Trichostatin A induces 5-lipoxygenase promoter activity and mRNA expression via inhibition of histone deacetylase 2 and 3

The 5-lipoxygenase (5-LO) is the key enzyme in the formation of leukotrienes. We have previously shown that the histone deacetylase (HDAC) inhibitor trichostatin A (TSA) activates 5-LO transcription via recruitment of Sp1, Sp3 and RNA polymerase II to the proximal promoter. To identify the HDACs involved in the regulation of 5-LO promoter activity isoform-specific HDAC inhibitors were applied. 5-LO promoter activity and mRNA expression were up-regulated by the class I HDAC inhibitors apicidin and MS-275 but not by class II inhibitors. Knockdown of HDAC 1, 2 and 3 revealed that HDAC2 and HDAC3 but not HDAC1 is involved in the up-regulation of 5-LO mRNA expression. To analyse the chromatin modifications at the 5-LO promoter associated with HDAC inhibition, the time course of 5-LO mRNA induction by trichostatin A was investigated and the concomitant changes in histone modifications at the 5-LO promoter in HL-60, U937 and Mono Mac6 cells were determined. Chromatin immunoprecipitation analysis revealed that trichostatin A increases acetylation of histones H3 and H4 at the 5-LO core promoter in HL-60 and U937 cells whereas no significant changes were observed in Mono Mac6 cells. The appearance of H3 and H4 acetylation preceded the 5-LO mRNA induction whereas in all three cell lines, induction of 5-LO mRNA expression correlated with histone H3 lysine 4 trimethylation (H3K4me3), a marker for transcriptional activity of gene promoters

Gas-phase dehydration of glycerol over thermally-stable SAPO-40 catalyst

SAPO-40 was used as catalyst for the gas-phase dehydration of glycerol towards acrolein. At 350 ºC the catalyst attained full conversion of glycerol with a negligible deactivation in the first 48 h, a glycerol conversion above 50 % after 120 h on stream and a nearly constant selectivity to acrolein above 70%. This catalyst proved to be highly resistant under the experimental conditions used and can be regenerated without loss of activity or significant structural damage. The comparison of SAPO-40 with SAPO-34 and SAPO-11 illustrates the importance of the porous structure and emphasizes the good catalytic performance of this material

Catalytic Dehydration of Glycerol to Acrolein in a Two-Zone Fluidized Bed Reactor

The gas-phase catalytic dehydration of glycerol to acrolein was carried out in a Two-Zone Fluidized-Bed Reactor (TZFBR) using a 20 wt. % phosphotungstic acid (H3PW12O40) catalyst supported on CARIACT-Q10 commercial silica. In the first step, a hydrodynamic study of the reactor was performed. A quality of fluidization of more than 80% was obtained. In the second step, the mechanical stability of the catalyst was studied. It was found that only the external layer of active phase is eliminated under the conditions of operation whereas the global composition of the catalyst was not significantly affected after 44 h of fluidization. Finally, in a third step, the influence of the main operating parameters on the overall catalytic performances (glycerol/oxygen molar ratio and relative volumes of the reaction and regeneration zones) was investigated, showing notably the importance of the O2/glycerol ratio, resulting in an inverse trend between conversion and selectivity. Increasing O2/glycerol ratio led to higher conversion (lower coke deposit as shown by TGA analysis), but to the detriment of the selectivity to acrolein, supposedly due to the presence of O2 in the reaction zone causing the degradation of glycerol and acrolein

Catalytic gas-phase glycerol processing over SiO2-, Cu-, Ni-and Fe-supported Au nanoparticles

In this study, we investigated different metal pairings of Au nanoparticles (NPs) as potential catalysts for glycerol dehydration for the first time. All of the systems preferred the formation of hydroxyacetone (HYNE). Although the bimetallics that were tested, i.e., Au NPs supported on Ni, Fe and Cu appeared to be more active than the Au/SiO2 system, only Cu supported Au NPs gave high conversion (ca. 63%) and selectivity (ca. 70%) to HYNE

Influence of Phase Composition of Bulk Tungsten Vanadium Oxides on the Aerobic Transformation of Methanol and Glycerol

