Homo- and heterobinuclear Cu2+ and Zn2+ complexes of abiotic cyclic hexaazapyridinocyclophanes as SOD mimics

The new receptor 3,7,11,15,19,23-hexaaza-1(2,6)-pyridinacyclotetracosaphane (L1) containing a complete sequence of propylenic chains has been synthesised. The acid–base behaviour and Cu2+ and Zn2+ coordination have been analysed by potentiometric measurements in 0.15 M NaClO4 for L1 and for the related compounds 3,7,11,14,18,22-hexaaza-1(2,6)-pyridinacyclotricosaphane (L2), 3,7,10,13,16,20-hexaaza-1(2,6)-pyridinacycloheneicosaphane (L3) and 3,7,10,12,15,19-hexaaza-1(2,6)-pyridinacycloicosaphane (L4). The crystal structure of [(CuH4L2)(H2O)(ClO4)](ClO4)5·3H2O shows an interesting combination of a metal ion coordinated by the pyridine nitrogen atom and the adjacent amine groups of the chain, …

Complexes of tetra(parasulphonatephenyl)porphyrinato ferrate(III), FeTPPs, with 1,10 phenanthroline and 2,2′ bipyridine ligands

Abstract Iron(III) porphyrin, FeTPPS, gives high-spin 1:1 monomeric complexes with the ligands 1,10 phenanthroline, 2,9 dimethylphenanthroline and 2,2 bipyridine in aqueous solution. Absorption spectrum of the complexes is very different to the one of the monomer metalloporphyrin, but nearly identical to the visible spectrum of the μ-oxo dimer Fe2(TPPS)2O. A spectrophotometric study of the formation equilibria yields the following values of the stability constants: Me2phen 4.3 × 104, phen 1.1 × 104, bipy 2.0 × 102 (25 °C, 0.1 M NaNO3). Analysis of the experimental data strongly suggest that the ligands are hydrogen bonded to one coordinated water molecule (TPPS)FeOH2 → (LL). Although the …

COBALT SUBSTITUTED PROTEINS

Cobalt(II) has been extensively used as a spectroscopic probe in many proteins, mainly replacing zinc, but also substituting iron, manganese and copper ions. The relatively short electronic relaxation times of high spin cobalt(II) makes this ion suitable as a paramagnetic probe for Nuclear Magnetic Resonance spectroscopy. A survey of the NMR studies performed in cobalt substituted proteins is shown. In the zinc enzymes Carboxypeptidase A, Carbonic Anhydrase and Superoxide Dismutase the implications of these studies on their catalytic mechanisms are commented. Finally, a further insight in the research of the blue copper protein Azurin by applying NMR to its cobalt derivative is also reporte…

Spectroscopic studies of water-soluble superstructured iron(III) porphyrin. Interaction with the bovine serum albumin protein

Acid-base equilibrium of the “one-face”-hindered sulfonated porphyrin, α5,15-[2,2′(dodecamethyleneoxy),(5-sulfonato)diphenyl]-10,20-bis(2-hydroxy,5-sulfonatophenyl)porphyrinato iron(III), has been ...

Preparation of Hg2+ selective fluorescent chemosensors based on surface modified core–shell aluminosilicate nanoparticles

A synthetic procedure for the preparation of functional structured inorganic–organic hybrid materials consisting of boehmite-silica core–shell nanoparticles and anthracene-containing amines covalently attached to the nanoparticles surface is reported. The system functionalised with the monoamine chain shows a very high sensing performance for Hg2+ detection in pure water reaching a detection limit of 0.2 ppb. Two additional advantages of these systems are their stability over a wide pH window and the feasibility to be recovered by a simple procedure.

