15 results on '"General Chemistry"'
Search Results
2. Zeolite-encapsulated copper(II) complexes with NNO-tridentate Schiff base ligands: catalytic activity for methylene blue (MB) degradation under near neutral conditions.
- Author
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Li S, Wu D, Wang X, Xiong J, Zhang L, and Ma K
- Abstract
Three novel copper Schiff base complexes, L
1 Cu(OAc)-L3 Cu(OAc), bearing NNO tridentate ligands were synthesized and successfully entrapped in zeolite. All free and encapsulated complexes were fully characterized through experiments combined with theoretical calculations, and were subsequently employed as catalysts to activate H2 O2 for degradation of methylene blue (MB). The catalytic activity of free complexes was tunable by substitution effects. The complex L3 Cu(OAc) displayed enhanced efficiency by adopting bulky and donor substitutions due to the lower oxidation states. However, the free complexes exhibited modified structural and catalytic properties upon encapsulation into the zeolite. The constraint from the zeolite holes and coordination geometry caused the alteration of electronic structures and subsequently modified the reactivity. This study revealed that upon encapsulation, the larger molecular dimension of L3 Cu(OAc) resulted in additional distorted geometry, leading to higher catalytic efficiency for MB degradation with more blue shifts in the UV-Vis spectrum. There was high catalytic activity by Ln Cu(OAc)-Y compared to that of the free complex, and high recyclability under near neutral conditions. In addition, the catalytic efficiency of L3 Cu(OAc)-Y was higher or equivalent compared to other catalysts. This work provides new complexes with NNO tridentate ligands encapsulated inside zeolite and explains the relationship between the modified structure and functionality.- Published
- 2024
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3. Dielectric, pyroelectric, and ferroelectric studies in (1 - x )AgNbO 3 - x FeNbO 4 lead-free ceramics.
- Author
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Moradi P, Taheri-Nassaj E, Yourdkhani A, Mykhailovych V, Diaconu A, and Rotaru A
- Abstract
In the present study, the effect of heterovalent Fe
3+ ions on the dielectric, pyroelectric, and ferroelectric properties of the (1 - x )AgNbO3 - x FeNbO4 ( x = 0.005, 0.01, 0.025, 0.05, and 0.1) system was investigated. The substitution of smaller ionic radius Fe3+ in B-sites and the formation of FeNbO4 as a secondary phase contributed to improved dielectric performance, especially the pyroelectric effect, of (1 - x )AgNbO3 - x FeNbO4 ceramics by generating electron-rich ceramics. The (1 - x )AgNbO3 - x FeNbO4 ceramics were prepared by conventional solid-state sintering. Pure AgNbO3 had a perovskite crystal structure with an orthorhombic crystal system, but the FeNbO4 in (1 - x )AgNbO3 - x FeNbO4 ceramics was formed as a secondary phase with a monoclinic structure. In addition, the XRD and Raman spectroscopy data showed that some Fe3+ was substituted into B-sites of AgNbO3 . The introduction of FeNbO4 effectively reduced the average grain size from 1.85 ± 0.09 μm to 1.22 ± 0.03 μm for pure AgNbO3 and 0.9AgNbO3 -0.1FeNbO4 , respectively. In addition, the relative density of the (1 - x )AgNbO3 - x FeNbO4 ceramics decreased from 97.96% ± 0.01 for x = 0 to 96.75% ± 0.03 for x = 0.1. The real part of the permittivity ε ', at room temperature, increased from 186.6 for x = 0 to a value of 738.7 for x = 0.1. Additionally, the maximum pyroelectric coefficient increased fivefold, reaching values of 2270 nC cm-2 K-1 for x = 0.1. Furthermore, a harvested pyroelectric energy density ( W ) of 1140 μJ cm-3 for x = 0.025 was achieved, which is appreciably higher than the 840 μJ cm-3 value for x = 0.- Published
- 2023
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4. Enhanced energy storage performance in reaction-sintered AgNbO 3 antiferroelectric ceramics.
