Why Do Silver Trimers Intercalated in DNA Exhibit Unique Nonlinear Properties That Are Promising for Applications?

Abstract

Our investigation of one-photon absorption (OPA) and nonlinear optical (NLO) properties such as two-photon absorption (TPA) of silver trimer intercalated in DNA based on TDDFT approach allowed us to propose a mechanism responsible for large TPA cross sections of such NLO-phores. We present a concept that illustrates the key role of quantum cluster as well as of nucleotide bases from the immediate neighborhood. For this purpose, different surroundings consisting of guanine-cytosine and adenine-thymine such as (GCGC) and (ATAT) have been investigated that are exhibiting substantially different values of TPA cross sections. This has been confirmed by extending the immediate surroundings as well as using the two-layer quantum mechanics/molecular mechanics (QM/MM) approach. We focus on the cationic closed-shell system and illustrate that the neutral open-shell system shifts OPA spectra into the NIR regime, which is suitable for applications. Thus, in this contribution, we propose novel NLO-phores inducing large TPA cross sections, opening the route for multiphoton imaging.

Tuning the Electronic Properties and Performance of Low-Temperature CO Oxidation of the Gold Cluster by Oriented External Electronic Field

“…Atomic clusters consisting of several to hundreds of atoms possess fascinating physical, chemical, electronic, and magnetic properties that differ notably from the properties of conventional atoms and bulk materials. − Their potential applications in catalysis, energy, and the environment together with materials have received great attention in the past several decades. In particular, in the field of cluster science, the superatom is a category of special atomic cluster that can mimic the chemistry of an atom in the periodic table. − Along with the suggestion of the theoretical superatom concept and the experimental discoveries, ,, a series of superatoms, including superhalogens, ,, superalkalis, , magnetic superatoms, rare-earth superatoms, and so on, have been discovered, among which the electronic properties, for example, the electron affinity (EA) and the ionization energy (IP), are fundamental principles in the design of superatoms.…”

Нанокластеры Серебра В Биохимии И Медицине (Обзор)

“…Èñïîëüçóÿ ñèëüíîå ñðîäñòâî A ê áèìåòàëëè-÷åñêîé ïîâåðõíîñòè ÷àñòèö Au/Ag èç èõ íàíîêîìïîçèòà ñ ñåðåáðÿíûì ÿäðîì èçãîòîâëåí ÷èï äëÿ âûñîêî÷óâñòâèòåëüíîãî îáíàðóaeåíèÿ àêòèâíîñòè â ñûâîðîòêå ó÷àñòêîâ ïîëèA äëÿ C-G-äèíóêëåîòèä-ìåòèë-òðàíñôåðàçû [17]. Êðîìå òîãî, ïðè èçó÷åíèè ñäâîåííûõ íóêëåîòèäíûõ ó÷àñòêîâ ÄÍÊ C-G è A-Thymine (A-T), òàêèõ GCGC è ATAT áûë óäà÷íî èñïîëüçîâàí òðèìåð êëàñòåðà Ag 3 + , êîòîðûé ãåíåðèðîâàë êîìïëåêñ [Ag 3 (GCGC) + ] è ÷ü¸óñïåøíîå ïðèìåíåíèå áûëî îáîñíîâàíî îñîáåííîñòÿìè îäíîôîòîííûõ ñïåêòðîâ ïîãëîùåíèÿ ñèñòåìû ñ çàêðûòîé êàòèîííîé îáîëî÷êîé [18].…”

“… òî aeå âðåìÿ âåñüìà âûñîêàÿ ñêëîííîñòü òèîëàòîâ çîëîòà ê îáðàçîâàíèþ ðàçíîîáðàçíûõ ñóïåðìîëåêóëÿðíûõ êîìáèíàöèé îòêðûâàåò íîâûå ïóòè äëÿ âîçíèêíîâåíèÿ òàêèõ ìàòåðèàëîâ, ñòðóêòóðà êîòîðûõ íåïîñðåäñòâåííî ñâÿçàíà ñ èõ îïòè÷åñêèìè ñâîéñòâàìè; ñâåaeèì ïðèìåðîì ïîäîáíûõ ìàòåðèàëîâ ÿâëÿþòñÿ 100 íì-ðàçìåðà ñâåðõìîëåêóëÿðíûå àíñàìáëè Au-C, â òîì ÷èñëå èõ îáëåïëåííûé êëàñòåðàìè Ag áèìåòàëëè-÷åñêèé âàðèàíò [49] 18 (x ³ 2) òàêaeå çàâèñåëî íå òîëüêî îò ìåòîäà ñèíòåçà, íî è îò âðåìåíè èõ íàõîaeäåíèÿ â ðàñòâîðå [51]. Ìåaeäó òåì äàaeå â òîíêèõ, âêëþ÷àâøèõ íàïû-ë¸ííûå ÷àñòèöû ñåðåáðà ïë¸íêàõ ìîäåëüíîãî îëèãîìåðà, äëÿ êîòîðîãî õàðàêòåðíà ñòðóêòóðà òèîôåíàa-ñåêñèòèîôåíà, áûëè çàðåãèñòðèðîâàíû èíòåíñèâíûå ìåaeïîâåðõíîñòíûå ðåàêöèè; ïî äåôîðìàöèè åãî êîëüöà, âûçâàííîãî âðàùåíèåì s-ñâÿçè, ñäåëàí âûâîä î ïðîíèêíîâåíèè îëèãîìåðà â ñàìè ÷àñòèöû âî âðåìÿ ùàäÿùåãî ðåaeèìà ðàáîòû äåâàéñà [52].…”

Collective Response in DNA-Stabilized Silver Cluster Assemblies from First-Principles Simulations

“…In addition, proper taking into account of the solvent environment is mandatory as well . Currently, significant progress has been made in understanding the structure and charge distributions in individual DNA-stabilized silver clusters employing force-field molecular dynamics simulations, , coupled quantum-mechanical/molecular-mechanical (QM/MM) methods, , and density functional theory (DFT). ,,− In contrast, the collective properties of DNA-stabilized silver cluster assemblies, although experimentally proven, still remain undeservedly beyond the scope of the up-to-date theoretical research. However, such aggregates could provide unique possibility of constructing nanosized optoelectronic devices based on spatially organized arrays of noble-metal clusters serving, for instance, as ultrasmall energy and charge transmission lines. − Therefore, an efficient theoretical method for a realistic description of exciton and charge propagation in such systems under the action of an external driving electric field is highly desired.…”

“…20,21 These systems represent considerable challenge to theory because of their size. Indeed, the simulations show that in order to reliably reproduce the experimental results, accurate quantum-chemical calculations are required, 22,23 which include not only a silver cluster core but also adjacent nucleobases, because the latter can dramatically change the optical properties of the cluster. 24 In addition, proper taking into account of the solvent environment is mandatory as well.…”