629-62-9Relevant academic research and scientific papers
Palladium-catalyzed transformation of renewable oils into diesel components
Han, Junxing,Sun, Hui,Duan, Jinzhao,Ding, Yuqi,Lou, Hui,Zheng, Xiaoming
, p. 1805 - 1809 (2010)
A size-controlled palladium nanoparticle catalyst prepared by adsorption of colloidal palladium nanoparticles on barium sulfate is efficient and highly selective in transforming vegetable oils into diesel-like fuel. Preliminary kinetic investigations using model compounds indicated that decarboxylation of aliphatic esters on palladium in a hydrogenrich atmosphere showed a zero-order rate. Hydrogen temperature-programmed desorption measurements revealed that the high-temperature desorption of hydrogen species might be the rate-determining step.
Radical-based photoinactivation of fatty acid photodecarboxylases
Hedison, Tobias M.,Heyes, Derren J.,Hoeven, Robin,Lakavath, Balaji,Sakuma, Michiyo,Scrutton, Nigel S.,Shanmugam, Muralidharan,Tilakaratna, Viranga
, (2020)
Fatty acid photodecarboxylases (FAP) are a recently discovered family of FAD-containing, light-activated enzymes, which convert fatty acids to n-alkanes/alkenes with potential applications in the manufacture of fine and speciality chemicals and fuels. Poor catalytic stability of FAPs is however a major limitation. Here, we describe a methodology to purify catalytically stable and homogeneous samples of recombinant Chlorella variabilis NC64A FAP (CvFAP) from Escherichia coli. We demonstrate however that blue light-exposure, which is required for photodecarboxylase activity, also leads to irreversible inactivation of the enzyme, especially in the absence of palmitate substrate. Photoinactivation is attributed to formation of protein based organic radicals, which were observed by EPR spectroscopy. To suppress photoinactivation, we prepared stable and catalytically active FAP in the dark. The steady-state kinetic parameters of CvFAP (kcat: 0.31 ± 0.06 s?1 and KM: 98.8 ± 53.3 μM) for conversion of palmitic acid to pentadecane were determined using gas chromatography. Methods described here should now enable studies of the catalytic mechanism and exploitation of FAPs in biotechnology.
New and Improved Methods for the Radical Decarboxylation of Acids
Barton, Derek H. R.,Crich, David,Motherwell, William B.
, p. 939 - 941 (1983)
Carboxylic acid esters derived from N-hydroxypyridine-2-thione undergo efficient radical chain decarboxylation to the corresponding nor-alkane on treatment with either tri-n-butylstannane or t-butylmercaptan; in the absence of these hydrogen atom donors a smooth decarboxylative rearrangement giving noralkyl 2-pyridyl sulphides is observed.
A Reconstructed Common Ancestor of the Fatty Acid Photo-decarboxylase Clade Shows Photo-decarboxylation Activity and Increased Thermostability
Sun, Yue,Calderini, Elia,Kourist, Robert
, p. 1833 - 1840 (2021)
Light-dependent enzymes are a rare type of biocatalyst with high potential for research and biotechnology. A recently discovered fatty acid photo-decarboxylase from Chlorella variabilis NC64A (CvFAP) converts fatty acids to the corresponding hydrocarbons only when irradiated with blue light (400 to 520 nm). To expand the available catalytic diversity for fatty acid decarboxylation, we reconstructed possible ancestral decarboxylases from a set of 12 extant sequences that were classified under the fatty acid decarboxylases clade within the glucose-methanol choline (GMC) oxidoreductase family. One of the resurrected enzymes (ANC1) showed activity in the decarboxylation of fatty acids, showing that the clade indeed contains several photo-decarboxylases. ANC1 has a 15 °C higher melting temperature (Tm) than the extant CvFAP. Its production yielded 12-fold more protein than this wild type decarboxylase, which offers practical advantages for the biochemical investigation of this photoenzyme. Homology modelling revealed amino acid substitutions to more hydrophilic residues at the surface and shorter flexible loops compared to the wild type. Using ancestral sequence reconstruction, we have expanded the existing pool of confirmed fatty acid photo-decarboxylases, providing access to a more robust catalyst for further development via directed evolution.
