1539-42-0Relevant articles and documents
Polypyridyl-Based Copper Phenanthrene Complexes: Combining Stability with Enhanced DNA Recognition
Fantoni, Nicoló Zuin,Molphy, Zara,O'Carroll, Sinéad,Menounou, Georgia,Mitrikas, George,Krokidis, Marios G.,Chatgilialoglu, Chryssostomos,Colleran, John,Banasiak, Anna,Clynes, Martin,Roche, Sandra,Kelly, Suainibhe,McKee, Vickie,Kellett, Andrew
, p. 971 - 983 (2021)
We report a series of copper(II) artificial metallo-nucleases (AMNs) and demonstrate their DNA damaging properties and in-vitro cytotoxicity against human-derived pancreatic cancer cells. The compounds combine a tris-chelating polypyridyl ligand, di-(2-pycolyl)amine (DPA), and a DNA intercalating phenanthrene unit. Their general formula is Cu-DPA-N,N' (where N,N'=1,10-phenanthroline (Phen), dipyridoquinoxaline (DPQ) or dipyridophenazine (DPPZ)). Characterisation was achieved by X-ray crystallography and continuous-wave EPR (cw-EPR), hyperfine sublevel correlation (HYSCORE) and Davies electron-nuclear double resonance (ENDOR) spectroscopies. The presence of the DPA ligand enhances solution stability and facilitates enhanced DNA recognition with apparent binding constants (Kapp) rising from 105 to 107 m?1 with increasing extent of planar phenanthrene. Cu-DPA-DPPZ, the complex with greatest DNA binding and intercalation effects, recognises the minor groove of guanine–cytosine (G-C) rich sequences. Oxidative DNA damage also occurs in the minor groove and can be inhibited by superoxide and hydroxyl radical trapping agents. The complexes, particularly Cu-DPA-DPPZ, display promising anticancer activity against human pancreatic tumour cells with in-vitro results surpassing the clinical platinum(II) drug oxaliplatin.
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Nakon et al.
, p. 2117 (1974)
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CO2 fixation by dicopper(ii) complexes in hypodentate framework of N8O2
Ho, Yi-Hsueh,Chang, Mu-Chieh,Yu, Kuo-Hsuan,Liu, Yi-Hung,Wang, Yu,Cheng, Yuan-Chung,Chen, Jwu-Ting
, p. 6287 - 6290 (2014)
A new ligand with N8O2 donors containing three potential metal-binding sites (H2L) and its tricopper(ii) complex 1 are synthesized. The tricopper species is found to be formed from a hypodentate dicopper(ii) complex 2 in basic solutions. Complex 2 may be isolated from the reaction of H2L with a copper source under acidic conditions. Complex 2 can undergo CO2-abstraction to yield an octacopper(ii) complex 3. The single crystal structures of complexes 2 and 3 are characterized by X-ray crystallography. This journal is the Partner Organisations 2014.
A novel ditopic ligand derived from 8-hydroxyquinoline: Synthesis, characterisation, and its coordination chemistry with selected metal ions
Xie, Xiang,Jiang, Xiujuan,Liu, Jian,Ren, Xingye,Wang, Hongming,Liu, Xiaoming
, p. 132 - 136 (2012)
A novel multidentate ligand, 5-(bis(pyridin-2-ylmethyl)amino)quinolin-8-ol (HL) was synthesised and characterised. Its coordination modes with a variety of metal ions (Mg2+, Co2+, Cu2+, Zn2+, and Hg2+) were investigated using UV-Vis spectroscopic titration. Among the examined metal ions, coordination ratios (M2+: HL) between the metal ion and the ligand at 1:2, 1:1, and 3:2 were observed due to the ditopic nature of the ligand. In acetonitrile, Mg2+ showed relatively strong fluorescent response upon binding to the ligand among the examined metal ions, Li+, K+, Mg2+, Ca2+, Al 3+, Cu2+, Fe3+, Cr3+, Zn 2+, Co2+, Ni2+, and Hg2+.
Zn(II)-DPA Coordinative fluorescent probe for enhancing G4 DNA binding
Bai, Yi-Tong,Gao, Juan-Juan,Lang, Xue-Xian,Li, Hong-Yao,Wang, Hai-Jiao,Wang, Ming-Qi,Yu, Quan-Qi
, (2021)
Novel dipicolylamino functionalized styryl-carbazole derivative (YCJ) was designed and synthesized. This derivative in combination with Zn(II) has exhibited large fluorescence intensity enhancement and prominent red-shift in absorption spectra with G4 DNA. Systematical analysis indicats that YCJ-Zn(II) complex shows much higher binding affinity and spectral response to G4 DNA than our previously reported styryl-carbazole scaffold (E1) due to the incorporationc of a Zn(II)-DPA moiety which could decrease the carbazole core electron density and consequently enhance the ability to display π-π stacking interaction with G4 DNA. Spectroscopic and molecular docking studies have unraveled YCJ-Zn(II) complex can stack both 3′ and 5′-ends and an associated with partial loop/groove interactions. The application of this Zn(II) complex as a fluorescent agent for living cell imaging was also demonstrated. The conjugation of the Zn-DPA moiety results in good cell permeability, endogenous DNA labeling, which is suitable for monitoring of nucleus activities.
