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1. A highly selective pyridoxal-based chemosensor for the detection of Zn( ii ) and application in live-cell imaging; X-ray crystallography of pyridoxal-TRIS Schiff-base Zn( ii ) and Cu( ii ) complexes

   https://doi.org/10.1039/D1RA05763D  

   Hussain, Anwar ; Mariappan, Kadarkaraisamy ; Cork, Dawson C. ; Lewandowski, Luke D. ; Shrestha, Prem K. ; Giri, Samiksha ; Wang, Xuejun ; Sykes, Andrew G. ( October 2021 , RSC Advances)

   In a simple, one-step reaction, we have synthesized a pyridoxal-based chemosensor by reacting tris(hydroxymethyl)aminomethane (TRIS) together with pyridoxal hydrochloride to yield a Schiff-base ligand that is highly selective for the detection of Zn( ii ) ion. Both the ligand and the Zn( ii ) complex have been characterized by 1 H & 13 C NMR, ESI-MS, CHN analyses, and X-ray crystallography. The optical properties of the synthesized ligand were investigated in an aqueous buffer solution and found to be highly selective and sensitive toward Zn( ii ) ion through a fluorescence turn-on response. The competition studies reveal the response for zinc ion is unaffected by all alkali and alkaline earth metals; and suppressed by Cu( ii ) ion. The ligand itself shows a weak fluorescence intensity (quantum yield, Φ = 0.04), and the addition of zinc ion enhanced the fluorescence intensity 12-fold (quantum yield, Φ = 0.48). The detection limit for zinc ion was 2.77 × 10 −8 M, which is significantly lower than the WHO's guideline (76.5 μM). Addition of EDTA to a solution containing the ligand–Zn( ii ) complex quenched the fluorescence, indicating the reversibility of Zn( ii ) binding. Stoichiometric studies indicated the formation of a 2 : 1more »L 2 Zn complex with a binding constant of 1.2 × 10 9 M −2 (±25%). The crystal structure of the zinc complex shows the same hydrated L 2 Zn complex, with Zn( ii ) ion binding with an octahedral coordination geometry. We also synthesized the copper( ii ) complex of the ligand, and the crystal structure showed the formation of a 1 : 1 adduct, revealing 1-dimensional polymeric networks with octahedral coordinated Cu( ii ). The ligand was employed as a sensor to detect zinc ion in HEK293 cell lines derived from human embryonic kidney cells grown in tissue culture which showed strong luminescence in the presence of Zn( ii ). We believe that the outstanding turn-on response, sensitivity, selectivity, lower detection limit, and reversibility toward zinc ion will find further application in chemical and biological science.« less
2. Highly Emitting Near-Infrared Lanthanide “Encapsulated Sandwich” Metallacrown Complexes with Excitation Shifted Toward Lower Energy

   https://doi.org/10.1021/ja4113337  

   Trivedi, Evan R. ; Eliseeva, Svetlana V. ; Jankolovits, Joseph ; Olmstead, Marilyn M. ; Petoud, Stéphane ; Pecoraro, Vincent L. ( January 2014 , Journal of the American Chemical Society)
3. Visible, Near-Infrared, and Dual-Range Luminescence Spanning the 4f Series Sensitized by a Gallium(III)/Lanthanide(III) Metallacrown Structure

   https://doi.org/10.1021/acs.jpca.0c08819  

   Salerno, Elvin V. ; Eliseeva, Svetlana V. ; Schneider, Bernadette L. ; Kampf, Jeff W. ; Petoud, Stéphane ; Pecoraro, Vincent L. ( December 2020 , The Journal of Physical Chemistry A)
4. One-Step Assembly of Visible and Near-Infrared Emitting Metallacrown Dimers Using a Bifunctional Linker

   https://doi.org/10.1002/chem.201703911  

   Nguyen, Tu N. ; Chow, Chun Y. ; Eliseeva, Svetlana V. ; Trivedi, Evan R. ; Kampf, Jeff W. ; Martinić, Ivana ; Petoud, Stéphane ; Pecoraro, Vincent L. ( January 2018 , Chemistry - A European Journal)
5. Lower Energy Excitation of Water Soluble Near‐Infrared Emitting Mixed‐Ligand Metallacrowns

   https://doi.org/10.1002/chem.202300226  

   Nguyen, Tu N. ; Eliseeva, Svetlana V. ; Martinić, Ivana ; Carver, Peggy L. ; Lathion, Timothée ; Petoud, Stéphane ; Pecoraro, Vincent L. ( April 2023 , Chemistry – A European Journal)

   By combining advantages of two series of lanthanide(III)/zinc(II) metallacrowns (MCs) assembled using pyrazine‐ (pyzHA²⁻) and quinoxaline‐ (quinoHA²⁻) hydroximate building blocks ligands, we created here water‐soluble mixed‐ligand MCs with extended absorption to the visible range. The Yb^IIIanalogue demonstrated improved photophysical properties in the near‐infrared (NIR) range in cell culture media, facilitating its application for NIR optical imaging in living HeLa cells.