Online citations, reference lists, and bibliographies.
Please confirm you are human
(Sign Up for free to never see this)
← Back to Search

A Ruthenium Nitrosyl Cyclam Complex With Appended Anthracenyl Fluorophore

Rodrigo Gibaut de Souza Góis, E. Boffo, José Carlos Toledo Júnior, Karla F Andriani, G. Caramori, A. Gomes, F. G. Doro
Published 2019 · Chemistry

Save to my Library
Download PDF
Analyze on Scholarcy
Share
Abstract The complex trans-[Ru(NO)(H2O)(L)](ClO4)3 (L = (1-anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane) (RuNOL) was synthesized and characterized, and its photophysics and reactivity were investigated. The FTIR spectrum displays a νNO band at 1840 cm−1, indicating a nitrosonium character. 1H and 13C signals in 1D and 2D NMR spectra were assigned and are consistent with the trans configuration. The UV–Vis spectrum displays maximal absorption bands at 341 nm (log e 3.74), 363 nm (log e 3.91), 378 nm (log e 3.97) and 397 nm (log e 3.91). Coordination of the [RuNO] moiety to the L ligand strongly quenches the anthracenyl fluorescence, and thus RuNOL exhibits only very weak emission at 390, 418, 440 and 472 nm. Electrochemical studies indicate that cathodic peak potentials at +1.10 V(Ic), −0.1 V(IIc) and −0.4 V(IIIc) (vs Ag/AgCl) are related to An+/An, {RuNO}6/7 and {RuNO}7/8 reduction processes, respectively. The pKa of coordinated water was estimated as 2.8 ± 0.2 by DPV. The emission of the pendant fluorophore increases upon electrochemical or chemical reduction of RuNOL, and the resulting switch-ON fluorescence is possibly due to NO release from the target complex. Spectroscopic titrations with DNA resulted in hypochromism and red shifts and allowed estimation of binding constants of 1.9 × 103 (L) and 1.8 × 103 (RuNOL). Molecular docking showed that RuNOL complex has a great affinity with DNA. The RuNOL complex showed low cytotoxicity toward MCF-7 and NIH-3T3 and was ineffective in healthy HUVEC and A7r5 cell lines in the range of concentration of 1 × 10−7–1 × 10−4 mol L−1.
This paper references
10.5860/choice.50-6768
Purification of laboratory chemicals
D. D. Perrin (1966)
10.1021/ic500283y
Theoretical spectroscopy and photodynamics of a ruthenium nitrosyl complex.
L. Freitag (2014)
10.1063/1.472460
The zero order regular approximation for relativistic effects: the effect of spin-orbit coupling in closed shell molecules.
E. V. Lenthe (1996)
10.1016/S0005-2736(96)00171-X
Interaction of surfactants with DNA. Role of hydrophobicity and surface charge on intercalation and DNA melting.
S. Bhattacharya (1997)
10.1016/J.POLY.2006.12.003
Synthesis and structural characterisation of a series of cobalt complexes of N-appended anthracenyl cyclam
S. Boyd (2007)
The manipulation of air-sensitive compounds
D. F. Shriver (1969)
10.1016/j.niox.2011.11.005
Biological activity of ruthenium nitrosyl complexes.
E. Tfouni (2012)
10.1021/IC951563S
Ruthenium Nitrosyl Complexes with N-Heterocyclic Ligands.
S. D. S. S. Borges (1998)
10.1002/CHEM.19960020114
Fluorescent Sensors for Transition Metals Based on Electron‐Transfer and Energy‐Transfer Mechanisms
L. Fabbrizzi (1996)
10.1016/J.JPHOTOCHEM.2005.05.010
Tuning the DNA binding modes of an anthracene derivative with salt
N. K. Modukuru (2006)
10.1016/J.CCR.2004.09.009
Ru(II) and Ru(III) complexes with cyclam and related species
E. Tfouni (2005)
10.1002/EJIC.200300683
Ruthenium Tetraammines as a Model of Nitric Oxide Donor Compounds
J. C. Toledo (2004)
10.1016/0009-2614(73)80293-3
The absorption spectrum of the anthracene molecule in the vacuum ultraviolet
E. E. Koch (1973)
10.1021/BI00394A013
Polycyclic aromatic hydrocarbons physically intercalate into duplex regions of denatured DNA.
