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1.
Analyst ; 149(11): 3097-3107, 2024 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-38713504

RESUMEN

We have successfully synthesized quinoline derivatives that exhibit easy scalability and responsiveness to multiple stimuli. These derivatives are capable of forming self-assembled nanoscopic aggregates in an aqueous medium. Consequently, when placed in an aqueous environment, we observe dual fluorescence originating from both twisted intramolecular charge transfer and aggregation-induced emission. The introduction of nerve gas agents, such as diethyl chlorophosphate (DClP) or diethylcyanophosphate (DCNP), to the probe molecules facilitates the charge-transfer process, resulting in a red-shift in absorption maxima. Notably, when operating in fluorescence mode, both of these analytes produce distinct output signals, making them easily distinguishable. DCNP generates a blue fluorescence, while the addition of DClP yields cyan fluorescence. Our mechanistic investigation reveals that the initial step involves phosphorylation of the quinoline nitrogen end. However, in the case of DCNP, the released cyanide ion subsequently attacks the carbonyl carbon centre, forming a cyanohydrin derivative. The response to these target analytes appears to be influenced by the nucleophilicity of the quinoline nitrogen end and the electrophilic nature of the carbonyl unit.

2.
J Colloid Interface Sci ; 607(Pt 1): 729-741, 2022 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-34536933

RESUMEN

Multi component reactions over heterogeneous solid acid catalysts are extremely important owing to easy separation, amenable recycling, and prospective scaling up of the process. Here, we are reporting the synthesis of biologically important dihydropyrimidinones over postsynthetic modified Cr-based metal-organic framework materials as heterogeneous catalysts containing the bifunctional Lewis and Brønsted acid sites. Cr-based metal-organic frameworks contained coordinatively unsaturated metal sites as inherent Lewis acid sites, whereas postsynthetic modifications introduced the Brønsted acid sites in the framework. A direct one pot synthesis route was employed to produce the pristine MOF in pure aqueous medium without using any additives. The bulk structure, morphology, surface and bonding properties of the synthesized materials were thoroughly characterized with powder XRD, FTIR, XPS, FE-SEM, TGA, and N2 sorption isotherms. A qualitative evolution of acid strength was carried out over the functionalized MOFs. Among the post synthetic functionalized materials, carboxylic acid functionalized framework exhibited a very high yield of dihydropyrimidinones under solvent less moderate reaction conditions. The catalyst also demonstrated a robust recyclability and wide substrate scope. Comparative study showed a very high catalytic activity of the postsynthetic modified MOFs in comparison to the reported literature. The reaction condition was optimized by varying parameters like solvent, temperature, reaction duration and catalyst loadings. The mechanistic studies indicated the involvement of both the Lewis and Brønsted sites acid sites of the catalysts in the multicomponent reaction.


Asunto(s)
Estructuras Metalorgánicas , Catálisis , Metales , Estudios Prospectivos , Solventes
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