- Author
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Moradi P, Taheri-Nassaj E, Yourdkhani A, Mykhailovych V, Diaconu A, and Rotaru A
- Abstract
In this research, AgNbO
3 ceramics were produced by two sintering methods: reaction sintering (RS) and conventional solid-state sintering (CSSS). The process was similar for both methods, except that in RS, Ag2 O and Nb2 O5 precursors were mixed, then formed into pellets, skipping the calcination step, and sintered at 1100 °C for 6 hours. Both prepared ceramics had the same perovskite crystal structure with an orthorhombic crystal system and Pbcm and Pmc 21 space groups with similar lattice dynamic vibration modes at room temperature. The average grain size of the polycrystalline samples prepared by RS and CSSS was found to be ∼2.03 ± 0.77 and ∼1.85 ± 0.96 μm, respectively. The relative bulk densities of the ceramics produced by RS and CSSS were found to be ∼94.0 ± 1.8 and ∼96.5 ± 1.3%, respectively. Ceramics prepared by both methods showed antiferroelectric behavior, and reaction-sintered AgNbO3 ceramics exhibited lower energy loss density than CSSS samples. In addition, a recoverable energy storage density ( Wrec ) of 3.1 J cm-3 and higher energy storage efficiency ( η ) for RS samples were measured at 175 kV cm-1 . Moreover, the η values of 74.2% and 57.7% were measured for samples sintered by RS and CSSS, respectively. This energy storage efficiency is the highest ever reported for pure AgNbO3 ceramics. Furthermore, reaction-sintered samples showed good temperature stability for Wrec and η in the 30-80 °C temperature range.- Published
- 2023
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5. Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5'-bisphenanthroline linked RuPt complex.
- Author
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Lämmle M, Pilz TD, Kutta RJ, Müßler M, Mengele AK, Görls H, Heinemann FW, and Rau S
- Abstract
Herein, the synthesis in conjunction with the structural, electrochemical, and photophysical characterization of a 5,5'-bisphenanthroline (phenphen) linked heterodinuclear RuPt complex (Ru(phenphen)Pt) and its light-driven hydrogen formation activity are reported. A single crystal X-ray diffraction (SC-XRD) analysis identified a perpendicular orientation of the two directly linked 1,10-phenanthroline moieties. The disruption of π-conjugation blocks intramolecular electron transfer as evidenced by a comparative time-resolved optical spectroscopy study of Ru(phenphen)Pt and the reference complexes Ru(phenphen) and Ru(phenphen)Ru. However, reductive quenching is observed in the presence of an external electron donor such as triethylamine. Irradiating Ru(phenphen)Pt with visible light (470 nm) leads to H
2 formation. We discuss a potential mechanism that mainly proceeds via Pt colloids and provide indications that initial hydrogen generation may also proceed via a molecular pathway. As previous reports on related heterodinuclear RuPt-based photocatalysts revealed purely molecular hydrogen evolution, the present work thus highlights the role of the bridging ligand in stabilizing the catalytic center and consequently determining the mechanism of light-induced hydrogen evolution in these systems.- Published
- 2022
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6. Building trans-philicity (trans-effect/trans-influence) ladders for octahedral complexes by using an NMR probe.
- Author
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Tsipis AC
- Abstract
NMR trans-philicity (trans-effect/trans-influence) ladders have been built for a broad series of octahedral [Cr(CO)
5 L]-/0/+ complexes (50 ligands used) by using a13 C NMR probe and quantified through calculation of the Δσ = σCr(CO) -σ5 LCr(CO) NMR parameter employing DFT computational methods. This quantification notably retrieves the experimental trans-orienting series. The excellent linear correlations between the calculated Δσ NMR parameter and well established ligand electronic parameters, such as the ligand constant P5 L and the ligand electrochemical parameter EL (L), that measure the ligand bonding effects in coordination and organometallic chemistry prompt us to introduce the trans-philicity concept as a unified term to cover both the kinetic trans-effect and its thermodynamic (ground state) trans-influence cousin. The trans-philicity for ligand L is defined as the strength of philicity of the coordination site in trans-position to itself. trans-Effect and trans-influence ladders have also been built for the octahedral [Cr(CO)5 L]-/0/+ complexes based on the calculated intrinsic bond dissociation energy of the Cr-COtrans bond, IBDE(Cr-COtrans ) to account for the trans-effect and the ν(C[triple bond, length as m-dash]Otrans ) and ν(Cr-COtrans ) vibrational frequencies, and R(Cr-COtrans ) bond lengths to develop the trans-influence series and compared with the NMR trans-philicity ladder.- Published
- 2019
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7. Synthesis of new photosensitive H 2 BBQ 2+ [ZnCl 4 ] 2- /[(ZnCl) 2 (μ-BBH)] complexes, through selective oxidation of H 2 O to H 2 O 2 .
