- A selenium-containing ruthenium complex as a cancer radiosensitizer, rational design and the important role of ROS-mediated signalling
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A novel selenium-containing ruthenium complex Ru(phtpy)(phenSe)Cl(ClO4) (phtpy = 4-phenyl-2,2′:6′,2′′-terpyridine, phenSe = 2-selenicimidazole[4,5-f]1,10-phenanthroline) has been synthesized and found be able to enhance radiation-induced DNA damage through superoxide overproduction, which leads to G2/M arrest and apoptosis in cancer cells by activating ROS-mediated pathways. This journal is
- Deng, Zhiqin,Yu, Lianling,Cao, Wenqiang,Zheng, Wenjie,Chen, Tianfeng
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- Aromatic TpyRu2+(L)2Cl derivatives as water oxidation catalysts (Tpy?=?2,2″:6″,2″-terpyridine, Ru?=?ruthenium, L?=?pyridine or isoquinoline)
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Several mononuclear complexes with structure of [TpyRu2+(Py)2Cl]+ and [TpyRu2+(Isoq)2Cl]+ have been designed and synthesized. The structures of these complexes were confirmed by NMR and ESI
- Liu, Qianqian,Wu, Linlin,Chen, Mingzhao,Guo, Yuan,Xie, Tingzheng,Wang, Pingshan
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- Catalytic Water-Oxidation Activity of a Weakly Coupled Binuclear Ruthenium Polypyridyl Complex
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The catalytic oxidation of water by the binuclear complex [Ru2(H2O)2(bpy)2(tpy2ph)](PF6)4[bpy = 2,2′-bipyridine; tpy2ph = 1,3-bis(4′-2,2′:6′,2′′-terpyridin-4-yl)benzene] was investigated comparatively to its mononuclear counterpart [Ru(H2O)(bpy)(phtpy)](PF6)2(phtpy = 4′-phenyl-2,2′:6′,2′′-terpyridine). These catalysts were prepared from the synthesis of their precursor chloride complexes, which were also extensively characterized in this work. The H2O–RuIIcomplexes were found to undergo proton-coupled electron-transfer processes to generate the redox species HO–RuIII, O=RuIV, and O=RuV. The catalytically active species, [RuV2(O)2(bpy)2(tpy2ph)]6+and [RuV(O)(bpy)(phtpy)]3+, were generated electrochemically and by using cerium(IV) ammonium nitrate. In the presence of CeIV, the catalytic rates for O2production by the binuclear and mononuclear species were 1.9 × 10–3and 9.5 × 10–5s–1, respectively. This superior catalytic performance of the binuclear complex suggests that, despite weak electronic coupling between the Ru centers, the second site could play an important mechanistic role in the formation of the activated species [(bpy)(OO)RuIV(tpy2ph)RuIII(OH)(bpy)]4+.
- Matias, Tiago A.,Mangoni, Ana P.,Toma, Sergio H.,Rein, Francisca N.,Rocha, Reginaldo C.,Toma, Henrique E.,Araki, Koiti
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- Near infra-red emission from a mer-Ru(ii) complex: Consequences of strong σ-donation from a neutral, flexible ligand with dual binding modes
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A rare example of dual coordination modes by a novel tridentate ligand gives rise to unique fac-and mer-Ru(II/III) complexes. The mer-RuII-complex displays the farthest red-shift of a triplet metal-to-ligand charge transfer (3MLCT) emission with a tridentate ligand for a mononuclear complex. This observation is a consequence of large bite angle and strong σ-donation by the ligand, the combined effect of which helps to separate the energy of the 3MLCT and 3MC states. the Partner Organisations 2014.
- Pal, Amlan K.,Zaccheroni, Nelsi,Campagna, Sebastiano,Hanan, Garry S.
