TY - JOUR

T1 - Interactions of deprotonated phenylalanine with gold Clusters: Theoretical study with prospects for amino acid detection

AU - Буглак, Андрей Андреевич

AU - Кононов, Алексей Игоревич

PY - 2024/4/1

Y1 - 2024/4/1

N2 - Nanomaterials are widely used nowadays in industry and medicine. The specific properties of gold nanoclusters (Au NCs) are chemical stability, low cytotoxicity, low photobleaching, high sensitivity to the molecular environment. This set of properties allows to use Au NCs as nanosensors in bioimaging and diagnostics. We have investigated gold cluster complexes with proteinogenic amino acid phenylalanine (Phe). Detection of phenylalanine is essential for diagnostics of phenylketonuria, vitiligo, sclerosis, cancer, tuberculosis, etc. We have studied the complexes of Phe with Aunq clusters with atomic number equal 1–6, 8, 20 and a charge equal 0–2. We have established that the clusters Au40, Au21+ and Au32+ form the most stable complexes with Phe among NCs with charge 0, +1 and + 2, respectively. Intracomplex interactions have been studied using Atoms-In-Molecules (AIM) theory and Natural Bond Orbital (NBO) analysis. It has been shown that metal–ligand intracomplex interactions are partially covalent and partially electrostatic. Also, we have simulated the UV–vis absorption and Raman spectra of the Phe-Au NCs. We have established that the clusters possess prospective features if being used for colorimetric and Raman detection of Phe. Au20 cluster is remarkable for its six-times enhancement of the Raman signal. Moreover, our study provides insights into metal–ligand interactions for clusters synthesized inside a polypeptide globula. Hence, to the best of our knowledge this is a first attempt to perform a detailed analysis of Phe interactions with gold using quantum chemical calculations.

AB - Nanomaterials are widely used nowadays in industry and medicine. The specific properties of gold nanoclusters (Au NCs) are chemical stability, low cytotoxicity, low photobleaching, high sensitivity to the molecular environment. This set of properties allows to use Au NCs as nanosensors in bioimaging and diagnostics. We have investigated gold cluster complexes with proteinogenic amino acid phenylalanine (Phe). Detection of phenylalanine is essential for diagnostics of phenylketonuria, vitiligo, sclerosis, cancer, tuberculosis, etc. We have studied the complexes of Phe with Aunq clusters with atomic number equal 1–6, 8, 20 and a charge equal 0–2. We have established that the clusters Au40, Au21+ and Au32+ form the most stable complexes with Phe among NCs with charge 0, +1 and + 2, respectively. Intracomplex interactions have been studied using Atoms-In-Molecules (AIM) theory and Natural Bond Orbital (NBO) analysis. It has been shown that metal–ligand intracomplex interactions are partially covalent and partially electrostatic. Also, we have simulated the UV–vis absorption and Raman spectra of the Phe-Au NCs. We have established that the clusters possess prospective features if being used for colorimetric and Raman detection of Phe. Au20 cluster is remarkable for its six-times enhancement of the Raman signal. Moreover, our study provides insights into metal–ligand interactions for clusters synthesized inside a polypeptide globula. Hence, to the best of our knowledge this is a first attempt to perform a detailed analysis of Phe interactions with gold using quantum chemical calculations.

KW - Aromatic amino acids

KW - Density functional theory

KW - Gold nanoclusters

KW - Phenylalanine

KW - Raman spectroscopy

KW - SERS

UR - https://www.mendeley.com/catalogue/31186f94-d70b-359c-99e9-2857ea01c86e/

U2 - 10.1016/j.saa.2024.124004

DO - 10.1016/j.saa.2024.124004

M3 - Article

VL - 311

JO - SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY

JF - SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY

SN - 1386-1425

M1 - 124004

ER -