- Author
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Stylianou M, Hadjiadamou I, Drouza C, Hayes SC, Lariou E, Tantis I, Lianos P, Tsipis AC, and Keramidas AD
- Abstract
A new two-electron photosensitizer, H
2 BBQ2+ [ZnCl4 ]2- /[(ZnCl)2 (μ-BBH)] (BBQ stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-quinone and BBH stands for 2,5-bis[bis(pyridin-2-ylmethyl)amino]-1,4-hydroquinone), has been synthesized and the oxidation state of the ligand was determined by X-ray crystallography and NMR spectroscopy. Under light illumination the H2 BBQ2+ [ZnCl4 ]2- + ZnCl2 is reduced quantitatively to [(ZnCl)2 (μ-BBH)] (pH ∼ 5) oxidizing H2 O to H2 O2 as is evident by trap experiments. Electrochemistry gave a reversible two-electron ligand-centered redox wave for [(ZnCl)2 (μ-BBH)]. UV-Vis, luminescence and EPR spectroscopies reveal the slow formation of a stable quinone diradical, intermediate of the reaction. DFT calculations are in agreement with the proposed mechanism. Based on this property an aqueous {[(ZnCl)2 (μ-BBH)]||H2 O2 } solar rechargeable galvanic cell has been constructed.- Published
- 2017
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8. π-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(ii)/Au(iii) complex.
- Author
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Sorsche D, Schaub M, Heinemann FW, Habermehl J, Kuhri S, Guldi D, Guthmuller J, and Rau S
- Abstract
The synthesis and characterization of a mixed metal ruthenium(ii)/gold(iii) complex bridged by tetrapyridophenazine (tpphz) are described. It is isostructural and isoelectronic to the well-known photocatalysts with palladium(ii) or platinum(ii). Concentration dependent (1)H-NMR spectroscopy and XRD studies show that the electrostatic repulsion between the gold(iii) moieties exceeds the attractive π-stacking interaction. Theoretical calculations based on the new structural data confirm an increased positive charge on the bridging ligand as well as significantly altered orbital symmetry as compared to the previously investigated palladium(ii) complex. This is the first example of a tpphz ruthenium(ii) complex where π-stacking is completely inhibited. The detailed investigation of the solid-state structure showed for the first time in bimetallic tpphz bridged complexes no significant torsion within the bridging ligand itself. Although catalytic performance for proton reduction by gold(iii) is naturally not observed, its photochemical decomposition in colloidal gold particles could be shown by TEM and DLS.
- Published
- 2016
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9. Versatile coordination modes of bis[5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl]alkanes in Cu(II) complexes.
- Author
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Gusev AN, Nemec I, Herchel R, Bayjyyev E, Nyshchimenko GA, Alexandrov GG, Eremenko IL, Trávníček Z, Hasegawa M, and Linert W
- Abstract
Nine new mononuclear and polynuclear Cu(II) complexes [Cu(H2L(2))Cl]Cl·3H2O (1), [Cu(H2L(3))Cl]Cl·H2O (2), [Cu(H2L(4))Cl]Cl·2.5H2O (3), [Cu3(μ(3)-L(1))2(H2O)3](ClO4)2·H2O (4), [Cu4(μ-HL(1))4](ClO4)8·CH3OH·5H2O (5), [Cu2(HL(3))2](ClO4)2·2H2O (6a), [Cu2(μ-HL(3))2](ClO4)2·H2O (6b), [Cu2(μ-HL(3))(L(3))Cu(teta)](ClO4)3·2H2O (7) and [Cu2(H2L(3))2(ox)](ClO4)2·2H2O·2MeOH (8) containing [5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl]alkanes (H2L(n), n = 1-4) in combination with other ligands, such as chlorido, aqua, triethylenetetramine (teta) and/or oxalato (ox(2-)), were synthesized and characterized by various techniques such as elemental analysis, FTIR, NMR and UV-Vis spectroscopy. X-ray structures of H2L(3) and H2L(4) as well as complexes 1-8 were determined. The X-ray structures revealed that relatively small composition and structural changes in the H2L(n) ligands have a substantial impact on the coordination geometries of the complexes themselves as well as on their resulting magnetic properties. It has been found that the geometries of the complexes vary from square-pyramidal to trigonal-bipyramidal (with τ ranging from 0.00 to 0.96) and, moreover, that the trigonal bipyramidal geometry becomes more preferable with the increase in the length of the polymethylene chain within the corresponding H2L(n) ligand. The magnetic properties of the polynuclear compounds 4, 5, 6, 7 and 8 were analysed using the spin Hamiltonian formalism, which revealed the presence of antiferromagnetic exchange in the polynuclear systems mediated by the title ligands. The significant effect of the geometric parameters on the Cu···Cu exchange interactions in the polynuclear complexes is discussed.