[EN] A series of W-V-O catalysts with different m-WO3 and h-WO3 phase contents were hydrothermally synthesized by employing different tungsten, vanadium, and ammonium precursors and characterized by powder XRD, N-2 adsorption, SEM, X-ray energy-dispersive spectroscopy, thermogravimetric analysis, Raman and FTIR spectroscopy, NH3 temperature programmed desorption, H-2 temperature-programmed reduction, and XPS. Finally, the acid/redox properties were analyzed by using aerobic transformation of methanol as a characterization reaction. A correlation between phase composition as well as acid and redox properties was observed, which were correlated to the catalytic performance of the title materials in a one-pot oxydehydration reaction of glycerol. The hexagonal tungsten bronze (h-WO3) phase shows a significantly higher concentration of acid sites than monoclinic m-WO3, so that the acid properties of W-V-O oxides are directly related to the presence of h-WO3 crystals. The presence of a higher concentration of acid sites in V-containing h-WO3 crystals is a key factor to achieve high selectivity to both acrolein and acrylic acid during one-pot glycerol oxydehydration. Also, V sites in h-WO3 show higher selectivity in the consecutive reaction (partial oxidation of acrolein to acrylic acid), while V sites in the m-WO3 phase fundamentally lead to the formation of carbon oxides.The authors acknowledge the DGICYT in Spain, CTQ2015-68951-C3-1-R and CTQ2015-68951-C3-3-R. Authors from ITQ also thank Project SEV-2016-0683 for financial support. D. D. thanks MINECO and Severo Ochoa Excellence Program for his fellowship (SVP-2014-068669). The research group of Prof. Fabrizio Cavani (University of Bologna, Italy)and Consorzio INSTM (Firenze) are gratefully acknowledged for a PhD grant to A. C. Authors also thank the Electron Microscopy Service of Universitat Politecnica de Valencia for their support.Delgado-Muñoz, D.; Chieregato, A.; Soriano Rodríguez, MD.; Rodríguez-Aguado, E.; Ruiz-Rodríguez, L.; Rodriguez-Castellon, E.; López Nieto, JM. (2018). Influence of Phase Composition of Bulk Tungsten Vanadium Oxides on the Aerobic Transformation of Methanol and Glycerol. European Journal of Inorganic Chemistry. 10:1204-1211. https://doi.org/10.1002/ejic.201800059S1204121110GUO, J.-D., & WHITTINGHAM, M. S. (1993). TUNGSTEN OXIDES AND BRONZES: SYNTHESIS, DIFFUSION AND REACTIVITY. International Journal of Modern Physics B, 07(23n24), 4145-4164. doi:10.1142/s0217979293003607Long, H., Zeng, W., & Zhang, H. (2015). Synthesis of WO3 and its gas sensing: a review. Journal of Materials Science: Materials in Electronics, 26(7), 4698-4707. doi:10.1007/s10854-015-2896-4Haldolaarachchige, N., Gibson, Q., Krizan, J., & Cava, R. J. (2014). 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Promoted Hexagonal Tungsten Bronzes as Selective Catalysts in the Aerobic Transformation of Alcohols: Glycerol and Methanol. Topics in Catalysis, 59(2-4), 178-185. doi:10.1007/s11244-015-0440-7Nagy, D., Nagy, D., Szilágyi, I. M., & Fan, X. (2016). Effect of the morphology and phases of WO3 nanocrystals on their photocatalytic efficiency. RSC Advances, 6(40), 33743-33754. doi:10.1039/c5ra26582gLin, S., Guo, Y., Li, X., & Liu, Y. (2015). Glycine acid-assisted green hydrothermal synthesis and controlled growth of WO3 nanowires. Materials Letters, 152, 102-104. doi:10.1016/j.matlet.2015.03.099Miao, B., Zeng, W., Hussain, S., Mei, Q., Xu, S., Zhang, H., … Li, T. (2015). Large scale hydrothermal synthesis of monodisperse hexagonal WO3 nanowire and the growth mechanism. Materials Letters, 147, 12-15. doi:10.1016/j.matlet.2015.02.020Marques, A. C., Santos, L., Costa, M. N., Dantas, J. M., Duarte, P., Gonçalves, A., … Fortunato, E. (2015). 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Structure-reactivity correlations in Vanadium containing catalysts for the one-pot glycerol oxidehydration to acrylic acid

