In this research, the absorbance and luminescence response of two osmium(II) phenathrane (phen) carbonyl complexes to various DNA, heparin and i-carrageenan polyanions were studied. The [Os(phen)2CO(L)]2+ complexes with L either a 4-phenyl pyridine (4-phpy) or phenyl imidazole (phimd) group exhibit moderate luminescent intensity in the visible region, their intensities are highly altered by the addition of DNA and other polyanion samples. These luminescent responses to polyanions were also compared with the [Ru(phen)3]2+ complex. In ethanol solution, the presence of polyanions significantly enhanced the luminescent emission intensity of [Os(phen)2CO(L)]2+ complexes with a blue shift. While the polyanions all showed emission enhancement on the highly lumi-nescent [Ru(phen)3]2+ complex in ethanol solution with a red spectra shift. The [Os(phen)2CO(L)] 2+ with (phimd) ligand has the lowest emission in ethanol solution, its intensity can be enhanced up to 11 times in the presence of DNA polyanions. This enhancement for all the complexes in ethanol is mainly due to their electrostatic interaction with the anion sites and with some degree of ligand intercalation into the polyanion hydrophobic structure which reduced the solvent quenching of the complexes. The blue shift of the (4-phpy) and particularly (phimd) Os(II)CO complexes indicate an insertion of the (4-phpy) or (phimd) group into the polymer chains. The two new Os(II)CO complexes has great potential to be used as luminescence sensors for DNA and polyanion detection in the low micro molar range with high sensitivity.
References
[1]
Wang, J. (2000) Survey and Summary: From DNA Biosensors to Gene Chips. Nucleic Acids Research, 28, 3011-3016. https://doi.org/10.1093/nar/28.16.3011
[2]
Huanga, R., Hea, N. and Li, Z. (2018) Recent Progresses in DNA Nanostructure-Based Biosensors for Detection of Tumor Markers. Biosensors and Bioelectronics, 109, 27-34. https://doi.org/10.1016/j.bios.2018.02.053
[3]
Reyes, J.B., Kuimova, M.K. and Vilar, R. (2021) Metal Complexes as Optical Probes for DNA Sensing and Imaging. Current Opinion in Chemical Biology, 61, 179-190. https://doi.org/10.1016/j.cbpa.2021.02.007
[4]
Hirsh, J., Raschke, C.R., Warkentin, T.E., Dalen, J.E., Deykin, D. and Poller, L. (1992) Heparin: Mechanism of Action, Pharmacokinetics, Dosing Considerations, Monitoring, Efficacy, and Safety. Chest, 102, 258S-275S. https://doi.org/10.1378/chest.108.4_Supplement.258S
[5]
Guerrini, M., Beccati, D., Shriver, Z., Naggi, A., Viswanathan, K., Bisio, A., et al. (2008) Oversulfated Chondroitin Sulfate Is a Contaminant in Heparin Associated with Adverse Clinical Events. Nature Biotechnology, 26, 669-675. https://doi.org/10.1038/nbt1407
[6]
Bromfield, S.M., Wilde, E. and Smith, D.K. (2013) Heparin Sensing and Binding—Taking Supramolecular Chemistry towards Clinical Applications. Chemical Society Reviews, 42, 9184-9195. https://doi.org/10.1039/C3CS60278H
[7]
Campo, V.L., Kawano, D.F., da Silva Jr., D.B. and Carvalho, I. (2009) Carrageenans: Biological Properties, Chemical Modifications and Structural Analysis—A Review. Carbohydrate Polymers, 77, 167-180. https://doi.org/10.1016/j.carbpol.2009.01.020
[8]
Necas, J. and Bartosikova, L. (2013) Carrageenan: A Review. Veterinarni Medicina, 58, 187-205. https://doi.org/10.17221/6758-VETMED
[9]
Barton, J.K., Danishefsky, A.T. and Goldberg, J.M. (1984) Tris-(phenanthroline)ruthenium(II): Stereoselectivity in Binding to DNA. Journal of the American Chemical Society, 106, 2172-2176. https://doi.org/10.1021/ja00319a043
[10]
Friedman, A.E., Chambron, J.C., Sauvage, J.P., Turro, N.J. and Barton, J.K. (1990) A Molecular Light Switch for DNA: Ru(bpy)2(dppz)2+. Journal of the American Chemical Society, 112, 4960-4962. https://doi.org/10.1021/ja00168a052
[11]
Ling, L.-S., He, Z.-K., Song, G.-W., Zeng, Y.-E, Wang, C., Bai, C.-L., Chen, X.-D. and Chen, P. (2001) High Sensitive Determination of DNA by Use of Molecular “Light Switch’’ Complex of Ru(phen)2(dppx)2+. Analytica Chimica Acta, 436, 207-214. https://doi.org/10.1016/S0003-2670(01)00922-9
[12]
