This interaction was confirmed by subsequent experiments, in which 5-HMF entered into cells and reduced the VC content. The enhanced stability of HIF-1α by 5-HMF was reversed by VC supplementation, and the improved survival of mice caused by 5-HMF under hypoxia was abrogated by VC supplementation. Thus, we demonstrated for the first time that 5-HMF increases HIF-1α stability by reducing the VC content, which mediates the protection against hypoxia. PMID:25333920

  7. In house validation from direct determination of 5-hydroxymethyl-2-furfural (HMF) in Brazilian corn and cane syrups samples by HPLC-UV.

    PubMed

    de Andrade, Jucimara K; Komatsu, Emy; Perreault, Hélène; Torres, Yohandra R; da Rosa, Marcos R; Felsner, Maria L

    2016-01-01

    In this work the development and in house validation of the HMF direct determination in corn and cane syrups by HPLC-UV was carried out for the first time. The separation was done with isocratic elution of a mobile phase comprising water (with 0.5% formic acid) and acetonitrile (90:10, v/v) on Phenomenex C18 column (5.0 μm, 4.6 × 150 mm), at 30 °C, flow rate of 0.8 mL min(-1) and detection at 285 nm. The validated method showed excellent performance with low limits (LOD and LOQ of 0.09 and 0.26 mg L(-1), respectively), good accuracy (recovery rates between 100% and 104%) and precision (RSD's for repeatability and intermediate precision between 0.57% and 6.43%). Good selectivity and linearity were also observed. HMF contents in both foods were very high (406.6-2121.3 mg kg(-1) for corn syrup and 109.2-893.1 mg kg(-1) for cane syrup), which arouses concern about food safety of these products. PMID:26213000

  8. Efficient whole-cell biotransformation of 5-(hydroxymethyl)furfural into FDCA, 2,5-furandicarboxylic acid.

    PubMed

    Koopman, Frank; Wierckx, Nick; de Winde, Johannes H; Ruijssenaars, Harald J

    2010-08-01

    2,5-furandicarboxylic acid (FDCA) is a promising bio-based platform chemical that may serve as a 'green' substitute for terephthalate in polyesters. Recently, a novel HMF/furfural oxidoreductase from Cupriavidus basilensis HMF14 was identified that converts 5-(hydroxymethyl)furfural (HMF) into FDCA. The hmfH gene encoding this oxidoreductase was introduced into Pseudomonas putida S12 and the resulting whole-cell biocatalyst was employed to produce FDCA from HMF. In fed-batch experiments using glycerol as the carbon source, 30.1 g l(-1) of FDCA was produced from HMF at a yield of 97%. FDCA was recovered from the culture broth as a 99.4% pure dry powder, at 76% recovery using acid precipitation and subsequent tetrahydrofuran extraction. PMID:20363622

  9. Catalytic conversion of cellulose to 5-hydroxymethyl furfural using acidic ionic liquids and co-catalyst.

    PubMed

    Ding, Zhen-Dong; Shi, Jin-Cai; Xiao, Jing-Jing; Gu, Wen-Xiu; Zheng, Chang-Ge; Wang, Hai-Jun

    2012-10-01

    Efficient catalytic conversion of microcrystalline cellulose (MCC) to 5-hydroxymethyl furfural (HMF), is achieved using acidic ionic liquids (ILs) as the catalysts and metal salts as co-catalysts in the solvent of 1-ethyl-3-methylimidazo-lium acetate ([emim][Ac]). A series of acidic ILs has been synthesized and tested in conversion of MCC to HMF. The effect of reaction conditions, such as reaction time, temperature, catalyst dosage, metal salts, water dosage, Cu(2+) concentration and various acidic ILs are investigated in detail. The results show that CuCl(2) in 1-(4-sulfonic acid) butyl-3-methylimidazolium methyl sulfate ([C(4)SO(3)Hmim][CH(3)SO(3)]), is found to be an efficient catalyst for catalytic conversion of MCC to HMF, and 69.7% yield of HMF is obtained. A mechanism to explain the high activity of CuCl(2) in [C(4)SO(3)Hmim][CH(3)SO(3)] is proposed. To the best of our knowledge, this report first proposes that the Cu(2+) and [C(4)SO(3)Hmim][CH(3)SO(3)] show better catalytic performance in catalytic conversion of MCC to HMF. PMID:22840003

  10. [Rapid method for determination of furfural and 5-hydroxymethyl furfural in pre-extraction stream of biomass using UV spectroscopy].

    PubMed

    Zhang, Cui; Chai, Xin-sheng; Luo, Xiao-lin; Fu, Shi-yu; Zhan, Huai-yu

    2010-01-01

    The present paper reports a rapid method for the determination of furfural (F) and 5-hydroxymethyl furfural (HMF) in pre-extraction liquors of lignocellulosic biomass based on UV spectroscopy. In a concentrated acetic acid medium, F and HMF have an isosbestic point at 276 nm. It was found that the acidic soluble lignin in the pre-extraction sample is the major interference species in the F and HMF spectroscopic quantification However, only acidic soluble lignins have the absorption at the wavelengths above 325 nm. Based on the absorption of the acidic soluble lignins at 325 nm, their absorptions at either F or HMF absorbed wavelengths can be determined. Thus, with a simple triple-wavelength technique, both F and HMF in the pre-extraction liquors of lignocellulosic biomass can be quantified based on the spectroscopic measurement at the isosbestic point wavelength (276 nm), maximum absorption wavelength of F (272 nm) and the acid soluble lignin absorbed wavelength (325 nm). The present method does not require the hazardous organic compounds (such as phenolic compounds etc.) acting as a color reagent in the experiment. It is not only simple and rapid, but also has a good measurement precision and accuracy, with the relative standard deviations of 3.02% and 2.72%, and recoveries of 95%-107% and 96%-101%, respectively, in the F and HMF quantification. The present method is suitable for use in the research on pre-extraction hemicellulose of the lignocellulosic biomass in bio-refinery area in order to achieve a high selective sugar conversion. PMID:20302124

  11. Developing an effective means to reduce 5-hydroxymethyl-2-furfural from caramel colour.

    PubMed

    Guan, Yongguang; Chen, Mingshun; Yu, Shujuan; Tang, Qiang; Yan, He

    2014-01-15

    Supercritical carbon dioxide fluid extraction was used to extract 5-hydroxymethyl-2-furfural from caramel colour (solid content was about 75%). The procedure was carried out by response surface methodology using a quadratic polynomial model. Extraction pressure, time, temperature and ethanol content were selected as the independent variables. Conditions to obtain the highest extraction ratio of 5-hydroxymethyl-2-furfural were determined to be an extraction pressure of 21.65MPa, time of 46.7min, temperature of 35°C and 70% ethanol content of caramel colour. The predicted 5-hydroxymethyl-2-furfural extraction ratio was 87.42%. Under the conditions stated above, the experimental value of 5-hydroxymethyl-2-furfural extraction ratio was 86.98%, which was similar to the predicted value by the model. This study indicated that supercritical carbon dioxide fluid extraction can effectively reduce 5-hydroxymethyl-2-furfural from caramel colour, which can help food industry to improve the safety of the food material, as well as provide more healthy caramel colour for human beings. PMID:24054213

  12. Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water.

    PubMed

    Ventura, Maria; Aresta, Michele; Dibenedetto, Angela

    2016-05-23

    A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The catalyst does not require any pretreatment or additives, such as bases, to obtain high yield and selectivity in water as solvent and using oxygen as oxidant. When a physical mixture of the oxides is used, low conversion and selectivity are observed. Air can be used instead of oxygen, but a lower conversion rate is observed if the same overall pressure is used, and the selectivity remains high. The catalyst can be recovered almost quantitatively and reused. Deactivation of the catalyst, observed in repeated runs, is due to the deposition of humins on its surface. Upon calcination the catalyst almost completely recovers its activity and selectivity, proving that the catalyst is robust. PMID:27101568

  13. Bis-sulfonic acid ionic liquids for the conversion of fructose to 5-hydroxymethyl-2-furfural.

    PubMed

    Sim, Sang Eun; Kwon, Sunjeong; Koo, Sangho

    2012-01-01

    Homogenous bis-sulfonic acid ionic liquids (1 mol equiv.) in DMSO (10 mol equiv.) at 100 °C efficiently mediated the conversion of D-fructose into 5-hydroxymethyl-2-furfural in 75% isolated yield, which was roughly a 10% increment compared to the case of the mono-sulfonic acid ionic liquids. PMID:23114616

  14. Protein Engineering of GRE2 from Saccharomyces cerevisiae for Enhanced Detoxification of 5-Hydroxymethyl Furfural

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 Saccharomy...

  15. Reporter gene mutation in the livers of gpt delta mice treated with 5-(hydroxymethyl)-2-furfural, a contaminant of various foods.

    PubMed

    Matsushita, Kohei; Ishii, Yuji; Kijima, Aki; Jin, Meilan; Takasu, Shinji; Kuroda, Ken; Kodama, Yukio; Ogawa, Kumiko; Umemura, Takashi

    2012-01-01

    A major product formed during the Maillard reaction is 5-(hydroxymethyl)-2-furfural (HMF), which is present in various foods and beverages such as honey and fruit juice. HMF was shown to be a hepatocarcinogen in female mice using long-term bioassays. Although HMF is not a mutagen in conventional in vitro mutation assays, 5-sulfoxymethylfurfural (SMF), a reactive metabolite of HMF produced following sulfotransferase conjugation, does show mutagenicity. Thus, HMF-induced hepatocarcinogenesis likely involves genotoxic mechanisms. To clarify the mechanisms underlying HMF-induced hepatocarcinogenesis, female B6C3F(1) gpt delta mice were given HMF at carcinogenic doses (188 or 375 mg/kg b.w.) by gavage for 5 days per week for 4 weeks. This treatment produced no significant differences in mutant frequencies (MFs) of gpt and red/gam (Spi(-)) genes among the groups. These results suggest that genotoxicity does not contribute to HMF-induced hepatocarcinogenesis. Parameters related to cell proliferation, such as proliferation cell nuclear antigen-labeling index and Cyclin D1 and E1 mRNA expression, exhibited no significant changes in the livers of HMF-treated groups. In view of the lack of carcinogenicity in rats, HMF may be considered to be a weak carcinogen. These results help us to understand the underlying mechanisms of action of HMF carcinogenesis. PMID:23038016

  16. Organocatalytic Upgrading of Furfural and 5-Hydroxymethyl Furfural to C10 and C12 Furoins with Quantitative Yield and Atom-Efficiency

    PubMed Central

    Zang, Hongjun; Chen, Eugene Y. X.

    2015-01-01

    There is increasing interest in the upgrading of C5 furfural (FF) and C6 5-hydroxymethyl furfural (HMF) into C10 and C12 furoins as higher energy-density intermediates for renewable chemicals, materials, and biofuels. This work utilizes the organocatalytic approach, using the in situ generated N,S-heterocyclic carbene catalyst derived from thiazolium ionic liquids (ILs), to achieve highly efficient self-coupling reactions of FF and HMF. Specifically, variations of the thiazolium IL structure have led to the most active and efficient catalyst system of the current series, which is derived from a new thiazolium IL carrying the electron-donating acetate group at the 5-ring position. For FF coupling by this IL (0.1 mol %, 60 °C, 1 h), when combined with Et3N, furoin was obtained in >99% yield. A 97% yield of the C12 furoin was also achieved from the HMF coupling by this catalyst system (10 mol % loading, 120 °C, 3 h). On the other hand, the thiazolium IL bearing the electron-withdrawing group at the 5-ring position is the least active and efficient catalyst. The mechanistic aspects of the coupling reaction by the thiazolium catalyst system have also been examined and a mechanism has been proposed. PMID:25830482

  17. Sulfonated graphene oxide as effective catalyst for conversion of 5-(hydroxymethyl)-2-furfural into biofuels.

    PubMed

    Antunes, Margarida M; Russo, Patrícia A; Wiper, Paul V; Veiga, Jacinto M; Pillinger, Martyn; Mafra, Luís; Evtuguin, Dmitry V; Pinna, Nicola; Valente, Anabela A

    2014-03-01

    The acid-catalyzed reaction of 5-(hydroxymethyl)-2-furfural with ethanol is a promising route to produce biofuels or fuel additives within the carbohydrate platform; specifically, this reaction may give 5-ethoxymethylfurfural, 5-(ethoxymethyl)furfural diethylacetal, and/or ethyl levulinate (bioEs). It is shown that sulfonated, partially reduced graphene oxide (S-RGO) exhibits a more superior catalytic performance for the production of bioEs than several other acid catalysts, which include sulfonated carbons and the commercial acid resin Amberlyst-15, which has a much higher sulfonic acid content and stronger acidity. This was attributed to the cooperative effects of the sulfonic acid groups and other types of acid sites (e.g., carboxylic acids), and to the enhanced accessibility to the active sites as a result of the 2D structure. Moreover, the acidic functionalities bonded to the S-RGO surface were more stable under the catalytic reaction conditions than those of the other solids tested, which allowed its efficient reuse. PMID:24497470

  18. Effects of 5-hydroxymethyl-2-furfural on the volume and membrane permeability of red blood cells from patients with sickle cell disease

    PubMed Central

    Hannemann, Anke; Cytlak, Urszula M; Rees, David C; Tewari, Sanjay; Gibson, John S

    2014-01-01

    The heterocyclic aldehyde 5-hydroxymethyl-2-furfural (5HMF) interacts allosterically with the abnormal form of haemoglobin (Hb), HbS, in red blood cells (RBCs) from patients with sickle cell disease (SCD), thereby increasing oxygen affinity and decreasing HbS polymerization and RBC sickling during hypoxia. We hypothesized that should 5HMF also inhibit the main cation pathways implicated in the dehydration of RBCs from SCD patients – the deoxygenation-induced cation pathway (Psickle), the Ca2+-activated K+ channel (the Gardos channel) and the K+–Cl− cotransporter (KCC) – it would have a synergistic effect in protection against sickling, directly through interacting with HbS, and indirectly through maintaining hydration and reducing [HbS]. This study was therefore designed to investigate the effects of 5HMF on RBC volume and K+ permeability in vitro. 5HMF markedly reduced the deoxygenation-induced dehydration of RBCs whether in response to maintained deoxygenation or to cyclical deoxygenation/re-oxygenation. 5HMF was found to inhibit Psickle, an effect which correlated with its effects on sickling. Deoxygenation-induced activation of the Gardos channel and exposure of phosphatidylserine were also inhibited, probably indirectly via reduced entry of Ca2+ through the Psickle pathway. Effects of 5HMF on KCC were more modest with a slight inhibition in N-ethylmaleimide (NEM, 1 mm)-treated RBCs and stimulation in RBCs untreated with NEM. These findings support the hypothesis that 5HMF may also be beneficial through effects on RBC ion and water homeostasis. PMID:25015917

  19. Impurities in a morphine sulfate drug product identified as 5-(hydroxymethyl)-2-furfural, 10-hydroxymorphine and 10-oxomorphine.

    PubMed

    Kelly, Seán S; Glynn, Padraig M; Madden, Stuart J; Grayson, David H

    2003-03-01

    Stability testing of morphine sulfate formulated with nonpareil sugar seeds (consisting of sucrose and starch) and fumaric acid revealed the formation of the three impurities 5-(hydroxymethyl)-2-furfural, 10-hydroxymorphine and 10-oxomorphine. 5-(Hydroxymethyl)-2-furfural was isolated via semipreparative HPLC utilizing volatile mobile phase constituents and was identified by analysis of its HRMS and NMR spectra. 10-Hydroxymorphine and 10-oxomorphine were obtained via semipreparative HPLC and subsequent removal of ion-pair reagents using an anion exchange resin, or by solid phase extraction, and identified by spectroscopic analysis followed by comparison with authentic materials. 5-(Hydroxymethyl)-2-furfural is a degradation product of hexose sugars, and its formation in the presence of morphine sulfate formulated with fumaric acid suggests that caution should be exercised when including nonpareil seeds in formulations that contain acidic drug salts and/or acid excipients. The preliminary results of tests on the interaction of acidic salts of some other drugs with nonpareil seeds are presented. PMID:12587110

  20. Effect of Sodium Chloride on α-Dicarbonyl Compound and 5-Hydroxymethyl-2-furfural Formations from Glucose under Caramelization Conditions: A Multiresponse Kinetic Modeling Approach.

    PubMed

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-08-17

    This study aimed to investigate the kinetics of α-dicarbonyl compound formation in glucose and glucose-sodium chloride mixture during heating under caramelization conditions. Changes in the concentrations of glucose, fructose, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural (HMF), glyoxal, methylglyoxal, and diacetyl were determined. A comprehensive reaction network was built, and the multiresponse model was compared to the experimentally observed data. Interconversion between glucose and fructose became 2.5 times faster in the presence of NaCl at 180 and 200 °C. The effect of NaCl on the rate constants of α-dicarbonyl compound formation varied across the precursor and the compound itself and temperature. A decrease in rate constants of 3-deoxyglucosone and 1-deoxyglucosone formations by the presence of NaCl was observed. HMF formation was revealed to be mainly via isomerization to fructose and dehydration over cyclic intermediates, and the rate constants increase 4-fold in the presence of NaCl. PMID:27477785

  1. Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO4(2-)/MxOy solid superacid catalyst.

    PubMed

    Yang, Fang; Li, Yang; Zhang, Qian; Sun, Xiaofeng; Fan, Hongxian; Xu, Nian; Li, Gang

    2015-10-20

    This paper presented a mild hydrothermal process for degradation of cotton cellulose with solid superacid catalyst and selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural (HMF). Five kinds of solid superacid catalyst such as SO4(2-)/SnO2, SO4(2-)/TiO2, SO4(2-)/ZrO2, SO4(2-)/Fe2O3 and SO4(2-)/Al2O3 were prepared by impregnation method. The BET surface area of catalyst SO4(2-)/SnO2 was up to 118.8m(2)g(-1) when impregnation was performed with 1molL(-1) H2SO4 of impregnating solution at 550°C calcination temperature for 3h. It made the hydrothermal temperature of cellulose degradation decrease to 190°C successfully and suppressed the side reaction. The NH3-TPD profile of SO4(2-)/SnO2 indicated there was a wide region of stronger acid sites on the catalyst surface. The depolymerization of cotton cellulose obtained 11.0% yield and 22.0% selectivity of HMF and 26.8% yield and 53.4% selectivity of glucose, respectively. The regeneration and reuse of solid superacid catalyst were also discussed in this paper. PMID:26256154

  2. A continuous flow strategy for the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural using Lewis acid zeolites.

    PubMed

    Lewis, Jennifer D; Van de Vyver, Stijn; Crisci, Anthony J; Gunther, William R; Michaelis, Vladimir K; Griffin, Robert G; Román-Leshkov, Yuriy

    2014-08-01

    Hf-, Zr- and Sn-Beta zeolites effectively catalyze the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural with primary and secondary alcohols into 2,5-bis(alkoxymethyl)furans, thus making it possible to generate renewable fuel additives without the use of external hydrogen sources or precious metals. Continuous flow experiments reveal nonuniform changes in the relative deactivation rates of the transfer hydrogenation and etherification reactions, which impact the observed product distribution over time. We found that the catalysts undergo a drastic deactivation for the etherification step while maintaining catalytic activity for the transfer hydrogenation step. (119) Sn and (29) Si magic angle spinning (MAS) NMR studies show that this deactivation can be attributed to changes in the local environment of the metal sites. Additional insights were gained by studying effects of various alcohols and water concentration on the catalytic reactivity. PMID:25045144

  3. 5-hydroxymethyl-2-furfural and derivatives formed during acid hydrolysis of conjugated and bound phenolics in plant foods and the effects on phenolic content and antioxidant capacity.

    PubMed

    Chen, Peter X; Tang, Yao; Zhang, Bing; Liu, Ronghua; Marcone, Massimo F; Li, Xihong; Tsao, Rong

    2014-05-21

    A common protocol for the extraction of phenolic aglycons or bound phenolics in plants generally involves hydrothermal hydrolysis in an aqueous methanol or ethanol solution containing 2-4 N HCl. However, as shown in the present study, this process also forms 5-(hydroxymethyl)furan-2-carbaldehyde (HMF) and its derivative products 5-(methoxymethyl)furan-2-carbaldehyde (MMF) and 5-(ethoxymethyl)furan-2-carbaldehyde (EMF), as identified by HPLC-DAD-ESI-MS/MS and NMR. These compounds are commonly misidentified as phenolics due to similar UV absorption at 280 nm. In this study, production of HMF, MMF, and EMF was shown to be dependent on the solvent condition and duration and temperature of hydrolysis. Fruits and vegetables produced HMF more readily than grains. HMF and its derivatives were subjected to various spectrophotometric antioxidant assays [2-diphenyl-1-picryhydrazyl radical scavenging activity (DPPH), ferric-reducing antioxidant power (FRAP), and oxygen radical absorbing capacity (ORAC)] and displayed antioxidant activity mainly in the ORAC assay. Results of this study help avoid overestimation of phenolic content and antioxidant activities of plant foods. PMID:24796380

  4. Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media.

    PubMed

    Choudhary, Vinit; Mushrif, Samir H; Ho, Christopher; Anderko, Andrzej; Nikolakis, Vladimiros; Marinkovic, Nebojsa S; Frenkel, Anatoly I; Sandler, Stanley I; Vlachos, Dionisios G

    2013-03-13

    5-(Hydroxymethyl)furfural (HMF) and levulinic acid production from glucose in a cascade of reactions using a Lewis acid (CrCl3) catalyst together with a Brønsted acid (HCl) catalyst in aqueous media is investigated. It is shown that CrCl3 is an active Lewis acid catalyst in glucose isomerization to fructose, and the combined Lewis and Brønsted acid catalysts perform the isomerization and dehydration/rehydration reactions. A CrCl3 speciation model in conjunction with kinetics results indicates that the hydrolyzed Cr(III) complex [Cr(H2O)5OH](2+) is the most active Cr species in glucose isomerization and probably acts as a Lewis acid-Brønsted base bifunctional site. Extended X-ray absorption fine structure spectroscopy and Car-Parrinello molecular dynamics simulations indicate a strong interaction between the Cr cation and the glucose molecule whereby some water molecules are displaced from the first coordination sphere of Cr by the glucose to enable ring-opening and isomerization of glucose. Additionally, complex interactions between the two catalysts are revealed: Brønsted acidity retards aldose-to-ketose isomerization by decreasing the equilibrium concentration of [Cr(H2O)5OH](2+). In contrast, Lewis acidity increases the overall rate of consumption of fructose and HMF compared to Brønsted acid catalysis by promoting side reactions. Even in the absence of HCl, hydrolysis of Cr(III) decreases the solution pH, and this intrinsic Brønsted acidity drives the dehydration and rehydration reactions. Yields of 46% levulinic acid in a single phase and 59% HMF in a biphasic system have been achieved at moderate temperatures by combining CrCl3 and HCl. PMID:23432136

  5. Mechanisms of in situ detoxification of furfural and HMF by ethanologenic yeast Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Furfural and 5-hydroxymethylfurfural (HMF) are major inhibitory compounds generated from biomass pretreatment using dilute acid hydrolysis. Remediation of inhibitors adds cost and generates extra waste products. Few yeast strains tolerant to inhibitors are available and the need for tolerant strai...

  6. Dynamic model-based analysis of furfural and HMF detoxification by pure and mixed batch cultures of S. cerevisiae and S. stipitis.

    PubMed

    Hanly, Timothy J; Henson, Michael A

    2014-02-01

    Inhibitory compounds that result from biomass hydrolysis are an obstacle to the efficient production of second-generation biofuels. Fermentative microorganisms can reduce compounds such as furfural and 5-hydroxymethyl furfural (HMF), but detoxification is accompanied by reduced growth rates and ethanol yields. In this study, we assess the effects of these furan aldehydes on pure and mixed yeast cultures consisting of a respiratory deficient mutant of Saccharomyces cerevisiae and wild-type Scheffersomyces stipitis using dynamic flux balance analysis. Uptake kinetics and stoichiometric equations for the intracellular reduction reactions associated with each inhibitor were added to genome-scale metabolic reconstructions of the two yeasts. Further modification of the S. cerevisiae metabolic network was necessary to satisfactorily predict the amount of acetate synthesized during HMF reduction. Inhibitory terms that captured the adverse effects of the furan aldehydes and their corresponding alcohols on cell growth and ethanol production were added to attain qualitative agreement with batch experiments conducted for model development and validation. When the two yeasts were co-cultured in the presence of the furan aldehydes, inoculums that reduced the synthesis of highly toxic acetate produced by S. cerevisiae yielded the highest ethanol productivities. The model described here can be used to generate optimal fermentation strategies for the simultaneous detoxification and fermentation of lignocellulosic hydrolysates by S. cerevisiae and/or S. stipitis. PMID:23983023

  7. 5-(Chloromethyl)furfural is the New HMF: Functionally Equivalent But More Practical in Terms of its Production From Biomass.

    PubMed

    Mascal, Mark

    2015-10-26

    5-(Chloromethyl)furfural (CMF) is a disruptive innovation in the biorefinery. Chemically, it is at least as versatile as the well-known HMF but, unlike HMF, it is accessible in high yield directly from cellulosic biomass due to its lipophilicity and stability under acidic conditions, which facilitate isolation. It has a rich derivative chemistry that includes biofuels, renewable polymers, specialty chemicals, and value-added agrochemical and pharmaceutical products. PMID:26373463

  8. Acquired tolerance and in situ detoxification of furfural and HMF through glucose metabolic pathways by Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lignocellulosic biomass conversion inhibitors furfural and HMF inhibit microbial growth and interfere with subsequent fermentation of ethanol. Numerous yeast genes were found to be associated with the inhibitor tolerance. However, little is known about system mechanisms of the tolerance and detoxi...

  9. The influence of HMF and furfural on redox-balance and energy-state of xylose-utilizing Saccharomyces cerevisiae

    PubMed Central

    2013-01-01

    Background Pretreatment of biomass for lignocellulosic ethanol production generates compounds that can inhibit microbial metabolism. The furan aldehydes hydroxymethylfurfural (HMF) and furfural have received increasing attention recently. In the present study, the effects of HMF and furfural on redox metabolism, energy metabolism and gene expression were investigated in anaerobic chemostats where the inhibitors were added to the feed-medium. Results By cultivating the xylose-utilizing Saccharomyces cerevisiae strain VTT C-10883 in the presence of HMF and furfural, it was found that the intracellular concentrations of the redox co-factors and the catabolic and anabolic reduction charges were significantly lower in the presence of furan aldehydes than in cultivations without inhibitors. The catabolic reduction charge decreased from 0.13(±0.005) to 0.08(±0.002) and the anabolic reduction charge decreased from 0.46(±0.11) to 0.27(±0.02) when HMF and furfural were present. The intracellular ATP concentration was lower when inhibitors were added, but resulted only in a modest decrease in the energy charge from 0.87(±0.002) to 0.85(±0.004) compared to the control. Transcriptome profiling followed by MIPS functional enrichment analysis of up-regulated genes revealed that the functional group “Cell rescue, defense and virulence” was over-represented when inhibitors were present compared to control cultivations. Among these, the ATP-binding efflux pumps PDR5 and YOR1 were identified as important for inhibitor efflux and possibly a reason for the lower intracellular ATP concentration in stressed cells. It was also found that genes involved in pseudohyphal growth were among the most up-regulated when inhibitors were present in the feed-medium suggesting nitrogen starvation. Genes involved in amino acid metabolism, glyoxylate cycle, electron transport and amino acid transport were enriched in the down-regulated gene set in response to HMF and furfural. It was

  10. Quantification of glucose, xylose, arabinose, furfural, and HMF in corncob hydrolysate by HPLC-PDA-ELSD.

    PubMed

    Liu, Xuejun; Ai, Ning; Zhang, Haiyan; Lu, Meizhen; Ji, Dengxiang; Yu, Fengwen; Ji, Jianbing

    2012-05-15

    Lignocellulose and other carbohydrates are being studied extensively as potential renewable carbon sources for liquid biofuels and other valuable chemicals. In the present study, a simple, sensitive, selective, and reliable HPLC method using a photodiode array (PDA) detector and an evaporative light scattering detector (ELSD) was developed for the simultaneous determination of important sugars (D(+)-cellobiose, glucose, xylose, and arabinose), furfural and 5-hydroxymethylfurfural (5-HMF) in lignocellulose hydrolysate. The analysis was carried out on an Aminex HPX-87H column (250 mm × 4.6 mm, 5 μm particle size). Ultra-pure water with 0.00035 M H(2)SO(4) was used as the mobile phase with a flow rate of 0.6 mL/min. The temperature of the ELSD drift tube was kept at 50 °C, the carrier gas pressure was 350 kPa, and the gain was set at 7. Furfural and 5-HMF were quantified on a PDA detector at 275 nm and 284 nm, respectively. The sugar concentrations were determined by ELSD. This method was validated for accuracy and precision. The regression equation revealed a good linear relationship (r(2) = 0.9986 ± 0.0012) within the test ranges. The method showed good reproducibility for the quantification of six analytes in corncob hydrolysate, with intra- and inter-day variations less than 1.12%. This method is also convenient because it allows the rapid analysis of the primary products of biomass hydrolysis and carbohydrate degradation. PMID:22516168

  11. Glycosylated haemoglobin: high-performance liquid chromatographic determination of 5-(hydroxymethyl)-2-furfuraldehyde after haemoglobin hydrolysis.

    PubMed

    Ménez, J F; Berthou, F; Meskar, A; Picart, D; Le Bras, R; Bardou, L G

    1984-08-01

    A specific and accurate method for the quantitation of the azomethine linkage present in non-enzymatically glycosylated haemoglobin is described. This protein is hydrolysed for 5 h in 1 M oxalic acid at 100 degrees C to yield 5-(hydroxymethyl)-2-furfur-aldehyde (5-HMF), known as a specific degradation product of hexoses linked to the protein. 5-HMF is then purified through a Sep-Pak C18 cartridge and measured by its absorption at 280 nm after separation on a C18 reversed-phase silica column. Quantitation is made accurate by using 1-methylxanthine as internal standard throughout the whole procedure. The identity and the purity of the 5-HMF chromatographic peak was ascertained by UV spectroscopy, gas chromatography on a glass capillary column and mass spectrometry. The method has been successfully used for 5-HMF determinations in monitoring diabetes mellitus patients. The mean values, expressed as nmol of 5-HMF per mg of haemoglobin were 0.64 +/- 0.13 (S.D.) for 27 controls and 1.32 +/- 0.39 for 78 diabetic patients. Unlike the usually employed thiobarbituric acid assay, the present procedure is truly specific for the 5-HMF determination. PMID:6490766

  12. Quality evaluation of honey harvested from selected areas in Tanzania with special emphasis on hydroxymethyl furfural (HMF) levels.

    PubMed

    Gidamis, Andrew B; Chove, Bernard E; Shayo, Nicholas B; Nnko, Siphuel A; Bangu, Nicholas T

    2004-01-01

    The physicochemical properties of honey harvested from popular honey-producing areas in Tanzania were investigated. Honey from Shibe-Dodoma had the highest values of specific gravity, total acidity, free fatty acid content, diastatic number, overall acceptability, and lowest hydroxymethyl-furfural (HMF) level as compared to honey samples from other areas. There was no significant difference (p > 0.05) in terms of HMF in the other honey samples from Tanga, Morogoro, Same, Arusha, and Tabora. HMF levels in all honey samples were far below the maximum acceptable level of 40 mg/kg as recommended by the Codex Alimentarius Commission Standards before storage for 6 months. No traces of streptomycin and phenol were detected in all honey samples. It was concluded that according to the values of the studied quality parameters, the types of Tanzanian honey obtained from the popular honey producing areas may be judged to be of high quality. PMID:15678719

  13. Multiple Gene Mediated NAD(P)H-Dependent Aldehyde Reduction is a Mechanism of in situ Detoxification of Furfural and HMF by Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Furfural and 5-hydroxymethylfurfural (HMF) are representative inhibitors to ethanologenic yeast generated from biomass pretreatment using dilute acid hydrolysis. Few yeast strains tolerant to inhibitors are available. In this study, we report a tolerant strain 12HF10 of Saccharomyces cerevisiae ha...

  14. Pulsed addition of HMF and furfural to batch-grown xylose-utilizing Saccharomyces cerevisiae results in different physiological responses in glucose and xylose consumption phase

    PubMed Central

    2013-01-01

    Background Pretreatment of lignocellulosic biomass generates a number of undesired degradation products that can inhibit microbial metabolism. Two of these compounds, the furan aldehydes 5-hydroxymethylfurfural (HMF) and 2-furaldehyde (furfural), have been shown to be an impediment for viable ethanol production. In the present study, HMF and furfural were pulse-added during either the glucose or the xylose consumption phase in order to dissect the effects of these inhibitors on energy state, redox metabolism, and gene expression of xylose-consuming Saccharomyces cerevisiae. Results Pulsed addition of 3.9 g L-1 HMF and 1.2 g L-1 furfural during either the glucose or the xylose consumption phase resulted in distinct physiological responses. Addition of furan aldehydes in the glucose consumption phase was followed by a decrease in the specific growth rate and the glycerol yield, whereas the acetate yield increased 7.3-fold, suggesting that NAD(P)H for furan aldehyde conversion was generated by acetate synthesis. No change in the intracellular levels of NAD(P)H was observed 1 hour after pulsing, whereas the intracellular concentration of ATP increased by 58%. An investigation of the response at transcriptional level revealed changes known to be correlated with perturbations in the specific growth rate, such as protein and nucleotide biosynthesis. Addition of furan aldehydes during the xylose consumption phase brought about an increase in the glycerol and acetate yields, whereas the xylitol yield was severely reduced. The intracellular concentrations of NADH and NADPH decreased by 58 and 85%, respectively, hence suggesting that HMF and furfural drained the cells of reducing power. The intracellular concentration of ATP was reduced by 42% 1 hour after pulsing of inhibitors, suggesting that energy-requiring repair or maintenance processes were activated. Transcriptome profiling showed that NADPH-requiring processes such as amino acid biosynthesis and sulfate and

  15. Effects of L-cysteine and N-acetyl-L-cysteine on 4-hydroxy-2, 5-dimethyl-3(2H)-furanone (furaneol), 5-(hydroxymethyl)furfural, and 5-methylfurfural formation and browning in buffer solutions containing either rhamnose or glucose and arginine.

    PubMed

    Haleva-Toledo, E; Naim, M; Zehavi, U; Rouseff, R L

    1999-10-01

    Solutions of L-cysteine (Cys) and N-acetyl-L-cysteine (AcCys), containing glucose or rhamnose, with or without arginine, were buffered to pH 3, 5, and 7 and incubated at 70 degrees C for 48 h. Cys and AcCys inhibited the formation of (hydroxymethyl)furfural (HMF) from glucose and methylfurfural (MF) from rhamnose under acidic conditions. AcCys inhibited the accumulation of 4-hydroxy-2, 5-dimethyl- 3(2H)-furanone (DMHF, Furaneol) from rhamnose, but Cys, under our experimental conditions, enhanced Furaneol accumulation from rhamnose. Cys and AcCys reacted directly with Furaneol but not with HMF or MF. Both Cys and AcCys inhibited nonenzymatic browning at pH 7. At pH 3, however, Cys reacted with both glucose and rhamnose to produce unidentified compounds that increased the visible absorbency. PMID:10552780

  16. Furfural

    Integrated Risk Information System (IRIS)

    Furfural ; CASRN 98 - 01 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

  17. Flow Injection Analysis of 5-(Hydroxymethyl)-2-furaldehyde in Honey by a Modified Winkler Method.

    PubMed

    Castoldi, Karine; Milani, Maria Izabel; Rossini, Eduardo L; Pezza, Leonardo; Pezza, Helena R

    2016-01-01

    One of the quality indicators for honey is 5-(hydroxymethyl)-2-furaldehyde (HMF), which is formed during the heating or aging of honey. The International Honey Commission recommends three methods for the determination of HMF in honey: the Winkler method, the White method, and determination by HPLC. The Winkler method uses the carcinogenic substance p-toluidine, which is not in accordance with the principles of Green Chemistry. The present work describes the determination of HMF in honey by flow injection analysis (FIA) using a modified Winkler method, replacing p-toluidine with p-aminobenzoic acid. The linear range was 1.00 to 40.0 mg L(-1), the limit of detection (LOD) was 0.43 mg L(-1), and the limit of quantification (LOQ) was 1.32 mg L(-1). The method is an efficient and environmentally friendly technique for the analysis of HMF in honey. PMID:27063713

  18. Rapid and complete urinary elimination of (/sup 14/C)-5-hydroxymethyl-2-furaldehyde administered orally or intravenously to rats

    SciTech Connect

    Germond, J.E.; Philippossian, G.; Richli, U.; Bracco, I.; Arnaud, M.J.

    1987-01-01

    5-Hydroxymethyl-2-furaldehyde (HMF), is a major product of sugar degradation found in food and solutions used in parenteral nutrition. Labeled (/sup 14/C)HMF was synthesized by dehydration of (/sup 14/C)fructose on ion-exchange resin and administered per os (po) and intravenously (iv) to rats. Metabolic balance of radioactivity demonstrated that HMF or its metabolites are rapidly eliminated in the urine with a recovery of 95-100% after 24 h. Literature reported, in some cases, 50% retention in the body. HMF was completely converted to two metabolites, which have been identified by nuclear magnetic resonance (NMR) and mass spectroscopy (MS) as 5-hydroxymethyl-2-furoic acid and N-(5-hydroxymethyl-2-furoyl)glycine. Administration of high doses of HMF showed a similar rapid elimination, but a proportional reduction of the amount of the glycine conjugate produced. Whole-animal-body autoradiography confirm that shortly after administration radioactive material was present in the liver but was mostly in the kidney and the bladder. The only significant difference between po and iv administration was the presence of a higher level of radioactive material in the brain of iv-treated rats.

  19. 5-(Hydroxymethyl)-2-furaldehyde inhibits adipogenic and enhances osteogenic differentiation of rat bone mesenchymal stem cells.

    PubMed

    Tan, Xiang-Ling; Zhang, Yan-Hong; Cai, Jian-Ping; Zhu, Li-Hua; Ge, Wen-Jie; Zhang, Xian

    2014-04-01

    Eucommiae Cortex (Eucommia ulmoides Oliver Bark) has been used for anti-osteoporosis usually as an ethnic drug for hundred years in China. In this study, a bioactive compound, 5-(hydroxymethyl)-2-furaldehyde (5-HMF), was isolated from Eucommiae Cortex. We found that after rat bone mesenchymal stem cells (bMSCs) were induced by 5-HMF at the concentration of 0.05, 0.10 and 0.20 microg/mL in the normal medium for 7 and 14 days, the mRNA expression of ALP, COL1alpha1 (7 days only), OCN and OPN increased. However, in the adipogenic induction medium (AIM), the mRNA expression of PPARgamma, FABP4, C/EBPalpha and LPL decreased with the 5-HMF treatment. Mineralized nodule formations were enhanced after bMSCs were induced by 5-HMF for 14 and 21 days in normal medium. In the AIM medium, 5-HMF not only inhibited the formation of adipose cells obviously, but also stimulated the mineralized nodule formation after induced for 21 days. These results indicated that 5-HMF was a powerful inhibitor of adipogenesis and enhancer of osteoblastogenesis. It may be one of the constituents contributing to anti-osteoporosis in Eucommiae Cortex. PMID:24868876

  20. Biorefining: heterogeneously catalyzed reactions of carbohydrates for the production of furfural and hydroxymethylfurfural.

    PubMed

    Karinen, Reetta; Vilonen, Kati; Niemelä, Marita

    2011-08-22

    Furfurals are important intermediates in the chemical industry. They are typically produced by homogeneous catalysis in aqueous solutions. However, heterogeneously catalyzed processes would be beneficial in view of the principles of green chemistry: the elimination of homogeneous mineral acids makes the reaction mixtures less corrosive, produces less waste, and facilitates easy separation and recovery of the catalyst. Finding an active and stable water-tolerant solid acid catalyst still poses a challenge for the production of furfural (furan-2-carbaldehyde) and 5-(hydroxymethyl)-2-furaldehyde (HMF). Furfural is produced in the dehydration of xylose, and HMF is formed from glucose and fructose in the presence of an acidic catalyst. Bases are not active in dehydration reaction but do catalyze the isomerization of monosaccharides, which is favorable when using glucose as a raw material. In addition to the desired dehydration of monosaccharides, many undesired side reactions take place, reducing the selectivity and deactivating the catalyst. In addition, the catalyst properties play an important role in the selectivity. In this Review, catalytic conversion approaches are summarized, focusing on the heterogeneously catalyzed formation of furfural. The attractiveness of catalytic concepts is evaluated, keeping in mind productivity, sustainability, and environmental footprint. PMID:21728248

  1. Thermochemical pretreatment of lignocellulose to enhance methane fermentation. I. Monosaccharide and furfurals hydrothermal decomposition and product formation rates

    SciTech Connect

    Baugh, K.D.; McCarty, P.L.

    1988-01-01

    Over a pH range 1-4 and temperatures from 170 to 230/sup 0/C, the decomposition rates of xylose, galactose, mannose, glucose, 2-furfural, and 5-hydroxymethyl-2-furfural (5-HMF) were pseudo first order. The effect of temperature and pH on the pseudo first-order decomposition rate constants was modeled using the Arrhenius equation and acid-base catalysis, respectively. Decomposition rates of the monosaccharides were minimum at a pH 2-2.5. Above pH 2.5, the monosaccharide decomposition was base catalyzed, with acid catalysis occurring at a pH of less than 2 for glucose. The furfurals were subject to acid catalysis at below ca. pH 3.5. The hydrothermal conversion of glucose to its decomposition products during thermochemical pretreatment can be modeled as a combination of series and parallel reactions. The formation rates of identified soluble products from glucose decomposition, 5-HMF and levulinic acid, were also functions of temperature and pH. The rate of 5-HMF formation relative to glucose decomposition decreased as the pH increased from 2.0 to 4.0, with levulinic acid formation only detected when the pH was 2.5 or less. For glucose decomposition, humic solids accounted for ca. 20% of the decomposition products.

  2. Supercritical fluid extraction of 5-hydroxymethyl-2-furaldehyde from raisins.

    PubMed

    Palma, M; Taylor, L T

    2001-02-01

    An extraction method based on supercritical CO(2) has been developed for the analysis of 5-hydroxymethyl-2-furaldehyde in raisins. To optimize extraction variables, a fractional factorial experimental design was applied. Six extraction variables were optimized. The organic modifier used for increasing the extraction fluid solvating power was the most important factor. Methanol as organic modifier produced 10-fold higher recoveries of 5-hydroxymethyl-2-furaldehyde than ethyl acetate. The efficiency of the organic modifier in the static extraction phase was compared with using it in the dynamic extraction phase. Repeatability of the analysis method was evaluated, which resulted in an RSD of <5%. 5-Hydroxymethyl-2-furaldehyde was quantified in raisins, and the concentration was found to be 0.128 mg/g of raisin. PMID:11262003

  3. Investigation on influencing factors of 5-HMF content in Schisandra *

    PubMed Central

    Xu, Qing; Li, Ying-hua; Lü, Xiu-yang

    2007-01-01

    In order to investigate the influencing factors of 5-hydroxymethyl-2-furaldehyde (5-HMF) content in Schisandra, confirm the theory of 5-HMF deriving mainly from Schisandra processing course, and give some suggestions about the Schisandra processing method, the 5-HMF contents in decoctions of Schisandra under different heating temperature, decocting time, soaking time, processing methods and treatment with different solvents before decocting the Schisandra were measured by RP-HPLC method. The results showed that there is great difference of 5-HMF level in decoctions from differently processed Schisandra and unprocessed Schisandra; decocting time of 60 min has some effects on 5-HMF level in decoctions and there is certain quantity 5-HMF in processed Schisandra itself and very little 5-HMF in unprocessed Schisandra. Heating time, heating temperature and treating solvents all have effect on 5-HMF level in decoction of Schisandra. 5-HMF in Schisandra was mainly from processing course. Both long heating time and high heating temperature can increase 5-HMF level in Schisandra. The production of 5-HMF in Schisandra may have some relationships with some polar components, which can dissolve in water, ethanol and acetone, especially in ethanol. To control processing temperature, processing time and treatment with some solvent is very important for controlling 5-HMF level in Schisandra. PMID:17565516

  4. Effects of glucose, fructose and 5-hydroxymethyl-2-furaldehyde on the presystemic metabolism and absorption of glycyrrhizin in rabbits.

    PubMed

    Hou, Y C; Ching, H; Chao, P D L; Tsai, S Y; Wen, K C; Hsieh, P H; Hsiu, S L

    2005-02-01

    Our previous study reported that co-administration of honey significantly increased the serum levels of glycyrrhetic acid (GA) after oral administration of glycyrrhizin (GZ) in rabbits. The components of honey are sucrose, glucose, fructose and 5-hydroxymethyl-furaldehyde (HMF). To clarify the causative component(s) in honey that altered the metabolic pharmacokinetics of GZ, rabbits were given GZ (150 mg kg(-1)) with and without glucose (5 g/rabbit), fructose (5 g/rabbit) and HMF (1 mg kg(-1)), respectively, in crossover designs. An HPLC method was used to determine concentrations of GZ and GA in serum as well as GA and 3-dehydroglycyrrhetic acid (3-dehydroGA) in faeces suspension. A noncompartment model was used to calculate the pharmacokinetic parameters and analysis of variance was used for statistical comparison. Our results indicated that the area under curve (AUC) of GA was significantly increased by 29% when HMF was coadministered, whereas the pharmacokinetics of GZ and GA were not significantly altered by coadministration of glucose or fructose. An in-vitro study, using faeces to incubate GZ and GA individually, indicated that HMF significantly inhibited the oxidation of GA to 3-dehydroGA and this may explain the enhanced GA absorption in-vivo. It was concluded that HMF is the causative component in honey that affects the presystemic metabolism and pharmacokinetics of GZ in-vivo. PMID:15720790

  5. Determination of the main impurities formed after acid hydrolysis of soybean extracts and the in vitro mutagenicity and genotoxicity studies of 5-ethoxymethyl-2-furfural.

    PubMed

    Nemitz, Marina C; Picada, Jaqueline N; da Silva, Juliana; Garcia, Ana Letícia H; Papke, Débora K M; Grivicich, Ivana; Steppe, Martin; von Poser, Gilsane L; Teixeira, Helder F

    2016-09-10

    Soybean acid hydrolyzed extracts are raw-materials widely used for manufacturing of pharmaceuticals and cosmetics products due to their high content of isoflavone aglycones. In the present study, the main sugar degradation products 5-hydroxymethyl-2-furfural (HMF) and 5-ethoxymethyl-2-furfural (EMF) were quantitatively determined after acid hydrolysis of extracts from different soybean cultivars by a validated liquid chromatography method. The furanic compounds determined in samples cover the range of 0.16-0.21mg/mL and 0.22-0.33mg/mL for HMF and EMF, respectively. Complementarily, due to the scarce literature regarding the EMF toxicology, this study also assessed the EMF mutagenicity by the Salmonella/microsome test and genotoxicity by the comet assay. The results revealed that EMF did not show mutagenicity at the range of 50-5000μg/plate in S. typhimurium strains TA98, TA97a, TA100, TA102 and TA1535, but induced DNA damage in HepG2 cells at non-cytotoxic doses of 0.1-1.3mg/mL, mainly by oxidative stress mechanisms. Based on literature of HMF genotoxicity, and considering the EMF genotoxicity results herein shown, purification procedures to remove these impurities from extracts are recommended during healthcare products development to ensure the security of the products. PMID:27475406

  6. A reversed-phase HPLC method for measurement of 5-hydroxymethyl furfuraldehyde and furfuraldehyde in processed juices.

    PubMed

    Roig, M G; Bello, J F; Kennedy, J F; Rivera, Z S; Lloyd, L L

    1992-01-01

    An HPLC method using a reversed-phase macroreticular PLRP-S column and phosphate buffer as eluent is described for the analysis of L-ascorbic acid degradation products, 5-hydroxymethyl furfuraldehyde and furfuraldehyde, in processed fruit juices. Measurement of the levels of 5-HMF and furfuraldehyde in citrus juices against time showed the presence of 5-HMF (0.45 mg l-1) even at zero time. An assessment on the effect of the additives on the formation of 5-HMF of reconstituted single-strength orange juice showed virtually the same results for all the samples stored at 4 degrees C and 20 degrees C, irrespective of the additive. For citrus juice samples which had been subjected to accelerated degradation, those that showed the highest decomposition of L-ascorbic acid, produced the highest level of 5-HMF. The presence of furfuraldehyde in any of the samples was not detected, probably due to the fact that furfuraldehyde was formed in such small amounts which are below the minimum detectability limit of the method (0.050 mg l-1). PMID:1369241

  7. Analysis of biodegradation performance of furfural and 5-hydroxymethylfurfural by Amorphotheca resinae ZN1

    PubMed Central

    2014-01-01

    Background Furfural and 5-hydroxymethylfurfural (HMF) are the degradation products of lignocellulose during pretreatment operations and significantly inhibit the consequent enzymatic hydrolysis and fermentation processes. The biodetoxification fungus Amorphotheca resinae ZN1 had demonstrated its excellent capacity on degrading lignocellulose derived inhibitors and helped the fermentation processes to achieve high yield of ethanol and biochemicals. Analysis of the biological degradation performance of furfural and HMF by A. resinae ZN1 will provide essential information for their fast and complete removal from the pretreated lignocellulose materials and facilitate the consequent ethanol fermentation. Results The degradation performance of furfural and HMF by A. resinae ZN1 was investigated by capturing intermediate metabolic products at various culture conditions. A. resinae ZN1 converts furfural/HMF into furfuryl/HMF alcohols and furoic/HMF acids simultaneously at aerobic condition, and only the corresponding furfuryl/HMF alcohols are obtained at anaerobic condition. The existence of glucose accelerates the degradation rate of furfural and HMF by A. resinae ZN1 and the cell mass growth rate aerobically. Remarkably, glucose is not consumed before furfural or HMF is degraded to a low threshold concentration. The finding suggests that furfural or HMF has a substrate priority of utilization by A. resinae ZN1 than glucose. This property may help the detoxification of furfural and HMF to be operated without consuming glucose. Conclusions The biological degradation performance of furfural and HMF by A. resinae ZN1 was investigated experimentally. Oxygen supply is important on the complete biodegradation of furfural and HMF by A. resinae ZN1. Furfural or HMF has the priority of substrate utilization than glucose by A. resinae ZN1. This study provided important information for detoxification enhancement and strain modification. PMID:24708699

  8. Solvent effect on pathways and mechanisms for D-fructose conversion to 5-hydroxymethyl-2-furaldehyde: in situ 13C NMR study.

    PubMed

    Kimura, Hiroshi; Nakahara, Masaru; Matubayasi, Nobuyuki

    2013-03-14

    Noncatalytic reactions of D-fructose were kinetically investigated in dimethylsulfoxide (DMSO), water, and methanol as a function of time at temperatures of 30-150 °C by applying in situ (13)C NMR spectroscopy. The products were quantitatively analyzed with distinction of isomeric species by taking advantage of site-selective (13)C labeling technique. In DMSO, D-fructose was converted first into 3,4-dihydroxy-2-dihydroxymethyl-5-hydroxymethyltetrahydrofuran having no double bond in the ring, subsequently into 4-hydroxy-5-hydroxymethyl-4,5-dihydrofuran-2-carbaldehyde having one double bond through dehydration, and finally into 5-hydroxymethyl-2-furaldehyde (5-HMF) having two double bonds. No other reaction pathways were involved, as shown from the carbon mass balance. In water, 5-HMF, the final product in DMSO, was generated with the precursors undetected and furthermore transformed predominantly into formic and levulinic acids and slightly into 1,2,4-benzenetriol accompanied by polymerization. D-glucose was also produced through the reversible transformation of the reactant D-fructose. In methanol, some kinds of anhydro-D-fructoses were generated instead of 5-HMF. The reaction pathways can thus be controlled by taking advantage of the solvent effect. The D-fructose conversion reactions are of the first order with respect to the concentration of D-fructose and proceed on the order of minutes in DMSO but on the order of hours in water and methanol. The rate constant was three orders of magnitude larger in DMSO than in water or methanol. PMID:23458365

  9. Investigation on the origin of 5-HMF in Shengmaiyin decoction by RP-HPLC method*

    PubMed Central

    Li, Ying-hua; Lu, Xiu-yang

    2005-01-01

    The origin of 5-HMF (5-hydroxymethyl-2-furaldehyde) in a Shengmaiyin decoction was investigated by the RP-HPLC method below. A C18 column (250 mm×4.6 mm, i.d. 5 μm) with a column temperature of 25 °C was used. The mobile phase was a mixture of ultra-pure water-acetonitrile (95:5, V/V) and the flow rate was 1.0 ml/min. The detection wavelength was 280 nm. The injection volume was 1 μl and the running time was about 20 min. The addition of Schisandra was regulated to assess the contribution of an acid environment to the production of 5-HMF. In order to confirm the role of saccharides in the production of 5-HMF, different amount of fructose was used. The 5-HMF level in decoctions of processed and unprocessed Schisandra was investigated in order to determine the origin of 5-HMF. The results showed that 5-HMF was derived mainly from the decoction of Schisandra only and not the mixed decoction of Ophionpogon and Schisandra. The appearance of 5-HMF is not simply the result of the decomposition of saccharides under the acid environment created by Schisandra, but the processing procedure plays an important role in the production of 5-HMF. PMID:16187416

  10. Nematicidal activity of 5-hydroxymethyl-2-furoic acid against plant-parasitic nematodes.

    PubMed

    Kimura, Yasuo; Tani, Satoko; Hayashi, Asami; Ohtani, Kouhei; Fujioka, Shozo; Kawano, Tsuyoshi; Shimada, Atsumi

    2007-01-01

    A nematicide, 5-hydroxymethyl-2-furoic acid (1), was isolated from cultures of the fungus Aspergillus sp. and its structure was identified by spectroscopic analysis. Compound 1 showed effective nematicidal activities against the pine wood nematode Bursaphelenchus xylophilus and the free-living nematode Caenorhabditis elegans without inhibitory activity against plant growth, but 1 did not show any effective nematicidal activity against Pratylenchus penetrans. PMID:17542490

  11. Short communication: Amino trap column improves the separation of methylimidazoles, 5-hydroxymethyl-2-furaldehyde, and sugars in Maillard reaction.

    PubMed

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

    2014-11-01

    A simultaneous analysis of methylimidazoles, reducing sugars, and 5-hydroxymethyl-2-furaldehyde in the Maillard reaction was improved by use of an amino trap column. Analysis was carried out by using high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) coupled with an amino trap column. The amino trap column was a useful tool to improve the separation of methylimidazoles, reducing sugars, and 5-hydroxymethyl-2-furaldehyde. This technique is useful for simultaneous analysis of methylimidazoles, reducing sugars, and 5-hydroxymethyl-2-furaldehyde in risk assessment for dairy products. PMID:25200783

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  13. Biphasic catalytic conversion of fructose by continuous hydrogenation of HMF over a hydrophobic ruthenium catalyst.

    PubMed

    Yang, Yanliang; Du, Zhongtian; Ma, Jiping; Lu, Fang; Zhang, Junjie; Xu, Jie

    2014-05-01

    The production of chemicals directly from sugars is an important step in biomass conversion. Herein, tetrahydro-2,5-furandimethanol (THFDM), obtained from fructose, is formed by using a combination of acid and hydrophobic Ru/SiO2 in a water/cyclohexane biphasic system. Two key factors enable the high selectivity towards THFDM: modifying the hydrogenation catalyst so that it has hydrophobic properties, and the continuous hydrogenation of generated 5-(hydroxymethyl)furfural in the cyclohexane phase. Moreover, the selectivity towards THFDM is found to depend strongly on the acid catalyst used. PMID:24644062

  14. 5-hydroxymethylation of the EBV genome regulates the latent to lytic switch

    PubMed Central

    Wille, Coral K.; Nawandar, Dhananjay M.; Henning, Amanda N.; Ma, Shidong; Oetting, Kayla M.; Lee, Dennis; Lambert, Paul; Johannsen, Eric C.; Kenney, Shannon C.

    2015-01-01

    Latent Epstein–Barr virus (EBV) infection and cellular hypermethylation are hallmarks of undifferentiated nasopharyngeal carcinoma (NPC). However, EBV infection of normal oral epithelial cells is confined to differentiated cells and is lytic. Here we demonstrate that the EBV genome can become 5-hydroxymethylated and that this DNA modification affects EBV lytic reactivation. We show that global 5-hydroxymethylcytosine (5hmC)-modified DNA accumulates during normal epithelial-cell differentiation, whereas EBV+ NPCs have little if any 5hmC-modified DNA. Furthermore, we find that increasing cellular ten–eleven translocation (TET) activity [which converts methylated cytosine (5mC) to 5hmC] decreases methylation, and increases 5hmC modification, of lytic EBV promoters in EBV-infected cell lines containing highly methylated viral genomes. Conversely, inhibition of endogenous TET activity increases lytic EBV promoter methylation in an EBV-infected telomerase-immortalized normal oral keratinocyte (NOKs) cell line where lytic viral promoters are largely unmethylated. We demonstrate that these cytosine modifications differentially affect the ability of the two EBV immediate-early proteins, BZLF1 (Z) and BRLF1 (R), to induce the lytic form of viral infection. Although methylation of lytic EBV promoters increases Z-mediated and inhibits R-mediated lytic reactivation, 5hmC modification of lytic EBV promoters has the opposite effect. We also identify a specific CpG-containing Z-binding site on the BRLF1 promoter that must be methylated for Z-mediated viral reactivation and show that TET-mediated 5hmC modification of this site in NOKs prevents Z-mediated viral reactivation. Decreased 5-hydroxymethylation of cellular and viral genes may contribute to NPC formation. PMID:26663912

  15. 5-hydroxymethylation of the EBV genome regulates the latent to lytic switch.

    PubMed

    Wille, Coral K; Nawandar, Dhananjay M; Henning, Amanda N; Ma, Shidong; Oetting, Kayla M; Lee, Dennis; Lambert, Paul; Johannsen, Eric C; Kenney, Shannon C

    2015-12-29

    Latent Epstein-Barr virus (EBV) infection and cellular hypermethylation are hallmarks of undifferentiated nasopharyngeal carcinoma (NPC). However, EBV infection of normal oral epithelial cells is confined to differentiated cells and is lytic. Here we demonstrate that the EBV genome can become 5-hydroxymethylated and that this DNA modification affects EBV lytic reactivation. We show that global 5-hydroxymethylcytosine (5hmC)-modified DNA accumulates during normal epithelial-cell differentiation, whereas EBV+ NPCs have little if any 5hmC-modified DNA. Furthermore, we find that increasing cellular ten-eleven translocation (TET) activity [which converts methylated cytosine (5mC) to 5hmC] decreases methylation, and increases 5hmC modification, of lytic EBV promoters in EBV-infected cell lines containing highly methylated viral genomes. Conversely, inhibition of endogenous TET activity increases lytic EBV promoter methylation in an EBV-infected telomerase-immortalized normal oral keratinocyte (NOKs) cell line where lytic viral promoters are largely unmethylated. We demonstrate that these cytosine modifications differentially affect the ability of the two EBV immediate-early proteins, BZLF1 (Z) and BRLF1 (R), to induce the lytic form of viral infection. Although methylation of lytic EBV promoters increases Z-mediated and inhibits R-mediated lytic reactivation, 5hmC modification of lytic EBV promoters has the opposite effect. We also identify a specific CpG-containing Z-binding site on the BRLF1 promoter that must be methylated for Z-mediated viral reactivation and show that TET-mediated 5hmC modification of this site in NOKs prevents Z-mediated viral reactivation. Decreased 5-hydroxymethylation of cellular and viral genes may contribute to NPC formation. PMID:26663912

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

    DOEpatents

    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.

  17. Transcriptome analysis of Zymomonas mobilis ZM4 reveals mechanisms of tolerance and detoxification of phenolic aldehyde inhibitors from lignocellulose pretreatment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Background: Phenolic aldehydes generated from lignocellulose pretreatment exhibited severe toxic inhibitions on microbial growth and fermentation. Numerous tolerance studies against furfural, 5-hydroxymethyl-2-furaldehyde (HMF), acetate, and ethanol were reported, but studies on inhibition of phenol...

  18. Simple gas chromatographic method for furfural analysis.

    PubMed

    Gaspar, Elvira M S M; Lopes, João F

    2009-04-01

    A new, simple, gas chromatographic method was developed for the direct analysis of 5-hydroxymethylfurfural (5-HMF), 2-furfural (2-F) and 5-methylfurfural (5-MF) in liquid and water soluble foods, using direct immersion SPME coupled to GC-FID and/or GC-TOF-MS. The fiber (DVB/CAR/PDMS) conditions were optimized: pH effect, temperature, adsorption and desorption times. The method is simple and accurate (RSD<8%), showed good recoveries (77-107%) and good limits of detection (GC-FID: 1.37 microgL(-1) for 2-F, 8.96 microgL(-1) for 5-MF, 6.52 microgL(-1) for 5-HMF; GC-TOF-MS: 0.3, 1.2 and 0.9 ngmL(-1) for 2-F, 5-MF and 5-HMF, respectively). It was applied to different commercial food matrices: honey, white, demerara, brown and yellow table sugars, and white and red balsamic vinegars. This one-step, sensitive and direct method for the analysis of furfurals will contribute to characterise and quantify their presence in the human diet. PMID:18976770

  19. High performance liquid chromatography of furfural and hydroxymethylfurfural in spirits and honey.

    PubMed

    Jeuring, H J; Kuppers, F J

    1980-11-01

    Furfural (2-furaldehyde) and hydroxymethylfurfural (5-hydroxy-2-furaldehyde, HMF) are determined in brandy and honey by reverse phase high performance liquid chromatography. Brandies and other spirits are injected without sample preparation; honey is diluted with water and the solution is filtered before injection onto a reverse phase column with detection at 285 nm. The mobile phase is methanol--water (10 + 90) and the effluent flow rate is maintained at 1.0 mL/min. External standardization is used for quantitative determination. Recoveries from cognac and honey spiked at different levels ranged from 95 to 99% (furfural) and 95 to 100% (HMF). The furfural content of the brandies was also determined by the existing colorimetric method of the Bureau National Interprofessionel du Cognac. The HMF content of the honey was correlated to the results of the classic method of Winkler. PMID:7451383

  20. Synthesis of 5-Hydroxymethylcytidine- and 5-Hydroxymethyl-uridine-Modified RNA

    PubMed Central

    Riml, Christian; Micura, Ronald

    2016-01-01

    We report on the syntheses of 5-hydroxymethyl-uridine [5hm(rU)] and -cytidine [5hm(rC)] phosphoramidites and their incorporation into RNA by solid-phase synthesis. Deprotection of the oligonucleotides is accomplished in a straightforward manner using standard conditions, confirming the appropriateness of the acetyl protection used for the pseudobenzylic alcohol moieties. The approach provides robust access to 5hm(rC/U)-modified RNAs that await applications in pull-down experiments to identify potential modification enzymes. They will also serve as synthetic probes for the development of high-throughput-sequencing methods in native RNAs. 1Introduction2Protection Strategies Reported for the Synthesis of 5hm(dC)-Modified DNA3Synthesis of 5-Hydroxymethylpyrimidine-Modified RNA3.1Synthesis of 5hm(rC) Phosphoramidite3.2Synthesis of 5hm(rU) Phosphoramidite3.3Synthesis of 5hm(rC)- and 5hm(rU)-Modified RNA4Conclusions PMID:27413246

  1. Furfural and hydroxymethylfurfural tolerance in Escherichia coli ΔacrR regulatory mutants.

    PubMed

    Luhe, Annette Lin; Lim, Chan Yuen; Gerken, Henri; Wu, Jinchuan; Zhao, Hua

    2015-01-01

    The presence of the highly toxic furfural and hydroxymethylfurfural (HMF) in the hydrolysate of lignocellulosic biomass prompted the investigation of the Escherichia coli ΔacrR regulatory mutant for higher tolerance to these compounds, to facilitate the production of biofuels and biochemicals, and further biocatalytic conversions. In comparison with the parental strain, the regulatory mutant with the upregulated efflux pump AcrAB-TolC produced moderately better growth and higher tolerance to concentrations of furfural and HMF between 1 and 2 g L(-1) . PMID:24716991

  2. Effect of cellulosic sugar degradation products (furfural and hydroxymethylfurfural) on acetone-butanol-ethanol (ABE) fermentation using Clostridium beijerinckii P260

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Studies were performed to identify chemicals present in wheat straw hydrolysate (WSH) that enhance acetone butanol ethanol (ABE) productivity. These chemicals were identified as furfural and hydroxymethyl furfural (HMF). Control experiment resulted in the production of 21.09-21.66 gL**-1 ABE with a ...

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

    PubMed

    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

  4. Glycerol supplementation of the growth medium enhances in situ detoxification of furfural by Clostridium beijerinckii during butanol fermentation.

    PubMed

    Ujor, Victor; Agu, Chidozie Victor; Gopalan, Venkat; Ezeji, Thaddeus Chukwuemeka

    2014-01-01

    Lignocellulose-derived microbial inhibitors such as furfural and 5-hydroxymethyl furfural adversely affect fermentation of lignocellulosic biomass hydrolysates to fuels and chemicals due to their toxicity on fermenting microbes. To harness the potential of lignocellulose as a cheap source of fermentable sugars, in situ detoxification of furfural and other lignocellulose-derived microbial inhibitors is essential. To enhance in situ detoxification and tolerance of furfural by Clostridium beijerinckii NCIMB 8052 during acetone-butanol-ethanol (ABE) fermentation, the effect of glycerol on NADH/NADPH generation and ABE production by furfural (4, 5, and 6 g/L)-challenged cultures was investigated in this study. In all instances, beneficial outcomes were observed. For example, the fermentation medium supplemented with glycerol and subjected to 5 g/L furfural elicited up to 1.8- and 3-fold increases, respectively, in NADH and NADPH levels in C. beijerinckii 8052 relative to the control culture. These critical changes are the likely underpinnings for the glycerol-mediated 2.3-fold increase in the rate of detoxification of 5 g/L furfural, substrate consumption, and ABE production compared to the unsupplemented medium. Collectively, these results demonstrate that increased intracellular NADH/NADPH in C. beijerinckii 8052 due to glycerol utilization engenders favorable effects on many aspects of cellular metabolism, including enhanced furfural reduction and increased ABE production. PMID:24839212

  5. Study of hydroxymethylfurfural and furfural formation in cakes during baking in different ovens, using a validated multiple-stage extraction-based analytical method.

    PubMed

    Petisca, Catarina; Henriques, Ana Rita; Pérez-Palacios, Trinidad; Pinho, Olívia; Ferreira, Isabel M P L V O

    2013-12-15

    A procedure for extraction of hydroxymethylfurfural (HMF) and furfural from cakes was validated. Higher yield was achieved by multiple step extraction with water/methanol (70/30) and clarification with Carrez I and II reagents. Oven type and baking time strongly influenced HMF, moisture and volatile profile of model cakes, whereas furfural content was not significantly affected. No correlation was found between these parameters. Baking time influenced moisture and HMF formation in cakes from traditional and microwave ovens but not in steam oven cakes. Significant moisture decrease and HMF increase (3.63, 9.32, and 41.9 mg kg(-1)dw at 20, 40 and 60 min, respectively) were observed during traditional baking. Cakes baked by microwave also presented a significant increase of HMF (up to 16.84 mg kg(-1)dw at 2.5 min). Steam oven cakes possessed the highest moisture content and no significant differences in HMF and furfural. This oven is likely to form low HMF and furfural, maintaining cake moisture and aroma compounds. PMID:23993492

  6. YNL134C from Saccharomyces cerevisiae encodes a novel protein with aldehyde reductase activity for detoxification of furfural derived from lignocellulosic biomass.