A Binuclear MnIII Complex of a Scorpiand-Like Ligand Displaying a Single Unsupported MnIII–O–MnIII Bridge

The crystal structure of a binuclear Mn(III) complex of a scorpiand-like ligand (L) displays an unsupported single oxo bridging ligand with a Mn(III)-O-Mn(III) angle of 174.7°. Magnetic susceptibility measurements indicate strong antiferromagnetic coupling between the two metal centers. DFT calculations have been carried out to understand the magnetic behavior and to analyze the nature of the observed Jahn-Teller distortion. Paramagnetic (1)H NMR has been applied to rationalize the formation and magnetic features of the complexes formed in solution.

Equilibrium and kinetic studies on complex formation and decomposition and the movement of Cu2+metal ions within polytopic receptors

Potentiometric studies carried out on the interaction of two tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties are linked with 2,9-dimethylphenanthroline (L1) and 2,6-dimethylpyridine (L2) establish the formation of mono-, bi- and trinuclear Cu(2+) complexes. The values of the stability constants and paramagnetic (1)H NMR studies permit one to infer the most likely coordination modes of the various complexes formed. Kinetic studies on complex formation and decomposition have also been carried out. Complex formation occurs with polyphasic kinetics for both receptors, although a significant difference is found between bot…

NMR and homology modeling studies of copper(II)-halocyanin from Natronobacterium pharaonis bacteria

Abstract Halocyanin from the haloalkaliphilic archaean Natronobacterium pharaonis is a peripheral membrane type 1 blue copper protein with a single polypeptide chain of 163 amino acid residues. Halocyanin participates as putative electron carrier protein associated to an electron acceptor role for a terminal oxidase and has the lowest redox potential value reported to date for a BCP. NMR studies and homology modeling calculations were performed to evaluate the electronic properties of Cu(II)-halocyanin from Natronobacterium pharaonis . The copper coordination site properties of Cu(II)-halocyanin are discussed. The 1 H NMR spectra, isotropic chemical shifts and relaxation times for halocyani…

Binuclear Cu2+ complex mediated discrimination between L-glutamate and L-aspartate in water.

L-Glutamate and L-aspartate selectivity is achieved by the action of two Cu2+ metal ions rightly disposed in a cyclophanetype macrocyclic framework; electrochemical sensing of glutamate has been achieved by adsorption of the copper complexes on graphite electrodes. Verdejo Viu, Begoña, Begona.Verdejo@uv.es ; Domenech Carbo, Antonio, Antonio.Domenech@uv.es ; Jimenez Garcia, Hermas Rafael, Hermas.Jimenez@uv.es ; Soriano Soto, Concepción, Concepcion.Soriano@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es

EPR and Magnetic Susceptibility Studies of Cobalt(II)- and Nickel(II)-Substituted Azurins from Pseudomonas aeruginosa. Electronic Structure of the Active Sites

The electronic properties of cobalt(II)- and nickel(II)-substituted azurins from Pseudomonas aeruginosa have been investigated. EPR data for the cobalt derivative and paramagnetic susceptibility data for the nickel derivative are reported. The EPR spectrum of Co(II)−azurin shows the typical pattern of a Kramers' doublet (±1/2) associated with an S = 3/2 ground state in a distorted axial symmetry environment. The temperature dependence of the EPR intensities shows that this Kramers' doublet is the excited doublet and, therefore, that the corresponding zero-field splitting parameter D is negative (∼−3.5 cm-1). The mean g value is equal to 2.3. Nickel(II) azurin exhibits an effective magnetic …

CO 2 Fixation and Activation by Cu II Complexes of 5,5″‐Terpyridinophane Macrocycles

An aza-terpyridinophane receptor containing the polyamine 4,7,10,13-tetraazahexadecane-1,16-diamine linked through methylene groups to the 5,5″ positions of a terpyridine unit has been prepared and characterized (L). The acid-base behaviour, CuII speciation and ability to form ternary complexes (CuII-L-carbonate) have been explored by potentiometric titrations in 0.15 M NaClO4 and by UV/Vis and paramagnetic NMR spectroscopy. Comparisons are made with a previously reported terpyridinophane containing the polyamine 4,7,10-triazatridecane-1,13-diamine (L1). For this latter receptor, reductive coupling between indigo and carbon dioxide at indigo-modified electrodes produces carboxylated derivat…

