55-22-1Relevant articles and documents
Continuous flow metal-free oxidation of picolines using air
Hamano, Masaya,Nagy, Kevin D.,Jensen, Klavs F.
, p. 2086 - 2088 (2012)
The metal free, direct oxidation of 2-, 3-, and 4-picoline to the corresponding carboxylic acid using either oxygen or air has been developed under continuous flow conditions. Complete conversion for all three substrates was obtained at moderate temperatures and pressures within minutes.
Bench-scale biosynthesis of isonicotinic acid from 4-cyanopyridine by Pseudomonas putida
Zhu, Xiao-Yan,Gong, Jin-Song,Li, Heng,Lu, Zhen-Ming,Shi, Jin-Song,Xu, Zheng-Hong
, p. 739 - 744 (2014)
Pseudomonas putida CGMCC3830 harboring nitrilase was used in isonicotinic acid production from 4-cyanopyridine. This nitrilase showed optimum activities towards 4-cyanopyridine at pH 7.5 and 45°C. The half-life of P. putida nitrilase was 93.3 h, 33.9 h, and 9.5 h at 30°C, 38°C, and 45°C, respectively. 4-Cyanopyridine (100 mM) was fully converted into isonicotinic acid within 20 min. The bench-scale production of isonicotinic acid was carried out using 3 mg of resting cells per mL in a 1 L system at 30°C and finally, 123 g L-1 of isonicotinic acid were obtained within 200 min without any by-products. The conversion reaction suffered from the product inhibition effect after the tenth feeding. The volumetric productivity was 36.9 g L -1 h-1. P. putida shows significant potential in nitrile hydrolysis for isonicotinic acid production. This paper is the first report on isonicotinic acid biosynthesis using Pseudomonas putida and it represents the highest isonicotinic acid production reported so far.
Bimetallic cobalt-iron diselenide nanorod modified glassy carbon electrode: an electrochemical sensing platform for the selective detection of isoniazid
Sultan, Sundas,Zulqarnain, Muhammad,Shah, Afzal,Firdous, Naveeda,Nisar, Jan,Ashiq, Muhammad Naeem,Bakhsh, Esraa M.,Khan, Sher Bahadar
, p. 12649 - 12657 (2021)
The increasing demand of a sensitive and portable electrochemical sensing platform in pharmaceutical analysis has developed widespread interest in preparing electrode materials possessing remarkable properties for the electrochemical determination of target drug analytes. Herein, we report the synthesis, characterization and application of bimetallic cobalt-iron diselenide (FeCoSe2) nanorods as electrode modifiers for the selective detection of a commonly used anti-tuberculosis drug Isoniazid (INZ). We prepared FeCoSe2nanorods by a simple hydrothermal route and characterized these by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and temperature-programmed reduction (TPR) techniques. The electrochemical characterization of FeCoSe2modified GCE was performed by cyclic voltammetry (CV) and square wave anodic stripping voltammetry (SWASV). Under optimized experimental conditions, a linear current-concentration response was obtained for INZ in the range of 0.03-1.0 μM, with very low limit of detection 1.24 × 10?10M. The real applicability of the designed FeCoSe2/GCE sensing platform was adjudicated by the detection of INZ in biological samples.
Assembly of three organic-inorganic hybrid supramolecular materials based on reduced molybdenum(V) phosphates
Zhang, He,Yu, Kai,Lv, Jing-Hua,Wang, Chun-Mei,Wang, Chun-Xiao,Zhou, Bai-Bin
, p. 22 - 30 (2014)
Three supramolecular materials based on {P4Mo6} polyoxoanions, (Hbbi)2(H2bbi)[Cu3Mo 12VO24(OH)6(H2O) 6(HPO4)4(H
Decoration of copper foam with Ni nanorods and copper oxide nanosheets to produce a high-stability electrocatalyst for the reduction of CO2: Characterization of the electrosynthesis of isonicotinic acid
Mohammadzadeh, Safoora,Zare, Hamid R.,Khoshro, Hossein
, p. 678 - 685 (2019)
CuO–Cu2O (CuxO) nanosheets were coated on a copper foam substrate by the electrochemical anodization method in an alkaline solution. Constant current coulometry was performed to electrodeposit Ni nanorods on the surface of a Cu/CuxO electrode. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) proved that the copper oxide nanosheets were anchored on the copper foam substrate and modified by Ni nanorods (Cu/CuxO/Ni). The process took place via a facile and inexpensive electrodeposition method. As the results indicate, owing to the synergistic effect of adjacent CuxO and Ni sites, a Cu/CuxO/Ni electrode has a very good and stable electrocatalytic activity to reduce CO2. As tested in this study, the product of the electrocatalytic reduction of CO2 (i.e. activated CO2, or CO2 ??) can be used for the electrocarboxylation of pyridine in mild conditions. Once an electron is transferred from CO2 ?? to pyridine, a pyridine radical anion is formed. Based on the EC'C′CC mechanism, this radical anion reacts with CO2 ?? and produces isonicotinic acid as the main product. In addition, two pyridine radical anions react together and produce a 4,4′-bipyridine dimer. The high stability of the electrocatalyst during the electrolysis process and the simplicity of the workup make the proposed modified electrode appropriate for the electrosynthesis of some organic compounds.
Communication-electrosynthesis of isonicotinic acid via indirect electrochemical reduction of pyridine in the presence of CO2
Ghobadi, Kobra,Zare, Hamid R.,Khoshro, Hossein,Gorji, Alireza
, p. H240 - H242 (2016)
The electrocatalytic reduction of CO2 by Schiff base of N, N'-bis(3-hydroxy-2-naphthaldehyde)-1,3-phenylenediimino (NMPD) was studied in an acetonitrile solvent and at room temperature. Indirect electrocatalytic activity of NMPD for reduction of pyridine was empirically demonstrated. It is rational, to view electrocatalytically activated CO2, CO2·-, with a dual activity toward pyridine. The spectral characteristics of the coulometric product indicated that isonicotinic acid is the final product of pyridine reduction in the presence of NMPD and CO2.