    PubMed

    Zhao, Xianxian; Tang, Juan; Wang, Xu; Yang, Ruoheng; Zhang, Xiaoping; Gu, Yunfu; Li, Xi; Ma, Menggen

    2015-05-01

    Furfural and 5-hydroxymethylfurfural (HMF) are the two main aldehyde compounds derived from pentoses and hexoses, respectively, during lignocellulosic biomass pretreatment. These two compounds inhibit microbial growth and interfere with subsequent alcohol fermentation. Saccharomyces cerevisiae has the in situ ability to detoxify furfural and HMF to the less toxic 2-furanmethanol (FM) and furan-2,5-dimethanol (FDM), respectively. Herein, we report that an uncharacterized gene, YNL134C, was highly up-regulated under furfural or HMF stress and Yap1p and Msn2/4p transcription factors likely controlled its up-regulated expression. Enzyme activity assays showed that YNL134C is an NADH-dependent aldehyde reductase, which plays a role in detoxification of furfural to FM. However, no NADH- or NADPH-dependent enzyme activity was observed for detoxification of HMF to FDM. This enzyme did not catalyse the reverse reaction of FM to furfural or FDM to HMF. Further studies showed that YNL134C is a broad-substrate aldehyde reductase, which can reduce multiple aldehydes to their corresponding alcohols. Although YNL134C is grouped into the quinone oxidoreductase family, no quinone reductase activity was observed using 1,2-naphthoquinone or 9,10-phenanthrenequinone as a substrate, and phylogenetic analysis indicates that it is genetically distant to quinone reductases. Proteins similar to YNL134C in sequence from S. cerevisiae and other microorganisms were phylogenetically analysed. PMID:25656244

  7. Direct Observation of Self-Organized Water-Containing Structures in the Liquid Phase and Their Influence on 5-(Hydroxymethyl)furfural Formation in Ionic Liquids.

    PubMed

    Kashin, Alexey S; Galkin, Konstantin I; Khokhlova, Elena A; Ananikov, Valentine P

    2016-02-01

    Water-containing organic solutions are widespread reaction media in organic synthesis and catalysis. This type of multicomponent liquid system has a number of unique properties because of the tendency for water to self-organize in mixtures with other liquids. The characterization of these water domains is a challenging task because of their soft and dynamic nature. In the present study, the morphology and dynamics of micrometer- and nanometer-scale water-containing compartments in ionic liquids were directly observed by electron microscopy. A variety of morphologies, including isolated droplets, dense structures, aggregates, and 2D meshworks, have been experimentally detected and studied. Using the developed method, the impact of water on the acid-catalyzed biomass conversion reaction was studied at the microscopic level. The process that produced nanostructured domains in solution led to better yields and higher selectivities compared with reactions involving the bulk system. PMID:26754786

  8. Conversion of corn stalk into furfural using a novel heterogeneous strong acid catalyst in γ-valerolactone.

    PubMed

    Xu, Zhiping; Li, Wenzhi; Du, Zhijie; Wu, Hao; Jameel, Hasan; Chang, Hou-Min; Ma, Longlong

    2015-12-01

    A novel solid acid catalyst was prepared by the copolymerization of p-toluenesulfonic acid and paraformaldehyde and then characterized by FT-IR, TG/DTG, HRTEM and N2-BET. Furfural was successfully produced by the dehydration of xylose and xylan using the novel catalyst in γ-valerolactone. This investigation focused on effects of various reaction conditions including solvent, acid catalyst, reaction temperature, residence time, water concentration, xylose loading and catalyst dosage on the dehydration of xylose to furfural. It was found that the solid catalyst displayed extremely high activity for furfural production. 80.4% furfural yield with 98.8% xylose conversion was achieved at 170°C for 10 min. The catalyst could be recycled at least five times without significant loss of activity. Furthermore, 83.5% furfural yield and 19.5% HMF yield were obtained from raw corn stalk under more severe conditions (190°C for 100 min). PMID:26454364

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  10. Comparative transcriptome profiling analyses during the lag phase uncover YAP1, PDR1, PDR3, RPN4, and HSF1 as key regulatory genes in genomic adaptation to the lignocellulose derived inhibitor HMF for Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The yeast Saccharomyces cerevisiae is able to adapt and in situ detoxify lignocellulose derived inhibitors such as furfural and hydroxymethylfurfural (HMF). The length of lag phase for cell growth in response to the inhibitor challenge has been used to measure tolerance of strain performance. Mechan...

  11. One-Pot Conversion of Carbohydrates into Furan Derivatives via Furfural and 5-Hydroxylmethylfurfural as Intermediates.

    PubMed

    Liu, Bing; Zhang, Zehui

    2016-08-23

    Recently, there has been growing interest in the transformation of renewable biomass into value-added fuels and chemicals. The catalytic conversion of naturally abundant carbohydrates can generate two-important furan chemicals: 5-hydroxymethylfurfural (HMF) from C6 carbohydrates and furfural from C5 carbohydrates. Both HMF and furfural have received great interest as precursors in the synthesis of commodity chemicals and liquid fuels. In recent years, a trend has emerged to integrate sequential catalytic processes involving multistep reactions for the direct one-pot transformation of carbohydrates into the aimed fuels and chemicals. One-pot reactions have remarkably unique and environmentally friendly benefits, including the fact that isolation and purification of intermediate compounds can be avoided. Herein, the present article aims to review recent advances in the one-pot conversion of carbohydrates into furan derivatives via furfural and HMF as intermediates. Special attention will be paid to the catalytic systems, mechanistic insight, reaction pathways, and catalyst stability. It is expected that this review will guide researchers to develop effective catalytic systems for the one-pot transformation of carbohydrates into furan derivatives. PMID:27396713

  12. A kinetic study on microwave-assisted conversion of cellulose and lignocellulosic waste into hydroxymethylfurfural/furfural.

    PubMed

    da Silva Lacerda, Viviane; López-Sotelo, Juan Benito; Correa-Guimarães, Adriana; Hernández-Navarro, Salvador; Sánchez-Bascones, Mercedes; Navas-Gracia, Luis M; Martín-Ramos, Pablo; Pérez-Lebeña, Eduardo; Martín-Gil, Jesús

    2015-03-01

    Native cellulose, lignocellulosic materials from Brazil (carnauba palm leaves and macauba pulp and shell) and pine nut shell from Spain have been studied as substrates for the production of HMF and furfural in a conventional microwave oven. In order to promote the dissolution of native cellulose, several ionic liquids, catalysts, organic solvents and water doses have been assessed. The most suitable mixture (5mL of choline chloride/oxalic acid, 2mL of sulfolane, 2mL of water, 0.02g of TiO2 and 0.1g of substrate) has been chosen to conduct kinetic studies at different reaction times (5-60min) and various temperatures (120-200°C) and to evaluate the best conditions for HMF+furfural production according to Seaman's model. The best production yields of HMF+furfural have been attained for native cellulose, with a yield of 53.24% when an ultrasonic pretreatment was used prior to a microwave treatment with stirring. PMID:25590423

  13. One-pot conversions of raffinose into furfural derivatives and sugar alcohols by using heterogeneous catalysts.

    PubMed

    Dabral, Saumya; Nishimura, Shun; Ebitani, Kohki

    2014-01-01

    Inedible and/or waste biomass reserves are being strongly focused upon as a suitable new energy and chemical source. Raffinose, which is an indigestible trisaccharide composed of glucose, galactose, and fructose, is found abundantly in beet molasses, sugar cane, and seeds of many leguminous plants. Herein, we demonstrate the one-pot synthesis of furan derivatives and sugar alcohols from raffinose by using heterogeneous acid, base, and/or metal-supported catalysts. The combination of Amberlyst-15 and hydrotalcite (HT) showed a high activity (37% yield) for 5-hydroxymethyl-2-furaldehyde (HMF) through continuous hydrolysis, isomerization, and dehydration reactions. In addition, the use of a hydrotalcite-supported ruthenium catalyst (Ru/HT) successfully afforded 2,5-diformylfuran (DFF, 27% yield) from HMF produced by raffinose, directly. Moreover, the hydrogenation of hexoses obtained by raffinose hydrolysis into sugar alcohols (galactitol, mannitol, sorbitol) was also achieved in a high yield (91%) with Amberlyst-15 and Ru/HT catalysts. Thus, we suggest that raffinose has great potential for the synthesis of important industrial intermediates under mild reaction conditions. PMID:24193816

  14. Lipase-mediated selective oxidation of furfural and 5-hydroxymethylfurfural.

    PubMed

    Krystof, Monika; Pérez-Sánchez, María; Domínguez de María, Pablo

    2013-05-01

    Furfural and 5-hydroxymethylfurfural (HMF) are important biomass-derived platform chemicals that can be obtained from the dehydration of lignocellulosic sugars. A possible route for the derivatization of furanics is their oxidation to afford a broad range of chemicals with promising applications (e.g., diacids, hydroxyl acids, aldehyde acids, monomers for novel polymers). Herein we explore the organic peracid-assisted oxidation of furanics under mild reaction conditions. Using lipases as biocatalysts, alkyl esters as acyl donors, and aqueous solutions of hydrogen peroxide (30 % v/v) added stepwise, peracids are formed in situ, which subsequently oxidize the aldehyde groups to afford carboxylic acids with high yields and excellent selectivities. Furthermore, the use of an immobilized silica-based 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) affords the selective oxidation of the hydroxymethyl group of HMF to afford 2,5-diformylfuran. That product can be subsequently oxidized using again lipases for the in situ peracid formation to yield 2,5-furandicarboxylic acid, which is considered to be a key building block for biorefineries. These lipase-mediated reactions proceeded efficiently even with high substrate loadings under still non-optimized conditions. Overall, a proof-of-concept for the oxidation of furanics (based on in situ formed organic peracids as oxidants) is provided. PMID:23576295

  15. Synthesis of 1-benzyl-3-(5-hydroxymethyl-2-furyl)selenolo[3,2-c]pyrazole derivatives as new anticancer agents.

    PubMed

    Chou, Li-Chen; Huang, Li-Jiau; Hsu, Mei-Hua; Fang, Mei-Chi; Yang, Jai-Sing; Zhuang, Shi-Hong; Lin, Hui-Yi; Lee, Fang-Yu; Teng, Che-Ming; Kuo, Sheng-Chu

    2010-04-01

    As part of our continuing search for potential anticancer drug candidates among YC-1 analogs, 1, 3-disubstituted selenolo[3,2-c]pyrazole derivatives were synthesized and evaluated for their cytotoxicity against NCI-H226 non-small cell lung cancer and A-498 renal cancer cell lines. Significant cytotoxicity was observed in 3-(5-hydroxymethyl-2-furyl) derivatives (2, 33, 36 and 37). Among them, compound 2 was found to have the most potent activity. The mode of action of compound 2 seems to differ from those of the 175 anticancer agents listed in NCI's standard database and resembles that of YC-1. Thus, we recommend that compound 2 should be developed further as new drug candidate for treatment of non-small cell lung cancer and renal cancer. PMID:20097456

  16. A review of 5-hydroxymethylfurfural (HMF) in parenteral solutions.

    PubMed

    Ulbricht, R J; Northup, S J; Thomas, J A

    1984-10-01

    The chemical formation, toxicity, and pharmacokinetics of 5-hydroxymethylfurfural (HMF) and certain other decomposition products found in parenteral solutions are reviewed. Heat sterilization-induced hexose decomposition to furan derivatives is promoted at low pH. Based upon infusion studies with rats and dogs, HMF does not appear to be acutely toxic at concentrations ordinarily encountered in parenteral infusion solutions (e.g., 10 mg/liter). Dosages of parenterally administered HMF exceeding 75 mg/kg body wt have led to some toxic effects, including increased activity of hepatic enzymes, altered serum-protein fractions, increased relative spleen weight, and hepatic fatty degeneration. Approximately 50% of parenterally administered HMF is oxidized and eliminated by the kidneys. From a clinical standpoint, the amount of HMF formed as a result of the heat sterilization of parenteral solutions containing hexoses does not seem to pose any significant toxicologic problem. PMID:6391997

  17. Enhanced stabilization of collagen by furfural.

    PubMed

    Lakra, Rachita; Kiran, Manikantan Syamala; Usha, Ramamoorthy; Mohan, Ranganathan; Sundaresan, Raja; Korrapati, Purna Sai

    2014-04-01

    Furfural (2-furancarboxaldehyde), a product derived from plant pentosans, has been investigated for its interaction with collagen. Introduction of furfural during fibril formation enhanced the thermal and mechanical stability of collagen. Collagen films treated with furfural exhibited higher denaturation temperature (Td) (p<0.04) and showed a 3-fold increase in Young's modulus (p<0.04) at higher concentration. Furfural and furfural treated collagen films did not have any cytotoxic effect. Rheological characterization showed an increase in shear stress and shear viscosity with increasing shear rate for treated collagen. Circular dichroism (CD) studies indicated that the furfural did not have any impact on triple helical structure of collagen. Scanning electron microscopy (SEM) of furfural treated collagen exhibited small sized porous structure in comparison with untreated collagen. Thus this study provides an alternate ecologically safe crosslinking agent for improving the stability of collagen for biomedical and industrial applications. PMID:24468046

  18. Interconversion algorithm between mechanical and dielectric relaxation measurements for acetate of cis- and trans-2-phenyl-5-hydroxymethyl-1,3-dioxane

    NASA Astrophysics Data System (ADS)

    Garcia-Bernabé, A.; Lidón-Roger, J. V.; Sanchis, M. J.; Díaz-Calleja, R.; del Castillo, L. F.

    2015-10-01

    The dielectric and mechanical spectroscopies of acetate of cis- and trans-2-phenyl-5-hydroxymethyl-1,3-dioxane are reported in the frequency domain from 10-2 to 106Hz . This ester has been selected in this study for its predominant α relaxation with regard to the β relaxation, which can be neglected. This study consists of determining an interconversion algorithm between dielectric and mechanical measurements, given by using a relation between rotational and translational complex viscosities. These important viscosities were obtained from measures of the dielectric complex permittivity and by dynamic mechanical analysis, respectively. The definitions of rotational and translational viscosities were evaluated by means of fractional calculus, by using the fit parameters of the Havriliak-Negami empirical model obtained in the dielectric and mechanical characterization of the α relaxation. This interconversion algorithm is a generalization of the break of the Stokes-Einstein-Debye relationship. It uses a power law with an exponent defined as the shape factor, which modifies the translational viscosity. Two others factors are introduced for the interconversion, a shift factor, which displaces the translational viscosity in the frequency domain, and a scale factor, which makes equal values of the two viscosities. In this paper, the shape factor has been identified as the relation between the slopes of the moduli of the complex viscosities at higher frequency. This is interpreted as the degree of kinetic coupling between the molecular rotation and translational movements. Alternatively, another interconversion algorithm has been expressed by means of dielectric and mechanical moduli.

  19. Vortex-assisted liquid-liquid microextraction coupled with high performance liquid chromatography for the determination of furfurals and patulin in fruit juices.

    PubMed

    Abu-Bakar, Nur-Bahiyah; Makahleh, Ahmad; Saad, Bahruddin

    2014-03-01

    A fast and simple solvent microextraction technique using salting out-vortex-assisted liquid-liquid microextraction (salting out-VALLME) was developed for the extraction of furfurals (2-furfural (2-F), 3-furfural (3-F), 5-methylfurfural (5-MF) and 5-hydroxymethylfurfural (5-HMF)) and patulin (PAT) in fruit juice samples. The optimum extraction conditions for 5 mL sample were: extraction solvent, 1-hexanol; volume of extractant, 200 µL; vortex time, 45 s; salt addition, 20%. The simultaneous determination of the furfurals and PAT were investigated using high performance liquid chromatography coupled with diode array detector (HPLC-DAD). The separation was performed using ODS Hypersil C18 column (4.6 mm i.d × 250 mm, 5 μm) under gradient elution. The detection wavelengths used for all compounds were 280 nm except for 3-F (210 nm). The furfurals and PAT were successfully separated in less than 9 min. Good linearities (r(2)>0.99) were obtained within the range 1-5000 μg L(-1) for all compounds except for 3-F (10-5000 µg L(-1)) and PAT (0.5-100 μg L(-1)). The limits of detection (0.28-3.2 µg L(-1)) were estimated at S/N ratio of 3. The validated salting out-VALLME-HPLC method was applied for the analysis of furfurals and PAT in fruit juice samples (apple, mango and grape). PMID:24468341

  20. Furfural production using ionic liquids: A review.

    PubMed

    Peleteiro, Susana; Rivas, Sandra; Alonso, José Luis; Santos, Valentín; Parajó, Juan Carlos

    2016-02-01

    Furfural, a platform chemical with a bright future, is commercially obtained by acidic processing of xylan-containing biomass in aqueous media. Ionic liquids (ILs) can be employed in processed for furfural manufacture as additives, as catalysts and/or as reaction media. Depending on the IL utilized, externally added catalysts (usually, Lewis acids, Brönsted acids and/or solid acid catalysts) can be necessary to achieve high reaction yields. Oppositely, acidic ionic liquids (AILs) can perform as both solvents and catalysts, enabling the direct conversion of suitable substrates (pentoses, pentosans or xylan-containing biomass) into furfural. Operating in IL-containing media, the furfural yields can be improved when the product is continuously removed along the reaction (for example, by stripping or extraction), to avoid unwanted side-reactions leading to furfural consumption. These topics are reviewed, as well as the major challenges involved in the large scale utilization of ILs for furfural production. PMID:26708486

  1. Effects of furan derivatives on biohydrogen fermentation from wet steam-exploded cornstalk and its microbial community.

    PubMed

    Liu, Zhidan; Zhang, Chong; Wang, Linjun; He, Jianwei; Li, Baoming; Zhang, Yuanhui; Xing, Xin-Hui

    2015-01-01

    Understanding the role of furan derivatives, furfural (FUR) and 5-hydroxymethyl furfural (HMF), is important for biofuel production from lignocellulosic biomass. In this study, the effects of furan derivatives on hydrogen fermentation from wet steam-exploded cornstalk were investigated. The control experiments with only seed sludge indicated that HMF addition of up to 1g/L stimulated hydrogen production. Similar results were obtained using steam-exploded cornstalk as the feedstock. Hydrogen productivity was increased by up to 40% with the addition of HMF. In addition, over 90% of furan derivatives with an initial concentration below 1g/L were degraded. Pyosequencing showed that the addition of HMF and FUR resulted in different microbial communities. HMF led to a higher proportion of the genera Clostridium and Ruminococcaceae, supporting the increased hydrogen production. This study suggested that hydrogen fermentation could be a detoxifying step for steam-exploded cornstalk, and HMF and FUR exhibited different functions for hydrogen fermentation. PMID:25459816

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

    PubMed

    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

  3. Process for producing furan from furfural aldehyde

    DOEpatents

    Diebold, James P.; Evans, Robert J.

    1988-01-01

    A process of producing furan and derivatives thereof is disclosed. The process includes generating furfural aldehyde vapors and then passing those vapors over a zeolite catalyst at a temperature and for a residence time effective to decarbonylate the furfural aldehydes to form furans and derivatives thereof. The resultant furan vapors and derivatives are then separated. In a preferred form, the furfural aldehyde vapors are generated during the process of converting biomass materials to liquid and gaseous fuels.

  4. Process for producing furan from furfural aldehyde

    DOEpatents

    Diebold, J.P.; Evans, R.J.

    1987-04-06

    A process of producing furan and derivatives thereof as disclosed. The process includes generating furfural aldehyde vapors and then passing those vapors over a zeolite catalyst at a temperature and for a residence time effective to decarbonylate the furfural aldehydes to form furans and derivatives thereof. The resultant furan vapors and derivatives are then separated. In a preferred form, the furfural aldehyde vapors are generated during the process of converting biomass materials to liquid and gaseous fuels.

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

    PubMed

    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

  6. Interconversion algorithm between mechanical and dielectric relaxation measurements for acetate of cis- and trans-2-phenyl-5-hydroxymethyl-1,3-dioxane.

    PubMed

    Garcia-Bernabé, A; Lidón-Roger, J V; Sanchis, M J; Díaz-Calleja, R; del Castillo, L F

    2015-10-01

    The dielectric and mechanical spectroscopies of acetate of cis- and trans-2-phenyl-5-hydroxymethyl-1,3-dioxane are reported in the frequency domain from 10(-2) to 10(6)Hz. This ester has been selected in this study for its predominant α relaxation with regard to the β relaxation, which can be neglected. This study consists of determining an interconversion algorithm between dielectric and mechanical measurements, given by using a relation between rotational and translational complex viscosities. These important viscosities were obtained from measures of the dielectric complex permittivity and by dynamic mechanical analysis, respectively. The definitions of rotational and translational viscosities were evaluated by means of fractional calculus, by using the fit parameters of the Havriliak-Negami empirical model obtained in the dielectric and mechanical characterization of the α relaxation. This interconversion algorithm is a generalization of the break of the Stokes-Einstein-Debye relationship. It uses a power law with an exponent defined as the shape factor, which modifies the translational viscosity. Two others factors are introduced for the interconversion, a shift factor, which displaces the translational viscosity in the frequency domain, and a scale factor, which makes equal values of the two viscosities. In this paper, the shape factor has been identified as the relation between the slopes of the moduli of the complex viscosities at higher frequency. This is interpreted as the degree of kinetic coupling between the molecular rotation and translational movements. Alternatively, another interconversion algorithm has been expressed by means of dielectric and mechanical moduli. PMID:26565240

  7. Associations of urinary 5-methyl-2'-deoxycytidine and 5-hydroxymethyl-2'-deoxycytidine with phthalate exposure and semen quality in 562 Chinese adult men.

    PubMed

    Pan, Yitao; Jing, Jun; Yeung, Leo W Y; Sheng, Nan; Zhang, Hongxia; Yao, Bing; Dai, Jiayin

    2016-09-01

    5-methyl-2'-deoxycytidine (5mdC) and 5-hydroxymethyl-2'-deoxycytidine (5hmdC), products of DNA methylation and hydroxymethylation processes, have been detected previously in human urine, but their associations with environmental chemicals or healthy outcomes are unclear. The present investigation explored the associations between urinary 5mdC and 5hmdC with phthalate exposure and semen quality. We assessed semen parameters including sperm concentration, motility, and morphology, before measuring urinary 5mdC, 5hmdC and 13 phthalate metabolites among 562 subfertile men from Nanjing, China. Urinary 5mdC and 5hmdC were positively associated with the levels of low molecular weight phthalate metabolites (Low-MWP), high molecular weight phthalate metabolites (High-MWP), and the sum of all phthalate metabolites (ΣPAEs), respectively. Urinary 5mdC was associated with below-reference sperm concentration (odds ratios for increasing quartiles=1.0, 2.2, 3.0, 2.0; p for trend =0.02), sperm motility (1.0, 1.1, 1.9, 1.3; p for trend =0.05), and sperm morphology (1.0, 1.4, 2.3, 1.5; p for trend =0.05). Sperm concentration was associated with the highest quartile of urinary 5hmdC [odds ratio=1.9 (95% CI: 1.1, 3.6)]. Our findings showed significant associations between urinary 5mdC and 5hmdC with phthalate metabolites and semen parameters, which suggested urinary 5mdC and 5hmdC may be promising biomarkers in future epidemiological studies. PMID:27346742

  8. Extraction of furfural with carbon dioxide

    SciTech Connect

    Gamse, T.; Marr, R.; Froeschl, F.; Siebenhofer, M.

    1997-01-01

    A new approach to separate furfural from aqueous waste has been investigated. Recovery of furfural and acetic acid from aqueous effluents of a paper mill has successfully been applied on an industrial scale since 1981. The process is based on the extraction of furfural and acetic acid by the solvent trooctylphosphineoxide (TOPO). Common extraction of both substances may cause the formation of resin residues. Improvement was expected by selective extraction of furfural with chlorinated hydrocarbons, but ecological reasons stopped further development of this project. The current investigation is centered in the evaluation of extraction of furfural by supercritical carbon dioxide. The influence of temperature and pressure on the extraction properties has been worked out. The investigation has considered the multi-component system furfural-acetic acid-water-carbon dioxide. Solubility of furfural in liquid and supercritical carbon dioxide has been measured, and equilibrium data for the ternary system furfural-water-CO{sub 2} as well as for the quaternary system furfural-acetic acid-water-CO{sub 2} have been determined. A high-pressure extraction column has been used for evaluation of mass transfer rates.

  9. Aerosol Chemistry of Furfural and Sugars

    NASA Astrophysics Data System (ADS)

    Srithawirat, T.; Brimblecombe, P.

    2008-12-01

    Furfural and sugars (as levoglucosan equivalent) are derived from biomass burning and contribute to aerosol composition. This study examined the potential of furfural and levoglucosan to be tracers of biomass burning. Furfural is likely to be oxidized quickly so comparison with levoglucosan may give a sense of the age of the aerosols in forest fire smoke. However, few furfural emissions are available for biomass combustion. Furfural and sugars were determined in coarse aerosols (>2.4μm aerodynamic diameter) and fine aerosols (<2.4μm aerodynamic diameter) collected in 24 hour periods during different seasons in the United Kingdom and PM10 collected from Thailand and Malaysia including haze episodes. Also total suspended particulate matter (TSP) samples were collected from Taiwan. Furfural and sugars dominated in fine fractions, especially in the UK autumn. Sugars were found at 5.96-18.37 nmol m-3 in fine mode and 1.36-5.75 nmol m-3 in coarse mode aerosols in the UK. Furfural was found at 0.18-0.91 nmol m-3 and 0.05-0.51 nmol m-3 respectively in the same aerosols. Sugars were a dominant contributor to aerosol derived from biomass burning. Sugars and furfural were about 10 and 20 times higher during haze episodes in Malaysia. Laboratory experimental simulation suggested furfural is more rapid destroyed by UV and sunlight than levoglucosan.

  10. Process for producing furan from furfural aldehyde

    SciTech Connect

    Diebold, J.P.; Evans, R.J.

    1988-08-16

    A process is described for producing furans and derivatives thereof comprising generating furfural vapors, passing the vapors over a zeolite catalyst at a WHSV ratio of about 18-38 in an acidic environment, and at a temperature and for a residence time effective to decarbonylate the furfural to the furans and derivatives thereof, and separating the resultant furan and furan derivative vapors.

  11. Solvent Extraction of Furfural From Biomass

    NASA Technical Reports Server (NTRS)

    Humphrey, M. F.

    1984-01-01

    Solvent-extraction method reduces energy required to remove furfural produced during acid hydrolysis of biomass. Acid hydrolysis performed in vessel containing both solvents and reacting ingredients. With intimate contact between solvents and aqueous hydrolyis liqour, furfural removed form liquor almost as fast as it forms.

  12. Studies of the Raman spectra of cyclic and acyclic molecules: Combination and prediction spectrum methods

    NASA Astrophysics Data System (ADS)

    Kim, Taejin; Assary, Rajeev S.; Marshall, Christopher L.; Gosztola, David J.; Curtiss, Larry A.; Stair, Peter C.

    2012-04-01

    A combination of Raman spectroscopy and density functional methods was employed to investigate the spectral features of selected molecules: furfural, 5-hydroxymethyl furfural (HMF), methanol, acetone, acetic acid, and levulinic acid. The computed spectra and measured spectra are in excellent agreement, consistent with previous studies. Using the combination and prediction spectrum method (CPSM), we were able to predict the important spectral features of two platform chemicals, HMF and levulinic acid. The results have shown that CPSM is a useful alternative method for predicting vibrational spectra of complex molecules in the biomass transformation process.

  13. Studies of the Raman Spectra of Cyclic and Acyclic Molecules: Combination and Prediction Spectrum Methods

    SciTech Connect

    Kim, Taijin; Assary, Rajeev S.; Marshall, Christopher L.; Gosztola, David J.; Curtiss, Larry A.; Stair, Peter C.

    2012-04-02

    A combination of Raman spectroscopy and density functional methods was employed to investigate the spectral features of selected molecules: furfural, 5-hydroxymethyl furfural (HMF), methanol, acetone, acetic acid, and levulinic acid. The computed spectra and measured spectra are in excellent agreement, consistent with previous studies. Using the combination and prediction spectrum method (CPSM), we were able to predict the important spectral features of two platform chemicals, HMF and levulinic acid.The results have shown that CPSM is a useful alternative method for predicting vibrational spectra of complex molecules in the biomass transformation process.

  14. Ethanologenic bacteria with increased resistance to furfural

    SciTech Connect

    Miller, Elliot Norman; Jarboe, Laura R.; Yomano, Lorraine P.; York, Sean W.; Shanmugam, Keelnatham; Ingram, Lonnie O'Neal

    2015-10-06

    The invention relates to bacterium that have increased resistance to furfural and methods of preparation. The invention also relates to methods of producing ethanol using the bacterium and corresponding kits.

  15. Value of furfural/ethanol coproduction from acid hydrolysis processes

    SciTech Connect

    Parker, S.; Calnon, M.; Feinberg, D.; Power, A.; Weiss, L.

    1983-08-01

    The benefits of two modifications in the acid hydrolysis of cellulosic feedstocks for the production of ethanol fuels were investigated: marketing of the by-product furfural and xylose fermentation. Preliminary analysis indicate that the furfural by-product furfural and xylose fermentation. Perliminary analyses indicate that the furfural by-product credit is more beneficial at a minimum net profit of $0.08/lb of furfural. For this credit to have a major impact on ethanol production costs, new markets for large quantities of furfural must be identified. Furfural can be an alternative feedstock for hydrocarbon-based commodity chemicals. The costs and profitabilities of producing five chemicals from furfurals as opposed to conventional hydrocarbon-based feedstocks were studied. The furfural processes for production of styrene and butadiene were found to be marginally competitive or not competitive. The furfural processes for adipic acid, maleic anhydride, and butanol could be competitive. Results of analysis by a computer model of the petrochemical industry indicate that with furfural markets additional to these three furfural processes, over 2.5 x 10/sup 9/ gal of ethanol could be marketed at about $1.00/gal. Converting the xylose stream to ethanol has about the same effect on the selling price of ethanol as the furfural credit. The greatest ethanol production will result from xylose fermentation, but the furfural credit offers large near-term profits and has a more diversified impact on reducing petroleum product demand. 6 figures, 17 tables.

  16. Microwave spectrum and structure of furfural

    NASA Astrophysics Data System (ADS)

    Motiyenko, R. A.; Alekseev, E. A.; Dyubko, S. F.; Lovas, F. J.

    2006-11-01

    The microwave spectrum of furfural was investigated in the frequency range 7 GHz-21 GHz and 49 GHz-330 GHz. The ground and first torsional state of trans-furfural and ground state of cis-furfural were assigned and analyzed. A total of 1720 rotational lines with J up to 100 and Ka up to 53 were assigned to the ground state of trans-furfural, 1406 rotational lines with J up to 100 and Ka up to 48 were assigned to the first torsional state of trans-furfural and 2103 rotational lines with J up to 90 and Ka up to 48 to the ground state of cis-furfural. Accurate sets of centrifugal distortion constants for both conformations have been determined for the first time. The spectra of all 13C and 18O singly substituted isotopic species were observed in natural abundance in the 7 GHz-21 GHz range. Molecular structure co-ordinates, bond lengths and angles of the Kraitchman substitution type ( rs) and pseudo-Kraitchman type ( rpKr) are derived from the isotopic studies.

  17. Malassezia furfur in infantile seborrheic dermatitis.

    PubMed

    Tollesson, A; Frithz, A; Stenlund, K

    1997-01-01

    Malassezia furfur is important in the pathogenesis of a number of dermatologic diseases including seborrheic dermatitis in adults. It has also recently been suggested that M. furfur might be the etiologic agent in infantile seborrheic dermatitis (ISD). We studied the presence of M. furfur in 21 children with the clinical diagnosis of infantile seborrheic dermatitis. Laboratory analyses showed aberrant patterns of essential fatty acids (EFA) in serum characterized by elevated levels of 18:1w9 and 20:2w6. Samples for M. furfur were taken from the foreheads and chests of children with infantile seborrheic dermatitis at the time of diagnosis, directly after treatment to complete healing, and after 1 year with no signs of infantile seborrheic dermatitis. All the patients were treated topically with borage oil containing 25% gammalinolenic acid (GLA). No reduced growth of M. furfur was seen on contact plates prepared with borage oil. The growth of M. furfur seems not to be related to the clinical symptoms in ISD. PMID:9436835

  18. First identification of primary nanoparticles in the aggregation of HMF.

    PubMed

    Zhang, Mu; Yang, Hong; Liu, Yinong; Sun, Xudong; Zhang, Dongke; Xue, Dongfeng

    2012-01-01

    5-Hydroxymethylfurfural [HMF] is an important intermediate compound for fine chemicals. It is often obtained via hydrothermal treatment of biomass-derived carbohydrates, such as fructose, glucose and sucrose. This study investigates the formation of carbonaceous spheres from HMF created by dehydration of fructose under hydrothermal conditions. The carbonaceous spheres, ranging between 0.4 and 10 μm in diameter, have granulated morphologies both on the surface and in the interior. The residual solution is found to contain a massive number of primary nanoparticles. The chemical structure of the carbonaceous spheres was characterised by means of FTIR and NMR spectroscopies. Based on these observations, a mechanism involving the formation and aggregation of the nanoparticles is proposed. This mechanism differs considerably from the conventional understanding in the open literature. PMID:22221552

  19. First identification of primary nanoparticles in the aggregation of HMF

    NASA Astrophysics Data System (ADS)

    Zhang, Mu; Yang, Hong; Liu, Yinong; Sun, Xudong; Zhang, Dongke; Xue, Dongfeng

    2012-01-01

    5-Hydroxymethylfurfural [HMF] is an important intermediate compound for fine chemicals. It is often obtained via hydrothermal treatment of biomass-derived carbohydrates, such as fructose, glucose and sucrose. This study investigates the formation of carbonaceous spheres from HMF created by dehydration of fructose under hydrothermal conditions. The carbonaceous spheres, ranging between 0.4 and 10 μm in diameter, have granulated morphologies both on the surface and in the interior. The residual solution is found to contain a massive number of primary nanoparticles. The chemical structure of the carbonaceous spheres was characterised by means of FTIR and NMR spectroscopies. Based on these observations, a mechanism involving the formation and aggregation of the nanoparticles is proposed. This mechanism differs considerably from the conventional understanding in the open literature.

  20. First identification of primary nanoparticles in the aggregation of HMF

    PubMed Central

    2012-01-01

    5-Hydroxymethylfurfural [HMF] is an important intermediate compound for fine chemicals. It is often obtained via hydrothermal treatment of biomass-derived carbohydrates, such as fructose, glucose and sucrose. This study investigates the formation of carbonaceous spheres from HMF created by dehydration of fructose under hydrothermal conditions. The carbonaceous spheres, ranging between 0.4 and 10 μm in diameter, have granulated morphologies both on the surface and in the interior. The residual solution is found to contain a massive number of primary nanoparticles. The chemical structure of the carbonaceous spheres was characterised by means of FTIR and NMR spectroscopies. Based on these observations, a mechanism involving the formation and aggregation of the nanoparticles is proposed. This mechanism differs considerably from the conventional understanding in the open literature. PMID:22221552

  1. A new β-glucosidase producing yeast for lower-cost cellulosic ethanol production from xylose-extracted corncob residues by simultaneous saccharification and fermentation.

    PubMed

    Liu, Z Lewis; Weber, Scott A; Cotta, Michael A; Li, Shi-Zhong

    2012-01-01

    This study reports a new yeast strain of Clavispora NRRL Y-50464 that is able to utilize cellobiose as sole source of carbon and produce sufficient native β-glucosidase enzyme activity for cellulosic ethanol production using SSF. In addition, this yeast is tolerant to the major inhibitors derived from lignocellulosic biomass pre-treatment such as 2-furaldehyde (furfural) and 5-(hydroxymethyl)-2-furaldehyde (HMF), and converted furfural into furan methanol in less than 12h and HMF into furan-2,5-dimethanol within 24h in the presence of 15 mM each of furfural and HMF. Using xylose-extracted corncob residue as cellulosic feedstock, an ethanol production of 23 g/l was obtained using 25% solids loading at 37 °C by SSF without addition of exogenous β-glucosidase. Development of this yeast aids renewable biofuels development efforts for economic consolidated SSF bio-processing. PMID:22133603

  2. Separating acetic acid from furol (furfural) by electrodialysis method

    SciTech Connect

    Guan, S.F.; Li, C.S. Ye, S.T.; Shen, S.Y.; Wang, Y.T.; Yu, S.H.

    1981-01-01

    Furfural production by hydrolysis of fibrous plant materials is accompanied by formation of acetic acid in amounts depending on the material used. The amount of acetic formed in the hydrolysis of the fruit shell of oil-tea camellia (Camellia oleosa) (an oilseed-bearing tree) is equal to the amount of furfural. The acetic acid can be separated from the furfural and concentrated to 10% by electrodialysis. A smaller amount of furfural is separated with acetic acid.

  3. In vitro susceptibility of Malassezia furfur.

    PubMed

    Schmidt, A; Rühl-Hörster, B

    1996-04-01

    Malassezia (M.) furfur is an anthropophilic fungus with complex growth requirements. Apart from its physiological appearance on human skin it is the causative agent of several skin disorders. A method for in vitro antifungal susceptibility testing of M. furfur in a microtiter plate assay has been developed. Read-out was performed colorimetrically in modified Leeming-Notman medium after incubation with alamarBlue. Twenty-two strains of M. furfur were tested, minimum inhibitory concentrations (MICs) were determined for climbazole, piroctone-olamine, selenium disulfide, zinc pyrithione. These substances are of common use in topical therapy of M. furfur-associated skin conditions. For climbazole, the range of MICs was between < 0.03 and 2 micrograms/ml with an empirical median mean of 0.03 micrograms/ml. For piroctoneolamine the range of MICs was between 16 and 64 micrograms/ml (mean = 64 micrograms/ml), for selenium disulfide between 2 and 64 micrograms/ml (mean = 8 micrograms/ml), and for zinc pyrithione between 0.12 and 8 micrograms/ml (mean = 1 micrograms/ml). These data indicate the high in vitro activity of climbazole against M. furfur, followed by zinc pyrithione. Selenium disulfide and piroctone-olamine were less active. PMID:8740097

  4. Adsorption of HMF from water/DMSO solutions onto hydrophobic zeolites: experiment and simulation.

    PubMed

    Xiong, Ruichang; León, Marta; Nikolakis, Vladimiros; Sandler, Stanley I; Vlachos, Dionisios G

    2014-01-01

    The adsorption of 5-hydroxymethylfurfural (HMF), DMSO, and water from binary and ternary mixtures in hydrophobic silicalite-1 and dealuminated Y (DAY) zeolites at ambient conditions was studied by experiments and molecular modeling. HMF and DMSO adsorption isotherms were measured and compared to those calculated using a combination of grand canonical Monte Carlo and expanded ensemble (GCMC-EE) simulations. A method based on GCMC-EE simulations for dilute solutions combined with the Redlich-Kister (RK) expansion (GCMC-EE-RK) is introduced to calculate the isotherms over a wide range of concentrations. The simulations, using literature force fields, are in reasonable agreement with experimental data. In HMF/water binary mixtures, large-pore hydrophobic zeolites are much more effective for HMF adsorption but less selective because large pores allow water adsorption because of H2 O-HMF attraction. In ternary HMF/DMSO/water mixtures, HMF loading decreases with increasing DMSO fraction, rendering the separation of HMF from water/DMSO mixtures by adsorption difficult. The ratio of the energetic interaction in the zeolite to the solvation free energy is a key factor in controlling separation from liquid mixtures. Overall, our findings could have an impact on the separation and catalytic conversion of HMF and the rational design of nanoporous adsorbents for liquid-phase separations in biomass processing. PMID:24106213

  5. Diffusion of air (1); furfural (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) air; (2) furfural

  6. Effect of hydroxymethylfurfural (HMF) on mortality of artificially reared honey bee larvae (Apis mellifera carnica).

    PubMed

    Krainer, Sophie; Brodschneider, Robert; Vollmann, Jutta; Crailsheim, Karl; Riessberger-Gallé, Ulrike

    2016-03-01

    Hydroxymethylfurfural (HMF) is a heat-formed, acid-catalyzed contaminant of sugar syrups, which find their way into honey bee feeding. As HMF was noted to be toxic to adult honey bees, we investigated the toxicity of HMF towards larvae. Therefore we exposed artificially reared larvae to a chronic HMF intoxication over 6 days using 6 different concentrations (5, 50, 750, 5000, 7500 and 10,000 ppm) and a control. The mortality was assessed from day 2 to day 7 (d7) and on day 22 (d22). Concentrations ranging from 5 to 750 ppm HMF did not show any influence on larval or pupal mortality compared to controls (p > 0.05; Kaplan-Meier analysis). Concentrations of 7500 ppm or higher caused a larval mortality of 100%. An experimental LC50 of 4280 ppm (d7) and 2424 ppm (d22) was determined. The calculated LD50 was 778 µg HMF per larva on d7 and 441 µg HMF on d22. Additionally, we exposed adult honey bees to high concentrations of HMF to compare the mortality to the results from larvae. On d7 larvae are much more sensitive against HMF than adult honey bees after 6 days of feeding. However, on d22 after emergence adults show a lower LC50, which indicates a higher sensitivity than larvae. As toxicity of HMF against honey bees is a function of time and concentration, our results indicate that HMF in supplemental food will probably not cause great brood losses. Yet sublethal effects might decrease fitness of the colony. PMID:26590927

  7. Biological marker of furfural, chemicals without administrative control level.

    PubMed

    Morimoto, Yasuo; Hori, Hajime; Higashi, Toshiaki; Nagatomo, Hiroko; Hino, Yoshiyuki; Ohsato, Atsushi; Uchino, Bungo

    2007-06-01

    Furfural, a colorless liquid used in solvent-extraction processes, petroleum refining and as a rubber additive, has been assigned an occupational exposure limit of 2.5 ppm by the Japan Society for Occupational Health, but an administrative control level for furfural has not been established. In order to conduct effective occupational health management in workplaces where furfural is used, we measured furfural concentrations in working environments and collected urine samples to measure furoic acid levels (one of the principal metabolites), which act as a biomarker of exposure to furfural. The measurements of airborne concentrations in a working environment where furfural or a solution containing furfural was handled were made in 2004. Workers answered a questionnaire on working conditions, urine samples were collected at the end of the workshift, and furoic acid in the urine was measured by gas chromatography/flame ionization detector (GC/FID). The ambient concentrations of furfural during the period were 2.1 ppm in a mixer room and 1.6 ppm in a filling room. The mean concentrations of furoic acid in the workers' urine were 7.7 +/- 7.8 mg/g-creatinine in summer and winter, respectively (normal range: 3 - 60 mg/g-creatinine). The average exposure to furfural per month calculated by multiplying the concentration in the working environment by working hours for a month was 86.4 +/- 108.6 ppm hours/months (mean +/- standard deviation) (range; 0 - 336 ppm hours/month). The relationship between average exposure to furfural and furoic acid in the urine was analyzed by simple linear regression analysis and a positive correlation was found. These findings suggest that furoic acid in urine is useful for biological monitoring of exposure to furfural, and that the measurement of both furfural in the environment and furoic acid in the urine are beneficial in occupational health management of furfural. PMID:17582986

  8. Lipase-catalyzed (trans)esterification of 5-hydroxy- methylfurfural and separation from HMF esters using deep-eutectic solvents.

    PubMed

    Krystof, Monika; Pérez-Sánchez, María; Domínguez de María, Pablo

    2013-04-01

    5-Hydroxymethylfurfural (HMF) is a valuable biomass-derived building block. Among possible HMF valorization products, a broad range of HMF esters can be synthesized. These HMF esters have found some promising applications, such as monomers, fuels, additives, surfactants, and fungicides, and thus several catalytic approaches for HMF (trans)esterifications have been reported. The intrinsic reactivity of HMF is challenging, forcing the use of mild reaction conditions to avoid by-product formation. This paper explores the lipase-catalyzed (trans)esterification of HMF with different acyl donors (carboxylic acids and methyl- and ethyl esters) mostly in solvent-free conditions. The results demonstrate that lipases may be promising alternatives for the synthesis of HMF esters-with high productivities and reactions at high substrate loadings-provided that robust systems for lipase immobilization are applied to assure an adequate reusability of the enzymes. Once (trans)esterifications have been conducted, the separation of unreacted HMF and HMF esters is performed by using deep-eutectic solvents (DES) as separation agents. DES are able to dissolve hydrogen-bond donors (e.g., HMF), whereas non-hydrogen-bond donors (in this case HMF esters) form a second phase. By using this approach, high ester purities (>99 %) and efficiencies (up to >90 % HMF ester recovery) in separations were obtained by using choline chloride-based DES. PMID:23456887

  9. 5-HMF and carbohydrates content in stingless bee honey by CE before and after thermal treatment.

    PubMed

    Biluca, Fabíola C; Della Betta, Fabiana; de Oliveira, Gabriela Pirassol; Pereira, Lais Morilla; Gonzaga, Luciano Valdemiro; Costa, Ana Carolina Oliveira; Fett, Roseane

    2014-09-15

    This study aimed to assess 5-hydroximethylfurfural and carbohydrates (fructose, glucose, and sucrose) in 13 stingless bee honey samples before and after thermal treatment using a capillary electrophoresis method. The methods were validated for the parameters of linearity, matrix effects, precision, and accuracy. A factorial design was implemented to determine optimal thermal treatment conditions and then verify the postprocedural 5-HMF formation, but once 5-HMF were HMF, and carbohydrate levels ranged from 48.59% to 69.36%. In the same conditions of thermal treatment, Apis mellifera honey presented higher 5-HMF content than stingless bee honey. Results suggest that a high temperature related to briefer thermal treatment could be an efficient way to extend shelf life without affecting 5-HMF content in stingless bee honey. PMID:24767051

  10. Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods

    SciTech Connect

    Assary, Rajeev S.; Redfern, Paul C.; Greeley, Jeffrey P.; Curtiss, Larry A.

    2011-04-21

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

  11. Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods

    SciTech Connect

    Assary, Rajeev S.; Redfern, Paul C.; Greeley, Jeffrey; Curtiss, Larry A.

    2011-03-28

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

  12. Mechanistic insights into the decomposition of fructose to hydroxy methyl furfural in neutral and acidic environments using high-level quantum chemical methods.

    PubMed

    Assary, Rajeev S; Redfern, Paul C; Greeley, Jeffrey; Curtiss, Larry A

    2011-04-21

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved. PMID:21443225

  13. Mechanistic insights into the decomposition of fructose to hydroxy methyl furfural in neutral and acidic environments using high-level quantum chemical methods.

    SciTech Connect

    Assary, R. S.; Redfern, P. C.; Greeley, J.; Curtiss, L. A.

    2011-03-28

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

  14. Factors affecting furfural as a nematicide on turf.

    PubMed

    Luc, J E; Crow, W T

    2013-12-01

    Recently a furfural nematicide Multiguard Protect EC was launched for use on turfgrasses in the United States. A series of greenhouse experiments were conducted to determine the concentration and exposure time required for this formulation to irreversibly affect Belonolaimus longicaudatus, and to study factors that might affect the practicality of furfural use in turfgrass systems. One experiment exposed B. longicaudatus to increasing concentrations of furfural (0 to 990 ppm) in vitro for either 24 or 48 hr, followed by inoculation onto bermudagrass. A second experiment evaluated effects of exposure of B. longicaudatus to increasing concentrations of furfural in soil solution on bermudagrass with or without an organic thatch layer. A third experiment evaluated effects on B. longicaudatus of increasing concentrations of furfural applied as a spray treatment to creeping bentgrass. Results from the in vitro exposure experiment found decreasing numbers of B. longicaudatus with increasing furfural concentration beginning with the lowest concentration tested (270 ppm). Belonolaimus longicaudatus were virtually eliminated with furfural concentrations ≥ 720 ppm. Similarly, exposure to increasing concentration of furfural in soil solution resulted in increasing reduction in numbers of B. longicaudatus. Presence of thatch slightly reduced the population density of B. longicaudatus. Spray application of furfural only reduced numbers of B. longicaudatus at the two highest rates (3,600 and 4,950 ppm). PMID:24379484

  15. Allergenic evaluation of Malassezia furfur crude extracts.

    PubMed

    Gandra, R F; Melo, T A; Matsumoto, F E; Pires, M F C; Croce, J; Gambale, W; Paula, C R

    2002-01-01

    Crude extracts of the lipophilic yeast Malassezia furfur were obtained from 2, 6, 10 and 28 day old cultures. The in vitro cultivation periods corresponded, respectively, to the lag phase, middle of the log phase, end of log phase and the decline phase of the growth curve, which was based on viable cell counts obtained with a fluorescent viability test. Biochemical analyses showed that the protein and carbohydrate contents were greater in day 10 extracts. Seventy patients with different allergic manifestations and 30 healthy volunteers were skin prick tested using the extracts. Of these, thirteen (18.57%) patients gave positive responses. SDS PAGE gradient electrophoretic profiles of the preparations indicated that the 28 day extracts contained the greatest number of protein bands with molecular weights ranging mostly between 30 and 94 kDa. Immunoblots incubated with individual patient sera showed that four IgE binding M. furfur allergens of approximately 88, 61, 52 and 39 kDa were present in the 28 day extracts. The components identified could be used for detecting IgE mediated responses to M. furfur among individuals affected with different allergic conditions. PMID:12650593

  16. Towards a new reference model of hmF2 for IRI

    NASA Astrophysics Data System (ADS)

    Gulyaeva, T. L.; Bradley, P. A.; Stanislawska, I.; Juchnikowski, G.

    2008-08-01

    A numerical model of the peak height of the F2 layer, hmF2_ top, is derived from the topside sounding database of 90,000 electron density profiles for a representative set of conditions provided by ISIS1, ISIS2, IK19 and Cosmos-1809 satellites for the period of 1969-1987. The model of regular hmF2 variations is produced in terms of local time, season, geomagnetic latitude, geodetic longitude and solar radio flux. No geomagnetic activity trends were discernible in the topside sounding data. The nighttime peak of hmF2_ top evident for mid-latitudes disappears near the geomagnetic equator where a maximum of hmF2_ top occurs at sunset hours when it can exceed 500 km at solar maximum. The hmF2 given by the IRI exceeds hmF2_ top at the low solar activities. The hmF2_ top, obtained by extrapolation of the first derivative of the topside profile to zero shows saturation similar to foF2 the greater the solar activity. The proposed model differs from hmF2 given by IRI based on M( 3000) F2 to hmF2 conversion by empirical relationships in terms of foF2, foE and R12 with these quantities mapped globally by the ITU-R (former CCIR) from ground-based ionosonde data. The differences can be attributed to the different techniques of the peak height derivation, different epochs and different global distribution of the source data as well as the different mathematical functions involved in the maps and the model presentation.

  17. Direct conversion from Jerusalem artichoke to hydroxymethylfurfural (HMF) using the Fenton reaction.

    PubMed

    Seo, Yeong Hwan; Han, Jong-In

    2014-05-15

    A simple method for hydroxymethylfurfural (HMF) production from non-crop biomass of the Jerusalem artichoke was developed using the Fenton reaction, in a mixture of 2-butanol and water. Four parameters (temperature, reaction time, Fe(2+) concentration, and H2O2 concentration) were identified as experimental factors, and HMF yield was selected as the response parameter. The experimental factors were optimised by employing Response Surface Methodology (RSM). The maximum HMF yield, of 46%, was obtained with a reaction time of 90 min, Fe(2+) concentration of 1.3 mM, and 0.47 M of H2O2 at 180 °C. PMID:24423522

  18. Biodegradation of furfural by Bacillus subtilis strain DS3.

    PubMed

    Zheng, Dan; Bao, Jianguo; Lu, Jueming; Lv, Quanxi

    2015-07-01

    An aerobic bacterial strain DS3, capable of growing on furfural as sole carbon source, was isolated from actived sludge of wastewater treatment plant in a diosgenin factory after enrichment. Based on morphological physiological tests as well as 16SrDNA sequence and Biolog analyses it was identified as Bacillus subtilis. The study revealed that strain DS3 utilized furfural, as analyzed by high-performance liquid chromatography (HPLC). Under following conditions: pH 8.0, temperature 35 degrees C, 150 rpm and 10% inoculum, strain DS3 showed 31.2% furfural degradation. Furthermore, DS3 strain was found to tolerate furfural concentration as high as 6000 mg(-1). The ability of Bacillus subtilis strain DS3 to degrade furfural has been demonstrated for the first time in the present study. PMID:26387346

  19. Antifungal effect of TONS504-photodynamic therapy on Malassezia furfur.

    PubMed

    Takahashi, Hidetoshi; Nakajima, Susumu; Sakata, Isao; Iizuka, Hajime

    2014-10-01

    Numerous reports indicate therapeutic efficacy of photodynamic therapy (PDT) against skin tumors, acne and for skin rejuvenation. However, few reports exist regarding its efficacy for fungal skin diseases. In order to determine the antifungal effect, PDT was applied on Malassezia furfur. M. furfur was cultured in the presence of a novel cationic photosensitizer, TONS504, and was irradiated with a 670-nm diode laser. TONS504-PDT showed a significant antifungal effect against M. furfur. The effect was irradiation dose- and TONS504 concentration-dependent and the maximal effect was observed at 100 J/cm2 and 1 μg/mL, respectively. In conclusion, TONS504-PDT showed antifungal effect against M. furfur in vitro, and may be a new therapeutic modality for M. furfur-related skin disorders. PMID:25226792

  20. Transcriptional profiling of Saccharomyces cerevisiae T2 cells upon exposure to hardwood spent sulphite liquor: comparison to acetic acid, furfural and hydroxymethylfurfural.

    PubMed

    Bajwa, Paramjit K; Ho, Chi-Yip; Chan, Chi-Kin; Martin, Vincent J J; Trevors, Jack T; Lee, Hung

    2013-06-01

    Global gene expression was analyzed in Saccharomyces cerevisiae T2 cells grown in the presence of hardwood spent sulphite liquor (HW SSL) and each of the three main inhibitors in HW SSL, acetic acid, hydroxymethyfurfural (HMF) and furfural, using a S. cerevisiae DNA oligonucleotide microarray. The objective was to compare the gene expression profiles of T2 cells in response to the individual inhibitors against that elicited in response to HW SSL. Acetic acid mainly affected the expression of genes related to the uptake systems of the yeast as well as energy generation and metabolism. Furfural and HMF mainly affected the transcription of genes involved in the redox balance of the cell. On the other hand, the effect of HW SSL on S. cerevisiae T2 cells was distinct and considerably more diverse as compared to the effect of individual inhibitors found in lignocellulosic hydrolysates. This is not surprising as HW SSL contains a complex mixture of inhibitors which may act synergistically. HW SSL elicited significant changes in expression of genes involved in diverse and multiple effects on several aspects of the cellular structure and function. A notable response to HW SSL was decreased expression of the ribosomal protein genes in T2 cells. In addition, HW SSL decreased the expression of genes functioning in the synthesis and transport of proteins as well as metabolism of carbohydrates, lipids, vitamins and vacuolar proteins. Furthermore, the expression of genes involved in multidrug resistance, iron transport and pheromone response was increased, suggesting that T2 cells grown in the presence of HW SSL may have activated pheromone response and/or activated pleiotropic drug response. Some of the largest changes in gene expression were observed in the presence of HW SSL and the affected genes are involved in mating, iron transport, stress response and phospholipid metabolism. A total of 59 out of the 400 genes differentially expressed in the presence of HW SSL, acetic

  1. Power generation from furfural using the microbial fuel cell

    NASA Astrophysics Data System (ADS)

    Luo, Yong; Liu, Guangli; Zhang, Renduo; Zhang, Cuiping

    Furfural is a typical inhibitor in the ethanol fermentation process using lignocellulosic hydrolysates as raw materials. In the literature, no report has shown that furfural can be utilized as the fuel to produce electricity in the microbial fuel cell (MFC), a device that uses microbes to convert organic compounds to generate electricity. In this study, we demonstrated that electricity was successfully generated using furfural as the sole fuel in both the ferricyanide-cathode MFC and the air-cathode MFC. In the ferricyanide-cathode MFC, the maximum power densities reached 45.4, 81.4, and 103 W m -3, respectively, when 1000 mg L -1 glucose, a mixture of 200 mg L -1 glucose and 5 mM furfural, and 6.68 mM furfural were used as the fuels in the anode solution. The corresponding Coulombic efficiencies (CE) were 4.0, 7.1, and 10.2% for the three treatments, respectively. For pure furfural as the fuel, the removal efficiency of furfural reached up to 95% within 12 h. In the air-cathode MFC using 6.68 mM furfural as the fuel, the maximum values of power density and CE were 361 mW m -2 (18 W m -3) and 30.3%, respectively, and the COD removal was about 68% at the end of the experiment (about 30 h). Increase in furfural concentrations from 6.68 to 20 mM resulted in increase in the maximum power densities from 361 to 368 mW m -2, and decrease in CEs from 30.3 to 20.6%. These results indicated that some toxic and biorefractory organics such as furfural might still be suitable resources for electricity generation using the MFC technology.

  2. Stereochemistry of Furfural Reduction by a Saccharomyces cerevisiae Aldehyde Reductase That Contributes to In Situ Furfural Detoxification

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ari1p from Saccharomyces cerevisiae, recently identified as an intermediate subclass short-chain dehydrogenase/reductase, contributes in situ to the detoxification of furfural. Furfural inhibits efficient ethanol production by the yeast, particularly when the carbon source is acid-treated lignocell...

  3. The Margin of Exposure of 5-Hydroxymethylfurfural (HMF) in Alcoholic Beverages

    PubMed Central

    Monakhova, Yulia B

    2012-01-01

    Objectives 5-Hydroxymethylfurfural (HMF) regularly occurs in foods and in alcoholic beverages. However, the risk of HMF associated with alcohol consumption has not been systematically studied, so that this study will provide the first quantitative risk assessment of HMF for consumers of alcoholic beverages. Methods Human dietary intake of HMF via alcoholic beverages in the European Union was estimated based on WHO alcohol consumption data combined with our own survey data (n=944) and literature data (n=147) about the HMF contents of different beverage groups (beer, wine, spirits and unrecorded alcohol). The risk assessment was conducted using the margin of exposure (MOE) approach. Results For olfactory epithelium metaplasia in female mice, a benchmark dose (BMD) of 127 mg/kg bodyweight (bw)/d and a BMD lower confidence limit (BMDL) of 79 mg/kg bw/d were calculated from National Toxicology Program oral long-term animal experiments. The average human exposure to HMF from alcoholic beverages was estimated at 6.0E-3 mg/kg bw/d, which is approximately 8.5% of the total dietary exposure. In comparison of the human exposure with BMDL, the MOE was 13,167 for average alcohol consumption scenarios, which is a value that would be generally assumed as safe for threshold based compounds. Conclusions The results show that the risk from HMF to the alcohol-consuming population is rather low and the priority for risk management (e.g. to reduce the contamination) is also low. Further toxicological research about HMF is required to further elucidate its mechanism. PMID:23106038

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

    SciTech Connect

    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.

  5. Hydrogenation of furfural on polymer-containing catalysts

    SciTech Connect

    Karakhanov, E.A.; Neimerovets, E.B.; Pshezhetskii, V.S.; Dedov, A.G.

    1986-09-01

    The catalytic hydrogenation of furfural with molecular hydrogen has been investigated under mild conditions in the presence of metal complex catalysts with a polymeric macroligand. It has been shown that the reaction proceeds according to a consecutive scheme with the formation of furfuryl and tetrahydrofurfuryl alcohols. The kinetics of furfural hydrogenation has been investigated and the order of the reaction established; the rate constants of the first and second stages have been determined. The influence of the solvent and of the metal-to-polymer ratio on the furfural conversion have been investigated.

  6. Phosphorylated mesoporous carbon as effective catalyst for the selective fructose dehydration to HMF

    SciTech Connect

    Villa, Alberto; Schiavoni, Marco; Fulvio, Pasquale F; Mahurin, Shannon Mark; Dai, Sheng; Mayes, Richard T; Veith, Gabriel M; Prati, Laura

    2013-01-01

    Phosphorylated mesoporous carbons (PMCs) have been synthesized using an already reported one pot methodology. These materials have been applied as acidic catalysts in the dehydration of fructose to hydroxymethylfurfural (HMF). PMCs showed better selectivity to HMF compared to sulfonated carbon catalyst (SC) despite lower activity. The concentration of P-O groups correlates to the activity/selectivity of the catalysts; the higher the P-O concentration the higher the activity. However, the higher the P-O content the lower the selectivity to HMF. Indeed a lower concentration of the P-O groups (and even the acidic groups) minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines, water insoluble by-products derived from the dehydration of fructose, blocking the active site of the catalyst. Increasing the amount of P-O groups, higher amount of humines are formed; therefore carbons containing lower amount of phosphorylated groups, such as P/N-0.25, are less prone to deactivation. Keywords: Phosphorylated mesoporous carbons; fructose dehydration; HMF

  7. Microwave spectroscopy of furfural in vibrationally excited states

    NASA Astrophysics Data System (ADS)

    Motiyenko, R. A.; Alekseev, E. A.; Dyubko, S. F.

    2007-07-01

    The results of microwave spectrum investigation of the excited vibrational states of furfural in the frequency range between 49 and 149 GHz are reported. In total 15 excited vibrational states (9 for trans-furfural and 6 for cis-furfural) were assigned and analyzed. Six of the 15 investigated states were assigned for the first time. Accurate values of rigid rotor and quartic centrifugal distortion constants of asymmetric top Hamiltonian have been determined for 13 excited states. Also for some states several sextic and octic level constants were needed in order to fit the data within experimental accuracy. The vt = 3 and vs = 1, va = 1 states of trans-furfural were found to be strongly perturbed and only rotational transitions with low Ka values can be reliably identified in this study.

  8. Nature of the chemical reaction for furfural modified asphalt

    SciTech Connect

    Memon, G.M.; Chollar, B.H.

    1994-12-31

    Three of the most serious problems of asphalt pavements today are rutting, cracking, and susceptibility to moisture damage (stripping). Asphalt manufacturers have been mixing asphalts with polymers to produce polymer-modified asphalts with improved rheological properties. However, the costs for these improved polymer-modified asphalts are almost double that of regular asphalts. FHWA researchers have found that asphalt modified by the chemical, furfural (which is prepared by simple elimination reaction of aldopentoses obtained from oat hulls), exhibited better stripping properties and was less temperature susceptible than the virgin asphalt while costing less than polymer-modified asphalts. This paper discusses the possible structure of the furfural-modified asphalt, data for the virgin and furfural-modified asphalts and their Corbett fractions, data from a model reaction between phenol and furfural, and a possible explanation of this structure based on these data.

  9. [Taxonomy of Malassezia furfur: state of the art].

    PubMed

    Aspíroz, M C; Moreno, L A; Rubio, M C

    1997-12-01

    Malassezia furfur is a lipophilic yeast considered as a normal component of the human skin flora. Apart from pityriasis versicolor, M. furfur has been linked to several skin diseases such as seborrheic dermatitis, folliculitis or atopic dermatitis. Moreover, these yeasts have been reported as agent of invasive human diseases including pneumonia, catheter-associated sepsis and peritonitis. The existence of morphological, serological, metabolical, biochemical and karyotipical differences has been described among isolates of these yeasts. These observations gave arguments for a possible intraspecific division, and this hypothesis has been confirmed by the existence of six species within the formerly called M. furfur (lipid-dependent Malassezia strains): M. furfur, Malassezia sympodialis, Malassezia globosa, Malassezia obtusa, Malassezia restricta and Malassezia slooffiae. PMID:15538815

  10. Method for selectively preparing 5-hydroxymethylfurfual (HMF) from biomass in polar aprotic solvents

    DOEpatents

    Dumesic, James A.; Huber, George W.; Weingarten, Ronen

    2016-01-26

    A method to produce 5-hydroxymethylfurfural (HMF) is described in which a reactant including cellulose, lignocellulose, or a combination thereof, in a reaction mixture of a polar, aprotic solvent and an acid is reacted for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to HMF. The reaction mixture is initially substantially devoid of water. As the reaction proceeds, dehydration of intermediates causes the water concentration in the reaction mixture to rise to no more than about 0.2 wt % water.

  11. Landau Damping in Sobolev Spaces for the Vlasov-HMF Model

    NASA Astrophysics Data System (ADS)

    Faou, Erwan; Rousset, Frédéric

    2016-02-01

    We consider the Vlasov-HMF (Hamiltonian Mean-Field) model. We consider solutions starting in a small Sobolev neighborhood of a spatially homogeneous state satisfying a linearized stability criterion (Penrose criterion). We prove that these solutions exhibit a scattering behavior to a modified state, which implies a nonlinear Landau damping effect with polynomial rate of damping.

  12. Simultaneous determination of 2-furfural and 5-methyl-2-furfural using corona discharge ion mobility spectrometry.

    PubMed

    Jafari, M T; Khayamian, T

    2009-06-01

    A novel technique, corona discharge ion mobility spectrometry (CD-IMS), was developed for the qualitative and quantitative determination of 2-furfural (F) and 5-methyl-2-furfural (MF) in aqueous solutions. The limits of detection (LODs) were 5.3 x 10(-3) microg/mL for F and 6.7 x 10(-3) microg/mL for MF. The linear dynamic ranges of 1.16 x 10(-2) to 1.04 microg/mL and 2.20 x 10(-2) to 1.10 microg/mL were obtained for F and MF, respectively. The relative standard deviation was below 12% for both compounds. In addition to analysis of the individual compound, simultaneous determination of F and MF was also investigated. It was realized that F imposes a matrix effect on the MF signal and vice versa. The standard addition method was used to deal with the matrix effect. The recovery of the compounds in the synthetic samples validates the capability of the method. PMID:19531891

  13. Furfural as a marker of cellulose degradation. A quantitative approach

    NASA Astrophysics Data System (ADS)

    Łojewski, Tomasz; Sawoszczuk, Tomasz; Łagan, Janusz Marek; Zięba, Katarzyna; Barański, Andrzej; Łojewska, Joanna

    2010-09-01

    Non-destructive methods of sampling during the physicochemical studies of historical objects such as old books and manuscripts seem to be an obvious choice. Since furfural has been shown to be one of the most abundant gaseous products of cellulose degradation, it can be considered as a convenient marker of degradation progress. The number of quantitative data concerning correlations between the emission of furfural and physicochemical and mechanical properties of paper is rather scarce in the literature. In the present studies, a model paper containing more than 99% of cellulose was aged inside closed vials at 90°C. Gaseous products of paper degradation were measured using sorption tubes filled with Tenax TA sorbent and GC-MS. The method has proved to be sufficiently sensitive for measuring furfural emission not only in accelerated degradation at 90°C but also during natural ageing of paper at room temperature even in relatively short time intervals of 2-28 days. The correlations between furfural emission and polymerization degree, pH, color, tear index, number of double folds and breaking length have been statistically confirmed at confidence level α=0.001. Basing on them it was possible to estimate the number of broken glycosidic bonds per one molecule of furfural formed during degradation—we found a value equal to 9.2.

  14. Method for removal of furfural coke from metal surfaces

    SciTech Connect

    Turner, J.D.

    1990-02-27

    This patent describes a process for preparing furfural coke for removal from metallic surfaces. It comprises: heating ship furfural coke without causing an evolution of heat capable of undesirably altering metallurgical properties of the surfaces in the presence of a gas with a total pressure of less than 100 psig containing molecular oxygen. The gas being at a sufficient temperature below 800{degrees}F. (427{degrees}C.) for a sufficient time to change the crush strength of the coke so as to permit removal with a water jet at a pressure of about 5000 psi.

  15. A different method to update monthly median hmF2 values

    NASA Astrophysics Data System (ADS)

    Brunini, Claudio; Federico Conte, J.; Azpilicueta, Francisco; Bilitza, Dieter

    2013-06-01

    The height, hmF2, and the electron density, NmF2, of the F2 peak are key model parameters to characterize the actual state of the ionosphere. These parameters, or alternatively the propagation factor, M3000F2, and the critical frequency, foF2, of the F2 peak, which are related to hmF2 and NmF2, are used to anchor the electron density vertical profile computed with different models such as the International Reference Ionosphere (Bilitza, 2002), as well as for radio propagation forecast purposes. Long time series of these parameters only exist in an inhomogeneous distribution of points over the surface of Earth, where dedicated instruments (typically ionosondes) have been working for many years. A commonly used procedure for representing median values of the aforementioned parameters all over the globe is the one recommended by the ITU-R (ITU-R, 1997). This procedure, known as the Jones and Gallet mapping technique, was based on ionosondes measurements gathered from 1954 to 1958 by a global network of around 150 ionospheric stations (Jones and Gallet, 1962; Jones and Obitts, 1970). Even though several decades have passed since the development of that innovative work, only few efforts have been dedicated to establish a new mapping technique for computing hmF2 and NmF2 median values at global scale or to improve the old method using the increased observational database. Therefore, in this work three different procedures to describe the daily and global behavior of the height of the F2 peak are presented. All of them represent a different and simplified method to estimate hmF2 and are based on different mathematical expressions. The advantages and disadvantages of these three techniques are analyzed, leading to the conclusion that the recommended procedure to represent hmF2 is best characterized by a Spherical Harmonics expansion of degree and order equal to 15, since the differences between the hmF2 values obtained with the Jones and Gallet technique and those obtained

  16. Purification and characterization of a furfural reductase (FFR) from Escherichia coli strain LYO1--an enzyme important in the detoxification of furfural during ethanol production.

