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Highly NIR-emitting ytterbium complexes containing 2-tosylaminobenzaldehyde-4-azidomethylbenzoylhydrazone anions as perspective emissive part of luminescent biomarkerтезисы доклада Тезисы
- Авторы: Koshelev D.S., Mustakimov R.E., Utochnikova V.V.
- Сборник: Всероссийская конференция с международным участием «VII Российский день редких земель» Р Д Р З-2022 Тезисы конференции
- Тезисы
- Год издания: 2022
- Место издания: Казань
- Первая страница: 50
- Последняя страница: 51
- Аннотация: Lanthanide coordination compounds (CC) combine both the high absorption of organic ligands and the lanthanide luminescent properties that make them perspective in different areas such as sensing, OLED or bioimaging. In the latter lanthanides long excited states lifetimes, as well as the narrow emission bands and their stable positions in the spectra facilitate detection in living tissues due to high photons concentration in the luminescence spectra and the possibility of autofluorescence depletion.Earlier 1 ytterbium complexes with the Schiff bases – 2-tosylaminobenzaldehyde-benzoylhydrazone - demonstrated a high quantum yield (QY) of NIR luminescence up to 1.4%, and a molar extinction coefficient (ε) up to 40 000 (M•cm)-1, which makes these compounds perspective for use in bioimaging. However, the low solubility and lack of targeting groups require further ligand design. To increase solubility in this work, a halogen substituent was introduced into the benzylidene fragment of the ligand, and for the possibility of attaching target groups, an azido substituent was introduced into the benzoyl fragment of the ligand, since the azido group easily react with biological fragments and molecules by, so-called, click-reaction. Thus, modified 2-tosylamino(5-bromo)benzylidene-(4-azidomethyl)benzoyl hydrazone (H2L2) and its non-halogenated analogue (H2L1) were obtained by the condensation reaction of the corresponding aldehyde and (4-azidomethyl)benzohydrazide (Fig. 1a).а) b) Fig. 1. Synthesis of a) organic ligands H2L, b) lanthanide CC - Yb(L)(HL) (L =L1, L2).Ytterbium complexes Yb(L)(HL) (L=L1, L2) were obtained with the corresponding Schiff bases by the hydroxide method (Fig. 1b). Potassium salts - K[Yb(L)2] were obtained by the reaction with a stoichiometric amount of KOH and suspension of the complex: Ln(L)(HL)+KOH K[Ln(L)2](H2O)n (n=2 for L1; 1 for L2)The compositions of the obtained compounds were confirmed by a combination of TG with MS of released gases, IR and NMR spectroscopy. Single-crystal XRD allows solving structures of the 6 different complexes and 2 organic ligand H2L1. It turned out that the complexes structure is consist of mononuclear fragments Yb(L)(HL) (Fig. 2a) or [Yb(L)2], which in the latter case are connected either to a polymer chain via a K+ ion (Fig. 2b) or to binuclear fragments via two K+ ions (Fig. 2c).а) b) c) Fig. 2. Mononuclear fragments of а) Yb(L1)(HL1) and b) K[Yb(L2)2]. c) Binuclear fragment of K2[Yb(L1)2]2 structure.The solubility measurement showed a significant increase in the solubility of complexes during halogenation or the K[Yb(L)2] obtaining. The maximum solubility reached 40 g/L in THF, and for K[Yb(L)2] even water solubility was detected (<0.1 g/L).Since complexes are supposed to be used as a biomarker in the solution form, the luminescent properties of CC were studied in a DMSO solution. It was shown that the molar absorption coefficient reaches up to 45300 (M•cm)-1 and the quantum yield of NIR-luminescence reach 1.64% for K[Yb(L2)2], which is 1.5 times higher than the quantum yield for Yb(L2)(HL2). This could be explained by the NMR spectroscopy data, which demonstrate dissociation according to the equations: 2Yb(L)(HL) ↔ H2L + [Yb(L)]++[Yb(L)2]-K[Yb(L)2] ↔ K+ + [Yb(L)2]-which means decreasing sensitization efficiency due to only three ligands linking to the two Yb3+ in Yb(L*)(HL*) solution compared to four ligands linking to the two Yb3+ in K[Yb(L*)2] solution. Quantum efficiency (QE) = QY•ε of the obtained compounds reaches up to 680 (M•cm)-1 that is comparable to the QEs of the biomarkers with only high ε or high QY. Therefore, cytotoxicity of the K[Yb(L)2] was measured, and it turned out that non-toxic concentrations are less than 80 mmol/L. The combination of the non-toxicity, high QE and solubility make obtained compounds promising candidates to the emissive part of the targeted biomarkers.[1] A. D. Kovalenko, P. O. Rublev, L. O. Tcelykh, A. S. Goloveshkin, L. S. Lepnev, A. S. Burlov, A. A. Vashchenko, Ł. Marciniak, A. M. Magerramov, N. G. Shikhaliyev, S. Z. Vatsadze and V. V Utochnikova, Chem. Mater., 2019, 31, 759–773
- Добавил в систему: Кошелев Даниил Сергеевич
Прикрепленные файлы
| № | Имя | Описание | Имя файла | Размер | Добавлен |
|---|---|---|---|---|---|
| 1. | Тезисы на русском | Koshelev_Tezisyi_DRZ7.docx | 225,3 КБ | 21 февраля 2022 [Lamblador] | |
| 2. | Краткий текст | Тезисы на английском | Koshelev_Thesis_DREE7.docx | 215,7 КБ | 21 февраля 2022 [Lamblador] |
| 3. | Полный текст | Сборник тезисов | Abstracts_RDRZ_2022.pdf | 6,7 МБ | 21 февраля 2022 [Lamblador] |