[EN] The design of suitable catalysts for the one-pot conversion of glycerol into acrylic acid (AA) is a complex matter, as only fine-tuning of the redox and acid properties makes it possible to obtain significant yields of AA. However, fundamental understanding behind the catalytic phenomenon is still unclear. Structure-reactivity correlations are clearly behind these results, and acid sites are involved in the dehydration of glycerol into acrolein with vanadium as the main (or only) redox element. For the first time, we propose an in-depth study to shed light on the molecular-level relations behind the overall catalytic results shown by several types of V-containing catalysts. Different multifunctional catalysts were synthesized, characterized (>X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, temperature-programmed reduction, and temperature-programmed desorption of ammonia), and tested in a flow reactor. Combining the obtained results with those acquired from an in situ FTIR spectroscopy study with acrolein (a reaction intermediate), it was possible to draw conclusions on the role played by the various physicochemical features of the different oxides in terms of the adsorption, surface reactions, and desorption of the reagents and reaction products.The Instituto de Tecnologia Quimica thanks the Spanish Government-MINECO projects (CTQ2015-68951-C3-1-R and SEV-2012-0267). CIRI Energia e Ambiente (University of Bologna) is acknowledged for a Ph.D. grant to A.C. Consorzio INSTM (Firenze) is acknowledged for a Ph.D. grant to C.B.Chieregato, A.; Bandinelli, C.; Concepción Heydorn, P.; Soriano Rodríguez, MD.; Puzzo, F.; Basile, F.; Cavani, F.... (2017). Structure-reactivity correlations in Vanadium containing catalysts for the one-pot glycerol oxidehydration to acrylic acid. ChemSusChem. 10(1):234-244. https://doi.org/10.1002/cssc.201600954S234244101T. Ohara T. Sato N. Shimizu G. Prescher H. 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Efficient Acrylic Acid Production through Bio Lactic Acid Dehydration over NaY Zeolite Modified by Alkali Phosphates. ACS Catalysis, 1(1), 32-41. doi:10.1021/cs100047pChu, H. S., Ahn, J.-H., Yun, J., Choi, I. S., Nam, T.-W., & Cho, K. M. (2015). Direct fermentation route for the production of acrylic acid. Metabolic Engineering, 32, 23-29. doi:10.1016/j.ymben.2015.08.005Sheldon, R. A. (2014). Green and sustainable manufacture of chemicals from biomass: state of the art. Green Chem., 16(3), 950-963. doi:10.1039/c3gc41935eZhou, C. H., Zhao, H., Tong, D. S., Wu, L. M., & Yu, W. H. (2013). Recent Advances in Catalytic Conversion of Glycerol. Catalysis Reviews, 55(4), 369-453. doi:10.1080/01614940.2013.816610Talebian-Kiakalaieh, A., Amin, N. A. S., & Hezaveh, H. (2014). Glycerol for renewable acrolein production by catalytic dehydration. Renewable and Sustainable Energy Reviews, 40, 28-59. doi:10.1016/j.rser.2014.07.168J. L. Dubois Arkema Fr. WO 2007090991 2007J. L. Dubois Arkema Fr. WO 2008007002 2008Wang, F., Xu, J., Dubois, J.-L., & Ueda, W. (2010). Catalytic Oxidative Dehydration of Glycerol over a Catalyst with Iron Oxide Domains Embedded in an Iron Orthovanadate Phase. ChemSusChem, 3(12), 1383-1389. doi:10.1002/cssc.201000245Soriano, M. D., Concepción, P., Nieto, J. M. L., Cavani, F., Guidetti, S., & Trevisanut, C. (2011). Tungsten-Vanadium mixed oxides for the oxidehydration of glycerol into acrylic acid. Green Chemistry, 13(10), 2954. doi:10.1039/c1gc15622eDeleplanque, J., Dubois, J.-L., Devaux, J.-F., & Ueda, W. (2010). Production of acrolein and acrylic acid through dehydration and oxydehydration of glycerol with mixed oxide catalysts. Catalysis Today, 157(1-4), 351-358. doi:10.1016/j.cattod.2010.04.012Omata, K., Matsumoto, K., Murayama, T., & Ueda, W. (2016). Direct oxidative transformation of glycerol to acrylic acid over Nb-based complex metal oxide catalysts. Catalysis Today, 259, 205-212. doi:10.1016/j.cattod.2015.07.016Chieregato, A., Soriano, M. D., Basile, F., Liosi, G., Zamora, S., Concepción, P., … López Nieto, J. M. (2014). One-pot glycerol oxidehydration to acrylic acid on multifunctional catalysts: Focus on the influence of the reaction parameters in respect to the catalytic performance. Applied Catalysis B: Environmental, 150-151, 37-46. doi:10.1016/j.apcatb.2013.11.045Chieregato, A., Soriano, M. D., García-González, E., Puglia, G., Basile, F., Concepción, P., … Cavani, F. (2014). Multielement Crystalline and Pseudocrystalline Oxides as Efficient Catalysts for the Direct Transformation of Glycerol into Acrylic Acid. ChemSusChem, 8(2), 398-406. doi:10.1002/cssc.201402721Chieregato, A., Basile, F., Concepción, P., Guidetti, S., Liosi, G., Soriano, M. D., … Nieto, J. M. L. (2012). Glycerol oxidehydration into acrolein and acrylic acid over W–V–Nb–O bronzes with hexagonal structure. Catalysis Today, 197(1), 58-65. doi:10.1016/j.cattod.2012.06.024Possato, L. G., Cassinelli, W. H., Garetto, T., Pulcinelli, S. 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W-Nb-O oxides with tunable acid properties as efficient catalysts for the transformation of biomass-derived oxygenates in aqueous systems