- Published
- 2014
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10. Accurate prediction of 195Pt NMR chemical shifts for a series of Pt(II) and Pt(IV) antitumor agents by a non-relativistic DFT computational protocol.
- Author
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Tsipis AC and Karapetsas IN
- Subjects
- Ligands, Magnetic Resonance Spectroscopy, Models, Molecular, Antineoplastic Agents chemistry, Platinum chemistry
- Abstract
The GIAO-PBE0/SARC-ZORA(Pt)∪6-31+G(d)(E) (E = main group element) computational protocol without including relativistic and spin-orbit effects is offered here for the accurate prediction of the (195)Pt NMR chemical shifts of a series of cis-(amine)2PtX2 (X = Cl, Br, I) anticancer agents (in total 42 complexes) and cis-diacetylbis(amine)platinum(II) complexes (in total 12) in solutions employing the Polarizable Continuum Model (PCM) solvation model, thus contributing to the difficult task of computation of (195)Pt NMR. Calculations of the torsional energy curves along the diabatic (unrelaxed) rotation around the Pt-N bond of the cis-(amine)2PtX2 (X = Cl, Br, I) anticancer agents revealed the high sensitivity of the (195)Pt NMR chemical shifts to conformational changes. The crucial effect of the conformational preferences on the electron density of the Pt central atom and consequently on the calculated δ(195)Pt chemical shifts was also corroborated by the excellent linear plots of δ(calcd)((195)Pt) chemical shifts vs. the natural atomic charge Q(Pt). Furthermore, for the accurate prediction of the (195)Pt NMR chemical shifts of the cis-bis(amine)Pt(II) anticancer agents bearing carboxylato- as the leaving ligands (in total 8) and a series of octahedral Pt(IV) antitumor agents (in total 20 complexes) the non-relativistic GIAO-PBE0/SARC-ZORA(Pt)∪6-31+G(d)(E) computational protocol performs best in combination with the universal continuum solvation model based on solute electron density called SMD for aqueous solutions. Despite neglecting relativistic and spin orbit effects the agreement of the calculated δ(195)Pt chemical shifts with experimental values is surprising probably due to effective error compensation. Moreover, the observed solvent effects on the structural parameters of the complexes probably overcome the relativistic effects, and therefore the successful applicability of the non-relativistic GIAO-PBE0/SARC-ZORA(Pt)∪6-31+G(d)(E) computational protocol in producing reliable δ(calcd)((195)Pt) chemical shifts could be understood. In a few cases (e.g. the dihydroxo Pt(IV) complexes) the higher deviations of the calculated from the experimental values of δ(195)Pt chemical shifts are probably due to the fact that the experimental assignments refer to a different composition of the complexes in solutions than that used in the calculations, and different hydrogen bonding and formation of dimeric species.
- Published
- 2014
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11. Spacer-armed copper(II) complexes with benzenecarboxylic acids and trifluoroacetylacetone aroylhydrazones.
- Author
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Shul'gin VF, Konnik OV, Gusev AN, Boča R, Dlháň L, Rusanov EB, Alexandrov GG, Eremenko IL, and Linert W
- Abstract
New bi- and trinuclear copper(ii) complexes of aroylhydrazones of TFA and benzenecarboxylic acids were synthesized and characterized. Despite long range intramolecular CuCu distances of about 10 Å, exchange couplings between paramagnetic centres are observed with J values of 0.33 and 0.37 cm(-1) in binuclear complexes, and -0.33 cm(-1) in trinuclear complexes. Seven hyperfine peaks with a value of aCu = 37.0 × 10(-4) cm(-1) are observed in EPR spectra of binuclear complexes. The possible mechanisms responsible for the observed weak long range coupling via aromatic spacers are discussed.
- Published
- 2013
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12. The molecular, electronic, bonding, and photophysical features of the [(c-Pt3)Tl(c-Pt3)]+ inorganic metallocenes.
