Heteroleptic Ruthenium(II) Complexes with Bathophenanthroline and Bathophenanthroline Disulfonate Disodium Salt as Fluorescent Dyes for In-Gel Protein Staining

Babak, Maria V.; Faouder, Pauline Le; Trivelli, Xavier; Venkatesan, Gopalakrishnan; Bezzubov, Stanislav I.; Kajjout, Mohammed; Gushchin, Artem L.; Hanif, Muhammad; Poizat, O.; Vezin, Hervé; Rolando, Christian

doi:10.1021/acs.inorgchem.9b03679

Cited by 10 publications

(7 citation statements)

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“…Second and third row d 6 transition metals, specifically Ru(II), Re(I), Os(II), and Ir(III), form photoactive coordination complexes suitable for varied applications including light emitting diodes, oxygen sensing, organic photocatalysis, bioimaging, photodynamic therapy, and solar fuel generation. − Heteroleptic [Ir(C^N) 2 (N^N)] + complexes (where C^N is a cyclometalating 2-phenylpyridyl ligand and N^N is a 1,2-diimine ancillary ligand, Figure A) are popular scaffolds due to their modular synthesis, enhanced photostability, and long-lived triplet excited state lifetimes arising from strong spin–orbital effects of Ir(III). − Large ligand-field splitting, caused by the high quantum number of the central Ir d -electrons and the strongly σ-donating carbanions of the cyclometalating ligands, significantly destabilizes metal-centered (MC) antibonding orbitals compared to other 4 d and 5 d metal ion complexes . The substantial increase in these e g *-like orbitals inhibits thermal population of the deactivating 3 MC excited state and allows the large variability in emission color of reported Ir(III) complexes, spanning the visible spectrum (Figure A).…”

Section: Introductionmentioning

confidence: 99%

High-Throughput Screening and Automated Data-Driven Analysis of the Triplet Photophysical Properties of Structurally Diverse, Heteroleptic Iridium(III) Complexes

et al. 2021

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Steady state emission spectra and excited state lifetimes were measured for 1440 distinct heteroleptic [Ir(C^N)2(N^N)]+ complexes prepared via combinatorial parallelized synthesis; 72% of the complexes were found to be luminescent, and the emission maxima of the library spanned the visible spectrum (652–459 nm). Spectral profiles ranged from broad structureless bands to narrow emissions exhibiting vibrational substructure. Measured excited state lifetimes ranged between ∼0.1–14 μs. Automated emission spectral fitting with successive Gaussian functions revealed four distinct measured classes of excited states; in addition to well understood metal–ligand to ligand-charge transfer (3MLLCT) and ligand-centered (3LC) excited states, our classification also identified photophysical characteristics of less explored mixed 3MLLCT/3LC states. Electronic structure features obtained from DFT calculations performed on a large subset of these Ir(III) chromophores offered clear insights into the excited state properties and allowed the prediction of structure/luminescence relationships in this class of commonly used photocatalysts. Models with high prediction accuracy (R2 = 0.89) for emission color were developed on the basis of experimental data. Furthermore, different degrees of nuclear reorganization in the excited state were shown to significantly impact emission energy and excited state lifetimes.

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Section: Introductionmentioning

confidence: 99%

High-Throughput Screening and Automated Data-Driven Analysis of the Triplet Photophysical Properties of Structurally Diverse, Heteroleptic Iridium(III) Complexes

et al. 2021

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“…In both studies by Gasser et al ., the BPhen ligands likely contribute to good cellular uptake (log P = 1.4 for 8 ). Other studies have used BPhen ruthenium complexes for cellular imaging based upon their luminescent properties making them potential theranostic agents and dyes for in‐gel protein staining (38–41). Herein, we demonstrate that BPhen ligands enhance the photocytotoxicity of ruthenium complexes using dihydroxybipyridine ligands.…”

Section: Introductionmentioning

confidence: 99%

Light‐responsive and Protic Ruthenium Compounds Bearing Bathophenanthroline and Dihydroxybipyridine Ligands Achieve Nanomolar Toxicity towards Breast Cancer Cells^†

Oladipupo

Brown

Lamb

et al. 2021

Photochem & Photobiology

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We report new ruthenium complexes bearing the lipophilic bathophenanthroline (BPhen) ligand and dihydroxybipyridine (dhbp) ligands which differ in the placement of the OH groups ([(BPhen)2Ru(n,n′‐dhbp)]Cl2 with n = 6 and 4 in 1A and 2A, respectively). Full characterization data are reported for 1A and 2A and single crystal X‐ray diffraction for 1A. Both 1A and 2A are diprotic acids. We have studied 1A, 1B, 2A, and 2B (B = deprotonated forms) by UV‐vis spectroscopy and 1 photodissociates, but 2 is light stable. Luminescence studies reveal that the basic forms have lower energy 3MLCT states relative to the acidic forms. Complexes 1A and 2A produce singlet oxygen with quantum yields of 0.05 and 0.68, respectively, in acetonitrile. Complexes 1 and 2 are both photocytotoxic toward breast cancer cells, with complex 2 showing EC50 light values as low as 0.50 μM with PI values as high as >200 vs. MCF7. Computational studies were used to predict the energies of the 3MLCT and 3MC states. An inaccessible 3MC state for 2B suggests a rationale for why photodissociation does not occur with the 4,4′‐dhbp ligand. Low dark toxicity combined with an accessible 3MLCT state for 1O2 generation explains the excellent photocytotoxicity of 2.