A. Wolfe (1987)
10.1016/S0003-2670(98)00089-0
Design, synthesis and characterization of a novel fluorescent probe for nitric oxide (nitrogen monoxide)
Y. Katayama (1998)
10.1021/ja801823f
Sensitization of ruthenium nitrosyls to visible light via direct coordination of the dye resorufin: trackable NO donors for light-triggered NO delivery to cellular targets.
M. Rose (2008)
10.1063/1.458517
A Simple Measure of Electron Localization in Atomic and Molecular-Systems
A. Becke (1990)
10.1002/jcc.20084
UCSF Chimera—A visualization system for exploratory research and analysis
E. F. Pettersen (2004)
10.1016/j.niox.2013.02.001
Photochemical delivery of nitric oxide.
P. Ford (2013)
10.1016/S0898-8838(09)00201-3
Controlling Platinum, Ruthenium and Osmium Reactivity for Anticancer Drug Design.
P. Bruijnincx (2009)
Cytotoxic (salen)ruthenium(III) anticancer complexes exhibit different modes of cell death directed by axial ligands
Cai Li (2017)
10.1103/PHYSREVB.33.8822
Density-functional approximation for the correlation energy of the inhomogeneous electron gas.
Perdew (1986)
10.2174/092986710793213788
Tailoring NO donors metallopharmaceuticals: ruthenium nitrosyl ammines and aliphatic tetraazamacrocycles.
E. Tfouni (2010)
10.1039/c4dt02700k
Metal complex interactions with DNA.
Benjamin J Pages (2015)
10.3390/molecules19079628
Ruthenium complexes as NO donors for vascular relaxation induction.
R. G. de Lima (2014)
10.1021/acs.jpcb.8b11287
Shedding Light on the Hydrolysis Mechanism of cis, trans-[Ru(dmso)4Cl2] Complexes and Their Interactions with DNA-A Computational Perspective.
Karla F Andriani (2019)
10.1021/IC0112802
Syntheses of ruthenium(II) quinonediimine complexes of cyclam and characterization of their DNA-binding activities and cytotoxicity.
Hing-Leung Chan (2002)
10.1038/sj.bjp.0707363
In vitro and in vivo antiproliferative and trypanocidal activities of ruthenium NO donors
J. J. Silva (2007)
10.1021/IC048312G
Synthesis and luminescence properties of Cr(III) complexes with cyclam-type ligands having pendant chromophores, trans-[Cr(L)Cl(2)]Cl.
F. Derosa (2005)
10.1039/A708164B
cis- and trans-nitrosyltetraammineruthenium(II). Spectral and electrochemical properties and reactivity
Maria das Graças Gomes (1998)
10.1016/J.INOCHE.2016.03.019
Synthesis and crystal structure of mer-nitroaquatriamminenitrosylruthenium(II) nitrate [RuNO(NH3)3(NO2)(H2O)](NO3)2
V. Vorobyev (2016)
10.1039/c0dt01541e
Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.
F. G. Doro (2011)
10.1016/J.ICA.2004.08.004
A nitric oxide releaser based on the μ-oxo-hexaacetate-bis(4-methylpyridine)triruthenium nitrosyl complex
H. Toma (2005)
10.1021/mp3005534
trans-[Ru(NO)Cl(cyclam)](PF6)2 and [Ru(NO)(Hedta)] incorporated in PLGA nanoparticles for the delivery of nitric oxide to B16-F10 cells: cytotoxicity and phototoxicity.
A. Gomes (2013)
10.1021/OM700271R
The Nature of the Ru−NO Bond in Ruthenium Tetraammine Nitrosyl Complexes
Giovanni F. Caramori and (2007)
10.1016/J.POLY.2007.04.038
A new ruthenium nitrosyl species based on a pendant-arm 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative: An experimental and theoretical study
A. D. Candia (2007)
Python: a programming language for software integration and development.
M. Sanner (1999)
10.1006/NIOX.1996.0112
A tutorial on the diffusibility and reactivity of free nitric oxide.
J. Lancaster (1997)
10.1021/IC990210G
Water π-Donation in trans-Tetraammineruthenium(II): Effect on Coordinated-Water Properties Induced by a Trans NO Ligand
C. W. B. Bezerra (1999)
10.1016/S0162-0134(01)00414-7
Release of NO by a nitrosyl complex upon activation by the mitochondrial reducing power.
