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Jan Reedijk

Publications and source records attributed to Jan Reedijk.

At least 19 recordsLinked to original sources
PubMed2006

Synthesis, characterization, and DNA-binding studies of nitro(oligopyridine)ruthenium(II) complexes.

The complexes of general formulas [RuII(terpy)(4-CO2H-4'-Mebpy)(X)]n+ (X = NO (n = 3) and NO2 (n = 1); 1, 2) and [RuII(terpy)(4-COGHK-4'-Mebpy)(X)] (X = NO (n = 3) and NO2 (n = 1); 3, 4) were synthesized and characterized. The complex [RuII(terpy)(4-CO2-4'-Mebpy)(NO2)]_7.5H2O has also been characterized by X-ray crystallographic studies. It crystallizes in the triclinic system: a = 9.4982(1) A, b = 13.1330(1) A, c = 14.2498(2) A; alpha = 110.5870(6) x bc, beta = 98.4048(5) x bc, gamma = 106.4353(5), P1, Z = 2. The crystal structure reveals an extended hydrogen-bonding network. Two water molecules form strong hydrogen bonds with the nitro and the carboxylic oxygen atoms of two separate units of the complex, resulting in a dimeric unit. The dimers are bridged by a (H2O)15 cluster, consisting of two cyclo-(H2O)6 species, while an exo-H2O(8) connects them. Two more exo-H2O molecules are joined together and connect the cyclo-(H2O)6 units with the H2O(1) of the dimeric unit. It was found that complexes 1 and 3 can be transformed into their nitro derivatives in aqueous media at neutral pH. Photorelease of NO in dry MeCN solutions was observed for complexes 1 and 3. Also, complex 2 partially releases (NO2)- in MeCN upon visible light irradiation. Complex 2 interacts with short fragments (70-300 bp) of calf thymus DNA shortening slightly the apparent polynucleotide length, while the conjugation of the peptide GHK to it (2) affects its DNA-binding mode. The peptide moiety of complex 4 was found to interact with the DNA helix in a synergistic way with the whole complex. Preliminary results of photocleavage of DNA by complex 2 are also reported.

Crystallography, X-Ray↗
PubMed2006

Bis[bis(2-pyridylcarbonyl)aminato]iron(III) perchlorate acetonitrile disolvate.

The title compound, [Fe(C12H8N3O2)2]ClO4.2C2H3N, contains Fe(III) in a distorted octahedral coordination environment, with the Fe-N(pyridine) bonds significantly longer than the Fe-N(amine) bonds. The crystal packing involves a bifurcated C-H...(O,O) contact that is also found in all other [M(C12H8N3O2)2] complexes reported previously.

Acetonitriles↗
PubMed2006

Three new asymmetric trans-amine(azole)dichloridoplatinum complexes that overcome cisplatin resistance and their reactions with 5'-GMP.

Three new asymmetric platinum(II) complexes comprising an isopropylamine ligand trans to an azole ligand were synthesized and fully characterized by (1)H NMR, (195)Pt NMR, IR and elemental analysis. In addition the X-ray crystal structure of all three complexes was determined. The reaction kinetics of the complexes with DNA model base guanosine-5'-monophosphate (GMP) was studied, revealing reaction kinetics comparable to cisplatin. To gain insight in the complexes as potential antitumor agents, cytotoxicity assays were performed on a variety of human tumor cell lines. These assays showed the complexes all to possess cytotoxicity profiles comparable to cisplatin. Furthermore, the complexes largely retain their activity in a human ovarian carcinoma cell line resistant to cisplatin, A2780R, compared to the cisplatin sensitive parent cell line A2780. These results are of fundamental importance, illustrating how platinum complexes of trans geometry can show improved activity compared to cisplatin in both cisplatin sensitive and cisplatin resistant cell lines.

Antineoplastic Agents↗
PubMed2006

Crystallographic evidence of nitrate-pi interactions involving the electron-deficient 1,3,5-triazine ring.