Salem, A.A. (2006) Fluorimetric Determinations of Nucleic Acids Using Iron, Osmium and Samarium Complexes of 4,7-diphenyl-1,10-phenanthroline. Spectrochimica Acta Part A, 65, 235-248. https://doi.org/10.1016/j.saa.2005.10.037
[13]
Liu, W., Shen, Y.-M., Li, Z.-X., Zhong, X., Chen, Y.-D. and Zhang, S.-B. (2015) Study on DNA Binding Behavior and Light Switch Effect of New Coumarin-Derived Ru(II) Complexes. Spectrochimica Acta Part A, 149, 150-156. https://doi.org/10.1016/j.saa.2015.04.063
[14]
Mardanya, S., Karmakar, S., Maity, D. and Baitalik, S. (2015) Ruthenium(II) and Osmium(II) Mixed Chelates Based on Pyrenyl-Pyridylimidazole and 2,2’-bipyridine Ligands as Efficient DNA Intercalators and Anion Sensors. Inorganic Chemistry, 54, 513-526. https://doi.org/10.1021/ic502271k
[15]
Boynton, A.N., Marcelis, L. and Barton, J.K. (2016) [Ru-(Me4phen)2(dppz)]2+, a Light Switch for DNA Mismatches. Journal of the American Chemical Society, 138, 5020-5023. https://doi.org/10.1021/jacs.6b02022
[16]
Boynton, A.N., Marcélis, L., McConnell, A.J. and Barton, J.K. (2017) A Ruthenium(II) Complex as a Luminescent Probe for DNA Mismatches and Abasic Sites. Inorganic Chemistry, 56, 8381-8389. https://doi.org/10.1021/acs.inorgchem.7b01037
[17]
Li, B., Zhou, X., Liu, H., Deng, H., Huang, R. and Xing, D. (2018) Simultaneous Detection of Antibiotic Resistance Genes on Paper-Based Chip Using [Ru(phen)2dppz]2+ Turn-on Fluorescence Probe. ACS Applied Materials & Interfaces, 10, 4494-4501. https://doi.org/10.1021/acsami.7b17653
[18]
Zhang, P., Wang, Y., Qiu, K., Zhao, Z., Hu, R., He, C., Zhang, Q. and Chao, H. (2017) A NIR Phosphorescent Osmium(II) Complex as a Lysosome Tracking Reagent and Photodynamic Therapeutic Agent. Chemical Communications, 53, 12341-12344. https://doi.org/10.1039/C7CC07776A
[19]
Shun, J., Leung, P.K.-K. and Lo, K.K.-W. (2019) Luminescent Ruthenium(II) Polypyridine Complexes for a Wide Variety of Biomolecular and Cellular Applications. Inorganic Chemistry, 58, 2231-2247. https://doi.org/10.1021/acs.inorgchem.8b02979
[20]
Nabiyeva, T., Marschner, C. and Blom, B. (2020) Synthesis, Structure and Anti-Cancer Activity of Osmium Complexes Bearing π-Bound Arene Substitutuents and Phosphane Co-Ligands: A Review. European Journal of Medicinal Chemistry, 201, Article ID: 112483. https://doi.org/10.1016/j.ejmech.2020.112483
[21]
Erkkila, K.E., Odom, D.T. and Barton, J.K. (1999) Recognition and Reaction of Metallointercalators with DNA. Chemical Society Reviews, 99, 277-2796. https://doi.org/10.1021/cr9804341
[22]
Lin, H.K. and Sadler, P.J. (2011) Metal Complexes as DNA Intercalators. Accounts of Chemical Research, 44, 349-359. https://doi.org/10.1021/ar100140e
[23]
Komor, A.C. and Barton, J.K. (2013) The Path for Metal Complexes to a DNA Target. Chemical Communications, 49, 3617-3630. https://doi.org/10.1039/C3CC00177F
[24]
Zeng, L., Gupta, P., Chen, Y., Wang, E., Ji, L., Chao, H. and Chen, Z.-S. (2017) The Development of Anti-cancer Ruthenium(II) Complexes: From Single Molecule Compounds to Nanomaterials. Chemical Society Reviews, 46, 5711-5804. https://doi.org/10.1039/C7CS00195A
[25]
Cheng, T.-T., Yao, J.-J., Gao, X., Sun, W., Shi, S. and Yao, T.-M. (2013) A New Fluorescence “Switch on” Assay for Heparin Detection by Using a Functional Ruthenium Polypyridyl Complex. Analyst, 138, 3483-3489. https://doi.org/10.1039/C3AN00242J
[26]
Xie, Y., Lei, Y., Shah, S., Wu, H., Wu, J., Megehee, E. and Wang, E. (2013) Investigation of Luminescence Characteristics of Osmium(II) Complexes in the Presence of Heparin Polyanions. International Journal of Analytical Chemistry, 2013, Article ID: 419716. https://doi.org/10.1155/2013/419716
[27]
Wu, H., Wu, J., Saez, C., Campana, M., Megehee, E. and Wang, E. (2013) Study of Luminescence Osmium Complex Response to Macromolecular Polyanions for the Detection of Heparin and Chondroitin Sulfate in Biomedical Preparations. Analytica Chimica Acta, 804, 221-227. https://doi.org/10.1016/j.aca.2013.10.028
[28]
Piotrowski, C. (2017) Synthesis, Comparison, and Characterization of bis-diimine-carbonyl-osmium(II) Complexes upon Variation of the Sixth Ligand. Master Thesis, St. John’s University, Queens, NY.