    PubMed

    Gutiérrez, Tony; Ingram, Lonnie O; Preston, James F

    2006-01-24

    Furfural, an inhibitor of ethanol production from hemicellulose acid hydrolysates, is reductively detoxified to furfuryl alcohol by the ethanologenic bacterium Escherichia coli strain LYO1. Furfural reductase was purified 106-fold from this bacterium to approximately 50% homogeneity. It has a native molecular mass of 135 kDa, determined by gel filtration, and subunit molecular mass of approximately 68 kDa, determined by denaturing gel electrophoresis, indicating the holoenzyme is a dimer of two similar if not identical subunits. The enzyme shows strong activity from pH 4 to 8 (optimum pH 7.0), relatively high temperature tolerance (50-55 degrees C), and an apparent Km and Vmax for furfural of 1.5x10(-4)M and 28.5 micromol/min/mg of protein, respectively. It catalyzes the essentially irreversible reduction of furfural with NADPH, is specific for NADPH as cofactor, and is relatively specific for the reduction of furfural and benzaldehyde; 2-acetylfuran, xylose, and glucose were not reduced, while acetaldehyde was reduced at a rate 25-fold lower than furfural. This is the first description of a furfural reductase which, based upon size and substrate specificity, appears to represent a new type of alcohol-aldehyde oxido-reductase. The conversion of relatively toxic furfural to less toxic furfuryl alcohol suggests a beneficial role for this enzyme in mitigating furfural toxicity encountered during ethanol production from lignocellulosic biomass. PMID:16111779

  17. Furfural induces reactive oxygen species accumulation and cellular damage in Saccharomyces cerevisiae

    PubMed Central

    2010-01-01

    Background Biofuels offer a viable alternative to petroleum-based fuel. However, current methods are not sufficient and the technology required in order to use lignocellulosic biomass as a fermentation substrate faces several challenges. One challenge is the need for a robust fermentative microorganism that can tolerate the inhibitors present during lignocellulosic fermentation. These inhibitors include the furan aldehyde, furfural, which is released as a byproduct of pentose dehydration during the weak acid pretreatment of lignocellulose. In order to survive in the presence of furfural, yeast cells need not only to reduce furfural to the less toxic furan methanol, but also to protect themselves and repair any damage caused by the furfural. Since furfural tolerance in yeast requires a functional pentose phosphate pathway (PPP), and the PPP is associated with reactive oxygen species (ROS) tolerance, we decided to investigate whether or not furfural induces ROS and its related cellular damage in yeast. Results We demonstrated that furfural induces the accumulation of ROS in Saccharomyces cerevisiae. In addition, furfural was shown to cause cellular damage that is consistent with ROS accumulation in cells which includes damage to mitochondria and vacuole membranes, the actin cytoskeleton and nuclear chromatin. The furfural-induced damage is less severe when yeast are grown in a furfural concentration (25 mM) that allows for eventual growth after an extended lag compared to a concentration of furfural (50 mM) that prevents growth. Conclusion These data suggest that when yeast cells encounter the inhibitor furfural, they not only need to reduce furfural into furan methanol but also to protect themselves from the cellular effects of furfural and repair any damage caused. The reduced cellular damage seen at 25 mM furfural compared to 50 mM furfural may be linked to the observation that at 25 mM furfural yeast were able to exit the furfural-induced lag phase and resume

  18. [Adsorption mechanism of furfural onto modified rice husk charcoals].

    PubMed

    Deng, Yong; Wang, Xianhua; Li, Yunchao; Shao, Jing'ai; Yang, Haiping; Chen, Hanping

    2015-10-01

    To evaluate the absorptive characteristics of furfural onto biomass charcoals derived from rice husk pyrolysis, we studied the information of the structure and surface chemistry properties of the rice husk charcoals modified by thermal treatment under nitrogen and carbon dioxide flow and adsorption mechanism of furfural. The modified samples are labeled as RH-N2 and RH-CO2. Fresh rice husk charcoal sample (RH-450) and modified samples were characterized by elemental analysis, nitrogen adsorption-desorption isotherms, Fourier-transform infrared spectroscopy and Boehm titration. The results show that fresh rice husk charcoal obtained at 450 degrees C had a large number of organic groups on its surface and poor pore structure. After the modification under nitrogen and carbon dioxide flow, oxygenic organics in rice husk charcoals decompose further, leading to the reduction of acidic functional groups on charcoals surface, and the increase of the pyrone structures of the basic groups. Meanwhile, pore structure was improved significantly and the surface area was increased, especially for the micropores. This resulted in the increase of π-π dispersion between the surfaces of rice husk charcoals and furfural molecular. With making comprehensive consideration of π-π dispersion and pore structure, the best removal efficiency of furfural was obtained by rice husk charcoal modified under carbon dioxide flow. PMID:26964338

  19. Furfural--a promising platform for lignocellulosic biofuels.

    PubMed

    Lange, Jean-Paul; van der Heide, Evert; van Buijtenen, Jeroen; Price, Richard

    2012-01-01

    Furfural offers a promising, rich platform for lignocellulosic biofuels. These include methylfuran and methyltetrahydrofuran, valerate esters, ethylfurfuryl and ethyltetrahydrofurfuryl ethers as well as various C(10)-C(15) coupling products. The various production routes are critically reviewed, and the needs for improvements are identified. Their relative industrial potential is analysed by defining an investment index and CO(2) emissions as well as determining the fuel properties for the resulting products. Finally, the most promising candidate, 2-methylfuran, was subjected to a road trial of 90,000 km in a gasoline blend. Importantly, the potential of the furfural platform relies heavily on the cost-competitive production of furfural from lignocellulosic feedstock. Conventional standalone and emerging coproduct processes-for example, as a coproduct of cellulosic ethanol, levulinic acid or hydroxymethyl furfural-are expensive and energetically demanding. Challenges and areas that need improvement are highlighted. In addition to providing a critical review of the literature, this paper also presents new results and analysis in this area. PMID:22213717

  20. Physiological and molecular characterization of atypical isolates of Malassezia furfur.

    PubMed

    González, A; Sierra, R; Cárdenas, M E; Grajales, A; Restrepo, S; Cepero de García, M C; Celis, A

    2009-01-01

    The species constituting the genus Malassezia are considered to be emergent opportunistic yeasts of great importance. Characterized as lipophilic yeasts, they are found in normal human skin flora and sometimes are associated with different dermatological pathologies. We have isolated seven Malassezia species strains that have a different Tween assimilation pattern from the one typically used to differentiate M. furfur, M. sympodialis, and M. slooffiae from other Malassezia species. In order to characterize these isolates of Malassezia spp., we studied their physiological features and conducted morphological and molecular characterization by PCR-restriction fragment length polymorphism and sequencing of the 26S and 5.8S ribosomal DNA-internal transcribed spacer 2 regions in three strains from healthy individuals, four clinical strains, and eight reference strains. The sequence analysis of the ribosomal region was based on the Blastn algorithm and revealed that the sequences of our isolates were homologous to M. furfur sequences. To support these findings, we carried out phylogenetic analyses to establish the relationship of the isolates to M. furfur and other reported species. All of our results confirm that all seven strains are M. furfur; the atypical assimilation of Tween 80 was found to be a new physiological pattern characteristic of some strains isolated in Colombia. PMID:18971363

  1. Furfural/ethanol coproduction from biomass feedstocks using acid hydrolysis

    SciTech Connect

    Barrier, J.W.; Bulls, M.M.; Broder, J.D.

    1996-12-31

    The Tennessee Valley Authority (TVA) has been involved in research and development to produce high-value chemicals from biomass for over 15 years. Use of biomass releases less carbon dioxide than use of fossil fuels, and thus represents a more environmentally friendly source of chemicals and fuels. Two biomass conversion processes have been developed as a result of TVA`s work--concentrated acid hydrolysis and dilute acid hydrolysis. Both processes use sulfuric acid as a catalyst. Early hydrolysis research focused on improving ethanol yields through hydrolysis and five-carbon sugar fermentation research. Both processes have been demonstrated at the pilot plant scale. Current work is focused on the development of integrated systems for producing ethanol and a variety of other chemicals and products from biomass. Production of furfural and ethanol from high hemicellulose feedstocks has been identified by TVA as an integrated system with technical and economic potential for commercial success. A system design has been developed to produce ethanol and furfural using dilute acid hydrolysis of sycamore. Furfural yields for the system are estimated at 180--240 pound/ton. Ethanol process yields are 25--38 gallon/ton. Capital and operating costs for a 4,500 ton/day facility are estimated to be $609 million and $183 million, respectively. The dilute acid hydrolysis process proposed by TVA will be described along with additional process economics and potential furfural markets.

  2. Combining quiet- and disturbance-hmF2 models to provide a forecasting tool for hmF2

    NASA Astrophysics Data System (ADS)

    Magdaleno, Sergio; Blanch, Estefanía.; Herraiz, Miguel; Altadill, David; de La Morena, Benito

    2010-05-01

    The quiet behavior of the ionospheric electron density peak height of the F2 region, hmF2, at mid latitude has been evaluated from average electron density profiles providing more reliable hmF2 measurement than converting hmF2 from M(3000)F2. A model temporal extent has been obtained by considering the daily and seasonal variations and the solar activity influence on them. The quiet-hmF2 model provides better performance than current IRI does. A disturbance-hmF2 model has been added to the quiet-hmF2 providing a forecasting tool for hmF2 in response to the configuration and variation of the interplanetary magnetic field. The performance of this tool under particular events will be presented.

  3. In vitro antifungal susceptibility of Malassezia furfur from bloodstream infections.

    PubMed

    Iatta, Roberta; Figueredo, Luciana A; Montagna, Maria Teresa; Otranto, Domenico; Cafarchia, Claudia

    2014-11-01

    Fungaemia caused by Malassezia spp. in hospitalized patients requires prompt and appropriate therapy, but standard methods for the definition of the in vitro antifungal susceptibility have not been established yet. In this study, the in vitro susceptibility of Malassezia furfur from bloodstream infections (BSIs) to amphotericin B (AMB), fluconazole (FLC), itraconazole (ITC), posaconazole (POS) and voriconazole (VRC) was assessed using the broth microdilution (BMD) method of the Clinical and Laboratory Standards Institute (CLSI) with different media such as modified Sabouraud dextrose broth (SDB), RPMI and Christensen's urea broth (CUB). Optimal broth media that allow sufficient growth of M. furfur, and produce reliable and reproducible MICs using the CLSI BMD protocol were assessed. Thirty-six M. furfur isolates collected from BSIs of patients before and during AMB therapy, and receiving FLC prophylaxis, were tested. A good growth of M. furfur was observed in RPMI, CUB and SDB at 32 °C for 48 and 72 h. No statistically significant differences were detected between the MIC values registered after 48 and 72 h incubation. ITC, POS and VRC displayed lower MICs than FLC and AMB. These last two antifungal drugs showed higher and lower MICs, respectively, when the isolates were tested in SDB. SDB is the only medium in which it is possible to detect isolates with high FLC MICs in patients receiving FLC prophylaxis. A large number of isolates showed high AMB MIC values regardless of the media used. In conclusion, SDB might be suitable to determine triazole susceptibility. However, the media, the drug formulation or the breakpoints herein applied might not be useful for assessing the AMB susceptibility of M. furfur from BSIs. PMID:25168965

  4. Cupriavidus necator JMP134 rapidly reduces furfural with a Zn-dependent alcohol dehydrogenase.

    PubMed

    Li, Qunrui; Metthew Lam, L K; Xun, Luying

    2011-11-01

    Ethanol is a renewable biofuel, and it can be produced from lignocellulosic biomass. The biomass is usually converted to hydrolysates that consist of sugar and sugar derivatives, such as furfural. Yeast ferments sugar to ethanol, but furfural higher than 3 mM is inhibitory. It can take several days for yeast cells to reduce furfural to non-inhibitory furfuryl alcohol before producing ethanol. Bioreduction of furfural to furfuryl alcohol before fermentation may relieve yeast from furfural toxicity. We observed that Cupriavidus necator JMP134, a strict aerobe, rapidly reduced 17 mM furfural to less than 3 mM within 14 min with cell turbidity of 1.0 at 600 nm at 50°C. The rapid reduction consumed ethanol. The "furfural reductase" (FurX) was purified, and it oxidized ethanol to acetaldehyde and reduced furfural to furfuryl alcohol with NAD(+) as the cofactor. The protein was identified with mass spectrometry fingerprinting to be a hypothetical protein belonging to Zn-dependent alcohol dehydrogenase family. The furX-inactivation mutant of C. necator JMP134 lost the ability to rapidly reduce furfural, and Escherichia coli producing recombinant FurX gained the ability. Thus, an alcohol dehydrogenase enabled bacteria to rapidly reduce furfural with ethanol as the reducing power. PMID:21526390

  5. Synthesis and structural features of U VI and V IV chelate complexes with (hhmmbH)Cl·H 2O [hhmmb = {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide], a new Schiff base ligand derived from vitamin B6

    NASA Astrophysics Data System (ADS)

    Back, Davi Fernando; Ballin, Marco Aurélio; de Oliveira, Gelson Manzoni

    2009-10-01

    The Schiff base ligand {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide hydrochloride monohydrated {(hhmmbH)Cl·H 2O} ( 1) was prepared by reaction of pyridoxine hydrochloride with benzoic acid hydrazide. The reaction of 1 with [VO(acac) 2] and triethylamine yields the neutral vanadium IV complex [VO 2(hhmmb)]·Py ( 2), with a distorted quadratic pyramidal configuration. The Schiff base 1 reacts also with UO 2(NO 3) 2·6H 2O and triethylamine under deprotonation giving the uranium VI cationic complexes [UO 2(hhmmb)(H 2O)Cl] + ( 3) and [UO 2(hhmmb)(CH 3OH)Cl] + ( 4), both showing the classical pentagonal bipyrimidal geometry of UO22+ complexes. The structural features of all compounds are discussed.

  6. Degradation of 5-hydroxymethylfurfural during yeast fermentation.

    PubMed

    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 (p<0.05). The conversion of HMF into hydroxymethyl furfuryl alcohol seems to be a primary activity of yeast cells, and presence of sugars in the fermentation medium increases this activity. PMID:22010851

  7. In vivo detoxification of furfural during lipid production by the oleaginous yeast Trichosporon fermentans.

    PubMed

    Huang, Chao; Wu, Hong; Smith, Thomas J; Liu, Zong-Jun; Lou, Wen-Yong; Zong, Min-Hua

    2012-09-01

    In vivo detoxification of furfural by the oleaginous yeast, Trichosporon fermentans, under lipid-producing (i.e., nitrogen-limited) conditions was evaluated for the first time. During the initial fermentation phase, furfural was rapidly reduced to furfuryl alcohol, which is more toxic to T. fermentans than furfural. Furfuryl alcohol was subsequently oxidized to furoic acid which has low toxicity to T. fermentans and is the end product of the in vivo detoxification of furfural in this organism. These observations explain how T. fermentans can grow and accumulate lipids in medium containing furfural. They also indicate that strategies to minimize the transient production of furfuryl alcohol could further improve the capacity of the strain to produce lipids from furfural-containing lignocellulosic hydrolysates. PMID:22648683

  8. A high performance liquid chromatography method for determination of furfural in crude palm oil.

    PubMed

    Loi, Chia Chun; Boo, Huey Chern; Mohammed, Abdulkarim Sabo; Ariffin, Abdul Azis

    2011-09-01

    A modified steam distillation method was developed to extract furfural from crude palm oil (CPO). The collected distillates were analysed using high performance liquid chromatography (HPLC) coupled with an ultraviolet diode detector at 284nm. The HPLC method allowed identification and quantification of furfural in CPO. The unique thermal extraction of CPO whereby the fresh fruit bunches (FFB) are first subjected to steam treatment, distinguishes itself from other solvent-extracted or cold-pressed vegetable oils. The presence of furfural was also determined in the fresh palm oil from FFB (without undergoing the normal extraction process), palm olein, palm stearin, olive oil, coconut oil, sunflower oil, soya oil and corn oil. The chromatograms of the extracts were compared to that of standard furfural. Furfural was only detected in CPO. The CPO consignments obtained from four mills were shown to contain 7.54 to 20.60mg/kg furfural. PMID:25214353

  9. Ab initio study on the dynamics of furfural at the liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Dang, Hongli; Xue, Wenhua; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2013-03-01

    Catalytic biomass conversion sometimes occurs at the liquid-solid interfaces. We report ab initio molecular dynamics simulations at finite temperatures for the catalytic reactions involving furfural at the water-Pd and water-Cu interfaces. We found that, during the dynamic process, the furan ring of furfural prefers to be parallel to the Pd surface and the aldehyde group tends to be away from the Pd surface. On the other hand, at the water-Cu(111) interface, furfural prefers to be tilted to the Cu surface while the aldehyde group is bonded to the surface. In both cases, interaction of liquid water and furfural is identified. The difference of dynamic process of furfural at the two interfaces suggests different catalytic reaction mechanisms for the conversion of furfural, consistent with the experimental investigations. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSED's and NERSC's supercomputers

  10. Decarboxylation of furfural on Pd(111): Ab initio molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Xue, Wenhua; Dang, Hongli; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2013-03-01

    Furfural conversion over metal catalysts plays an important role in the studies of biomass-derived feedstocks. We report ab initio molecular dynamics simulations for the decarboxylation process of furfural on the palladium surface at finite temperatures. We observed and analyzed the atomic-scale dynamics of furfural on the Pd(111) surface and the fluctuations of the bondlengths between the atoms in furfural. We found that the dominant bonding structure is the parallel structure in which the furfural plane, while slightly distorted, is parallel to the Pd surface. Analysis of the bondlength fluctuations indicates that the C-H bond is the aldehyde group of a furfural molecule is likely to be broken first, while the C =O bond has a tendency to be isolated as CO. Our results show that the reaction of decarbonylation dominates, consistent with the experimental measurements. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSEDE's and NERSC's supercomputers.

  11. A study of surface enhanced Raman scattering for furfural adsorbed on silver surface

    NASA Astrophysics Data System (ADS)

    Jia, Ting-jian; Li, Peng-wei; Shang, Zhi-guo; Zhang, Ling; He, Ting-chao; Mo, Yu-jun

    2008-02-01

    The normal Raman spectrum (NRS) and the surface enhanced Raman scattering (SERS) spectrum of furfural in silver colloid were recorded and analyzed in this paper. The assignment of these bands to furfural molecules was performed by density functional theory (DFT) calculation. The data of the SERS by comparing with the one of NRS show that furfural molecules are adsorbed on the silver surface via the nonbonding electrons of the carbonyl oxygen.

  12. Synthesis and Verification of Biobased Terephthalic Acid from Furfural

    PubMed Central

    Tachibana, Yuya; Kimura, Saori; Kasuya, Ken-ichi

    2015-01-01

    Exploiting biomass as an alternative to petrochemicals for the production of commodity plastics is vitally important if we are to become a more sustainable society. Here, we report a synthetic route for the production of terephthalic acid (TPA), the monomer of the widely used thermoplastic polymer poly(ethylene terephthalate) (PET), from the biomass-derived starting material furfural. Biobased furfural was oxidised and dehydrated to give maleic anhydride, which was further reacted with biobased furan to give its Diels-Alder (DA) adduct. The dehydration of the DA adduct gave phthalic anhydride, which was converted via phthalic acid and dipotassium phthalate to TPA. The biobased carbon content of the TPA was measured by accelerator mass spectroscopy and the TPA was found to be made of 100% biobased carbon. PMID:25648201

  13. Synthesis and Verification of Biobased Terephthalic Acid from Furfural

    NASA Astrophysics Data System (ADS)

    Tachibana, Yuya; Kimura, Saori; Kasuya, Ken-Ichi

    2015-02-01

    Exploiting biomass as an alternative to petrochemicals for the production of commodity plastics is vitally important if we are to become a more sustainable society. Here, we report a synthetic route for the production of terephthalic acid (TPA), the monomer of the widely used thermoplastic polymer poly(ethylene terephthalate) (PET), from the biomass-derived starting material furfural. Biobased furfural was oxidised and dehydrated to give maleic anhydride, which was further reacted with biobased furan to give its Diels-Alder (DA) adduct. The dehydration of the DA adduct gave phthalic anhydride, which was converted via phthalic acid and dipotassium phthalate to TPA. The biobased carbon content of the TPA was measured by accelerator mass spectroscopy and the TPA was found to be made of 100% biobased carbon.

  14. Synthesis and verification of biobased terephthalic acid from furfural.

    PubMed

    Tachibana, Yuya; Kimura, Saori; Kasuya, Ken-ichi

    2015-01-01

    Exploiting biomass as an alternative to petrochemicals for the production of commodity plastics is vitally important if we are to become a more sustainable society. Here, we report a synthetic route for the production of terephthalic acid (TPA), the monomer of the widely used thermoplastic polymer poly(ethylene terephthalate) (PET), from the biomass-derived starting material furfural. Biobased furfural was oxidised and dehydrated to give maleic anhydride, which was further reacted with biobased furan to give its Diels-Alder (DA) adduct. The dehydration of the DA adduct gave phthalic anhydride, which was converted via phthalic acid and dipotassium phthalate to TPA. The biobased carbon content of the TPA was measured by accelerator mass spectroscopy and the TPA was found to be made of 100% biobased carbon. PMID:25648201

  15. LCA of bioethanol and furfural production from vetiver.

    PubMed

    Raman, Jegannathan Kenthorai; Gnansounou, Edgard

    2015-06-01

    In this study a prospective life cycle assessment of biorefinery system from vetiver leaves was carried out to know the environmental benefits of this system over conventional systems considering the geographical context of India. The composition of vetiver leaves from the experimental analysis revealed that vetiver is rich in cellulose (32.6%), hemicellulose (31.5%) and lignin (17.3%) that could be used as a feedstock for biorefinery. The comparative life cycle assessment results show that the carbon dioxide emission and fossil oil depletion could be reduced by 95% and 23% respectively in case of standalone bioethanol system, and 99% and 17% respectively in case of bioethanol and furfural system compared to that of conventional petrol and furfural systems. The sensitivity study indicates that the impact could be further reduced if vetiver biomass is used as a source of energy in biorefinery plant instead to the coal. PMID:25770467

  16. Psychiatric components of a Health Maintenance Facility (HMF) on Space Station

    NASA Technical Reports Server (NTRS)

    Santy, Patricia A.

    1987-01-01

    The operational psychiatric requirements for a comprehensive Health Maintenance Facility (HMF) on a permanently manned Space Station are examined. Consideration is given to the psychological health maintenance program designed for the diagnosis of mental distress in astronauts during flight and for prevention of mental breakdown. The types of mental disorders that can possibly affect the astronauts in flight are discussed, including various organic, psychotic, and affective mental disorders, as well as anxiety, adjustment, and somatoform/dissociative disorders. Special attention is given to therapeutic considerations for psychiatric operations on Space Station, such as restraints, psychopharmacology, psychotherapy, and psychosocial support.

  17. Degradation of furfural (2-furaldehyde) to methane and carbon dioxide by an anaerobic consortium

    SciTech Connect

    Rivard, C.J.; Grohmann, K.

    1991-12-31

    Furfural, a byproduct formed during the thermal/chemical pretreatment of hemicellulosic biomass, was degraded to methane and carbon dioxide under anaerobic conditions. The consortium of anaerobic microbes responsible for the degradation was enriched using small continuously stirred tank reactor (CSTR) systems with daily batch feeding of biomass pretreatment liquor and continuous addition of furfural. Although the continuous infusion of furfural was initially inhibitory to the anaerobic CSTR system, adaptation of the consortium occurred rapidly with high rates of furfural addition. Addition rates of 7.35 mg furfural/700-mL reactor/d resulted in biogas productions of 375%, of that produced in control CSTR systems, fed the biomass pretreatment liquor only. The anaerobic CSTR system fed high levels of furfural was stable, with a sludge pH of 7.1 and methane gas composition of 69%, compared to the control CSTR, which had a pH of 7.2 and 77% methane. CSTR systems in which furfural was continuously added resulted in 80% of the theoretically expected biogas. Intermediates in the anaerobic biodegradation of furfural were determined by spike additions in serum-bottle assays using the enriched consortium from the CSTR systems. Furfural was converted to several intermediates, including furfuryl alcohol, furoic acid, and acetic acid, before final conversion to methane and carbon dioxide.

  18. Genome-Wide Mapping of Furfural Tolerance Genes in Escherichia coli

    PubMed Central

    Glebes, Tirzah Y.; Sandoval, Nicholas R.; Reeder, Philippa J.; Schilling, Katherine D.; Zhang, Min; Gill, Ryan T.

    2014-01-01

    Advances in genomics have improved the ability to map complex genotype-to-phenotype relationships, like those required for engineering chemical tolerance. Here, we have applied the multiSCale Analysis of Library Enrichments (SCALEs; Lynch et al. (2007) Nat. Method.) approach to map, in parallel, the effect of increased dosage for >105 different fragments of the Escherichia coli genome onto furfural tolerance (furfural is a key toxin of lignocellulosic hydrolysate). Only 268 of >4,000 E. coli genes (∼6%) were enriched after growth selections in the presence of furfural. Several of the enriched genes were cloned and tested individually for their effect on furfural tolerance. Overexpression of thyA, lpcA, or groESL individually increased growth in the presence of furfural. Overexpression of lpcA, but not groESL or thyA, resulted in increased furfural reduction rate, a previously identified mechanism underlying furfural tolerance. We additionally show that plasmid-based expression of functional LpcA or GroESL is required to confer furfural tolerance. This study identifies new furfural tolerant genes, which can be applied in future strain design efforts focused on the production of fuels and chemicals from lignocellulosic hydrolysate. PMID:24489935

  19. HMF sectors since 1926: Comparison of two ground-based data sets

    NASA Astrophysics Data System (ADS)

    Hiltula, T.; Mursula, K.

    In this paper, we compare two recent long-term data sets of daily HMF sector polarities since 1926 based on ground-based geomagnetic measurements: the combined data set by Echer and Svalgaard [Echer, E., Svalgaard, L. Asymmetry in the Rosenberg-Coleman effect around solar minimum revealed by wavelet analysis of the interplanetary magnetic field polarity data (1927-2002). Geophys. Res. Lett. 31, 12808, 2004] (ES data set) and a three-station data set derived by Vennerstroem et al. [Vennerstroem, S., Zieger, B., Friis-Christensen, E. An improved method of inferring interplanetary sector structure, 1905-present. J. Geophys. Res. 106 (15), 16011-16020, 2001] (VZF data set). The Rosenberg-Coleman rule is consistently valid in the ES data during the last 80 years, but fails in the VZF data set in the early cycles. There is a clear bias (T sector dominance) in the VZF data that is not observed in satellite measurements collected in the OMNI-2 data set, or in the ES data. Also, there is a difference on the success rates between the two sectors in the VZF data. Therefore, we conclude that the ES data set is more reliable, especially in cycles 16-18, in reproducing the HMF sector structure. Both data sets reproduce the southward shift of the heliospheric current sheet during the OMNI-2 interval. However, only the more reliable ES data set depicts this systematically also during the early cycles 16-18.

  20. Furfural and its biochar improve the general properties of a saline soil

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Xu, G.; Shao, H. B.

    2014-07-01

    Organic materials (e.g., furfural residue) are generally believed to improve the physical and chemical properties of saline soils with low fertility. Recently, biochar has been received more attention as a possible measure to improve the carbon balance and improve soil quality in some degraded soils. However, little is known about their different amelioration of a sandy saline soil. In this study, 56 d incubation experiment was conducted to evaluate the influence of furfural and its biochar on the properties of saline soil. The results showed that both furfural and biochar greatly reduced pH, increased soil organic carbon (SOC) content and cation exchange capacity (CEC), and enhanced the available phosphorus (P) in the soil. Furfural is more efficient than biochar in reducing pH: 5% furfural lowered the soil pH by 0.5-0.8 (soil pH: 8.3-8.6), while 5% biochar decreased by 0.25-0.4 due to the loss of acidity in pyrolysis process. With respect to available P, furfural addition at a rate of 5% increased available P content by 4-6 times in comparison to 2-5 times with biochar application. In reducing soil exchangeable sodium percentage (ESP), biochar is slightly superior to furfural because soil ESP reduced by 51% and 43% with 5% furfural and 5% biochar at the end of incubation. In addition, no significant differences were observed between furfural and biochar about their capacity to retain N, P in leaching solution and to increase CEC in soil. These facts may be caused by the relatively short incubation time. In general, furfural and biochar exhibited a different effect depending on the property: furfural was more effective in decreasing pH and increasing available P, whereas biochar played a more important role in increasing SOC and reducing ESP of saline soil.

  1. Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip

    NASA Astrophysics Data System (ADS)

    Navin, Chelliah V.; Krishna, Katla Sai; Theegala, Chandra S.; Kumar, Challa S. S. R.

    2016-03-01

    Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors.Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06752a

  2. Hydrolysis of sorghum straw using phosphoric acid: evaluation of furfural production.

    PubMed

    Vázquez, Manuel; Oliva, Martha; Téllez-Luis, Simón J; Ramírez, José A

    2007-11-01

    Sorghum straw is a waste that has been studied scarcely. The main application is its use as raw material for xylose production. Xylose is a hemicellulosic sugar mainly used for its bioconversion toward xylitol. An alternative use could be its conversion toward furfural. The objective of this work was to study the furfural production by hydrolysis of sorghum straw with phosphoric acid at 134 degrees C. Several concentrations of H(3)PO(4) in the range 2-6% and reaction time (range 0-300 min) were evaluated. Kinetic parameters of mathematical models for predicting the concentration of xylose, glucose, arabinose, acetic acid and furfural in the hydrolysates were found. Optimal conditions for furfural production by acid hydrolysis were 6% H(3)PO(4) at 134 degrees C for 300 min, which yielded a solution with 13.7 g furfural/L, 4.0 g xylose/L, 2.9 g glucose/L, 1.1g arabinose/L and 1.2g acetic acid/L. The furfural yield of the process was 0.1336 g furfural/g initial dry matter was obtained. The results confirmed that sorghum straw can be used for furfural production when it is hydrolyzed using phosphoric acid. PMID:17145181

  3. High temperature dilute phosphoric acid pretreatment of corn stover for furfural and ethanol production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Furfural was produced from corn stover by one stage pretreatment process using dilute H3PO4 and solid residues following furfural production were used for ethanol production by Saccharomyces cerevisiae NRRL- Y2034. A series of experiments were conducted at varied temperatures (140-200 oC) and acid ...

  4. Detoxification of furfural in Corynebacterium glutamicum under aerobic and anaerobic conditions.

    PubMed

    Tsuge, Yota; Hori, Yoshimi; Kudou, Motonori; Ishii, Jun; Hasunuma, Tomohisa; Kondo, Akihiko

    2014-10-01

    The toxic fermentation inhibitors in lignocellulosic hydrolysates raise serious problems for the microbial production of fuels and chemicals. Furfural is considered to be one of the most toxic compounds among these inhibitors. Here, we describe the detoxification of furfural in Corynebacterium glutamicum ATCC13032 under both aerobic and anaerobic conditions. Under aerobic culture conditions, furfuryl alcohol and 2-furoic acid were produced as detoxification products of furfural. The ratio of the products varied depending on the initial furfural concentration. Neither furfuryl alcohol nor 2-furoic acid showed any toxic effect on cell growth, and both compounds were determined to be the end products of furfural degradation. Interestingly, unlike under aerobic conditions, most of the furfural was converted to furfuryl alcohol under anaerobic conditions, without affecting the glucose consumption rate. Both the NADH/NAD(+) and NADPH/NADP(+) ratio decreased in the accordance with furfural concentration under both aerobic and anaerobic conditions. These results indicate the presence of a single or multiple endogenous enzymes with broad and high affinity for furfural and co-factors in C. glutamicum ATCC13032. PMID:25112225

  5. Value of Coproduction of Ethanol and Furfural from Acid Hydrolysis Processes

    SciTech Connect

    Parker, S.; Calnon, M.; Feinberg, D.; Power, A.; Weiss, L.

    1984-05-01

    In the acid hydrolysis of a cellulosic feedstock (wood, wood wastes, or crop residues), up to 3.65 lb of furfural may be coproduced with each gallon of ethanol for only the cost of recovering and purifying it. Each plant producing 50 x 106 gal/yr of ethanol would produce an amount of by-product furfural equal to the total current domestic production. Thus, the need arises for investigation into potentially suitable processes for deriving profitable end products from furfural and thus expanding the market. The objectives of this study were to determine the economic potential of five selected, large volume derivatives of furfural that could displace hydrocarbon-based chemicals, and the consequent value of furfural as a by-product to the cellulose hydrolysis process of ethanol production.

  6. Organocatalytic Conversion of Cellulose into a Platform Chemical†

    PubMed Central

    Caes, Benjamin R.; Palte, Michael J.

    2014-01-01

    The search for a source of fuels and chemicals that is both abundant and renewable has become of paramount importance. The polysaccharide cellulose meets both criteria, and methods have been developed for its transformation into the platform chemical 5-(hydroxymethyl)furfural (HMF). These methods employ harsh reaction conditions or toxic heavy metal catalysts, deterring large-scale implementation. Here, we describe a low-temperature, one-pot route that uses ortho-carboxyl-substituted phenylboronic acids as organocatalysts in conjunction with hydrated magnesium chloride and mineral acids to convert cellulose and cellulose-rich municipal waste to HMF in yields comparable to processes that use toxic heavy metal catalysts. Isotopic labeling studies indicate that the key aldose-to-ketose transformation occurs via an enediol intermediate. The route, which also allows for facile catalyst recovery and recycling, provides a green prototype for cellulose conversion. PMID:24596655

  7. Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde

    NASA Astrophysics Data System (ADS)

    Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney

    2013-09-01

    The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

  8. The potential of residues of furfural and biogas as calcareous soil amendments for corn seed production.

    PubMed

    Zhao, Yunchen; Yan, Zhibin; Qin, Jiahai; Ma, Zhijun; Zhang, Youfu; Zhang, Li

    2016-04-01

    Intensive corn seed production in Northwest of China produced large amounts of furfural residues, which represents higher treatment cost and environmental issue. The broad calcareous soils in the Northwest of China exhibit low organic matter content and high pH, which led to lower fertility and lower productivity. Recycling furfural residues as soil organic and nutrient amendment might be a promising agricultural practice to calcareous soils. A 3-year field study was conducted to evaluate the effects of furfural as a soil amendment on corn seed production on calcareous soil with compared to biogas residues. Soil physical-chemical properties, soil enzyme activities, and soil heavy metal concentrations were assessed in the last year after the last application. Corn yield was determined in each year. Furfural residue amendments significantly decreased soil pH and soil bulk density. Furfural residues combined with commercial fertilizers resulted in the greater cumulative on soil organic matter, total phosphorus, available phosphorus, available potassium, and cation exchange capacity than that of biogas residue. Simultaneously, urease, invertase, catalase, and alkaline phosphatase increased even at the higher furfural application rates. Maize seed yield increased even with lower furfural residue application rates. Furfural residues resulted in lower Zn concentration and higher Cd concentration than that of biogas residues. Amendment of furfural residues led to higher soil electrical conductivity (EC) than that of biogas residues. The addition of furfural residues to maize seed production may be considered to be a good strategy for recycling the waste, converting it into a potential resource as organic amendment in arid and semi-arid calcareous soils, and may help to reduce the use of mineral chemical fertilizers in these soils. However, the impact of its application on soil health needs to be established in long-term basis. PMID:26606935

  9. Antioxidants in heat-processed koji and the production mechanisms.

    PubMed

    Okutsu, Kayu; Yoshizaki, Yumiko; Ikeda, Natsumi; Kusano, Tatsuro; Hashimoto, Fumio; Takamine, Kazunori

    2015-11-15

    We previously developed antioxidative heat-processed (HP)-koji via two-step heating (55 °C/2days → 75 °C/3 days) of white-koji. In this study, we isolated antioxidants in HP-koji and investigated their formation mechanisms. The antioxidants were identified to be 5-hydroxymethyl furfural (HMF) and 5-(α-D-glucopyranosyloxymethyl)-2-furfural (GMF) based on nuclear magnetic resonance spectral analysis. HMF and GMF were not present in intact koji, but were formed by heating at 75 °C. As production of these antioxidants was more effective by two-step heating than by constant heating at 55 °C or 75 °C, we presumed that the antioxidant precursors are derived enzymatically at 55°C and that the antioxidants are formed subsequently by thermal reaction at 75 °C. The heating assay of saccharide solutions revealed glucose and isomaltose as HMF and GMF precursors, respectively, and thus the novel finding of GMF formation from isomaltose. Finally, HMF and GMF were effectively formed by two-step heating from glucose and isomaltose present in koji. PMID:25977038

  10. Molecular characterization of the thi3 gene involved in thiamine biosynthesis in Zea mays: cDNA sequence and enzymatic and structural properties of the recombinant bifunctional protein with 4-amino-5-hydroxymethyl-2-methylpyrimidine (phosphate) kinase and thiamine monophosphate synthase activities.

    PubMed

    Rapala-Kozik, Maria; Olczak, Mariusz; Ostrowska, Katarzyna; Starosta, Agata; Kozik, Andrzej

    2007-12-01

    A thiamine biosynthesis gene, thi3, from maize Zea mays has been identified through cloning and sequencing of cDNA and heterologous overexpression of the encoded protein, THI3, in Escherichia coli. The recombinant THI3 protein was purified to homogeneity and shown to possess two essentially different enzymatic activities of HMP(-P) [4-amino-5-hydroxymethyl-2-methylpyrimidine (phosphate)] kinase and TMP (thiamine monophosphate) synthase. Both activities were characterized in terms of basic kinetic constants, with interesting findings that TMP synthase is uncompetitively inhibited by excess of one of the substrates [HMP-PP (HMP diphosphate)] and ATP. A bioinformatic analysis of the THI3 sequence suggested that these activities were located in two distinct, N-terminal kinase and C-terminal synthase, domains. Models of the overall folds of THI3 domains and the arrangements of active centre residues were obtained with the SWISS-MODEL protein modelling server, on the basis of the known three-dimensional structures of Salmonella enterica serotype Typhimurium HMP(-P) kinase and Bacillus subtilis TMP synthase. The essential roles of Gln98 and Met134 residues for HMP kinase activity and of Ser444 for TMP synthase activity were experimentally confirmed by site-directed mutagenesis. PMID:17696876

  11. Extreme furfural tolerance of a soil bacterium Enterobacter cloacae GGT036.

    PubMed

    Choi, Sun Young; Gong, Gyeongtaek; Park, Hong-Sil; Um, Youngsoon; Sim, Sang Jun; Woo, Han Min

    2015-01-10

    Detoxification process of cellular inhibitors including furfural is essential for production of bio-based chemicals from lignocellulosic biomass. Here we isolated an extreme furfural-tolerant bacterium Enterobacter cloacae GGT036 from soil sample collected in Mt. Gwanak, Republic of Korea. Among isolated bacteria, only E. cloacae GGT036 showed cell growth with 35 mM furfural under aerobic culture. Compared to the maximal half inhibitory concentration (IC50) of well-known industrial strains Escherichia coli (24.9 mM furfural) and Corynebacterium glutamicum (10 mM furfural) based on the cell density, IC50 of E. cloacae GGT036 (47.7 mM) was significantly higher after 24 h, compared to E. coli and C. glutamicum. Since bacterial cell growth was exponentially inhibited depending on linearly increased furfural concentrations in the medium, we concluded that E. cloacae GGT036 is an extreme furfural-tolerant bacterium. Recently, the complete genome sequence of E. cloacae GGT036 was announced and this could provide an insight for engineering of E. cloacae GGT036 itself or other industrially relevant bacteria. PMID:25444876

  12. Facile electrochemical method and corresponding automated instrument for the detection of furfural in insulation oil.

    PubMed

    Wang, Ruili; Huang, Xinjian; Wang, Lishi

    2016-02-01

    Determining the concentration of furfural contained in the insulation oil of a transformer has been established as a method to evaluate the health status of the transformer. However, the detection of furfural involves the employment of expensive instruments and/or time-consuming laboratorial operations. In this paper, we proposed a convenient electrochemical method to make the detection. The quantification of furfural was realized by extraction of furfural from oil phase to aqueous phase followed by reductive detection of furfural with differential pulse voltammetry (DPV) at a mercury electrode. This method is very sensitive and the limit of detection, corresponding to furfural contained in oil, is estimated to be 0.03 μg g(-1). Furthermore, excellent linearity can be obtained in the range of 0-10 μg g(-1). These features make the method very suitable for the determination of furfural in real situation. A fully automated instrument that can perform the operations of extraction and detection was developed, and this instrument enables the whole measurement to be finished within eight minutes. The methodology and the instrument were tested with real samples, and very favorable agreement between results obtained with this instrument and HPLC indicates that the proposed method along with instrument can be employed as a facile tool to diagnose the health status of aged transformers. PMID:26653467

  13. Combinatorial application of two aldehyde oxidoreductases on isobutanol production in the presence of furfural.

    PubMed

    Seo, Hyung-Min; Jeon, Jong-Min; Lee, Ju Hee; Song, Hun-Suk; Joo, Han-Byul; Park, Sung-Hee; Choi, Kwon-Young; Kim, Yong Hyun; Park, Kyungmoon; Ahn, Jungoh; Lee, Hongweon; Yang, Yung-Hun

    2016-01-01

    Furfural is a toxic by-product formulated from pretreatment processes of lignocellulosic biomass. In order to utilize the lignocellulosic biomass on isobutanol production, inhibitory effect of the furfural on isobutanol production was investigated and combinatorial application of two oxidoreductases, FucO and YqhD, was suggested as an alternative strategy. Furfural decreased cell growth and isobutanol production when only YqhD or FucO was employed as an isobutyraldehyde oxidoreductase. However, combinatorial overexpression of FucO and YqhD could overcome the inhibitory effect of furfural giving higher isobutanol production by 110% compared with overexpression of YqhD. The combinatorial oxidoreductases increased furfural detoxification rate 2.1-fold and also accelerated glucose consumption 1.4-fold. When it compares to another known system increasing furfural tolerance, membrane-bound transhydrogenase (pntAB), the combinatorial aldehyde oxidoreductases were better on cell growth and production. Thus, to control oxidoreductases is important to produce isobutanol using furfural-containing biomass and the combinatorial overexpression of FucO and YqhD can be an alternative strategy. PMID:26660478

  14. FudC, a protein primarily responsible for furfural detoxification in Corynebacterium glutamicum.

    PubMed

    Tsuge, Yota; Kudou, Motonori; Kawaguchi, Hideo; Ishii, Jun; Hasunuma, Tomohisa; Kondo, Akihiko

    2016-03-01

    Lignocellulosic hydrolysates contain compounds that inhibit microbial growth and fermentation, thereby decreasing the productivity of biofuel and biochemical production. In particular, the heterocyclic aldehyde furfural is one of the most toxic compounds found in these hydrolysates. We previously demonstrated that Corynebacterium glutamicum converts furfural into the less toxic compounds furfuryl alcohol and 2-furoic acid. To date, however, the genes involved in these oxidation and reduction reactions have not been identified in the C. glutamicum genome. Here, we show that Cgl0331 (designated FudC) is mainly responsible for the reduction of furfural into furfuryl alcohol in C. glutamicum. Deletion of the gene encoding FudC markedly diminished the in vivo reduction of furfural to furfuryl alcohol. Purified His-tagged FudC protein from Escherichia coli was also shown to convert furfural into furfuryl alcohol in an in vitro reaction utilizing NADPH, but not NADH, as a cofactor. Kinetic measurements demonstrated that FudC has a high affinity for furfural but has a narrow substrate range for other aldehydes compared to the protein responsible for furfural reduction in E. coli. PMID:26541332

  15. [Effects of furfural on the growth and lipid production of oleaginous yeast Rhodotorula glutinis].

    PubMed

    Yong, Zihan; Zhang, Xu; Tan, Tianwei

    2015-10-01

    In order to illustrate the effects of furfural, one of the most common inhibitory compounds in lignocellulosic hydrolysate, on oleaginous yeast Rhodotorula glutinis, we investigated the effects of different concentrations of furfural (0.1, 0.4, 0.6 and 1.5 g/L) on the biomass and lipid production of R. glutinis, as well as the effects of 1.0 g/L furfural on the utilization of glucose and xylose. Results showed that: when the furfural concentration reached 1.5 g/L, the lag phrase time was extended to 96 h, and the residual glucose was up to 17.7 g/L, with maximum biomass of only 6.6 g/L, which accounted for 47% of that in the basic medium (furfural-free), and the corresponding lipid content was reduced about 50%. Furfural showed lighter inhibitory degree on R. glutinis when xylose acted as the carbon source than glucose was the carbon source; more C18 fatty acids or unsaturated C18 fatty acids were generated in the presence of furfural. PMID:26964337

  16. Genetic and biological features of catheter-associated Malassezia furfur from hospitalized adults.

    PubMed

    Kaneko, Takamasa; Murotani, Makiko; Ohkusu, Kiyofumi; Sugita, Takashi; Makimura, Koichi

    2012-01-01

    Malassezia furfur, an etiological agent of catheter-associated fungemia, requires long-chain fatty acids for in vitro growth. We examined the applicability of rDNA sequence analysis, autoaggregation testing in liquid culture, utilization of parenteral lipid emulsions, and phospholipase activity for discrimination of catheter-associated M. furfur strains. The rDNA sequence types of catheter-associated M. furfur strains were distinct from those of other isolates. All M. furfur isolates recovered from blood culture bottles and the tips of catheters from patients receiving fat emulsion therapy were type I-3. Only M. furfur isolate GIFU 01 from a blood culture bottle showed no autoaggregation in liquid culture. All strains of M. furfur examined grew well on Sabouraud's dextrose agar supplemented with Intralipid lipid emulsion as compared to individual Tweens (20, 40, 60, 80) and Cremophor EL. A high percentage of type I-3 M. furfur strains (80.0%) showed very high phospholipase activity compared to type I-1 and I-4 strains obtained from healthy skin of the same subjects or healthy control subjects (20.0% and 0.0%, respectively). The blood culture bottle isolate GIFU 01 showed very high lipolytic enzymes activity for Intralipid but no phospholipase activity. These results suggest that particular factors, such as non-autoaggregation and very high lipolytic enzyme activity for parenteral lipid emulsions, play important roles in the growth and pathogenicity of Malassezia-related sepsis. PMID:21619498

  17. Isolation and characterization of a furfural-degrading bacterium Bacillus cereus sp. strain DS1.

    PubMed

    Zheng, Dan; Bao, Jianguo; Lu, Jueming; Gao, Chunlei

    2015-02-01

    Furfural was found to be the main organic pollutant in the wastewater coming from the Diosgenin factory. This substance is derived from acidic pentosan in Dioscorea zingiberensis and is also found in a variety of agricultural byproducts, including corncobs, oat, wheat bran, and sawdust. It is regarded as a toxicant and an inhibitor to the growth of microorganism in both sewage disposal and biological fermentation. A furfural-degrading strain (DS1) was isolated from activated sludge of wastewater treatment plant in a diosgenin factory by continuous enrichment culture. The strain was identified as Bacillus cereus based on morphological, physiological tests, as well as on 16S rDNA sequence and Biolog analyses. The capacity of this strain to grow on a mineral salt medium, utilizing furfural as the sole carbon and energy source to degrade furfural, was investigated in this study. Under the condition of pH 9.0, temperature 35 °C, with rotating speed of 150 rpm, and an inoculum of 6 %, the strain showed that the furfural degradation capacity reaches 35 % in 7 days, as measured by high-performance liquid chromatography. The addition of inorganic carbon sources could bring down the biodegradation efficiency of the furfural. The strain DS1 showed better furfural removal capacity, as compared to other inorganic carbon sources in the media. Furthermore, a furfural concentration of as high as 4,000 mg L(-1) was tolerated by the culture. The capacity to degrade furfural was demonstrated for the first time by using the genus B. cereus. This study suggests the possible application in biodegradation strategies. PMID:25274411

  18. Furfural production from Eucalyptus wood using an Acidic Ionic Liquid.

    PubMed

    Peleteiro, Susana; Santos, Valentín; Garrote, Gil; Parajó, Juan Carlos

    2016-08-01

    Eucalyptus globulus wood samples were treated with hot, compressed water to separate hemicelluloses (as soluble saccharides) from a solid phase mainly made up of cellulose and lignin. The liquid phase was dehydrated, and the resulting solids (containing pentoses as well as poly- and oligo- saccharides made up of pentoses) were dissolved and reacted in media containing an Acidic Ionic Liquid (1-butyl-3-methylimidazolium hydrogen sulfate) and a co-solvent (dioxane). The effects of the reaction time on the product distribution were studied at temperatures in the range 120-170°C for reaction times up to 8h, and operational conditions leading to 59.1% conversion of the potential substrates (including pentoses and pentose structural units in oligo- and poly- saccharides) into furfural were identified. PMID:27112846

  19. Electron- and photon-impact ionization of furfural

    SciTech Connect

    Jones, D. B.; Ali, E.; Madison, D. H. E-mail: madison@mst.edu; Nixon, K. L.; Limão-Vieira, P. E-mail: madison@mst.edu; Hubin-Franskin, M.-J.; Delwiche, J.; Ning, C. G.; Colgan, J.; Murray, A. J.; and others

    2015-11-14

    The He(I) photoelectron spectrum of furfural has been investigated, with its vibrational structure assigned for the first time. The ground and excited ionized states are assigned through ab initio calculations performed at the outer-valence Green’s function level. Triple differential cross sections (TDCSs) for electron-impact ionization of the unresolved combination of the 4a″  +  21a′ highest and next-highest occupied molecular orbitals have also been obtained. Experimental TDCSs are recorded in a combination of asymmetric coplanar and doubly symmetric coplanar kinematics. The experimental TDCSs are compared to theoretical calculations, obtained within a molecular 3-body distorted wave framework that employed either an orientation average or proper TDCS average. The proper average calculations suggest that they may resolve some of the discrepancies regarding the angular distributions of the TDCS, when compared to calculations employing the orbital average.

  20. Anaerobic treatment of a furfural-production wastewater

    SciTech Connect

    Wirtz, R.A.; Dague, R.R. . Dept. of Civil and Construction Engineering)

    1993-01-01

    The laboratory-scale treatment of a furfural-byproduct wastewater containing approximately 1.2% acetic acid was investigated using one fully-packed anaerobic filter and one partially-packed anaerobic upflow blanket filter operated at 35 C. Hydraulic retention times of 24 and 12 h were investigated, with organic loading rates ranging from 3 to 26 g COD/L/day. COD removal efficiencies in excess of 90% were observed for both reactors at organic loading up to 23 g/L/day. Experiments at both HRTs were conducted to determine the effect on performance of a two-week shut-down of the reactors. Results from the shut-down studies indicated that the fully-packed filter handled the shut-down periods more efficiently than did the blanket filter.

  1. Electron- and photon-impact ionization of furfural

    NASA Astrophysics Data System (ADS)

    Jones, D. B.; Ali, E.; Nixon, K. L.; Limão-Vieira, P.; Hubin-Franskin, M.-J.; Delwiche, J.; Ning, C. G.; Colgan, J.; Murray, A. J.; Madison, D. H.; Brunger, M. J.

    2015-11-01

    The He(i) photoelectron spectrum of furfural has been investigated, with its vibrational structure assigned for the first time. The ground and excited ionized states are assigned through ab initio calculations performed at the outer-valence Green's function level. Triple differential cross sections (TDCSs) for electron-impact ionization of the unresolved combination of the 4a″ + 21a' highest and next-highest occupied molecular orbitals have also been obtained. Experimental TDCSs are recorded in a combination of asymmetric coplanar and doubly symmetric coplanar kinematics. The experimental TDCSs are compared to theoretical calculations, obtained within a molecular 3-body distorted wave framework that employed either an orientation average or proper TDCS average. The proper average calculations suggest that they may resolve some of the discrepancies regarding the angular distributions of the TDCS, when compared to calculations employing the orbital average.

  2. Production of furfural from waste aqueous hemicellulose solution of hardwood over ZSM-5 zeolite.

    PubMed

    Gao, Hongling; Liu, Haitang; Pang, Bo; Yu, Guang; Du, Jian; Zhang, Yuedong; Wang, Haisong; Mu, Xindong

    2014-11-01

    This study aimed to produce furfural from waste aqueous hemicellulose solution of a hardwood kraft-based dissolving pulp production processing in a green method. The maximum furfural yield of 82.4% and the xylose conversion of 96.8% were achieved at 463K, 1.0g ZSM-5, 1.05g NaCl and organic solvent-to-aqueous phase ratio of 30:15 (V/V) for 3h. The furfural yield was just 51.5% when the same concentration of pure xylose solution was used. Under the optimized condition, furfural yield was still up to 67.1% even after the fifth reused of catalyst. Catalyst recycling study showed that ZSM-5 has a certain stability and can be efficiently reused. PMID:25266687

  3. Influence of Biomass Pretreatment Process Time on Furfural Extraction from Birch Wood

    NASA Astrophysics Data System (ADS)

    Brazdausks, Prans; Puke, Maris; Vedernikovs, Nikolajs; Kruma, Irena

    2013-12-01

    Furfural is a biomass derived-chemical that can be used to replace petrochemicals. In this study, dilute sulphuric acid hydrolysis was used for hemicelluloses secession from birch wood. The reaction was investigated at different biomass treatment times (10-90 min, increasing it by 10 min). We found that the greatest amount of furfural 1.4-2.6%, which is 9.7-17.7% from theoretical possible yield, was formed in the first 30 min of the beginning of birch wood pentoses monosaccharide dehydration, but the greatest yield of furfural 10.3%, which is 70.0% from the theoretical yield, can be obtained after 90 min. Given that furfural yield generally does not exceed 50% from the theoretical amount, the result can be considered as very good.

  4. Competitive adsorption of furfural and phenolic compounds onto activated carbon in fixed bed column.

    PubMed

    Sulaymon, Abbas H; Ahmed, Kawther W

    2008-01-15

    For a multicomponent competitive adsorption of furfural and phenolic compounds, a mathematical model was builtto describe the mass transfer kinetics in a fixed bed column with activated carbon. The effects of competitive adsorption equilibrium constant, axial dispersion, external mass transfer, and intraparticle diffusion resistance on the breakthrough curve were studied for weakly adsorbed compound (furfural) and strongly adsorbed compounds (parachlorophenol and phenol). Experiments were carried out to remove the furfural and phenolic compound from aqueous solution. The equilibrium data and intraparticle diffusion coefficients obtained from separate experiments in a batch adsorber, by fitting the experimental data with theoretical model. The results show that the mathematical model includes external mass transfer and pore diffusion using nonlinear isotherms and provides a good description of the adsorption process for furfural and phenolic compounds in a fixed bed adsorber. PMID:18284136

  5. Reactions of aqueous glucose solution over solid-acid Y-zeolite catalyst at 110-160 C

    SciTech Connect

    Lourvanij, K.; Rorrer, G.L. )

    1993-01-01

    Reactions of glucose with solid-acid Y-zeolite catalyst were studied to see if this heterogeneous system could produce oxygenated hydrocarbons by shape-selective, acid-catalyzed processes at fairly low temperatures. Experimentally, aqueous solutions of glucose (12 wt %) were reacted with HY-zeolite powder in a well-mixed batch reactor at temperatures ranging from 110 to 160 C and catalyst concentrations ranging from 2 to 20 g/150 ml. Unreacted glucose and oxygenated hydrocarbon products were measured by HPLC as a function of reaction time (0-24 h) and process conditions. Glucose conversions of 100% were obtained at 160 C after an 8-h reaction time. The apparent activation energy based on glucose conversion was 23.25 [plus minus] 0.40 kcal/mol. Several acid-catalyzed reactions were identified, including isomerization of glucose to fructose, partial dehydration of glucose to 5-(hydroxymethyl)furfural (HMF), rehydration and cleavage of HMF to formic acid and 4-oxo-pentanoic acid, and carbonization . Polymers of HMF and seven minor additional products in the lower molecular weight organic acids/aldehydes/ketones elution range were also isolated by HPLC. High yields of organic acids relative to HMF and lowered selectivity of HMF in the bulk phase relative to the homogeneous acid-catalyzed reaction suggests the possibility of molecular sieving reactions within the Y-zeolite in addition to reactions on the outer surface of the Y-zeolite particle.

  6. Selective aerobic oxidation of HMF to 2,5-diformylfuran on covalent triazine frameworks-supported Ru catalysts.

    PubMed

    Artz, Jens; Mallmann, Sabrina; Palkovits, Regina

    2015-02-01

    The selective aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran has been performed under mild conditions at 80 °C and 20 bar of synthetic air in methyl t-butyl ether. Ru clusters supported on covalent triazine frameworks (CTFs) allowed excellent selectivity and superior catalytic activity compared to other support materials such as activated carbon, γ-Al2 O3 , hydrotalcite, or MgO. CTFs with varying pore size, specific surface area, and N content could be prepared from different monomers. The structural properties of the CTF materials influence the catalytic activity of Ru/CTF significantly in the aerobic oxidation of HMF, which emphasizes the superior activity of mesoporous CTFs. Recycling of the catalysts is challenging, but promising methods to maintain high catalytic activity were developed that facilitate only minor deactivation in five consecutive recycling experiments. PMID:25586312

  7. Diagnostic of material defects found in pipelines made of 13 HMF steel on the basis of acoustic emission

    NASA Astrophysics Data System (ADS)

    Skubis, Jerzy; Jeziorski, Grzegorz; Ranachowski, Jerzy

    1992-07-01

    Preparatory work performed in developing a diagnostic method for testing welded joints in pressure pipelines made of 13 HMF steel by means of acoustic emission (AE) measurements is described. Within the framework of these studies the mechanical strength characteristic of the 13 HMF steel was determined in a tension test with simultaneous AE measurements. Later AE measurements were conducted on real pipeline sections with joints, during heat treatment. Acoustic emission was investigated according to the requirements of the ASME standard. Preliminary analysis of the results indicated that the AE method may be used for diagnoses of welded joints in pressure pipelines. Technical specifications of a three-channel AE analyzer manufactured by IPPT PAN (Institute of Basic Technological Problems, Polish Academy of Sciences) and used for test are sufficient for such measurements. A detailed physical interpretation of the phenomena occurring during the tests is presented.

  8. A novel method for furfural recovery via gas stripping assisted vapor permeation by a polydimethylsiloxane membrane

    PubMed Central

    Hu, Song; Guan, Yu; Cai, Di; Li, Shufeng; Qin, Peiyong; Karim, M. Nazmul; Tan, Tianwei

    2015-01-01

    Furfural is an important platform chemical with a wide range of applications. However, due to the low concentration of furfural in the hydrolysate, the conventional methods for furfural recovery are energy-intensive and environmentally unfriendly. Considering the disadvantages of pervaporation (PV) and distillation in furfural separation, a novel energy-efficient ‘green technique’, gas stripping assisted vapor permeation (GSVP), was introduced in this work. In this process, the polydimethylsiloxane (PDMS) membrane was prepared by employing water as solvent. Coking in pipe and membrane fouling was virtually non-existent in this new process. In addition, GSVP was found to achieve the highest pervaporation separation index of 216200 (permeate concentration of 71.1 wt% and furfural flux of 4.09 kgm−2h−1) so far, which was approximately 2.5 times higher than that found in pervaporation at 95°C for recovering 6.0 wt% furfural from water. Moreover, the evaporation energy required for GSVP decreased by 35% to 44% relative to that of PV process. Finally, GSVP also displayed more promising potential in industrial application than PV, especially when coupled with the hydrolysis process or fermentation in biorefinery industry. PMID:25819091

  9. A novel method for furfural recovery via gas stripping assisted vapor permeation by a polydimethylsiloxane membrane

    NASA Astrophysics Data System (ADS)

    Hu, Song; Guan, Yu; Cai, Di; Li, Shufeng; Qin, Peiyong; Karim, M. Nazmul; Tan, Tianwei

    2015-03-01

    Furfural is an important platform chemical with a wide range of applications. However, due to the low concentration of furfural in the hydrolysate, the conventional methods for furfural recovery are energy-intensive and environmentally unfriendly. Considering the disadvantages of pervaporation (PV) and distillation in furfural separation, a novel energy-efficient `green technique', gas stripping assisted vapor permeation (GSVP), was introduced in this work. In this process, the polydimethylsiloxane (PDMS) membrane was prepared by employing water as solvent. Coking in pipe and membrane fouling was virtually non-existent in this new process. In addition, GSVP was found to achieve the highest pervaporation separation index of 216200 (permeate concentration of 71.1 wt% and furfural flux of 4.09 kgm-2h-1) so far, which was approximately 2.5 times higher than that found in pervaporation at 95°C for recovering 6.0 wt% furfural from water. Moreover, the evaporation energy required for GSVP decreased by 35% to 44% relative to that of PV process. Finally, GSVP also displayed more promising potential in industrial application than PV, especially when coupled with the hydrolysis process or fermentation in biorefinery industry.

  10. Engineering furfural tolerance in Escherichia coli improves the fermentation of lignocellulosic sugars into renewable chemicals

    PubMed Central

    Wang, Xuan; Yomano, Lorraine P.; Lee, James Y.; York, Sean W.; Zheng, Huabao; Mullinnix, Michael T.; Shanmugam, K. T.; Ingram, Lonnie O.

    2013-01-01

    Pretreatments such as dilute acid at elevated temperature are effective for the hydrolysis of pentose polymers in hemicellulose and also increase the access of enzymes to cellulose fibers. However, the fermentation of resulting syrups is hindered by minor reaction products such as furfural from pentose dehydration. To mitigate this problem, four genetic traits have been identified that increase furfural tolerance in ethanol-producing Escherichia coli LY180 (strain W derivative): increased expression of fucO, ucpA, or pntAB and deletion of yqhD. Plasmids and integrated strains were used to characterize epistatic interactions among traits and to identify the most effective combinations. Furfural resistance traits were subsequently integrated into the chromosome of LY180 to construct strain XW129 (LY180 ΔyqhD ackA::PyadC′fucO-ucpA) for ethanol. This same combination of traits was also constructed in succinate biocatalysts (Escherichia coli strain C derivatives) and found to increase furfural tolerance. Strains engineered for resistance to furfural were also more resistant to the mixture of inhibitors in hemicellulose hydrolysates, confirming the importance of furfural as an inhibitory component. With resistant biocatalysts, product yields (ethanol and succinate) from hemicellulose syrups were equal to control fermentations in laboratory media without inhibitors. The combination of genetic traits identified for the production of ethanol (strain W derivative) and succinate (strain C derivative) may prove useful for other renewable chemicals from lignocellulosic sugars. PMID:23431191

  11. Engineering furfural tolerance in Escherichia coli improves the fermentation of lignocellulosic sugars into renewable chemicals.

    PubMed

    Wang, Xuan; Yomano, Lorraine P; Lee, James Y; York, Sean W; Zheng, Huabao; Mullinnix, Michael T; Shanmugam, K T; Ingram, Lonnie O

    2013-03-01

    Pretreatments such as dilute acid at elevated temperature are effective for the hydrolysis of pentose polymers in hemicellulose and also increase the access of enzymes to cellulose fibers. However, the fermentation of resulting syrups is hindered by minor reaction products such as furfural from pentose dehydration. To mitigate this problem, four genetic traits have been identified that increase furfural tolerance in ethanol-producing Escherichia coli LY180 (strain W derivative): increased expression of fucO, ucpA, or pntAB and deletion of yqhD. Plasmids and integrated strains were used to characterize epistatic interactions among traits and to identify the most effective combinations. Furfural resistance traits were subsequently integrated into the chromosome of LY180 to construct strain XW129 (LY180 ΔyqhD ackA::PyadC'fucO-ucpA) for ethanol. This same combination of traits was also constructed in succinate biocatalysts (Escherichia coli strain C derivatives) and found to increase furfural tolerance. Strains engineered for resistance to furfural were also more resistant to the mixture of inhibitors in hemicellulose hydrolysates, confirming the importance of furfural as an inhibitory component. With resistant biocatalysts, product yields (ethanol and succinate) from hemicellulose syrups were equal to control fermentations in laboratory media without inhibitors. The combination of genetic traits identified for the production of ethanol (strain W derivative) and succinate (strain C derivative) may prove useful for other renewable chemicals from lignocellulosic sugars. PMID:23431191

  12. Towards forecasting IRTAM: patterns in foF2/hmF2 global assimilative maps during storm events

    NASA Astrophysics Data System (ADS)

    Vesnin, A.; Galkin, I. A.; Bilitza, D.; Reinisch, B. W.

    2014-12-01

    The IRI based Real Time Assimilative Mapping (IRTAM) implements a novel assimilation approach that fuses climatology descriptions of IRI with real time data from the Global Ionosphere Radio Observatory (GIRO). At its current stage of development, IRTAM is an ionospheric weather now-casting model that improves the classic climatology, on average, more than twofold. The IRTAM is able to reproduce major effects that are caused by various events of both solar and terrestrial origin. Next step in further IRTAM development is directed towards its forecasting capability. We would like to know how temporal harmonics of the IRTAM specification of foF2/hmF2 are affected during disturbed conditions. Can we find patterns in their behavior and relate them to particular geomagnetic and solar activity indices? Can we forecast ionospheric conditions using previously observed patterns of behavior? To answer these questions we first investigate known storm events during the latest solar cycle. We calculate IRTAM global foF2/hmF2 expansion maps to look for hidden associations of the underlying map constituents to identify those responsible for particular features in foF2/hmF2 global behavior. This effort will result in a classification catalog of the feature patterns corresponding to these known events. We will compare these patterns to the IRI storm-time foF2 timelines. We expect such analysis to reveal various categories of events and to guide our further efforts towards a forecasting IRTAM.

  13. Time-varying ionosonde trend: Case study of Sodankylä hmF2 data 1957-2014

    NASA Astrophysics Data System (ADS)

    Roininen, Lassi; Laine, Marko; Ulich, Thomas

    2015-08-01

    We discuss trend analysis of nonstationary ionosonde hmF2 time series measured at Sodankylä Geophysical Observatory (67.4∘N, 26.7∘E), Finland, 1957-2014. We model the hmF2 with a dynamic regression time series model with the following components: a slowly varying background level, seasonal variations, and solar effects. We analyze the time series with a dynamic linear state space model. Such an approach allows model components to vary in time, allowing us to study the dynamic stochastic nature of the underlying long-term trend. This feature is lacking in most time series models used in atmospheric and environmental long-term trend analyses. Our objective is to understand the long-term hmF2 trend with respect to increased levels of carbon dioxide and methane in the atmosphere. Based on model estimates, this phenomenon is predicted to cool the thermosphere and leads to decrease of the altitude of the so-called F2 layer peak. After accounting for the effects of solar activity variations on the data, we see that the estimated trend shows an almost 30 km decrease of the F2 layer peak during the observation period. The decrease of the peak during 1990-2010 is significantly greater than during earlier observation period.

  14. Reduction of furfural to furfuryl alcohol by ethanologenic strains of bacteria and its effect on ethanol production from xylose.

    PubMed

    Gutiérrez, Tony; Buszko, Marian L; Ingram, Lonnie O; Preston, James F

    2002-01-01

    The ethanologenic bacteria Escherichia coli strains KO11 and LYO1, and Klebsiella oxytoca strain P2, were investigated for their ability to metabolize furfural. Using high performance liquid chromatography and 13C-nuclear magnetic resonance spectroscopy, furfural was found to be completely biotransformed into furfuryl alcohol by each of the three strains with tryptone and yeast extract as sole carbon sources. This reduction appears to be constitutive with NAD(P)H acting as electron donor. Glucose was shown to be an effective source of reducing power. Succinate inhibited furfural reduction, indicating that flavins are unlikely participants in this process. Furfural at concentrations >10 mM decreased the rate of ethanol formation but did not affect the final yield. Insight into the biochemical nature of this furfural reduction process may help efforts to mitigate furfural toxicity during ethanol production by ethanologenic bacteria. PMID:12018260

  15. Over-expression of a putative oxidoreductase (UcpA) for increasing furfural or 5-hydroxymethylfurfural tolerance

    DOEpatents

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

    2016-05-24

    The subject invention pertains to overexpression of a putative oxidoreductase (ucpA) for increasing furfural tolerance in genetically modified microorganisms. Genetically modified microorganisms capable of overexpressing UcpA are also provided. Increased expression of ucpA was shown to increase furfural tolerance by 50%, and to permit the fermentation of sugars to products in the presence of 15 mM furfural.

  16. Evaluation of the DNA damaging effect of the heat-induced food toxicant 5-hydroxymethylfurfural (HMF) in various cell lines with different activities of sulfotransferases.