J. C. Toledo (2002)
10.1021/ic702078p
Cyclam kappa4 to kappa3 ligand denticity change upon mono-n-substitution with a carboxypropyl pendant arm in a ruthenium nitrosyl complex.
F. G. Doro (2008)
10.1016/J.ICA.2003.11.023
Photochemical reactions of trans-[Ru(NH3)4L(NO)]3+ complexes☆
R. M. Carlos (2004)
10.1016/S0020-1693(01)00487-X
Electrospray mass spectrometry of trans-[Ru(NO)Cl(dpaH)2]2+ (dpaH=2,2′-dipyridylamine) and ‘caged NO’, [RuCl3(NO)(H2O)2]: loss of HCl and NO from positive ions versus NO and Cl from negative ions
J. Slocik (2001)
10.1007/s00280-010-1293-1
Ruthenium-based chemotherapeutics: are they ready for prime time?
E. Antonarakis (2010)
10.1016/J.INOCHE.2011.09.046
Cis–trans isomerization in the syntheses of ruthenium cyclam complexes with nitric oxide
Robson da Silva Vidal (2012)
10.1016/0022-0728(65)80038-9
The real solvation energies of hydrocarbon ions in acetonitrile and the surface potential of acetonitrile
B. Case (1965)
10.1111/jphp.12755
Phenotypic switching prevention and proliferation/migration inhibition of vascular smooth muscle cells by the ruthenium nitrosyl complex trans‐[Ru(NO)Cl(cyclam](PF6)2
M. G. de Oliveira (2017)
10.1021/IC025826B
Water soluble molecular switches of fluorescence based on the Ni(III)/Ni(II) redox change.
L. Fabbrizzi (2002)
10.1002/HLCA.19860690832
Metal complexes with macrocyclic ligands. Part XXV. One‐step synthesis of mono‐N‐substituted azamacrocycles with a carboxylic group in the side‐chain and their complexes with Cu2+ and Ni2+
M. Studer (1986)
10.1016/j.vph.2016.05.007
Blood pressure variability provokes vascular β-adrenoceptor desensitization in rats.
M. Rocha (2016)
10.1016/J.NIOX.2006.10.001
The effects of ruthenium tetraammine compounds on vascular smooth muscle.
Patrícia Graça Zanichelli (2007)
10.1590/S0103-50532010000700022
Chemical and photochemical properties of a ruthenium nitrosyl complex with the N-monosubstituted cyclam 1-(3-Propylammonium)-1,4,8,11-tetraazacyclotetradecane
K. Q. Ferreira (2010)
10.1021/IC9912979
A controlled NO-releasing compound: synthesis, molecular structure, spectroscopy, electrochemistry, and chemical reactivity of R,R,S,S-trans-[RuCl(NO)(cyclam)]2+(1,4,8,11-tetraazacyclotetradecane).
D. R. Lang (2000)
10.1039/c2dt12094a
The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes--a computational study.
G. Caramori (2012)
Nitric oxide : biology and pathobiology
L. Ignarro (2000)
10.1073/PNAS.78.4.2179
Structure of a B-DNA dodecamer: conformation and dynamics.
H. Drew (1981)
10.1063/1.466059
Relativistic regular two‐component Hamiltonians
E. V. Lenthe (1993)
10.1021/ic201242d
Triggered dye release via photodissociation of nitric oxide from designed ruthenium nitrosyls: turn-ON fluorescence signaling of nitric oxide delivery.
Nicole L. Fry (2011)
10.1161/01.CIR.0000101919.00548.86
Ouabain- and Marinobufagenin-Induced Proliferation of Human Umbilical Vein Smooth Muscle Cells and a Rat Vascular Smooth Muscle Cell Line, A7r5
J. Abramowitz (2003)
10.1103/PHYSREVA.38.3098
Density-functional exchange-energy approximation with correct asymptotic behavior.
Becke (1988)
10.1016/j.jinorgbio.2017.06.001
New imidoyl-indazole platinum (II) complexes as potential anticancer agents: Synthesis, evaluation of cytotoxicity, cell death and experimental-theoretical DNA interaction studies.
A. Cabrera (2017)
10.1039/B305773A
Synthesis, structural studies and photochemistry of cobalt(III) complexes of anthracenylcyclam macrocycles
A. Funston (2003)
10.1016/j.ejmech.2010.06.010
Antileishmanial activity of ruthenium(II)tetraammine nitrosyl complexes.