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- Labile ruthenium(II) complexes with extended phenyl-substituted terpyridyl ligands: Synthesis, aquation and anticancer evaluation
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Ruthenium complexes have been considered as promising substitutes for cisplatin in cancer chemotherapy. However, novel ruthenium-based therapies are faced with some limitations, such as unimpressive cytotoxicity toward solid tumors. Herein, we designed and synthesized phenyl-substituted terpyridyl ruthenium(ii) complexes ([Ru(tpy)(bpy)Cl]+ (Ru1), [Ru(phtpy)(bpy)Cl]+ (Ru2) and [Ru(biphtpy)(bpy)Cl]+ (Ru3)) which exhibited distinctly different anticancer activity. Ru1-Ru3 all underwent moderate aquation in buffer solution and this process was significantly inhibited by high chloride concentration. Cancer cells were found to readily uptake the relatively hydrophobic Ru3, as quantified using inductively coupled plasma mass spectrometry (ICP-MS). Ru1 was found to be non-cytotoxic (IC50 > 100 μM) while Ru3 exhibited very promising cytotoxicity on both two-dimensional (2D) cancer cell monolayers and 3D MCTSs. An antiproliferative assay revealed that Ru3 significantly inhibited cellular DNA replication which ultimately induced apoptosis of cancer cells.
- Huang, Huaiyi,Zhang, Pingyu,Chen, Yu,Ji, Liangnian,Chao, Hui
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- Synthesis, characterization and anticancer mechanism studies of fluorinated cyclometalated ruthenium(ii) complexes
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The drug-resistance of cancer cells has become a major obstacle to the development of clinical drugs for chemotherapy. In order to overcome cisplatin-resistance, seven cyclometalated ruthenium(ii) complexes were synthesized with a varying degree of fluorine substitution, for use as anticancer agents. A cytotoxicity assay testified that the complexes possessed a more cytotoxic effect than cisplatin towards the cisplatin-resistant cell line A549R. The number of fluorine atoms regulated the lipophilicity of the complexes, but the relationship was not linear.Ru1containing one fluorine atom had the highest lipophilicity and the best therapeutic effect. The complexes enter cells through an energy-dependent pathway and then localize in the nuclei and mitochondria. The complexes induced nuclear dysfunction by the inhibition of DNA replication as well as mitochondrial dysfunction by the loss of membrane potential. The damage to these vital organelles leads to cell apoptosisviathe caspase 3/7 pathway. Our results indicated that the modulation of the number of fluorine atoms in therapeutic agents can have a profound effect andRu1is a complex with a high potential as a drug for the treatment of cisplatin-resistant cancer.
- Wen, Ya,Ouyang, Cheng,Li, Quanwen,Rees, Thomas W.,Qiu, Kangqiang,Ji, Liangnian,Chao, Hui
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- Synthesis, characterization, and biological evaluation of new RU(ii) polypyridyl photosensitizers for photodynamic therapy
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Two Ru(II) polypyridyl complexes, Ru(DIP)2(bdt) (1) and [Ru(dqpCO2Me)(ptpy)]2+(2) (DIP = 4,7-diphenyl-1,10-phenanthroline, bdt = 1,2-benzenedithiolate, dqpCO2Me = 4-methylcarboxy-2,6-di(quinolin-8-yl)pyridine),
- Frei, Angelo,Rubbiani, Riccardo,Tubafard, Solmaz,Blacque, Olivier,Anstaett, Philipp,Felgentr?ger, Ariane,Maisch, Tim,Spiccia, Leone,Gasser, Gilles
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- Chemical and photochemical behavior of ruthenium nitrosyl complexes with terpyridine ligands in aqueous media
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The synthesis and behavior in water of a set of various cis(Cl,Cl)-[R-tpyRuCl2(NO)](PF6) and trans(Cl,Cl)-[R-tpyRuCl2(NO)](PF6) (R = fluorenyl, phenyl, thiophenyl; tpy = 2,2′:6′,2′′-terpyridine) complexes are presented. In any case, one chlorido ligand is substituted by a hydroxo ligand and the final species arises as a single trans(NO,OH) isomer, whatever the nature of the starting cis/trans(Cl,Cl) complexes. Six X-ray crystal structures are presented for cis(Cl,Cl)-[thiophenyl-tpyRuCl2(NO)](PF6) (cis-3a), trans(Cl,Cl)-[thiophenyl-tpyRuCl2(NO)](PF6) (trans-3a), trans(NO,OH)-[phenyl-tpyRu(Cl)(OH)(NO)](PF6) (4a), trans(NO,OH)-[thiophenyl-tpyRu(Cl)(OH)(NO)](PF6) (4b), trans(NO,OEt)-[phenyl-tpyRu(Cl)(OEt)(NO)](PF6) (5a), and trans(NO,OH)-[phenyl-tpyRu(Cl)(OEt)(NO)](PF6) (5b) compounds. The different cis/trans(Cl,Cl) complexes exhibit an intense low-lying transition in the λ = 330-390 nm range, which appears to be slightly blue-shifted after Cl → OH substitution. In water, both cis/trans(Cl,Cl) isomers are converted to a single trans(NO,OH) isomer in which one chlorido- is replaced by one hydroxo-ligand, which avoids tedious separation workout. The water stable trans(NO,OH)-species all release NO with quantum yields of 0.010 to 0.075 under irradiation at 365 nm. The properties are discussed with computational analysis performed within the framework of Density Functional Theory.
