6268-38-8Relevant academic research and scientific papers
Identification of degradation products of indigoids by tandem mass spectrometry
Witkos?, Katarzyna,Lech, Katarzyna,Jarosz, MacIej
, p. 1245 - 1251 (2015/11/09)
The study concerns identification of photodegradation products of indigotin, indirubin and isoindigo. Experimental methodology consists of degradation of standard solutions of indigoids in a solar box and analysis of samples taken at different aging time by using capillary high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometric and spectrophotometric detectors. Identification of the formed compounds was based on careful interpretation of the electrospray ionization MS/MS spectra. Apart from the well-known degradation products of indigoids: isatin, isatoic anhydride and anthranilic acid, another seven species were also identified, and their proposed structures were confirmed by high-resolution molecular masses measurements; according to the best knowledge of authors, they have not been reported so far. The obtained results formed the basis for postulating mechanism of the process. Moreover, the MRM (Multiple Reaction Monitoring) method was developed for the identification of natural dyes and their degradation products in textiles of historical value. Apart from such colorants as indigotin and flavonoids, also presence of degradation products of indigoids was confirmed.
Catalytic Mechanism of Cofactor-Free Dioxygenases and How They Circumvent Spin-Forbidden Oxygenation of Their Substrates
Hernández-Ortega, Aitor,Quesne, Matthew G.,Bui, Soi,Heyes, Derren J.,Steiner, Roberto A.,Scrutton, Nigel S.,De Visser, Sam P.
supporting information, p. 7474 - 7487 (2015/06/30)
Dioxygenases catalyze a diverse range of biological reactions by incorporating molecular oxygen into organic substrates. Typically, they use transition metals or organic cofactors for catalysis. Bacterial 1-H-3-hydroxy-4-oxoquinaldine-2,4-dioxygenase (HOD) catalyzes the spin-forbidden transfer of dioxygen to its N-heteroaromatic substrate in the absence of any cofactor. We combined kinetics, spectroscopic and computational approaches to establish a novel reaction mechanism. The present work gives insight into the rate limiting steps in the reaction mechanism, the effect of first-coordination sphere amino acids as well as electron-donating/electron-withdrawing substituents on the substrate. We highlight the role of active site residues Ser101/Trp160/His251 and their involvement in the reaction mechanism. The work shows, for the first time, that the reaction is initiated by triplet dioxygen and its binding to deprotonated substrate and only thereafter a spin state crossing to the singlet spin state occurs. As revealed by steady- and transient-state kinetics the oxygen-dependent steps are rate-limiting, whereas Trp160 and His251 are essential residues for catalysis and contribute to substrate positioning and activation, respectively. Computational modeling further confirms the experimental observations and rationalizes the electron transfer pathways, and the effect of substrate and substrate binding pocket residues. Finally, we make a direct comparison with iron-based dioxygenases and explain the mechanistic and electronic differences with cofactor-free dioxygenases. Our multidisciplinary study confirms that the oxygenation reaction can take place in absence of any cofactor by a unique mechanism in which the specially designed fit-for-purpose active-site architecture modulates substrate reactivity toward oxygen.
A phosgene and peroxide-free one-pot tandem synthesis of isatoic anhydrides involving anthranilic acid, boc anhydride and 2-chloro-N-methyl pyridinium iodide
Verma, Chhaya,Sharma, Somesh,Pathak, Arunendra
, p. 6897 - 6899 (2019/04/10)
A phosgene and peroxide-free approach for the synthesis of isatoic anhydrides has been described. The synthesis involves the carbamate formation with boc anhydride followed by in situ cyclization to afford the isatoic anhydride. The importance of this synthetic strategy is in the ease of operation, scalability and preparation from readily available raw materials.
Structure of the 2-Isocyanatobenzoyl Chloride-Aluminium Chloride (1:2) Complex: Reactions with Some Nucleophiles
Acharya, Baman P.,Rao, Y. Ramachandra
, p. 1133 - 1139 (2007/10/02)
The reactions of 2-isocyanatobenzoyl chloride-aluminium chloride (1:2) complex with methanol, aniline, methyl anthranilate, ethyl anthranilate, 2-aminobenzophenone, 2-amino-5-chlorobenzophenone have been studied.Based on the products obtained in these reactions, the 1:2 complex has been shown to be a mixture of acyclic and cyclic structures (4) and (5) respectively.This is in accordance with the observations recorded in IR studies.