Light-Driven Enzymatic Decarboxylation of Dicarboxylic Acids
Chen, Bi-Shuang,Liu, Lan,Zeng, Yong-Yi,Zhang, Wuyuan
, p. 553 - 559 (2021/06/25)
Photodecarboxylase from Chlorella variabillis (CvFAP) is one of the three known light-activated enzymes that catalyzes the decarboxylation of fatty acids into the corresponding C1-shortened alkanes. Although the substrate scope of CvFAP has been altered by protein engineering and decoy molecules, it is still limited to mono-fatty acids. Our studies demonstrate for the first time that long chain dicarboxylic acids can be converted by CvFAP. Notably, the conversion of dicarboxylic acids to alkanes still represents a chemically very challenging reaction. Herein, the light-driven enzymatic decarboxylation of dicarboxylic acids to the corresponding (C2-shortened) alkanes using CvFAP is described. A series of dicarboxylic acids is decarboxylated into alkanes in good yields by means of this approach, even for the preparative scales. Reaction pathway studies show that mono-fatty acids are formed as the intermediate products before the final release of C2-shortened alkanes. In addition, the thermostability, storage stability, and recyclability of CvFAP for decarboxylation of dicarboxylic acids are well evaluated. These results represent an advancement over the current state-of-the-art.
A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids
Guin, Joyram,Paul, Subhasis
, p. 4412 - 4419 (2021/02/05)
Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.
Recent trends for clean fuel production by deoxygenation of pure palmitic acid using Ni/C catalyst
Rashad, Ahmed M.,El Sharkawy, Heba M.,Ebiad, Mohamed A.,El sayed, Hessin A.,Tantawy, Ahmed H.,Hebash, Kaouser A.,El sabagh, Seham M.,Taman, Afaf R.
, p. 883 - 892 (2021/02/09)
Deoxygenation of triglycerides is one of key processes making possible a convenient production of high quality automotive fuels components (sulfur-, oxygen- and aromatics-free). This reaction was studied over non noble metal catalysts 20wt%Ni/C and performed in batch reactor system (autoclave) by using pure palmitic acid, nhexane as a solvent and 200 psi pressure. The effect of different atmospheres (pure hydrogen, pure nitrogen, and mixture of 50 psi H2/150psiN2) and different temperature range (300 °C-350 °C) under a mixed atmosphere (50 psiH2/150psi N2) were studied in this paper. The main product was n-pentadecane (C15) which the catalyst Ni/C has lower cracking selectivity to light hydrocarbons. The total conversion of carboxylic groups of palmitic acid and the selectivity to C15 in case of pure nitrogen are (22.29% and 12.38%) respectively and in case of hydrogen they are (75.16% and 80.07%) respectively. In case of using H2/N2 as a mixture the total conversion and the selectivity are (81.18% and 75.32%) respectively for Ni/C catalyst. The total conversion increases from 81.18% to 99.99% by increase the temperature from 300 °C to 350 °C. The deoxygenation of palmitic acid over 20wt%Ni/C catalyst indicated that the high selectivity for n-alkane (C15) (75.32%) at 300 °C and reach maximum value (98.11%) at 350 °C. Analysis of liquid products by gas chromatography (GC) was used to determine n-alkane (C15) yield and other products (isomeres, olefins and dimers). Insights pertaining to the reaction scheme and an assessment of the reaction products as liquid transportation fuels are also provided in this contribution.