- Labra-Vázquez, Pablo,Bocé, Mathilde,Tassé, Marine,Mallet-Ladeira, Sonia,Lacroix, Pascal G.,Farfán, Norberto,Malfant, Isabelle
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p. 3138 - 3154
(2020/03/19)
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- Remote control of electronic coupling-modification of excited-state electron-transfer rates in Ru(tpy)2-based donor-acceptor systems by remote ligand design
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A comprehensive understanding of how the molecular structure influences the electronic coupling is crucial in optimizing (supra) molecular assemblies for photoinduced electron transfer. Here, we report that the electronic coupling underlying electron transfer from a phenothiazine donor to a photoexcited Ru(tpy)2 acceptor is modulated by substitution of the second (remote) tpy-ligand.
- Luo, Yusen,Tran, Jens H.,W?chtler, Maria,Schulz, Martin,Barthelmes, Kevin,Winter, Andreas,Rau, Sven,Schubert, Ulrich S.,Dietzek, Benjamin
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supporting information
p. 2273 - 2276
(2019/02/27)
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- Effect of substituent of terpyridines on the DNA-interaction of polypyridyl ruthenium(II) complexes
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An octahedral complexes of ruthenium with 2,9-dimethyl-1,10-phenanthroline (dmphen) and substituted terpyridine have been synthesized. The RuII complexes have been characterized by elemental analyses, thermogravimetric analyses, magnetic moment measurements, FT-IR, electronic, 1H NMR and FAB mass spectra. The binding strength and mode of interaction of the complexes with Herring Sperm DNA has been investigated using absorption titration and viscosity measurement studies. Results suggest that the substituent on terpyridine ligand affects the binding mode and binding ability of the complexes. Effect of time and ionic strength on DNA cleavage ability of complex has also been studied by gel electrophoresis. Results suggest that more than 200 mM concentration of NaCl decreases the cleavage ability of complex.
- Patel, Mohan N.,Gandhi, Deepen S.,Parmar, Pradhuman A.
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p. 243 - 248
(2011/12/03)
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- Syntheses and properties of new metal-carbon bonded heteroleptic complexes of ruthenium(II) containing terpyridine coligand
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Reactions of 2-(arylazo)aniline, HL [H represents the dissociable protons upon orthometallation and HL is p-RC6H4N = NC6H4-NH2; R = H for HL1; CH3 for HL2 and Cl for HL3] with Ru(R1-tpy)Cl3 (where R1-tpy is 4′-(R1)-2,2′,6′′,2′′-terpyridine and R1 = H or 4-N,N-dimethylaminophenyl or 4-methylphenyl) afford a group of complexes of type [Ru(L)(R1-tpy)]·ClO4 each of which contains C,N,N coordinated L- as a tridentate ligand along with a terpyridine. Structure of one such complex has been determined by X-ray crystallography. All the Ru(II) complexes are diamagnetic, display characteristic 1H NMR signals and intense dπ(RuII) → π*(tpy) MLCT transitions in the visible region. Cyclic voltammetric studies on [Ru(L)(R1-tpy)]·ClO4 complexes show Ru(II)-Ru(III) oxidation within 0.63-0.67 V versus SCE.
- Pratihar, Jahar Lal,Pattanayak, Poulami,Huang, Jui-Hsien,Chattopadhyay, Surajit
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p. 5170 - 5174
(2010/05/12)
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