Xi:Irritant;
617-48-1Relevant articles and documents
Photoinduced Carbon Dioxide Fixation forming Malic and Isocitric Acid
Willner, Itamar,Mandler, Daniel,Riklin, Azalia
, p. 1022 - 1024 (1986)
Photoinduced CO2-fixation into organic substrates is accomplished via enzyme-catalysed reactions.
Cyanide as a primordial reductant enables a protometabolic reductive glyoxylate pathway
Krishnamurthy, Ramanarayanan,Pulletikurti, Sunil,Yadav, Mahipal,Yerabolu, Jayasudhan R.
, p. 170 - 178 (2022/02/11)
Investigation of prebiotic metabolic pathways is predominantly based on abiotically replicating the reductive citric acid cycle. While attractive from a parsimony point of view, attempts using metal/mineral-mediated reductions have produced complex mixtures with inefficient and uncontrolled reactions. Here we show that cyanide acts as a mild and efficient reducing agent mediating abiotic transformations of tricarboxylic acid intermediates and derivatives. The hydrolysis of the cyanide adducts followed by their decarboxylation enables the reduction of oxaloacetate to malate and of fumarate to succinate, whereas pyruvate and α-ketoglutarate themselves are not reduced. In the presence of glyoxylate, malonate and malononitrile, alternative pathways emerge that bypass the challenging reductive carboxylation steps to produce metabolic intermediates and compounds found in meteorites. These results suggest a simpler prebiotic forerunner of today’s metabolism, involving a reductive glyoxylate pathway without oxaloacetate and α-ketoglutarate—implying that the extant metabolic reductive carboxylation chemistries are an evolutionary invention mediated by complex metalloproteins. [Figure not available: see fulltext.].
Selective C?O Bond Cleavage of Bio-Based Organic Acids over Palladium Promoted MoOx/TiO2
Albarracín-Suazo, Sandra,Nacy, Ayad,Nikolla, Eranda,Pagán-Torres, Yomaira J.,Roberts, Charles A.,Ruiz-Valentín, Génesis,de Lima e Freitas, Lucas Freitas
, p. 1294 - 1298 (2020/12/29)
Hydrodeoxygenation chemistries play a key role in the upgrading of biomass-derived feedstocks. Among these, the removal of targeted hydroxyl groups through selective C?O bond cleavage from molecules containing multiple functionalities over heterogeneous catalysts has shown to be a challenge. Herein, we report a highly selective and stable heterogeneous catalyst for hydrodeoxygenation of tartaric acid to succinic acid. The catalyst consists of reduced Mo5+ centers promoted by palladium, which facilitate selective C?O bond cleavage, while leaving intact carboxylic acid end groups. Stable catalytic performance over multiple cycles is demonstrated. This catalytic system opens up opportunities for selective processing of biomass-derived sugar acids with a high degree of chemical functionality.
Directly Microwave-Accelerated Cleavage of C?C and C?O Bonds of Lignin by Copper Oxide and H2O2
Qu, Chen,Ito, Keigo,Katsuyama, Isamu,Mitani, Tomohiko,Kashimura, Keiichiro,Watanabe, Takashi
, p. 4510 - 4518 (2020/05/18)
Model erythro, phenolic, and nonphenolic lignin β-O-4 dimer compounds are treated with copper oxide and H2O2 at the electronic field maximum position of a single-mode 2.45 GHz microwave system equipped with a cavity resonator. The products obtained through microwave heating and oil-bath heating with the same reaction vessel and temperature profile are quantitatively compared. Dimer degradation is found to proceed through consecutive elementary reactions. The phenolic dimer is dehydroxylated and this is followed by the spontaneous cleavage of Cα?Cβ and C?O?C bonds to produce guaiacol, vanillin, and vanillic acid. The reaction of the nonphenolic dimer produces veratric acid, veratraldehyde, and guaiacol. Microwave irradiation accelerates cleavage of the side chain and the oxidation of vanillin to vanillic acid. However, no acceleration of veratraldehyde oxidation to veratric acid or aromatic ring cleavage to produce dicarboxylic acids is observed. The selective acceleration of elementary reactions during the degradation of model lignin compounds indicates that microwaves interact with reaction intermediates that are sensitive to electromagnetic waves.