    PubMed

    Durling, Louise J K; Busk, Leif; Hellman, Björn E

    2009-04-01

    5-Hydroxymethylfurfural (HMF), a heat-induced food toxicant present in a vast number of food items, has been suggested to be genotoxic after being bioactivated by the sulfotransferase SULT1A1. The comet assay was used to evaluate the DNA damaging effect of HMF in cell lines with different activities of SULT1A1: two human cell lines (Caco-2, low activity; and HEK293, higher activity), one cell line from mouse (L5178Y, no activity) and two cell lines from Chinese hamster (V79, negligible activity; and V79-hP-PST, high activity of human SULT1A1). HMF induced significant DNA damage in all cell lines after 3 h exposure to 100 mM. Most sensitive were V79 and V79-hP-PST where HMF induced significant DNA damage at 25 mM. Consequently, in the present study we have shown that HMF is a DNA damaging agent in vitro independent of the activity of SULT1A1 in the cells. The HMF-induced DNA damage was only observed at rather high concentrations which usually was associated with a concomitant decrease in cell viability. PMID:19271322

  17. Furfural Determination with Disposable Polymer Films and Smartphone-Based Colorimetry for Beer Freshness Assessment.

    PubMed

    Rico-Yuste, Alberto; González-Vallejo, Victoria; Benito-Peña, Elena; de Las Casas Engel, Tomás; Orellana, Guillermo; Moreno-Bondi, María Cruz

    2016-04-01

    We have developed disposable color-changing polymeric films for quantification of furfural-a freshness indicator-in beer using a smartphone-based reader. The films are prepared by radical polymerization of 4-vinylaniline, as a furfural-sensitive indicator monomer, 2-hydroxymethyl methacrylate as a comonomer, and ethylene dimethyl methacrylate (EDMA) as a cross-linker. The sensing mechanism is based on the Stenhouse reaction in which aniline and furfural react in acidic media with the generation of a deep red cyanine derivative, absorbing at 537 nm, which is visible to the naked eye. The colorimetric response has been monitored using either a portable fiber-optic spectrophotometer or the built-in camera of a smartphone. Under the optimized conditions, a linear response to furfural in beer was obtained in the 39 to 500 μg L(-1) range, with a detection limit of 12 μg L(-1), thus improving the performance of other well-established colorimetric or chromatographic methods. The novel films are highly selective to furfural, and no cross-reactivity has been observed from other volatile compounds generated during beer aging. A smartphone application (app), developed for Android platforms, measures the RGB color coordinates of the sensing membranes after exposure to the analyte. Following data processing, the signals are converted into concentration values by preloaded calibration curves. The method has been applied to determination of furfural in pale lager beers with different storage times at room temperature. A linear correlation (r > 0.995) between the storage time and the furfural concentration in the samples has been confirmed; our results have been validated by HPLC with diode-array detection. PMID:26965182

  18. Characterization and fermentation of dilute-acid hydrolyzates from wood

    SciTech Connect

    Taherzadeh, M.J.; Niklasson, C.; Liden, G.; Eklund, R.; Gustafsson, L.

    1997-11-01

    Dilute-acid hydrolyzates from alder, aspen, birch, willow, pine, and spruce were fermented without prior detoxification. The hydrolyzates were prepared by a one-stage hydrolysis process using sulfuric acid (5 g/L) at temperatures between 188 and 234 C and with a holding time of 7 min. The fermentations were carried out anaerobically by Saccharomyces cerevisiae (10 g of d.w./L) at a temperature of 30 C and an initial pH of 5.5. The fermentabilities were quite different for the different wood species, and only hydrolyzates of spruce produced at 188 and 198 C, hydrolyzates of pine produced at 188 C, and hydrolyzates of willow produced at 198 C could be completely fermented within 24 h. From the sum of the concentrations of the known inhibitors furfural and 5-(hydroxymethyl)furfural (HMF), a good prediction of the maximum ethanol production rate could be obtained, regardless of the origin of the hydrolyzate. Furthermore, in hydrolyzates that fermented well, furfural and HMF were found to be taken up and converted by the yeast, concomitant with the uptake of glucose.

  19. Catalytic conversion of cellulose to chemicals in ionic liquid.

    PubMed

    Tao, Furong; Song, Huanling; Chou, Lingjun

    2011-01-01

    A simple and effective route for the production of 5-hydroxymethyl furfural (HMF) and furfural from microcrystalline cellulose (MCC) has been developed. CoSO(4) in an ionic liquid, 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate (IL-1), was found to be an efficient catalyst for the hydrolysis of cellulose at 150°C, which led to 84% conversion of MCC after 300min reaction time. In the presence of a catalytic amount of CoSO(4), the yields of HMF and furfural were up to 24% and 17%, respectively; a small amount of levulinic acid (LA) and reducing sugars (8% and 4%, respectively) were also generated. Dimers of furan compounds were detected as the main by-products through HPLC-MS, and with the help of mass spectrometric analysis, the components of gas products were methane, ethane, CO, CO(2,) and H(2). A mechanism for the CoSO(4)-IL-1 hydrolysis system was proposed and IL-1 was recycled for the first time, which exhibited favorable catalytic activity over five repeated runs. This catalytic system may be valuable to facilitate energy-efficient and cost-effective conversion of biomass into biofuels and platform chemicals. PMID:21092940

  20. Polyamine transporters and polyamines increase furfural tolerance during xylose fermentation with ethanologenic Escherichia coli strain LY180.

    PubMed

    Geddes, Ryan D; Wang, Xuan; Yomano, Lorraine P; Miller, Elliot N; Zheng, Huabao; Shanmugam, Keelnatham T; Ingram, Lonnie O

    2014-10-01

    Expression of genes encoding polyamine transporters from plasmids and polyamine supplements increased furfural tolerance (growth and ethanol production) in ethanologenic Escherichia coli LY180 (in AM1 mineral salts medium containing xylose). This represents a new approach to increase furfural tolerance and may be useful for other organisms. Microarray comparisons of two furfural-resistant mutants (EMFR9 and EMFR35) provided initial evidence for the importance of polyamine transporters. Each mutant contained a single polyamine transporter gene that was upregulated over 100-fold (microarrays) compared to that in the parent LY180, as well as a mutation that silenced the expression of yqhD. Based on these genetic changes, furfural tolerance was substantially reconstructed in the parent, LY180. Deletion of potE in EMFR9 lowered furfural tolerance to that of the parent. Deletion of potE and puuP in LY180 also decreased furfural tolerance, indicating functional importance of the native genes. Of the 8 polyamine transporters (18 genes) cloned and tested, half were beneficial for furfural tolerance (PotE, PuuP, PlaP, and PotABCD). Supplementing AM1 mineral salts medium with individual polyamines (agmatine, putrescine, and cadaverine) also increased furfural tolerance but to a smaller extent. In pH-controlled fermentations, polyamine transporter plasmids were shown to promote the metabolism of furfural and substantially reduce the time required to complete xylose fermentation. This increase in furfural tolerance is proposed to result from polyamine binding to negatively charged cellular constituents such as nucleic acids and phospholipids, providing protection from damage by furfural. PMID:25063650

  1. Polyamine Transporters and Polyamines Increase Furfural Tolerance during Xylose Fermentation with Ethanologenic Escherichia coli Strain LY180

    PubMed Central

    Geddes, Ryan D.; Wang, Xuan; Yomano, Lorraine P.; Miller, Elliot N.; Zheng, Huabao; Shanmugam, Keelnatham T.

    2014-01-01

    Expression of genes encoding polyamine transporters from plasmids and polyamine supplements increased furfural tolerance (growth and ethanol production) in ethanologenic Escherichia coli LY180 (in AM1 mineral salts medium containing xylose). This represents a new approach to increase furfural tolerance and may be useful for other organisms. Microarray comparisons of two furfural-resistant mutants (EMFR9 and EMFR35) provided initial evidence for the importance of polyamine transporters. Each mutant contained a single polyamine transporter gene that was upregulated over 100-fold (microarrays) compared to that in the parent LY180, as well as a mutation that silenced the expression of yqhD. Based on these genetic changes, furfural tolerance was substantially reconstructed in the parent, LY180. Deletion of potE in EMFR9 lowered furfural tolerance to that of the parent. Deletion of potE and puuP in LY180 also decreased furfural tolerance, indicating functional importance of the native genes. Of the 8 polyamine transporters (18 genes) cloned and tested, half were beneficial for furfural tolerance (PotE, PuuP, PlaP, and PotABCD). Supplementing AM1 mineral salts medium with individual polyamines (agmatine, putrescine, and cadaverine) also increased furfural tolerance but to a smaller extent. In pH-controlled fermentations, polyamine transporter plasmids were shown to promote the metabolism of furfural and substantially reduce the time required to complete xylose fermentation. This increase in furfural tolerance is proposed to result from polyamine binding to negatively charged cellular constituents such as nucleic acids and phospholipids, providing protection from damage by furfural. PMID:25063650

  2. New organic aerogels based upon a phenolic-furfural reaction

    SciTech Connect

    Hrubesh, L.W.

    1994-09-01

    The aqueous polycondensation of (1) resorcinol with formaldehyde and (2) melamine with formaldehyde are two proven synthetic routes for the formation of organic aerogels. Recently, we have discovered a new type of organic aerogel based upon a phenolic-furfural (PF) reaction. This sol-gel polymerization has a major advantage over past approaches since it can be conducted in alcohol (e.g., 1-propanol), thereby eliminating the need for a solvent exchange step prior to supercritical drying from carbon dioxide. The resultant aerogels are dark brown in color and can be converted to a carbonized version upon pyrolysis in an inert atmosphere. BET surface areas of 350--600 m{sup 2}/g have been measured, and transmission electron microscopy reveals an interconnected structure of irregularly-shaped particles or platelets with {approximately}10 nm dimensions. Thermal conductivities as low as 0.015 W/m-K have been recorded for PF aerogels under ambient conditions. This paper describes the chemistry-structure-property relationships of these new materials in detail.

  3. Investigation of furfural biodegradation in a continuous inflow cyclic biological reactor.

    PubMed

    Moussavi, Gholamreza; Leili, Mostafa; Nadafi, Kazem

    2016-01-01

    The performance of a continuous inflow cyclic biological reactor (CBR) containing moving media was investigated for the degradation of high concentrations of furfural. The effects of hydraulic retention time (HRT) and furfural initial concentrations (loading rate), as main operating parameters, on the bioreactor performance were studied. The results indicated that the CBR could remove over 98% of furfural and 71% of its chemical oxygen demand (COD) at inlet furfural concentrations up to 1,200 mg L(-1) (2.38 g L(-1) d(-1)), a 6-h cycle time and HRT of 12.1 h. The removal efficiency decreased slightly from 98 to 94% when HRT decreased from 12.1 to 10.5 h. The average removal efficiency of furfural and COD during the 345-day operational period under steady-state conditions were 97.7% and 82.1%, respectively. The efficiency also increased approximately 17.2% after addition of synthetic polyurethane cubes as moving media at a filling ratio of 10%. PMID:26819384

  4. Azole susceptibility of Malassezia pachydermatis and Malassezia furfur and tentative epidemiological cut-off values.

    PubMed

    Cafarchia, Claudia; Iatta, Roberta; Immediato, Davide; Puttilli, Maria Rita; Otranto, Domenico

    2015-09-01

    This study aims to determine the minimal inhibitory concentration (MIC) distribution and the epidemiological cut-off values (ECVs) of Malassezia pachydermatis and Malassezia furfur isolates for fluconazole (FLZ), itraconazole (ITZ), posaconazole (POS), and voriconazole (VOR). A total of 62 M. pachydermatis strains from dogs with dermatitis and 78 M. furfur strains from humans with bloodstream infections (BSI) were tested by a modified broth microdilution Clinical and Laboratory Standards Institute (CLSI) method. ITZ and POS displayed lower MICs than VOR and FLZ, regardless of the Malassezia species. The MIC data for azoles of M. pachydermatis were four two-fold dilutions lower than those of M. furfur. Based on the ECVs, about 94% of Malassezia strains might be categorized within susceptible population for all azoles, except for FLZ, and azole cross-resistance was detected in association with FLZ in M. pachydermatis but not in M. furfur.The study proposes, for the first time, tentative azole ECVs for M. pachydermatis and M. furfur for monitoring the emergence of isolates with decreased susceptibilities and shows that the azole MIC distribution varied according to the Malassezia species tested, thus suggesting the usefulness of determining the susceptibility profile for effective treatment of each species. PMID:26162472

  5. Study of the Influence of Key Process Parameters on Furfural Production.

    PubMed

    Fele Žilnik, Ljudmila; Grilc, Viktor; Mirt, Ivan; Cerovečki, Željko

    2016-01-01

    The present work reports the influence of key process variables on the furfural formation from leached chestnut-wood chips in a pressurized reactor. Effect of temperature, pressure, type and concentration of the catalyst solution, the steam flow rate or stripping module, the moisture content of the wood particles and geometric characteristics such as size and type of the reactor, particle size and bed height were considered systematically. One stage process was only taken into consideration. Lab-scale and pilot-scale studies were performed. The results of the non-catalysed laboratory experiments were compared with an actual non-catalysed (auto-catalysed) industrial process and with experiments on the pilot scale, the latter with 28% higher furfural yield compared to the others. Application of sulphuric acid as catalyst, in an amount of 0.03-0.05 g (H2SO4 100%)/g d.m. (dry material), enables a higher production of furfural at lower temperature and pressure of steam in a shorter reaction time. Pilot scale catalysed experiments have revealed very good performance for furfural formation under less severe operating conditions, with a maximum furfural yield as much as 88% of the theoretical value. PMID:27333552

  6. Improving furfural tolerance of Zymomonas mobilis by rewiring a sigma factor RpoD protein.

    PubMed

    Tan, Fu-Rong; Dai, Li-Chun; Wu, Bo; Qin, Han; Shui, Zong-Xia; Wang, Jing-Li; Zhu, Qi-Li; Hu, Qi-Chun; Ruan, Zhi-Yong; He, Ming-Xiong

    2015-06-01

    Furfural from lignocellulosic hydrolysates is the key inhibitor for bio-ethanol fermentation. In this study, we report a strategy of improving the furfural tolerance in Zymomonas mobilis on the transcriptional level by engineering its global transcription sigma factor (σ(70), RpoD) protein. Three furfural tolerance RpoD mutants (ZM4-MF1, ZM4-MF2, and ZM4-MF3) were identified from error-prone PCR libraries. The best furfural-tolerance strain ZM4-MF2 reached to the maximal cell density (OD600) about 2.0 after approximately 30 h, while control strain ZM4-rpoD reached its highest cell density of about 1.3 under the same conditions. ZM4-MF2 also consumed glucose faster and yield higher ethanol; expression levels and key Entner-Doudoroff (ED) pathway enzymatic activities were also compared to control strain under furfural stress condition. Our results suggest that global transcription machinery engineering could potentially be used to improve stress tolerance and ethanol production in Z. mobilis. PMID:25895089

  7. Effect of structural characteristics of corncob hemicelluloses fractionated by graded ethanol precipitation on furfural production.

    PubMed

    Li, Huiling; Dai, Qingqing; Ren, Junli; Jian, Longfei; Peng, Feng; Sun, Runcang; Liu, Guoliang

    2016-01-20

    In the present study, a graded ethanol precipitation technique was employed to obtain hemicelluloses from the alkali-extracted corncob liquid. The relationship between the structural characteristics of alkali-soluble corncob hemicelluloses and the production of furfural was investigated by a heterogeneous process in a biphasic system. Results showed that alkali-soluble corncob hemicelluloses mainly consisted of glucuronoarabinoxylans and L-arabino-(4-O-methylglucurono)-D-xylans, and the drying way had less influence on the sugar composition, molecular weights and the functional groups of hemicelluloses obtained by the different ethanol concentration precipitation except for the thermal property, the amorphous structure and the ability for the furfural production. Furthermore, alkali-soluble corncob hemicelluloses with higher xylose content, lower branch degree, higher polydispersity and crystallinity contributed to the furfural production. A highest furfural yield of 45.41% with the xylose conversion efficiency of 99.06% and the furfural selectivity of 45.84% was obtained from the oven-dried hemicelluloses precipitated at the 30% (v/v) ethanol concentration. PMID:26572347

  8. A combined process of adsorption and Fenton-like oxidation for furfural removal using zero-valent iron residue.

    PubMed

    Li, Furong; Bao, Jianguo; Zhang, Tian C; Lei, Yutian

    2015-01-01

    In this study, the feasibility of using a combined adsorption and Fenton-like oxidation process (with zero-valent iron (ZVI) residue from heat wraps as an absorbent and catalyst) to remove furfural in the solution was evaluated. The influencing parameters (e.g. pH, H2O2 concentration, initial furfural concentration) and the reusability of ZVI residue (to replace the iron powder) were estimated. The ZVI residue was found to have much better adsorption effect on furfural at pH 2.0 compared with pH 6.7. For Fenton-like reaction alone with ZVI residue, the highest furfural removal of 97.5% was observed at the concentration of 0.176 mol/L H2O2, and all of the samples had >80% removal efficiency at different initial furfural concentrations of 2, 10, 20, 30 and 40 mmol/L. However, with a combined adsorption and Fenton-like oxidation, the removal efficiency of furfural was nearly 100% for all treatments. The ZVI residue used for furfural removal was much better than that of iron powder in the Fenton-like reaction at a seven-cycle experiment. This study suggests the combined process of adsorption and Fenton-like oxidation using ZVI residue is effective for the treatment of furfural in the liquid. PMID:26006292

  9. Pre-treatment step with Leuconostoc mesenteroides or L. pseudomesenteroides strains removes furfural from Zymomonas mobilis ethanolic fermentation broth

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Furfural (furan-2-carboxaldehyde), formed during dilute acid hydrolysis of biomass, is an inhibitor of growth and ethanol production by Zymomonas mobilis. The present study used a biological pre-treatment to reduce that amount of furfural in a model biofuel fermentation broth. The pre-treatment in...

  10. Pd modified Au on carbon as an effective and durable catalyst for the direct oxidation of HMF to FDCA

    SciTech Connect

    Villa, Alberto; Schiavoni, Marco; Campisi, Sebastiano; Veith, Gabriel M; Prati, Laura

    2013-01-01

    We show that the modification of a gold/carbon catalyst with Pt or Pd produces stable and recyclable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). This finding is a significant advance over current conversion technology because of the technological importance of FDCA. Indeed, FDCA has been identified as one of twelve potential building blocks for the production of value added chemicals derived from biosources.1 FDCA is a potential replacement source of terephthalic acid, the monomer presently used for the production of polyethylene terephthalate (PET) and derived from hydrocarbon sources.2

  11. Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

    NASA Astrophysics Data System (ADS)

    Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2014-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

  12. Solid acids as catalysts for the conversion of D-xylose, xylan and lignocellulosics into furfural in ionic liquid.

    PubMed

    Zhang, Luxin; Yu, Hongbing; Wang, Pan

    2013-05-01

    With the aim to develop an ecologically viable catalytic pathway for furfural production without the use of inorganic acids, H3PW12O40, Amberlyst-5 and NKC-9 (macroporous styrene-based sulfonic acid resin) were used as catalysts for producing furfural from xylose, xylan and lignocellulosic biomass in [BMIM]Cl under microwave irradiation at atmospheric pressure. A surprisingly high furfural yield of 93.7% from xylan was obtained by H3PW12O40 at 160 °C in 10 min. The degradation of furfural affected by single addition of [BMIM]Cl and solid acids was also investigated. The IL could be easily recycled and reused with stable solvent capacity for multiple runs (5×) after the product furfural was extracted with ethyl acetate. PMID:23567725

  13. Excitation of vibrational quanta in furfural by intermediate-energy electrons.

    PubMed

    Jones, D B; Neves, R F C; Lopes, M C A; da Costa, R F; Varella, M T do N; Bettega, M H F; Lima, M A P; García, G; Blanco, F; Brunger, M J

    2015-12-14

    We report cross sections for electron-impact excitation of vibrational quanta in furfural, at intermediate incident electron energies (20, 30, and 40 eV). The present differential cross sections are measured over the scattered electron angular range 10°-90°, with corresponding integral cross sections subsequently being determined. Furfural is a viable plant-derived alternative to petrochemicals, being produced via low-temperature plasma treatment of biomass. Current yields, however, need to be significantly improved, possibly through modelling, with the present cross sections being an important component of such simulations. To the best of our knowledge, there are no other cross sections for vibrational excitation of furfural available in the literature, so the present data are valuable for this important molecule. PMID:26671372

  14. Low acid hydrothermal fractionation of Giant Miscanthus for production of xylose-rich hydrolysate and furfural.

    PubMed

    Kim, Tae Hyun; Ryu, Hyun Jin; Oh, Kyeong Keun

    2016-10-01

    Low acid hydrothermal (LAH) fractionation was developed for the effective recovery of hemicellulosic sugar (mainly xylose) from Miscanthus sacchariflorus Goedae-Uksae 1 (M. GU-1). The xylose yield was maximized at 74.75% when the M. GU-1 was fractionated at 180°C and 0.3wt.% of sulfuric acid for 10min. At this condition, the hemicellulose (mainly xylan) degradation was 86.41%. The difference between xylan degradation and xylose recovery yield, i.e., xylan loss, was 11.66%, as indicated by the formation of decomposed products. The furfural, the value added biochemical product, was also obtained by 0.42g/L at this condition, which was 53.82% of furfural production yield based on the xylan loss. After then, the furfural production continued to increase to a maximum concentration of 1.87g/L, at which point the xylan loss corresponded to 25.87%. PMID:27380022

  15. Excitation of vibrational quanta in furfural by intermediate-energy electrons

    NASA Astrophysics Data System (ADS)

    Jones, D. B.; Neves, R. F. C.; Lopes, M. C. A.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; García, G.; Blanco, F.; Brunger, M. J.

    2015-12-01

    We report cross sections for electron-impact excitation of vibrational quanta in furfural, at intermediate incident electron energies (20, 30, and 40 eV). The present differential cross sections are measured over the scattered electron angular range 10°-90°, with corresponding integral cross sections subsequently being determined. Furfural is a viable plant-derived alternative to petrochemicals, being produced via low-temperature plasma treatment of biomass. Current yields, however, need to be significantly improved, possibly through modelling, with the present cross sections being an important component of such simulations. To the best of our knowledge, there are no other cross sections for vibrational excitation of furfural available in the literature, so the present data are valuable for this important molecule.

  16. Excitation of vibrational quanta in furfural by intermediate-energy electrons

    SciTech Connect

    Jones, D. B.; Neves, R. F. C.; Lopes, M. C. A.; Costa, R. F. da; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; García, G.; and others

    2015-12-14

    We report cross sections for electron-impact excitation of vibrational quanta in furfural, at intermediate incident electron energies (20, 30, and 40 eV). The present differential cross sections are measured over the scattered electron angular range 10°–90°, with corresponding integral cross sections subsequently being determined. Furfural is a viable plant-derived alternative to petrochemicals, being produced via low-temperature plasma treatment of biomass. Current yields, however, need to be significantly improved, possibly through modelling, with the present cross sections being an important component of such simulations. To the best of our knowledge, there are no other cross sections for vibrational excitation of furfural available in the literature, so the present data are valuable for this important molecule.

  17. Differential Expression of Extracellular Lipase and Protease Activities of Mycelial and Yeast Forms in Malassezia furfur.

    PubMed

    Juntachai, Weerapong; Kajiwara, Susumu

    2015-10-01

    Malassezia furfur is a dimorphic yeast that is part of the human skin microflora. This fungus is a pathogen of a certain skin diseases, such as pityriasis versicolor, and in rare cases causes systemic infection in neonates. However, the role of dimorphism in the pathogenicity remains unclear. A modified induction medium (IM) was successfully able to induce mycelial growth of M. furfur under both solid and liquid condition. Filamentous elements with branching hyphae were observed when cultured in the IM. Furthermore, addition of bovine fetus serum into the liquid IM did not promote hyphal formation; on the contrary, it retrograded hyphae to the yeast form. Plate-washing assay showed that M. furfur hyphae did not possess the ability of invasive growth. Secretory proteins from both yeast and hyphal forms were isolated, and lipase and protease activities were analyzed. Intriguingly, the hyphal form showed higher activities than those of the yeast form, particularly the protease activity. PMID:26173769

  18. Control system for a furfural refining unit receiving heavy sweet charge oil

    SciTech Connect

    Barger, F.; Begnaud, J.; Sequeira, A.

    1980-07-08

    A control system is described for a furfural refining unit receiving heavy sweet charge oil and furfural solvent, one of which is maintained at a fixed rate while the flow rate of the other is controlled by the control system, wherein the system treats the received heavy sweet charge oil with the received furfural to yield extract mix and raffinate, comprising gravity analyzer means for sampling the heavy sweet charge oil and providing a signal API corresponding to the API gravity of the heavy sweet charge oil, flash point analyzer means for sampling the heavy sweet charge oil and providing a signal FL corresponding to the flash point temperature of the heavy sweet charge oil, viscosity analyzer means for sampling the heavy sweet charge oil and providing signals KV/sub 150/ and KV/sub 210/ corresponding to the kinematic viscosities, corrected to 150 and 210/sup 0/F, respectively, sulfur analyzer means for sampling the heavy sweet charge oil and providing a signal S corresponding to the sulfur content of the heavy sweet charge oil, flow rate sensing means for sensing the flow rates of the heavy sweet charge oil and of the furfural and providing signals chg and solv, corresponding to the charge oil flow rate and the furfural flow rate, respectively, temperature sensing means sensing the temperature of the extract mix and providing a corresponding signal t, and control means connected to all of the analyzer means, and to all the sensing means for controlling the other flow rate of the heavy sweet charge oil and the furfural flow rates in accordance with signals API, FL, KV/sub 150/, KV/sub 210/, S, T, CHG and SOLV; wherein said control means includes VI signal means connected to the viscosity analyzer means for providing a signal VI corresponding to the viscosity index of the heavy sweet charge oil in accordance with the kinematic viscosity signals KV/sub 150/, KV/sub 210/ and SUS/sub 210/.

  19. Adaptive laboratory evolution of ethanologenic Zymomonas mobilis strain tolerant to furfural and acetic acid inhibitors.

    PubMed

    Shui, Zong-Xia; Qin, Han; Wu, Bo; Ruan, Zhi-yong; Wang, Lu-shang; Tan, Fu-Rong; Wang, Jing-Li; Tang, Xiao-Yu; Dai, Li-Chun; Hu, Guo-Quan; He, Ming-Xiong

    2015-07-01

    Furfural and acetic acid from lignocellulosic hydrolysates are the prevalent inhibitors to Zymomonas mobilis during cellulosic ethanol production. Developing a strain tolerant to furfural or acetic acid inhibitors is difficul by using rational engineering strategies due to poor understanding of their underlying molecular mechanisms. In this study, strategy of adaptive laboratory evolution (ALE) was used for development of a furfural and acetic acid-tolerant strain. After three round evolution, four evolved mutants (ZMA7-2, ZMA7-3, ZMF3-2, and ZMF3-3) that showed higher growth capacity were successfully obtained via ALE method. Based on the results of profiling of cell growth, glucose utilization, ethanol yield, and activity of key enzymes, two desired strains, ZMA7-2 and ZMF3-3, were achieved, which showed higher tolerance under 7 g/l acetic acid and 3 g/l furfural stress condition. Especially, it is the first report of Z. mobilis strain that could tolerate higher furfural. The best strain, Z. mobilis ZMF3-3, has showed 94.84% theoretical ethanol yield under 3-g/l furfural stress condition, and the theoretical ethanol yield of ZM4 is only 9.89%. Our study also demonstrated that ALE method might also be used as a powerful metabolic engineering tool for metabolic engineering in Z. mobilis. Furthermore, the two best strains could be used as novel host for further metabolic engineering in cellulosic ethanol or future biorefinery. Importantly, the two strains may also be used as novel-tolerant model organisms for the genetic mechanism on the "omics" level, which will provide some useful information for inverse metabolic engineering. PMID:25935346

  20. Pretreatment of furfural industrial wastewater by Fenton, electro-Fenton and Fe(II)-activated peroxydisulfate processes: a comparative study.

    PubMed

    Yang, C W; Wang, D; Tang, Q

    2014-01-01

    The Fenton, electro-Fenton and Fe(II)-activated peroxydisulfate (PDS) processes have been applied for the treatment of actual furfural industrial wastewater in this paper. Through the comparative study of the three processes, a suitable pretreatment technology for actual furfural wastewater treatment was obtained, and the mechanism and dynamics process of this technology is discussed. The experimental results show that Fenton technology has a good and stable effect without adjusting pH of furfural wastewater. At optimal conditions, which were 40 mmol/L H₂O₂ initial concentration and 10 mmol/L Fe²⁺ initial concentration, the chemical oxygen demand (COD) removal rate can reach 81.2% after 90 min reaction at 80 °C temperature. The PDS process also has a good performance. The COD removal rate could attain 80.3% when Na₂S₂O₈ initial concentration was 4.2 mmol/L, Fe²⁺ initial concentration was 0.1 mol/L, the temperature remained at 70 °C, and pH value remained at 2.0. The electro-Fenton process was not competent to deal with the high-temperature furfural industrial wastewater and only 10.2% COD was degraded at 80 °C temperature in the optimal conditions (2.25 mA/cm² current density, 4 mg/L Na₂SO₄, 0.3 m³/h aeration rate). For the Fenton, electro-Fenton and PDS processes in pretreatment of furfural wastewater, their kinetic processes follow the pseudo first order kinetics law. The pretreatment pathways of furfural wastewater degradation are also investigated in this study. The results show that furfural and furan formic acid in furfural wastewater were preferentially degraded by Fenton technology. Furfural can be degraded into low-toxicity or nontoxic compounds by Fenton pretreatment technology, which could make furfural wastewater harmless and even reusable. PMID:25098869

  1. Development and Evaluation of Cefadroxil Drug Loaded Biopolymeric Films Based on Chitosan-Furfural Schiff Base

    PubMed Central

    Dixit, Ritu B.; Uplana, Rahul A.; Patel, Vishnu A.; Dixit, Bharat C.; Patel, Tarosh S.

    2010-01-01

    Cefadroxil drug loaded biopolymeric films of chitosan-furfural schiff base were prepared by reacting chitosan with furfural in presence of acetic acid and perchloric acid respectively for the external use. Prepared films were evaluated for their strength, swelling index, thickness, drug content, uniformity, tensile strength, percent elongation, FTIR spectral analysis and SEM. The results of in vitro diffusion studies revealed that the films exhibited enhanced drug diffusion as compared to the films prepared using untreated chitosan. The films also demonstrated good to moderate antibacterial activities against selective gram positive and gram negative bacteria. PMID:21179325

  2. One-step Conversion of Furfural into 2-Methyltetrahydrofuran under Mild Conditions.

    PubMed

    Dong, Fang; Zhu, Yulei; Ding, Guoqiang; Cui, Jinglei; Li, Xianqing; Li, Yongwang

    2015-05-11

    One-step direct conversion of biomass-derived furfural to 2-methyltetrahydrofuran was realized under atmospheric pressure over a dual solid catalyst based on two-stage-packed Cu-Pd in a reactor; this is the first report that one-step conversion of furfural resulted in high yield of 2-methyltetrahydrofuran (97.1 %) under atmospheric pressure. This strategy provided a successive hydrogenation process, which avoids high H2 pressure, uses the reactor efficiently, and eliminates the product-separation step. Therefore, it could enhance the overall efficiency as a result of low cost and high yield. PMID:25873007

  3. Organic Carbonates: Efficient Extraction Solvents for the Synthesis of HMF in Aqueous Media with Cerium Phosphates as Catalysts.

    PubMed

    Dibenedetto, Angela; Aresta, Michele; di Bitonto, Luigi; Pastore, Carlo

    2016-01-01

    We describe a process for the selective conversion of C6 -polyols into 5-hydroxymethylfurfural (5-HMF) in biphasic systems of organic carbonate/water (OC/W), with cerium(IV) phosphates as catalysts. Different reaction parameters such as the OC/W ratio, catalyst loading, reaction time, and temperature, were investigated for the dehydration of fructose. Under the best reaction conditions, a yield of 67.7 % with a selectivity of 93.2 % was achieved at 423 K after 6 h of reaction using [(Ce(PO4)1.5 (H2 O)(H3 O)0.5 (H2 O)0.5)] as the catalyst. A maximum yield of 70 % with the same selectivity was achieved after 12 h. At the end of the reaction, the catalyst was removed by centrifugation, the organic phase was separated from water and evaporated in vacuo (with solvent recovery), and solid 5-HMF was isolated (purity >99 %). The recovery and reuse of the catalyst and the relationship between the structure of the OC and the efficiency of the extraction are discussed. The OC/W system influences the lifetime of the catalysts positively compared to only water. PMID:26676974

  4. Increased hemoglobin O2 affinity protects during acute hypoxia.

    PubMed

    Yalcin, Ozlem; Cabrales, Pedro

    2012-08-01

    Acclimatization to hypoxia requires time to complete the adaptation mechanisms that influence oxygen (O(2)) transport and O(2) utilization. Although decreasing hemoglobin (Hb) O(2) affinity would favor the release of O(2) to the tissues, increasing Hb O(2) affinity would augment arterial O(2) saturation during hypoxia. This study was designed to test the hypothesis that pharmacologically increasing the Hb O(2) affinity will augment O(2) transport during severe hypoxia (10 and 5% inspired O(2)) compared with normal Hb O(2) affinity. RBC Hb O(2) affinity was increased by infusion of 20 mg/kg of 5-hydroxymethyl-2-furfural (5HMF). Control animals received only the vehicle. The effects of increasing Hb O(2) affinity were studied in the hamster window chamber model, in terms of systemic and microvascular hemodynamics and partial pressures of O(2) (Po(2)). Pimonidazole binding to hypoxic areas of mice heart and brain was also studied. 5HMF decreased the Po(2) at which the Hb is 50% saturated with O(2) by 12.6 mmHg. During 10 and 5% O(2) hypoxia, 5HMF increased arterial blood O(2) saturation by 35 and 48% from the vehicle group, respectively. During 5% O(2) hypoxia, blood pressure and heart rate were 58 and 30% higher for 5HMF compared with the vehicle. In addition, 5HMF preserved microvascular blood flow, whereas blood flow decreased to 40% of baseline in the vehicle group. Consequently, perivascular Po(2) was three times higher in the 5HMF group compared with the control group at 5% O(2) hypoxia. 5HMF also reduced heart and brain hypoxic areas in mice. Therefore, increased Hb O(2) affinity resulted in hemodynamics and oxygenation benefits during severe hypoxia. This acute acclimatization process may have implications in survival during severe environmental hypoxia when logistic constraints prevent chronic acclimatization. PMID:22636677

  5. Increased hemoglobin O2 affinity protects during acute hypoxia

    PubMed Central

    Yalcin, Ozlem

    2012-01-01

    Acclimatization to hypoxia requires time to complete the adaptation mechanisms that influence oxygen (O2) transport and O2 utilization. Although decreasing hemoglobin (Hb) O2 affinity would favor the release of O2 to the tissues, increasing Hb O2 affinity would augment arterial O2 saturation during hypoxia. This study was designed to test the hypothesis that pharmacologically increasing the Hb O2 affinity will augment O2 transport during severe hypoxia (10 and 5% inspired O2) compared with normal Hb O2 affinity. RBC Hb O2 affinity was increased by infusion of 20 mg/kg of 5-hydroxymethyl-2-furfural (5HMF). Control animals received only the vehicle. The effects of increasing Hb O2 affinity were studied in the hamster window chamber model, in terms of systemic and microvascular hemodynamics and partial pressures of O2 (Po2). Pimonidazole binding to hypoxic areas of mice heart and brain was also studied. 5HMF decreased the Po2 at which the Hb is 50% saturated with O2 by 12.6 mmHg. During 10 and 5% O2 hypoxia, 5HMF increased arterial blood O2 saturation by 35 and 48% from the vehicle group, respectively. During 5% O2 hypoxia, blood pressure and heart rate were 58 and 30% higher for 5HMF compared with the vehicle. In addition, 5HMF preserved microvascular blood flow, whereas blood flow decreased to 40% of baseline in the vehicle group. Consequently, perivascular Po2 was three times higher in the 5HMF group compared with the control group at 5% O2 hypoxia. 5HMF also reduced heart and brain hypoxic areas in mice. Therefore, increased Hb O2 affinity resulted in hemodynamics and oxygenation benefits during severe hypoxia. This acute acclimatization process may have implications in survival during severe environmental hypoxia when logistic constraints prevent chronic acclimatization. PMID:22636677

  6. Toll-like receptor 2 (TLR2) mediates intracellular signalling in human keratinocytes in response to Malassezia furfur.

    PubMed

    Baroni, Adone; Orlando, Manuela; Donnarumma, Giovanna; Farro, Pietro; Iovene, Maria Rosaria; Tufano, Maria Antonietta; Buommino, Elisabetta

    2006-01-01

    Toll-like receptors (TLRs) are crucial players in the innate immune response to microbial invaders. The lipophilic yeast Malassezia furfur has been implicated in the triggering of scalp lesions in psoriasis. The aim of the present study was to assess the role of TLRs in the defence against M. furfur infection. The expression of the myeloid differentiation factor 88 (MyD88) gene, which is involved in the signalling pathway of many TLRs, was also analysed. In addition, a possible correlation of antimicrobial peptides of the beta-defensin family to TLRs was tested. Human keratinocytes infected with M. furfur and a variety of M. furfur-positive psoriatic skin biopsies were analysed by RT-PCR, for TLRs, MyD88, human beta-defensin 2 (HBD-2), HBD-3 and interleukin-8 (IL-8) mRNA expression. When keratinocytes were infected with M. furfur, an up-regulation for TLR2, MyD88, HBD-2, HBD-3 and IL-8 mRNA was demonstrated, compared to the untreated cells. The same results were obtained when psoriatic skin biopsies were analysed. The M. furfur-induced increase in HBD-2 and IL-8 gene expression is inhibited by anti-TLR2 neutralising antibodies, suggesting that TLR2 is involved in the M. furfur-induced expression of these molecules. These findings suggest the importance of TLRs in skin protection against fungi and the importance of keratinocytes as a component of innate immunity. PMID:16283346

  7. Synthesis of the insecticide prothrin and its analogues from biomass-derived 5-(Chloromethyl) furfural

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Prothrin, a synthetic pyrethroid insecticide, was synthesized from the biomass-derived platform chemical 5 (chloromethyl)furfural in six steps and overall 65% yield. Two structural analogues of prothrin were also prepared following the same synthetic approach. Preliminary testing of these furan-base...

  8. Role of Brønsted acid in selective production of furfural in biomass pyrolysis.

    PubMed

    Zhang, Haiyan; Liu, Xuejun; Lu, Meizhen; Hu, Xinyue; Lu, Leigang; Tian, Xiaoning; Ji, Jianbing

    2014-10-01

    In this work, the role of Brønsted acid for furfural production in biomass pyrolysis on supported sulfates catalysts was investigated. The introduction of Brønsted acid was shown to improve the degradation of polysaccharides to intermediates for furfural, which did not work well when only Lewis acids were used in the process. Experimental results showed that CuSO4/HZSM-5 catalyst exhibited the best performance for furfural (28% yield), which was much higher than individual HZSM-5 (5%) and CuSO4 (6%). The optimum reaction conditions called for the mass ratio of CuSO4/HZSM-5 to be 0.4 and the catalyst/biomass mass ratio to be 0.5. The recycled catalyst exhibited low productivity (9%). Analysis of the catalysts by Py-IR revealed that the CuSO4/HZSM-5 owned a stronger Brønsted acid intensity than HZSM-5 or the recycled CuSO4/HZSM-5. Therefore, the existence of Brønsted acid is necessary to achieve a more productive degradation of biomass for furfural. PMID:25106779

  9. Effects of furfural on nematode populations and galling on tomato and pepper

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A commercial formulation of furfural (Multiguard® Protect) was evaluated in greenhouse trials over three seasons for effects on parasitic and beneficial nematode populations in roots and soil, plant growth, and galling on tomato and bell pepper caused by Meloidogyne incognita. ‘Tiny Tim’ tomato (So...

  10. Biomass conversion to high value chemicals: from furfural to chiral hydrofuroins in two steps.

    PubMed

    Kabro, Anzhelika; Escudero-Adán, Eduardo C; Grushin, Vladimir V; van Leeuwen, Piet W N M

    2012-08-01

    Catalytic asymmetric transfer hydrogenation of rac-furoin and furil produces hydrofuroin with up to 99% ee and 9:1 dr. This reaction provides an exceptionally easy access to optically active hydrofuroins in two straightforward steps from biomass-derived furfural (global production 200,000-300,000 t annually) using benzoin condensation. PMID:22831386

  11. Acid-catalyzed conversion of xylose, xylan and straw into furfural by microwave-assisted reaction.

    PubMed

    Yemiş, Oktay; Mazza, Giuseppe

    2011-08-01

    Furfural is a biomass derived-chemical that can be used to replace petrochemicals. In this study, the acid-catalyzed conversion of xylose and xylan to furfural by microwave-assisted reaction was investigated at selected ranges of temperature (140-190°C), time (1-30 min), substrate concentration (1:5-1:200 solid:liquid ratio), and pH (2-0.13). We found that a temperature of 180°C, a solid:liquid ratio of 1:200, a residence time of 20 min, and a pH of 1.12 gave the best furfural yields. The effect of different Brønsted acids on the conversion efficiency of xylose and xylan was also evaluated, with hydrochloric acid being found to be the most effective catalyst. The microwave-assisted process provides highly efficient conversion: furfural yields obtained from wheat straw, triticale straw, and flax shives were 48.4%, 45.7%, and 72.1%, respectively. PMID:21620690

  12. Furfural reduction mechanism of a zinc-dependent alcohol dehydrogenase from Cupriavidus necator JMP134

    PubMed Central

    Kang, ChulHee; Hayes, Robert; Sanchez, Emiliano J.; Webb, Brian N.; Li, Qunrui; Hooper, Travis; Nissen, Mark S.; Xun, Luying

    2012-01-01

    Summary FurX is a tetrameric Zn-dependent alcohol dehydrogenase (ADH) from Cupriavidus necator JMP134. The enzyme rapidly reduces furfural with NADH as the reducing power. For the first time among characterized ADHs, the high-resolution structures of all reaction steps were obtained in a time-resolved manner, thereby illustrating the complete catalytic events of NADH-dependent reduction of furfural and the dynamic Zn2+ coordination among Glu66, water, substrate and product. In the fully closed conformation of the NADH complex, the catalytic turnover proved faster than observed for the partially closed conformation due to an effective proton transfer network. The domain motion triggered by NAD(H) association/dissociation appeared to facilitate dynamic interchanges in Zn2+ coordination with substrate and product molecules, ultimately increasing the enzymatic turnover rate. NAD+ dissociation appeared to be a slow process, involving multiple steps in concert with a domain opening and reconfiguration of Glu66. This agrees with the report that the cofactor is not dissociated from FurX during ethanol-dependent reduction of furfural, in which ethanol reduces NAD+ to NADH that is subsequently used for furfural reduction. PMID:22081946

  13. The FEMA GRAS assessment of furfural used as a flavour ingredient. Flavor and Extract Manufacturers' Association.

    PubMed

    Adams, T B; Doull, J; Goodman, J I; Munro, I C; Newberne, P; Portoghese, P S; Smith, R L; Wagner, B M; Weil, C S; Woods, L A; Ford, R A

    1997-08-01

    The Expert Panel of the Flavor and Extract Manufacturers' Association (FEMA) has assessed the safety of furfural for its continued use as a flavour ingredient. The safety assessment takes into account the current scientific information on exposure, metabolism, pharmacokinetics, toxicology, carcinogenicity and genotoxicity. Furfural was reaffirmed as GRAS (GRASr) as a flavour ingredient under conditions of intended use based on: (1) its mode of metabolic detoxication in humans; (2) its low level of flavour use compared with higher intake levels as a naturally occurring component of food; (3) the safety factor calculated from results of subchronic and chronic studies, (4) the lack of reactivity with DNA; and (5) the conclusion that the only statistically significant finding in the 2-year NTP bioassays, an increased incidence of hepatocellular adenomas and carcinomas in the high-dose group of male mice, was secondary to pronounced hepatotoxicity. Taken together, these data do not indicate any risk to human health under conditions of use as a flavour ingredient. This evidence of safety is supported by the occurrence of furfural as a natural component of traditional foods, at concentrations in the diet resulting in a 'natural intake' that is at least 100 times higher than the intake of furfural from use as a flavour ingredient. PMID:9350219

  14. The Role of L-DOPA on Melanization and Mycelial Production in Malassezia Furfur

    PubMed Central

    Youngchim, Sirida; Nosanchuk, Joshua D.; Pornsuwan, Soraya; Kajiwara, Susumu; Vanittanakom, Nongnuch

    2013-01-01

    Melanins are synthesized by organisms of all biological kingdoms and comprise a heterogeneous class of natural pigments. Certain of these polymers have been implicated in the pathogenesis of several important human fungal pathogens. This study investigated whether the fungal skin pathogen Malassezia furfur produces melanin or melanin-like compounds. A melanin-binding monoclonal antibody (MAb) labelled in vitro cultivated yeast cells of M. furfur. In addition, melanization of Malassezia yeasts and hyphae was detected by anti-melanin MAb in scrapings from patients with pityriasis versicolor. Treatment of Malassezia yeasts with proteolytic enzymes, denaturant and concentrated hot acid yielded dark particles and electron spin resonance spectroscopy revealed that these particles contained a stable free radical compound, consistent with their identification as melanins. Malassezia yeasts required phenolic compounds, such as L-DOPA, in order to synthesize melanin. L-DOPA also triggered hyphal formation in vitro when combined with kojic acid, a tyrosinase inhibitor, in a dose-dependent manner. In this respect, L-DOPA is thought to be an essential substance that is linked to both melanization and yeast-mycelial transformation in M. furfur. In summary, M. furfur can produce melanin or melanin-like compounds in vitro and in vivo, and the DOPA melanin pathway is involved in cell wall melanization. PMID:23762233

  15. The role of L-DOPA on melanization and mycelial production in Malassezia furfur.

    PubMed

    Youngchim, Sirida; Nosanchuk, Joshua D; Pornsuwan, Soraya; Kajiwara, Susumu; Vanittanakom, Nongnuch

    2013-01-01

    Melanins are synthesized by organisms of all biological kingdoms and comprise a heterogeneous class of natural pigments. Certain of these polymers have been implicated in the pathogenesis of several important human fungal pathogens. This study investigated whether the fungal skin pathogen Malassezia furfur produces melanin or melanin-like compounds. A melanin-binding monoclonal antibody (MAb) labelled in vitro cultivated yeast cells of M. furfur. In addition, melanization of Malassezia yeasts and hyphae was detected by anti-melanin MAb in scrapings from patients with pityriasis versicolor. Treatment of Malassezia yeasts with proteolytic enzymes, denaturant and concentrated hot acid yielded dark particles and electron spin resonance spectroscopy revealed that these particles contained a stable free radical compound, consistent with their identification as melanins. Malassezia yeasts required phenolic compounds, such as L-DOPA, in order to synthesize melanin. L-DOPA also triggered hyphal formation in vitro when combined with kojic acid, a tyrosinase inhibitor, in a dose-dependent manner. In this respect, L-DOPA is thought to be an essential substance that is linked to both melanization and yeast-mycelial transformation in M. furfur. In summary, M. furfur can produce melanin or melanin-like compounds in vitro and in vivo, and the DOPA melanin pathway is involved in cell wall melanization. PMID:23762233

  16. Increase in furfural tolerance in ethanologenic Escherichia coli LY180 by plasmid-based expression of thyA.

    PubMed

    Zheng, Huabao; Wang, Xuan; Yomano, Lorraine P; Shanmugam, Keelnatham T; Ingram, Lonnie O

    2012-06-01

    Furfural is an inhibitory side product formed during the depolymerization of hemicellulose by mineral acids. Genomic libraries from three different bacteria (Bacillus subtilis YB886, Escherichia coli NC3, and Zymomonas mobilis CP4) were screened for genes that conferred furfural resistance on plates. Beneficial plasmids containing the thyA gene (coding for thymidylate synthase) were recovered from all three organisms. Expression of this key gene in the de novo pathway for dTMP biosynthesis improved furfural resistance on plates and during fermentation. A similar benefit was observed by supplementation with thymine, thymidine, or the combination of tetrahydrofolate and serine (precursors for 5,10-methylenetetrahydrofolate, the methyl donor for ThyA). Supplementation with deoxyuridine provided a small benefit, and deoxyribose was of no benefit for furfural tolerance. A combination of thymidine and plasmid expression of thyA was no more effective than either alone. Together, these results demonstrate that furfural tolerance is increased by approaches that increase the supply of pyrimidine deoxyribonucleotides. However, ThyA activity was not directly affected by the addition of furfural. Furfural has been previously shown to damage DNA in E. coli and to activate a cellular response to oxidative damage in yeast. The added burden of repairing furfural-damaged DNA in E. coli would be expected to increase the cellular requirement for dTMP. Increased expression of thyA (E. coli, B. subtilis, or Z. mobilis), supplementation of cultures with thymidine, and supplementation with precursors for 5,10-methylenetetrahydrofolate (methyl donor) are each proposed to increase furfural tolerance by increasing the availability of dTMP for DNA repair. PMID:22504824

  17. PREFACE: 19th International Conference on the Application of High Magnetic Fields in Semiconductor Physics and Nanotechnology (HMF-19)

    NASA Astrophysics Data System (ADS)

    Muraki, Koji; Takeyama, Shojiro

    2011-12-01

    This volume contains invited and contributed papers from the 19th International Conference on the Application of High Magnetic Fields in Semiconductor Physics and Nanotechnology (HMF-19) held in Fukuoka, Japan, from 1-6 August 2010. This conference was mainly sponsored by the Tokyo University-'Horiba International fund', which was donated by Dr Masao Horiba, the founder of Horiba Ltd. The scientific program of HMF-19 consisted of 37 invited talks, 24 contributed talks, and 83 posters, which is available from the conference homepage http://www.hmf19.iis.u-tokyo.ac.jp/index.html. Each manuscript submitted for publication in this volume has been independently reviewed. The Editor is very grateful to all the reviewers for their quick responses and helpful reports and to all the authors for their submissions and patience for the delay in the editorial process. Finally, the Editor would like to express his sincere gratitude to all the individuals involved in the conference organization and all the attendees, who made this conference so successful. Koji Muraki Conference photograph Committees Chair Conference chairS Takeyama(ISSP-UT) Conference secretary T Machida (IIS-UT) Program chair K Muraki (NTT) Local organizing chair K Oto (Chiba Univ.) Advisory Committee International Domestic L Brey (ES) T Ando (TIT) Z H Chen (CN) Y Hirayama (Tohoku Univ.) S Das Sarma (US) G Kido (NIMS) L Eaves (GB) N Miura (JP) J P Eisenstein (US) J Nitta (Tohoku Univ.) K Ensslin (CH) T Takamasu (NIMS) J Furdyna (US) G M Gusev (BR) I Kukushkin (RU) Z D Kvon (RU) G Landwehr (DE) J C Maan (NL) A H MacDonald (US) N F Oliveira Jr (BR) A Pinczuk (US) J C Portal (FR) A Sachrajda (CA) M K Sanyal(IN) R Stepniewski(PL) Program Committee Chair: K Muraki(NTT) International Domestic G Bauer (AU) H Ajiki (Osaka Univ.) G Boebinger (US) H Aoki (Hongo, UT) S Ivanov (RU) K Nomura (RIKEN) K von Klitzing (DE) T Okamoto (Hongo, UT) R Nicholas (GB) T Osada (ISSP-UT ) M Potemski (FR) N Studart (BR) U Zeitler (NL

  18. Chemical changes during fermentation of Abhayarishta and its standardization by HPLC-DAD.

    PubMed

    Lal, Uma Ranjan; Tripathi, Shailendra Mani; Jachak, Sanjay M; Bhutani, Kamlesh Kumar; Singh, Inder Pal

    2010-04-01

    Abhayarishta is an Ayurvedic formulation prepared traditionally by the fermentation of the decoction of Terminalia chebula (pericarp), Vitis vinifera (fruits), Embelia ribes (fruits) and Madhuca indica (flowers). In the present communication, chemical changes occurring during fermentation in Abhayarishta have been studied for the purpose of its standardization. An HPLC-DAD method for quantitative estimation of selected marker constituents in the formulation has been developed and validated. A comparison of decoction and final processed formulation revealed that major polyphenolics (chebulagic and chebulinic acid) of T. chebula were hydrolyzed to their respective monomers and, consequently, there was an increase in the amount of chebulic acid, gallic acid, ellagic acid and ethyl gallate after fermentation. 5-Hydroxymethyl furfural (5-HMF) was also found in the formulation. Thus, emphasis is laid upon consideration of processing methods of formulation which has been lacking in the standardization of most of Ayurvedic formulations. PMID:20433076

  19. Polyoxometalates as efficient catalysts for transformations of cellulose into platform chemicals.

    PubMed

    Deng, Weiping; Zhang, Qinghong; Wang, Ye

    2012-09-01

    Efficient utilisation of renewable biomass resources, particularly lignocellulosic biomass, for the production of chemicals and fuels has attracted much attention in recent years. The catalytic conversion of cellulose, the main component of lignocellulosic biomass, selectively into a platform chemical such as glucose, 5-hydroxymethyl furfural (HMF), sorbitol or gluconic acid under mild conditions is the most desirable route. Acid catalysis plays a crucial role in the conversion of cellulose via the cleavage of its glycosidic bonds. Owing to their unique features such as strong acidity, water-tolerance, low corrosiveness and recoverability, polyoxometalates have shown promising performances in transformations of cellulose into platform chemicals both in homogeneous and heterogeneous systems. This article highlights recent studies on polyoxometalates and polyoxometalate-based bifunctional catalysts or catalytic systems for the selective conversions of cellulose and cellobiose, a model molecule of cellulose, into platform chemicals. PMID:22653050

  20. Review of the medicinal effects of tualang honey and a comparison with manuka honey.

    PubMed

    Ahmed, Sarfarz; Othman, Nor Hayati

    2013-05-01

    Tualang honey (TH) is a Malaysian multifloral jungle honey. In recent years, there has been a marked increase in the number of studies published in medical databases regarding its potential health benefits. The honey is produced by the rock bee (Apis dorsata), which builds hives on branches of tall Tualang trees located mainly in the north-western region of Peninsular Malaysia. This review collates the results of the various studies of TH that range from research on tissue culture to randomised control clinical trials. Findings thus far show that, TH has antimicrobial, anti-inflammatory, antioxidant, antimutagenic, antitumor, and antidiabetic properties, in addition to wound-healing attributes. Some of its properties are similar to the well-researched Manuka honey (New Zealand and/or Australian monofloral honey). Distinct differences include higher phenolics, flavonoids, and 5-(hydroxymethyl) furfural (HMF). Compared with Manuka honey, TH is also more effective against some gram-negative bacterial strains in burn wounds. PMID:23966819

  1. Review of the Medicinal Effects of Tualang Honey and a Comparison with Manuka Honey

    PubMed Central

    Ahmed, Sarfarz; Othman, Nor Hayati

    2013-01-01

    Tualang honey (TH) is a Malaysian multifloral jungle honey. In recent years, there has been a marked increase in the number of studies published in medical databases regarding its potential health benefits. The honey is produced by the rock bee (Apis dorsata), which builds hives on branches of tall Tualang trees located mainly in the north-western region of Peninsular Malaysia. This review collates the results of the various studies of TH that range from research on tissue culture to randomised control clinical trials. Findings thus far show that, TH has antimicrobial, anti-inflammatory, antioxidant, antimutagenic, antitumor, and antidiabetic properties, in addition to wound-healing attributes. Some of its properties are similar to the well-researched Manuka honey (New Zealand and/or Australian monofloral honey). Distinct differences include higher phenolics, flavonoids, and 5-(hydroxymethyl) furfural (HMF). Compared with Manuka honey, TH is also more effective against some gram-negative bacterial strains in burn wounds. PMID:23966819

  2. Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip.

    PubMed

    Navin, Chelliah V; Krishna, Katla Sai; Theegala, Chandra S; Kumar, Challa S S R

    2016-03-01

    Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors. PMID:26888331

  3. Sequential hydrothermal fractionation of yeast Cryptococcus curvatus biomass.

    PubMed

    Miao, Chao; Chakraborty, Moumita; Dong, Tao; Yu, Xiaochen; Chi, Zhanyou; Chen, Shulin

    2014-07-01

    A sequential hydrothermal liquefaction (SEQHTL) process was evaluated in this work for fractionating different component of yeast biomass. Sugar and protein were separated first at a lower temperature, and the remaining biomass was then converted to bio-oil at a higher temperature. The separated aqueous products were investigated to be recycled as a carbon and nitrogen sources for the yeast culture. In the first step of SEQHTL, the temperature effect on the yield of sugar/protein and inhibitory compounds (acetic acid and 5-hydroxymethyl furfural (5HMF)) was investigated. The highest yields of sugar and protein and a minimal level of inhibitory compounds were obtained at 180°C. At the second step of SEQHTL, the highest bio-oil yield was achieved at 240°C. In comparison to the one-step hydrothermal liquefaction process, SEQHTL produced a higher quality bio-oil with higher fatty acid and lower nitrogen contents. PMID:24844164

  4. Novel Ordered Mesoporous Carbon Based Sulfonic Acid as an Efficient Catalyst in the Selective Dehydration of Fructose into 5-HMF: the Role of Solvent and Surface Chemistry.

    PubMed

    Karimi, Babak; Mirzaei, Hamid M; Behzadnia, Hesam; Vali, Hojatollah

    2015-09-01

    Novel ionic liquid derived ordered mesoporous carbons functionalized with sulfonic acid groups IOMC-ArSO3H and GIOMC-ArSO3H were prepared, characterized, and examined in the dehydration reaction of fructose into 5-hydroxymethylfurfural (5-HMF) both in aqueous and nonaqueous systems. To study and correlate the surface properties of these carbocatalysts and some other SBA-15 typed solid acids with 5-HMF yield, hydrophilicity index (H-index) were employed in the fructose dehydration. Our study systematically declared that almost a criterion may be expected for application of solid acids in which by increasing H-index value up to 0.8 the HMF yield enhances accordingly. More increase in H-index up to 1.3 did not change the HMF yield profoundly. Although, it has been shown that the catalyst with larger H-index (∼1.3) resulted in higher activity both in aqueous and 2-propanol systems, during the recycling process deactivation occurs because of more water uptake and the catalysts with optimum amount of H-index (∼0.8) is more robust in the dehydration of fructose. PMID:26259108

  5. Selective aerobic oxidation of 5-HMF into 2,5-furandicarboxylic acid with Pt catalysts supported on TiO2 - and ZrO2 -based supports.

    PubMed

    Ait Rass, Hicham; Essayem, Nadine; Besson, Michèle

    2015-04-13

    Pt catalysts prepared over different metallic oxide supports were investigated in the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in alkaline aqueous solutions with air, to examine the combined effect of the support and base addition. The base (nature and amount) played a significant role in the degradation or oxidation of HMF. Increasing amounts of the weak NaHCO3 base improved significantly the overall catalytic activity of Pt/TiO2 and Pt/ZrO2 by accelerating the oxidation steps, especially for the aldehyde group. This was highlighted by a proposed kinetic model that gave very good concentration-time fittings. Moreover, the promotion of the catalyst with bismuth yielded a PtBi/TiO2 catalytic system with improved activity and stability. Y2 O3  and La2 O3 ZrO2 -supported catalysts exhibited lower activity than Pt/ZrO2 , which suggests no cooperative effect of the weakly basic properties introduced and the homogeneous base. Quantitative oxidation of HMF (0.1 M) and high yields of FDCA (>99 %) were obtained in less than 5 h by using an HMF/Pt molar ratio of 100 and Na2 CO3 as a weak base over PtBi/TiO2 (Bi/Pt=0.22). PMID:25736596

  6. Malassezia furfur: a cause of occlusion of percutaneous central venous catheters in infants in the intensive care nursery.

    PubMed

    Azimi, P H; Levernier, K; Lefrak, L M; Petru, A M; Barrett, T; Schenck, H; Sandhu, A S; Duritz, G; Valesco, M

    1988-02-01

    Growth of Malassezia furfur in the intravascular catheter used for administration of lipid emulsion resulted in occlusion of deep intravascular Silastic catheters in 12 infants in 2 intensive care nurseries. At the time of occlusion visible growth was noted in the clear catheter which was connected to the Silastic intravascular line. Five infants showed clinical signs suggestive of sepsis. The yield of M. furfur from blood cultures and catheter tips was low even when oil enrichment was used. The highest yield of M. furfur was found in the connecting catheter (11 of 11). The source from and the route by which M. furfur entered the catheter remain unclear. The potential portals of entry include the proximal and distal ends of the connecting catheter as well as the colonized skin of the infants and caretakers. PMID:3125516

  7. Catalytic conversion of xylose and corn stalk into furfural over carbon solid acid catalyst in γ-valerolactone.

    PubMed

    Zhang, Tingwei; Li, Wenzhi; Xu, Zhiping; Liu, Qiyu; Ma, Qiaozhi; Jameel, Hasan; Chang, Hou-min; Ma, Longlong

    2016-06-01

    A novel carbon solid acid catalyst was synthesized by the sulfonation of carbonaceous material which was prepared by carbonization of sucrose using 4-BDS as a sulfonating agent. TEM, N2 adsorption-desorption, elemental analysis, XPS and FT-IR were used to characterize the catalyst. Then, the catalyst was applied for the conversion of xylose and corn stalk into furfural in GVL. The influence of the reaction time, temperature and dosage of catalyst on xylose dehydration were also investigated. The Brønsted acid catalyst exhibited high activity in the dehydration of xylose, with a high furfural yield of 78.5% at 170°C in 30min. What's more, a 60.6% furfural yield from corn stalk was achieved in 100min at 200°C. The recyclability of the sulfonated carbon catalyst was perfect, and it could be reused for 5times without the loss of furfural yields. PMID:26967333

  8. Mediated electrochemical measurement of the inhibitory effects of furfural and acetic acid on Saccharomyces cerevisiae and Candida shehatae.

    PubMed

    Zhao, Jinsheng; Wang, Min; Yang, Zhenyu; Gong, Qintao; Lu, Yao; Yang, Zhengyu

    2005-02-01

    The toxic effects of furfural and acetic acid on two yeasts, Saccharomyces cerevisiae and Candida shehatae, were evaluated using an electrochemical method. Intracellular redox activities were lowered by 40% and 78% for S. cerevisiae and C. shehatae, respectively, by 8 g furfural l(-1), and by 46% and 67%, respectively, by 8 g acetic acid l(-1). The proposed method can accurately measure the effects of inhibitors on cell cultures. PMID:15717131

  9. Catalytic conversion of furfural into a 2,5-furandicarboxylic acid-based polyester with total carbon utilization.

    PubMed

    Pan, Tao; Deng, Jin; Xu, Qing; Zuo, Yong; Guo, Qing-Xiang; Fu, Yao

    2013-01-01

    One divided into two combined into one: The catalytic conversion of furfural into a 2,5-furandicarboxylic acid-based polyester, linked by the disproportionation of furoate to furan and 2,5-furandicarboxylate, is reported. In this manner, all carbons are utilized, demonstrating the success of combining a platform molecule from C(5) sugars (furfural) to one from C(6) sugars (2,5-FDCA). PMID:23239596

  10. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms.

    PubMed

    Rasmussen, Helena; Sørensen, Hanne R; Meyer, Anne S

    2014-02-19

    The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes for the formation of HMF from glucose and three routes for furfural formation from xylose are possible. In addition, new findings show that biomass monosaccharides themselves can react further to form pseudo-lignin and humins as well as a wide array of other compounds when exposed to high temperatures. Hence, several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing strategies and forms an important basis for the development of new biorefinery products from lignocellulosic biomass as well. PMID:24412507

  11. Pre-treatment step with Leuconostoc mesenteroides or L. pseudomesenteroides strains removes furfural from Zymomonas mobilis ethanolic fermentation broth.

    PubMed

    Hunter, William J; Manter, Daniel K

    2014-10-01

    Furfural is an inhibitor of growth and ethanol production by Zymomonas mobilis. This study used a naturally occurring (not GMO) biological pre-treatment to reduce that amount of furfural in a model fermentation broth. Pre-treatment involved inoculating and incubating the fermentation broth with strains of Leuconostoc mesenteroides or Leuconostoc pseudomesenteroides. The Leuconostoc strains converted furfural to furfuryl alcohol without consuming large amounts of dextrose in the process. Coupling this pre-treatment to ethanolic fermentation reduced furfural in the broth and improved growth, dextrose uptake and ethanol formation. Pre-treatment permitted ethanol formation in the presence of 5.2 g L(-1) furfural, which was otherwise inhibitive. The pre-treatment and presence of the Leuconostoc strains in the fermentation broth did not interfere with Z. mobilis ethanolic fermentation or the amounts of ethanol produced. The method suggests a possible technique for reducing the effect that furfural has on the production of ethanol for use as a biofuel. PMID:25048957

  12. Production of furfural from xylose, xylan and corncob in gamma-valerolactone using FeCl3·6H2O as catalyst.

    PubMed

    Zhang, Luxin; Yu, Hongbing; Wang, Pan; Li, Yong

    2014-01-01

    An efficient and simple one-pot monophasic reaction system with small carbon footprint for converting xylose, xylan and corncob into furfural was developed in gamma-valerolactone (GVL, an ideal sustainable solvent derived from lignocelluloses) by using FeCl3·6H2O as catalyst. Good yields of furfural from xylose were obtained, and the system was shown to work for xylan and corncob as well. A surprisingly high furfural yield of 79.6% from untreated corncob was achieved at 458 K for 100 min. Contrary to what was generally believed, the addition of water, reduced the rate of the reactions, but showed positive effect on preventing the furfural from degradation in GVL. Besides, the C6 sugars (glucose and cellulose) afforded 11.4-24.5% furfural yields when employing this catalytic approach. The reaction system proposed in this manuscript showed great potential for optimizing the catalytic process in furfural production. PMID:24262845

  13. Effects of aliphatic acids, furfural, and phenolic compounds on Debaryomyces hansenii CCMI 941.

    PubMed

    Duarte, Luís C; Carvalheiro, Florbela; Neves, Inês; Gírio, Francisco M

    2005-01-01

    Debaryomyces hansenii is a polyol overproducing yeast that can have a potential use for upgrading lignocellulosic hydrolysates. Therefore, the establishment of its tolerance to metabolic inhibitors found in hydrolysates is of major interest. We studied the effects of selected aliphatic acids, phenolic compounds, and furfural. Acetic acid favored biomass production for concentrations <6.0 g/L. Formic acid was more toxic than acetic acid and induced xylitol accumulation (maximum yield of 0.21 g/g of xylose). All tested phenolics strongly decreased the specific growth rate. Increased toxicity was found for hydroquinone, syringaldehyde, and 4-methylcatechol and was correlated to the compound's hydrophobicity. Increasing the amount of furfural led to longer lag phases and had a detrimental effect on specific growth rate and biomass productivity. PMID:15917618

  14. Malassezia furfur: a fungus belonging to the physiological skin flora and its relevance in skin disorders.

    PubMed

    Schmidt, A

    1997-01-01

    Malassezia furfur is an anthropophilic fungus that belongs to the physiological skin flora. The fungus can grow in a yeast phase as well as in a mycelial phase; on nonaffected skin the fungus is mainly prevalent in the yeast phase. The organism has complex lipid requirements for growth, which also explains its occurrence on the skin. This also leads to the requirement for specially supplemented media for in vitro cultivation. Malassezia furfur is the causative agent of pityriasis versicolor. It also seems to be associated with seborrheic dermatitis and dandruff formation, folliculitis, confluent and reticulate papillomatosis, and the provocation of psoriatic lesions. Many substances for topical application, such as azole antimycotics, ciclopirox olamine, piroctone-olamine, zinc pyrithione, or sulfur-containing substances are effective in the treatment of these diseases. In recent years rare cases of systemic infections and fungemias caused by Malassezia have been reported. PMID:9013067

  15. Furfural Synthesis from d-Xylose in the Presence of Sodium Chloride: Microwave versus Conventional Heating.

    PubMed

    Xiouras, Christos; Radacsi, Norbert; Sturm, Guido; Stefanidis, Georgios D

    2016-08-23

    We investigate the existence of specific/nonthermal microwave effects for the dehydration reaction of xylose to furfural in the presence of NaCl. Such effects are reported for sugars dehydration reactions in several literature reports. To this end, we adopted three approaches that compare microwave-assisted experiments with a) conventional heating experiments from the literature; b) simulated conventional heating experiments using microwave-irradiated silicon carbide (SiC) vials; and at c) different power levels but the same temperature by using forced cooling. No significant differences in the reaction kinetics are observed using any of these methods. However, microwave heating still proves advantageous as it requires 30 % less forward power compared to conventional heating (SiC vial) to achieve the same furfural yield at a laboratory scale. PMID:27416892

  16. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, R.W.