Synthesis and properties of a heterobimetallic iron-manganese complex and its comparison with homobimetallic analogues
Bedin, Michele,Agarwala, Hemlata,Marx, Jennifer,Schünemann, Volker,Ott, Sascha,Thapper, Anders
, p. 254 - 260 (2019)
Heterobimetallic cofactors containing one manganese and one iron ion have recently been found within the di-metal carboxylate protein family. Herein we report the synthesis and characterization of three binuclear metal complexes with Fe-Fe, Mn-Mn, and Fe-Mn metal composition. All three complexes use the same ligand framework, the BPMP ligand (HBPMP = 2,6-bis[(bis (-2-pyridylmethyl)amine) methyl]-4-methylphenol)) with two additional acetate ligands bridging the two metals. In terms of stability towards metal exchange, the Fe-Mn is more stable than the Mn-Mn complex but less stable than the Fe-Fe complex. Cyclic voltammetry shows that the Fe-Mn complex behaves markedly different than the homobimetallic complexes. The Fe-Mn complex also shows higher reactivity with O2 than both the Fe-Fe and the Mn-Mn counterparts.
Optical detection of di- And triphosphate anions with mixed monolayer-protected gold nanoparticles containing zinc(II)-dipicolylamine complexes
Reinke, Lena,Bartl, Julia,Koch, Marcus,Kubik, Stefan
, p. 2687 - 2700 (2020)
Gold nanoparticles covered with a mixture of ligands of which one type contains solubilizing triethylene glycol residues and the other peripheral zinc(II)-dipicolylamine (DPA) complexes allowed the optical detection of hydrogenphosphate, diphosphate, and triphosphate anions in water/methanol 1:2 (v/v). These anions caused the bright red solutions of the nanoparticles to change their color because of nanoparticle aggregation followed by precipitation, whereas halides or oxoanions such as sulfate, nitrate, or carbonate produced no effect. The sensitivity of phosphate sensing depended on the nature of the anion, with diphosphate and triphosphate inducing visual changes at significantly lower concentrations than hydrogenphosphate. In addition, the sensing sensitivity was also affected by the ratio of the ligands on the nanoparticle surface, decreasing as the number of immobilized zinc(II)-dipicolylamine groups increased. A nanoparticle containing a 9:1 ratio of the solubilizing and the anion-binding ligand showed a color change at diphosphate and triphosphate concentrations as low as 10 μmol/L, for example, and precipitated at slightly higher concentrations. Hydrogenphosphate induced a nanoparticle precipitation only at a concentration of ca. 400 μmol/L, at which the precipitates formed in the presence of diphosphates and triphosphates redissolved. A nanoparticle containing fewer binding sites was more sensitive, while increasing the relative number of zinc(II)-dipicolylamine complexes beyond 25% had a negative impact on the limit of detection and the optical response. Transmission electron microscopy provided evidence that the changes of the nanoparticle properties observed in the presence of the phosphates were due to a nanoparticle crosslinking, consistent with the preferred binding mode of zinc(II)-dipicolylamine complexes with phosphate anions which involves binding of the anion between two metal centers. This work thus provided information on how the behavior of mixed monolayer-protected gold nanoparticles is affected by multivalent interactions, at the same time introducing a method to assess whether certain biologically relevant anions are present in an aqueous solution within a specific concentration range.