Carbon nanotubes as catalysts for wet peroxide oxidation: The effect of surface chemistry
Martin-Martinez, Maria,Machado, Bruno F.,Serp, Philippe,Morales-Torres, Sergio,Silva, Adrián M.T.,Figueiredo, José L.,Faria, Joaquim L.,Gomes, Helder T.
, p. 332 - 340 (2019/03/17)
Three magnetic carbon nanotube (CNT) samples, named A30 (N-doped), E30 (undoped) and E10A20 (selectively N-doped), synthesized by catalytic chemical vapor deposition, were modified by introducing oxygenated surface groups (oxidation with HNO3, samples CNT-N), and by heat treatment at 800 °C for the removal of surface functionalities (samples CNT-HT). Both treatments lead to higher specific surface areas. The acid treatment results in more acidic surfaces, with higher amounts of oxygenated species being introduced on N-doped surfaces. Heat-treated samples are less hydrophilic than those treated with nitric acid, heat treatment leading to neutral or basic surfaces, only N-quaternary and N-pyridinic species being found by XPS on N-doped surfaces. These materials were tested in the catalytic wet peroxide oxidation (CWPO) of highly concentrated 4-nitrophenol solutions (4-NP, 5 g L?1) at atmospheric pressure, T = 50 °C and pH = 3, using a catalyst load of 2.5 g L?1 and the stoichiometric amount of H2O2 needed for the complete mineralization of 4-NP. The high temperature treatment enhanced significantly the activity of the CNTs towards CWPO, evaluated in terms of 4-NP and total organic carbon conversion, due to the increased hydrophobicity of their surface. In particular, E30HT and E10A20HT were able to remove ca. 100% of 4-NP after 8 h of operation. On the other hand, by treating the CNTs with HNO3, the activity of the less hydrophilic samples decreased upon increasing the concentration of surface oxygen-containing functionalities, whilst the reactivity generated inside the opened nanotubes improved the activity of the highly hydrophilic A30 N.
Catalytic transfer hydrogenation of maleic acid with stoichiometric amounts of formic acid in aqueous phase: Paving the way for more sustainable succinic acid production
López Granados,Moreno,Alba-Rubio,Iglesias,Martín Alonso,Mariscal
supporting information, p. 1859 - 1872 (2020/04/07)
The aqueous phase hydrogenation of maleic acid (MAc) to succinic acid (SAc) is demonstrated in the absence of any organic solvent and using stoichiometric amount of formic acid (FAc) as source of H2. Among the different noble metals (Pd, Au, Ru, Pt and Rh) and supports investigated (γ-Al2O3, TiO2, CeO2, ZrO2, WO3, CeZrO4, carbon, nicanite, SiO2 and TS-1), Pd/C was identified as the best catalyst. We observe that the undesirable formation of malic acid (MalAc) by hydration of MAc must be prevented. The transformation of MAc to SAc with negligible formation of MalAc is possible by using relatively mild temperature (140-150 °C) and a high catalyst to MAc ratio (i.e. fixed bed continuous flow reactor). Using the carboxylate forms (disodium maleate and sodium formate) instead of the acids results in an increase of the reaction rate. In a fixed bed reactor under a continuous flow of 15 wt% of MAc at a WHSV = 12 h-1 (contact time = 5 min), at 150 °C, 10 bar of N2 and using a formic acid/maleic acid molar ratio = 1, a yield of SAc close to 98% was obtained, equivalent to a productivity of 1.87 g SAc per gcat per·h. Leaching of Pd was below 0.02 ppm. No deactivation was observed in long term experiments at 150 °C (ca. 730 h), although the characterization of the used catalyst by CO chemisorption and TEM and XPS studies showed certain sintering of Pd particles. Regarding the mechanism of the reaction, kinetic isotopic experiments using deuterated DCOOH indicated that the reaction must essentially proceed via catalytic transfer hydrogenation, formyl H of formic acid is involved in the rate determining step of the reaction. When using maleate and formate sodium salts, the second H needed for the reaction is supplied by the solvent (H2O molecules). A preliminary environmental assessment (Life Cycle Analysis, LCA) of this CTH approach indicates that for relevant environmental categories of the LCA (such as climate change and consumption of fossil resources) the CTH process is greener than conventional hydrogenation process; the benefits are even larger if biomass-derived FAc is involved.