    1996-09-17

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1,000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1,050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

  17. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, R.W.

    1995-12-19

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes{<=}1000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

  18. Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, R.W.

    1998-04-28

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1000 {angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

  19. DSC and curing kinetics study of epoxy grouting diluted with furfural -acetone slurry

    NASA Astrophysics Data System (ADS)

    Yin, H.; Sun, D. W.; Li, B.; Liu, Y. T.; Ran, Q. P.; Liu, J. P.

    2016-07-01

    The use of furfural-acetone slurry as active diluents of Bisphenol-A epoxy resin (DGEBA) groutings has been studied by dynamic and non-isothermal DSC for the first time. Curing kinetics study was investigated by non-isothermal differential scanning calorimetries at different heating rates. Activation enery (Ea) was calculated based on Kissinger and Ozawa Methods, and the results showed that Ea increased from 58.87 to 71.13KJ/mol after the diluents were added. The furfural-acetone epoxy matrix could cure completely at the theoretical curing temperature of 365.8K and the curing time of 139mins, which were determined by the kinetic model parameters.

  20. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, Richard W.

    1995-01-01

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes.ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

  1. Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, Richard W.

    1998-04-28

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000 .ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

  2. Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

    DOEpatents

    Pekala, Richard W.

    1996-01-01

    The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

  3. Impact of direct and indirect application of rising furfural concentrations on viability, infectivity and reproduction of the root-knot nematode, Meloidogyne incognita in Pisum sativum.

    PubMed

    Abdelnabby, Hazem; Wang, Yunhe; Xiao, Xueqiong; Wang, Gaofeng; Yang, Fan; Xiao, Yannong

    2016-07-01

    The gradual withdraw of several broadly used nematicides from market has enhanced the need to develop sustainable and eco-friendly alternatives with nematicidal properties. Furfural is one of the promising alternatives to fill this need. Baseline information about the impact of furfural on egg hatch, penetration potential and ultrastructure of nematode is lacking. In this study, the reagent-grade (purity ≥ 99.0%) of furfural was applied against Meloidogyne incognita. In vitro tests showed gradual reduction in either the rate of egg hatch or second stage juvenile (J2) viability of M. incognita when immersed in concentrations ranging from 0 to 10.0 μl/ml furfural. The mean EC50 for J2 and egg hatch was 0.37 and 0.27 μl/ml furfural, respectively. Furfural, even at low concentrations, resulted in a considerable suppression in egg hatch. Hatch was <5% after 8 days at 0.63 μl/ml furfural. The same furfural concentrations after 12 h caused 57.25% loss of viability in J2. Moreover, the penetration rate of juveniles to pea roots was suppressed when furfural was even applied at low rates. In pot experiments, furfural was applied as liquid (direct) or vapor (indirect) treatments at rates of 0-1.5 ml/kg soil. Significant reduction in galling, egg production and population density of M. incognita observed when furfural was applied at rates >0.2 ml/kg soil. No adverse effect was detected on plants or free-living nematodes as a result of furfural application. Liquid furfural proved to have superior juvenile-suppressive effect whereas its vapor has such superiority against eggs. Scanning electron microscope (SEM) study showed irregular appearance of the body surface accompanied with some cuticle disfigurement of furfural-treated juveniles. These results indicated that furfural can adversely affect egg hatch, juvenile viability, penetration potential and ultrastructure of M. incognita. Furfural may therefore be of a considerable potential as an appropriate

  4. Increased furfural tolerance due to overexpression of NADH-dependent oxidoreductase FucO in Escherichia coli strains engineered for the production of ethanol and lactate.

    PubMed

    Wang, X; Miller, E N; Yomano, L P; Zhang, X; Shanmugam, K T; Ingram, L O

    2011-08-01

    Furfural is an important fermentation inhibitor in hemicellulose sugar syrups derived from woody biomass. The metabolism of furfural by NADPH-dependent oxidoreductases, such as YqhD (low K(m) for NADPH), is proposed to inhibit the growth and fermentation of xylose in Escherichia coli by competing with biosynthesis for NADPH. The discovery that the NADH-dependent propanediol oxidoreductase (FucO) can reduce furfural provided a new approach to improve furfural tolerance. Strains that produced ethanol or lactate efficiently as primary products from xylose were developed. These strains included chromosomal mutations in yqhD expression that permitted the fermentation of xylose broths containing up to 10 mM furfural. Expression of fucO from plasmids was shown to increase furfural tolerance by 50% and to permit the fermentation of 15 mM furfural. Product yields with 15 mM furfural were equivalent to those of control strains without added furfural (85% to 90% of the theoretical maximum). These two defined genetic traits can be readily transferred to enteric biocatalysts designed to produce other products. A similar strategy that minimizes the depletion of NADPH pools by native detoxification enzymes may be generally useful for other inhibitory compounds in lignocellulosic sugar streams and with other organisms. PMID:21685167

  5. Synthesis of high-quality diesel with furfural and 2-methylfuran from hemicellulose.

    PubMed

    Li, Guangyi; Li, Ning; Wang, Zhiqiang; Li, Changzhi; Wang, Aiqin; Wang, Xiaodong; Cong, Yu; Zhang, Tao

    2012-10-01

    Hydroxyalkylation-alkylation (HAA) coupled with hydrodeoxygenation is a promising route for the synthesis of renewable high-quality diesel or jet fuel. In this work, a series of solid-acid catalysts were firstly used for HAA between lignocellulose-derived furan and carbonyl compounds. Among the investigated catalysts, Nafion-212 resin demonstrated the highest activity and stability. Owing to the high activity of the reactants and the advantage in industrial integration, the HAA of 2-methylfuran (2-MF) and furfural can be considered as a prospective route in future applications. Catalyst loading, reaction temperature, and time had evident effects on the HAA of 2-MF and furfural over Nafion-212 resin. Finally, the HAA product of 2-MF and furfural was hydrogenated over a Pd/C catalyst and hydrodeoxygenated over Pt-loaded solid-acid catalysts. Pt/zirconium phosphate (Pt/ZrP) was found to be the best catalyst for hydrodeoxygenation. Over the 4 % Pt/ZrP catalyst, a 94 % carbon yield of diesel and 75 % carbon yield of C15 hydrocarbons (with 6-butylundecane as the major component) was achieved. PMID:22907772

  6. Integral elastic, electronic-state, ionization, and total cross sections for electron scattering with furfural

    NASA Astrophysics Data System (ADS)

    Jones, D. B.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; Blanco, F.; García, G.; Brunger, M. J.

    2016-04-01

    We report absolute experimental integral cross sections (ICSs) for electron impact excitation of bands of electronic-states in furfural, for incident electron energies in the range 20-250 eV. Wherever possible, those results are compared to corresponding excitation cross sections in the structurally similar species furan, as previously reported by da Costa et al. [Phys. Rev. A 85, 062706 (2012)] and Regeta and Allan [Phys. Rev. A 91, 012707 (2015)]. Generally, very good agreement is found. In addition, ICSs calculated with our independent atom model (IAM) with screening corrected additivity rule (SCAR) formalism, extended to account for interference (I) terms that arise due to the multi-centre nature of the scattering problem, are also reported. The sum of those ICSs gives the IAM-SCAR+I total cross section for electron-furfural scattering. Where possible, those calculated IAM-SCAR+I ICS results are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, but only for the band I and band II excited electronic states, we also present results from our Schwinger multichannel method with pseudopotentials calculations. Those results are found to be in good qualitative accord with the present experimental ICSs. Finally, with a view to assembling a complete cross section data base for furfural, some binary-encounter-Bethe-level total ionization cross sections for this collision system are presented.

  7. Antifungal activity of ketoconazole and other azoles against Malassezia furfur in vitro and in vivo.

    PubMed

    Strippoli, V; Piacentini, A; D'Auria, F D; Simonetti, N

    1997-01-01

    The in vitro activity of several antifungal agents (ketoconazole, miconazole, econazole, fenticonazole, itraconazole, fluconazole) in routine clinical use against Malassezia furfur infections has been studied with freshly isolated strains of M. furfur from pityriasis versicolor lesions. The results indicate that the drugs tested exert a good activity, and both ketoconazole and itraconazole appear very active (0.8 mg/l respectively). Hair samples from the beards of volunteer patients affected by pityriasis versicolor but otherwise healthy were examined to determine ketoconazole levels during oral therapy (one or two 200 mg tablets daily). It was shown that the drug progressively accumulates in the beard, reaching levels proportional to the dose administered, although blood levels did not increase in parallel. The study of drug concentration profile has evidenced a long ketoconazole persistence in the beard at therapeutic levels. In conclusion, the possibility of reaching high and lasting ketoconazole levels in the keratin layer of the epidermis indicates that systemic ketoconazole therapy could be useful for eradication of M. furfur in patients affected by pityriasis versicolor. PMID:9334866

  8. Inhibitory effect of formulated lemongrass shampoo on Malassezia furfur: a yeast associated with dandruff.

    PubMed

    Wuthi-Udomlert, Mansuang; Chotipatoomwan, Ployphand; Panyadee, Sasikan; Gritsanapan, Wandee

    2011-03-01

    Lemongrass (Cymbopogon citratus Stapf) has been used in cooking and in many traditional medicines; the essential oil contains citral as a major constituent. This study evaluated the antifungal activity of lemongrass oil against Malassezia furfur, an opportunistic yeast associated with dandruff, by using a broth dilution assay. From the minimum fungicidal concentration (MFC) obtained, the oil was then incorporated at different percentages into shampoo formulations. The formulated shampoos were kept at room temperature (28 degrees-30 degrees C) and under accelerated condition (45 degrees C). At the end of the first and sixth weeks, after preparation, all formulations were tested again and the appearance was recorded. Selection of an appropriate formula was based on antifungal activity against M. furfur, the physical appearance, the chemical properties and stability of the formula. Two percent lemongrass oil shampoo provided the required qualities necessary for commercial use. After being kept for 6 weeks at 28 degrees-30 degrees C and 45 degrees C, this formulated shampoo gave MFCs against M. furfur of 75 microl/ml and 18.75 microl/ml, respectively. PMID:21710859

  9. Integral elastic, electronic-state, ionization, and total cross sections for electron scattering with furfural.

    PubMed

    Jones, D B; da Costa, R F; Varella, M T do N; Bettega, M H F; Lima, M A P; Blanco, F; García, G; Brunger, M J

    2016-04-14

    We report absolute experimental integral cross sections (ICSs) for electron impact excitation of bands of electronic-states in furfural, for incident electron energies in the range 20-250 eV. Wherever possible, those results are compared to corresponding excitation cross sections in the structurally similar species furan, as previously reported by da Costa et al. [Phys. Rev. A 85, 062706 (2012)] and Regeta and Allan [Phys. Rev. A 91, 012707 (2015)]. Generally, very good agreement is found. In addition, ICSs calculated with our independent atom model (IAM) with screening corrected additivity rule (SCAR) formalism, extended to account for interference (I) terms that arise due to the multi-centre nature of the scattering problem, are also reported. The sum of those ICSs gives the IAM-SCAR+I total cross section for electron-furfural scattering. Where possible, those calculated IAM-SCAR+I ICS results are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, but only for the band I and band II excited electronic states, we also present results from our Schwinger multichannel method with pseudopotentials calculations. Those results are found to be in good qualitative accord with the present experimental ICSs. Finally, with a view to assembling a complete cross section data base for furfural, some binary-encounter-Bethe-level total ionization cross sections for this collision system are presented. PMID:27083717

  10. Pityriazepin and other potent AhR ligands isolated from Malassezia furfur yeast.

    PubMed

    Mexia, Nikitia; Gaitanis, Georgios; Velegraki, Aristea; Soshilov, Anatoly; Denison, Michael S; Magiatis, Prokopios

    2015-04-01

    Malassezia furfur yeast strains isolated from diseased human skin preferentially biosynthesize indole alkaloids which can be detected in the human skin and are highly potent activators of the aryl hydrocarbon receptor (AhR) and AhR-dependent gene expression. Chemical analysis of an EtOAc extract of a M. furfur strain obtained from diseased human skin and grown on l-tryptophan agar revealed several known AhR active tryptophan metabolites along with a previously unidentified compound, pityriazepin. While its structure resembled that of the known alkaloid pityriacitrin, the comprised pyridine ring had been transformed into an azepinone. The indoloazepinone scaffold of pityriazepin is extremely rare in nature and has only been reported once previously. Pityriazepin, like the other isolated compounds, was found to be a potent activator of the AhR-dependent reporter gene assay in recombinant cell lines derived from four different species, although significant species differences in relative potency were observed. The ability of pityriazepin to competitively bind to the AhR and directly stimulate AhR DNA binding classified it as a new naturally-occurring potent AhR agonist. M. furfur produces an expanded collection of extremely potent naturally occurring AhR agonists, which produce their biological effects in a species-specific manner. PMID:25721496

  11. Pityriazepin and other potent AhR ligands isolated from Malassezia furfur yeast

    PubMed Central

    Mexia, Nikitia; Gaitanis, George; Velegraki, Aristea; Soshilov, Anatoly; Denison, Michael S.; Magiatis, Prokopios

    2015-01-01

    Malassezia furfur yeast strains isolated from diseased human skin preferentially biosynthesize indole alkaloids which can be detected in human skin and are highly potent activators of the aryl hydrocarbon receptor (AhR) and AhR-dependent gene expression. Chemical analysis of an EtOAc extract of a M. furfur strain obtained from diseased human skin and grown on L-tryptophan agar revealed several known AhR active tryptophan metabolites along with a previously unidentified compound, pityriazepin. While its structure resembled that of the known alkaloid pityriacitrin, the comprised pyridine ring had been transformed into an azepinone. The indoloazepinone scaffold of pityriazepin is extremely rare in nature and has only been reported once previously. Pityriazepin, like the other isolated compounds, was found to be a potent activator of the AhR-dependent reporter gene assays in recombinant cell lines derived from four different species, although significant species differences in relative potency was observed. The ability of pityriazepin to competitively bind to the AhR and directly stimulate AhR DNA binding classified it as a new naturally-occurring potent AhR agonist. Malassezia furfur produces an expanded collection of extremely potent naturally occurring AhR agonists, which produce their biological effects in a species-specific manner.1 PMID:25721496

  12. Characterization of tryptophan aminotransferase 1 of Malassezia furfur, the key enzyme in the production of indolic compounds by M. furfur.

    PubMed

    Preuss, Janina; Hort, Wiebke; Lang, Sarah; Netsch, Anette; Rahlfs, Stefan; Lochnit, Günter; Jortzik, Esther; Becker, Katja; Mayser, Peter A

    2013-11-01

    Malassezia yeasts are responsible for the widely distributed skin disease Pityriasis versicolor (PV), which is characterized by a hyper- or hypopigmentation of affected skin areas. For Malassezia furfur, it has been shown that pigment production relies on tryptophan metabolism. A tryptophan aminotransferase was found to catalyse the initial catalytic step in pigment formation in the model organism Ustilago maydis. Here, we describe the sequence determination, recombinant production and biochemical characterization of tryptophan aminotransferase MfTam1 from M. furfur. The enzyme catalyses the transamination from l-tryptophan to keto acids such as α-ketoglutarate with Km values for both substrates in the low millimolar range. Furthermore, MfTam1 presents a temperature optimum at 40°C and a pH optimum at 8.0. MfTam1 activity is highly dependent on pyridoxal phosphate (PLP), whereas compounds interfering with PLP, such as cycloserine (CS) and aminooxyacetate, inhibit the MfTam1 reaction. CS is known to reverse hyperpigmentation in PV. Thus, the results of the present study give a deeper insight into the role of MfTam1 in PV pathogenesis and as potential target for the development of novel PV therapeutics. PMID:24118363

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

    PubMed

    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

  14. Production of hybrid diesel fuel precursors from carbohydrates and petrochemicals using formic acid as a reactive solvent.

    PubMed

    Zhou, Xiaoyuan; Rauchfuss, Thomas B

    2013-02-01

    We report the one-pot alkylation of mesitylene with carbohydrate-derived 5-(hydroxymethyl)furfural (HMF) as a step toward diesel-range liquids. Using FeCl(3) as a catalyst, HMF is shown to alkylate toluene, xylene, and mesitylene in high yields in CH(2)Cl(2) and MeNO(2) solvents. Efforts to extend this reaction to greener or safer solvents showed that most ether-based solvents are unsatisfactory. Acid catalysts (e.g, p-TsOH) also proved to be ineffective. Using formic acid as a reactive solvent, mesitylene could be alkylated to give mesitylmethylfurfural (MMF) starting from fructose with yields up to approximately 70 %. The reaction of fructose with formic acid in the absence of mesitylene gave rise to low yields of the formate ester of HMF, which indicates the stabilizing effect of replacing the hydroxyl substituent with mesityl. The arene also serves as a second phase into which the product is extracted. Even by using formic acid, the mesitylation of less expensive precursors such as glucose and cellulose proceeded only in modest yields (ca. 20 %). These simpler substrates were found to undergo mesitylation by using hydrogen chloride/formic acid via the intermediate chloromethylfurfural. PMID:23281330

  15. The Empirical Canadian High Arctic Ionospheric Model (E-CHAIM): NmF2 and hmF2 specification

    NASA Astrophysics Data System (ADS)

    Themens, David; Jayachandran, Thayyil

    2016-07-01

    It is well known that the IRI suffers reduced accuracy in its representation of monthly median ionospheric variability at high latitudes (Themens et al. 2014, Themens et al. 2016). These inaccuracies are believed to stem from a historical lack of data from these regions. Now, roughly thirty and forty years after the development of the original URSI and CCIR foF2 maps, respectively, there exists a much larger dataset of high latitude observations of ionospheric electron density. These new measurements come in the form of new ionosonde deployments, such as those of the Canadian High Arctic Ionospheric Network, the CHAMP, GRACE, and COSMIC radio occultation missions, and the construction of the Poker Flat, Resolute, and EISCAT Incoherent Scatter Radars systems. These new datasets afford an opportunity to revise the IRI's representation of the high latitude ionosphere. For this purpose, we here introduce the Empirical Canadian High Arctic Ionospheric Model (E-CHAIM), which will incorporate all of the above datasets, as well as the older observation records, into a new climatological representation of the high latitude ionosphere. In this presentation, we introduce the NmF2 and hmF2 portions of the model and present a validation of the new model with respect to ionosonde observations in Alert, Canada. A comparison with respect to IRI performance will also be presented.

  16. Clostridium thermocellum Transcriptomic Profiles after Exposure to Furfural or Heat Stress

    SciTech Connect

    Wilson, Charlotte M; Yang, Shihui; Rodriguez, Jr., Miguel; Ma, Qin; Johnson, Courtney M; Dice, Lezlee T; Xu, Ying; Brown, Steven D

    2013-01-01

    Background The thermophilic anaerobe Clostridium thermocellum is a candidate consolidated bioprocessing (CBP)biocatalyst for cellulosic ethanol production. It is capable of both cellulose solubilization and its fermentation to produce lignocellulosic ethanol. Intolerance to stresses routinely encountered during industrial fermentations may hinder the commercial development of this organism. A previous C. thermocellum ethanol stress study showed that largest transcriptomic response was in genes and proteins related to nitrogen uptake and metabolism. Results In this study, C. thermocellum was grown to mid-exponential phase and treated with furfural or heat to a final concentration of 3 g.L-1 or 68 C respectively to investigate general and specific physiological and regulatory stress responses. Samples were taken at 10, 30, 60 and 120 min post-shock, and from untreated control fermentations, for transcriptomic analyses and fermentation product determinations and compared to a published dataset from an ethanol stress study. Urea uptake genes were induced following furfural stress, but not to the same extent as ethanol stress and transcription from these genes was largely unaffected by heat stress. The largest transcriptomic response to furfural stress was genes for sulfate transporter subunits and enzymes in the sulfate assimilatory pathway, although these genes were also affected late in the heat and ethanol stress responses. Lactate production was higher in furfural treated culture, although the lactate dehydrogenase gene was not differentially expressed under this condition. Other redox related genes such as a copy of the rex gene, a bifunctional acetaldehyde-CoA/alcohol dehydrogenase and adjacent genes did show lower expression after furfural stress compared to the control, heat and ethanol fermentation profiles. Heat stress induced expression from chaperone related genes and overlap was observed with the responses to the other stresses. This study suggests the

  17. Direct transformation of xylan-type hemicelluloses to furfural via SnCl₄ catalysts in aqueous and biphasic systems.

    PubMed

    Wang, Wenju; Ren, Junli; Li, Huiling; Deng, Aojie; Sun, Runcang

    2015-05-01

    Direct catalytic transformation of xylan-type hemicelluloses to furfural in the aqueous system and the biphasic system were comparatively investigated under mild conditions. Screening of several promising chlorides for conversion of beech xylan in the aqueous system revealed the Lewis acid SnCl4 was the most effective catalyst. Comparing to the single aqueous system, the bio-based 2-methyltetrahydrofuran (2-MTHF)/H2O biphasic system was more conducive to the synthesis of furfural, in which the highest furfural yield of 78.1% was achieved by using SnCl4 as catalysts under the optimized reaction conditions (150°C, 120 min). Additionally, the influences of xylan-type hemicelluloses with different chemical and structural features from beech, corncob and bagasse on the furfural production were studied. It was found that furfural yield to some extent was determined by the xylose content in hemicelluloses and also had relationships with the molecular weight of hemicelluloses and the degree of crystallization. PMID:25742750

  18. Selective conversion of furfural to maleic anhydride and furan with VO(x)/Al(2)O(3) catalysts.

    PubMed

    Alonso-Fagúndez, Noelia; Granados, Manuel López; Mariscal, Rafael; Ojeda, Manuel

    2012-10-01

    Furfural can be converted into maleic anhydride (73 % yield) through selective gas phase oxidation at 593 K with O(2) by using VO(x)/Al(2)O(3) (10 at(V) nm(-2)) as solid catalysts. The use of lower temperatures and/or O(2) pressures result in the additional formation of furan (maximum 9 % yield). Mechanistically, furfural (C(5)H(4)O(2)) is oxidized stepwise to furan (C(4)H(4)O), 2-furanone (C(4)H(4)O(2)), and finally, maleic anhydride (C(4)H(2)O(3)). The specific structure of the supported vanadium oxides and reaction conditions (temperature and reactants pressures) all influence furfural oxidation catalysis. We have found that Al(2)O(3)-supported polyvanadates are intrinsically more active (2.70 mmol h(-1) g-at V(-1)) than monovanadates (VO(4)) and V(2)O(5) crystals (0.89 and 0.70 mmol h(-1) g-at V(-1), respectively) in maleic anhydride and furan formation rates (553 K, 1.6 kPa furfural, 2.5 kPa O(2)). Our alternative approach enables the use of biomass instead of petroleum to synthesize maleic anhydride and furan from furfural. The potential variety of industrial applications is of enormous interest for the development of future biorefineries. PMID:22847991

  19. Dynamic flux balancing elucidates NAD(P)H production as limiting response to furfural inhibition in Saccharomyces cerevisiae.

    PubMed

    Pornkamol, Unrean; Franzen, Carl J

    2015-08-01

    Achieving efficient and economical lignocellulose-based bioprocess requires a robust organism tolerant to furfural, a major inhibitory compound present in lignocellulosic hydrolysate. The aim of this study was to develop a model that could generate quantitative descriptions of cell metabolism for elucidating the cell's adaptive response to furfural. Such a modelling tool could provide strategies for the design of more robust cells. A dynamic flux balance (dFBA) model of Saccharomyces cerevisiae was created by coupling a kinetic fermentation model with a previously published genome-scale stoichiometric model. The dFBA model was used for studying intracellular and extracellular flux responses to furfural perturbations under steady state and dynamic conditions. The predicted effects of furfural on dynamic flux profiles agreed well with previously published experimental results. The model showed that the yeast cell adjusts its metabolism in response to furfural challenge by increasing fluxes through the pentose phosphate pathway, TCA cycle, and proline and serine biosynthesis in order to meet the high demand of NAD(P)H cofactors. The model described here can be used to aid in systematic optimization of the yeast, as well as of the fermentation process, for efficient lignocellulosic ethanol production. PMID:25880365

  20. First-principles quantum-mechanical investigations: The role of water in catalytic conversion of furfural on Pd(111)

    NASA Astrophysics Data System (ADS)

    Xue, Wenhua; Borja, Miguel Gonzalez; Resasco, Daniel E.; Wang, Sanwu

    2015-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of water has attracted wide attention. Recent experiments showed that the proportion of alcohol product from catalytic reactions of furfural conversion with palladium in the presence of water is significantly increased, when compared with other solvent including dioxane, decalin, and ethanol. We investigated the microscopic mechanism of the reactions based on first-principles quantum-mechanical calculations. We particularly identified the important role of water and the liquid/solid interface in furfural conversion. Our results provide atomic-scale details for the catalytic reactions. Supported by DOE (DE-SC0004600). This research used the supercomputer resources at NERSC, of XSEDE, at TACC, and at the Tandy Supercomputing Center.

  1. Mechanistic Insights into the Structure-Dependent Selectivity of Catalytic Furfural Conversion on Platinum Catalysts

    SciTech Connect

    Cai, Qiuxia; Wang, Jianguo; Wang, Yang-Gang; Mei, Donghai

    2015-11-01

    The effects of structure and size on the selectivity of catalytic furfural conversion over supported Pt catalysts in the presence of hydrogen have been studied using first principles density functional theory (DFT) calculations and microkinetic modeling. Four Pt model systems, i.e., periodic Pt(111), Pt(211) surfaces, as well as small nanoclusters (Pt13 and Pt55) are chosen to represent the terrace, step, and corner sites of Pt nanoparticles. Our DFT results show that the reaction routes for furfural hydrogenation and decarbonylation are strongly dependent on the type of reactive sites, which lead to the different selectivity. On the basis of the size-dependent site distribution rule, we correlate the site distributions as a function of the Pt particle size. Our microkinetic results indicate the critical particle size that controls the furfural selectivity is about 1.0 nm, which is in good agreement with the reported experimental value under reaction conditions. This work was supported by National Basic Research Program of China (973 Program) (2013CB733501) and the National Natural Science Foundation of China (NSFC-21306169, 21176221, 21136001, 21101137 and 91334103). This work was also partially supported by the US Department of Energy (DOE), the Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

  2. 5-Hydroxymethylfurfural: assessment of mutagenicity, DNA-damaging potential and reactivity towards cellular glutathione.

    PubMed

    Janzowski, C; Glaab, V; Samimi, E; Schlatter, J; Eisenbrand, G

    2000-09-01

    5-(hydroxymethyl)-2-furfural (HMF), a common product of the Maillard reaction, occurs in many foods in high concentrations, sometimes exceeding 1 g/kg (in certain dried fruits and caramel products). The toxicological relevance of this exposure has not yet been clarified. Induction of aberrant colonic crypt foci had been reported for HMF, in vitro studies on genotoxicity/mutagenicity have given controversial results. To elucidate the toxic potential of HMF, cytotoxicity (trypan blue exclusion), growth inhibition (SRB assay), mutagenicity (HPRT assay), DNA damage (single-cell gel electrophoresis) and depletion of cellular glutathione were investigated in mammalian cells. Genotoxicity (SOS repair) was monitored in Salmonella typhimurium (umu assay). HMF induced moderate cytotoxicity in V79 cells (LC(50): 115 mM, 1 hr incubation) and in Caco-2 cells (LC(50): 118 mM, 1 hr incubation). Growth inhibition was monitored following 24 hr of incubation (V79, IC(50): 6.4 mM). DNA damage was detectable neither in these cell lines nor in primary rat hepatocytes up to the cytotoxic threshold concentration (75% absolute viability). Likewise, in primary human colon cells, obtained from biopsy material, DNA damage was not measurable. At 120 mM, already exhibiting some reduction in cell viability, HMF was weakly mutagenic at the hprt-locus in V79 cells (mutants/10(6) cells: HMF 120 mM: 16 vs control: 3). Intracelluar glutathione was depleted by HMF (>/=50 mM) in V79 cells, in the human colon adenocarcinoma cell line Caco-2 and in primary rat hepatocytes down to approximately 30% of control (120 mM). Genotoxicity was observed with HMF in the umu assay without external activation (16 mM: 185 rel. umu units, %, P<0.001). The genotoxic potential was not altered by addition of rat liver microsomes. By comparison, the natural flavour constituent (E)-2-hexenal (HEX) was already cytotoxic, mutagenic and depleted glutathione at about 1000-fold lower concentrations. It induced DNA damage in

  3. Xylose Isomerization to Xylulose and Its Dehydration to Furfural in Aqueous Media

    SciTech Connect

    Choudhary, Vinit; Pinar, Ana B; Sandler, Stanley I; Vlachos, Dion G.; Lobo, Raul F

    2011-12-02

    A nonenzymatic route for xylose isomerization in an aqueous medium using zeolite Sn-beta as a catalyst is demonstrated. Xylulose and lyxose are the primary and secondary products. The maximum yield to xylulose is 27%, with an 11% yield to lyxose at ~60% xylose conversion at 100 °C. When the Sn-beta zeolite is combined with a Brønsted acid catalyst, furfural forms in a single pot from xylose in an aqueous medium at much lower temperatures than typically employed for this reaction.

  4. Complete genome sequence of Enterobacter cloacae GGT036: a furfural tolerant soil bacterium.

    PubMed

    Gong, Gyeongtaek; Um, Youngsoon; Park, Tai Hyun; Woo, Han Min

    2015-01-10

    Enterobacter cloacae is a facultative anaerobic bacterium to be an important cause of nosocomial infection. However, the isolated E. cloacae GGT036 showed higher furfural-tolerant cellular growth, compared to industrial relevant strains such as Escherichia coli and Corynebacterium glutamicum. Here, we report the complete genome sequence of E. cloacae GGT036 isolated from Mt. Gwanak, Seoul, Republic of Korea. The genomic DNA sequence of E. cloacae GGT036 will provide valuable genetic resources for engineering of industrially relevant strains being tolerant to cellular inhibitors present in lignocellulosic hydrolysates. PMID:25444880

  5. Kinetics of vapor-phase hydrogenation of furfural on a copper-chromium catalyst

    SciTech Connect

    Borts, M.S.; Gil'chenok, N.D.; Gurevich, G.S.; Ignat'ev, V.M.

    1986-08-01

    This paper studies the principal kinetic relationships of hydrogenation of furfural to furfuryl alcohol, which must be known for development of the industrial process. Prelininary experiments showed that at linear velocities of the vapor-gas stream (calculated for the free cross section of the reactor) above 0.26 matsec and with an average catalyst particle size less than 0.30 mm neither external nor internal diffusio resistance has any effect. In all the subsequent experiments a 0.20-0.25-mm catalyst fraction was used at a linear vapor-gas velocity of 0.50 m/sec, when the reaction proceeded with kinetic control.

  6. Furfural production in biphasic media using an acidic ionic liquid as a catalyst.

    PubMed

    Peleteiro, Susana; Santos, Valentín; Parajó, Juan C

    2016-11-20

    Ionic liquids are valuable tools for biorefineries. This study provides an experimental assessment on the utilization of an acidic ionic liquid (1-butyl-3-methylimidazolium hydrogen sulfate) as a catalyst for furfural production in water/solvent media. The substrates employed in experiments were commercial xylose (employed as a reference compound) or hemicellulosic saccharides obtained by hydrothermal processing of Eucalyptus globulus wood (which were employed as produced, after membrane concentration or after freeze-drying). A variety of reaction conditions (defined by temperature, reaction time and type of organic solvent) were considered. The possibility of recycling the catalyst was assessed in selected experiments. PMID:27561513

  7. Formation of furfurylthiol exhibiting a strong coffee aroma during oak barrel fermentation from furfural released by toasted staves.

    PubMed

    Blanchard, L; Tominaga, T; Dubourdieu, D

    2001-10-01

    Furfurylthiol (FFT) is formed in white wines during alcoholic fermentation in the barrel from the furfural released by toasted staves. The quantity of furfural released into the must has a decisive effect on the quantity of FFT in the finished wine. Wines fermented in new barrels thus contain larger quantities of FFT than those fermented in used barrels. Fermentation conditions favorable to an excess production of H(2)S (hydrogen sulfide) by the yeast promote the formation of this volatile thiol. The presence of this volatile thiol in white wines is, therefore, closely related to the yeast's sulfur metabolism. PMID:11600030

  8. In vitro and occupational induction of sister-chromatid exchanges in human lymphocytes with furfuryl alcohol and furfural.

    PubMed

    Gomez-Arroyo, S; Souza, V

    1985-06-01

    Sister-chromatid exchanges (SCEs) in human lymphocytes were studied using the FPG technique in order to determine the cytogenetic effect of furfural and furfuryl alcohol. The induction of SCEs was also investigated in workers occupationally exposed to these solvents that are commonly used in the manufacture of furoic resins. The results obtained from the in vitro treatments show that furfural increased the number of SCEs, while furfuryl alcohol did not. In exposed workers, neither of these solvents increased the spontaneous frequency of SCEs per metaphase. PMID:4000179

  9. Effect of Furfural, Vanillin and Syringaldehyde on Candida guilliermondii Growth and Xylitol Biosynthesis

    NASA Astrophysics Data System (ADS)

    Kelly, Christine; Jones, Opal; Barnhart, Christopher; Lajoie, Curtis

    Xylitol is a five-carbon sugar alcohol with established commercial use as an alternative sweetener and can be produced from hemicellulose hydrolysate. However, there are difficulties with microbiological growth and xylitol biosynthesis on hydrolysate because of the inhibitors formed from hydrolysis of hemicellulose. This research focused on the effect of furfural, vanillin, and syringaldehyde on growth of Candida guilliermondii and xylitol accumulation from xylose in a semi-synthetic medium in microwell plate and bioreactor cultivations. All three compounds reduced specific growth rate, increased lag time, and reduced xylitol production rate. In general, increasing concentration of inhibitor increased the severity of inhibition, except in the case of 0.5 g vanillin per liter, which resulted in a faster late batch phase growth rate and increased biomass yield. At concentrations of 1 g/1 or higher, furfural was the least inhibitory to growth, followed by syringaldehyde. Vanillin most severely reduced specific growth rate. All three inhibitors reduced xylitol production rate approximately to the same degree.

  10. Synthesis and characterization of carbon cryogel microspheres from lignin-furfural mixtures for biodiesel production.

    PubMed

    Zainol, Muzakkir Mohammad; Amin, Nor Aishah Saidina; Asmadi, Mohd

    2015-08-01

    The aim of this work was to study the potential of biofuel and biomass processing industry side-products as acid catalyst. The synthesis of carbon cryogel from lignin-furfural mixture, prepared via sol-gel polycondensation at 90°C for 0.5h, has been investigated for biodiesel production. The effect of lignin to furfural (L/F) ratios, lignin to water (L/W) ratios and acid concentration on carbon cryogel synthesis was studied. The carbon cryogels were characterized and tested for oleic acid conversion. The thermally stable amorphous spherical carbon cryogel has a large total surface area with high acidity. Experimental results revealed the optimum FAME yield and oleic acid conversion of 91.3wt.% and 98.1wt.%, respectively were attained at 65°C for 5h with 5wt.% catalyst loading and 20:1 methanol to oleic acid molar ratio. Therefore, carbon cryogel is highly potential for heterogeneous esterification of free fatty acid to biodiesel. PMID:25919936

  11. [Rapid quantitative analysis of hydrocarbon composition of furfural extract oils using attenuated total reflection infrared spectroscopy].

    PubMed

    Li, Na; Yuan, Hong-Fu; Hu, Ai-Qin; Liu, Wei; Song, Chun-Feng; Li, Xiao-Yu; Song, Yi-Chang; He, Qi-Jun; Liu, Sha; Xu, Xiao-Xuan

    2014-07-01

    A set of rapid analysis system for hydrocarbon composition of heavy oils was designed using attenuated total reflection FTIR spectrometer and chemometrics to determine the hydrocarbon composition of furfural extract oils. Sixty two extract oil samples were collected and their saturates and aromatics content data were determined according to the standard NB/SH/T0509-2010, then the total contents of resins plus asphaltenes were calculated by the subtraction method in the percentage of weight. Based on the partial least squares (PLS), calibration models for saturates, aromatics, and resin+asphaltene contents were established using attenuated total reflection FTIR spectroscopy, with their SEC, 1.43%, 0.91% and 1.61%, SEP, 1.56%, 1.24% and 1.81%, respectively, meeting the accuracy and repeatability required for the standard. Compared to the present standard method, the efficiency of hydrocarbon composition analysis for furfural extract oils is significantly improved by the new method which is rapid and simple. The system could also be used for other heavy oil analysis, with excellent extension and application foreground. PMID:25269288

  12. Integrated catalytic process to directly convert furfural to levulinate ester with high selectivity.

    PubMed

    Chen, Bingfeng; Li, Fengbo; Huang, Zhijun; Lu, Tao; Yuan, Yin; Yuan, Guoqing

    2014-01-01

    Levulinic acid is an important platform molecule from biomass-based renewable resources. A sustainable manufacturing process for this chemical and its derivatives is the enabling factor to harness the renewable resource. An integrated catalytic process to directly convert furfural to levulinate ester was developed based on a bifunctional catalyst of Pt nanoparticles supported on a ZrNb binary phosphate solid acid. The hydrogenation of furfural and the following alcoholysis of furfuryl alcohol were performed over this catalyst in a one-pot conversion model. Mesoporous ZrNb binary phosphate was synthesized by a sol-gel method and had a high surface area of 170.1 m(2) g(-1) and a large average pore size of around 8.0 nm. Pt nanoparticles remained in a monodisperse state on the support, and the reaction over Pt/ZrNbPO4 (Pt loading: 2.0 wt%; Zr/Nb, 1:1) gave a very high selectivity to levulinate derivatives (91% in total). The sustainability of this conversion was greatly improved by the process intensification based on the new catalyst, mild reaction conditions, cost abatement in separation and purification, and utilization of green reagents and solvents. PMID:24194497

  13. Glycine as a regulator of tryptophan-dependent pigment synthesis in Malassezia furfur.

    PubMed

    Barchmann, Thorsten; Hort, Wiebke; Krämer, Hans-Joachim; Mayser, Peter

    2011-01-01

    The effects of the addition of different amino nitrogens on growth, morphology and secondary metabolism of Malassezia furfur were investigated. After primary culture on Dixon agar, M. furfur CBS 1878 was transferred into a fluid medium together with the nitrogen sources, glycine (Gly) or tryptophan (Trp), or a combination of both. Growth was measured by means of a direct cell counting method and pigment synthesis was photometrically assessed. Addition of glycine resulted in an exponential increase in biomass, but not in pigment production. Tryptophan as the sole nitrogen source caused distinct brown staining of the medium, without increasing biomass. Simultaneous equimolar addition of both amino acids resulted in an initial increase in biomass as a sign of preferential metabolism of glycine, followed by a growth plateau and pigment production which, caused by higher biomass, occurred more rapidly than after addition of tryptophan alone. The yeast-cell morphology changed from round to oval. Addition of glycine to the tryptophan-containing liquid culture stopped pigment formation with simultaneous growth induction. These in vitro on-off phenomena depending on the nitrogen source might be significant in the pathogenesis of pityriasis versicolor: hyperhidrosis followed by preferential consumption of individual nitrogen sources such as glycine with exponential growth and thereafter transamination of tryptophan and TRP-dependent pigment synthesis. PMID:19702622

  14. Screening of Yeasts for Selection of Potential Strains and Their Utilization for In Situ Microbial Detoxification (ISMD) of Sugarcane Bagasse Hemicellulosic Hydrolysate.

    PubMed

    Soares, Luma C S R; Chandel, Anuj K; Pagnocca, Fernando C; Gaikwad, Swapnil C; Rai, Mahendra; da Silva, Silvio S

    2016-06-01

    Many toxic compounds are produced and released in the hemicellulosic hydrolyzates during the acid pretreatment step, which are required for the disruption of the lignocelluloses matrix and sugars release. The conventional methods of detoxification i.e. overliming, activated charcoal, ion exchange or even membrane-based separations have the limitations in removal of these toxic inhibitors in fermentation process. Hence, it is imperative to explore biological methods to overcome the inhibitors by minimizing the filtration steps, sugar loss and chemical additions. In the present study we screened sixty-four strains of yeasts to select potential strains for detoxification of furfural, acetic acid, ferulic acid, 5-hydroxymethyl furfural (5-HMF) as carbon and energy source. Among these strains Pichia occidentalis M1, Y1'a, Y1'b and Y3' showed a significant decrease in the toxic compounds but we selected two best yeast strains i.e. P. occidentalis Y1'a and P. occidentalis M1 for the further experiments with an aim to remove the fermentation inhibitors. The yeasts P. occidentalis Y1'a and P. occidentalis M1 were grown aerobically in sugarcane bagasse hemicellulose hydrolysate under submerged cultivation. For each yeast, a 2(2) full factorial design was performed considering the variables-pH (4.0 or 5.0) and agitation rate (100 or 300 rpm), and the percentage removal of HMF, furfural, acetic acid and phenols from hemicellulosic hydrolysates were responsive variables. After 96 h of biological treatment, P. occidentalis M1 and P. occidentalis Y1'a showed 42.89 and 46.04 % cumulative removal of inhibitors, respectively. PMID:27570309

  15. Comparison of NmF2 and hmF2 values derived from IRI and FORMOSAT-3/COSMIC ionospheric radio occultations

    NASA Astrophysics Data System (ADS)

    Brunini, Claudio; Limberger, Marco; Schmidt, Michael; Dettmering, Denise; Wenjing, Liang

    2014-05-01

    The electron density, NmF2, and the height, hmF2, of the ionospheric F2 peak are key parameters for modeling the electron density distribution in the ionosphere (e.g. within the International Reference Ionosphere (IRI) model), for radio-communication forecast (e.g. in the radio-communication sector of the International Telecommunication Union Recommendations (ITU-R)), and other space weather related issues. A commonly applied procedure to compute the values of these parameters, in case that direct measurements are not available, is the use of the ITU-R global maps which were established in the early 60s but still belong to the ITU-R standards. Accompanying the efforts the community is making to update those maps, we have recently presented a technique based on the assimilation of FORMOSAT-3/COSMIC (F3/C) ionospheric radio occultations (IRO) in the La Plata Ionospheric Model (LPIM). The global mean error of our maps, estimated by the data assimilation algorithm, ranged from 0.5×10**10 el/m3 and 3.6×10**10 el/m3 for NmF2 (which is equivalent to approximately 7% of the value of the estimated parameter), and from 2.0 to 5.6 km for hmF2 (around 2 %), depending on the solar activity. Further, we compared the NmF2 and hmF2 values retrieved with our technique to the ones computed by IRI, and found systematic differences between both estimations. The comparison has been made for low solar activity and showed systematic differences up to 50% for NmF2 and 12% for hmF2. It seems reasonable to conjecture that the aforementioned differences are caused by systematic errors in IRI as well as in the F3/C IRO + LPIM. Hence, a comparison to a third data source could help to assess the contribution of each party. In this paper we compared the vertical Total Electron Content (vTEC) provided by the Jason mission to the corresponding values derived from F3/C IRO + LPIM and from IRI. We found that approximately 50% of the systematic differences reported in our previous paper could be

  16. Evaluation of prototype Advanced Life Support (ALS) pack for use by the Health Maintenance Facility (HMF) on Space Station Freedom (SSF)

    NASA Technical Reports Server (NTRS)

    Krupa, Debra T.; Gosbee, John; Murphy, Linda; Kizzee, Victor D.

    1991-01-01

    The purpose is to evaluate the prototype Advanced Life Support (ALS) Pack which was developed for the Health Maintenance Facility (HMF). This pack will enable the Crew Medical Officer (CMO) to have ready access to advanced life support supplies and equipment for time critical responses to any situation within the Space Station Freedom. The objectives are: (1) to evaluate the design of the pack; and (2) to collect comments for revision to the design of the pack. The in-flight test procedures and other aspects of the KC-135 parabolic test flight to simulate weightlessness are presented.

  17. Noontime Latitudinal Behavior of the Ionospheric Peak Parameters (foF2 and hmF2) to the Variation of Solar Energy Input for the American Sector

    NASA Astrophysics Data System (ADS)

    Cabassa-Miranda, E.; Garnett Marques Brum, C.

    2013-12-01

    We are presenting a statistical study of the behavior of the noontime F2 peak parameters (foF2 and hmF2) to the variation of solar energy input based on digisonde data and EUV-UV solar emissions registered by SOHO satellite for geomagnetic quiet-to-normal condition. For this, we selected digisonde data from fourteen different stations spread along the American sector (ten of them located above and four below the equator). These registers were collected from 2000 to 2012 and encompass the last unusual super minimum period.

  18. Integrated phospholipidomics and transcriptomics analysis of Saccharomyces cerevisiae with enhanced tolerance to a mixture of acetic acid, furfural, and phenol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A mixture of acetic acid, furfural and phenol (AFP), three representative lignocellulose derived inhibitors, significantly inhibited the growth and bioethanol production of Saccharomyces cerevisiae. In order to uncover mechanisms behind the enhanced tolerance of an inhibitor-tolerant S.cerevisiae s...

  19. Selective Hydrogenation of Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/SBA-15 Catalyst.

    PubMed

    Audemar, Maïté; Ciotonea, Carmen; De Oliveira Vigier, Karine; Royer, Sébastien; Ungureanu, Adrian; Dragoi, Brindusa; Dumitriu, Emil; Jérôme, François

    2015-06-01

    The hydrogenation of furfural to furfuryl alcohol was performed in the presence of a Co/SBA-15 catalyst. High selectivity (96 %) at a conversion higher than 95 % is reported over this catalytic system. As the conversion of furfural to furfuryl alcohol occurs over metallic Co sites, the effect of reduction temperature, H2 pressure, and reaction temperature were studied. Optimum reaction conditions were: 150 °C, 1.5 h, 2.0 MPa of H2 . The catalyst was recyclable, and furfuryl alcohol was recovered with a purity higher than 90 %. The effect of the solvent concentration was also studied. With a minimum of 50 wt % of solvent, the selectivity to furfuryl alcohol and the conversion of furfural remained high (both over 80 %). Likewise, the activity of the catalyst is maintained even in pure furfural, which confirms the real potential of the proposed catalytic system. This catalyst was also used in the hydrogenation of levulinic acid to produce γ-valerolactone selectively. PMID:25891431

  20. Tacrolimus does not alter the production of several cytokines and antimicrobial peptide in Malassezia furfur-infected-keratinocytes.

    PubMed

    Balato, Anna; Paoletti, Iole; De Gregorio, Vincenza; Cantelli, Mariateresa; Ayala, Fabio; Donnarumma, Giovanna

    2014-03-01

    Topical immunosuppressant therapy is widely used in the treatment of inflammatory skin diseases, such as atopic dermatitis and psoriasis. Besides its beneficial therapeutic effects, application of topical anti-inflammatory drugs may render the epidermis more vulnerable to invading pathogens by suppressing innate immune responses in keratinocytes (KCs). Cytokines, chemokines and antimicrobial peptides (AMPs) produced by epithelial cells enable them to participate in innate and acquired immune responses. The aim of the present work was to study the influence of tacrolimus (FK506) on KCs infected with Malassezia furfur (M. furfur), evaluating the expression of pro-inflammatory cytokines IL-1α and IL-6, chemokine IL-8, anti-inflammatory cytokines transforming growth factor beta1 (TGF-β1) and IL-10 and AMP β-defensin-2. Human KCs were obtained from surgical specimens of normal adult skin. The expression of mRNAs in KCs: FK506-treated, FK506-treated and M. furfur-infected as well as only M. furfur-infected was quantified by real-time quantitative polymerase chain reaction. Next, the production of the AMP β-defensin-2 and of the above-mentioned pro-inflammatory and anti-inflammatory cytokines was evaluated using enzyme-linked immunosorbent assay. In this study, FK506 did not alter cytokine and AMP production by KCs; this led us to hypothesise that it may not enhance the risk of mycotic skin infections. PMID:24512536

  1. Overexpression of the yeast transcription activator Msn2 confers furfural resistance and increases the initial fermentation rate in ethanol production.

    PubMed

    Sasano, Yu; Watanabe, Daisuke; Ukibe, Ken; Inai, Tomomi; Ohtsu, Iwao; Shimoi, Hitoshi; Takagi, Hiroshi

    2012-04-01

    Lignocellulosic biomass is a promising source for bioethanol production, because it is abundant worldwide and has few competing uses. However, the treatment of lignocelllulosic biomass with weak acid to release cellulose and hemicellulose generates many kinds of byproducts including furfural and 5-hydroxymethylfurfural, which inhibit fermentation by yeast, because they generate reactive oxygen species (ROS) in cells. In order to acquire high tolerance to oxidative stress in bioethanol yeast strains, we focused on the transcription activator Msn2 of Saccharomyces cerevisiae, which regulates numerous genes involved in antioxidative stress responses, and constructed bioethanol yeast strains that overexpress Msn2 constitutively. The Msn2-overexpressing bioethanol strains showed tolerance to oxidative stress, probably due to the high-level expression of various antioxidant enzyme genes. Unexpectedly, these strains showed ethanol sensitivity compared with the control strain, probably due to imbalance of the expression level between Msn2 and Msn4. In the presence of furfural, the engineered strains exhibited reduced intracellular ROS levels, and showed rapid growth compared with the control strain. The fermentation test in the presence of furfural revealed that the Msn2-overexpressing strains showed improvement of the initial rate of fermentation. Our results indicate that overexpression of the transcription activator Msn2 in bioethanol yeast strains confers furfural tolerance by reducing the intracellular ROS levels and enhances the initial rate of fermentation in the presence of furfural, suggesting that these strains are capable of adapting rapidly to various compounds that inhibit fermentation by inducing ROS accumulation. Our results not only promise to improve bioethanol production from lignocellulosic biomass, but also provide novel insights for molecular breeding of industrial yeast strains. PMID:22178024

  2. NMR structure and comparison of the archaeal histone HFoB from the mesophile Methanobacterium formicicum with HMfB from the hyperthermophile Methanothermus fervidus.

    PubMed

    Zhu, W; Sandman, K; Lee, G E; Reeve, J N; Summers, M F

    1998-07-28

    The solution-state structure of the recombinant archaeal histone rHFoB, from the mesophile Methanobacterium formicicum, has been determined by two- and three-dimensional (3D) proton homonuclear correlated nuclear magnetic resonance (NMR) methods. On the basis of 951 nuclear Overhauser effect (NOE)-derived distance restraints, rHFoB monomers form the histone fold and assemble into symmetric (rHFoB)2 dimers that have a structure consistent with assembly into archaeal nucleosomes. rHFoB exhibits approximately 78% sequence homology with rHMfB from the hyperthermophile Methanothermus fervidus, and the results obtained demonstrate that these two proteins have very similar 3D structures, with a root-mean-square deviation for backbone atoms of 0.65 +/- 0.13 A2. (rHFoB)2 dimers however unfold at lower temperatures and require a higher salt environment for stability than (rHMfB)2 dimers, and comparing the structures, we predict that these differences result from unfavorable surface-located ionic interactions and a larger, more solvent-accessible cavity adjacent to residue G36 in the hydrophobic core of (rHFoB)2. PMID:9692946

  3. Antimicrobial and anti-inflammatory effects of Cecropin A(1-8)-Magainin2(1-12) hybrid peptide analog p5 against Malassezia furfur infection in human keratinocytes.

    PubMed

    Ryu, Sunhyo; Choi, Soon-Yong; Acharya, Samudra; Chun, Young-Jin; Gurley, Catherine; Park, Yoonkyung; Armstrong, Cheryl A; Song, Peter I; Kim, Beom-Joon

    2011-08-01

    The lipophilic fungus Malassezia furfur (M. furfur) is a commensal microbe associated with several chronic diseases such as pityriasis versicolor, folliculitis, and seborrheic dermatitis. Because M. furfur-related diseases are difficult to treat and require prolonged use of medications, the treatment for M. furfur-related skin diseases is supposed to gain control over M. furfur growth and the inflammation associated with it, as well as to prevent secondary infections. In this study, we investigated the antifungal and anti-inflammatory effects of cecropin A(1-8)-magainin 2(1-12) hybrid peptide analog P5 on M. furfur. The minimal inhibitory concentration of P5 against M. furfur was 0.39 μM, making it 3-4 times more potent than commonly used antifungal agents such as ketoconazole (1.5 μM) or itraconazole (1.14 μM). P5 efficiently inhibited the expression of IL-8 and Toll-like receptor 2 in M. furfur-infected human keratinocytes without eukaryotic cytotoxicity at its fungicidal concentration. Moreover, P5 significantly downregulated NF-κB activation and intracellular calcium fluctuation, which are closely related with enhanced responses of keratinocyte inflammation induced by M. furfur infection. Taken together, these observations suggest P5 may be a potential therapeutic agent for M. furfur-associated human skin diseases because of its distinct antifungal and anti-inflammatory action. PMID:21593770

  4. Furfural resin-based bio-nanocomposites reinforced by reactive nanocrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Wang, C.; Sun, S.; Zhao, G.; He, B.; Xiao, H.

    2009-07-01

    The work presented herein has been focused on reinforcing the furfural resins (FA) by reactive-modified nanocrystalline cellulose (NCC) in an attempt to create a bio-nanocomposite completely based on natural resources. FA prepolymers were synthesized with an acid catalyst, and NCC was rendered reactive via the grafting of maleic anhydride (MAH). The resulting NCC and nanocomposites were characterized using TEM, SEM and FT-IR. It was found that NCC appeared to be spherical in shape with diameters under 100 nm. FT-IR confirmed that there were hydrogen and esterification bonding between MAH and NCC or FA prepolymer. After solidified with paratoluenesulfonic acid, NCC-reinforced FA resin composites showed granular cross-section while FA resin with layered structures. Mechanical property tests indicated that NCC-reinforced FA resin composites possessed the improved tensile and flexural strengths, in comparison with FA resin.

  5. Controlling Catalytic Selectivity via Adsorbate Orientation on the Surface: From Furfural Deoxygenation to Reactions of Epoxides.

    PubMed

    Pang, Simon H; Medlin, J Will

    2015-04-16

    Specificity to desired reaction products is the key challenge in designing solid catalysts for reactions involving addition or removal of oxygen to/from organic reactants. This challenge is especially acute for reactions involving multifunctional compounds such as biomass-derived aromatic molecules (e.g., furfural) and functional epoxides (e.g., 1-epoxy-3-butene). Recent surface-level studies have shown that there is a relationship between adsorbate surface orientation and reaction selectivity in the hydrogenation pathways of aromatic oxygenates and the ring-opening or ring-closing pathways of epoxides. Control of the orientation of reaction intermediates on catalytic surfaces by modifying the surface or near-surface environment has been shown to be a promising method of affecting catalytic selectivity for reactions of multifunctional molecules. In this Perspective, we review recent model studies aimed at understanding the surface chemistry for these reactions and studies that utilize this insight to rationally design supported catalysts. PMID:26263134

  6. From furfural to fuel: synthesis of furoins by organocatalysis and their hydrodeoxygenation by cascade catalysis.

    PubMed

    Wegenhart, Benjamin L; Yang, Linan; Kwan, Soon Cheong; Harris, Remi; Kenttämaa, Hilkka I; Abu-Omar, Mahdi M

    2014-09-01

    The synthesis of furoins from biomass-derived furfural and 2-methylfurfural is demonstrated in high yields in green and renewable solvents using N-heterocyclic carbene organocatalysts. The resulting furoin molecules are used as precursors for fuels using cascade catalysis, first by using Pd/C with acidic co-catalysts under very mild conditions to yield oxygenated C12 molecules. Two main products were formed, which we identified as 1,2-bis(5-methyltetrahydrofuran-2-yl)ethane and 1-(5-methyltetrahydrofuran-2-yl)heptanol. The use of a Pd/Zeolite-β catalyst under more extreme conditions resulted in the complete hydrodeoxygenation of 5,5'-dimethylfuroin to dodecanes in high yields (76%) and exceptional selectivity (94%) for n-dodecane. PMID:25088205

  7. Inhibiting effect of furfural on corrosion of zinc in ethanolic solutions

    SciTech Connect

    Chagas, L.V. das; Goncalves, R.S.

    1996-09-01

    Interest in the corrosion of metals in alcohol systems is increasing because of the fact that alcohol can substitute for conventional fuels as an energy source. A large fraction of Brazilian vehicles use this compound instead of conventional hydrocarbon fuels. Since some components of engines are made with Zn or Zn alloys, corrosion problems are possible. Furfural (C{sub 4}H{sub 3}OCHO) was shown to inhibit the corrosion processes of Zn in ethanolic solutions. Results obtained from different electrochemical methods confirmed this effect. Inhibition depended upon the adsorption step and was affected by the incidence of polychromatic light on the metal surface. Protection efficiency of C{sub 4}H{sub 3}OCHO was higher when the system was kept in the dark than when under illumination. An inhibition process involving an adsorption step of C{sub 4}H{sub 3}OCHO was proposed.

  8. Design and synthesis of donor-acceptor Stenhouse adducts: a visible light photoswitch derived from furfural.

    PubMed

    Helmy, Sameh; Oh, Saemi; Leibfarth, Frank A; Hawker, Craig J; Read de Alaniz, Javier

    2014-12-01

    The development of an easily synthesized, modular, and tunable organic photoswitch that responds to visible light has been a long-standing pursuit. Herein we provide a detailed account of the design and synthesis of a new class of photochromes based on furfural, termed donor-acceptor Stenhouse adducts (DASAs). A wide variety of these derivatives are easily prepared from commercially available starting materials, and their photophysical properties are shown to be dependent on the substituents of the push-pull system. Analysis of the switching behavior provides conditions to access the two structural isomers of the DASAs, reversibly switch between them, and use their unique solubility behavior to provide dynamic phase-transfer materials. Overall, these negative photochromes respond to visible light and heat and display an unprecedented level of structural modularity and tunabilty. PMID:25390619

  9. A feasible process for furfural production from the pre-hydrolysis liquor of corncob via biochar catalysts in a new biphasic system.

    PubMed

    Deng, Aojie; Lin, Qixuan; Yan, Yuhuan; Li, Huiling; Ren, Junli; Liu, Chuanfu; Sun, Runcang

    2016-09-01

    A feasible approach was developed to produce furfural from the pre-hydrolysis liquor of corncob via biochar catalysts as the solid acid catalyst in a new biphasic system with dichloromethane (DCM) as the organic phase and the concentrated pre-hydrolysis liquor (CPHL) containing NaCl as the aqueous phase. The biochar catalyst possessing many acidity groups (SO3H, COOH and phenolic OH groups) was prepared by the carbonization and sulfonation process of the corncob hydrolyzed residue. The influence of the catalytic condition on furfural yield and selectivity was comparatively studied. It was found that 81.14% furfural yield and 83.0% furfural selectivity were obtained from CPHL containing 5wt% xylose using this biochar catalyst in the CPHL-NaCl/DCM biphasic system at 170°C for 60min. In addition, with the regeneration process, this catalyst displayed the high performance and excellent recyclability. PMID:27295253

  10. The electron-furfural scattering dynamics for 63 energetically open electronic states.

    PubMed

    da Costa, Romarly F; do N Varella, Márcio T; Bettega, Márcio H F; Neves, Rafael F C; Lopes, Maria Cristina A; Blanco, Francisco; García, Gustavo; Jones, Darryl B; Brunger, Michael J; Lima, Marco A P

    2016-03-28

    We report on integral-, momentum transfer- and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C5H4O2). The calculations were performed with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (N(open)) at either the static-exchange (N(open) ch-SE) or the static-exchange-plus-polarisation (N(open) ch-SEP) approximation was employed to calculate the scattering amplitudes at impact energies lying between 5 eV and 50 eV, using a channel coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections. PMID:27036451

  11. The electron-furfural scattering dynamics for 63 energetically open electronic states

    NASA Astrophysics Data System (ADS)

    da Costa, Romarly F.; do N. Varella, Márcio T.; Bettega, Márcio H. F.; Neves, Rafael F. C.; Lopes, Maria Cristina A.; Blanco, Francisco; García, Gustavo; Jones, Darryl B.; Brunger, Michael J.; Lima, Marco A. P.

    2016-03-01

    We report on integral-, momentum transfer- and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C5H4O2). The calculations were performed with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (Nopen) at either the static-exchange (Nopen ch-SE) or the static-exchange-plus-polarisation (Nopen ch-SEP) approximation was employed to calculate the scattering amplitudes at impact energies lying between 5 eV and 50 eV, using a channel coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections.

  12. Effects of furan derivatives and phenolic compounds on electricity generation in microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Catal, Tunc; Fan, Yanzhen; Li, Kaichang; Bermek, Hakan; Liu, Hong

    Lignocellulosic biomass is an attractive fuel source for MFCs due to its renewable nature and ready availability. Furan derivatives and phenolic compounds could be potentially formed during the pre-treatment process of lignocellulosic biomass. In this study, voltage generation from these compounds and the effects of these compounds on voltage generation from glucose in air-cathode microbial fuel cells (MFCs) were examined. Except for 5-hydroxymethyl furfural (5-HMF), all the other compounds tested were unable to be utilized directly for electricity production in MFCs in the absence of other electron donors. One furan derivate, 5-HMF and two phenolic compounds, trans-cinnamic acid and 3,5-dimethoxy-4-hydroxy-cinnamic acid did not affect electricity generation from glucose at a concentration up to 10 mM. Four phenolic compounds, including syringaldeyhde, vanillin, trans-4-hydroxy-3-methoxy, and 4-hydroxy cinnamic acids inhibited electricity generation at concentrations above 5 mM. Other compounds, including 2-furaldehyde, benzyl alcohol and acetophenone, inhibited the electricity generation even at concentrations less than 0.2 mM. This study suggests that effective electricity generation from the hydrolysates of lignocellulosic biomass in MFCs may require the employment of the hydrolysis methods with low furan derivatives and phenolic compounds production, or the removal of some strong inhibitors prior to the MFC operation, or the improvement of bacterial tolerance against these compounds through the enrichment of new bacterial cultures or genetic modification of the bacterial strains.

  13. Changes of antioxidant activity and formation of 5-hydroxymethylfurfural in honey during thermal and microwave processing.

    PubMed

    Kowalski, Stanisław

    2013-11-15

    The paper presents the results of microwave irradiation and conventional heating of honey. These two kinds of thermal treatment result in the formation of 5-hydroxymethyl-2-furfural (HMF), and changes in the antioxidant potential of honeys, which were studied as well. Four types of honey (honeydew, lime, acacia, buckwheat) were analyzed. Honey samples were subjected to conventional heating in a water bath (WB) at 90°C up to 60min or to the action of a microwave field (MW) with constant power of 1.26W/g of the sample up to 6min. Changes in the antioxidant capacity of honeys were measured as a percentage of free radical (ABTS(+)and DPPH) scavenging ability. Changes in the total polyphenols content (TPC) (equivalents of gallic acid mg/100g of honey) were also determined. Formation of HMF in honey treated with a microwave field was faster in comparison with the conventional process. Changes in the antioxidant properties of honey subjected to thermal or microwave processing might have been botanical origin dependent. PMID:23790927

  14. Detoxification of Eucheuma spinosum Hydrolysates with Activated Carbon for Ethanol Production by the Salt-Tolerant Yeast Candida tropicalis.

    PubMed

    Ra, Chae Hun; Jung, Jang Hyun; Sunwoo, In Young; Kang, Chang Han; Jeong, Gwi-Taek; Kim, Sung-Koo

    2015-06-01

    The objective of this study was to optimize the slurry contents and salt concentrations for ethanol production from hydrolysates of the seaweed Eucheuma spinosum. A monosaccharide concentration of 44.2 g/l as 49.6% conversion of total carbohydrate of 89.1 g/l was obtained from 120 g dw/l seaweed slurry. Monosaccharides from E. spinosum slurry were obtained by thermal acid hydrolysis and enzymatic hydrolysis. Addition of activated carbon at 2.5% (w/v) and the adsorption time of 2 min were used in subsequent adsorption treatments to prevent the inhibitory effect of HMF. The adsorption surface area of the activated carbon powder was 1,400-1,600 m(2)/g and showed selectivity to 5-hydroxymethyl furfural (HMF) from monosaccharides. Candida tropicalis KCTC 7212 was cultured in yeast extract, peptone, glucose, and high-salt medium, and exposed to 80, 90, 100, and 110 practical salinity unit (psu) salt concentrations in the lysates. The 100 psu salt concentration showed maximum cell growth and ethanol production. The ethanol fermentations with activated carbon treatment and use of C. tropicalis acclimated to a high salt concentration of 100 psu produced 17.9 g/l of ethanol with a yield (YEtOH) of 0.40 from E. spinosum seaweed. PMID:25649983

  15. Impact of 3,4-dideoxyglucosone-3-ene (3,4-DGE) on cytotoxicity of acidic heat-sterilized peritoneal dialysis fluid.

    PubMed

    Tomo, Tadashi; Okabe, Eiji; Yamamoto, Takashi; Namoto, Shinji; Iwashita, Tomohiko; Matsuyama, Kazuhiro; Kadota, Jun-ichi

    2007-01-01

    Of the glucose degradation products (GDPs) in glucose-rich peritoneal dialysate, we investigated the influence of 3,4-dideoxyglucosone-3-ene (3,4-DGE) on the cytotoxicity of acidic heat-sterilized peritoneal dialysis fluid (L-H PDF) using human peritoneal mesothelial cells (HPMC). We prepared acidified filtration-sterilized PDF (glucose concentration 3.86%) containing eight types of added GDP [3,4-DGE, glyoxal (GO), methylglyoxal (MGO), 3-deoxyglucosone (3-DG), formaldehyde (FA), acetaldehyde (AA), 5-hydroxymethyl-2-furaldehyde (5-HMF), and furfural (FF)] or seven types of GDP (GO, MGO, 3-DG, FA, AA, 5-HMF, and FF). HPMC were exposed to these two types of solution and acidic heat-sterilized PDF (glucose concentration 3.86%, L-H 3.86) for 4 h. Cell viability was determined by 3,(4,5-dimethythiazol-2-yl)2,5-diphenyl-terazolium bromide (MTT) assay. MTT viability was decreased significantly compared with the control when treated with L-H 3.86 or acidified neutral filtration-sterilized PDF (glucose concentration 3.86%) containing eight GDPs. However, no significant decrease in MTT viability was observed when HPMC were treated with acidified neutral filtration-sterilized PDF (glucose concentration 3.86%) containing seven GDPs. Thus, 3,4-DGE strongly affects the cytotoxicity of L-H PDF. It is suggested that the cytotoxicity of L-H PDF is based on the presence of 3,4-DGE. PMID:17380297

  16. A Novel Method for the Discrimination of Semen Arecae and Its Processed Products by Using Computer Vision, Electronic Nose, and Electronic Tongue

    PubMed Central

    Xu, Min; Yang, Shi-Long; Peng, Wei; Liu, Yu-Jie; Xie, Da-Shuai; Li, Xin-Yi; Wu, Chun-Jie

    2015-01-01

    Areca nut, commonly known locally as Semen Arecae (SA) in China, has been used as an important Chinese herbal medicine for thousands of years. The raw SA (RAW) is commonly processed by stir-baking to yellow (SBY), stir-baking to dark brown (SBD), and stir-baking to carbon dark (SBC) for different clinical uses. In our present investigation, intelligent sensory technologies consisting of computer vision (CV), electronic nose (E-nose), and electronic tongue (E-tongue) were employed in order to develop a novel and accurate method for discrimination of SA and its processed products. Firstly, the color parameters and electronic sensory responses of E-nose and E-tongue of the samples were determined, respectively. Then, indicative components including 5-hydroxymethyl furfural (5-HMF) and arecoline (ARE) were determined by HPLC. Finally, principal component analysis (PCA) and discriminant factor analysis (DFA) were performed. The results demonstrated that these three instruments can effectively discriminate SA and its processed products. 5-HMF and ARE can reflect the stir-baking degree of SA. Interestingly, the two components showed close correlations to the color parameters and sensory responses of E-nose and E-tongue. In conclusion, this novel method based on CV, E-nose, and E-tongue can be successfully used to discriminate SA and its processed products. PMID:26366185

  17. Physicochemical characterization of pure persimmon juice: nutritional quality and food acceptability.

    PubMed

    González, Eva; Vegara, Salud; Martí, Nuria; Valero, Manuel; Saura, Domingo

    2015-03-01

    Technological process for production of non-astringent persimmon (Diospyros kaki Thunb. cv. "Rojo Brillante") juice was described. The degree of fruit ripening expressed as color index (CI) varied between 12.37 and 16.33. Persimmon juice was characterized by determining physicochemical quality parameters as yield, total soluble solids (TSS), pH, titratable acidity (TA), organic acids, and main sugars. A thermal treatment of 90 ºC for 10 s was effective in controlling naturally occurring microorganisms for at least 105 d of storage without significantly affecting production of soluble brown pigments (BPs) and 5-hydroxymethyl furfural (5-HMF), total phenolic compounds (TPC), antioxidant capacity and acceptability of juice by panelists. Storage time affected all and each of the above parameters, reducing BPs, TPC and antioxidant capacity but increasing 5-HMF content. Refrigerated storage enhanced the acceptability of the juices. This information may be used by the juice industry as a starting point for production of pure persimmon juices. PMID:25619747

  18. Composting of food waste subjected to hydrothermal pretreatment and inoculated with Paecilomyces sp. FA13.

    PubMed

    Nakasaki, Kiyohiko; Mimoto, Hiroshi; Tran, Quyen Ngoc Minh; Oinuma, Akiko

    2015-03-01

    Food waste collected from restaurants, convenience stores, and food-processing factories was mixed with sawdust and subjected to hydrothermal pretreatment at 180°C for 30min to prepare compost raw material. Furan compounds such as 5-HMF (5-hydroxymethyl furfural) and furfural were produced at concentration levels of approximately 8 and 0.5mg/g-ds, respectively, through hydrothermal pretreatment. The furan compounds inhibited the activity of composting microorganisms, thus delaying the start of organic matter degradation during composting. A newly identified fungus, Paecilomyces sp. FA13, which possesses the ability to degrade furan compounds, was isolated and used as an inoculum for the composting of the raw material prepared by hydrothermal pretreatment. By inoculating the FA13 into the compost raw material at 10(5)CFU/g-ds, the degradation of furan compounds was accelerated. As a result, bacterial activity, which contributed to composting, was enhanced, significantly promoting the start of vigorous degradation of organic materials. PMID:25585259

  19. Impacts of lignocellulose-derived inhibitors on L-lactic acid fermentation by Rhizopus oryzae.

    PubMed

    Zhang, Li; Li, Xin; Yong, Qiang; Yang, Shang-Tian; Ouyang, Jia; Yu, Shiyuan

    2016-03-01

    Inhibitors generated in the pretreatment and hydrolysis of corn stover and corn cob were identified. In general, they inhibited cell growth, lactate dehydrogenase, and lactic acid production but with less or no adverse effect on alcohol dehydrogenase and ethanol production in batch fermentation by Rhizopus oryzae. Furfural and 5-hydroxymethyl furfural (HMF) were highly toxic at 0.5-1 g L(-1), while formic and acetic acids at less than 4 g L(-1) and levulinic acid at 10 g L(-1) were not toxic. Among the phenolic compounds at 1 g L(-1), trans-cinnamic acid and syringaldehyde had the highest toxicity while syringic, ferulic and p-coumaric acids were not toxic. Although these inhibitors were present at concentrations much lower than their separately identified toxic levels, lactic acid fermentation with the hydrolysates showed much inferior performance compared to the control without inhibitor, suggesting synergistic or compounded effects of the lignocellulose-degraded compounds on inhibiting lactic acid fermentation. PMID:26724548

  20. Global regulator engineering significantly improved Escherichia coli tolerances toward inhibitors of lignocellulosic hydrolysates.