Kinetics of the highly selective liquid-phase oxidation of side chain alkyl groups in 2-methylpyrazine and picolines by selenium dioxide
Mukhopadhyay, Sudip,Chandalia, Sampatraj B.
, p. 455 - 459 (1999)
Kinetics of the liquid-phase oxidation of alkyl groups in 2-methylpyrazine and picolines with selenium dioxide at moderate conditions were studied. Thus, 2-methylpyrazine was oxidized to pyrazinoic acid with selenium dioxide in pyridine at 115 °C with 99% selectivity at a 2-methylpyrazine conversion of 100% in 8 h. It was deduced that the reaction follows secondorder kinetics and the activation energy was found to be 35 kcal/mol. The same reaction-scheme was found to hold for picolines oxidation to obtain picolinic acids. The byproduct selenium, formed in the reaction, was converted back to selenium dioxide by nitric acid oxidation with 100% selectivity.
Aerobic oxidation of methylpyridines to pyridinecarboxylic acids catalyzed by N-hydroxyphthalimide
Shibamoto, Akihiro,Sakaguchi, Satoshi,Ishii, Yasutaka
, p. 505 - 508 (2000)
Selective aerobic oxidation of methylpyridines to pyridinecarboxylic acids was successfully achieved by the use of a radical catalyst, N-hydroxyphthalimide (NHPI), in the presence of Co(II) and/or Mn(II) salts. The oxidation of 3-methylpyridine by NHPI combined with Co(OAc)2 under O2 (1 atm) in AcOH at 100 °C gave 3-pyridinecarboxylic acid (76percent). The reaction was found to be enhanced by addition of a small amount of Mn(OAc)2 to the catalytic system. The reaction with 20 atm of air, catalyzed by NHPI-Co(OAc)2-Mn(OAc)2 at 150 °C for 1 h, gave 3-pyridinecarboxylic acid (85percent). 4-Methylpyridine was much less easily oxidized than 3-methylpyridine. The co-oxidation of 3-methylpyridine and 4-methylpyridine by NHPI-Co(OAc)2-Mn(OAc)2 at 150 °C for 5 h gave results that were better than those obtained from individual oxidations, forming 3-pyridinecarboxylic acid (93percent) and 4-pyridinecarboxylic acid (70percent). The NHPI-catalyzed oxidation of methylpyridines would provide an attractive direct method which has long been desired in the chemical industry for the manufacturing of pyridinecarboxylic acids.
Oxidation of Antitubercular Drug Isoniazid by a Lipopathic Oxidant, Cetyltrimethylammonium Dichromate: A Mechanistic Study
Garnayak, Sarita,Patel, Sabita
, p. 32 - 44 (2016)
The oxidation of an antitubercular drug isoniazid by a lipopathic oxidant cetyltrimethylammonium dichromate (CTADC) in a nonpolar medium generates isonicotinic acid both in the presence and the absence of acetic acid. The conventional UV–vis spectrophotometric method is used to study the reaction kinetics. The occurrence of the Michaelis–Menten–type kinetics with respect to isoniazid confirms the binding of oxidant and substrate to form a complex before the rate-determining step. The existence of the inverse solvent kinetic isotope effect, k(H2O)/ k(D2O) = 0.7, in an acid-catalyzed reaction proposes a multistep reaction mechanism. A decrease in the rate constant with an increase in [CTADC] reveals the formation of reverse micellar–type aggregates of CTADC in nonpolar solvents. In the presence of different ionic and nonionic surfactants, CTADC forms mixed aggregates and controls the reaction due to the charge on the interface and also due to partition of oxidant and substrate in two different domains. High negative entropy of activation (ΔS? = –145 and –159 J K?1 mol?1 in the absence and presence of acetic acid) proposes a more ordered and highly solvated transition state than the reactants. Furthermore, the solvent polarity-reactivity relationship reveals (i) the presence of less polar and less ionic transition state compared to the reactants during the oxidation, (ii) differential contribution from nonpolar and dipolar aprotic solvents toward the reaction process, and (iii) the existence of polarity/hydrophobic switch at log P = 0.73. A suitable mechanism has been proposed on the basis of experimental results. These results may provide insight into the mechanism of isoniazid oxidation in hydrophobic environment and may assist in understanding the drug resistance in different location.
Thermostable amidase catalyzed production of isonicotinic acid from isonicotinamide
Mehta, Praveen Kumar,Bhatia, Shashi Kant,Bhatia, Ravi Kant,Bhalla, Tek Chand
, p. 1400 - 1404 (2015)
The biotransformation of isonicotinamide was investigated using thermophilic intracellular amidase produced from Geobacillus subterraneus RL-2a. Various process parameters, including amount of biocatalyst, substrate feeding rate, enzyme-to-substrate ratio and operational thermostability were systematically examined with the aim of achieving complete substrate conversion and high productivity. In 1 L fed batch reaction containing 0.1 M isonicotinamide, in 0.2 M potassium phosphate buffer (pH 6.5, 200 rpm) and 8 U ml-1 amidase activity (12.48 mg dcw ml-1) of whole cells of G. subterraneus RL-2a (as biocatalyst) resulted in a yield of 0.1 M of isonicotinic acid after 50 min reaction time at 70°C and a total of 61.55 g isonicotinic acid was produced at a rate of 1.18 g h-1 g-1 dcw respectively. The volumetric productivity was 14.8 g h-1 l-1.