Pd/meso-CoO derived from: In situ reduction of the one-step synthesized Pd/meso-Co3O4: High-performance catalysts for benzene combustion
Zhao, Xingtian,Zhang, Ran,Liu, Yuxi,Deng, Jiguang,Xu, Peng,Lv, Sijie,Li, Shuang,Pei, Wenbo,Zhang, Kunfeng,Dai, Hongxing
supporting information, p. 12358 - 12368 (2019/08/12)
The chemical state of Pd plays an important role in the catalytic combustion of volatile organic compounds (VOCs). In this work, we adopted a novel one-step modified KIT-6-templating strategy with nitrates of cobalt and palladium as the metal source to successfully synthesize the three-dimensionally ordered mesoporous Co3O4-supported Pd nanoparticles (0.85 wt% Pd/meso-Co3O4, denoted as 0.85Pd/meso-Co3O4). The 0.93 wt% Pd/meso-CoO (denoted as 0.93Pd/meso-CoO) and 1.08 wt% Pd/meso-Co-CoO (denoted as 1.08Pd/meso-Co-CoO) samples were prepared via in situ reduction of 0.85Pd/meso-Co3O4 in a H2 flow at 200 and 350 °C, respectively. Among these samples, 0.93Pd/meso-CoO exhibited the highest catalytic activity for benzene combustion (T50% = 167 °C and T90% = 189 °C at a space velocity of 40000 mL (g h)-1). The chemical state of Pd on the 0.93Pd/meso-CoO surface was metallic Pd0, which favored oxygen activation to active adsorbed oxygen (Oads) species, hence rendering this sample to possess the largest desorption of Oads species below 400 °C. The intermediates of formate, acetate, maleate, and phenolate were generated via the interaction of benzene and Oads species. We conclude that the excellent catalytic performance of 0.93Pd/meso-CoO was related to the mainly formed Pd0 species, good oxygen activation ability, and high surface area.
Rearrangements and Tautomeric Transformations of Heterocyclic Compounds in Homogeneous Reaction Systems Furfural–Н2О2–Solvent
Badovskaya,Poskonin
, p. 1568 - 1579 (2018/11/10)
General information on the reactions of furfurals with hydrogen peroxide is given. We have discussed the Baeyer–Villiger rearrangement of furan 2-hydroxyhydroperoxides and tautomeric transformations with proton transfer of 2-hydroxyfuran and β-formylacrylic acid formed in a homogeneous reaction system furfural–Н2О2–solvent under the catalysis with the formed acids. The factors affecting these rearrangements and tautomeric transformations as well as their specificity in comparison with benzene type compounds, and the pathway of the reactions of furan aldehydes with Н2О2 in water have been analyzed. Ketoenol tautomerism of cyclic hemiacetal form of β-formylacrylic acid leading to its transformation into succinic anhydride has been described for the first time.
METHOD FOR MANUFACTURING ORGANIC ACID
-
Paragraph 0036-0044, (2018/09/12)
The present invention provides a method for manufacturing organic acids. The method for manufacturing organic acids may comprise a step of forming organic acids by conducting degradation of alginate in water using a catalyst. Otherwise, the method for manufacturing organic acids may comprise the steps of: forming a mixture by mixing water, a catalyst, and alginate; heating the mixture; forming a product containing an organic acid by conducting the degradation of alginate by the catalyst in the heated mixture; and cooling the product. According to embodiments of the present invention, a high-value organic acid can be manufactured by degrading the alginate. In addition, yields by kinds of organic acids can be controlled by varying reaction conditions, so the yield of the desired organic acid can be selectively increased.
Study on the Isomerization of Maleic Acid to Fumaric Acid without Catalyst
Gao, Zhuo,Chen, Wangmi,Chen, Xiaoting,Wang, Dali,Yi, Shouzhi
, p. 920 - 924 (2018/07/31)
Fumaric acid is an important food additive and industrial intermediate compound. The traditional methods of producing fumaric acid were catalyzed by maleic acid isomerization. In this study, isomerization of maleic acid in water without catalyst was inves