- Author
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Tsipis AC and Gkekas GN
- Abstract
The molecular, electronic, bonding and photophysical properties of a series of inorganic metallocenes with the general formula {[Pt3(μ2-L)3(L')3]2(μ6-Tl)}(+) (L = CO, CH3CN, PH2, C6F5, or SO2 and L' = CO, PH3, CH3CN, C6F5) have been studied by means of DFT electronic structure calculations. The estimated Tl-cd distances between Tl(+) cations and the centroids (cd) of the trimetallic Pt3(μ2-L)3(L')3 {3 : 3 : 3} decks were found in the range 2.932-3.397 Å. The predicted bond dissociation energy, D0, of the (c-Pt3)···Tl(+) bonds was found to lie within the range -31.5 up to -77.5 kcal mol(-1) at the B3LYP/LANL2TZ(f)(Pt) ∪ 6-31G(d,p)(E) ∪ SRLC(Tl) level of theory. Most of the [(c-Pt3)Tl(c-Pt3)](+) inorganic metallocenes adopt a bend titanocene-like structure. The Localized Orbital Locator (LOL) contour maps along with the 3D contour plots of the Reduced Gradient Density (RDG) mirror the composite nature of the interaction of Tl(+) with the triangular Pt3 metallic ring cores consisting of electrostatic, covalent and dispersion interaction components. The Pt3···Tl(+)···Pt3 bonding mode was further validated by Energy Decomposition Analysis (EDA) calculations which demonstrated that the electrostatic and covalent components of the interaction contribute almost equally to the bonding interactions. Furthermore, Charge Decomposition Analysis (CDA) and Natural Bond Orbital Analysis (NBO) calculations indicated that charge transfer from the Tl(+) cation to the Pt3(0) {3 : 3 : 3} decks also occurs. The {[Pt3(μ2-L)3(L')3]2(μ6-Tl)}(+) sandwiches absorb in the UV-Vis region (300-500 nm) and emit in the visible-near IR region (600-1000 nm). The absorption bands are mainly of MLCT/MC character while phosphorescence is predicted to occur via the first triplet excited state, T1, since the spin density of this excited state could be described as a SOMO - 1/SOMO combination. Generally, no significant distortions occur upon excitation of these systems from their S0 ground state to the first triplet excited state, T1. The S0 → T1 transition causes only an elongation of the Tl-cd distances by up to 0.7 Å accompanied in a few cases by a change in the
- Published
- 2013
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13. Shedding light on the bonding, photophysical and magnetotropic properties of triangular Pt3 complexes and their "open-face" TlPt3 half-sandwiches.
- Author
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Tsipis AC and Gkekas GN
- Abstract
The molecular and electronic structures, stabilities, bonding features, magnetotropic and spectroscopic properties of the triangular Pt(3)(μ(2)-L)(3)(L')(3) clusters and their [(μ(3)-Tl)Pt(3)(μ(2)-L)(3)(L')(3)](+) (L = CO, SnR(2), SnH(2), SiR(2), SiH(2), CH(3)CN, PH(2), C(6)F(5), SO(2) or HCN and L' = CO, PH(3), CH(3)CN, C(6)F(5), HCN) half-sandwiches have been studied by means of density functional theory (DFT) calculations. It is found that the optimized Pt-Pt intermetallic distances in the clusters are well below the sum of the van der Waals radii of the two Pt metal atoms (3.44 Å). The triangular Pt(3)(μ(2)-L)(3)(L')(3) clusters trap a thallium(I) cation forming stable "open face" half-sandwiches. The distance between Tl(I) and the centroids of the Pt(3) rings in the half-sandwiches is calculated to be within the range 2.52-2.86 Å. Energy decomposition analysis (EDA) calculations using a dispersion corrected B3LYP-D functional reveal that the interaction of Tl(I) with the Pt(3) ring in the half-sandwiches is dominated by the interplay of electrostatic and orbital interactions with a small contribution from dispersion forces as well. In addition, charge decomposition analysis (CDA) calculations indicate strong donor-acceptor interactions between Tl(I) and the rings. The estimated proton affinities (PAs) of the triangular Pt(3)(μ(2)-L)(3)(L')(3) clusters illustrate their relatively strong π-basic character. Furthermore, an excellent linear relationship between the PAs of the Pt(3)(μ(2)-L)(3)(L')(3) clusters and the bond dissociation energies (D(0)) of the [(μ(3)-Tl)Pt(3)(μ(2)-L)(3)(L')(3)](+) half-sandwiches was established. The magnetotropicity of these systems was studied by calculating the NICS(zz)-scan profiles. The spectroscopic properties of the triangular Pt(3) clusters and their TlPt(3) half-sandwiches were studied by means of TDDFT calculations. The simulated absorption spectra are dominated by strong absorption bands in the UV region. The emission band maxima of the triangular Pt(3) clusters are predicted to lie within the IR region. In order to gain insight into the phosphorescence process of these systems, we have optimized their first triplet excited state, T(1). The estimated deep HOMO energy for these compounds makes them promising candidates for use as "hole" blocking materials in LED devices. Also, it is expected to exhibit small non-radiative decay rate constants due to their relatively large S(0)-T(1) energy difference making them suitable PHOLED emitters or dopants in organic polymer matrices constituting the recombination layer of an OLED device.