J. M. C. Pereira (2010)
10.1055/S-2000-6589
Strategies for the Regioselective N-Functionalization of Tetraazacycloalkanes. From Cyclam and Cyclen Towards More Sophisticated Molecules
F. Denat (2000)
10.1039/A809466G
A convenient one-step synthesis of mono-N-functionalized tetraazamacrocycles
Hélène Fensterbank (1999)
10.1002/wcms.81
The ORCA program system
F. Neese (2012)
10.1016/j.niox.2008.10.001
Effects on mitochondria of mitochondria-induced nitric oxide release from a ruthenium nitrosyl complex.
C. Pestana (2009)
10.1016/S0010-8545(00)80259-3
Principles of structure, bonding, and reactivity for metal nitrosyl complexes
J. Enemark (1974)
10.1016/S0024-3205(02)01528-X
In vivo effects of the controlled NO donor/scavenger ruthenium cyclam complexes on blood pressure.
Fabiana G Marcondes (2002)
10.1039/B515623H
Accurate Coulomb-fitting basis sets for H to Rn.
F. Weigend (2006)
10.1016/j.jinorgbio.2007.11.012
trans-[Ru(NO)(NH3)4(py)](BF4)3.H2O encapsulated in PLGA microparticles for delivery of nitric oxide to B16-F10 cells: Cytotoxicity and phototoxicity.
A. Gomes (2008)
10.5935/abc.20140189
Vascular Response of Ruthenium Tetraamines in Aortic Ring from Normotensive Rats
Ana Gabriela Conceição-Vertamatti (2015)
10.1016/S0010-8545(02)00177-7
Structure, chemical and photochemical reactivity and biological activity of some ruthenium amine nitrosyl complexes
E. Tfouni (2003)
10.1021/IC048311O
Chromium(III) complexes for photochemical nitric oxide generation from coordinated nitrite: synthesis and photochemistry of macrocyclic complexes with pendant chromophores, trans-[Cr(L)(ONO)(2)]BF(4).
F. Derosa (2005)
10.1016/BS.ADIOCH.2014.11.001
Design, Reactivity, and Biological Activity of Ruthenium Nitrosyl Complexes
R. Silva (2015)
10.1016/j.ejps.2013.01.003
Nitric oxide generated by the compound RuBPY promotes the vascular smooth cell membrane hyperpolarization.
A. C. Pereira (2013)
10.1002/jcc.21334
AutoDock Vina: Improving the speed and accuracy of docking with a new scoring function, efficient optimization, and multithreading
Oleg Trott (2010)
10.1021/ic900604j
Syntheses, structures, and photochemistry of manganese nitrosyls derived from designed Schiff base ligands: potential NO donors that can be activated by near-infrared light.
C. G. Hoffman-Luca (2009)
10.1002/(SICI)1521-4109(199911)11:15<1108::AID-ELAN1108>3.0.CO;2-Z
Determination of Surface pKa of SAM Using an Electrochemical Titration Method
J. Zhao (1999)
10.1016/J.CCR.2005.04.022
Light-emitting molecular devices based on transition metals
V. Amendola (2006)
10.1021/JA01640A067
A Further Examination of the Molecular Weight and Size of Desoxypentose Nucleic Acid
M. Reichmann (1954)
10.1016/j.ejmech.2011.04.064
A new nitrosyl ruthenium complex: synthesis, chemical characterization, in vitro and in vivo antitumor activities and probable mechanism of action.
T. A. Heinrich (2011)
10.1039/C7NJ01998J
One new azido bridged dinuclear copper(II) thiosemicarbazide complex: synthesis, DNA/protein binding, molecular docking study and cytotoxicity activity
N. Biswas (2017)
10.1021/J100803A520
THE FORMAL REDUCTION POTENTIAL OF THE EUROPIUM(III)—EUROPIUM(II) SYSTEM
L. B. Anderson (1963)
10.1021/IC051723S
Toward development of water soluble dye derivatized nitrosyl compounds for photochemical delivery of NO.
Stephen R Wecksler (2006)
10.1021/CR000040L
Nitric oxide donors: chemical activities and biological applications.
P. Wang (2002)
10.1016/J.CCR.2015.03.021
The versatile ruthenium(II/III) tetraazamacrocycle complexes and their nitrosyl derivatives
F. G. Doro (2016)



Semantic Scholar Logo Some data provided by SemanticScholar