Iron(iii) complexes of multidentate pyridinyl ligands: Synthesis, characterization and catalysis of the direct hydroxylation of benzene
Xu, Beibei,Zhong, Wei,Wei, Zhenhong,Wang, Hailong,Liu, Jian,Wu, Li,Feng, Yonggang,Liu, Xiaoming
, p. 15337 - 15345 (2014)
Three multidentate ligands, L1-L3, derived from bis(pyridin-2-ylmethyl)amine (L1) were synthesized. Reaction of these ligands with FeCl3·6H2O in methanol led to the formation of the iron complexes Fe1-Fe3 (Fe1: [FeL1Cl3]; Fe2: [FeL2Cl3]; Fe3: [FeL3Cl3]) in good yields. These complexes have been fully characterized. The structures of complexes Fe1-Fe3 have been determined using X-ray single crystal diffraction analysis. Electrochemical investigation revealed that complex Fe3 partially converts to Fe4 ([FeL3Cl2]PF6) by the replacement of one of its three chlorides with its pendant triazolyl group in solution. Fe4 was also synthesized by dechlorination using AgPF6 as the Cl- abstractor and its composition was further confirmed by both elemental analysis and X-ray single crystal diffraction analysis. All four complexes catalyze the direct hydroxylation of benzene to phenol with hydrogen peroxide as an oxidant in a mixed medium of water and acetonitrile. The reactivity of the complexes correlates well with their reduction potentials. The more negative the potential, the more reactive (high conversion rate) the catalysts. These complexes catalyze not only the oxidation of benzene, but also the further oxidation of the product, phenol. In the oxidation, a radical mechanism is certainly involved but an alternative pathway may also exist. This journal is
Microwave-assisted synthesis of N,N-bis-(2-pyridylmethyl)amine derivatives. Useful ligands in coordination chemistry
Pimentel, Luiz Claudio F.,de Souza, Andréa Luzia F.,Fernández, Tatiana López,Wardell, James L.,Antunes
, p. 831 - 833 (2007)
Microwave-assisted synthesis of the ligands N,N-bis-(2-pyridylmethyl)amine (BMPA), N-(methylpropanoate)-N,N-bis-(2-pyridylmethyl)amine (MPBMPA), N-(propanamide)-N,N-bis-(2-pyridylmethyl)amine (PABMPA), PNBMPA (N-(3-propionitrile)-N,N-bis-(2-pyridylmethyl)amine), N-(3-aminopropyl)-N,N-bis-(2-pyridylmethyl)amine (APBMPA), and lithium N-(proponoate)-N,N-bis-(2-pyridylmethyl)amine (LiPBMPA) are reported. High yields and short reaction time were obtained for condensation and Michael addition.
LMCT transition-based red-light photochemotherapy using a tumour-selective ferrocenyl iron(iii) coumarin conjugate
Banerjee, Samya,Bhattacharyya, Arnab,Hussain, Akhtar,Sarkar, Tukki
, p. 7981 - 7984 (2020)
A rationally designed iron(iii) complex (2a) with pendant ferrocene and naturally occurring coumarin (esculetin) shows LMCT transition-based mitochondria-targeted red-light (600-720 nm) induced apoptotic toxicity against cancer cells but remains innocuous in the dark and to normal cells.
Synthesis, spectroscopic studies, thermal analyses, biological activity of tridentate coordinated transition metal complexes of bi(pyridyl-2-ylmethyl)amine]ligand
Abd El-Halim, Hanan F.,Mohamed, Gehad G.
, p. 91 - 95 (2016)
A new tridentate acyclic pincer ligand, [bi(pyridin-2-methyl)amine] (bpma, HL), was synthesized and reacted to form complexes with copper(II), nickel(II), iron(II), cobalt(II) and zinc(II) ions. Both the ligand and its complexes were characterized using elemental analysis, molar conductance, infrared, 1H-NMR-spectroscopy, mass and thermal analyses. According to the spectroscopic data, all of the complexes share the same coordination environment around the metal atoms, consisting two nitrogen-pyridine entities, one nitrogen-methylamine entity, one/two water molecules and/or one/two chloride or bromide ions. Complexes also showed molar conductivity according to the presence of two halide anions outer the coordination sphere except Co(II) and Zn(II) complexes are non electrolytes. Analysis indicates that the metal ions have trigonal bipyramidal structure. Cu(II), Ni(II), Fe(II), Co(II), and Zn(II) metal complexes were screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus (G+) and Escherichia coli, and Pseudomonas aeruginosa (G-) bacteria. They showed remarkable antimicrobial activity.
Evaluation of cobalt complexes with tripod ligands for zinc finger targeting
Aealsteinsson, Heiear Mar,Abbehausen, Camilla,Galuppo, Carolina,Lima, Frederico A.
supporting information, p. 16143 - 16153 (2020/12/03)
Cobalt complexes have been demonstrated to target zinc fingers, as shown by investigations of Doxovir, the trade name of the [CoIII(acacen)(2-Me-Imz)2]+ drug in clinical trials. Mechanistic studies indicate zinc finger disruption by metal coordination to His residues. Other than Doxovir, a few studies have investigated other ligands and geometries for cobalt complexes for zinc finger targeting. Tripod ligands demonstrated good zinc and cobalt chelation. In this manuscript, we report the ability of CoII and CoIII complexes of tri(2-pyridylmethyl)amine and N,N-di(2-pyridylmethyl)glycinate to disrupt zinc fingers. The results obtained by mass spectrometry and X-ray absorption spectroscopy demonstrate that the complexes were able to remove zinc from the zinc fingers. The product was oxidised apo-peptide. In contrast, the ligands themselves were able to remove zinc, and they did not promote oxidation, resulting in free Cys residues. Cobalt finger adducts were not detected for the complexes with tripod ligands unless they were coordinated to planar ligands such as salen or acacen. Studies of the interactions of cobalt complexes with amino acids demonstrated that tripod ligands promote the cysteine reaction, while the salen ligands promote histidine coordination, demonstrating a different mechanism of action. The results reported here are significant for better understanding and further design of zinc finger targeting compounds.