Highly stable and selective catalytic deoxygenation of renewable bio-lipids over Ni/CeO2-Al2O3 for N-alkanes
Ba, Wenxia,Cui, Huamin,Fu, Lin,Li, Yongfei,Liu, Yuejin
, (2021/07/31)
Ni-based catalysts are easy deactivated in bio-lipids deoxygenation due to metal aggregation and Ni leaching. They also suffer from the hydrocracking of C–C bonds due to strong acidity at high reaction temperature (≥ 300 ℃). Herein, a series of Ni/CeO2-Al2O3 catalysts with different Ce/Al ratio were prepared by one-pot sol-gel method. The characteristic results showed that an appropriate addition of Ce both increase the catalytic activity and stability in bio-lipids deoxygenation. The oxygen vacancies formed by Ce introduction weaken the strong interaction of Ni-Al, thus improving Ni sites dispersion. Additional, Ce-addition in NiCeAl system increases weak and medium acidity and decreases strong acidity, preventing the C–C bond cleavage of hydrocarbon. As the result, the Ni/CeAl-3.0 catalyst afforded a 97.1 % n-C17 yield at 99.9 % MO conversion under 2.5 MPa H2 at 300 ℃ for 6 h. Minor C15-16 alkanes (17 yield). After simple regeneration, n-C17 yield was recovered to 95 %. Furthermore, non-edible bio-lipids (JO and WCO) can be converted to C13-18 alkanes with 95.2 % and 93.8 % yields, respectively.
Catalytic ketonization of palmitic acid over a series of transition metal oxides supported on zirconia oxide-based catalysts
Aleem, S. A.,Asikin-Mijan, N.,Dolfi, A.,Hussain, A. S.,Sivasangar, S.,Taufiq-Yap, Y. H.,Voon, C. H.
, p. 31972 - 31982 (2021/12/01)
Modification of a ZrO2 based catalyst with selected transition metals dopants has shown promising improvement in the catalytic activity of palmitic acid ketonization. Small amounts of metal oxide deposition on the surface of the ZrO2 catalyst enhances the yield of palmitone (16-hentriacontanone) as the major product with pentadecane as the largest side product. This investigation explores the effects of addition of carefully chosen metal oxides (Fe2O3, NiO, MnO2, CeO2, CuO, CoO, Cr2O3, La2O3 and ZnO) as dopants on bulk ZrO2. The catalysts are prepared via a deposition-precipitation method followed by calcination at 550 °C and characterized by XRD, BET-surface area, TPD-CO2, TPD-NH3, FESEM, TEM and XPS. The screening of synthesized catalysts was carried out with 5% catalyst loading onto 15 g of pristine palmitic acid and the reaction carried out at 340 °C for 3 h. Preliminary studies show catalytic activity improvement with addition of dopants in the order of La2O3/ZrO2 CoO/ZrO2 MnO2/ZrO2 with the highest palmitic acid conversion of 92% and palmitone yield of 27.7% achieved using 5% MnO2/ZrO2 catalyst. Besides, NiO/ZrO2 exhibits high selectivity exclusively for pentadecane compared to other catalysts with maximum yield of 24.9% and conversion of 64.9% is observed. Therefore, the changes in physicochemical properties of the dopant added ZrO2 catalysts and their influence in palmitic acid ketonization reaction is discussed in detail. This journal is
Surfactant-Free Synthesis of Ultrafine Pt Nanoparticles on MoS2Nanosheets as Bifunctional Catalysts for the Hydrodeoxygenation of Bio-Oil
Fan, Xiaobin,Li, Yang,Liang, Junmei,Lin, Qianqian,Peng, Wenchao,Xu, Danyun,Zhang, Fengbao,Zhang, Qicheng
, p. 14710 - 14716 (2020/12/23)
Hydrodeoxygenation (HDO) of bio-oil is a crucial step for improving the bio-fuel quality, but developing highly dispersed Pt-based catalysts with high selectivity for target alkanes remains a great challenge. This study presents a fast surfactant-free method to prepare the MoS2-supported Pt catalyst for HDO. Ultrafine Pt nanoparticles with sizes of 5 nm can be readily grown on chemically exfoliated MoS2 nanosheets (NSs) via the direct microwave-assisted thermal reduction. The obtained Pt NPs/MoS2 composites show excellent catalytic performance in the conversion of palmitic acid, and the best selectivity (also the yield) of hexadecane and pentadecane is 80.56 and 19.43%, respectively.
