Transformation of PMMA from sunlight-blocking to sunlight-activated coupled with DNH photocatalytic platform for oxidative coupling of amines and generation/regeneration of LDC/NADH

Satyam Singh; Rajesh K Yadav; Ahmad Umar; Ahmed A Ibrahim; Tae Wu Kim; Atul Pratap Singh; Rajesh Kumar; Sandeep Chaudhary; Dilip K Dwivedi; Ravindra Vikram Singh; Navneet Kumar Gupta; Chandani Singh; Jin-O Baeg; Sotirios Baskoutas

doi:10.1111/php.13888

Transformation of PMMA from sunlight-blocking to sunlight-activated coupled with DNH photocatalytic platform for oxidative coupling of amines and generation/regeneration of LDC/NADH

Photochem Photobiol. 2023 Dec 13. doi: 10.1111/php.13888. Online ahead of print.

Authors

Affiliations

¹ Department of Chemistry and Environmental Science, Madan Mohan Malaviya University of Technology, Gorakhpur, India.
² Department of Chemistry, College of Science and Arts and Promising Centre for Sensors and Electronic Devices (PCSED), Najran University, Najran, Saudi Arabia.
³ Department of Materials Science and Engineering, The Ohio State University, Columbus, Ohio, USA.
⁴ Department of Chemistry, Mokpo National University, Muan-gun, Korea.
⁵ Department of Chemistry, Chandigarh University, Mohali, India.
⁶ Department of Chemistry, Banaras Hindu University, Varanasi, India.
⁷ Department of Medicinal Chemistry, Laboratory of Organic and Medicinal Chemistry, NIPER, Raebareli, India.
⁸ Department of Physics and Materials Science, Madan Mohan Malaviya University of Technology, Gorakhpur, India.
⁹ R&D, Technology and Innovation, Merck-Living Innovation, Sigma Aldrich Chemicals Pvt. Ltd., Bengaluru, India.
¹⁰ Centre for Sustainable Technologies, IISC Bangalore Gulmohar Marg, Bangalore, India.
¹¹ Korea Research Institute of Chemical Technology, Daejeon, South Korea.
¹² Department of Materials Science, University of Patras, Patras, Greece.

PMID: 38088069
DOI: 10.1111/php.13888

Abstract

The photocatalytic oxidation and generation/regeneration of amines to imines and leucodopaminechrome (LDC)/NADH are subjects of intense interest in contemporary research. Imines serve as crucial intermediates for the synthesis of solar fuels, fine chemicals, agricultural chemicals, and pharmaceuticals. While significant progress has been made in developing efficient processes for the oxidation and generation/regeneration of secondary amines, the oxidation of primary amines has received comparatively less attention until recently. This discrepancy can be attributed to the high reactivity of imines generated from primary amines, which are prone to dehydrogenation into nitriles. In this study, we present the synthesis and characterization of a novel polymer-based photocatalyst, denoted as PMMA-DNH, designed for solar light-harvesting applications. PMMA-DNH incorporates the light-harvesting molecule dinitrophenyl hydrazine (DNH) at varying concentrations (5%, 10%, 20%, 30%, and 40%). Leveraging its high molar extinction coefficient and slow charge recombination, the 30% DNH-incorporated PMMA photocatalyst proves to be particularly efficient. This photocatalytic system demonstrates exceptional yields (96.5%) in imine production and high generation/regeneration rates for LDC/NADH (65.27%/78.77%). The research presented herein emphasizes the development and application of a newly engineered polymer-based photocatalyst, which holds significant promise for direct solar-assisted chemical synthesis in diverse commercial applications.

Keywords: DNH-incorporated PMMA photocatalyst; NADH regeneration; leucodopaminechrome; oxidative amine coupling; photocatalysis.