Protein Unfolding:1H-NMR Studies of Paramagnetic Ferricytochrome c-550 from Horse Heart

Electronic transfer protein cytochrome c-550 from horse heart is studied in the unfolded state by means of paramagnetic 1H NMR. The protein contains 104 aminoacid residues and a heme group with low spin FeIII ion in the oxidized form of protein. The global secondary structure is of the α-helix type as occurs in the case of very other cytochromes c investigated such as cyt c-550 from Thiobacillus versutus or cyt c-551 from Pseudomonas aeruginosa. We have studied the coordination characteristic and electronic properties of heme iron horse heart ferricytochrome c-550 at increasing denaturing conditions (up to 3.1 M GuHCl and 288-323 K). The 1H T1 values of the signals were measured and some re…

Grafted squaramide monoamine nanoparticles as simple systems for sulfate recognition in pure water.

New simple systems formed by a chain containing a squaramide function and a quaternised amine group attached to boehmite or silica-coated boehmite nanoparticles are able to discriminate anions in pure water.

1H 2D-NMR characterization of Ni(II)-substituted azurin fromPseudomonas aeruginosa

1 H two-dimemional NMR experiments on nickel(II)-substituted azurin have been succesfully applied. Despite the short relaxation time of the hyperfine-shifted resonances, the combined use of NOESY and COSY spectra allowed the alignment of 15 resonances belonging to the metal-coordinated residues Gly-45, His-46, His-117 and Met-121. Even in the case of the two broad and furthest downfield resonances, the NOESY spectra were successful in assigning these signals to the β-CH 2 protons of Cys-112. The protons of the non-coordinated residues Met-13, Phe-15 and Trp-48 were also assigned via NOESY, COSY and TOCSY experiments

1H-NMR study of a cobalt-substituted blue copper protein: Pseudomonas aeruginosa Co(II)-azurin.

Substitution of copper by cobalt in blue copper proteins gives a paramagnetic metalloderivative suitable for paramagnetic NMR studies. A thorough analysis of the 1H-NMR spectrum of Pseudomonas aeruginosa Co(II)-azurin is presented here. All the observable contact-shifted signals as well as many other paramagnetic signals from protons placed up to about 1.0 nm around the metal center, including some residues belonging to functionally important parts of the protein like the hydrophobic patch and the His35 region, have been assigned. The results obtained permit the detection and study of structural variations like those originated by the His35 ionization, and allow us to draw a feasible pictur…

Influence of the chain length and metal : ligand ratio on the self-organization processes of Cu2+ complexes of [1 + 1] 1H-pyrazole azamacrocycles

Three new [1 + 1] macrocycles formed by the reaction of 1H-3,5-bis(chloromethyl)pyrazole with the tosylated amines 1,4,7,10-tetraazadecane (L1), 1,4,8,11-tetraazaundecane (L2) and 1,5,10,14-tetraazatetradecane (L3) are described. Potentiometric studies and HR-ESI-Mass spectrometry show the formation of dimeric binuclear Cu2+ complexes whose organization depends on the type of hydrocarbon chains connecting the amine groups. Furthermore, trinuclear or/and tetranuclear complexes are formed depending also on the length of the polyaminic bridge and on the sequence of the hydrocarbon chains. The crystal structures of the [2 + 2] [Cu2(H(H−1L2))2](ClO4)4·4H2O (1) and [Cu2(H−1L2)2](ClO4)2 (2) comple…

1H NMR and UV-vis spectroscopic characterization of sulfonamide complexes of nickek(II)-carbonic anhydrase. Resonance assignments based on NOE effects