- Published
- 2013
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14. Synthesis, characterization, in vitro antitumor activity, DNA-binding properties and electronic structure (DFT) of the new complex cis-(Cl,Cl)[RuIICl2(NO+)(terpy)]Cl.
- Author
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Karidi K, Garoufis A, Tsipis A, Hadjiliadis N, den Dulk H, and Reedijk J
- Subjects
- Antineoplastic Agents chemical synthesis, Cell Line, Tumor, DNA chemistry, Electrophoretic Mobility Shift Assay, Humans, Magnetic Resonance Spectroscopy, Nucleic Acid Denaturation, Ruthenium Compounds chemical synthesis, Spectrometry, Mass, Electrospray Ionization, Antineoplastic Agents chemistry, Antineoplastic Agents pharmacology, DNA drug effects, Ruthenium Compounds chemistry, Ruthenium Compounds pharmacology
- Abstract
The complex cis-(Cl,Cl)-[RuCl2(terpy)(NO)]Cl (1) has been synthesized by the reaction of [RuCl3(H2O)2(NO)] with terpyridine (terpy) and characterized by various spectroscopic, analytical techniques and using electronic structure calculation (DFT) methods. The cytotoxic activity and the DNA-binding properties of have also been studied using biochemical techniques. The results establish unequivocally that corresponds to a so-called [RuNO]6 species, which readily releases the nitrosyl ligand upon irradiation with a mercury lamp in acetonitrile solution. DFT calculations provided a satisfactory description of structural, bonding, electronic and related properties of the new compound and throw light on the mechanism of the photo-induced NO release. Screening on A2780 (human ovarian carcinoma) cell lines showed significant cytotoxicity with an IC50 value of 0.49 microM. 31P and 23Na NMR spectroscopy along with electrophoretic mobility studies illustrated that complex primarily binds by coordination to DNA without any pi-interaction between the planar terpy ligand and the DNA bases, while weak electrostatic interactions could not be excluded. Studies on the inhibition of the restriction enzymes DraI and SmaI revealed that prefers the guanine and cytosine bases of DNA.
- Published
- 2005
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15. Solid-phase synthesis, characterization and DNA binding properties of the first chloro(polypyridyl)ruthenium conjugated peptide complex.
- Author
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Karidi K, Garoufis A, Hadjiliadis N, and Reedijk J
- Subjects
- Animals, Cattle, Circular Dichroism, DNA metabolism, DNA Adducts, Ligands, Magnetic Resonance Spectroscopy, Molecular Structure, Oligopeptides chemical synthesis, Oligopeptides chemistry, Oligopeptides metabolism, Ruthenium Compounds metabolism, Stereoisomerism, DNA chemistry, Ruthenium Compounds chemical synthesis, Ruthenium Compounds chemistry
- Abstract
A general method for the synthesis of chloro(polypyridyl)ruthenium conjugated peptide complexes via a solid-phase strategy is described. The method is applied to synthesize two positional isomers of the complex [Ru(terpy)(4-CO2H-4'-Mebpy-Gly-L-His-L-LysCONH2)Cl](PF6). Even though the separation of the isomers was only partially achieved chromatographically, the isomers were unambiguously assigned by NMR spectroscopy. The interactions of the complex [Ru(terpy)(4-CO2H-4'-Mebpy-Gly-L-His-L-LysCONH2)Cl](PF6) with CT-DNA and plasmid DNA, have been studied with various spectroscopic techniques, showing that (i) the complexes coordinatively bind to DNA preferring the bases guanine and cytosine over the bases thymine and adenine after hydrolysis of the coordinated chloride, (ii) electrostatic interactions between the complex cation and the polyanionic DNA chain assist this binding (iii) only in the case of one isomer the peptide does interact further with DNA as evidenced from 31P NMR spectroscopy, (iv) DNA unwinding occurs in all cases with high binding ratio (Ru/base) values (r > 0.3).
- Published
- 2005
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