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“…Regarding the d 6 transition-metal complexes to stain proteins, Ru(II) bathophenanthroline disulfonate (RuBPS) is a luminescent complex that efficiently stains proteins in polyacrylamide gels (Rabilloud et al, 2001;Babak et al, 2020). This feature can be attributed to the bathophenanthroline disulfonate moiety, which allows water solubility and permits electrostatic interactions similar to that described for CBB (Graham et al, 1978;Berggren et al, 2000;Steinberg et al, 2000;Rabilloud et al, 2001).…”

Section: Introductionmentioning

confidence: 99%

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

et al. 2021

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Sodium-dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) can be used to separate proteins based mainly on their size such as in denaturing gels. Different staining methods have been reported to observe proteins in the gel matrix, where the most used dyes are generally anionic. Anionic dyes allow for interactions with protonated amino acids, retaining the dye in the proteins. Fluorescent staining is an alternative technique considered to be sensitive, safe, and versatile. Some anionic complexes based on d6 transition metals have been used for this purpose, where cationic dyes have been less explored in this context. In this work, we synthesized and characterized a new monocationic rhenium complex fac-[Re(CO)3(deeb)B2]+ (where deeb is 4,4′-bis(ethoxycarbonyl)-2,2′-bpy and B2 is 2,4-di-tert-butyl-6-(3H-imidazo[4,5-c]pyridine-2-yl)phenol). We carried out a structural characterization of this complex by MS+, FTIR, 1H NMR, D2O exchange, and HHCOSY. Moreover, we carried out UV-Vis, luminescence, and cyclic voltammetry experiments to understand the effect of ligands on the complex’s electronic structure. We also performed relativistic theoretical calculations using the B3LYP/TZ2P level of theory and R-TDDFT within a dielectric continuum model (COSMO) to better understand electronic transitions and optical properties. We finally assessed the potential of fac-[Re(CO)3(deeb)B2]+ (as well as the precursor fac-Re(CO)3(deeb)Br and the free ligand B2) to stain proteins separated by SDS-PAGE. We found that only fac-[Re(CO)3(deeb)B2]+ proved viable to be directly used as a luminescent dye for proteins, presumably due to its interaction with negatively charged residues in proteins and by weak interactions provided by B2. In addition, fac-[Re(CO)3(deeb)B2]+ seems to interact preferentially with proteins and not with the gel matrix despite the presence of sodium dodecyl sulfate (SDS). In future applications, these alternative cationic complexes might be used alone or in combination with more traditional anionic compounds to generate counterion dye stains to improve the process.

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Heteroleptic Ruthenium(II) Complexes with Bathophenanthroline and Bathophenanthroline Disulfonate Disodium Salt as Fluorescent Dyes for In-Gel Protein Staining

Cited by 10 publications

References 31 publications

High-Throughput Screening and Automated Data-Driven Analysis of the Triplet Photophysical Properties of Structurally Diverse, Heteroleptic Iridium(III) Complexes

High-Throughput Screening and Automated Data-Driven Analysis of the Triplet Photophysical Properties of Structurally Diverse, Heteroleptic Iridium(III) Complexes

Light‐responsive and Protic Ruthenium Compounds Bearing Bathophenanthroline and Dihydroxybipyridine Ligands Achieve Nanomolar Toxicity towards Breast Cancer Cells^†

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

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Heteroleptic Ruthenium(II) Complexes with Bathophenanthroline and Bathophenanthroline Disulfonate Disodium Salt as Fluorescent Dyes for In-Gel Protein Staining

Cited by 10 publications

References 31 publications

High-Throughput Screening and Automated Data-Driven Analysis of the Triplet Photophysical Properties of Structurally Diverse, Heteroleptic Iridium(III) Complexes

High-Throughput Screening and Automated Data-Driven Analysis of the Triplet Photophysical Properties of Structurally Diverse, Heteroleptic Iridium(III) Complexes

Light‐responsive and Protic Ruthenium Compounds Bearing Bathophenanthroline and Dihydroxybipyridine Ligands Achieve Nanomolar Toxicity towards Breast Cancer Cells†

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE

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Light‐responsive and Protic Ruthenium Compounds Bearing Bathophenanthroline and Dihydroxybipyridine Ligands Achieve Nanomolar Toxicity towards Breast Cancer Cells^†