The reaction of Zn(NO3)2.6H2O or Cu(NO3)2.3H2O with the star-shaped ligand 2,4,6-tris(di-2-picolylamino)[1,3,5]triazine (dipicatriz) in acetonitrile results in the formation of the mono- or trinuclear coordination compounds [Zn(dipicatriz)(NO3)2] (1), [Zn3(dipicatriz)(NO3)6](CH3CN)3 (2), and [Cu3(dipicatriz)(NO3)2(H2O)6](NO3)4 (3), depending on the metal-to-ligand ratios used during the crystallization process. Their crystal structures exhibit unique supramolecular interactions. Compounds 1 and 2 show anion-pi interactions between coordinated nitrate ions and the s-triazine ring. Compound 3 exhibits remarkable interactions between two noncoordinated nitrate anions and the two faces of the electron-deficient heteroaromatic ring, corroborating earlier theoretical investigations in this area. New theoretical investigations have been carried out on nitrate-pi interactions, taking into account the particular position of the anion toward the aromatic ring observed in the crystal structures.

Acetonitriles↗
PubMed2006

Catecholase activity of a copper(II) complex with a macrocyclic ligand: unraveling catalytic mechanisms.

We report the structure, properties and a mechanism for the catecholase activity of a tetranuclear carbonato-bridged copper(II) cluster with the macrocyclic ligand [22]pr4pz (9,22-dipropyl-1,4,9,14,17,22,27,28,29, 30-decaazapentacyclo[22.2.1.1(4,7).1(11,14). 1(17,20)]triacontane-5,7(28),11(29),12,18, 20(30),24(27),25-octaene). In this complex, two copper ions within a macrocyclic unit are bridged by a carbonate anion, which further connects two macrocyclic units together. Magnetic susceptibility studies have shown the existence of a ferromagnetic interaction between the two copper ions within one macrocyclic ring, and a weak antiferromagnetic interaction between the two neighboring copper ions of two different macrocyclic units. The tetranuclear complex was found to be the major compound present in solution at high concentration levels, but its dissociation into two dinuclear units occurs upon dilution. The dinuclear complex catalyzes the oxidation of 3,5-di-tert-butylcatechol to the respective quinone in methanol by two different pathways, one proceeding via the formation of semiquinone species with the subsequent production of dihydrogen peroxide as a byproduct, and another proceeding via the two-electron reduction of the dicopper(II) center by the substrate, with two molecules of quinone and one molecule of water generated per one catalytic cycle. The occurrence of the first pathway was, however, found to cease shortly after the beginning of the catalytic reaction. The influence of hydrogen peroxide and di-tert-butyl-o-benzoquinone on the catalytic mechanism has been investigated. The crystal structures of the free ligand and the reduced dicopper(I) complex, as well as the electrochemical properties of both the Cu(II) and the Cu(I) complexes are also reported.

Catalysis↗
PubMed2006

Synthetic models of the active site of catechol oxidase: mechanistic studies.

The ability of copper proteins to process dioxygen at ambient conditions has inspired numerous research groups to study their structural, spectroscopic and catalytic properties. Catechol oxidase is a type-3 copper enzyme usually encountered in plant tissues and in some insects and crustaceans. It catalyzes the conversion of a large number of catechols into the respective o-benzoquinones, which subsequently auto-polymerize, resulting in the formation of melanin, a dark pigment thought to protect a damaged tissue from pathogens. After the report of the X-ray crystal structure of catechol oxidase a few years earlier, a large number of publications devoted to the biomimetic modeling of its active site appeared in the literature. This critical review (citing 114 references) extensively discusses the synthetic models of this enzyme, with a particular emphasis on the different approaches used in the literature to study the mechanism of the catalytic oxidation of the substrate (catechol) by these compounds. These are the studies on the substrate binding to the model complexes, the structure-activity relationship, the kinetic studies of the catalytic oxidation of the substrate and finally the substrate interaction with (per)oxo-dicopper adducts. The general overview of the recognized types of copper proteins and the detailed description of the crystal structure of catechol oxidase, as well as the proposed mechanisms of the enzymatic cycle are also presented.

Binding Sites↗
PubMed2006

A pyrazolato-bridged dinuclear platinum(II) complex induces only minor distortions upon DNA-binding.