    PubMed

    Wang, Jianqing; Zhang, Yan; Chen, Yilu; Lin, Min; Lin, Zhanglin

    2012-12-01

    Lignocellulosic biomass is regarded as the most viable source of feedstock for industrial biorefinery, but the harmful inhibitors generated from the indispensable pretreatments prior to fermentation remain a daunting technical hurdle. Using an exogenous regulator, irrE, from the radiation-resistant Deinococcus radiodurans, we previously showed that a novel global regulator engineering (GRE) approach significantly enhanced tolerances of Escherichia coli to alcohol and acetate stresses. In this work, an irrE library was subjected to selection under various stresses of furfural, a typical hydrolysate inhibitor. Three furfural tolerant irrE mutants including F1-37 and F2-1 were successfully obtained. The cells containing these mutants reached OD(600) levels of 4- to 16-fold of that for the pMD18T cells in growth assay under 0.2% (v/v) furfural stress. The cells containing irrE F1-37 and F2-1 also showed considerably reduced intracellular oxygen species (ROS) levels under furfural stress. Moreover, these two irrE mutants were subsequently found to confer significant cross tolerances to two other most common inhibitors, 5-hydroxymethyl-2-furaldehyde (HMF), vanillin, as well as real lignocellulosic hydrolysates. When evaluated in Luria-Bertani (LB) medium supplemented with corn stover cellulosic hydrolysate (prepared with a solid loading of 30%), the cells containing the mutants exhibited lag phases markedly shortened by 24-44 h in comparison with the control cells. This work thus presents a promising step forward to resolve the inhibitor problem for E. coli. From the view of synthetic biology, irrE can be considered as an evolvable "part" for various stresses. Furthermore, this GRE approach can be extended to exploit other exogenous global regulators from extremophiles, and the native counterparts in E. coli, for eliciting industrially useful phenotypes. PMID:22684885

  1. Field-aligned neutral wind bias correction scheme for global ionospheric modeling at midlatitudes by assimilating FORMOSAT-3/COSMIC hmF2 data under geomagnetically quiet conditions

    NASA Astrophysics Data System (ADS)

    Sun, Yang-Yi; Matsuo, Tomoko; Maruyama, Naomi; Liu, Jann-Yenq

    2015-04-01

    This study demonstrates the usage of a data assimilation procedure, which ingests the FORMOSAT-3/COSMIC (F3/C) hmF2 observations to correct the model wind biases to enhance the capability of the new global Ionosphere Plasmasphere Electrodynamics (IPE) model under geomagnetically quiet conditions. The IPE model is built upon the field line interhemispheric plasma model with a realistic geomagnetic field model and empirical model drivers. The hmF2 observed by the F3/C radio occultation technique is utilized to adjust global thermospheric field-aligned neutral winds (i.e., a component of the thermospheric neutral wind parallel to the magnetic field) at midlatitudes according to a linear relationship between time differentials of the field-aligned wind and hmF2. The adjusted winds are further applied to drive the IPE model. The comparison of the modeled electron density with the observations of F3/C and ground-based GPS receivers at the 2012 March equinox suggests that the modeled electron density can be significantly improved in the midlatitude regions of the Southern Hemisphere, if the wind correction scheme is applied. Moreover, the F3/C observation, the IPE model, and the wind bias correction scheme are applied to study the 2012 Southern Hemisphere Midlatitude Summer Nighttime Anomaly (southern MSNA)/Weddell Sea Anomaly (WSA) event at December solstice for examining the role of the neutral winds in controlling the longitudinal variation of the southern MSNA/WSA behavior. With the help of the wind bias correction scheme, the IPE model better tracks the F3/C-observed eastward movement of the southern MSNA/WSA feature. The apparent eastward movement of the southern MSNA/WSA features in the local time coordinate is primarily caused by the longitudinal variation in the declination angle of the geomagnetic field that controls the field-aligned projection of both geographic meridional and zonal components of the neutral wind. Both the IPE simulations and the F3/C

  2. Determination of carboxylic acids, carbohydrates, glycerol, ethanol, and 5-HMF in beer by high-performance liquid chromatography and UV-refractive index double detection.

    PubMed

    Castellari, M; Sartini, E; Spinabelli, U; Riponi, C; Galassi, S

    2001-06-01

    A high-performance liquid chromatographic method is proposed for the simultaneous separation of main carboxylic acids, carbohydrates, ethanol, glycerol, and 5-HMF in beer by direct injection. A column packed with a sulfonated divinyl benzene-styrene copolymer and an isocratic elution with 0.0045N sulfuric acid and acetonitrile (6%, v/v) are employed. UV and refractive index detectors connected in series are also used to reduce the matrix interference of phenolic compounds. In conditions described, nine compounds are quantitated in a single chromatographic run without any pretreatment except for sample dilution and filtration before injection. Precision, accuracy, linearity of response, limit of detection, and limit of quantitation are also evaluated for each compound. Satisfactory results are obtained to justify the application of this method to all phases of beer production for process and quality control. PMID:11396687

  3. In vitro activity of two amphotericin B formulations against Malassezia furfur strains recovered from patients with bloodstream infections.

    PubMed

    Iatta, Roberta; Immediato, Davide; Montagna, Maria Teresa; Otranto, Domenico; Cafarchia, Claudia

    2015-04-01

    Although guidelines for the treatment of Malassezia furfur fungemia are not yet defined, clinical data suggest that amphotericin B (AmB) is effective for treating systemic infections. In the absence of clinical breakpoints for Malassezia yeasts, epidemiological cut-off values (ECVs) are useful to discriminate between isolates with and without drug resistance. This study aimed to compare the distribution of minimal inhibitory concentration (MIC) and the ECVs for AmB of both deoxycholate (d-AmB) and liposomal (l-AmB) formulations of M. furfur isolates. The 84 M. furfur strains analyzed, which included 56 from blood, sterile sites and catheters, and 28 from skin, were isolated from patients with bloodstream infections. MICs were determined by the modified broth microdilution method of the Clinical and Laboratory Standards Institute (CLSI). The l-AmB MIC and the ECVs were two-fold lower than those of d-AmB and a lower l-AmB mean MIC value was found for blood isolates than from skin. The ECVs for l-AmB and d-AmB were 8 mg/l and 32 mg/l, respectively. Three strains (3.6%) showed l-AmB MIC higher than ECV (MIC > 8 mg/l) of which two were isolated from the catheter tip of patients treated with micafugin, l-Amb and fluconazole, and one from skin. The results showed that the l-AmB might be employed for assessing the in vitro antifungal susceptibility of M. furfur by a modified CLSI protocol and that ECVs might be useful for detecting the emergence of resistance. PMID:25631480

  4. Identification of furfural as a key toxin in lignocellulosic hydrolysates and evolution of a tolerant yeast strain.

    PubMed

    Heer, Dominik; Sauer, Uwe

    2008-11-01

    The production of fuel ethanol from low-cost lignocellulosic biomass currently suffers from several limitations. One of them is the presence of inhibitors in lignocellulosic hydrolysates that are released during pre-treatment. These compounds inhibit growth and hamper the production of ethanol, thereby affecting process economics. To delineate the effects of such complex mixtures, we conducted a chemical analysis of four different real-world lignocellulosic hydrolysates and determined their toxicological effect on yeast. By correlating the potential inhibitor abundance to the growth-inhibiting properties of the corresponding hydrolysates, we identified furfural as an important contributor to hydrolysate toxicity for yeast. Subsequently, we conducted a targeted evolution experiment to improve growth behaviour of the half industrial Saccharomyces cerevisiae strain TMB3400 in the hydrolysates. After about 300 generations, representative clones from these evolved populations exhibited significantly reduced lag phases in medium containing the single inhibitor furfural, but also in hydrolysate-supplemented medium. Furthermore, these strains were able to grow at concentrations of hydrolysates that effectively killed the parental strain and exhibited significantly improved bioconversion characteristics under industrially relevant conditions. The improved resistance of our evolved strains was based on their capacity to remain viable in a toxic environment during the prolonged, furfural induced lag phase. PMID:21261870

  5. Genetic polymorphism of Malassezia furfur isolates from Han and Tibetan ethnic groups in China using DNA fingerprinting.

    PubMed

    Zhang, Hao; Zhang, Ruifeng; Ran, Yuping; Dai, Yaling; Lu, Yao; Wang, Peng

    2010-12-01

    Reported isolation rates of Malassezia yeast from human skin show geographic variations. In China, the populations of the Han (1,182.95 million) and Tibetan (5.41 million) ethnic groups are distributed over 9.6 and 3.27 million square kilometers respectively, making biodiversity research feasible and convenient. Malassezia furfur clinical strains (n = 29) isolated from different individuals, with or without associated dermatoses, of these two ethnic groups (15 Han and 12 Tibetan) were identified and analyzed with DNA fingerprinting using single primers specific to minisatellites. Using the Bionumerics software, we found that almost all M. furfur clinical isolates and type strains formed five distinct group clusters according to their associated skin diseases and the ethnic groups of the patients. These findings are the first to focus on the genetic diversity and relatedness of M. furfur in the Tibetan and Han ethnic groups in China and reveal genetic variation associated with related diseases, host ethnicity and geographic origin. PMID:20507265

  6. Comparison of peak height of the F2-layer (hmF2) measurements with IRI-2012, IRI-2007 and IRI-2001 models predictions above Roquetes station (Spain) during the ascending phase of the solar cycle 24

    NASA Astrophysics Data System (ADS)

    Mohammed, Fahmi A.

    2015-09-01

    This research aims to validate IRI-2012 program and examine its accuracy in predicting peak height of the F2- layer (hmF2) above Roquetes. The seasonal hourly means of the ionosphere F2 peak height parameter (hmF2) above Roquetes station, Spain, (located at latitude close to the latitude of Iraq, 41°N) were analyzed and the results were compared with IRI-2012, IRI-2007 and IRI-2001, using CCIR (Comite´ Consultatif International des Radio Communications) option. The analysis covered quiet and disturbed days during various seasons of 2013 (the ascending phase of the solar cycle 24). In general, it is found that the predicted values of hmF2 overestimate the observed ones during all seasons, except Summer, whereas it underestimate at day hours. Also, it is found that the maximum percentage relative deviation of hmF2 occurred during Winter at 8 LT, while the minimum occurred during Autumnat 22 LT.

  7. Variation of NmF2 and hmF2 deduced from DPS-4 over Multan (Pakistan) and their comparisons with IRI-2007 & IRI-2012 during the deep solar minimum between 23rd and 24th solar cycles

    NASA Astrophysics Data System (ADS)

    Ayyaz Ameen, Muhammad; Raza, Kazim; Ayub, Muhammad

    Digisonde DPS-4 data of Multan (geog coord. 30.18(°) N, 71.48(°) E) is being reported for the first time. The variations in F2-layer peak electron density NmF2 and its height hmF2 have been studied during the deep solar minimum between 23rd and 24th solar cycles along their comparisons with International Reference Ionosphere, IRI-2007 & IRI-2012 predication. The observation results show that the NmF2 values are greater and smaller during daytime and nighttime, respectively. The hmF2 observations show sunrise peaks along with some prominent pre-sunrise peaks in some months. Seasonal variations show that the daytime NmF2 values are greater in the equinox and summer months, while the daytime hmF2 values are slightly greater in the equinox and winter months. For the comparison of observations with IRI-2007 and IRI-2012, the observed hmF2 values are closer to IRI-2007 than to IRI-2012. The NmF2 values of URSI map of IRI-2012 agree well with the observations in equinox. The IRI-2007 agrees better with the NmF2 observations for winter and summer than IRI-2012, whereas IRI-2012 is closer to the observations for equinox months. The variation in the observed parameters exhibits that the ionosphere over Multan is showing the properties of both equatorial and mid-latitude due to the location of station.

  8. Heat Activation of Phycomyces blakesleeanus Spores: Thermodynamics and Effect of Alcohols, Furfural, and High Pressure

    PubMed Central

    Thevelein, Johan M.; Van Assche, Jozef A.; Carlier, Albert R.; Heremans, Karel

    1979-01-01

    The thermodynamic parameters for the heat activation of the sporangiospores of Phycomyces blakesleeanus were determined. For the apparent activation enthalpy (ΔH#) a value of 1,151 kJ/mol was found, whereas a value of 3,644 J./°K·mol was calculated for the apparent activation entropy (ΔS#). n-Alcohols (from methanol to octanol), phenethyl alcohol, and furfural lowered the activation temperature of P. blakesleeanus spores. The heat resistance of the spores was lowered concomitantly. The effect of the alcohols was a linear function of the concentration in the range that could be applied. When the log of the concentration needed to produce an equal shift of the activation temperature was plotted for each alochol against the log of the octanol/water partition coefficient, a straight line was obtained. The free energy of adsorption of the n-alcohols to their active sites was calculated to be −2,487 J/mol of CH2 groups. Although still inconclusive, this points toward an involvement of protein in the activation process. The effect of phenethyl alcohol was similar to the effect of n-alcohols, but furfural produced a greater shift than would be expected from the value of its partition coefficient. When the heat activation of the spores was performed under high pressure, the activation temperature was raised by 2 to 4°K/1,000 atm. However, with pressures higher than 1,000 atm (1.013 × 105 kPa) the activation temperature was lowered until the pressure became lethal (more than 2,500 atm). It is known that membrane phase transition temperatures are shifted upward by about 20°K/1,000 atm and that protein conformational changes are shifted upward by 2 to 6°K/1,000 atm. Consequently, heat activation of fungal spores seems to be triggered by a protein conformational change and not by a membrane phase transition. Activation volumes of −54.1 cm3/mol at 38°C and −79.3 cm2/mol at 40°C were found for the lowering effect of high pressure on the heat activation temperature

  9. Cell Cycle-Dependent Turnover of 5-Hydroxymethyl Cytosine in Mouse Embryonic Stem Cells

    PubMed Central

    Sharif, Jafar; Endo, Takaho A.; Mishima, Yuichi; Kawakami, Toru; Koseki, Haruhiko; Shirakawa, Masahiro; Suetake, Isao; Tajima, Shoji

    2013-01-01

    Hydroxymethylcytosine in the genome is reported to be an intermediate of demethylation. In the present study, we demonstrated that maintenance methyltransferase Dnmt1 scarcely catalyzed hemi-hydroxymethylated DNA and that the hemi-hydroxymethylated DNA was not selectively recognized by the SRA domain of Uhrf1, indicating that hydroxymethylcytosine is diluted in a replication-dependent manner. A high level of 5-hydroxymethylcytosine in mouse embryonic stem cells was produced from the methylcytosine supplied mainly by de novo-type DNA methyltransferases Dnmt3a and Dnmt3b. The promoter regions of the HoxA gene cluster showed a high hydroxymethylation level whilst the methylcytosine level was quite low, suggesting that methylated CpG is actively hydroxylated during proliferation. All the results indicate that removal and production of hydroxymethylcytosine are regulated in replication-dependent manners in mouse embryonic stem cells. PMID:24340069

  10. Synergistic Effects of Alloying and Thiolate Modification in Furfural Hydrogenation over Cu-Based Catalysts.

    PubMed

    Pang, Simon H; Love, Nicole E; Medlin, J Will

    2014-12-01

    Control of bimetallic surface composition and surface modification with self-assembled monolayers (SAMs) represent two methods for modifying catalyst activity and selectivity. However, possible synergistic effects of employing these strategies in concert have not been previously explored. We investigated the effects of modifying Cu/Al2O3 catalysts by alloying with Ni and modifying with octadecanethiol (C18) SAMs, using furfural hydrogenation as a probe reaction. Incorporation of small amounts of Ni (Cu4Ni) improved catalytic activity while slightly reducing hydrogenation selectivity. Further incorporation of Ni resulted in high rates for decarbonylation and ring-opening. Modification of the Cu4Ni catalyst with C18-SAMs resulted in improvement in both the activity and hydrogenation selectivity. X-ray photoelectron spectroscopy experiments on bimetallic thin films and density functional theory calculations revealed that the C18-SAM kinetically stabilized Cu at the surface under hydrogenation conditions. These results indicate that thiolate monolayers can be used to control surface bimetallic composition to improve catalytic performance. PMID:26278941

  11. Furfural-based polymers for the sealing of reactor vessels dumped in the Arctic Kara Sea

    SciTech Connect

    HEISER,J.H.; COWGILL,M.G.; SIVINTSEV,Y.V.; ALEXANDROV,V.P.; DYER,R.S.

    1996-10-07

    Between 1965 and 1988, 16 naval reactor vessels were dumped in the Arctic Kara Sea. Six of the vessels contained spent nuclear fuel that had been damaged during accidents. In addition, a container holding {approximately} 60% of the damaged fuel from the No. 2 reactor of the atomic icebreaker Lenin was dumped in 1967. Before dumping, the vessels were filled with a solidification agent, Conservant F, in order to prevent direct contact between the seawater and the fuel and other activated components, thereby reducing the potential for release of radionuclides into the environment. The key ingredient in Conservant F is furfural (furfuraldehyde). Other constituents vary, depending on specific property requirements, but include epoxy resin, mineral fillers, and hardening agents. In the liquid state (prior to polymerization) Conservant F is a low viscosity, homogeneous resin blend that provides long work times (6--9 hours). In the cured state, Conservant F provides resistance to water and radiation, has high adhesion properties, and results in minimal gas evolution. This paper discusses the properties of Conservant F in both its cured and uncured states and the potential performance of the waste packages containing spent nuclear fuel in the Arctic Kara Sea.

  12. Theoretical and experimental differential cross sections for electron impact excitation of the electronic bands of furfural.

    PubMed

    Jones, D B; Neves, R F C; Lopes, M C A; da Costa, R F; do N Varella, M T; Bettega, M H F; Lima, M A P; García, G; Limão-Vieira, P; Brunger, M J

    2016-03-28

    We report results from a joint experimental and theoretical investigation into electron scattering from the important industrial species furfural (C5H4O2). Specifically, differential cross sections (DCSs) have been measured and calculated for the electron-impact excitation of the electronic states of C5H4O2. The measurements were carried out at energies in the range 20-40 eV, and for scattered-electron angles between 10° and 90°. The energy resolution of those experiments was typically ∼80 meV. Corresponding Schwinger multichannel method with pseudo-potential calculations, for energies between 6-50 eV and with and without Born-closure, were also performed for a sub-set of the excited electronic-states that were accessed in the measurements. Those calculations were undertaken at the static exchange plus polarisation-level using a minimum orbital basis for single configuration interaction (MOB-SCI) approach. Agreement between the measured and calculated DCSs was qualitatively quite good, although to obtain quantitative accord, the theory would need to incorporate even more channels into the MOB-SCI. The role of multichannel coupling on the computed electronic-state DCSs is also explored in some detail. PMID:27036450

  13. Furfural modified asphalt obtained by using a Lewis acid as a catalyst

    SciTech Connect

    Memon, G.M.

    1996-12-31

    Asphalt is solid or semi-solid at room temperature, becomes soft and starts flowing upon heating, and becomes hard and brittle at very low temperatures. States have been facing problems such as cracking, rutting, and asphalt adhesion to aggregates in their asphaltic pavements for years. Many polymer additives have been used in asphalt to reduce these problems, but little work has been done using chemically modified products of asphalt to attempt to solve these serious problems of asphalt pavements. The above mentioned problems decrease the life of the pavements, resulting in an increase of maintenance and/or replacement costs. There are two types of cracking which can occur in asphalt pavement; one related to load, and the other related to thermal stress. The load-related cracking is known as fatigue cracking and is defined as fracture under repeated or cyclic stress having a maximum value of less than the tensile strength of the material. The thermal cracking occurs due to pavement shrinkage at low temperature causing the shrinkage stresses to exceed the tensile strength. FHWA researchers have found furfural to be a suitable candidate for functional group modification of asphalt. The modified product shows improved performance as well as improved rheological properties.

  14. Theoretical and experimental differential cross sections for electron impact excitation of the electronic bands of furfural

    NASA Astrophysics Data System (ADS)

    Jones, D. B.; Neves, R. F. C.; Lopes, M. C. A.; da Costa, R. F.; do N. Varella, M. T.; Bettega, M. H. F.; Lima, M. A. P.; García, G.; Limão-Vieira, P.; Brunger, M. J.

    2016-03-01

    We report results from a joint experimental and theoretical investigation into electron scattering from the important industrial species furfural (C5H4O2). Specifically, differential cross sections (DCSs) have been measured and calculated for the electron-impact excitation of the electronic states of C5H4O2. The measurements were carried out at energies in the range 20-40 eV, and for scattered-electron angles between 10° and 90°. The energy resolution of those experiments was typically ˜80 meV. Corresponding Schwinger multichannel method with pseudo-potential calculations, for energies between 6-50 eV and with and without Born-closure, were also performed for a sub-set of the excited electronic-states that were accessed in the measurements. Those calculations were undertaken at the static exchange plus polarisation-level using a minimum orbital basis for single configuration interaction (MOB-SCI) approach. Agreement between the measured and calculated DCSs was qualitatively quite good, although to obtain quantitative accord, the theory would need to incorporate even more channels into the MOB-SCI. The role of multichannel coupling on the computed electronic-state DCSs is also explored in some detail.

  15. Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

    NASA Astrophysics Data System (ADS)

    McManus, Jesse R.; Vohs, John M.

    2014-12-01

    The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

  16. Lack of effect of furfural on unscheduled DNA synthesis in the in vivo rat and mouse hepatocyte DNA repair assays and in precision-cut human liver slices.

    PubMed

    Lake, B G; Edwards, A J; Price, R J; Phillips, B J; Renwick, A B; Beamand, J A; Adams, T B

    2001-10-01

    The ability of furfural to induce unscheduled DNA synthesis (UDS) in hepatocytes of male and female B6C3F(1) mice and male F344 rats after in vivo administration and in vitro in precision-cut human liver slices has been studied. Preliminary toxicity studies established the maximum tolerated dose (MTD) of furfural to be 320 and 50 mg/kg in the mouse and rat, respectively. Furfural was dosed by gavage at levels of 0 (control), 50, 175 and 320 mg/kg to male and female mice and 0, 5, 16.7 and 50 mg/kg to male rats. Hepatocytes were isolated by liver perfusion either 2-4 h or 12-16 h after treatment, cultured in medium containing [3H]thymidine for 4 h and assessed for UDS by grain counting of autoradiographs. Furfural treatment did not produce any statistically significant increase or any dose-related effects on UDS in mouse and rat hepatocytes either 2-4 h or 12-16 h after dosing. In contrast, UDS was markedly induced in mice and rats 2-4 h after treatment with 20 mg/kg dimethylnitrosamine and 12-16 h after treatment of mice and rats with 200 mg/kg o-aminoazotoluene and 50 mg/kg 2-acetylaminofluorene (2-AAF), respectively. Precision-cut human liver slices from four donors were cultured for 24 h in medium containing [3H]thymidine and 0-10 mM furfural. Small increases in the net grain count (i.e. nuclear grain count less mean cytoplasmic grain count) observed with 2-10 mM furfural were not due to any increase in the nuclear grain count. Rather, it was the result of concentration-dependent decreases in the mean cytoplasmic grain counts and to a lesser extent in nuclear grain counts, due to furfural-induced cytotoxicity. In contrast, marked increases in UDS (both net grain and nuclear grain counts) were observed in human liver slices treated with 0.02 and 0.05 mM 2-AAF, 0.002 and 0.02 mM aflatoxin B(1) and 0.005 and 0.05 mM 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine. This study demonstrates that furfural does not induce UDS in the hepatocytes of male and female B6C3F

  17. Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

    NASA Astrophysics Data System (ADS)

    Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

    2016-06-01

    Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g‑1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.

  18. Production of furfural from xylose, water-insoluble hemicelluloses and water-soluble fraction of corncob via a tin-loaded montmorillonite solid acid catalyst.

    PubMed

    Li, Huiling; Ren, Junli; Zhong, Linjie; Sun, Runcang; Liang, Lei

    2015-01-01

    The conversion of xylose, water-insoluble hemicelluloses (WIH) and water-soluble fraction (WSF) of corncob to furfural was performed using montmorillonite with tin ions (Sn-MMT) containing double acid sites as a solid acid catalyst. The co-existence of Lewis acids and Brønsted acids in Sn-MMT was shown to improve the furfural yield and selectivity. 76.79% furfural yield and 82.45% furfural selectivity were obtained from xylose using Sn-MMT as a catalyst in a biphasic system with 2-s-butylphenol (SBP) as the organic extracting layer and dimethyl sulfoxide (DMSO) as the co-solvent in contact with an aqueous phase saturated with NaCl (SBP/NaCl-DMSO) at 180°C for 30min. Furthermore, Sn-MMT also demonstrated the excellent catalytic performance in the conversion of pentose-rich materials of corncob and 39.56% and 54.15% furfural yields can be directly obtained from WIH and WSF in the SBP/NaCl-DMSO system, respectively. PMID:25461009

  19. Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water.

    PubMed

    Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

    2016-01-01

    Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m(2) g(-1) were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction. PMID:27328834

  20. Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

    PubMed Central

    Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

    2016-01-01

    Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction. PMID:27328834

  1. NmF2 and hmF2 measurements at 95° E and 127° E around the EIA northern crest during 2010-2014

    NASA Astrophysics Data System (ADS)

    Kalita, Bitap Raj; Bhuyan, Pradip Kumar; Yoshikawa, Akimasa

    2015-11-01

    The characteristics of the F2 layer parameters NmF2 and hmF2 over Dibrugarh (27.5° N, 95° E, 17° N geomagnetic, 43° dip) measured by a Canadian Advanced Digital Ionosonde (CADI) for the period of August 2010 to July 2014 are reported for the first time from this low mid-latitude station lying within the daytime peak of the longitudinal wave number 4 structure of equatorial anomaly (EIA) around the northern edge of anomaly crest. Equinoctial asymmetry is clearly observed at all solar activity levels whereas the midday winter anomaly is observed only during high solar activity years and disappears during the temporary dip in solar activity in 2013 but forenoon winter anomaly can be observed even at moderate solar activity. The NmF2/hmF2 variations over Dibrugarh are compared with that of Okinawa (26.5° N, 127° E, 17° N geomagnetic), and the eastward propagation speed of the wave number 4 longitudinal structure from 95° E to 127° E is estimated. The speed is found to be close to the theoretical speed of the wave number 4 (WN4) structure. The correlation of daily NmF2 over Dibrugarh and Okinawa with solar activity exhibits diurnal and seasonal variations. The highest correlation in daytime is observed during the forenoon hours in equinox. The correlation of daily NmF2 (linear or non-linear) with solar activity exhibits diurnal variation. A tendency for amplification with solar activity is observed in the forenoon and late evening period of March equinox and the postsunset period of December solstice. NmF2 saturation effect is observed only in the midday period of equinox. Non-linear variation of neutral composition at higher altitudes and variation of recombination rates with solar activity via temperature dependence may be related to the non-linear trend. The noon time maximum NmF2 over Dibrugarh exhibits better correlation with equatorial electrojet (EEJ) than with solar activity and, therefore, new low-latitude NmF2 index is proposed taking both solar

  2. Effects of Soluble Lignin on the Formic Acid-Catalyzed Formation of Furfural: A Case Study for the Upgrading of Hemicellulose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2016-03-01

    A comprehensive study is presented on the conversion of hemicellulose sugars in liquors obtained from the fractionation of Miscanthus, spruce bark, sawdust, and hemp by using formic acid. Experimental tests with varying temperature (130-170 °C), formic acid concentration (10-80 wt%), carbohydrate concentrations, and lignin separation were carried out, and experimental data were compared with predictions obtained by reaction kinetics developed in a previous study. The conversions of xylose and arabinose into furfural were inherently affected by the presence of polymeric soluble lignin, decreasing the maximum furfural yields observed experimentally by up to 24%. These results were also confirmed in synthetic mixtures of pentoses with Miscanthus and commercial alkali lignin. This observation was attributed to side reactions involving intermediate stable sugar species reacting with solubilized lignin during the conversion of xylose into furfural. PMID:26805656

  3. In vitro antifungal activity of extracts obtained from Hypericum perforatum adventitious roots cultured in a mist bioreactor against planktonic cells and biofilm of Malassezia furfur.

    PubMed

    Simonetti, Giovanna; Tocci, Noemi; Valletta, Alessio; Brasili, Elisa; D'Auria, Felicia Diodata; Idoux, Alicia; Pasqua, Gabriella

    2016-01-01

    Xanthone-rich extracts from Hypericum perforatum root cultures grown in a Mist Bioreactor as antifungal agents against Malassezia furfur. Extracts of Hypericum perforatum roots grown in a bioreactor showed activity against planktonic cells and biofilm of Malassezia furfur. Dried biomass, obtained from roots grown under controlled conditions in a ROOTec mist bioreactor, has been extracted with solvents of increasing polarity (i.e. chloroform, ethyl acetate and methanol). The methanolic fraction was the richest in xanthones (2.86 ± 0.43 mg g(-1) DW) as revealed by HPLC. The minimal inhibitory concentration of the methanol extract against M. furfur planktonic cells was 16 μg mL(-1). The inhibition percentage of biofilm formation, at a concentration of 16 μg mL(-1), ranged from 14% to 39%. The results show that H. perforatum root extracts could be used as new antifungal agents in the treatment of Malassezia infections. PMID:26166743

  4. Investigation of thermochemistry associated with the carbon-carbon coupling reactions of furan and furfural using ab initio methods.

    PubMed

    Liu, Cong; Assary, Rajeev S; Curtiss, Larry A

    2014-06-26

    Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons. PMID:24902118

  5. Vibrational spectra of partially oriented molecules having two conformers in nematic and isotropic solutions: furfural and 2-chlorobenzaldehyde

    NASA Astrophysics Data System (ADS)

    Rogojerov, M.; Keresztury, G.; Jordanov, B.

    2005-05-01

    Vibrational analysis of the two conformers of furfural and 2-chlorobenzaldehyde has been carried out on the basis of their IR and Raman spectra measured in isotropic and anisotropic (nematic liquid crystalline) solvent. The average orientation of the individual conformers in the nematic solvent has been determined by means of a recently developed approach for low symmetry planar molecules using DFT calculations of the vibrational transitions moments. The complex shape of the carbonyl band additionally split into several components is interpreted as an effect of Fermi resonance.

  6. A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation

    DOE PAGESBeta

    Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei; Wang, Lin -Lin; Gustafson, Jeffrey; Pei, Yuchen; Qi, Zhiyuan; Johnson, Duane D.; Zhang, Shiran; Tao, Franklin; et al

    2016-01-28

    In this paper, intermetallic compounds are garnering increasing attention as efficient catalysts for improved selectivity in chemical processes. Here, using a ship-in-a-bottle strategy, we synthesize single-phase platinum-based intermetallic nanoparticles (NPs) protected by a mesoporous silica (mSiO2) shell by heterogeneous reduction and nucleation of Sn, Pb, or Zn in mSiO2-encapsulated Pt NPs. For selective hydrogenation of furfural to furfuryl alcohol, a dramatic increase in activity and selectivity is observed when intermetallic NPs catalysts are used in comparison to Pt@mSiO2. Among the intermetallic NPs, PtSn@mSiO2 exhibits the best performance, requiring only one-tenth of the quantity of Pt used in Pt@mSiO2 for similarmore » activity and near 100% selectivity to furfuryl alcohol. A high-temperature oxidation–reduction treatment easily reverses any carbon deposition-induced catalyst deactivation. X-ray photoelectron spectroscopy shows the importance of surface composition to the activity, whereas density functional theory calculations reveal that the enhanced selectivity on PtSn compared to Pt is due to the different furfural adsorption configurations on the two surfaces.« less

  7. Efficient solid acid catalyst containing Lewis and Brønsted Acid sites for the production of furfurals.

    PubMed

    Mazzotta, Michael G; Gupta, Dinesh; Saha, Basudeb; Patra, Astam K; Bhaumik, Asim; Abu-Omar, Mahdi M

    2014-08-01

    Self-assembled nanoparticulates of porous sulfonated carbonaceous TiO2 material that contain Brønsted and Lewis acidic sites were prepared by a one-pot synthesis method. The material was characterized by XRD, FTIR spectroscopy, NH3 temperature-programmed desorption, pyridine FTIR spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, N2 -sorption, atomic absorbance spectroscopy, and inductively coupled plasma optical emission spectroscopy. The carbonaceous heterogeneous catalyst (Glu-TsOH-Ti) with a Brønsted-to-Lewis acid density ratio of 1.2 and more accessible acid sites was effective to produce 5-hydroxymethylfurfural and furfural from biomass-derived mono- and disaccharides and xylose in a biphasic solvent that comprised water and biorenewable methyltetrahydrofuran. The catalyst was recycled in four consecutive cycles with a total loss of only 3 % activity. Thus, Glu-TsOH-Ti, which contains isomerization and dehydration catalytic sites and is based on a cheap and biorenewable carbon support, is a sustainable catalyst for the production of furfurals, platform chemicals for biofuels and chemicals. PMID:24807741

  8. Main and interaction effects of acetic acid, furfural, and p-hydroxybenzoic acid on growth and ethanol productivity of yeasts

    SciTech Connect

    Palmqvist, E.; Grage, H.; Meinander, N.Q.; Hahn-Haegerdal, B.

    1999-04-05

    The influence of the factors acetic acid, furfural, and p-hydroxybenzoic acid on the ethanol yield (Y{sub EtOH}) of Saccharomyces cerevisiae, bakers` yeast, S. cerevisiae ATCC 96581, and Candida shehatae NJ 23 was investigated using a 2{sup 3}-full factorial design with 3 centerpoints. The results indicated that acetic acid inhibited the fermentation by C. shehatae NJ 23 markedly more than by bakers` yeast, whereas no significant difference in tolerance towards the compounds was detected between the S. cerevisiae strains. Furfural and the lignin derived compound p-hydroxybenzoic acid did not affect any of the yeasts at the cell mass concentration used. The results indicated that the linear model was not adequate to describe the experimental data. Based on the results from the 2{sup 3}-full factorial experiment, an extended experiment was designed based on a central composite design to investigate the influence of the factors on the specific growth rate ({mu}), biomass yield (Y{sub x}), volumetric ethanol productivity (Q{sub EtOH}), and Y{sub EtOH}. Bakers` yeast was chosen in the extended experiment due to its better tolerance towards acetic acid, which makes it a more interesting organism for use in industrial fermentations of lignocellulosic hydrolysates.

  9. Monitoring of Low Levels of Furfural in Power Transformer Oil with a Sensor System Based on a POF-MIP Platform

    PubMed Central

    Cennamo, Nunzio; De Maria, Letizia; D’Agostino, Girolamo; Zeni, Luigi; Pesavento, Maria

    2015-01-01

    In this work an innovative, miniaturized and low cost optical chemical sensor (POF-MIP platform), based on a molecular imprinted polymer (MIP) and surface plasmon resonance in a plastic optical fiber (POF), is presented and preliminarily tested for monitoring of furfural (furan-2-carbaldehyde) in transformer oil. To this end, the optical platform was coupled to an MIP layer, highly selective for furfural. The ability of the developed sensor to directly detect furfural in the insulating oil was investigated. The detection limit of the sensor has been found to be 9 ppb, with a linear response up to about 30 ppb. However there is a sensible response up to 0.15 ppm. Because of the small linearity range, the Hill equation is suggested for the quantification. The sensor has been effectively tested in real oil samples collected from aged electrical equipment removed from service. The assessed concentration of furfural is in good agreement with that evaluated by a high pressure liquid chromatography (HLPC) method, confirming the good selectivity of the proposed sensor. PMID:25871719

  10. Monitoring of low levels of furfural in power transformer oil with a sensor system based on a POF-MIP platform.

    PubMed

    Cennamo, Nunzio; De Maria, Letizia; D'Agostino, Girolamo; Zeni, Luigi; Pesavento, Maria

    2015-01-01

    In this work an innovative, miniaturized and low cost optical chemical sensor (POF-MIP platform), based on a molecular imprinted polymer (MIP) and surface plasmon resonance in a plastic optical fiber (POF), is presented and preliminarily tested for monitoring of furfural (furan-2-carbaldehyde) in transformer oil. To this end, the optical platform was coupled to an MIP layer, highly selective for furfural. The ability of the developed sensor to directly detect furfural in the insulating oil was investigated. The detection limit of the sensor has been found to be 9 ppb, with a linear response up to about 30 ppb. However there is a sensible response up to 0.15 ppm. Because of the small linearity range, the Hill equation is suggested for the quantification. The sensor has been effectively tested in real oil samples collected from aged electrical equipment removed from service. The assessed concentration of furfural is in good agreement with that evaluated by a high pressure liquid chromatography (HLPC) method, confirming the good selectivity of the proposed sensor. PMID:25871719

  11. Conversion of xylan, d-xylose and lignocellulosic biomass into furfural using AlCl3 as catalyst in ionic liquid.

    PubMed

    Zhang, Luxin; Yu, Hongbing; Wang, Pan; Dong, Heng; Peng, Xinhong

    2013-02-01

    In order to define a new green catalytic pathway for the production of furfural, the catalyzed conversion of xylan into furfural in 1-butyl-3-methylimidazolium chloride was studied by using mineral acids and metal chlorides as catalysts under microwave irradiation. Amongst these catalysts, AlCl(3) resulted in the highest furfural yield of 84.8% at 170°C for 10s. The effect of AlCl(3) on the conversion efficiency of d-xylose and untreated lignocellulosic biomass was also investigated, the yields of furfural from corncob, grass and pine wood catalyzed by AlCl(3) in [BMIM]Cl were in the range of 16-33%. [BMIM]Cl and AlCl(3) could be recycled for four runs with stable catalytic activity. AlCl(3) is less corrosive than mineral acids, and the use of ionic liquid as reaction medium will no longer generate toxic wastewater, thus this reaction system is more ecologically viable. PMID:23306118

  12. Tuning the synthesis of platinum-copper nanoparticles with a hollow core and porous shell for the selective hydrogenation of furfural to furfuryl alcohol

    NASA Astrophysics Data System (ADS)

    Huang, Shuangshuang; Yang, Nating; Wang, Shibin; Sun, Yuhan; Zhu, Yan

    2016-07-01

    Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol.Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03894h

  13. Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Transfer hydrogenation and hydrodeoxygenation of model bio-oil compounds (p-cresol and furfural) and bio-oils derived from biomass via traditional pyrolysis and tail-gas reactive pyrolysis (TGRP) were conducted. Mild batch reaction conditions were employed, using isopropanol as a hydrogen donor over...

  14. Differentially expressed genes associated with tryptophan-dependent pigment synthesis in Malassezia furfur--a comparison with the recently published genome of Malassezia globosa.

    PubMed

    Lang, S K; Hort, W; Mayser, P

    2011-07-01

    Malassezia (M.) furfur, a commensal organism found on the human skin, produces a wide range of pigments and fluorochromes when cultured with tryptophan as a sole nitrogen source. Some compounds of this pigment metabolism may provide an explanation for clinical characteristics of pityriasis versicolor (PV), a frequent skin disease in humans characterised by long-lasting pigmentary changes. Malassezia globosa is currently regarded as the causative agent of PV, but tryptophan-dependent pigment production has not yet been demonstrated in this species. In a previous study, we identified M. furfur genes that were differentially expressed 3 and 5 h, respectively, after induction of tryptophan-dependent pigment production. The recent publication of the genome of M. globosa prompted us to check the M. furfur sequences for homologues in M. globosa. The 3-h pool contained 79 sequences and the 5-h pool contained 91 sequences. A translated vs. translated BLAST search resulted in 62 sequences (78%) of the 3-h pool and 61 sequences (67%) of the 5-h pool showing similarity to a sequence from M. globosa. It appears that M. globosa possesses homologues to most of the genes that are differentially expressed during pigment production in M. furfur. PMID:20202114

  15. Culture conditions supporting inhibitor tolerance and rapid production of ethanol by P. stipitis NRRL Y-7124

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To expand the biomass to fuel ethanol industry, process strategies are needed to foster the production and utilization of microorganisms which can survive and ferment hexose and pentose sugars while exposed to inhibitors (such as ethanol, furfural, and hydroxymethylfurfural (HMF)). Furfural and HMF...

  16. Subacute (28-day) toxicity of furfural in Fischer 344 rats: a comparison of the oral and inhalation route.

    PubMed

    Arts, Josje H E; Muijser, Hans; Appel, Marko J; Frieke Kuper, C; Bessems, Jos G M; Woutersen, Ruud A

    2004-09-01

    The subacute oral and inhalation toxicity of furfural vapour was studied in Fischer 344 rats to investigate whether route-to-route extrapolation could be employed to derive the limit value for inhalation exposure from oral toxicity data. Groups of 5 rats per sex were treated by gavage daily for 28 days at dose levels of 6-192 mg/kg bw/day, or exposed by inhalation to concentrations of 20-1280 mg/m3 (6 h/day, 5 days/week) or 160-1280 mg/m3 (3 h/day, 5 days/week) for 28 days. Controls received vehicle (corn oil) or were exposed to clean air. Daily oral treatment with the highest dose of furfural (initially 192 mg/kg bw/day, later reduced to 144 mg/kg bw/day and finally to 120 mg/kg bw/day) resulted in mortality, and in increases in absolute and relative kidney and liver weight in surviving females of this group. Exposure of rats by inhalation for 6 h/day, 5 days/week for 28 days induced mortality at concentrations of 640 mg/m3 and above within 1-8 days. At 640 mg/m3 (3 h/day) and at 320 mg/m3 (3 and 6 h/day) and below, however, exposure was tolerated without serious clinical effects. In contrast, histopathological nasal changes were seen even at the lowest concentration of 20 mg/m3. With increasing exposure concentration, the nasal effects increased in incidence and severity and also expanded from the anterior part to the posterior part, including the olfactory epithelium. It was concluded that the no-observed-adverse-effect level (NOAEL) for oral toxicity was 96 mg/kg bw/day. The NOAEL for systemic inhalation toxicity was comparable, i.e. 92 mg/kg bw/day (corresponding to 320 mg/m3 (6 h/day) or 640 mg/m3 (3 h/day)) assuming 100% absorption. The presence of the histopathological nasal changes at the lowest tested concentration of 20 mg/m3 (corresponding to 6 mg/kg bw/day) proves that for locally acting substances like furfural extrapolation from the oral to the inhalation route is not valid. PMID:15234069

  17. Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts.

    PubMed

    Li, Jiang; Liu, Jun-Ling; Zhou, Hong-Jun; Fu, Yao

    2016-06-01

    Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen-iron species, the presence of crystallized Fe2 O3 phase, and the pore structure change were the main reasons for catalyst deactivation. PMID:27144965

  18. Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes.

    PubMed

    Bataev, Vadim A; Pupyshev, Vladimir I; Godunov, Igor A

    2016-05-15

    The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem. PMID:26971025

  19. Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes

    NASA Astrophysics Data System (ADS)

    Bataev, Vadim A.; Pupyshev, Vladimir I.; Godunov, Igor A.

    2016-05-01

    The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem.

  20. Fluorescence excitation-emission matrix spectroscopy as a tool for determining quality of sparkling wines.

    PubMed

    Elcoroaristizabal, Saioa; Callejón, Raquel M; Amigo, Jose M; Ocaña-González, Juan A; Morales, M Lourdes; Ubeda, Cristina

    2016-09-01

    Browning in sparkling wines was assessed by the use of excitation-emission fluorescence spectroscopy combined with PARAllel FACtor analysis (PARAFAC). Four different cava sparkling wines were monitored during an accelerated browning process and subsequently storage. Fluorescence changes observed during the accelerated browning process were monitored and compared with other conventional parameters: absorbance at 420nm (A420) and the content of 5-hydroxymethyl-2-furfural (5-HMF). A high similarity of the spectral profiles for all sparkling wines analyzed was observed, being explained by a four component PARAFAC model. A high correlation between the third PARAFAC factor (465/530nm) and the commonly used non-enzymatic browning indicators was observed. The fourth PARAFAC factor (280/380nm) gives us also information about the browning process following a first order kinetic reaction. Hence, excitation-emission fluorescence spectroscopy, together with PARAFAC, provides a faster alternative for browning monitoring to conventional methods, as well as useful key indicators for quality control. PMID:27041327

  1. Caramelization of maltose solution in presence of alanine.

    PubMed

    Fadel, H H M; Farouk, A

    2002-01-01

    Two solutions of maltose in water were used to prepare caramels. Alanine as a catalyst was added to one of these solutions. The caramelization was conducted at 130 degrees C for total time period 90 minutes. Convenient samples were taken of each caramel solution every 30 min and subjected to sensory analysis and isolation of volatile components. The odour and colour sensory tests were evaluated according to the international standard methods (ISO). The results showed that, the presence of alanine gave rise to a high significant (P < 0.01) decrease in acid attributes and remarkable increase in the sweet and caramel attributes, which are the most important caramel notes. On the other hand the increase in heating time in presence of alanine as a catalyst resulted in a high significant (P < 0.01) increase in the browning rate of caramel solution. The new technique Solid Phase Micro Extraction (SPME) was used for trapping the volatile components in the headspace of each caramel samples followed by thermal desorption and GC and GC - MS analysis. The 5-hydroxymethyl-2-furfural (HMF), the main characteristic caramel product, showed its highest value in sample containing alanine after heating for 60 minutes. The best sensory results of the sample contains alanine were confirmed by the presence of high concentrations of the most potent odorants of caramel besides to the formation of some volatile compounds have caramel like flavours such as 2-acetyl pyrrole, 2-furanones and 1-(2-furanyl)1,2-propandione. PMID:12395187

  2. [Simultaneous determination of 11 constituents in Citrus reticulate 'Chachi' by high performance liquid chromatography].

    PubMed

    Ye, Xiaolan; Song, Fenyun; Fan, Guorong; Wu, Fuhai

    2015-04-01

    An HPLC method was developed for the simultaneous determination of 11 constituents, 5-hydroxymethyl furfural (5-HMF), vicenin-2, hesperidin, hesperetin, isosinensetin, sinensetin, tetramethyl-O-isoscutellarein (TEOS), nobiletin, 3, 5, 6, 7, 8, 3', 4'-heptamethoxy- flavone (HEPTA), tangeretin, 5-demethylnobiletin in Citrus reticulate 'Chachi'. The separation was conducted on a Hanbon Benatach C18 column (250 mm x 4.6 mm, 5 µm) with acetonitrile and 0.2% formic acid as mobile phases with gradient elution. The flow rate was 1.0 mL/min. The detection wavelength was 280 nm. The column temperature was 25 °C. The results showed that the correlation coefficients (r) between concentration and chromatographic peak area of the 11 constituents were over 0.998 in the selected linear ranges. The limits of detection (LODs, S/N = 3) and limits of quantification (LOQs, S/N = 10) of the 11 constituents were in the range of 0.0125-1.25 mg/L and 0.0502-4.99 mg/L, respectively. The average recoveries (n = 3) of the 11 constituents were in the range of 96.4%-102.4% and the RSDs were 0.25%-4.01%. The developed method has been successfully applied for the analysis of eight samples from different cultivation regions in Guangdong Province. This method is simple, accurate and effective for the simultaneous determination of the 11 components, and suitable for the quality control of Citrus reticulate 'Chachi'. PMID:26292415

  3. Analysis of volatile compounds of Malaysian Tualang (Koompassia excelsa) honey using gas chromatography mass spectrometry.

    PubMed

    Nurul Syazana, M S; Gan, S H; Halim, A S; Shah, Nurul Syazana Mohamad; Gan, Siew Hua; Sukari, Halim Ahmad

    2013-01-01

    The constituents of honey's volatile compounds depend on the nectar source and differ depending on the place of origin. To date, the volatile constituents of Tualang honey have never been investigated. The objective of this study was to analyze the volatile compounds in local Malaysian Tualang honey. A continuous extraction of Tualang honey using five organic solvents was carried out starting from non-polar to polar solvents and the extracted samples were analysed using gas chromatography-mass spectrometry (GC-MS). Overall, 35 volatile compounds were detected. Hydrocarbons constitute 58.5% of the composition of Tualang honey. Other classes of chemical compounds detected included acids, aldehydes, alcohols, ketones, terpenes, furans and a miscellaneous group. Methanol yielded the highest number of extracted compounds such as acids and 5-(Hydroxymethyl) furfural (HMF). This is the first study to describe the volatile compounds in Tualang honey. The use of a simple one tube, stepwise, non-thermal liquid-liquid extraction of honey is a advantageous as it prevents sample loss. Further research to test the clinical benefits of these volatile compounds is recommended. PMID:24146441

  4. [Comparison of chemical composition between raw and vinegar-baked Paeoniae Radix Alba using NMR based metabolomic approach].

    PubMed

    Li, Zhen-Yu; Fan, Ma-Li; Qin, Xue-Mei

    2015-02-01

    To compare the chemical change of Paeoniae Radix Alba (PRA) after vinegar-baking processing, as well as the effect of vinegar types exerted on the processing, 1H NMR-based metabolomic approach combined with multivariate statistical analysis was used to investigate the different metabolites between the raw and two vinegar-baked PRA. More than thirty metabolites were identified in the 1H NMR spectrum of PRA, and the multivariate statistical analysis showed that raw and two vinegar-baked PRA could be separated obviously. After vinegar-baking, the contents of isoleucine, lactate, alanine, arginine, albiflorin, and 5-hydroxymethyl furfural (5-HMF) elevated, while those of sucrose, paeoniflorin and its analogues (calculated by benzoate) decreased. The chemical compositions of two vinegar-baked PRA were also different. Shanxi vinegar- baked PRA showed higher levels of leucine, isoleucine, valine, and albiflorin, while rice vinegar-baked PRA contained more sucrose and paeoniflorin's analogues (calculated by benzoate). And the chemical changes in Shanxi vinegar-baked PRA were greater than those of rice vinegar-baked PRA. The results revealed the chemical differences between raw and vinegar-baked PRA, as well as the influence of vinegar type on processing, in a holistic manner, the results obtained suggested that the correlations between the chemical change and the drug action after processing, as well as the vinegar type used in processing, should be further studied. PMID:25975031

  5. Biodiversity of Salix spp. honeydew and nectar honeys determined by RP-HPLC and evaluation of their antioxidant capacity.

    PubMed

    Tuberoso, Carlo I G; Jerković, Igor; Bifulco, Ersilia; Marijanović, Zvonimir

    2011-05-01

    Rare unifloral willow (Salix spp.) honeys obtained from nectar or honeydew were investigated by direct RP-HPLC-DAD method in order to identify and quantify compounds that can be used as possible markers of their origin. Antioxidant and antiradical activities of willow honeys were evaluated using FRAP (=ferric reducing antioxidant assay) and DPPH (=1,1-diphenyl-2-picrylhydrazyl radical) tests, respectively. Also HMF (=5-(hydroxymethyl)furfural), diastase activity, and CIE L*a*b*C*h* chromatic coordinates were evaluated. Abscisic acids (ABA) are typical of willow nectar honey, with a predominance of (Z,E)-ABA on (E,E)-ABA (98.2 and 31.7 mg/kg, resp.). Kinurenic acid and salicylic acid are useful to mark willow honeydew honey. The proposed HPLC-DAD method proved to be easy and reliable to identify the two different Salix spp. honeys, being not affected from any sample preparation artifact. Total antioxidant activity measured with the FRAP assay ranged from 3.2 to 12.6 mmol Fe(2+) /kg, and the antiradical activity measured with the DPPH assay ranged from 0.6 to 3.0 mmol TEAC (=Trolox equivalent antioxidant capacity)/kg in nectar and honeydew honeys, respectively. Salix spp. nectar and honeydew honeys proved to be two completely different honeys, because, besides color attributes, they show different antioxidant properties and specific compounds. PMID:21560235

  6. Modulation of Perfusion and Oxygenation by Red Blood Cell Oxygen Affinity during Acute Anemia

    PubMed Central

    Cabrales, Pedro; Tsai, Amy G.; Intaglietta, Marcos

    2008-01-01

    Responses to exchange transfusion using red blood cells (RBCs) with modified hemoglobin (Hb) oxygen (O2) affinity were studied in the hamster window chamber model during acute anemia to determine its role on microvascular perfusion and tissue oxygenation. Allosteric effectors were introduced in the RBCs by electroporation. Inositol hexaphosphate (IHP) and 5-hydroxymethyl-2-furfural (5HMF) were used to decrease and increase Hb-O2 affinity. In vitro P50s (partial pressure of O2 at 50% Hb saturation) were modified to 10, 25, 45, and 50 mm Hg (normal P50 is 32 mm Hg). Allosteric effectors also decreased the Hill coefficient. Anemic condition was induced by isovolemic hemodilution exchanges using 6% dextran 70 kD to 18% hematocrit (Hct). Modified RBCs (at 18% Hct in 5% albumin solution) were infused by exchange transfusion of 35% of blood volume. Systemic parameters, microvascular perfusion, capillary perfusion (functional capillary density, FCD), and microvascular Po2 levels were measured. RBcs with P50 of 45 mm Hg increased tissue Po2 and decreased O2 delivery (Do2) and extraction (Vo2) and RBCs with P50 of 60 mmHg reduced FCD, microvascular flow, tissue Po2, Do2 and Vo2. Erythrocytes with increased Hb-O2 affinity maintained hemodynamic conditions, Do2 and decreased tissue Po2. This study shows that in an anemic condition, maximal tissue Po2 does not correspond to maximal Do2 and Vo2. PMID:17884988

  7. Hydrothermal Syntheses of Colloidal Carbon Spheres from Cyclodextrins

    SciTech Connect

    Shin, Yongsoon; Wang, Li Q.; Bae, In-Tae; Arey, Bruce W.; Exarhos, Gregory J.

    2008-09-18

    Colloidal carbon spheres have been prepared from aqueous alpha-, beta-, and gamma-cyclodextrin (CD) solutions in closed systems under hydrothermal conditions at 160 oC. Both liquid and solid-state 13C NMR spectra taken for samples at different reaction times have been used to monitor the dehydration and carbonization pathways. CD slowly hydrolyzes to glucose and forms 5-hydroxymethyl furfural (HMF) followed by carbonization into colloidal carbon spheres. The isolated carbon spheres are 70-150 nm in diameter, exhibit a core-shell structure, and are comprised of a condensed core (C=C) peppered with resident chemical functionalities including carboxylate and hydroxyl groups. Evidence from 13C solid-state NMR and FT-IR spectra reveal that the evolving carbon spheres show a gradual increase in the amount of aromatic carbon as a function of reaction time and that the carbon spheres generated from gamma-CD contain significantly higher aromatic carbon than those derived from alpha- and beta-CD.

  8. Impact of caramelization on the glass transition temperature of several caramelized sugars. Part II: Mathematical modeling.

    PubMed

    Jiang, Bin; Liu, Yeting; Bhandari, Bhesh; Zhou, Weibiao

    2008-07-01

    Further to part I of this study, this paper discusses mathematical modeling of the relationship between caramelization of several sugars including fructose, glucose, and sucrose and their glass transition temperatures ( T g). Differential scanning calorimetry (DSC) was used for creating caramelized sugar samples and determining their glass transition temperatures ( T g). UV-vis absorbance measurement and high-performance liquid chromatography (HPLC) analysis were used for quantifying the extent of caramelization. Specifically, absorbances at 284 and 420 nm were obtained from UV-vis measurement, and the contents of sucrose, glucose, fructose, and 5-hydroxymethyl-furfural (HMF) in the caramelized sugars were obtained from HPLC measurements. Results from the UV and HPLC measurements were correlated with the Tg values measured by DSC. By using both linear and nonlinear regressions, two sets of mathematical models were developed for the prediction of Tg values of sugar caramels. The first set utilized information obtained from both UV-vis measurement and HPLC analysis, while the second set utilized only information from the UV-vis measurement, which is much easier to perform in practice. As a caramelization process is typically characterized by two stages, separate models were developed for each of the stages within a set. Furthermore, a third set of nonlinear equations were developed, serving as criteria to decide at which stage a caramelized sample is. The models were evaluated through a validation process. PMID:18553880

  9. Kinetic study of the thermal hydrolysis of Agave salmiana for mezcal production.

    PubMed

    Garcia-Soto, M J; Jimenez-Islas, H; Navarrete-Bolanos, J L; Rico-Martinez, R; Miranda-Lopez, R; Botello-Alvarez, J E

    2011-07-13

    The kinetics of the thermal hydrolysis of the fructans of Agave salmiana were determined during the cooking step of mezcal production in a pilot autoclave. Thermal hydrolysis was achieved at different temperatures and cooking times, ranging from 96 to 116 °C and from 20 to 80 h. A simple kinetic model of the depolymerization of fructans to monomers and other reducing sugars and of the degradation of reducing sugars to furans [principally 5-(hydroxymethyl)furfural, HMF] was developed. From this model, the rate constants of the reactions were calculated, as well as the pre-exponential factors and activation energies of the Arrhenius equation. The model was found to fit the experimental data well. The tradeoff between a maximum fructan hydrolysis and a critical furan concentration in allowing for the best ethanol yield during fermentation was investigated. The results indicated that the thermal hydrolysis of agave was optimal, from the point of view of ethanol yield in the ensuing fermentation, in the temperature range of 106-116 °C and the cooking range time of 6-14 h. The optimal conditions corresponded to a fructan hydrolysis of 80%, producing syrups with furan and reducing sugar concentrations of 1 ± 0.1 and 110 ± 10 g/L, respectively. PMID:21604807

  10. Furfural Production from d-Xylose and Xylan by Using Stable Nafion NR50 and NaCl in a Microwave-Assisted Biphasic Reaction.

    PubMed

    Le Guenic, Sarah; Gergela, David; Ceballos, Claire; Delbecq, Frederic; Len, Christophe

    2016-01-01

    Pentose dehydration and direct transformation of xylan into furfural were performed in a water-cyclopentyl methyl ether (CPME) biphasic system under microwave irradiation. Heated up between 170 and 190 °C in the presence of Nafion NR50 and NaCl, d-xylose, l-arabinose and xylan gave furfural with maximum yields of 80%, 42% and 55%, respectively. The influence of temperature and reaction time on the reaction kinetics was discussed. This study was also completed by the survey of different reactant ratios, such as organic layer-water or catalyst-inorganic salt ratios. The exchange between proton and cation induced by an excess of NaCl was monitored, and a synergetic effect between the remaining protons and the released HCl was also discovered. PMID:27556444

  11. Chemical synthesis of fully biomass-based poly(butylene succinate) from inedible-biomass-based furfural and evaluation of its biomass carbon ratio.

    PubMed

    Tachibana, Yuya; Masuda, Takashi; Funabashi, Masahiro; Kunioka, Masao

    2010-10-11

    We have produced fully biomass-based poly(butylene succinate) (PBS) from furfural produced from inedible agricultural cellulosic waste. Furfural was oxidized to give fumaric acid. Fumaric acid was hydrogenated under high pressure with a palladium-rhenium/carbon catalyst to give 1,4-butanediol, and with a palladium/carbon catalyst to give succinic acid. Dimethyl succinate was synthesized from fumaric acid by esterification and hydrogenation under normal pressure. Fully biomass-based PBS was obtained by polycondensation of biomass-based 1,4-butanediol and biomass-based succinic acid or dimethyl succinate. The biomass carbon ratio calculated from (14)C concentrations measured by accelerator mass spectroscopy (AMS) verified that the PBS obtained in this study contained only biomass carbon. The polycondensation of biomass-based 1,4-butanediol and petroleum-based terephthalic acid or dimethyl terephthalate gave partially biomass-based poly(butylene terephthalate), which is an engineering plastic. PMID:20815381

  12. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P.; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J.; Neves, R. F. C.; Lopes, M. C. A.; de Oliveira, E. M.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Blanco, F.; García, G.; Lima, M. A. P.; Jones, D. B.

    2015-10-01

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

  13. Tuning the synthesis of platinum-copper nanoparticles with a hollow core and porous shell for the selective hydrogenation of furfural to furfuryl alcohol.

    PubMed

    Huang, Shuangshuang; Yang, Nating; Wang, Shibin; Sun, Yuhan; Zhu, Yan

    2016-08-01

    Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol. PMID:27403580

  14. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations.

    PubMed

    Ferreira da Silva, F; Lange, E; Limão-Vieira, P; Jones, N C; Hoffmann, S V; Hubin-Franskin, M-J; Delwiche, J; Brunger, M J; Neves, R F C; Lopes, M C A; de Oliveira, E M; da Costa, R F; Varella, M T do N; Bettega, M H F; Blanco, F; García, G; Lima, M A P; Jones, D B

    2015-10-14

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range. PMID:26472380

  15. Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

    SciTech Connect

    Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P. E-mail: michael.brunger@flinders.edu.au; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J. E-mail: michael.brunger@flinders.edu.au; and others

    2015-10-14

    The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5–10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

  16. A one-pot method for the selective conversion of hemicellulose from crop waste into C5 sugars and furfural by using solid acid catalysts.

    PubMed

    Sahu, Ramakanta; Dhepe, Paresh Laxmikant

    2012-04-01

    We present a solid-acid catalyzed one-pot method for the selective conversion of solid hemicellulose without its separation from other lignocellulosic components, such as cellulose and lignin. The reactions were carried out in aqueous and biphasic media to yield xylose, arabinose, and furfural. To overcome the drawbacks posed by mineral acid methods in converting hemicelllulose, we used heterogeneous catalysts that work at neutral pH. In a batch reactor, these heterogeneous catalysts, such as solid acids (zeolites, clays, metal oxides etc.), resulted in >90 % conversion of hemicellulose. It has been shown that the selectivity for the products can be tuned by changing the reaction conditions, for example, a reaction carried out in water at 170 °C for 1 h with HBeta (Si/Al=19) and HUSY (Si/Al=15) catalysts gave yields of 62 and 56 % for xylose and arabinose, respectively. With increased reaction time (6 h) and in presence of only water, HUSY resulted in yields of 30 % xylose + arabinose and 18 % furfural. However, in a biphasic reaction system (water + p-xylene, 170 °C, 6 h) yields of 56 % furfural with 17 % xylose+arabinose could be achieved. It was shown that with the addition of organic solvent the furfural yield could be increased from 18 to 56 %. Under optimized reaction conditions, >90 % carbon balance was observed. The study revealed that catalysts were recyclable with a 20 % drop in activity for each subsequent run. It was observed that temperature, pressure, reaction time, substrate to catalyst ratio, solvent, and so forth had an effect on product formation. The catalysts were characterized by means of X-ray diffraction, temperature-programmed desorption of NH(3), inductively coupled plasma spectroscopy, elemental analysis, and solid-state NMR ((29)Si, (27)Al) spectroscopy techniques. PMID:22411884

  17. Effects of van der Waals density functional corrections on trends in furfural adsorption and hydrogenation on close-packed transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Bin; Cheng, Lei; Curtiss, Larry; Greeley, Jeffrey

    2014-04-01

    The hydrogenation of furfural to furfuryl alcohol on Pd(111), Cu(111) and Pt(111) is studied with both standard Density Functional Theory (DFT)-GGA functionals and with van der Waals-corrected density functionals. VdW-DF functionals, including optPBE, optB88, optB86b, and Grimme's method, are used to optimize the adsorption configurations of furfural, furfuryl alcohol, and related intermediates resulting from hydrogenation of furfural, and the results are compared to corresponding values determined with GGA functionals, including PW91 and PBE. On Pd(111) and Pt(111), the adsorption geometries of the intermediates are not noticeably different between the two classes of functionals, while on Cu(111), modest changes are seen in both the perpendicular distance and the orientation of the aromatic ring with respect to the planar surface. In general, the binding energies increase substantially in magnitude as a result of van der Waals contributions on all metals. In contrast, however, dispersion effects on the kinetics of hydrogenation are relatively small. It is found that activation barriers are not significantly affected by the inclusion of dispersion effects, and a Brønsted-Evans-Polanyi relationship developed solely from PW91 calculations on Pd(111) is capable of describing corresponding results on Cu(111) and Pt(111), even when the dispersion effects are included. Finally, the reaction energies and barriers derived from the dispersion-corrected and pure GGA calculations are used to plot simple potential energy profiles for furfural hydrogenation to furfuryl alcohol on the three considered metals, and an approximately constant downshift of the energetics due to the dispersion corrections is observed.

  18. First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface

    NASA Astrophysics Data System (ADS)

    Xue, Wenhua

    Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL

  19. Effects of van der Waals Density Functional Corrections on Trends in Furfural Adsorption and Hydrogenation on Close-Packed Transition Metal Surfaces

    SciTech Connect

    Liu, Bin; Cheng, Lei; Curtiss, Larry A.; Greeley, Jeffrey P.

    2014-04-01

    The hydrogenation of furfural to furfuryl alcohol on Pd(111), Cu(111) and Pt(111) is studied with both standard Density Functional Theory (DFT)-GGA functionals and with van der Waals-corrected density functionals. VdWDF functionals, including optPBE, optB88, optB86b, and Grimme's method, are used to optimize the adsorption configurations of furfural, furfuryl alcohol, and related intermediates resulting from hydrogenation of furfural, and the results are compared to corresponding values determined with GGA functionals, including PW91 and PBE. On Pd(111) and Pt(111), the adsorption geometries of the intermediates are not noticeably different between the two classes of functionals, while on Cu(111), modest changes are seen in both the erpendicular distance and the orientation of the aromatic ringwith respect to the planar surface. In general, the binding energies increase substantially in magnitude as a result of van derWaals contributions on all metals. In contrast, however, dispersion effects on the kinetics of hydrogenation are relatively small. It is found that activation barriers are not significantly affected by the inclusion of dispersion effects, and a Brønsted–Evans–Polanyi relationship developed solely fromPW91 calculations on Pd(111) is capable of describing corresponding results on Cu(111) and Pt(111), even when the dispersion effects are included. Finally, the reaction energies and barriers derived from the dispersion-corrected and pure GGA calculations are used to plot simple potential energy profiles for furfural hydrogenation to furfuryl alcohol on the three considered metals, and an approximately constant downshift of the energetics due to the dispersion corrections is observed.

