TY - JOUR

T1 - Silver cluster interactions with Pterin

T2 - Complex structure, binding energies and spectroscopy

AU - Buglak, Andrey A

AU - Kononov, Alexei I

N1 - Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/10/15

Y1 - 2022/10/15

N2 - Metal nanoclusters (NCs) are widely present today in biosensing, bioimaging, and diagnostics due to their small size, great biocompatibility, and sensitivity to the biomolecular environment. Silver (Ag) NCs often possess intense fluorescence, photostability, and low photobleaching, which is in high demand during the detection of organic molecules. Pterins are small compounds, which are used in medicine as biomarkers of oxidative stress, cardiovascular diseases, neurotransmitter synthesis, inflammation and immune system activation. It is experimentally possible to detect pterin (Ptr) through the adsorption on Ag colloid. We optimized geometries and evaluated the binding energy in Ptr-Agnq complexes (n = 1-6; q = 0, +1, +2) using quantum chemistry methods. Different Ptr atoms were preferential for silver attachment depending on NC charge and size. The highest Eb was obtained for the complexes between the Ptr0 and Ag32+ (-50.8 kcal mol-1), between Ptr-1 and Ag32+ (-64.8 kcal mol-1), which means that these complexes should be formed preferably in aqueous solutions in acidic and alkaline media, respectively. The colorimetric detection of pterin with silver clusters does not seem to be promising. However, intense S0→S1 transitions of Ag5+ complexes look promising for luminescent Ptr detection. SERS detection of pterin is better to be done at pH > 8 since deprotonated pterin Raman undergo more dramatic changes upon addition of Ag than the neutral pterin. The characteristics of absorption and vibrational spectra of silver-pterin should be exploited during biosensor development.

AB - Metal nanoclusters (NCs) are widely present today in biosensing, bioimaging, and diagnostics due to their small size, great biocompatibility, and sensitivity to the biomolecular environment. Silver (Ag) NCs often possess intense fluorescence, photostability, and low photobleaching, which is in high demand during the detection of organic molecules. Pterins are small compounds, which are used in medicine as biomarkers of oxidative stress, cardiovascular diseases, neurotransmitter synthesis, inflammation and immune system activation. It is experimentally possible to detect pterin (Ptr) through the adsorption on Ag colloid. We optimized geometries and evaluated the binding energy in Ptr-Agnq complexes (n = 1-6; q = 0, +1, +2) using quantum chemistry methods. Different Ptr atoms were preferential for silver attachment depending on NC charge and size. The highest Eb was obtained for the complexes between the Ptr0 and Ag32+ (-50.8 kcal mol-1), between Ptr-1 and Ag32+ (-64.8 kcal mol-1), which means that these complexes should be formed preferably in aqueous solutions in acidic and alkaline media, respectively. The colorimetric detection of pterin with silver clusters does not seem to be promising. However, intense S0→S1 transitions of Ag5+ complexes look promising for luminescent Ptr detection. SERS detection of pterin is better to be done at pH > 8 since deprotonated pterin Raman undergo more dramatic changes upon addition of Ag than the neutral pterin. The characteristics of absorption and vibrational spectra of silver-pterin should be exploited during biosensor development.

KW - silver nanoclusters

KW - PTERIN

KW - Binding energy

KW - Density Functional Theory

KW - absorption spectroscopy

KW - SERS

KW - Absorption spectroscopy

KW - Pterin

KW - Silver nanoclusters

UR - http://www.scopus.com/inward/record.url?scp=85131946353&partnerID=8YFLogxK

U2 - 10.1016/j.saa.2022.121467

DO - 10.1016/j.saa.2022.121467

M3 - Article

C2 - 35689845

VL - 279

SP - 121467

JO - SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY

JF - SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY

SN - 1386-1425

M1 - 121467

ER -