The cytotoxic, pyrazolato-bridged dinuclear platinum(II) complex [(cis-{Pt(NH3)2})2(mu-OH)(mu-pz)]2+ (pz=pyrazolate) has been found to cross-link two adjacent guanines of a double-stranded DNA decamer without destabilizing the duplex and without changing the directionality of the helix axis. A 1H NMR study of the oligonucleotide d(CTCTG*G*TCTC)-d(GAGACCAGAG), cross-linked at the two G* guanines by [(cis-{Pt(NH3)2})2(mu-pz)]3+, and molecular dynamics simulations of the explicitly solvated duplex were performed to characterize the structural details of the adduct. The dinuclear platinum cross-link unwinds the helix by approximately 15 degrees , that is, to a similar extent as the widely used antitumor drug cisplatin, but, in contrast to the latter, induces no significant bend in the helix axis. The Watson-Crick base-pairing remains intact, and the melting temperature of the duplex is unaffected by the cross-link. The helical twist is considerably reduced between the two platinated bases, as becomes manifest in an unusually short sequential H1'-H1' distance. This unwinding also affects the sugar ring of the guanosine in the 3'-position to the cross-link, which presents an N<-->S equilibrium. This is the first cytotoxic platinum complex that has been successfully designed by envisioning the structural consequences of its binding to DNA.

Base Pairing↗
PubMed2006

Structure-toxicity relationships for different types of dinuclear platinum complexes.

Nine structurally distinct dinuclear platinum complexes have been evaluated in a novel model system for the investigation of renal epithelial toxicity of platinum drugs. The results showed that these compounds are toxic when applied at the basolateral side of renal epithelia, whereas their toxic effects on the apical side are negligible. Such a difference in toxicity of the complexes has been found to result from their poor uptake through the apical membrane, as compared to the basolateral membrane. Toxicity of the compounds on the basolateral side varies depending on their structure. Structure-toxicity relationships for the group of complexes with rigid ligands and for the group of complexes with flexible ligands are discussed. Among the dinuclear complexes with rigid ligands, sterically hindered complexes are less toxic, due to their poor uptake and low reactivity towards glutathione. Within the group of complexes with flexible ligands, cis-configured isomers are more toxic than their trans-counterparts.

Animals↗
PubMed2006

Binding of novel azole-bridged dinuclear platinum(II) anticancer drugs to DNA: insights from hybrid QM/MM molecular dynamics simulations.

Dinuclear Pt-containing compounds might be used to overcome the intrinsic and acquired cell resistance of widely used anticancer drugs such as cisplatin. Recently, the complexes [[cis-Pt(NH3)2]2(mu-OH)(mu-pz)](NO3)2 (with pz = pyrazolate) (1), [[cis-Pt(NH3)2]2(mu-OH)(mu-1,2,3-ta-N(1),N(2))](NO3)2 (with ta = 1,2,3-triazolate) (2), and the binding of 1 to d(CpTpCpTpG*pG*pTpCpTpCp) have been characterized. Here we provide the structural and electronic properties of the free drugs, of the intermediates of binding to guanine bases, and of the products, by performing DFT calculations. Our results show that in 2 an isomerization of the Pt-coordination sphere from N(2) to N(3) of the triazolate unit determines a thermodynamic stabilization of approximately 20 kcal/mol as a consequence of the formation of an allylic structure. In addition, hybrid quantum-classical molecular dynamics simulations of 1 and 2 DNA adducts have shed light on the structural distortions that the drugs induce to the DNA duplex. Our calculations show that the rise and the tilt of the two adjacent guanines are identical in the presence of 1 and 2, but they markedly increase when 2 binds in the N(1),N(3) fashion. In addition, the drugs do not provoke any kink upon binding to the double-stranded DNA, suggesting that they may act with a mechanism different than that of cisplatin. The accuracy of our calculations is established by a comparison with the NMR data for the corresponding complex with 1.

Algorithms↗
PubMed2006

The square-planar cytotoxic [Cu(II)(pyrimol)Cl] complex acts as an efficient DNA cleaver without reductant.

Chemical nucleases based on the transition-metal ions cleave DNA hydrolytically and/or oxidatively, with or without added reductant. We report here the novel DNA cleavage properties of the highly water-soluble, square-planar [Cu(Hpyrimol)Cl] complex, together with the results of cytotoxicities toward selected cancer cell lines. The copper complex cleaves PhiX174 supercoiled DNA efficiently without any reductant and shows high cytotoxicities toward L1210 murine leukemia and A2780 human ovarian carcinoma cancer cell lines that are sensitive and resistant to cisplatin. The IC50 values obtained for the copper complex in the sensitive cell lines are in the range of cisplatin, and for the cisplatin-resistant leukemia cell line, this value is even better.