[EN] W-Nb-O oxide bronzes, prepared hydrothermally, have been characterized and studied as catalysts for both the gas-phase dehydration of glycerol and the liquid-phase selective condensation of light oxygenates derived from primary treatments of biomass (a mixture containing acetic acid, ethanol, propanal, hydroxyacetone and water). By controlling the nominal composition of the catalysts, it is possible to tune their textural and acid properties (concentration and nature of acid sites) to selectively produce acrolein from glycerol or C-5-C-10 hydrocarbons (with low O contents and with high yields) from light oxygenates. Interestingly, these catalysts are stable when working in gas phase reactions and they are re-usable, with high resistance to leaching, when working in aqueous media.Financial support by the Spanish Government (CTQ-2015-68951-C3-1, CTQ-2015-67592, MAT2016-78362-C4-4-R and SEV-2016-0683) and Generalitat Valenciana (GVA, PROMETEO/2018/006) is gratefully acknowledged. A. 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Direct dehydration of 1,3-butanediol into butadiene over aluminosilicate catalysts

The catalytic dehydration of 1,3-butanediol into butadiene was investigated over various aluminosilicates with different SiO2/Al2O3 ratios and pore architectures. A correlation between the catalytic performance and the total number of acid sites and acid strength was established, with a better performance for lower acid site densities as inferred from combined NH3-TPD, pyridine adsorption and 27Al-NMR MAS spectroscopy. The presence of native Brønsted acid sites of medium strength was correlated to the formation of butadiene. A maximum butadiene yield of 60% was achieved at 300 °C over H-ZSM-5 with a SiO2/Al2O3 ratio of 260 with the simultaneous formation of propylene at a BD/propylene selectivity ratio of 2.5. This catalyst further exhibited a slight deactivation during a 102 h run with a decrease in the conversion from 100% to 80% due to coke deposition as evidenced by XPS and TGA-MS, resulting in a 36% loss of the specific surface area

Tungsten-niobium oxide bronzes: a bulk and surface structural study

[EN] Materials from the WO3-Nb2O5 system, presenting bronze-type crystal structures, display outstanding functional properties for several applications as thermoelectric materials, lithium-ion battery electrodes, or catalysts. In this work, a series of W-Nb-O oxide bronzes have been synthesized by the hydrothermal method (with Nb/(W + Nb) ratios in the range of 0-1). A combination of bulk and surface characterisation techniques has been applied to get further insights into: (i) the effect of thermal treatments on as-prepared materials and (ii) the surface chemical nature of W-Nb-O oxide bronzes. Thermal treatments promote the following structural changes: (i) loss of emerging long-range order and (ii) the elimination of NH4+ and H2O species from the structural channels of the as-synthesized materials. It has been observed that W-Nb-O bronzes with Nb at% of ca. 50% are able to retain a long-range order after heat-treatments, which is attributed to the presence of a Cs-0.5[W2.5Nb2.5O14]-type structure. Increasing amounts of Nb 5T in the materials (i) promote a phase transition to pseudocrystalline phases ordered along the c-axis; (ii) stabilize surface W s. species (elucidated by XPS); and (iii) increase the proportion of surface Lewis acid sites (as determined by the FTIR of adsorbed CO). Results suggest that pseudocrystalline oxides (with a Nb at% >= 50%) are closely related to NbO2 pentagonal bipyramid-containing structures. 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