NMR Study of Metal-mediated Base Pairs and Other N-Heterocyclic Derivatives in Solution by Ab Initio Molecular Dynamics and Relativistic Calculations

• Grant number: 25/03247-4
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• Start date: August 04, 2025
• End date: August 03, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Lucas Colucci Ducati
• Grantee: Lucas Pinheiro Coutinho
• Supervisor: Jochen Autschbach
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Institution abroad: State University of New York, Buffalo State (SUNY), United States
• Associated to the scholarship: 23/14766-7 - Study of Canonical and Artificial Metal-mediated Base Pairs in Solution by ab initio Molecular Dynamics and Relativistic NMR Calculations, BP.DR

Abstract

Metal-mediated base pairs (MMbp) are canonical and artificial nitrogenous bases that can pair withidentical nucleobases or form non-canonical pairs through coordination with transition metals insolution. The most studied MMpbs are those with Hg(II) and Ag(I) complexed with DNA duplexsystems, with applications ranging from heavy metal sensors to biological logic gate devices for cellsignaling. However, there is a large diversity of MMpbs and other N-heterocyclic aromaticsimilar-like molecules still in study, such as literature proposed thymine-guanine (T-Hg-G) mercurysystem, base-monomers, fluoro-mercuri-methylaniline nucleotides and a varied metal-substitutedderivatives of pyrrol, indole and carbazole molecules. These systems will be studied through nuclearmagnetic resonance (NMR) calculations of chemical shift (delta), shielding tensor (sigma) and indirectspin-spin coupling constant (J) to elucidate their structures and predict coordination sites. However,although there are studies in the literature using DFT (Density Functional Theory) calculations, thedynamic effect of the explicit solvent is not analyzed, implying variations in the obtained results.Thus in the proposed study, is intended to investigate the explicit solvent and relativistic effects onMMbp systems, mainly with Ag, Hg, Sn, carrying out a study on the dynamic effect of thecoordination of solvent molecules and conformational changes through the combination oftheoretical DFT calculations with the Ab initio molecular dynamics (AIMD) method.