Animals↗
PubMed2005

Versatility in the binding of 2-pyrazinecarboxylate with iron. Synthesis, structure and magnetic properties of iron(II) and iron(III) complexes.

The synthesis and characterization of two new iron(II) complexes, [Fe(pca)2(py)2].py (1) and {[Fe(pca)2(H2O)].H2O}n (2) and one new iron(III) complex, Na2{[Fe(pca)()]2O}.2H2O.2CH3CN (3) (pca- stands for 2-pyrazinecarboxylate), are reported. Complex 1 is obtained from the reaction of iron powder with 2-pyrazinecarboxylic acid. The reaction of Fe(ClO4)3.10H2O with Hpca in the presence of 3 equiv. of Bu4NOH yields 2, whereas the presence of NaOH yields 3. The molecular structure of 1 contains an iron(II) ion with a pseudo-octahedral environment resulting from the coordination of two pca- ligands in a bidentate chelating fashion and two pyridine molecules; pi-pi stacking interactions between pyridine and pyrazine rings lead to a one-dimensional chain. Complex 2 is an iron(II) coordination polymer with an infinite zig-zag motif and an Fe...Fe separation of 7.1 A. In 2, the pi-pi stacking interactions involving the pyrazine rings and the strong hydrogen bonds between the coordinated water molecule and the carboxylate oxygens of two pca- ligands result in a three-dimensional network structure. Complex 3 consists of an anionic micro-oxo-bridged diiron(III) core with two crystallographically distinct iron(iii) ions; the negative charge is compensated by two sodium cations. Complex 3 is assembled in a three dimensional network structure through coordination of Na(I) and hydrogen bond interactions. Temperature dependent magnetic susceptibility and Mössbauer spectroscopic studies indicate that 1 and 2 have similar magnetic properties. Both complexes are paramagnetic above 12 K, whereas antiferromagnetic ordering is observed below 12 K. The magnetic properties of reveal strong intramolecular antiferromagnetic interactions between the two iron(III) ions with a J value of -221 cm(-1); no long range intermolecular magnetic coupling is observed between 295 and 4.2 K.

Binding Sites↗
PubMed2005

New antitumour active platinum compounds containing carboxylate ligands in trans geometry: synthesis, crystal structure and biological activity.

New asymmetric trans-platinum(II) complexes, composed of an isopropylamine, an azole and two carboxylate leaving groups, are presented. The crystal and molecular structures of one of the complexes has been determined and the cytotoxicity and reactivity with 5'-guanosine monophosphate is reported. The complexes show a reduced reactivity, but no decrease in cytotoxic activity compared to their chloro-counterparts. Furthermore the complexes largely overcome cisplatin resistance, they therefore present an interesting class of antitumour active trans-platinum complexes.

Animals↗
PubMed2005

Catecholase activity of a mu-hydroxodicopper(II) macrocyclic complex: structures, intermediates and reaction mechanism.

The monohydroxo-bridged dicopper(II) complex (1), its reduced dicopper(I) analogue (2) and the trans-mu-1,2-peroxo-dicopper(II) adduct (3) with the macrocyclic N-donor ligand [22]py4pz (9,22-bis(pyridin-2'-ylmethyl)-1,4,9,14,17,22,27,28,29,30- decaazapentacyclo -[22.2.1(14,7).1(11,14).1(17,20)]triacontane-5,7(28),11(29),12,18,20(30), 24(27),25-octaene), have been prepared and characterized, including a 3D structure of 1 and 2. These compounds represent models of the three states of the catechol oxidase active site: met, deoxy (reduced) and oxy. The dicopper(II) complex 1 catalyzes the oxidation of catechol model substrates in aerobic conditions, while in the absence of dioxygen a stoichiometric oxidation takes place, leading to the formation of quinone and the respective dicopper(I) complex. The catalytic reaction follows a Michaelis-Menten behavior. The dicopper(I) complex binds molecular dioxygen at low temperature, forming a trans-mu-1,2-peroxo-dicopper adduct, which was characterized by UV-Vis and resonance Raman spectroscopy and electrochemically. This peroxo complex stoichiometrically oxidizes a second molecule of catechol in the absence of dioxygen. A catalytic mechanism of catechol oxidation by 1 has been proposed, and its relevance to the mechanisms earlier proposed for the natural enzyme and other copper complexes is discussed.