  20. Comparative analysis of nocturnal vertical plasma drift velocities inferred from ground-based ionosonde measurements of hmF2 and h‧F

    NASA Astrophysics Data System (ADS)

    Adebesin, B. O.; Adeniyi, J. O.; Adimula, I. A.; Oladipo, O. A.; Olawepo, A. O.; Reinisch, B. W.

    2015-01-01

    during the equinoxes; whereas the drift inferred from hmF2 best represent the ISR magnitude for solstices. We established that both VzhmF2 and Vzh‧F are governed by the same mechanism at nighttime, and as such any of them can be used to infer vertical drift as long as the 300 km threshold value condition is considered, otherwise chemical correction may be required for the F-layer uplift.

  1. Kinetic features of xylan de-polymerization in production of xylose monomer and furfural during acid pretreatment for kenaf, forage sorghums and sunn hemp feedstocks

    SciTech Connect

    Kamireddy, Srinivas Reddy; Kozliak, Evguenii I.; Tucker, Melvin; Ji, Yun

    2014-08-01

    A kinetic study of acid pretreatment was conducted for sorghum non-brown mid rib (SNBMR) (Sorghum bicolor L Moench), sorghum-brown mid rib (SBMR), sunn hemp (Crotalaria juncea L) and kenaf (Gossypiumhirsutum L), focusing on rates of xylose monomer and furfural formation. The kinetics was investigated using two independent variables, reaction temperature (150 and 160°C) and acid concentration (1 and 2 wt%), with a constant dry biomass loading of 10 wt% and a treatment time up to 20 min while sampling the mixture every 2 min. The experimental data were fitted using a two-step kinetic model based on irreversible pseudo first order kinetics at each step. Varied kinetic orders on the acid concentration, ranging from 0.2 to >3, were observed for both xylose and furfural formation, the values depending on the feedstock. The crystallinity index of raw biomass was shown to be a major factor influencing the rate of both xylose and furfural formation. As a result, a positive correlation was observed between the activation energy and biomass crystallinity index for xylose formation.

  2. Kinetic features of xylan de-polymerization in production of xylose monomer and furfural during acid pretreatment for kenaf, forage sorghums and sunn hemp feedstocks

    DOE PAGESBeta

    Kamireddy, Srinivas Reddy; Kozliak, Evguenii I.; Tucker, Melvin; Ji, Yun

    2014-08-01

    A kinetic study of acid pretreatment was conducted for sorghum non-brown mid rib (SNBMR) (Sorghum bicolor L Moench), sorghum-brown mid rib (SBMR), sunn hemp (Crotalaria juncea L) and kenaf (Gossypiumhirsutum L), focusing on rates of xylose monomer and furfural formation. The kinetics was investigated using two independent variables, reaction temperature (150 and 160°C) and acid concentration (1 and 2 wt%), with a constant dry biomass loading of 10 wt% and a treatment time up to 20 min while sampling the mixture every 2 min. The experimental data were fitted using a two-step kinetic model based on irreversible pseudo first ordermore » kinetics at each step. Varied kinetic orders on the acid concentration, ranging from 0.2 to >3, were observed for both xylose and furfural formation, the values depending on the feedstock. The crystallinity index of raw biomass was shown to be a major factor influencing the rate of both xylose and furfural formation. As a result, a positive correlation was observed between the activation energy and biomass crystallinity index for xylose formation.« less

  3. Optimization of a Dynamic Headspace-Thermal Desorption-Gas Chromatography/Mass Spectrometry procedure for the determination of furfurals in vinegars.

    PubMed

    Manzini, Simona; Durante, Caterina; Baschieri, Carlo; Cocchi, Marina; Sighinolfi, Simona; Totaro, Sara; Marchetti, Andrea

    2011-08-15

    The use of a Dynamic Headspace System (DHS) device combined with a Thermal Desorption Unit (TDU) interfaced to a Gas Chromatography/Mass Spectrometry (GC/MS) system is proposed for the determination of furfurals in oenological products. An experimental design protocol has been employed for the optimization of the instrumental settings concerning DHS and TDU extraction and desorption steps. It has been possible to individuate the following optimized conditions: incubation temperature 40°C, purge volume 800 mL, dry volume 1500 mL, TDU hold time 5 min and incubation time 10 min. The performance of two different SPE sorbents, namely Tenax TA and Tenax GR used for the furfurals trapping, was investigated too. The developed DHS sampling procedure showed good reproducibility values with a RSD% lower than 10% for all the monitored species. The optimized experimental settings have been used to determine furfurals in several vinegar samples obtained by traditional procedure starting from cooked grape musts, i.e. in Aceto Balsamico Tradizionale di Modena (ABTM). In fact, the control of these species is extremely important for quality and safety issues. PMID:21726711

  4. Processed Lignin as a Byproduct of the Generation of 5-(Chloromethyl)furfural from Biomass: A Promising New Mesoporous Material.

    PubMed

    Budarin, Vitaliy L; Clark, James H; Henschen, Jonatan; Farmer, Thomas J; Macquarrie, Duncan J; Mascal, Mark; Nagaraja, Gundibasappa K; Petchey, Tabitha H M

    2015-12-21

    The lignin by-product of the conversion of lignocellulosic biomass to 5-(chloromethyl)furfural (CMF) has been characterised by thermogravimetric analysis, N2 physisorption porosimetry, attenuated internal reflectance IR spectroscopy, elemental analysis and solid-state NMR spectroscopy. The lignin (LCMF) has a moderate level of mesoporosity before thermal treatment and a surface area of 63 m(2)  g(-1) , which increases dramatically on pyrolysis at temperatures above 400 °C. An assessment of the functionality and textural properties of the material was achieved by analysing LCMF treated thermally over a range of pyrolysis temperatures. Samples were sulfonated to test their potential as heterogeneous acid catalysts in the esterification of levulinic acid. It was shown that unpyrolysed catalysts gave the highest ester yields of up to 93 %. To the best of our knowledge, this is the first example of mesoporous lignin with an appreciable surface area that is produced directly from a bio-refinery process and with further textural modification of the material demonstrated. PMID:26601798

  5. N-(furfural) chitosan hydrogels based on Diels-Alder cycloadditions and application as microspheres for controlled drug release.

    PubMed

    Montiel-Herrera, Marcelino; Gandini, Alessandro; Goycoolea, Francisco M; Jacobsen, Neil E; Lizardi-Mendoza, Jaime; Recillas-Mota, Maricarmen; Argüelles-Monal, Waldo M

    2015-09-01

    In this study, chitosan was chemically modified by reductive amination in a two-step process. The synthesis of N-(furfural) chitosan (FC) was confirmed by FT-IR and (1)H NMR analysis, and the degrees of substitution were estimated as 8.3 and 23.8%. The cross-linkable system of bismaleimide (BM) and FC shows that FC shared properties of furan-maleimide chemistry. This system produced non-reversible hydrogel networks by Diels-Alder cycloadditions at 85 °C. The system composed of BM and FC (23.8% substitution) generated stronger hydrogel networks than those of FC with an 8.3% degree of substitution. Moreover, the FC-BM system was able to produce hydrogel microspheres. Environmental scanning electron microscopy revealed the surface of the microspheres to be non-porous with small protuberances. In water, the microspheres swelled, increasing their volume by 30%. Finally, microspheres loaded with methylene blue were able to release the dye gradually, obeying second-order kinetics for times less than 600 min. This behavior suggests that diffusion is governed by the relaxation of polymer chains in the swelled state, thus facilitating drug release outside the microspheres. PMID:26005158

  6. CEDAR Electrodynamics Thermosphere Ionosphere (ETI) Challenge for Systematic Assessment of Ionosphere/Thermosphere Models: NmF2, hmF2, and Vertical Drift Using Ground-Based Observations

    NASA Technical Reports Server (NTRS)

    Shim, J. S.; Kuznetsova, M.; Rastatter, L.; Hesse, M.; Bilitza, D.; Butala, M.; Codrescu, M.; Emery, B.; Foster, B.; Fuller-Rowell, T.; Huba, J.; Mannucci, A. J.; Pi, X.; Ridley, A.; Scherliess, L.; Schunk, R. W.; Stephens, P.; Thompson, D. C.; Zhu, L.; Anderson, D.; Chau, J. L.; Sojka, J. J.; Rideout, B.

    2011-01-01

    Objective quantification of model performance based on metrics helps us evaluate the current state of space physics modeling capability, address differences among various modeling approaches, and track model improvements over time. The Coupling, Energetics, and Dynamics of Atmospheric Regions (CEDAR) Electrodynamics Thermosphere Ionosphere (ETI) Challenge was initiated in 2009 to assess accuracy of various ionosphere/thermosphere models in reproducing ionosphere and thermosphere parameters. A total of nine events and five physical parameters were selected to compare between model outputs and observations. The nine events included two strong and one moderate geomagnetic storm events from GEM Challenge events and three moderate storms and three quiet periods from the first half of the International Polar Year (IPY) campaign, which lasted for 2 years, from March 2007 to March 2009. The five physical parameters selected were NmF2 and hmF2 from ISRs and LEO satellites such as CHAMP and COSMIC, vertical drifts at Jicamarca, and electron and neutral densities along the track of the CHAMP satellite. For this study, four different metrics and up to 10 models were used. In this paper, we focus on preliminary results of the study using ground-based measurements, which include NmF2 and hmF2 from Incoherent Scatter Radars (ISRs), and vertical drifts at Jicamarca. The results show that the model performance strongly depends on the type of metrics used, and thus no model is ranked top for all used metrics. The analysis further indicates that performance of the model also varies with latitude and geomagnetic activity level.

  7. CEDAR Electrodynamics Thermosphere Ionosphere (ETI) Challenge for systematic assessment of ionosphere/thermosphere models: NmF2, hmF2, and vertical drift using ground-based observations

    NASA Astrophysics Data System (ADS)

    Shim, J. S.; Kuznetsova, M.; RastäTter, L.; Hesse, M.; Bilitza, D.; Butala, M.; Codrescu, M.; Emery, B.; Foster, B.; Fuller-Rowell, T.; Huba, J.; Mannucci, A. J.; Pi, X.; Ridley, A.; Scherliess, L.; Schunk, R. W.; Stephens, P.; Thompson, D. C.; Zhu, L.; Anderson, D.; Chau, J. L.; Sojka, J. J.; Rideout, B.

    2011-12-01

    Objective quantification of model performance based on metrics helps us evaluate the current state of space physics modeling capability, address differences among various modeling approaches, and track model improvements over time. The Coupling, Energetics, and Dynamics of Atmospheric Regions (CEDAR) Electrodynamics Thermosphere Ionosphere (ETI) Challenge was initiated in 2009 to assess accuracy of various ionosphere/thermosphere models in reproducing ionosphere and thermosphere parameters. A total of nine events and five physical parameters were selected to compare between model outputs and observations. The nine events included two strong and one moderate geomagnetic storm events from GEM Challenge events and three moderate storms and three quiet periods from the first half of the International Polar Year (IPY) campaign, which lasted for 2 years, from March 2007 to March 2009. The five physical parameters selected were NmF2 and hmF2 from ISRs and LEO satellites such as CHAMP and COSMIC, vertical drifts at Jicamarca, and electron and neutral densities along the track of the CHAMP satellite. For this study, four different metrics and up to 10 models were used. In this paper, we focus on preliminary results of the study using ground-based measurements, which include NmF2 and hmF2 from Incoherent Scatter Radars (ISRs), and vertical drifts at Jicamarca. The results show that the model performance strongly depends on the type of metrics used, and thus no model is ranked top for all used metrics. The analysis further indicates that performance of the model also varies with latitude and geomagnetic activity level.

  8. Effects of particulate matter exposure on blood 5-hydroxymethylation: results from the Beijing truck driver air pollution study.

    PubMed

    Sanchez-Guerra, Marco; Zheng, Yinan; Osorio-Yanez, Citlalli; Zhong, Jia; Chervona, Yana; Wang, Sheng; Chang, Dou; McCracken, John P; Díaz, Anaite; Bertazzi, Pier Alberto; Koutrakis, Petros; Kang, Choong-Min; Zhang, Xiao; Zhang, Wei; Byun, Hyang-Min; Schwartz, Joel; Hou, Lifang; Baccarelli, Andrea A

    2015-01-01

    Previous studies have reported epigenetic changes induced by environmental exposures. However, previous investigations did not distinguish 5-methylcytosine (5mC) from a similar oxidative form with opposite functions, 5-hydroxymethylcytosine (5hmC). Here, we measured blood DNA global 5mC and 5hmC by ELISA and used adjusted mixed-effects regression models to evaluate the effects of ambient PM10 and personal PM2.5 and its elemental components-black carbon (BC), aluminum (Al), calcium (Ca), potassium (K), iron (Fe), sulfur (S), silicon (Si), titanium (Ti), and zinc (Zn)-on blood global 5mC and 5hmC levels. The study was conducted in 60 truck drivers and 60 office workers in Beijing, China from The Beijing Truck Driver Air Pollution Study at 2 exams separated by one to 2 weeks. Blood 5hmC level (0.08%) was ∼83-fold lower than 5mC (6.61%). An inter-quartile range (IQR) increase in same-day PM10 was associated with increases in 5hmC of 26.1% in office workers (P = 0.004), 20.2% in truck drivers (P = 0.014), and 21.9% in all participants combined (P < 0.001). PM10 effects on 5hmC were increasingly stronger when averaged over 4, 7, and 14 d preceding assessment (up to 132.6% for the 14-d average in all participants, P < 0.001). PM10 effects were also significant after controlling for multiple testing (family-wise error rate; FWER < 0.05). 5hmC was not correlated with personal measures of PM2.5 and elemental components (FWER > 0.05). 5mC showed no correlations with PM10, PM2.5, and elemental components measures (FWER > 0.05). Our study suggests that exposure to ambient PM10 affects 5hmC over time, but not 5mC. This finding demonstrates the need to differentiate 5hmC and 5mC in environmental studies of DNA methylation. PMID:25970091

  9. Effects of particulate matter exposure on blood 5-hydroxymethylation: results from the Beijing truck driver air pollution study

    PubMed Central

    Sanchez-Guerra, Marco; Zheng, Yinan; Osorio-Yanez, Citlalli; Zhong, Jia; Chervona, Yana; Wang, Sheng; Chang, Dou; McCracken, John P; Díaz, Anaite; Bertazzi, Pier Alberto; Koutrakis, Petros; Kang, Choong-Min; Zhang, Xiao; Zhang, Wei; Byun, Hyang-Min; Schwartz, Joel; Hou, Lifang; Baccarelli, Andrea A

    2015-01-01

    Previous studies have reported epigenetic changes induced by environmental exposures. However, previous investigations did not distinguish 5-methylcytosine (5mC) from a similar oxidative form with opposite functions, 5-hydroxymethylcytosine (5hmC). Here, we measured blood DNA global 5mC and 5hmC by ELISA and used adjusted mixed-effects regression models to evaluate the effects of ambient PM10 and personal PM2.5 and its elemental components—black carbon (BC), aluminum (Al), calcium (Ca), potassium (K), iron (Fe), sulfur (S), silicon (Si), titanium (Ti), and zinc (Zn)—on blood global 5mC and 5hmC levels. The study was conducted in 60 truck drivers and 60 office workers in Beijing, China from The Beijing Truck Driver Air Pollution Study at 2 exams separated by one to 2 weeks. Blood 5hmC level (0.08%) was ∼83-fold lower than 5mC (6.61%). An inter-quartile range (IQR) increase in same-day PM10 was associated with increases in 5hmC of 26.1% in office workers (P = 0.004), 20.2% in truck drivers (P = 0.014), and 21.9% in all participants combined (P < 0.001). PM10 effects on 5hmC were increasingly stronger when averaged over 4, 7, and 14 d preceding assessment (up to 132.6% for the 14-d average in all participants, P < 0.001). PM10 effects were also significant after controlling for multiple testing (family-wise error rate; FWER < 0.05). 5hmC was not correlated with personal measures of PM2.5 and elemental components (FWER > 0.05). 5mC showed no correlations with PM10, PM2.5, and elemental components measures (FWER > 0.05). Our study suggests that exposure to ambient PM10 affects 5hmC over time, but not 5mC. This finding demonstrates the need to differentiate 5hmC and 5mC in environmental studies of DNA methylation. PMID:25970091

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

    PubMed

    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, P<0.001) between the estimated HMF intake and urinary HMFA. Further studies are needed to reveal alternative sources for HMF exposure. PMID:18929614

  11. Production of levulinic acid, furfural, and gamma valerolactone from C.sub.5 and C.sub.6 carbohydrates in mono- and biphasic systems using gamma-valerolactone as a solvent

    DOEpatents

    Dumesic, James A.; Alonso, David Martin; Gurbuz, Elif I.; Wettstein, Stephanie G.

    2013-03-19

    A method to make levulinic acid (LA), furfural, or gamma-valerolactone (GVL). React cellulose (and/or other C.sub.6 carbohydrates) or xylose (and/or other C.sub.5 carbohydrates) or combinations thereof in a monophasic reaction medium comprising GVL and an acid; or (ii) a biphasic reaction system comprising an organic layer comprising GVL, and a substantially immiscible aqueous layer. At least a portion of the cellulose (and/or other C.sub.6 carbohydrates), if present, is converted to LA and at least a portion of the xylose (and/or other C.sub.5 carbohydrates), if present, is converted into furfural.

  12. Novel Preparation of Nano-Composite CuO-Cr2O3 Using Ctab-Template Method and Efficient for Hydrogenation of Biomass-Derived Furfural

    NASA Astrophysics Data System (ADS)

    Yan, Kai; Wu, Xu; An, Xia; Xie, Xianmei

    2013-02-01

    A simple route to fabricate nano-composite oxides CuO-Cr2O3 using hexadecyltrimethylammonium bromide (CTAB)-templated Cu-Cr hydrotalcite as the precursor is presented. This novel method is based on CTAB-templating effect for mesostructure directing and using the cheap metal nitrate, followed by removal of CTAB. It was indicated that the nano-composite CuO-Cr2O3 was formed during the removal of CTAB. X-ray diffraction (XRD) and transitional electronic microscopy (TEM) revealed nice nano-composite oxides CuO-Cr2O3 were formed with high crystallinity. N2 adsorption and desorption indicated that a high surface area of 170.5 m2/g with a pore size of 2.7 nm of the nano-composite CuO-Cr2O3 was facilely resulted. The as-synthesized nano-composite oxides CuO-Cr2O3 display good catalytic activities for hydrogenation of furfural to furfuryl alcohol, whereas 86% selectivity was achieved at 75% conversion of furfural.

  13. Bacillus sp. strain P38: an efficient producer of L-lactate from cellulosic hydrolysate, with high tolerance for 2-furfural.

    PubMed

    Peng, Lili; Wang, Limin; Che, Chengchuan; Yang, Ge; Yu, Bo; Ma, Yanhe

    2013-12-01

    In this study, efficient polymer-grade L-lactic acid production was achieved with the strain Bacillus sp. P38 by using cellulosic hydrolysate as the sole carbon source. In fed-batch fermentation, 180 g L(-1)L-lactic acid was obtained with a volumetric productivity of 2.4 g L(-1)h(-1) and a yield of 0.96 g g(-1) total reducing sugars. No D-isomer of lactic acid was detected in the broth. Strain P38 tolerated up to 10 g L(-1) 2-furfural, and lactate production was sharply inhibited only when the 2-furfural concentration was higher than 6 g L(-1). Moreover, strain P38 also tolerated high concentrations (>6 g L(-1)) of other fermentation inhibitors in cellulosic hydrolysate, such as vanillin and acetic acid, although it was slightly sensitive to formic acid. The efficient L-lactic acid production, combined with high inhibitor tolerance and efficient pentose utilization, indicate that Bacillus sp. P38 is a promising producer of polymer-grade L-lactic acid from cellulosic biomass. PMID:24096283

  14. Antifungal susceptibility of Malassezia furfur, Malassezia sympodialis, and Malassezia globosa to azole drugs and amphotericin B evaluated using a broth microdilution method.

    PubMed

    Rojas, Florencia D; Sosa, María de los A; Fernández, Mariana S; Cattana, María E; Córdoba, Susana B; Giusiano, Gustavo E

    2014-08-01

    We studied the in vitro activity of fluconazole (FCZ), ketoconazole (KTZ), miconazole (MCZ), voriconazole (VCZ), itraconazole (ITZ) and amphotericin B (AMB) against the three major pathogenic Malassezia species, M. globosa, M. sympodialis, and M. furfur. Antifungal susceptibilities were determined using the broth microdilution method in accordance with Clinical and Laboratory Standards Institute reference document M27-A3. To support lipid-dependent yeast development, glucose, peptone, ox bile, malt extract, glycerol, and Tween supplements were added to Roswell Park Memorial Institute RPMI 1640 medium. The supplemented medium allowed good growth of all three species studied. The minimal inhibitory concentrations (MICs) were recorded after 72 h of incubation at 32ºC. The three species showed different susceptibility profiles for the drugs tested. Malassezia sympodialis was the most susceptible and M. furfur the least susceptible species. KTZ, ITZ, and VCZ were the most active drugs, showing low variability among isolates of the same species. FCZ, MCZ, and AMB showed high MICs and wide MIC ranges. Differences observed emphasize the need to accurately identify and evaluate antifungal susceptibility of Malassezia species. Further investigations and collaborative studies are essential for correlating in vitro results with clinical outcomes since the existing limited data do not allow definitive conclusions. PMID:24965946

  15. Membrane Extraction for Detoxification of Biomass Hydrolysates

    SciTech Connect

    Grzenia, D. L.; Schell, D. J.; Wickramasinghe, S. R.

    2012-05-01

    Membrane extraction was used for the removal of sulfuric acid, acetic acid, 5-hydroxymethyl furfural and furfural from corn stover hydrolyzed with dilute sulfuric acid. Microporous polypropylene hollow fiber membranes were used. The organic extractant consisted of 15% Alamine 336 in: octanol, a 50:50 mixture of oleyl alcohol:octanol or oleyl alcohol. Rapid removal of sulfuric acid, 5-hydroxymethyl and furfural was observed. The rate of acetic acid removal decreased as the pH of the hydrolysate increased. Regeneration of the organic extractant was achieved by back extraction into an aqueous phase containing NaOH and ethanol. A cleaning protocol consisting of flushing the hydrolysate compartment with NaOH and the organic phase compartment with pure organic phase enabled regeneration and reuse of the module. Ethanol yields from hydrolysates detoxified by membrane extraction using 15% Alamine 336 in oleyl alcohol were about 10% higher than those from hydrolysates detoxified using ammonium hydroxide treatment.

  16. Evolutionarily Engineered Ethanologenic Yeast Detoxifies Lignocellulosic Biomass Conversion Inhibitors by Reprogrammed Pathways

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lignocellulosic biomass conversion inhibitors furfural and HMF inhibit microbial growth and interfere with subsequent fermentation of ethanol, posing significant challenges for a sustainable cellulosic ethanol conversion industry. Numerous yeast genes were found to be associated with the inhibitor ...

  17. New Aldehyde Reductase Genes of Saccharomyces cerevisiae Contribute In Situ Detoxification of Lignocellulose-to-Ethanol Conversion Inhibitiors

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Furfural and 5-hydroxymethylfurfural (HMF) are inhibitory compounds commonly encountered during lignocellulose-to-ethanol conversion for cleaner transportation fuels. It is possible to in situ detoxify the aldehyde inhibitors by tolerant ethanologenic yeast strains. Multiple gene-mediated reductio...

  18. Culture Nutrition and Physiology Impact the Inhibitor Tolerance of the Yeast Pichia stipitis NRRL Y-7124

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Robust microorganisms are needed to consume both hexose and pentose sugars and to withstand, survive, and function in the presence of stress factors common to fermentations of lignocellulose hydrolysates, including the inhibitors furfural, 5-hydroxymethylfurfural (HMF), and ethanol. Pichia stipitis...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  20. Protein engineering of GRE2 from Saccharomyces cerevisiae for enhanced detoxification of 5-hydroxymethylfurfural

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  1. A Novel NADPH-Dependent Aldehyde Reductase Gene from Saccharomyces cerevisiae NRRL Y-12632 Involved in the Detoxification of Aldehyde Inhibitors Derived from Lignocellulosic Biomass Conversion

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aldehyde inhibitors such as furfural, 5-hydroxymethylfurfural (HMF), anisaldehyde, benzaldehyde, cinnamaldehyde, and phenylaldehyde are commonly generated during lignocellulosic biomass conversion process for low-cost cellulosic ethanol production that interferes with subsequent microbial growth and...

  2. Understanding the Mechanism of the Divergent Reactivity of Non-Heteroatom-Stabilized Chromium Carbene Complexes with Furfural Imines: Formation of Benzofurans and Azetines.

    PubMed

    Funes-Ardoiz, Ignacio; González, Jairo; Santamaría, Javier; Sampedro, Diego

    2016-02-19

    The mechanisms of the reaction between non-heteroatom-stabilized alkynyl chromium carbene complexes prepared in situ and furfural imines to yield benzofurans and/or azetines have been explored by means of density functional theory method calculations. The reaction proceeds through a complex cascade of steps triggered by a nucleophilic addition of the imine nitrogen atom. The formation of two benzofuran regioisomers has been explained in terms of competitive nucleophilic attacks to different positions of the carbene complex. Each of these regioisomers can be obtained as the major product depending on the starting materials. The overall sequence could be controlled to yield benzofurans or azetines by adjusting the substituents present in the initial carbene complex. This mechanistic information allowed for the preparation of new benzofurans and azetinylcarbenes in good yields. PMID:26799934

  3. Genomic adaptation of Saccharomyces cerevisiae to inhibitors involving biomass conversion to ethanol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The dose-dependent inhibition of the ethanologenic yeast allowed its potential adaptation to the inhibitors to transform furfural and 5-hydroxymethylfurfural (HMF) into less toxic compounds of furan methanol (FM) and furan-2,5-dimethanol (FDM), respectively. The isolation and identification of HMF ...

  4. BUTANOL PRODUCTION FROM AGRICULTURAL RESIDUES: IMPACT OF DEGRADATION PRODUCTS ON CLOSTRIDIUM BEIJERINCKII GROWTH AND BUTANOL FERMENTATION

    Technology Transfer Automated Retrieval System (TEKTRAN)

    During pretreatment and hydrolysis of fiber-rich agricultural biomass, compounds such as salts, furfural, hydroxymethyl furfural (HMF), acetic, ferulic, glucuronic, p-coumaric acids, and phenolic compounds are produced. Clostridium beijerinckii BA101 can utilize the individual sugars present in lig...

  5. Sustainable hydrogen production from bio-oil model compounds (meta-xylene) and mixtures (1-butanol, meta-xylene and furfural).

    PubMed

    Bizkarra, K; Barrio, V L; Arias, P L; Cambra, J F

    2016-09-01

    In the present work m-xylene and an equimolecular mixture of m-xylene, 1-butanol and furfural, all of them bio-oil model compounds, were studied in steam reforming (SR) conditions. Three different nickel catalysts, which showed to be active in 1-butanol SR (Ni/Al2O3, Ni/CeO2-Al2O3 and Ni/La2O3-Al2O3), were tested and compared with thermodynamic equilibrium values. Tests were carried out at temperatures from 800 to 600°C at atmospheric pressure with a steam to carbon ratio (S/C) of 5.0. Despite the different bio-oils fed, the amount of moles going through the catalytic bed was kept constant in order to obtain comparable results. After their use, catalysts were characterized by different techniques and those values were correlated with the activity results. All catalysts were deactivated during the SR of the mixture, mainly by coking. The highest hydrogen yields were obtained with Ni/Al2O3 and Ni/CeO2-Al2O3 catalysts in the SR of m-xylene and SR of the mixture, respectively. PMID:27253476

  6. Determination of furfural and hydroxymethylfurfural from baby formula using headspace solid phase microextraction based on nanostructured polypyrrole fiber coupled with ion mobility spectrometry.

    PubMed

    Kamalabadi, Mahdie; Ghaemi, Elham; Mohammadi, Abdorreza; Alizadeh, Naader

    2015-08-15

    Furfural (Fu) and hydroxymethylfurfural (HMFu) are extracted using a dodecylbenzenesulfonate-doped polypyrrole coating as a fiber for headspace solid phase microextraction (HS-SPME) method in baby formula samples and detected using ion mobility spectrometry (IMS). Sample pH, salt effect, extraction time and temperature were investigated and optimized as effective parameters in HS-SPME. The calibration curves were linear in the range of 20-300 ng g(-1) (R(2)>0.99). Limits of detection for Fu and HMFu were 6 ng g(-1) and 5 ng g(-1), respectively. The RSD% of Fu and HMFu for five analyses was 4.4 and 4.9, respectively. The proposed method was successfully applied to determine of Fu and HMFu in the different baby formula samples with satisfactory result. The results were in agreement with those obtained using HPLC analysis. The HS-SPME-IMS is precise, selective and sensitive analytical method for determination of Fu and HMFu in baby formula samples, without any derivatization process. PMID:25794723

  7. Hydrothermal Conversion of Giant Reed to Furfural and Levulinic Acid: Optimization of the Process under Microwave Irradiation and Investigation of Distinctive Agronomic Parameters.

    PubMed

    Antonetti, Claudia; Bonari, Enrico; Licursi, Domenico; Nassi O Di Nasso, Nicoletta; Raspolli Galletti, Anna Maria

    2015-01-01

    The hydrothermal conversion of giant reed (Arundo donax L.) to furfural (FA) and levulinic acid (LA) was investigated in the presence of dilute hydrochloric acid. FA and LA yields were improved by univariate optimization of the main reaction parameters: concentration of the acid catalyst, solid/liquid ratio of the reaction mixture, hydrolysis temperature, and reaction time. The catalytic performances were investigated adopting the efficient microwave (MW) irradiation, allowing significant energy and time savings. The best FA and LA yields were further confirmed using a traditionally heated autoclave reactor, giving very high results, when compared with the literature. Hydrolysis temperature and time were the main reaction variables to be carefully optimized: FA formation needed milder reaction conditions, while LA more severe ones. The effect of the crop management (e.g., harvest time) on FA/LA production was discussed, revealing that harvest time was not a discriminating parameter for the further optimization of both FA and LA production, due to the very high productivity of the giant reed throughout the year. The promising results demonstrate that giant reed represents a very interesting candidate for a very high contemporary production of FA and LA of up to about 70% and 90% of the theoretical yields, respectively. PMID:26633324

  8. Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

    PubMed

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-11-15

    The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. PMID:27283710

  9. Alcohol dehydrogenases from Scheffersomyces stipitis involved in the detoxification of aldehyde inhibitors derived from lignocellulosic biomass conversion.

    PubMed

    Ma, Menggen; Wang, Xu; Zhang, Xiaoping; Zhao, Xianxian

    2013-09-01

    Aldehyde inhibitors such as furfural and 5-hydroxymethylfurfural (HMF) are generated from biomass pretreatment. Scheffersomyces stipitis is able to reduce furfural and HMF to less toxic furanmethanol and furan-2,5-dimethanol; however, the enzymes involved in the reductive reaction still remain unknown. In this study, transcription responses of two known and five putative alcohol dehydrogenase genes from S. stipitis were analyzed under furfural and HMF stress conditions. All the seven alcohol dehydrogenase genes were also cloned and overexpressed for their activity analyses. Our results indicate that transcriptions of SsADH4 and SsADH6 were highly induced under furfural and HMF stress conditions, and the proteins encoded by them exhibited NADH- and/or NADPH-dependent activities for furfural and HMF reduction, respectively. For furfural reduction, NADH-dependent activity was also observed in SsAdh1p and NAD(P)H-dependent activities were also observed in SsAdh5p and SsAdh7p. For HMF reduction, NADPH-dependent activities were also observed in SsAdh5p and SsAdh7p. SsAdh4p displayed the highest NADPH-dependent specific activity and catalytic efficiency for reduction of both furfural and HMF among the seven alcohol dehydrogenases. Enzyme activities of all SsADH proteins were more stable under acidic condition. For most SsADH proteins, the optimum temperature for enzyme activities was 30 °C and more than 50 % enzyme activities remained at 60 °C. Reduction activities of formaldehyde, acetaldehyde, isovaleraldehyde, benzaldehyde, and phenylacetaldehyde were also observed in some SsADH proteins. Our results indicate that multiple alcohol dehydrogenases in S. stipitis are involved in the detoxification of aldehyde inhibitors derived from lignocellulosic biomass conversion. PMID:23912116

  10. Isolation and Characterization of Bacteria That Use Furans as the Sole Carbon Source.

    PubMed

    Lee, Sarah A; Wrona, Lindsey J; Cahoon, A Bruce; Crigler, Jacob; Eiteman, Mark A; Altman, Elliot

    2016-01-01

    Five bacterial strains were isolated from wastewater treatment facilities which were able to use furfural as the sole carbon source. Based on 16S rRNA phylogenetic analysis, these strains were identified as Cupriavidus pinatubonensis (designated ALS1280), Pigmentiphaga sp. (ALS1172), Pseudomonas sp. BWDY (ALS1279), Pseudomonas mendocina (ALS1131), and Pseudomonas putida (ALS1267). In all cases, growth under oxygenated conditions on furfural was accompanied by the transient accumulation of 2-furoic acid (furoate) with no furfuryl alcohol observed. ALS1267 and ALS1279 were also able to metabolize 5-(hydroxymethyl)furfural. The five isolates and their phylogenetic near neighbors were compared for furfural dehydrogenase activity and tolerance to furfural and furoate in defined and complex media. P. putida ALS1267 was the most tolerant to furans and tolerated 17 mM furfural or 195 mM furoate before its growth rate was reduced by 50 % in a defined medium. This strain also had the greatest specific growth rate on furfural (0.6/h at 27-30 °C) and showed the highest specific activity of furfural dehydrogenase (170 mIU/mg) of any furfural-utilizing strain that has been characterized to date. PMID:26419660

  11. Biotransformation of furanic and phenolic compounds with hydrogen gas production in a microbial electrolysis cell

    DOE PAGESBeta

    Zeng, Xiaofei; Borole, Abhijeet P.; Pavlostathis, Spyros G.

    2015-10-27

    In this study, furanic and phenolic compounds are problematic byproducts resulting from the decomposition of lignocellulosic biomass during biofuel production. This study assessed the capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the sole carbon and energy source in the bioanode. The rate and extent of biotransformation of the five compounds, efficiency of H2 production, as well as the anode microbial community structure were investigated. The five compounds were completelymore » transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H2 yield varied from 0.26 to 0.42 g H2-COD/g COD removed in the anode, and the bioanode volume-normalized H2 production rate was 0.07-0.1 L/L-d. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H2 production were inhibited at an initial substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The H2 production route demonstrated in this study has proven to be an alternative to the currently used process of reforming natural gas to supply H2 needed to upgrade bio-oils to stable hydrocarbon fuels.« less

  12. Biotransformation of furanic and phenolic compounds with hydrogen gas production in a microbial electrolysis cell

    SciTech Connect

    Zeng, Xiaofei; Borole, Abhijeet P.; Pavlostathis, Spyros G.

    2015-10-27

    In this study, furanic and phenolic compounds are problematic byproducts resulting from the decomposition of lignocellulosic biomass during biofuel production. This study assessed the capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the sole carbon and energy source in the bioanode. The rate and extent of biotransformation of the five compounds, efficiency of H2 production, as well as the anode microbial community structure were investigated. The five compounds were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H2 yield varied from 0.26 to 0.42 g H2-COD/g COD removed in the anode, and the bioanode volume-normalized H2 production rate was 0.07-0.1 L/L-d. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H2 production were inhibited at an initial substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The H2 production route demonstrated in this study has proven to be an alternative to the currently used process of reforming natural gas to supply H2 needed to

  13. Biotransformation of Furanic and Phenolic Compounds with Hydrogen Gas Production in a Microbial Electrolysis Cell.

    PubMed

    Zeng, Xiaofei; Borole, Abhijeet P; Pavlostathis, Spyros G

    2015-11-17

    Furanic and phenolic compounds are problematic byproducts resulting from the breakdown of lignocellulosic biomass during biofuel production. The capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the substrate in the bioanode was assessed. The rate and extent of biotransformation of the five compounds and efficiency of H2 production, as well as the structure of the anode microbial community, were investigated. The five compounds were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode Coulombic efficiency was 44-69%, which is comparable to that of wastewater-fed MECs. The H2 yield varied from 0.26 to 0.42 g H2-COD/g COD removed in the anode, and the bioanode volume-normalized H2 production rate was 0.07-0.1 L/L-d. The biotransformation of the five compounds took place via fermentation followed by exoelectrogenesis. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H2 production were inhibited at an initial substrate concentration of 1200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The MEC H2 production demonstrated in this study is an alternative to the currently used process of reforming natural gas to supply H2 needed to upgrade bio-oils to stable

  14. Improvement on the catalytic performance of Mg-Zr mixed oxides for furfural-acetone aldol condensation by supporting on mesoporous carbons.

    PubMed

    Faba, Laura; Díaz, Eva; Ordóñez, Salvador

    2013-03-01

    A new procedure for improving the performance of the most common catalysts used in aqueous-phase aldol condensation (Mg-Zr mixed oxides) reactions is presented. This reaction is of interest for upgrading carbohydrate feedstocks. The procedure involves supporting Mg-Zr oxides on non-microporous carbonaceous materials, such as carbon nanofibers (CNFs) or high-surface-area graphites (HSAGs), using either incipient wetness or coprecipitation procedures. The use of HSAGs together with the coprecipitation method provides the best performance. Results obtained for the cross-condensation of acetone and furfural at 323 K reveal that the catalyst performance is greatly improved compared to the bulk oxides (96.5 % conversion vs. 81.4 % with the bulk oxide; 87.8 % selectivity for C13 and C8 adducts vs. 76.2 % with the bulk oxide). This difference is even more prominent in terms of rates per catalytically active basic site (four and seven times greater for C8 and C13 adducts, respectively). The improved performance is explained in terms of a more appropriate basic site distribution and by greater interaction of the reactants with the carbon surface. In addition, deactivation behavior of the catalyst is improved by tuning the morphology of the carbonaceous support. An important enhancement of the catalytic stability can be obtained selecting a HSAG with an appropriate pore diameter. With HSAG100 the activity decreased by less than 20 % between successive reaction cycles and the selectivity for the condensation products remained almost unaltered. The decrease is greater than 80 % for the bulk oxides tested at these conditions, with important increases in the selectivity for by-product formation. PMID:23362138

  15. Furanic compounds and furfural in different coffee products by headspace liquid-phase micro-extraction followed by gas chromatography-mass spectrometry: survey and effect of brewing procedures.

    PubMed

    Chaichi, Maryam; Ghasemzadeh-Mohammadi, Vahid; Hashemi, Maryam; Mohammadi, Abdorreza

    2015-01-01

    In this study, the levels of furan, 2-methylfuran, 2,5-dimethylfuran, vinyl furan, 2-methoxymethyl-furan and furfural in different coffee products were evaluated. Simultaneous determination of these six furanic compounds was performed by a head space liquid-phase micro-extraction (HS-LPME) method. A total of 67 coffee powder samples were analysed. The effects of boiling and espresso-making procedures on the levels of furanic compounds were investigated. The results showed that different types of coffee samples contained different concentrations of furanic compounds, due to the various processing conditions such as temperature, degree of roasting and fineness of grind. Among the different coffee samples, the highest level of furan (6320 µg kg⁻¹) was detected in ground coffee, while coffee-mix samples showed the lowest furan concentration (10 µg kg⁻¹). Levels in brewed coffees indicated that, except for furfural, brewing by an espresso machine caused significant loss of furanic compounds. PMID:25356540

  16. Genome and transcriptome analyses reveal that MAPK- and phosphatidylinositol-signaling pathways mediate tolerance to 5-hydroxymethyl-2-furaldehyde for industrial yeast Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The industrial ethanologenic yeast Saccharomyces cerevisiae is a promising biocatalyst for next-generation advanced biofuels applications including lignocellulose-to-ethanol conversion. Here we present the first insight into the genomic background of NRRL Y-12632, a type strain from a worldwide coll...

  17. Catalytic selective etherification of hydroxyl groups in 5-hydroxymethylfurfural over H4SiW12O40/MCM-41 nanospheres for liquid fuel production.

    PubMed

    Che, Penghua; Lu, Fang; Zhang, Junjie; Huang, Yizheng; Nie, Xin; Gao, Jin; Xu, Jie

    2012-09-01

    5-Hydroxymethylfurfural (HMF) is an important biomass-derived building block, but production and sustainable utilization of HMF remain challenging due to reactions of the highly reactive functional groups of this compound. H(4)SiW(12)O(40)/MCM-41 nanospheres were developed that exhibit 84.1% selectivity to 5-ethoxymethylfurfural (EMF) when HMF conversion reaches 92.0%, during etherification of 5-hydroxymethylfurfural (HMF) with ethanol under mild conditions. The catalyst could be reused, and its activity remained unaffected over five cycles. The strong acidity of the catalyst significantly enhanced etherification. The acetalized byproducts, 5-(diethoxymethyl)-2-furanmethanol and the HMF-dimer (5,5'(oxy-bis(methylene))bis-2-furfural), can be converted into HMF and then transformed to the main product, EMF, by using this catalyst to shift the reaction equilibrium. PMID:22749371

  18. A comparative multidimensional LC-MS proteomic analysis reveals mechanisms for furan aldehyde detoxification in Thermoanaerobacter pseudethanolicus 39E

    SciTech Connect

    Clarkson, Sonya M.; Hamilton-Brehm, Scott D.; Giannone, Richard J.; Engle, Nancy L.; Tschaplinski, Timothy J.; Hettich, Robert L.; Elkins, James G.

    2014-12-03

    Background: Chemical and physical pretreatment of lignocellulosic biomass improves substrate reactivity for increased microbial biofuel production, but also restricts growth via the release of furan aldehydes such as furfural and 5-hydroxymethylfurfural (5-HMF). The physiological effects of these inhibitors on thermophilic, fermentative bacteria is important to understand; especially as cellulolytic strains are being developed for consolidated bioprocessing (CBP) of lignocellulosic feedstocks. Identifying mechanisms for detoxification of aldehydes in naturally resistant strains such as Thermoanaerobacter spp. may also enable improvements in candidate CBP microorganisms. Results: T. pseudethanolicus 39E, an anaerobic, saccharolytic thermophile, was found to grow readily in the presence of 30 mM furfural and 20 mM 5-HMF and reduce these aldehydes to their respective alcohols in situ. The proteomes of T. pseudethanolicus 39E grown in the presence or absence of 15 mM furfural were compared to identify upregulated enzymes potentially responsible for the observed reduction. A total of 225 proteins were differentially regulated in response to the 15 mM furfural treatment with 152 upregulated vs. 73 downregulated. Only 86 proteins exhibited a 2-fold change in abundance in either direction. Of these, 53 were upregulated in the presence of furfural and 33 were downregulated. Two oxidoreductases were upregulated at least 2-fold by furfural and were targeted for further investigation: Teth39_1597, encodes a predicted butanol dehydrogenase (BdhA) and Teth39_1598, a predicted aldo/keto reductase (AKR). Both genes were cloned from T. pseudethanolicus 39E, with the respective enzymes overexpressed in E. coli and specific activities determined against a variety of aldehydes. BdhA showed significant activity with all aldehydes tested, including furfural and 5-HMF, using NADPH as the cofactor. AKR also showed significant activity with NADPH

  19. A comparative multidimensional LC-MS proteomic analysis reveals mechanisms for furan aldehyde detoxification in Thermoanaerobacter pseudethanolicus 39E

    DOE PAGESBeta

    Clarkson, Sonya M.; Hamilton-Brehm, Scott D.; Giannone, Richard J.; Engle, Nancy L.; Tschaplinski, Timothy J.; Hettich, Robert L.; Elkins, James G.

    2014-12-03

    Background: Chemical and physical pretreatment of lignocellulosic biomass improves substrate reactivity for increased microbial biofuel production, but also restricts growth via the release of furan aldehydes such as furfural and 5-hydroxymethylfurfural (5-HMF). The physiological effects of these inhibitors on thermophilic, fermentative bacteria is important to understand; especially as cellulolytic strains are being developed for consolidated bioprocessing (CBP) of lignocellulosic feedstocks. Identifying mechanisms for detoxification of aldehydes in naturally resistant strains such as Thermoanaerobacter spp. may also enable improvements in candidate CBP microorganisms. Results: T. pseudethanolicus 39E, an anaerobic, saccharolytic thermophile, was found to grow readily in the presence of 30more » mM furfural and 20 mM 5-HMF and reduce these aldehydes to their respective alcohols in situ. The proteomes of T. pseudethanolicus 39E grown in the presence or absence of 15 mM furfural were compared to identify upregulated enzymes potentially responsible for the observed reduction. A total of 225 proteins were differentially regulated in response to the 15 mM furfural treatment with 152 upregulated vs. 73 downregulated. Only 86 proteins exhibited a 2-fold change in abundance in either direction. Of these, 53 were upregulated in the presence of furfural and 33 were downregulated. Two oxidoreductases were upregulated at least 2-fold by furfural and were targeted for further investigation: Teth39_1597, encodes a predicted butanol dehydrogenase (BdhA) and Teth39_1598, a predicted aldo/keto reductase (AKR). Both genes were cloned from T. pseudethanolicus 39E, with the respective enzymes overexpressed in E. coli and specific activities determined against a variety of aldehydes. BdhA showed significant activity with all aldehydes tested, including furfural and 5-HMF, using NADPH as the cofactor. AKR also showed significant activity with NADPH, but only with four carbon butyr

  20. Discovery and characterization of a xylose reductase from Zymomonas mobilis ZM4.

    PubMed

    Agrawal, Manoj; Chen, Rachel Ruizhen

    2011-11-01

    Formation of xylitol, a byproduct from xylose fermentation, is a major limiting factor in ethanol production from xylose in engineered Zymomonas strains, yet the postulated xylose reductase remains elusive. We report here the discovery of xylose reductase in Zymomonas mobilis and, for the first time, to associate the enzyme function with its gene. Besides xylose and xylulose, the enzyme was active towards benzaldehyde, furfural, 5-hydroxymethyl furfural, and acetaldehyde, exhibiting nearly 150-times higher affinity with benzaldehyde than xylose. The discovery of xylose reductase paves the way for further improvement of xylose fermentation in Z. mobilis. The enzyme may also be used to mitigate toxicity of furfural and other inhibitors from plant biomass. PMID:21720846

  1. Predicted thermochemistry for chemical conversions of 5-hydroxymethylfurfural

    NASA Astrophysics Data System (ADS)

    Assary, Rajeev S.; Redfern, Paul C.; Hammond, Jeff R.; Greeley, Jeffrey; Curtiss, Larry A.

    2010-09-01

    The thermochemistry of various chemical transformations of 5-hydroxy methyl furfural (HMF) were investigated using highly accurate G AUSSIAN-4 (G4) theory. The conversion of HMF to nonane through aldol condensation, hydrogenation, and hydrogenolysis reactions was found to be thermodynamically favorable. The hydrogenation reactions involving the keto groups in the nonane reaction sequence were found to be enhanced at low temperatures and high pressures of H 2. The hydrogenation, selective oxidation, and hydration of HMF were also found to be thermodynamically favorable. Gas phase enthalpies of formation of all the intermediate compounds were calculated at the G4 level of theory and compared against existing experimental data.

  2. Predicted thermochemistry for chemical conversions of 5-hydroxymethylfurfural.

    SciTech Connect

    Assary, R. S.; Redfern, P. C.; Hammond, J. R.; Greeley, J.; Curtiss, L. A.; Northwestern Univ.

    2010-09-10

    The thermochemistry of various chemical transformations of 5-hydroxy methyl furfural (HMF) were investigated using highly accurate Gaussian-4 (G4) theory. The conversion of HMF to nonane through aldol condensation, hydrogenation, and hydrogenolysis reactions was found to be thermodynamically favorable. The hydrogenation reactions involving the keto groups in the nonane reaction sequence were found to be enhanced at low temperatures and high pressures of H{sub 2}. The hydrogenation, selective oxidation, and hydration of HMF were also found to be thermodynamically favorable. Gas phase enthalpies of formation of all the intermediate compounds were calculated at the G4 level of theory and compared against existing experimental data.

  3. Optimization of a Dynamic Hot Water Pretreatment of Switchgrass using Catalysis by Carbonation to Maximize Carbochemical Yields

    NASA Astrophysics Data System (ADS)

    Dhamdere, Rohit Tanaji

    A bio-refinery is a facility that converts renewable bio-resources into value-added chemicals and products. In this context of a bio-refinery, the production of the carbochemicals such as HMF, furfural and organic acids illustrate that multiple products can be produced from a renewable source such as lignocellulosic biomass (switchgrass). Traditionally, carbochemicals such as furfural and HMF are produced using inorganic acids such as H 2SO4, HCL, and H3PO4. The use of such acids requires the application of high cost materials of construction such as Hastelloy-C, titanium etc. The objective of this study is to develop a semi-continuous process for the conversion of switchgrass to carbochemicals such as HMF, furfural and organic acids. Moreover, the application of water as a green reaction medium and the utilization of carbonated water as a "green catalyst" were studied in this research. For the purpose of this study, we constructed a semi-continuous flow apparatus using three high precision Isco syringe pumps and a constant temperature oven to allow carbonation of the water over a range of temperatures and pressure to reactively pretreat switchgrass. Carbochemicals (furan-based aldehydes) and acids that were formed were detected using a Waters HPLC employing a Bio-Rad Aminex HPX-87H column with a PDA (photo diode array) detector at wavelengths range of 210 and 280nm. Oligosaccharides were detected using Dionex HPLC employing Bio-Rad Aminex HPX-87P column using a Shodex RI-101 refractive index detector. The kinetics of the formation and degradation of HMF and furfural were studied using the solver function in Microsoft Excel. Carbonated water clearly showed catalytic activity by increasing the yields of the HMF and furfural at temperatures of 220, 250 and 280°C. The highest catalytic activity was observed for HMF formation in carbonated water with a nine-fold increase in yields over that using neat subcritical water.

  4. Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings

    SciTech Connect

    Zhang, Hongbo; Canlas, Christian; Kropf, A. Jeremy; Elam, Jeffrey W.; Dumesic, James A; Marshall, Christopher L.

    2015-01-01

    TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and the Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.

  5. Detoxification of a lignocellulosic biomass slurry by soluble polyelectrolyte adsorption for improved fermentation efficiency.

    PubMed

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

    2011-09-01

    This study investigated the detoxification of a dilute acid pretreated Ponderosa pine slurry using the polyelectrolyte polyethyleneimine (PEI). The addition of polyelectrolyte to remove enzymatic and/or fermentation inhibitory compounds, that is, acetic acid, furfural, and 5-hydroxymethylfurfural (HMF), was performed either before or after enzymatic hydrolysis to determine the optimal process sequence. Negligible acetic acid, glucose, and xylose were removed regardless of where in the process the polymer addition was made. Maximum furfural and HMF separation was achieved with the addition of PEI to a clarified pre-enzymatic hydrolysis liquor, which showed that 88.3% of furfural and 66.4% of HMF could be removed. On the other hand, only 23.1% and 13.4% of furfural and HMF, respectively, were removed from a post-enzymatic hydrolysis sample; thus, the effects of enzymes, glucose, and wood solids on inhibitor removal were also investigated. The presence of solid particles >0.2 µm and unknown soluble components <10 kDa reduced inhibitory compound removal, but the presence of elevated glucose levels and enzymes (cellulases) did not affect the separation. The fermentability of detoxified versus undetoxified hydrolysate was also investigated. An ethanol yield of 92.6% of theoretical was achieved with Saccharomyces cerevisiae fermenting the detoxified hydrolyzate, while no significant ethanol was produced in the undetoxified hydrolyzate. These results indicate that PEI may provide a practical alternative for furan removal and detoxification of lignocellolosic hydrolysates, and that application before enzymatic hydrolysis minimizes separation interferences. PMID:21455936

  6. GRE2 from Scheffersomyces stipitis as an aldehyde reductase contributes tolerance to aldehyde inhibitors derived from lignocellulosic biomass

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Scheffersomyces (Pichia) stipitis is one of the most promising yeasts for industrial bioethanol production from lignocellulosic biomass. S. stipitis is able to in situ detoxify aldehyde inhibitors [such as furfural and 5-hydroxymethylfurfural (HMF)] to less toxic corresponding alcohols. However, the...

  7. Direct enzyme assay evidence confirms aldehyde reductase function of Ydr541cp and Ygl039wp from Saccharomyces cerevisiae

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aldehyde reductase gene ARI1 is a recently characterized member of intermediate subfamily under SDR (short-chain dehydrogenase/reductase) superfamily that revealed mechanisms of in situ detoxification of furfural and HMF for tolerance of Saccharomyces cerevisiae. Uncharacterized open reading frames ...

  8. Process design considerations for optimal production of ethanol from lignocellulose using available yeasts, including natural pentose-fermenting yeasts, and their derivatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To expand the biomass to fuel ethanol industry, process strategies are needed to foster the production and utilization of microorganisms which can survive and ferment both hexose (C6) and pentose (C5) sugars while exposed to inhibitors (such as ethanol, furfural, and hydroxymethylfurfural, or HMF). ...

  9. REMOVAL OF INHIBITORS FROM BIOMASS SUGARS USING A BIOLOGICAL PROCESS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A major constraint to fermentation of sugars in biomass hydrolysates is the presence of side-products of hydrolysis that are toxic to microorganisms. These chemicals include products of sugar degradation (furfural, 5-hydroxymethylfurfural (HMF), and levulinic acid), organic acids released from hemi...

  10. Insecticidal compounds against Drosophila melanogaster from Cornus officinalis Sieb. et Zucc.

    PubMed

    Miyazawa, Mitsuo; Anzai, Jun; Fujioka, Jun; Isikawa, Yukio

    2003-10-01

    Dimethyl malate (1) and 5-hydroxymethyl furfural (2) were isolated as insecticidal compounds by bioassay-guided fractionation from MeOH extract of the fruits of Cornus officinalis Sieb. et Zucc. Insecticidal activity against larvae of D. melanogaster was demonstrated: 1 and 2 gave the LC50 value of 6.15 and 11.8 micromol/mL of diet concentration, respectively. Acute toxicity against adults of D. melanogaster, 1 and 2 had the insecticidal activity, with the LD50 value of 21.5 and 34.0 microg/adult. PMID:14526912

  11. Anti-arthritic active fraction of Capparis spinosa L. fruits and its chemical constituents.

    PubMed

    Feng, Xiaolu; Lu, Jincai; Xin, Hailiang; Zhang, Lei; Wang, Yuliang; Tang, Kexuan

    2011-03-01

    The aim of this study was to ascertain the anti-arthritic active fraction of Capparis spinosa L. (Capparidaceae) fruits and its chemical constituents. The adjuvant arthritic rat model was developed to evaluate the anti-arthritic effects of different fractions of ethanol extraction from C. spinosa L. The fraction eluted by ethanol-water (50:50, v/v) had the most significant anti-arthritic activity. The chemical constituents of this fraction were therefore studied; seven known compounds were isolated and identified as: P-hydroxy benzoic acid; 5-(hydroxymethyl) furfural; bis(5-formylfurfuryl) ether; daucosterol; α-D-fructofuranosides methyl; uracil; and stachydrine. PMID:21372539

  12. A sensitive high performance liquid chromatographic method for determining small amounts of glycosylproteins.

    PubMed

    Sampietro, T; Lenzi, S; Giampietro, O; Cecchetti, P; Masoni, A; Navalesi, R

    1987-01-01

    We developed a simple isocratic high performance liquid chromatography (HPLC) method for the quantitative determination of 5-hydroxymethyl-2-furfuraldehyde (5-HMF) liberated by mild hydrolysis of small amounts of glycosyl proteins. The absorbance of hydrolysate components after HPLC separation was recorded at 280 nm. To detect substances possibly interfering with the 5-HMF peak we always recorded the ratio of the peak heights A280 nm/A254 nm which was a constant value of 4.4. For each sample the blank was obtained by reduction with NaBH4 before hydrolysis with oxalic acid 1 mol/l. The best NaBH4/protein ratio was found to be 4 mg/mg. With this method we measured the nonenzymatic glycosylation (glycation) as 5-HMF in samples with a protein concentration as low as 0.8 mg/ml. 5-HMF produced per milligram of protein was independent from protein concentration for a wide range (0.8-10 mg/ml). The mean coefficient of variation for within assay and between precision was 6.8 and 11.6%, respectively. The 5-HMF measured on plasma proteins from normal subjects (n = 7) was 0.16 +/- 0.04 nmol/mg. Protein from insulin-dependent diabetic patients was 0.31 +/- 0.07 nmol/mg. With this method we succeeded in detecting an excessive glycation of platelet membrane proteins in 13 type-I diabetic patients. PMID:3581652

  13. Detoxification of acidic biorefinery waste liquor for production of high value amino acid.

    PubMed

    Christopher, Meera; Anusree, Murali; Mathew, Anil K; Nampoothiri, K Madhavan; Sukumaran, Rajeev Kumar; Pandey, Ashok

    2016-08-01

    The current study evaluates the detoxification of acid pretreatment liquor (APL) using adsorbent (ADS 400 & ADS 800) or ion-exchange (A-27MP & A-72MP) resins and its potential for amino acid production. The APL is generated as a by-product from the pretreatment of lignocellulosic biomass and is rich monomeric sugars as well as sugar degradation products (fermentation inhibitors) such as furfural and hydroxymethyl furfural (HMF). Of the four resins compared, ADS 800 removed approximately 85% and 60% of furfural and HMF, respectively. ADS 800 could be reused for up to six cycles after regeneration without losing its adsorption properties. The study was further extended by assessing the fermentability of detoxified APL for l-lysine production using wild and mutant strains of Corynebacterium glutamicum. The detoxified APL was superior to APL for l-lysine production. PMID:26996259

  14. Evolutionarily engineered ethanologenic yeast detoxifies lignocellulosic biomass conversion inhibitors by reprogrammed pathways.

    PubMed

    Liu, Z Lewis; Ma, Menggen; Song, Mingzhou

    2009-09-01

    Lignocellulosic biomass conversion inhibitors, furfural and HMF, inhibit microbial growth and interfere with subsequent fermentation of ethanol, posing significant challenges for a sustainable cellulosic ethanol conversion industry. Numerous yeast genes were found to be associated with the inhibitor tolerance. However, limited knowledge is available about mechanisms of the tolerance and the detoxification of the biomass conversion inhibitors. Using a robust standard for absolute mRNA quantification assay and a recently developed tolerant ethanologenic yeast Saccharomyces cerevisiae NRRL Y-50049, we investigate pathway-based transcription profiles relevant to the yeast tolerance and the inhibitor detoxification. Under the synergistic inhibitory challenges by furfural and HMF, Y-50049 was able to withstand the inhibitor stress, in situ detoxify furfural and HMF, and produce ethanol, while its parental control Y-12632 failed to function till 65 h after incubation. The tolerant strain Y-50049 displayed enriched genetic background with significantly higher abundant of transcripts for at least 16 genes than a non-tolerant parental strain Y-12632. The enhanced expression of ZWF1 appeared to drive glucose metabolism in favor of pentose phosphate pathway over glycolysis at earlier steps of glucose metabolisms. Cofactor NAD(P)H generation steps were likely accelerated by enzymes encoded by ZWF1, GND1, GND2, TDH1, and ALD4. NAD(P)H-dependent aldehyde reductions including conversion of furfural and HMF, in return, provided sufficient NAD(P)(+) for NAD(P)H regeneration in the yeast detoxification pathways. Enriched genetic background and a well maintained redox balance through reprogrammed expression responses of Y-50049 were accountable for the acquired tolerance and detoxification of furfural to furan methanol and HMF to furan dimethanol. We present significant gene interactions and regulatory networks involved in NAD(P)H regenerations and functional aldehyde reductions under

  15. Catalytic hydrothermal conversion of carboxymethyl cellulose to value-added chemicals over metal-organic framework MIL-53(Al).

    PubMed

    Zi, Guoli; Yan, Zhiying; Wang, Yangxia; Chen, Yongjuan; Guo, Yunlong; Yuan, Fagui; Gao, Wenyu; Wang, Yanmei; Wang, Jiaqiang

    2015-01-22

    Catalytic hydrolysis of biomass over solid catalysts can be one of the most efficient pathways for a future sustainable society dependent on cellulose biomass. In this work metal-organic framework MIL-53(Al) without any functionalization was directly employed as an efficient heterogeneous catalyst for the hydrolysis of carboxymethyl cellulose (CMC) to 5-hydroxymethyl-furaldehyde (5-HMF) in aqueous phase. A 5-HMF molar yield of 40.3% and total reducing sugar (TRS) molar yield of 54.2% were obtained with water as single solvent at 473 K for 4 h. The catalyst could be reused three times without losing activity to a greater extent. With the remarkable advantages such as the use of water as single solvent and MIL-53(Al) as a novel heterogeneous green catalyst, the work provides a new platform for the production of value added chemicals and liquid fuels from biomass. PMID:25439879

  16. A direct RP-HPLC method for the determination of furanic aldehydes and acids in honey.

    PubMed

    Spano, Nadia; Ciulu, Marco; Floris, Ignazio; Panzanelli, Angelo; Pilo, Maria I; Piu, Paola C; Salis, Severyn; Sanna, Gavino

    2009-04-15

    In this study 5-hydroxymethyl-2-furaldehyde (HMF), 2-furaldehyde, 3-furaldehyde, 2-furoic acid and 3-furoic acid are contemporarily determined in honey using a swift and direct RP-HPLC approach. The validation protocol was performed in terms of detection and quantification limits, precision (by repeatability and reproducibility), linearity and accuracy (by recovery tests); the acceptability of the precision and accuracy results was positively verified using Horwitz's model and AOAC guidelines, respectively. The method was tested on 18 honey samples of different ages, and botanical and geographical origin. HMF and 2-furaldehyde correlated highly with the age of the samples, whereas no correlation was observed with regards to 2-furaldehyde and 2-furoic acid. Hypotheses relating to the formation of minority furanic compounds are also proposed. PMID:19174244

  17. Dehydration and oxidation of cellulose hydrolysis products in acidic solution

    SciTech Connect

    Garves, K.

    1981-01-01

    The dehydration of cotton cellulose in aqueous solutions in the presence of Ac/sub 2/O, AcOH, HCl, H/sub 2/SO/sub 4/ or HBr proceeded by hydrolysis to carbohydrates with acetate groups, followed by conversion to 5-(hydroxymethyl)furfural (I) and then, to levulinic acid (II) accompanied by humic acids. For the formation of I, HCl was a more efficient and selective catalyst than H/sub 2/SO/sub 4/, and the formation of II was promoted by high acid and H/sub 2/O concentrations in the medium. The addition of FeCl/sub 3/ to the dehydration mixture with HCl and continuous distillation led to the isolation of furfural.

  18. [Effect of furfural on the respiratory system].

    PubMed

    Pawłowicz, A; Droszcz, W; Garlicki, A; Kutyła, J; Kowalczyk, M

    1984-01-01

    Fifty-one workers of Butadien Plant, exposed to furfurol , had their respiratory system examined. Questionnaire studies demonstrated chronic bronchitis in 23.5% of subjects. Spirometric tests do not show subjective complaints. This seems to be related to hypercortisolemia, as experiments on animals indicate that furfurol inhalations increase corticosteroids concentrations in blood serum. PMID:6738348

  19. Manothermosonication of foods and food-resembling systems: effect on nutrient content and nonenzymatic browning.

    PubMed

    Vercet, A; Burgos, J; López-Buesa, P

    2001-01-01

    The effect of manothermosonication (MTS), an emergent technology for food preservation, on thiamin, riboflavin, carotenoids, and ascorbic acid was evaluated in milk and orange juice. The effect of both heat treatment and MTS on several compounds produced in nonenzymatic browning in model systems was also studied. MTS does not affect significantly the nutrient content studied. However, it changes the behavior of nonenzymatic browning. No formation of 5-(hydroxymethyl)-2-furfuraldehyde (HMF) was detected in fruit juice model systems after heat and MTS treatments at the experimental conditions used. In a milk-resembling system, free HMF formation by MTS is higher compared to that by heat treatment. As the MTS temperature increases, free HMF production by both treatments equaled on another. For bound HMF the production rate is lower by MTS than by heat treatment under the experimental conditions used. Formation kinetics of brown pigments and that of fluorescent compounds are different for both treatments. Fluorescence and brown pigment production are faster in MTS. PMID:11170615

  20. Exploring the inhibitory characteristics of acid hydrolysates upon butanol fermentation: A toxicological assessment.

    PubMed

    Wang, Yue; Guo, Wanqian; Chen, Bor-Yann; Cheng, Chieh-Lun; Lo, Yung-Chung; Ho, Shih-Hsin; Chang, Jo-Shu; Ren, Nanqi

    2015-12-01

    This study aimed to quantitatively evaluate the inhibitor tolerance of butanol-producing bacterium Clostridium acetobutylicum. The inhibitory effect of the inhibitors generated by acid pretreatment of biomass feedstock on butanol fermentation decreased in the order of formic acid>oxalic acid>furfural>5-HMF>Na2SO4. C. acetobutylicum has a small tolerance range for furfural (1.06-2.6g/L) and 5-HMF (1.99-2.3g/L). However, the inhibitory effect of Na2SO4 appears to have a wide range, with a chronic toxicity for C. acetobutylicum. All the results could explain, in quantitative manner, the instability of butanol fermentation with C. acetobutylicum from various acid-pretreated feedstocks caused by the fermentation inhibitors. PMID:26433154

  1. Conversion of different part core oil palm trunk into methyl levulinate & hydroxymethylfurfural production

    NASA Astrophysics Data System (ADS)

    Khosnan, Afifah Aqilah Alias; Jahar, NoorHasmiera Abu; Jaafar, Sharifah Nabihah Syed; Zakaria, Sarani; Hua, Chin Chia

    2015-09-01

    In this study, sugar was extracted from the of core oil palm trunk (OPT) and undergoes methanolysis process. The objective of this research is to study the production of methyl levulinate (MLA) and hydroxymethyl furfurals (HMF) from four different parts of OPT such as inner, middle, outer and whole. After methanolysis, samples were characterized by gas chromatography mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC).

  2. GRE2 from Scheffersomyces stipitis as an aldehyde reductase contributes tolerance to aldehyde inhibitors derived from lignocellulosic biomass.

