Analyzing the N-H+center dot center dot center dot pi interactions of protonated tryptophan and phenylalkylamines using QTAIM, NCl, and NBO

Autor(es)

Rodrigues-Oliveira, Andre F. ^[1] ; Batista, Patrick R. ^[1] ; Ducati, Lucas C. ^[1] ; Correra, Thiago C. ^[1]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Dept Fundamental Chem, Inst Chem, Av Prof Lineu Prestes 748, BR-05508000 Sao Paulo, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: THEORETICAL CHEMISTRY ACCOUNTS; v. 139, n. 8 JUL 14 2020.
• Citações Web of Science: 0

Resumo

Tryptophan and phenylakylamines (PAAs) are important biomolecules, which are involved in a myriad of processes. These molecules have been experimentally reported to exhibit N-H+center dot center dot center dot pi interactions in their protonated form; however, this has not been theoretically investigated in detail. Generally, such interactions are observed in diverse biological systems, and their evaluation would be useful for understanding protein folding and functioning. Therefore, in this study, we have described the N-H+center dot center dot center dot pi interactions of the abovementioned classes of molecules using the Quantum Theory of Atoms In Molecules (QTAIM), Natural Bond Orbital (NBO), and Non-Covalent Interaction (NCI) analyses. The results of our N-H+center dot center dot center dot pi interaction energy calculations were consistent with the experimental energies derived from the redshift of the vibrational stretches. The energy values obtained using the QTAIM-based Espinosa's approach provided a relatively better result than similar approaches previously reported in the literature. Furthermore, we observed that the N-H+center dot center dot center dot pi interaction energy in tryptophan is weaker than the resonance-assisted hydrogen bond energy of the N-H+center dot center dot center dot O=C interactions of its three most stable conformers accessible at room temperature. In contrast, the strength of the N-H+center dot center dot center dot pi interaction in PAAs was observed to increase with increasing alkyl lateral chain length. The increased flexibility of longer chains increases the distance between nitrogen and the phenyl ring without disturbing the N-H+center dot center dot center dot pi interaction. (AU)

• Processo FAPESP: 19/25634-9 - Estudo de reações em tempo real e matrizes complexas por técnicas avançadas de espectrometria de massas
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• Processo FAPESP: 14/15962-5 - Mecanismos de reação de sistemas catalíticos assimétricos por espectrometria de massas e espectroscopia vibracional de íons na fase gasosa
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• Processo FAPESP: 15/08539-1 - EMU concedido no processo 2014/15962-5: espectrômetro de massas tipo íon TRAP modificado para realização de espectroscopia vibracional no infravermelho (IRMPD)
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• Processo FAPESP: 18/07308-4 - Efeito do solvente em cálculos de tensor blindagem e constante de acoplamento de complexos dinucleares de platina (III) via dinâmica molecular ab initio
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