Catalysis↗
PubMed2005

Ligand conformation enforces trigonal bipyramidal coordination geometry in a new dinuclear bis(pyrazolato)-bridged copper(II) complex: synthesis, crystal structure, and properties of [Cu(Npy2pz)]2(ClO4)2.2CH3CN.

The reaction of Cu(ClO(4))(2).6H(2)O with the new tripodal ligand HNpy(2)pz (N-bis[(pyridin-2-yl)methyl][1H-pyrazol-3-yl)methyl]amine) in the presence of 1 equiv of triethylamine results in the formation of a doubly pyrazolato-bridged dicopper(II) complex, [Cu(Npy(2)pz)](2)(ClO(4))(2).2CH(3)CN (1). The crystal structure of 1 was determined by X-ray crystallography and was found to consist of two nearly identical discrete dinuclear molecules with bis(pyrazolato) bridges. The copper(II) ion has a trigonal bipyramid geometry achieved by the coordination of an aliphatic nitrogen, two pyridine moieties, and two pyrazolato nitrogens. Variable temperature-dependent magnetic data show that antiferromagnetic interactions operate in 1 as a result of the binding angle of the pyrazolato bridge. In solution, the stability of the dinuclear cation, [Cu(py(2)pz)](2)(2+), is highly dependent on the concentration, as indicated by ESI-MS, ligand field, cyclic voltammetry, EPR, and (1)H NMR studies.

Journal Article↗
PubMed2005

Moisture-triggered 1,3,5-triazine-based Cu(II) molecular switch: a combined X-ray single-crystal and powder diffraction study.

A solvothermal synthetic procedure has been exploited to prepare the new [Cu(3)L(NO(3))(6)](n) coordination polymer (1) by reaction of the polydentate N,N'-{2,4-di-[(di-pyridin-2-yl)amine]-1,3,5-triazine}ethylenediamine ligand (opytrizediam L) with copper(II) nitrate. 1 has been structurally characterized by means of the conventional X-ray single-crystal diffraction technique. It crystallizes in the monoclinic C2/c space group with a = 16.830(3), b = 20.701(4), c = 18.170(4) Angstroms, beta = 113.26(3) degrees, V = 5816(2) Angstroms(3), Z = 4. 1 consists of trinuclear Cu(3)L(NO(3))(5) units connected by means of a nitrato-O,O' bridge. The resulting chains are involved in weak interchain head-to-tail pi-pi stacking interactions. In the presence of moisture, 1 is readily converted into the hydrated [Cu(3)L(NO(3))(5)](NO(3)).H(2)O form (2). This second phase, monoclinic P2(1)/c, consists of isolated [Cu(3)L(NO(3))(5)](+) and (NO(3))(-) ions which accommodate water molecules in the crystal lattice. These subtle chemical and structural modifications accompanying the moisture-triggered 1-to-2 transformation have been demonstrated through a X-ray powder diffraction study. A thermodiffractometric analysis has evidenced that this solid-to-solid transformation is fully reversible, i.e., thermally induced dehydration of 2 restores 1. The analysis of the temperature dependence of the magnetic susceptibility for 2 has revealed very weak ferromagnetic interactions, consistent with the large Cu...Cu separation (ca. 7.5 Angstroms) in the trinuclear units.

Journal Article↗
PubMed2005

Selective oxidative para C-C dimerization of 2,6-dimethylphenol.

Mechanistic investigations on the oxidative coupling of 2,6-dimethylphenol have led to the development of a selective and efficient procedure to prepare 3,5,3',5'-tetramethyl-biphenyl-4,4'-diol, via a C-C coupling, mediated by a hypervalent form of iodine, i.e. (diacetoxyiodo)benzene and for which a mechanism is proposed.

Journal Article↗
PubMed2005

Selective copper(II)-mediated oxidative coupling of a nucleophilic reagent to the para-methyl group of 2,4,6-trimethylphenol.

A copper(II) neocuproine system has been developed for the efficient and very selective 1,6-addition of a nucleophile to the para-methyl group of 2,4,6-trimethylphenol. Crystallographic and spectroscopic data point towards the involvement of a micro-methoxo-micro-phenoxo-bridged copper species which appears to generate a highly reactive quinone methide intermediate that can be attacked by a nucleophilic reagent.

Copper↗