    PubMed

    Wang, Xu; Ma, Menggen; Liu, Z Lewis; Xiang, Quanju; Li, Xi; Liu, Na; Zhang, Xiaoping

    2016-08-01

    Scheffersomyces (Pichia) stipitis is one of the most promising yeasts for industrial bioethanol production from lignocellulosic biomass. S. stipitis is able to in situ detoxify aldehyde inhibitors (such as furfural and 5-hydroxymethylfurfural (HMF)) to less toxic corresponding alcohols. However, the reduction enzymes involved in this reaction remain largely unknown. In this study, we reported that an uncharacterized open reading frame PICST_72153 (putative GRE2) from S. stipitis was highly induced in response to furfural and HMF stresses. Overexpression of this gene in Saccharomyces cerevisiae improved yeast tolerance to furfural and HMF. GRE2 was identified as an aldehyde reductase which can reduce furfural to FM with either NADH or NADPH as the co-factor and reduce HMF to FDM with NADPH as the co-factor. This enzyme can also reduce multiple aldehydes to their corresponding alcohols. Amino acid sequence analysis indicated that it is a member of the subclass "intermediate" of the short-chain dehydrogenase/reductase (SDR) superfamily. Although GRE2 from S. stipitis is similar to GRE2 from S. cerevisiae in a three-dimensional structure, some differences were predicted. GRE2 from S. stipitis forms loops at D133-E137 and T143-N145 locations with two α-helices at E154-K157 and E252-A254 locations, different GRE2 from S. cerevisiae with an α-helix at D133-E137 and a β-sheet at T143-N145 locations, and two loops at E154-K157 and E252-A254 locations. This research provided guidelines for the study of other SDR enzymes from S. stipitis and other yeasts on tolerant mechanisms to aldehyde inhibitors derived from lignocellulosic biomass. PMID:27003269

  3. The potential of biodetoxification activity as a probiotic property of Lactobacillus reuteri.

    PubMed

    van Niel, Ed W J; Larsson, Christer U; Lohmeier-Vogel, Elke M; Rådström, Peter

    2012-01-16

    Previous work on the metabolism of Lactobacillus reuteri ATCC 55730 anticipated a variability in the use of organic electron acceptors as a means to relieve metabolic redox problems. Therefore, investigations focusing on this unique metabolism of L. reuteri may reveal a basis for new probiotic properties. For instance, L. reuteri may use reactive aldehydes and ketones as electron acceptors to balance their redox metabolism, which opens the possibility to exploit this bacterium for in vivo bioreduction of deleterious compounds in the gastrointestinal tract (GIT). Herein we demonstrate that L. reuteri ATCC 55730 cultures on glucose are able to use furfural (1g/L), and hydroxymethylfurfural (HMF) (0.5g/L), as electron acceptors. The former enhances the growth rate by about 25% and biomass yield by 15%, whereas the latter is inhibitory. Furfural is stoichiometrically reduced to furfuryl alcohol by the culture. The conversion of furfural had no effect on the flux distribution between the simultaneously operating phosphoketolase and Embden-Meyerhof pathways, but initiated a flux to acetate production. In addition to furfural and HMF, cellular extracts showed potential to reoxidize NADH and/or NADPH with acrolein, crotonaldehyde, and diacetyl, indicating that conversion reactions take place intracellularly, however, utilization mechanisms for the latter compounds may not be present in this strain. The strain did not reduce other GIT-related reactive compounds, including acrylamide, glyoxal, and furan. PMID:22071286

  4. Molecular sieve adsorbents and membranes for applications in the production of renewable fuels and chemicals

    NASA Astrophysics Data System (ADS)

    Ranjan, Rajiv

    Metal organic frameworks (MOF), a new class of porous materials, have emerged as promising candidate for gas storage, separation membrane and chemical sensors. We used secondary growth method to grow microporous metal organic framework (MMOF) films on porous alumina supports. Examination of the film using SEM and XRD showed that the crystals were well inter-grown and preferentially oriented. Gas permeation study showed that membranes were defect free and moderate selectivity was achieved for H2/N2 gas pairs. The next project had to do with ethanol production from lignocellulosic biomass as an alternate energy source. However, toxic inhibitors produced from the hydrolysis of biomass decrease ethanol yield during the fermentation process. We demonstrated the use of zeolites for the pretreatment of hydrolyzate in order to remove inhibitors like 5-Hydroxymethylfurfuraldehyde (HMF) and furfural from aqueous solution. Zeolites exhibit preferential adsorption of the inhibitors and in effect improve the ethanol yield during fermentation. Ideal Adsorbed Solution Theory (IAST) was also used to predict adsorption isotherms for HMF-furfural mixtures using single component adsorption data. We also studied production of HMF, a potential substitute as a building block for plastic and chemical production, from renewable biomass resources. Catalytic dehydration of fructose for HMF production faces problems like low conversion and yield. Dimethyl sulfoxide (DMSO) can be used as the solvent as well as the catalyst resulting in high HMF yield. We studied a reaction-separation system for this dehydration reaction where the product (HMF) could be recovered by selective adsorption on solid adsorbents from the reaction mixture.

  5. Lanthanum(III)-catalyzed degradation of cellulose at 250 degrees C.

    PubMed

    Seri, Kei-ichi; Sakaki, Tsuyoshi; Shibata, Masao; Inoue, Yoshihisa; Ishida, Hitoshi

    2002-02-01

    Lanthanum(III) chloride was found to effectively catalyze the degradation of cellulose in water at 250 degrees C. The degradation conversion of cellulose in the presence of a catalytic amount of lanthanum chloride reached 80.3% after 180 s, which corresponded to the turnover number of 83, whereas the reaction did scarcely proceed in the absence of the catalyst. The degradation products were separately quantified as water-soluble (WS), methanol-soluble (MS), methanol-insoluble (MI), and gaseous (G) products. The HPLC and GC analyses revealed that the WS materials are mainly composed of 5-hydroxymethyl-2-furaldehyde (HMF), D-glucose, and levulinic acid. Cellobiose, the disaccharide component of cellulose, was scarcely detected during the reaction. PMID:11800491

  6. Separation of two constituents from purple sweet potato by combination of silica gel column and high-speed counter-current chromatography.

    PubMed

    He, Kai; Ye, Xiaoli; Li, Xuegang; Chen, Hongying; Yuan, Lujiang; Deng, Yafei; Chen, Xin; Li, Xiaoduo

    2012-01-15

    It is known that the choice of solvent system for high speed counter-current chromatography separation is of utmost importance. In this study, a simple and rapid thin layer chromatograph coupling with fluorometric (TLC-F) method has been used to determine the partition coefficient of target compounds in HSCCC solvent system. Two components, 6,7-dimethoxycoumarin and 5-hydroxymethyl-2-furfural were successfully separated from purple sweet potato extracts by successive sample injection for the first time, using n-hexane-ethyl acetate-methanol-water (1:2:1:1, v/v/v/v) as the solvent system. Additionally, statistical analysis showed that there was no significant difference in partition coefficient obtained by the TLC-F method and by HPLC, which demonstrated the usefulness of TLC-F method. PMID:22197606

  7. Nickel-tungsten carbide catalysts for the production of 2,5-dimethylfuran from biomass-derived molecules.

    PubMed

    Huang, Yao-Bing; Chen, Meng-Yuan; Yan, Long; Guo, Qing-Xiang; Fu, Yao

    2014-04-01

    The development of new catalytic systems for the conversion of biomass-derived molecules into liquid fuels has attracted much attention. We propose a non-noble bimetallic catalyst based on nickel-tungsten carbide for the conversion of the platform molecules 5-(hydroxymethyl)furfural into the liquid-fuel molecule 2,5-dimethylfuran (DMF). Different catalysts, metal ratios and reaction conditions have been tested and give rise to a 96% yield of DMF. The catalysts have been characterized and are discussed. The reaction mechanism is also explored through capture of reaction intermediates. The analysis of the reaction mixture over different catalysts is presented and helps to understand the role of nickel and tungsten carbide during the reaction. PMID:24574062

  8. On the Diels-Alder approach to solely biomass-derived polyethylene terephthalate (PET): conversion of 2,5-dimethylfuran and acrolein into p-xylene.

    PubMed

    Shiramizu, Mika; Toste, F Dean

    2011-10-24

    Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels-Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels-Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34% overall yield over four steps. PMID:21922576

  9. Acid-catalyzed conversion of mono- and poly-sugars into platform chemicals: effects of molecular structure of sugar substrate.

    PubMed

    Hu, Xun; Wu, Liping; Wang, Yi; Song, Yao; Mourant, Daniel; Gunawan, Richard; Gholizadeh, Mortaza; Li, Chun-Zhu

    2013-04-01

    Hydrolysis/pyrolysis of lignocellulosic biomass always produces a mixture of sugars with distinct structures as intermediates or products. This study tried to elucidate the effects of molecular structure of sugars on their acid-catalyzed conversions in ethanol/water. Location of carbonyl group in sugars (fructose versus glucose) and steric configuration of hydroxyl groups (glucose versus galactose) significantly affected yields of levulinic acid/ester (fructose>glucose>galactose). The dehydration of fructose to 5-(hydroxymethyl)furfural produces much less soluble polymer than that from glucose and galactose, which results in high yields of levulinic acid/ester from fructose. Anhydrate sugar such as levoglucosan tends to undergo the undesirable decomposition to form less levulinic acid/ester. Catalytic behaviors of the poly-sugars (sucrose, maltose, raffinose, β-cyclodextrins) were determined much by their basic units. However, their big molecular sizes create the steric hindrance that significantly affects their followed conversion over solid acid catalyst. PMID:23454803

  10. Chromatographic Evaluation and Characterization of Components of Gentian Root Extract Used as Food Additives.

    PubMed

    Amakura, Yoshiaki; Yoshimura, Morio; Morimoto, Sara; Yoshida, Takashi; Tada, Atsuko; Ito, Yusai; Yamazaki, Takeshi; Sugimoto, Naoki; Akiyama, Hiroshi

    2016-01-01

    Gentian root extract is used as a bitter food additive in Japan. We investigated the constituents of this extract to acquire the chemical data needed for standardized specifications. Fourteen known compounds were isolated in addition to a mixture of gentisin and isogentisin: anofinic acid, 2-methoxyanofinic acid, furan-2-carboxylic acid, 5-hydroxymethyl-2-furfural, 2,3-dihydroxybenzoic acid, isovitexin, gentiopicroside, loganic acid, sweroside, vanillic acid, gentisin 7-O-primeveroside, isogentisin 3-O-primeveroside, 6'-O-glucosylgentiopicroside, and swertiajaposide D. Moreover, a new compound, loganic acid 7-(2'-hydroxy-3'-O-β-D-glucopyranosyl)benzoate (1), was also isolated. HPLC was used to analyze gentiopicroside and amarogentin, defined as the main constituents of gentian root extract in the List of Existing Food Additives in Japan. PMID:26726749

  11. High-performance liquid chromatographic determination of methyl anthranilate, hydroxymethylfurfural and related compounds in honey.

    PubMed

    Nozal, M J; Bernal, J L; Toribio, L; Jiménez, J J; Martín, M T

    2001-05-11

    A high-performance liquid chromatographic method for determining 5-hydroxymethyl-2-furaldehyde (hydroxymethylfurfural), 2-furaldehyde (furfural), furan-2-carboxylic acid (2-furoic acid), furan-3-carboxylic acid (3-furoic acid), furan-3-carboxaldehyde (3-furaldehyde) and 2-aminobenzoic acid methyl ester (methyl anthranilate) in honey and honeydew samples is described. To prevent matrix interference and to isolate the compounds, a clean-up step which implies a solid-phase extraction on polymeric cartridges and an elution with 0.5 ml methanol is recommended. The compounds are separated on a reversed-phase column with a gradient of (A) 1% aqueous acetic acid-acetonitrile (97:3, v/v) and (B) acetonitrile-water (50:50, v/v), with UV detection at 250 nm. The method is applied to the analysis of samples from different botanical origin. PMID:11403496

  12. First report about pharmaceutical properties and phytochemicals analysis of Rosa abyssinica R. Br. ex Lindl. (Rosaceae).

    PubMed

    Moustafa, Mahmoud Fawzy; Alrumman, Sulaiman Abdullah

    2015-11-01

    In vitro antimicrobial efficacy of seven solvent extracts from leaves and hips of Saudi Arabian weed Rosa abyssinica against a variety of human pathogenic bacteria and Candida species have been evaluated using well diffusion methods. Phytochemicals present in the leaves and hips of Rosa abyssinica has been characterized using Gas Chromatogram Mass spectrometry analysis. The extracts comparative efficacy against tested microbes gained from the fresh and dry leaves exhibited more prominent activity than fresh and dry hips. The methanol, chloroform, petroleum ether, acetone and diethyl ether extracts have a greater lethal effect on pathogenic microbes than hot water extracts, while cold-water extracts showed no activity. Twenty-four phytochemicals have been characterized from ethanol extract of the leaves of Rosa abyssinica and fifteen from hips by GC-MS. The major compounds detected in the leaves were squalene (38.21%), ethane, 1,1-diethoxy- (9.65%), β-D-glucopyranose, 1,6-anhydro- (8.55%), furfural (5.50%) and 2-furancarboxaldehyde 5-(hydroxymethyl)- (5.19%). The major compounds in the hips were 2-furancarboxaldehyde 5-(hydroxymethyl)- (51.27%), β-D-glucopyranose, 1,6-anhydro- (8.18%), 4H-pyran-4-one, 2,3-dihydro-3,5-dihydroxy-6-methyl- (7.42%), 2,5-furandione, dihydro-3-methylene- (6.79%) and furfural (5.99%). Current findings indicate that extract from leaves and hips of Rosa abyssinica and the bioactive components present could be used as pharmaceutical agents. PMID:26639478

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

    PubMed Central

    Pacheco, Joshua J.; Davis, Mark E.

    2014-01-01

    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

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

    PubMed

    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

  15. Study of Influence of Heat Treatment on Cyclic Properties of L21HMF Cast Steel

    NASA Astrophysics Data System (ADS)

    Mroziński, Stanisław; Golański, Grzegorz

    2016-07-01

    This work presents the results of studies of CrMoV cast steel after long-term service and after regenerative heat treatment (RHT). The cast steel was investigated in the conditions of static and changeable load. The tests were carried out at room temperature and 550 °C. The fatigue lifetime curves were determined and described using the Basquin-Manson-Coffin relationship. It has been shown that the cast steel after RHT is characterized by smaller range of plastic strain and bigger range of stress amplitude, with the same value of total strain, compared with the cast steel after service. For the cast steel after RHT, the observed fatigue properties were different in comparison with the cast steel after service at small and large strains. At room temperature (20 °C) and at elevated temperature (550 °C), there is an increase in the life of samples of the cast steel after RHT in comparison with the samples of the cast steel after service only in the area of large strains ( ɛ ac > 1.2%). For small strains ɛ ac < 0.50%, the life of the cast steel after RHT at the examined temperatures is shorter than that of the cast steel after service. The paper shows that regardless of an explicit improvement in the strength properties (the static and cyclic ones), as a result of the performed RHT, a complete improvement in the fatigue properties of the cast steel does not occur.

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

    PubMed

    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

  17. An investigation of process contaminants' formation during the deep frying of breadcrumbs using a bread coat model.

    PubMed

    Mesías, M; Holgado, F; Márquez-Ruiz, G; Morales, F J

    2016-03-01

    The formation of acrylamide, hydroxymethylfurfural (HMF) and furfural was investigated in a deep fried breadcrumb coat model resembling the coat batter of breaded foods. The influence of the composition of the breadcrumb and the frying conditions on the formation of these contaminants was evaluated. Six wheat-based flour formulations of breadcrumbs were deep fried in sunflower oil at temperatures between 170-200 °C and for frying times of 1-5 minutes. Results showed significant differences in the levels of contaminants according to the concentration of the potential precursors in the breadcrumbs. HMF was influenced by the sugar content in the breadcrumbs whereas levels of acrylamide were significantly correlated with the ratio between asparagine and reducing sugars. Acrylamide, HMF and furfural were directly related to the frying time and temperature. The composition of the breadcrumb and the compounds formed during frying contributed to the total antioxidant capacity of the fried samples. The bread coat model is a useful tool in the formulation of breaded foods since it allows the evaluation of the contribution of breadcrumbs in the formation of process contaminants after frying. PMID:26938951

  18. Evaluation of antioxidant capacity in coffees marketed in Colombia: Relationship with the extent of non-enzymatic browning.

    PubMed

    Contreras-Calderón, José; Mejía-Díaz, Diana; Martínez-Castaño, Marcela; Bedoya-Ramírez, Daniel; López-Rojas, Natalia; Gómez-Narváez, Faver; Medina-Pineda, Yaqueline; Vega-Castro, Oscar

    2016-10-15

    Fifty-eight samples of commercial Colombian coffee with different characteristics (soluble, ground, decaffeinated, etc) were evaluated for antioxidant capacity (AC) (ABTS and FRAP), total soluble phenolics (TP), browning index (BI), color parameters (L(∗), a(∗), b(∗), c(∗) and h(∗)), HMF and furfural. The AC in Colombian coffees was very varied (164-1000, 100.8-885.9μmol of Trolox equiv/g and 12.5-127mg gallic acid equiv/g, respectively for ABTS, FRAP and TP). AC, TP, BI, color, HMF and furfural values were higher (p<0.05) in soluble coffees than in ground ones, showing the lyophilized samples which showed the highest average values. Significant lineal correlations (p<0.05) were found between AC and color parameters, BI, HMF. No significant (p<0.05) differences in the AC between the different types of coffee were found. This work confirms the direct relationship between the rate of non-enzymatic browning and antioxidant capacity. PMID:27173548

  19. Co-Utilization of Glucose and Xylose for Enhanced Lignocellulosic Ethanol Production with Reverse Membrane Bioreactors.

    PubMed

    Ishola, Mofoluwake M; Ylitervo, Päivi; Taherzadeh, Mohammad J

    2015-01-01

    Integrated permeate channel (IPC) flat sheet membranes were examined for use as a reverse membrane bioreactor (rMBR) for lignocellulosic ethanol production. The fermenting organism, Saccharomyces cerevisiae (T0936), a genetically-modified strain with the ability to ferment xylose, was used inside the rMBR. The rMBR was evaluated for simultaneous glucose and xylose utilization as well as in situ detoxification of furfural and hydroxylmethyl furfural (HMF). The synthetic medium was investigated, after which the pretreated wheat straw was used as a xylose-rich lignocellulosic substrate. The IPC membrane panels were successfully used as the rMBR during the batch fermentations, which lasted for up to eight days without fouling. With the rMBR, complete glucose and xylose utilization, resulting in 86% of the theoretical ethanol yield, was observed with the synthetic medium. Its application with the pretreated wheat straw resulted in complete glucose consumption and 87% xylose utilization; a final ethanol concentration of 30.3 g/L was obtained, which corresponds to 83% of the theoretical yield. Moreover, complete in situ detoxification of furfural and HMF was obtained within 36 h and 60 h, respectively, with the rMBR. The use of the rMBR is a promising technology for large-scale lignocellulosic ethanol production, since it facilitates the co-utilization of glucose and xylose; moreover, the technology also allows the reuse of the yeast for several batches. PMID:26633530

  20. Co-Utilization of Glucose and Xylose for Enhanced Lignocellulosic Ethanol Production with Reverse Membrane Bioreactors

    PubMed Central

    Ishola, Mofoluwake M.; Ylitervo, Päivi; Taherzadeh, Mohammad J.

    2015-01-01

    Integrated permeate channel (IPC) flat sheet membranes were examined for use as a reverse membrane bioreactor (rMBR) for lignocellulosic ethanol production. The fermenting organism, Saccharomyces cerevisiae (T0936), a genetically-modified strain with the ability to ferment xylose, was used inside the rMBR. The rMBR was evaluated for simultaneous glucose and xylose utilization as well as in situ detoxification of furfural and hydroxylmethyl furfural (HMF). The synthetic medium was investigated, after which the pretreated wheat straw was used as a xylose-rich lignocellulosic substrate. The IPC membrane panels were successfully used as the rMBR during the batch fermentations, which lasted for up to eight days without fouling. With the rMBR, complete glucose and xylose utilization, resulting in 86% of the theoretical ethanol yield, was observed with the synthetic medium. Its application with the pretreated wheat straw resulted in complete glucose consumption and 87% xylose utilization; a final ethanol concentration of 30.3 g/L was obtained, which corresponds to 83% of the theoretical yield. Moreover, complete in situ detoxification of furfural and HMF was obtained within 36 h and 60 h, respectively, with the rMBR. The use of the rMBR is a promising technology for large-scale lignocellulosic ethanol production, since it facilitates the co-utilization of glucose and xylose; moreover, the technology would also allow the reuse of the yeast for several batches. PMID:26633530

  1. Validation of a HPLC method for determination of hydroxymethylfurfural in crude palm oil.

    PubMed

    Ariffin, Abdul Azis; Ghazali, H M; Kavousi, Parviz

    2014-07-01

    For the first time 5-hydroxymethyl-2-furaldehyde (HMF) was separated from crude palm oil (CPO), and its authenticity was determined using an RP-HPLC method. Separation was accomplished with isocratic elution of a mobile phase comprising water and methanol (92:8 v/v) on a Purospher Star RP-18e column (250mm×4.6mm, 5.0μm). The flow rate was adjusted to 1ml/min and detection was performed at 284nm. The method was validated, and results obtained exhibit a good recovery (95.58% to 98.39%). Assessment of precision showed that the relative standard deviations (RSD%) of retention times and peak areas of spiked samples were less than 0.59% and 2.66%, respectively. Further, the limit of detection (LOD) and LOQ were 0.02, 0.05mg/kg, respectively, and the response was linear across the applied ranges. The crude palm oil samples analysed exhibited HMF content less than 2.27mg/kg. PMID:24518321

  2. Production of ethanol and furfural from corn stover

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Corn stover has potential for economical production of biofuels and value-added chemicals. The conversion of corn stover to sugars involves pretreatment and enzymatic hydrolysis. We have optimized hydrothermal, dilute H2SO4 and dilute H3PO4 pretreatments of corn stover for enzymatic saccharificati...

  3. Development of corn silk as a biocarrier for Zymomonas mobilis biofilms in ethanol production from rice straw.

    PubMed

    Todhanakasem, Tatsaporn; Tiwari, Rashmi; Thanonkeo, Pornthap

    2016-01-01

    Z. mobilis cell immobilization has been proposed as an effective means of improving ethanol production. In this work, polystyrene and corn silk were used as biofilm developmental matrices for Z. mobilis ethanol production with rice straw hydrolysate as a substrate. Rice straw was hydrolyzed by dilute sulfuric acid (H2SO4) and enzymatic hydrolysis. The final hydrolysate contained furfural (271.95 ± 76.30 ppm), 5-hydroxymethyl furfural (0.07 ± 0.00 ppm), vanillin (1.81 ± 0.00 ppm), syringaldehyde (5.07 ± 0.83 ppm), 4-hydroxybenzaldehyde (4-HB) (2.39 ± 1.20 ppm) and acetic acid (0.26 ± 0.08%). Bacterial attachment or biofilm formation of Z. mobilis strain TISTR 551 on polystyrene and delignified corn silk carrier provided significant ethanol yields. Results showed up to 0.40 ± 0.15 g ethanol produced/g glucose consumed when Z. mobilis was immobilized on a polystyrene carrier and 0.51 ± 0.13 g ethanol produced/g glucose consumed when immobilized on delignified corn silk carrier under batch fermentation by Z. mobilis TISTR 551 biofilm. The higher ethanol yield from immobilized, rather than free living, Z. mobilis could possibly be explained by a higher cell density, better control of anaerobic conditions and higher toxic tolerance of Z. mobilis biofilms over free cells. PMID:27118074

  4. Recovery of reducing sugars and volatile fatty acids from cornstalk at different hydrothermal treatment severity.

    PubMed

    Zhu, Zhangbing; Liu, Zhidan; Zhang, Yuanhui; Li, Baoming; Lu, Haifeng; Duan, Na; Si, Buchun; Shen, Ruixia; Lu, Jianwen

    2016-01-01

    This study focused on the degradation of cornstalk and recovery of reducing sugars and volatile fatty acids (VFAs) at different hydrothermal treatment severity (HTS) (4.17-8.28, 190-320°C). The highest recovery of reducing sugars and VFAs reached 92.39% of aqueous products, equal to 34.79% based on dry biomass (HTS, 6.31). GC-MS and HPLC identified that the aqueous contained furfural (0.35-2.88 g/L) and 5-hydroxymethyl furfural (0-0.85 g/L) besides reducing sugars and VFAs. Hemicellulose and cellulose were completely degraded at a HTS of 5.70 and 7.60, respectively. SEM analysis showed that cornstalk was gradually changed from rigid and highly ordered fibrils to molten and grainy structure as HTS increased. FT-IR and TGA revealed the significant changes of organic groups for cornstalk before and after hydrothermal treatment at different HTS. Hydrothermal treatment might be promising for providing feedstocks suitable for biohythane production. PMID:26316401

  5. Development and validation of a fast high pressure liquid chromatography method for the analysis of lignocellulosic biomass hydrolysis and fermentation products.

    PubMed

    Scarlata, Christopher J; Hyman, Deborah A

    2010-04-01

    A simple, precise, and accurate 10-min high pressure liquid chromatography (HPLC) method was developed and validated for the analysis of organic acids, alcohols, and furans from processing biomass into renewable fuels. The method uses an H(+) form cation-exchange resin stationary phase that has a five-fold shorter analysis time versus that in the traditional method. The new method was used for the analysis of acetic acid, ethanol, 5-hydroxymethyl furfural, and furfural. Results were compared with a legacy method that has historically has been used to analyze the same compounds but with a 55 min run time. Linearity was acceptable on the new method with r(2)>0.999 for all compounds using refractive index detection. Limits of detection were between 0.003 and 0.03 g/L and limits of quantification were between 0.1 and 0.01 g/L. The relative standard deviations for precision were less than 0.4% and recoveries ranged from 92% to 114% for all compounds. PMID:20202640

  6. Valorization of humin-based byproducts from biomass processing-a route to sustainable hydrogen.

    PubMed

    Hoang, Thi Minh Chau; Lefferts, Leon; Seshan, K

    2013-09-01

    The synthesis of biomass-based top value-added chemical platforms, for example, 5-hydroxymethyl furfural, furfural, or levulinic acid from the acid-catalyzed dehydration of sugars results in high yields of insoluble by-products, referred to as humin. Valorization of humin by steam reforming for H2 is discussed. Both thermal and catalytic steam gasification were investigated systematically. Humin undergoes drastic changes under thermal pre-treatment to the gasification temperature. Alkali-metal-based catalysts were screened for the reactions. Na2 CO3 showed the highest activity and was selected for further study. The presence of Na2 CO3 enhances the gasification rate drastically, and gas-product analysis shows that the selectivity to CO and CO2 is 75% and 25%, respectively, which is a H2 /CO ratio of 2 (corresponding to 81.3% H2 as compared to the thermodynamic equilibrium). A possible process for the complete, efficient conversion of humin is outlined. PMID:23939662

  7. Unorthodox methods for enhancing solvent production in solventogenic Clostridium species.

    PubMed

    Ujor, Victor; Okonkwo, Christopher; Ezeji, Thaddeus Chukwuemeka

    2016-02-01

    While production of biofuels from renewable resources is currently receiving increased attention globally, concerns on availability and sustainability of cheap substrates for their production are growing as well. Lignocellulose-derived sugars (LDS) remain underutilized and merit consideration as a key feedstock. Among other obstacles such as low yield and low solvent titer, mitigation of stresses stemming from lignocellulose-derived microbial inhibitory compounds (LDMICs) that severely impair cell growth and solvent production is a major area of research interest. In addition to attempts at developing LDMIC-tolerant strains via metabolic engineering to enhance utilization of LDS, unconventional approaches that elicit different metabolic perturbations in microorganisms to relieve solvent- and LDMIC-mediated stresses have been explored to increase solvent production from LDS. In this review, the impacts of metabolic perturbations including medium supplementation with glycerol; furfural and 5-hydroxymethyl furfural; allopurinol, an inhibitor of xanthine dehydrogenase; calcium (Ca(2+)) and zinc (Zn(2+)) ions); and artificial electron carriers, methyl viologen and neutral red, on butanol production are discussed. Although these approaches have brought about considerable increases in butanol production, both from LDS and defined glucose-based media, the modes of action for most of these perturbations have yet to be fully characterized. Better understanding of these mechanisms would likely inform development of LDMIC-tolerant, butanol-overproducing strains, as well as possible combinatorial application of these approaches for enhanced butanol production. Hence, delineating the underlying mechanisms of these perturbations deserves further attention. PMID:26596572

  8. Effects of biopretreatment on pyrolysis behaviors of corn stalk by methanogen.

    PubMed

    Wang, Tipeng; Ye, Xiaoning; Yin, Jun; Lu, Qiang; Zheng, Zongming; Dong, Changqing

    2014-07-01

    The study investigated the effects of methanogen pretreatment on pyrolysis behaviors of corn stalk (CS) by using Py-GC/MS analysis and thermogravimetric analysis. Results indicated that biopretreatment changed considerably the pyrolysis behaviors of CS from four weight loss stages to two weight loss stages. Increasing biopretreatment time from 5 days to 25 days enhanced the kinds and contents of chemicals in volatile products. In pyrolysis products, the contents of sugars, linear ketones and furans decreased from 1.43%, 12.60% and 7.38% to 1.25%, 10.22% and 3.25%, respectively, and the contents of phenols increased from 15.08% to 27.84%. The most content change from 6.83% to 13.63% indicated that methanogen pretreatment improved the pyrolysis selectivity of CS to product the 4-VP, but it was disadvantageous to 5-hydroxymethyl furfural, levoglucose and furfural. The changes of chemical compositions and structure of CS after biopretreatment were the main reason of the differences. PMID:24855936

  9. Effect of carbonyl inhibitors and their H₂O₂ detoxification on lactic acid fermentation.

    PubMed

    Li, Jing; Zhu, Caiqing; Tu, Maobing; Han, Pingping; Wu, Yonnie

    2015-04-01

    Biomass degradation compounds significantly inhibit biochemical conversion of biomass prehydrolysates to biofuels and chemicals, such as lactic acid. To characterize the structure-activity relationship of carbonyl inhibition on lactic acid fermentation, we examined effects of eight carbonyl compounds (furfural, 5-hydroxymethyl furfural, vanillin, syringaldehyde, 4-hydroxybenzaldehyde, phthalaldehyde, benzoic acid, and pyrogallol aldehyde) and creosol on lactic acid production by Lactobacillus delbrueckii. Pyrogallol aldehyde reduced the cell growth rate by 35 % at 1.0 mM and inhibited lactic acid production completely at 2.0 mM. By correlating the molecular descriptors to the inhibition constants in lactic acid fermentation, we found a good relationship between the hydrophobicity (Log P) of aldehydes and their inhibition constants in fermentation. The inhibitory effect of carbonyl inhibitors appeared to correlate with their thiol reactivity as well. In addition, we found that H2O2 detoxified pyrogallol aldehyde and phthalaldehyde inhibitory activity. H2O2 detoxification was applied to real biomass prehydrolysates in lactic acid fermentation. PMID:25666370

  10. Adaptation and Transcriptome Analysis of Aureobasidium pullulans in Corncob Hydrolysate for Increased Inhibitor Tolerance to Malic Acid Production

    PubMed Central

    Zou, Xiang; Wang, Yongkang; Tu, Guangwei; Zan, Zhanquan; Wu, Xiaoyan

    2015-01-01

    Malic acid is a dicarboxylic acid widely used in the food industry, and is also a potential C4 platform chemical. Corncob is a low-cost renewable feedstock from agricultural industry. However, side-reaction products (furfural, 5-hydroxymethylfurfural (HMF), formic acid, and acetic acid) that severely hinder fermentation are formed during corncob pretreatment. The process for producing malic acid from a hydrolysate of corncob was investigated with a polymalic acid (PMA)-producing Aureobasidium pullulans strain. Under the optimal hydrolysate sugar concentration 110 g/L, A. pullulans was further adapted in an aerobic fibrous bed bioreactor (AFBB) by gradually increasing the sugar concentration of hydrolysate. After nine batches of fermentation, the production and productivity of malic acid reached 38.6 g/L and 0.4 g/L h, respectively, which was higher than that in the first batch (27.6 g/L and 0.29 g/L h, respectively). The adapted strain could grow under the stress of 0.5 g/L furfural, 3 g/L HMF, 2g/L acetic acid, and 0.5 g/L formic acid, whereas the wild type did not. Transcriptome analysis revealed that the differentially expressed genes were related to carbohydrate transport and metabolism, lipid transport and metabolism, signal transduction mechanism, redox metabolism, and energy production and conversion under 0.5 g/L furfural and 3 g/L HMF stress conditions. In total, 42 genes in the adapted strain were upregulated by 15-fold or more, and qRT-PCR also confirmed that the expression levels of key genes (i.e. SIR, GSS, CYS, and GSR) involved in sulfur assimilation pathway were upregulated by over 10-fold in adapted strain for cellular protection against oxidative stress. PMID:25793624

  11. Effects of the Deslagging Process on some Physicochemical Parameters of Honey

    PubMed Central

    Ranjbar, Ali Mohammad; Sadeghpour, Omid; Khanavi, Mahnaz; Shams Ardekani, Mohammad Reza; Moloudian, Hamid; Hajimahmoodi, Mannan

    2015-01-01

    Some physicochemical parameters of honey have been introduced by the International Honey Commission to evaluate its quality and origin but processes such as heating and filtering can affect these parameters. In traditional Iranian medicine, deslagging process involves boiling honey in an equal volume of water and removing the slag formed during process. The aim of this study was to determine the effects of deslagging process on parameters of color intensity, diastase evaluation, electrical conductivity, pH, free acidity, refractive index, hydroxy methyl furfural (HMF), proline and water contents according to the International Honey Committee (IHC) standards. The results showed that deslagged honey was significantly different from control honey in terms of color intensity, pH, diastase number, HMF and proline content. It can be concluded that the new standards are needed to regulate deslagged honey. PMID:25901175

  12. Effects of the Deslagging Process on some Physicochemical Parameters of Honey.

    PubMed

    Ranjbar, Ali Mohammad; Sadeghpour, Omid; Khanavi, Mahnaz; Shams Ardekani, Mohammad Reza; Moloudian, Hamid; Hajimahmoodi, Mannan

    2015-01-01

    Some physicochemical parameters of honey have been introduced by the International Honey Commission to evaluate its quality and origin but processes such as heating and filtering can affect these parameters. In traditional Iranian medicine, deslagging process involves boiling honey in an equal volume of water and removing the slag formed during process. The aim of this study was to determine the effects of deslagging process on parameters of color intensity, diastase evaluation, electrical conductivity, pH, free acidity, refractive index, hydroxy methyl furfural (HMF), proline and water contents according to the International Honey Committee (IHC) standards. The results showed that deslagged honey was significantly different from control honey in terms of color intensity, pH, diastase number, HMF and proline content. It can be concluded that the new standards are needed to regulate deslagged honey. PMID:25901175

  13. Glucose and fructose to platform chemicals: understanding the thermodynamic landscapes of acid-catalysed reactions using high-level ab initio methods.

    PubMed

    Assary, Rajeev S; Kim, Taejin; Low, John J; Greeley, Jeff; Curtiss, Larry A

    2012-12-28

    Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2-OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2-OH position, which includes a C-C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future. PMID:22932938

  14. Industrial robust yeast isolates with great potential for fermentation of lignocellulosic biomass.

    PubMed

    Pereira, Francisco B; Romaní, Aloia; Ruiz, Héctor A; Teixeira, José A; Domingues, Lucília

    2014-06-01

    The search of robust microorganisms is essential to design sustainable processes of second generation bioethanol. Yeast strains isolated from industrial environments are generally recognised to present an increased stress tolerance but no specific information is available on their tolerance towards inhibitors that come from the pretreatment of lignocellulosic materials. In this work, a strategy for the selection of different yeasts using hydrothermal hydrolysate from Eucalyptus globulus wood, containing different concentrations of inhibitors, was developed. Ten Saccharomyces cerevisiae and four Kluyveromyces marxianus strains isolated from industrial environments and four laboratory background strains were evaluated. Interestingly, a correlation between final ethanol titer and percentage of furfural detoxification was observed. The results presented here highlight industrial distillery environments as a remarkable source of efficient yeast strains for lignocellulosic fermentation processes. Selected strains were able to resourcefully degrade furfural and HMF inhibitors, producing 0.8g ethanol/Lh corresponding to 94% of the theoretical yield. PMID:24704884

  15. Biorefineries based on coffee cut-stems and sugarcane bagasse: furan-based compounds and alkanes as interesting products.

    PubMed

    Aristizábal M, Valentina; Gómez P, Álvaro; Cardona A, Carlos A

    2015-11-01

    This work presents a techno-economic and environmental assessment for a biorefinery based on sugarcane bagasse (SCB), and coffee cut-stems (CCS). Five scenarios were evaluated at different levels, conversion pathways, feedstock distribution, and technologies to produce ethanol, octane, nonane, furfural, and hydroxymethylfurfural (HMF). These scenarios were compared between each other according to raw material, economic, and environmental characteristics. A single objective function combining the Net Present Value and the Potential Environmental Impact was used through the Analytic Hierarchy Process approach to understand and select the best configurations for SCB and CCS cases. The results showed that the configuration with the best economic and environmental performance for SCB and CCS is the one that considers ethanol, furfural, and octane production (scenario 1). The global economic margin was 62.3% and 61.6% for SCB and CCS respectively. The results have shown the potential of these types of biomass to produce fuels and platform products. PMID:26280100

  16. Degradation kinetics of the main carbohydrates in birch wood during hot water extraction in a batch reactor at elevated temperatures.

    PubMed

    Borrega, Marc; Nieminen, Kaarlo; Sixta, Herbert

    2011-11-01

    Hot water extraction of wood at elevated temperatures may be a suitable method to produce hemicellulose-lean pulps and to recover xylan-derived products from the water extract. In this study, water extractions of birch wood were conducted at temperatures between 180 and 240 °C in a batch reactor. Xylan was extensively removed, whereas cellulose was partly degraded only at temperatures above 180 °C. Under severe extraction conditions, acetic acid content in the water extract was higher than the corresponding amount of acetyl groups in wood. In addition to oligo- and monosaccharides, considerable amounts of furfural and 5-hydroxymethylfurfural (HMF) were recovered from the extracts. After reaching a maximum, the furfural yield remained constant with increasing extraction time. This maximum slightly decreased with increasing extraction temperature, suggesting the preferential formation of secondary degradation products from xylose. Kinetic models fitting experimental data are proposed to explain degradation and conversion reactions of xylan and glucan. PMID:21967712

  17. Decomposition of cellulose by ultrasonic welding in water

    NASA Astrophysics Data System (ADS)

    Nomura, Shinfuku; Miyagawa, Seiya; Mukasa, Shinobu; Toyota, Hiromichi

    2016-07-01

    The use of ultrasonic welding in water to decompose cellulose placed in water was examined experimentally. Filter paper was used as the decomposition material with a horn-type transducer 19.5 kHz adopted as the ultrasonic welding power source. The frictional heat at the point where the surface of the tip of the ultrasonic horn contacts the filter paper decomposes the cellulose in the filter paper into 5-hydroxymethylfurfural (5-HMF), furfural, and oligosaccharide through hydrolysis and thermolysis that occurs in the welding process.

  18. Micellar electrokinetic chromatography method for the simultaneous determination of furanic compounds in honey and vegetable oils.

    PubMed

    Foo Wong, Yong; Makahleh, Ahmad; Al Azzam, Khaldun M; Yahaya, Noorfatimah; Saad, Bahruddin; Sulaiman, Siti Amrah

    2012-08-15

    A simple micellar electrokinetic chromatography (MEKC) method for the simultaneous determination of 2-furfural (2-F), 3-furfural (3-F), 5-methylfurfural (5-MF), 5-hydroxymethylfurfural (5-HMF), 2-furoic acid (2-FA) and 3-furoic acid (3-FA) in honey and vegetable oils is described. Parameters affecting the separation such as pH, buffer and surfactant concentrations, applied voltage, capillary temperature, injection time and capillary length were studied and optimized. The separation was carried out in normal polarity mode at 20 °C, 22 kV and using hydrodynamic injection (17 s). The separation was achieved in a bare fused-silica capillary (46 cm × 50 μm i.d.) with a background electrolyte of 75 mM phosphoric acid (pH 7.3), containing 200 mM of sodium dodecyl sulphate (SDS). The detection wavelengths were at 200 nm (2-FA and 3-FA) and 280 nm (2-F, 3-F, 5-MF, 5-HMF). The furfurals were well separated in less than 20 min. The method was validated in terms of linearity, limit of detection and quantitation, precision and recoveries. Calibration curves of the six furfurals were well correlated (r(2)>0.991) within the range 1-25 μg mL(-1). Relative standard deviations of intra- and inter-day migration times and corrected peak areas ≤9.96% were achieved. The limit of detection (signal:noise, 3) was 0.33-0.70 μg mL(-1) whereas the limit of quantitation (signal:noise, 10) was 1.00-2.12 μg mL(-1). The method was applied to the determination of furanic compounds in honeys and vegetable oils (palm, walnut, grape seed and rapeseed). The effects of thermal treatment and gamma irradiation on the formation of the furanic compounds in honey were also investigated. PMID:22841043

  19. Discovery of N-(4-Fluoro-3-methoxybenzyl)-6-(2-(((2S,5R)-5-(hydroxymethyl)-1,4-dioxan-2-yl)methyl)-2H-tetrazol-5-yl)-2-methylpyrimidine-4-carboxamide. A Highly Selective and Orally Bioavailable Matrix Metalloproteinase-13 Inhibitor for the Potential Treatment of Osteoarthritis.

    PubMed

    Ruminski, Peter G; Massa, Mark; Strohbach, Joseph; Hanau, Cathleen E; Schmidt, Michelle; Scholten, Jeffrey A; Fletcher, Theresa R; Hamper, Bruce C; Carroll, Jeffery N; Shieh, Huey S; Caspers, Nicole; Collins, Brandon; Grapperhaus, Margaret; Palmquist, Katherine E; Collins, Joe; Baldus, John E; Hitchcock, Jeffrey; Kleine, H Peter; Rogers, Michael D; McDonald, Joseph; Munie, Grace E; Messing, Dean M; Portolan, Silvia; Whiteley, Laurence O; Sunyer, Teresa; Schnute, Mark E

    2016-01-14

    Matrix metalloproteinase-13 (MMP-13) is a zinc-dependent protease responsible for the cleavage of type II collagen, the major structural protein of articular cartilage. Degradation of this cartilage matrix leads to the development of osteoarthritis. We previously have described highly potent and selective carboxylic acid containing MMP-13 inhibitors; however, nephrotoxicity in preclinical toxicology species precluded development. The accumulation of compound in the kidneys mediated by human organic anion transporter 3 (hOAT3) was hypothesized as a contributing factor for the finding. Herein we report our efforts to optimize the MMP-13 potency and pharmacokinetic properties of non-carboxylic acid leads resulting in the identification of compound 43a lacking the previously observed preclinical toxicology at comparable exposures. PMID:26653735

  20. Improvement of the fermentability of oxalic acid hydrolysates by detoxification using electrodialysis and adsorption.

    PubMed

    Jeong, So-Yeon; Trinh, Ly Thi Phi; Lee, Hong-Joo; Lee, Jae-Won

    2014-01-01

    A two-step detoxification process consisting of electrodialysis and adsorption was performed to improve the fermentability of oxalic acid hydrolysates. The constituents of the hydrolysate differed significantly between mixed hardwood and softwood. Acetic acid and furfural concentrations were high in the mixed hardwood, whereas 5-hydroxymethylfurfural (HMF) concentration was relatively low compared with that of the mixed softwood. The removal efficiency of acetic acid reached 100% by electrodialysis (ED) process in both hydrolysates, while those of furfural and HMF showed very low, due to non-ionizable properties. Most of the remaining inhibitors were removed by XAD-4 resin. In the mixed hardwood hydrolysate without removal of the inhibitors, ethanol fermentation was not completed. Meanwhile, both ED-treated hydrolysates successfully produced ethanol with 0.08 and 0.15 g/Lh ethanol productivity, respectively. The maximum ethanol productivity was attained after fermentation with 0.27 and 0.35 g/Lh of detoxified hydrolysates, which were treated by ED, followed by XAD-4 resin. PMID:24321607

  1. Inhibitory effects of furan derivatives and phenolic compounds on dark hydrogen fermentation.

    PubMed

    Lin, Richen; Cheng, Jun; Ding, Lingkan; Song, Wenlu; Zhou, Junhu; Cen, Kefa

    2015-11-01

    The inhibitory effects of furan derivatives [i.e. furfural and 5-hydroxymethylfurfural (5-HMF)] and phenolic compounds (i.e. vanillin and syringaldehyde) on dark hydrogen fermentation from glucose were comparatively evaluated. Phenolic compounds exhibited stronger inhibition on hydrogen production and glucose consumption than furan derivatives under the same 15mM concentration. Furan derivatives were completely degraded after 72h fermentation, while over 55% of phenolic compounds remained unconverted after 108h fermentation. The inhibition coefficients of vanillin (14.05) and syringaldehyde (11.21) were higher than those of 5-HMF (4.35) and furfural (0.64). Vanillin exhibited the maximum decrease of hydrogen yield (17%). The consumed reducing power by inhibitors reduction from R-CHO to RCH2OH was a possible reason contributed to the decreased hydrogen yield. Vanillin exhibited the maximum delay of peak times of hydrogen production rate and glucose consumption. Soluble metabolites and carbon conversion efficiency decreased with inhibitors addition, which were consistent with hydrogen production. PMID:26247976

  2. Isolation of microorganisms for biological detoxification of lignocellulosic hydrolysates.

    PubMed

    López, M J; Nichols, N N; Dien, B S; Moreno, J; Bothast, R J

    2004-03-01

    Acid pretreatment of lignocellulosic biomass releases furan and phenolic compounds, which are toxic to microorganisms used for subsequent fermentation. In this study, we isolated new microorganisms for depletion of inhibitors in lignocellulosic acid hydrolysates. A sequential enrichment strategy was used to isolate microorganisms from soil. Selection was carried out in a defined mineral medium containing a mixture of ferulic acid (5 mM), 5-hydroxymethylfurfural (5-HMF, 15 mM), and furfural (20 mM) as the carbon and energy sources, followed by an additional transfer into a corn stover hydrolysate (CSH) prepared using dilute acid. Subsequently, based on stable growth on these substrates, six isolates--including five bacteria related to Methylobacterium extorquens, Pseudomonas sp, Flavobacterium indologenes, Acinetobacter sp., Arthrobacter aurescens, and one fungus, Coniochaeta ligniaria--were chosen. All six isolates depleted toxic compounds from defined medium, but only C. ligniaria C8 (NRRL 30616) was effective at eliminating furfural and 5-HMF from CSH. C. ligniaria NRRL 30616 may be useful in developing a bioprocess for inhibitor abatement in the conversion of lignocellulosic biomass to fuels and chemicals. PMID:12908085

  3. Oil production by oleaginous yeasts using the hydrolysate from pretreatment of wheat straw with dilute sulfuric acid.

    PubMed

    Yu, Xiaochen; Zheng, Yubin; Dorgan, Kathleen M; Chen, Shulin

    2011-05-01

    This paper explores the use of the hydrolysate from the dilute sulfuric acid pretreatment of wheat straw for microbial oil production. The resulting hydrolysate was composed of pentoses (24.3g/L) and hexoses (4.9 g/L), along with some other degradation products, such as acetic acid, furfural, and hydroxymethylfurfural (HMF). Five oleaginous yeast strains, Cryptococcus curvatus, Rhodotorula glutinis, Rhodosporidium toruloides, Lipomyces starkeyi, and Yarrowia lipolytica, were evaluated by using this hydrolysate as substrates. The results showed that all of these strains could use the detoxified hydrolysate to produce lipids while except R. toruloides non-detoxified hydrolysate could also be used for the growth of all of the selective yeast strains. C. curvatus showed the highest lipid concentrations in medium on both the detoxified (4.2g/L) and non-detoxified (5.8 g/L) hydrolysates. And the inhibitory effect studies on C. curvatus indicated HMF had insignificant impacts at a concentration of up to 3g/L while furfural inhibited cell growth and lipid content by 72.0% and 62.0% at 1g/L, respectively. Our work demonstrates that lipid production is a promising alternative to utilize hemicellulosic sugars obtained during pretreatment of lignocellulosic materials. PMID:21463940

  4. Connecting lignin-degradation pathway with pre-treatment inhibitor sensitivity of Cupriavidus necator.

    PubMed

    Wang, Wei; Yang, Shihui; Hunsinger, Glendon B; Pienkos, Philip T; Johnson, David K

    2014-01-01

    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. PMID:24904560

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

    SciTech Connect

    Wang, W.; Yang, S.; Hunsinger, G. B.; Pienkos, P. T.; Johnson, D. K.

    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.

  6. Connecting lignin-degradation pathway with pre-treatment inhibitor sensitivity of Cupriavidus necator

    PubMed Central

    Wang, Wei; Yang, Shihui; Hunsinger, Glendon B.; Pienkos, Philip T.; Johnson, David K.

    2014-01-01

    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. PMID:24904560

  7. [Effect of byproducts in lignocellulose hydrolysates on ethanol fermentation by Issatchenkia orientalis].

    PubMed

    Wang, Fengqin; Liu, Yaqiong; Zhang, Rui; Wang, Yuanyuan; Xie, Hui; Song, Andong

    2014-05-01

    Byproducts in lignocellulose hydrolysates, namely sodium formate (1 to 5 g/L), sodium acetic (2.5 to 8.0 g/L), furfural (0.2-2 g/L), 5-hydroxymethylfurfural (5-HMF, 1 to 1.0 g/L) or vanillin (0.5 to 2 g/L) were used to evaluate their effects on ethanol fermentation by Issatchenkia orientalis HN-1 using single factor test and the response surface central composite experiment. Results showed that most of the byproducts had no obvious inhibition on the production of ethanol, except for the addition of 2 g/L vanillin or 1 g/L of 5-HMF, which reduced the ethanol production by 20.38% and 11.2%, respectively. However, high concentration of some byproducts in lignocellulose hydrolysates, such as sodium formate (1 to 5 g/L), sodium acetic (2.5 to 8.0 g/L), furfural (0.2 to 2 g/L) and vanillin (0.5 to 2 g/L) inhibited the growth of I. orientalis HN-1 significantly. Compared with the control, the dry cell weight of I. orientalis HN-1 decreased by 25.04% to 37.02%, 28.83% to 43.82%, 20.06% to 37.60% and 26.39% to 52.64%, respectively, when the above components were added into the fermentation broth and the fermentation lasted for 36 h. No significant interaction effect of the various inhibitors (sodium formate, sodium acetic, furfural and vanillin) except for vanillin single factor on the ethanol production was observed based on the central composite experiments. The concentrations of byproducts in most lignocellulose hydrolysates were below the initial inhibition concentration on ethanol production by Issatchenkia orientalis HN-1, which indicated that Issatchenkia orientalis HN-1 can be used for ethanol production from lignocellulose hydrolysates. PMID:25118399

  8. Saccharomyces cerevisiae strain improvement using selection, mutation, and adaptation for the resistance to lignocellulose-derived fermentation inhibitor for ethanol production.

    PubMed

    Jang, Youri; Lim, Younghoon; Kim, Keun

    2014-05-01

    Twenty-five Saccharomyces cerevisiae strains were screened for the highest sugar tolerance, ethanol-tolerance, ethanol production, and inhibitor resistance, and S. cerevisiae KL5 was selected as the best strain. Inhibitor cocktail (100%) was composed of 75 mM formic acid, 75 mM acetic acid, 30 mM furfural, 30 mM hydroxymethyl furfural (HMF), and 2.7 mM vanillin. The cells of strain KL5 were treated with γ-irradiation, and among the survivals, KL5- G2 with improved inhibitor resistance and the highest ethanol yield in the presence of inhibitor cocktail was selected. The KL5-G2 strain was adapted to inhibitor cocktail by sequential transfer of cultures to a minimal YNB medium containing increasing concentrations of inhibitor cocktail. After 10 times of adaptation, most of the isolated colonies could grow in YNB with 80% inhibitor cocktail, whereas the parental KL5 strain could not grow at all. Among the various adapted strains, the best strain (KL5-G2-A9) producing the highest ethanol yield in the presence of inhibitor cocktail was selected. In a complex YP medium containing 60% inhibitor cocktail and 5% glucose, the theoretical yield and productivity (at 48 h) of KL5- G2-A9 were 81.3% and 0.304 g/l/h, respectively, whereas those of KL5 were 20.8% and 0.072 g/l/h, respectively. KL5-G2-A9 reduced the concentrations of HMF, furfural, and vanillin in the medium in much faster rates than KL5. PMID:24608567

  9. One-pot conversions of lignocellulosic and algal biomass into liquid fuels.

    PubMed

    De, Sudipta; Dutta, Saikat; Saha, Basudeb

    2012-09-01

    The one-pot conversion of lignocellulosic and algal biomass into a liquid fuel, 2,5-dimethylfuran (DMF), has been achieved by using a multicomponent catalytic system comprising [DMA]⁺ [CH₃SO₃]⁻ (DMA=N,N-dimethylacetamide), Ru/C, and formic acid. The synthesis of DMF from all substrates was carried out under mild reaction conditions. The reaction progressed via 5-hydroxyemthylfurfural (HMF) in the first step followed by hydrogenation and hydrogenolysis of HMF with the Ru/C catalyst and formic acid as a hydrogen source. This report discloses the effectiveness of the Ru/C catalyst for the first time for DMF synthesis from inexpensive and readily abundant biomass sources, which gives a maximum yield of 32 % DMF in 1 h. A reaction route involving 5-(formyloxymethyl)furfural (FMF) as an intermediate has been elucidated based on the ¹H and ¹³C NMR spectroscopic data. Another promising biofuel, 5-ethoxymethylfurfural (EMF), was also synthesized with high selectivity from polymeric carbohydrate-rich biomass substrates by using a Brønsted acidic ionic liquid catalyst, that is [DMA]⁺ [CH₃SO₃]⁻, by etherification of HMF in ethanol. PMID:22639414

  10. Characterization and quantification of major constituents of Xue Fu Zhu Yu by UPLC-DAD-MS/MS.

    PubMed

    Zhang, Lei; Zhu, Lin; Wang, Yuefei; Jiang, Zhenzuo; Chai, Xin; Zhu, Yan; Gao, Xiumei; Qi, Aidi

    2012-03-25

    Xue Fu Zhu Yu (XFZY), a classic recipe in traditional Chinese medicine (TCM), has been demonstrated to show protective effects on cardiovascular system. For quality control of XFZY products, qualitative analysis using ultra high performance liquid chromatography with diode-array detector-tandem mass spectrometry (UPLC-DAD-MS) was undertaken. Twenty-eight compounds from XFZY were simultaneously detected; among them, seventeen compounds were unequivocally identified, and another eight compounds were tentatively characterized. According to qualitative results, a new method for quantitative analysis of XFZY has been established by ultra high performance liquid chromatography coupled with diode array detector (UPLC-DAD). Twelve representative compounds unequivocally identified were used as chemical markers in quantitative analysis, including 5-hydroxymethyl-2-furaldehyde (5-HMF), hydroxysafflor yellow A (HSYA), amygdalin, albiflorin, paeoniflorin, liquiritin, ferulic acid (FA), naringin, hesperidin, neohesperidin (NH), isoliquiritigenin (IL) and glycyrrhizic acid (GA), which were derived from nine of eleven herbs of XFZY except Platycodon grandiflorum (Jacq.) A. DC. (Jiegeng) and Bupleurum chinense DC. (Chaihu). This UPLC method was validated in terms of linearity, LOD and LOQ, precision, repeatability, stability, and recovery tests. Quality control of XFZY products in total fourteen samples by four dosage forms was examined by this method, and results confirmed its feasibility and reliability in practice. PMID:22264846

  11. A mass spectrometric study of the acid-catalysed d-fructose dehydration in the gas phase.

    PubMed

    Pepi, Federico; Ricci, Andreina; Garzoli, Stefania; Troiani, Anna; Salvitti, Chiara; Di Rienzo, Brunella; Giacomello, Pierluigi

    2015-09-01

    5-hydroxymethylfuraldehyde (5-HMF) and simpler compounds, such as levulinic acid (LA) and glyceraldehyde, are platform molecules produced by the thermal acid-catalyzed dehydration of carbohydrates coming from biomass. Understanding sugar degradation pathways on a molecular level is necessary to increase selectivity, reduce degradation by-products yields and optimize catalytic strategies, fundamental knowledge for the development of a sustainable renewable industry. In this work gaseous protonated d-fructose ions, generated in the ESI source of a triple quadrupole mass spectrometer, were allowed to undergo Collisionally Activated Decomposition (CAD) into the quadrupole collision cell. The ionic intermediates and products derived from protonated d-fructose dehydration were structurally characterized by their fragmentation patterns and the relative water-loss dehydration energies measured by energy-resolved CAD mass spectra. The data were compared with those obtained from protonated d-glucose decomposition in the same experimental conditions. In the gas phase, d-fructose dehydration leads to the formation of a mixed population of isomeric [C6H6O3]H(+) ions, whose structures do not correspond exclusively to 5-hydroxymethyl-2-furaldehyde protonated at the more basic aldehydic group. PMID:26122965

  12. Antibacterial activity of Alpinia galanga (L) Willd crude extracts.

    PubMed

    Rao, Kiranmayee; Ch, Bhuvaneswari; Narasu, Lakshmi M; Giri, Archana

    2010-10-01

    Methanol, acetone and diethyl ether extracts of Alpinia galanga have been evaluated against pathogens viz. Bacillus subtilis MTCC 2391, Enterobacter aerogene, Enterobacter cloacae, Enterococcus faecalis, Escherichia coli MTCC 1563, Klebsiella pneumoniae, Pseudomonas aeruginosa MTCC 6642, Salmonella typhimurium, Staphylococcus aureus and Streptococcus epidermis using Agar well diffusion method. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of all the extracts were determined using the macrodilution method. Methanol extracts have shown excellent activity towards all the pathogens with MIC and MBC values ranging from 0.04-1.28 mg/ml and 0.08-2.56 mg/ml, respectively. The GC-MS analysis of methanol extracts have yielded compounds like 5-hydroxymethyl furfural (59.9%), benzyl alcohol (57.6%), 1,8 cineole (15.65%), methylcinnamate (9.4%), 3-phenyl-2-butanone (8.5%) and 1,2 benzenedicarboxylic acid (8.9%), which could be responsible for its broad spectrum activity. So, A. galanga can be quite resourceful for the development of new generation drugs. PMID:20387130

  13. Quality Evaluation of Polar and Active Components in Crude and Processed Fructus Corni by Quantitative Analysis of Multicomponents with Single Marker

    PubMed Central

    Jiang, Yuhong; Chen, Hui; Wang, Liling; Zou, Jing; Zheng, Xiao

    2016-01-01

    Objective. To develop a quantitative analysis of multicomponents by single-marker (QAMS) method for the simultaneous determination of polar active components in Fructus Corni. Methods. Loganin was selected as the internal reference, and the relative correction factors (RCFs) of gallic acid, 5-hydroxymethyl-2-furfural, morroniside, sweroside, cornin, 7α-O-methylmorroniside, 7β-O-methylmorroniside, 7α-O-ethylmorroniside, 7β-O-ethylmorroniside, and cornuside were established. The contents of multicomponents were then calculated based on their RCFs, respectively. Contents of the 11 components were also calculated by external standard method and compared with those of the QAMS method. Results. The contents of the 11 components in 21 crude and 10 processed Fructus Corni products were measured. No significant difference was found in the quantitative results of the QAMS and external standard methods. Conclusion. QAMS could serve as an accurate and convenient method in determining the polar and active components in Fructus Corni and its processed products. PMID:27446632

  14. Protective Effect of Salicornia europaea Extracts on High Salt Intake-Induced Vascular Dysfunction and Hypertension

    PubMed Central

    Panth, Nisha; Park, Sin-Hee; Kim, Hyun Jung; Kim, Deuk-Hoi; Oak, Min-Ho

    2016-01-01

    High salt intake causes and aggravates arterial hypertension and vascular dysfunction. We investigated the effect of Salicornia europaea extracts (SE) on vascular function and blood pressure. SE constituents were analyzed using high performance liquid chromatography, and SE’s effect on vascular function was evaluated in isolated porcine coronary arteries. SE’s vascular protective effect was also evaluated in vivo using normotensive and spontaneous hypertensive rats (SHRs). SE mainly contained sodium chloride (55.6%), 5-(hydroxymethyl)furfural, p-coumaric acid, and trans-ferulic acid. High sodium (160 mmol/L) induced vascular dysfunction; however, SE containing the same quantity of sodium did not cause vascular dysfunction. Among the compounds in SE, trans-ferulic acid accounts for the vascular protective effect. Normotensive rats fed a high-salt diet showed significantly increased systolic blood pressure (SBP), diastolic blood pressure (DBP), and mean arterial pressure (MAP), which decreased significantly in the SE-treated groups. In SHRs, high edible salt intake significantly increased SBP, DBP, and MAP, but SE intake was associated with a significantly lower MAP. Thus, SE did not induce vascular dysfunction, and trans-ferulic acid might be at least partly responsible for the vasoprotective effect of SE. Taken together, SE could be used as an alternative to purified salt to prevent and ameliorate hypertension. PMID:27455235

  15. Phytochemistry, antioxidant capacity, total phenolic content and anti-inflammatory activity of Hibiscus sabdariffa leaves.

    PubMed

    Zhen, Jing; Villani, Thomas S; Guo, Yue; Qi, Yadong; Chin, Kit; Pan, Min-Hsiung; Ho, Chi-Tang; Simon, James E; Wu, Qingli

    2016-01-01

    A liquid chromatography-mass spectrometry method was developed for the simultaneous separation, and determination of natural compounds including phenolic acids and flavonoids in the leaves of Hibiscus sabdariffa. By analyzing the UV and MS data, and comparison with authenticated standards, 10 polyphenols including neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, quercetin, kaempferol and their glycosides were identified together with 5-(hydroxymethyl)furfural. Major constituents in the leaves of 25 different populations from worldwide accessions were quantified and compared with each other. The total phenolic content of each accession was determined using Folin-Ciocalteu assay, ranging from 18.98 ± 2.7 to 29.9 ± 0.5 mg GAE/g. Their in vitro antioxidant activities were measured by ABTS radical cation decolorization assay, varying from 17.5 to 152.5 ± 18.8 μmol Trolox/g. After the treatment of H. sabdariffa leaf extract, the reduction of LPS-induced NO production dose-dependently in RAW 264.7 cell indicates the extract's potential anti-inflammatory activity. PMID:26213025

  16. Protective Effect of Salicornia europaea Extracts on High Salt Intake-Induced Vascular Dysfunction and Hypertension.

    PubMed

    Panth, Nisha; Park, Sin-Hee; Kim, Hyun Jung; Kim, Deuk-Hoi; Oak, Min-Ho

    2016-01-01

    High salt intake causes and aggravates arterial hypertension and vascular dysfunction. We investigated the effect of Salicornia europaea extracts (SE) on vascular function and blood pressure. SE constituents were analyzed using high performance liquid chromatography, and SE's effect on vascular function was evaluated in isolated porcine coronary arteries. SE's vascular protective effect was also evaluated in vivo using normotensive and spontaneous hypertensive rats (SHRs). SE mainly contained sodium chloride (55.6%), 5-(hydroxymethyl)furfural, p-coumaric acid, and trans-ferulic acid. High sodium (160 mmol/L) induced vascular dysfunction; however, SE containing the same quantity of sodium did not cause vascular dysfunction. Among the compounds in SE, trans-ferulic acid accounts for the vascular protective effect. Normotensive rats fed a high-salt diet showed significantly increased systolic blood pressure (SBP), diastolic blood pressure (DBP), and mean arterial pressure (MAP), which decreased significantly in the SE-treated groups. In SHRs, high edible salt intake significantly increased SBP, DBP, and MAP, but SE intake was associated with a significantly lower MAP. Thus, SE did not induce vascular dysfunction, and trans-ferulic acid might be at least partly responsible for the vasoprotective effect of SE. Taken together, SE could be used as an alternative to purified salt to prevent and ameliorate hypertension. PMID:27455235

  17. Analytical method of free and conjugated neutral aroma components in tobacco by solvent extraction coupled with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

    PubMed

    Ding, Yu; Zhu, Lijun; Liu, Shaomin; Yu, Hanqing; Dai, Ya

    2013-03-01

    A reliable and simple method for quantitative analysis of free and conjugated neutral aroma components (including aldehydes, ketones, alcohols, esters and alkenes) in tobacco using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC × GC-TOFMS) is described. Simple solvent extraction using methyl tert-butyl ether (MTBE) ensured extraction of the neutral aroma components in their free form. The components present as conjugates were isolated using MTBE extraction following acid-catalysed hydrolysis. The GC × GC-TOFMS analysis was performed to comprehensively identify different forms of neutral aroma components in tobacco. Compared with the conventional methods, our method not only simplified the process but also saved time and solvent. It also exhibited higher selectivity and sensitivity and demonstrated the following results: the limit of detection of the neutral aroma components varied from 0.006 μg/g for 2-acetylfuran to 0.133 μg/g for 5-(hydroxymethyl)-2-furfural, the relative standard deviations were from 0.5% to 6.8% and the recovery ranged from 82.4% to 118.2%. The optimized method was successfully employed to analyse real tobacco samples. Eighty-three neutral aroma components of interest were identified. PMID:23357748

  18. Generation of Maillard compounds from inulin during the thermal processing of Agave tequilana Weber Var. azul.

    PubMed

    Mancilla-Margalli, Norma A; López, Mercedes G

    2002-02-13

    During the cooking process of Agave tequilana Weber var. azul to produce tequila, besides the hydrolysis of inulin to generate fermentable sugars, many volatiles, mainly Maillard compounds, are produced, most of which may have a significant impact on the overall flavor of tequila. Exudates (agave juice) from a tequila company were collected periodically, and color, Brix, fructose concentration, and reducing sugars were determined as inulin breakdown took place. Maillard compounds were obtained by extraction with CH(2)Cl(2), and the extracts were analyzed by GC-MS. Increments in color, Brix, and reducing sugars were observed as a function of time, but a decrease in fructose concentration was found. Many Maillard compounds were identified in the exudates, including furans, pyrans, aldehydes, and nitrogen and sulfur compounds. The most abundant Maillard compounds were methyl-2-furoate, 2,3-dihydroxy-3,5-dihydro-6-methyl-4(H)-pyran-4-one, and 5-(hydroxymethyl)furfural. In addition, a series of short- and long-chain fatty acids was also found. A large number of the volatiles in A. tequilana Weber var. azul were also detected in tequila extracts, and most of these have been reported as a powerful odorants, responsible for the unique tequila flavor. PMID:11829648

  19. Yeast metabolic state identification using micro-fiber optics spectroscopy

    NASA Astrophysics Data System (ADS)

    Silva, J. S.; Castro, C. C.; Vicente, A. A.; Tafulo, P.; Jorge, P. A. S.; Martins, R. C.

    2011-05-01

    Saccharomyces cerevisiae morphology is known to be dependent on the cell physiological state and environmental conditions. On their environment, wild yeasts tend to form complex colonies architectures, such as stress response and pseudohyphal filaments morphologies, far away from the ones found inside bioreactors, where the regular cell cycle is observed under controlled conditions (e.g. budding and flocculating colonies). In this work we explore the feasibility of using micro-fiber optics spectroscopy to classify Saccharomyces cerevisiae S288C colony structures in YPD media, under different growth conditions, such as: i) no alcohol; ii) 1 % (v/v) Ethanol; iii) 1 % (v/v) 1-butanol; iv) 1 % (v/v) Isopropanol; v) 1 % (v/v) Tert-Amyl alcohol (2 Methyl-2-butanol); vi) 0,2 % (v/v) 2-Furaldehyde; vii) 5 % (w/v) 5 (Hydroxymethyl)-furfural; and viii) 1 % (w/v) (-)-Adenosine3', 5'cyclic monophosphate. The microscopy system includes a hyperspectral camera apparatus and a micro fiber (sustained by micro manipulator) optics system for spectroscopy. Results show that micro fiber optics system spectroscopy has the potential for yeasts metabolic state identification once the spectral signatures of colonies differs from each others. This technique associated with others physico-chemical information can benefit the creation of an information system capable of providing extremely detailed information about yeast metabolic state that will aid both scientists and engineers to study and develop new biotechnological products.

  20. Imaging flow cytometry for automated detection of hypoxia-induced erythrocyte shape change in sickle cell disease.

    PubMed

    van Beers, Eduard J; Samsel, Leigh; Mendelsohn, Laurel; Saiyed, Rehan; Fertrin, Kleber Y; Brantner, Christine A; Daniels, Mathew P; Nichols, James; McCoy, J Philip; Kato, Gregory J

    2014-06-01

    In preclinical and early phase pharmacologic trials in sickle cell disease, the percentage of sickled erythrocytes after deoxygenation, an ex vivo functional sickling assay, has been used as a measure of a patient's disease outcome. We developed a new sickle imaging flow cytometry assay (SIFCA) and investigated its application. To perform the SIFCA, peripheral blood was diluted, deoxygenated (2% oxygen) for 2 hr, fixed, and analyzed using imaging flow cytometry. We developed a software algorithm that correctly classified investigator tagged "sickled" and "normal" erythrocyte morphology with a sensitivity of 100% and a specificity of 99.1%. The percentage of sickled cells as measured by SIFCA correlated strongly with the percentage of sickle cell anemia blood in experimentally admixed samples (R = 0.98, P ≤ 0.001), negatively with fetal hemoglobin (HbF) levels (R = -0.558, P = 0.027), negatively with pH (R = -0.688, P = 0.026), negatively with pretreatment with the antisickling agent, Aes-103 (5-hydroxymethyl-2-furfural) (R = -0.766, P = 0.002), and positively with the presence of long intracellular fibers as visualized by transmission electron microscopy (R = 0.799, P = 0.002). This study shows proof of principle that the automated, operator-independent SIFCA is associated with predictable physiologic and clinical parameters and is altered by the putative antisickling agent, Aes-103. SIFCA is a new method that may be useful in sickle cell drug development. PMID:24585634