The binding of acetazolamide, p-fluorobenzensulfonamide, p-toluenesulfonamide, and sulfanilamide to nickel(II)-substituted carbonic anhydrase II has been studied by 1H NMR and electronic absorption spectroscopies. These inhibitors bind to the metal ion forming 1:1 complexes and their affinity constants were determined. The 1H NMR spectra of the formed complexes show a number of isotropically shifted signals corresponding to the histidine ligands. The complexes with benzene-sulfonamides gave rise to very similar 1H NMR spectra. The NMR data suggest that these aromatic sulfonamides bind to the metal ion altering its coordination sphere. In addition, from the temperature dependence of 1H NMR s…

Iron(II) Complexes with Scorpiand-Like Macrocyclic Polyamines: Kinetico-Mechanistic Aspects of Complex Formation and Oxidative Dehydrogenation of Coordinated Amines.

The Fe(II) coordination chemistry of a pyridinophane tren-derived scorpiand type ligand containing a pyridine ring in the pendant arm is explored by potentiometry, X-ray, NMR, and kinetics methods. Equilibrium studies in water show the formation of a stable [FeL]2+ complex that converts to monoprotonated and monohydroxylated species when the pH is changed. A [Fe(H–2L)]2+ complex containing an hexacoordinated dehydrogenated ligand has been isolated, and its crystal structure shows the formation of an imine bond involving the aliphatic nitrogen of the pendant arm. This complex is low spin Fe(II) both in the solid state and in solution, as revealed by the Fe–N bond lengths and by the NMR spect…

CuIIand ZnIICoordination Chemistry of Pyrazole‐Containing Polyamine Receptors − Influence of the Hydrocarbon Side Chain Length on the Metal Coordination

The synthesis of a new macrocyclic receptor (L 4 ) containing two 3,5-dimethylpyrazole units connected by dipropylenetriamine bridges is reported for the first time; pH-metric titrations indicate that L 4 shows six protonation steps in the pH range 2-11. In the absence of metal ions, the pyrazole moieties are not involved in acid-base processes in this pH range. Addition of Cu I I and Zn I I results in deprotonation of the pyrazole moieties which act as bis(monodentate) η 1 :η 1 ligands. This induced deprotonation occurs at higher pH values than in the complexes of the analogous ligand containing diethylenetriamine bridges (L 1 ). The crystal structures of [Cu 2 (H - 2 L 4 )](ClO 4 ) 2 and …

1H NMR studies of paramagnetic ferricytochrome c-551 from Pseudomonas aeruginosa at high pH: The role of histidine 16 in the spin transition

Abstract Cytochrome c-551 from the mesophile Pseudomonas aeruginosa is an electronic transfer protein that contains 82 amino-acid residues and a c-type heme as the prosthetic group with low spin Fe(II) in the reduced form and low spin Fe(III) in the oxidized form of cytochrome c-551. We have studied the electronic properties of ferricytochrome c-551 from P. aeruginosa at high pH (9–11.4) by means of paramagnetic 1H NMR spectra and the T1 and T2 values of isotropically shifted proton resonances. We have also analyzed the temperature dependence of the hyperfine-shifts. Resonance assignment of some signals was based on 2D saturation transfer experiments, EXSY. These results indicate the existe…

Selective encapsulation of a chloride anion in a 1H-pyrazole Cu2+ metallocage

A self-assembled metallobox from copper(ii) and two macrocycles containing 1H-pyrazole ligands has been prepared. The internal cavity of the box is able to selectively encapsulate a single chloride anion over any other halide anion.

Oxidative stress protection by manganese complexes of tail-tied aza-scorpiand ligands.

The Mn2+ coordination chemistry of double scorpiand ligands in which two polyazacyclophane macrocycles have been connected by pyridine, phenanthroline and bipyridine spacers has been studied by potentiometry, paramagnetic NMR and electrochemistry. All ligands show high stability with Mn2+ and the complexes were formed in a wide pH range. DFT calculations support the structures and coordination geometries derived from the study. A remarkable antioxidant activity was evidenced for these systems by the McCord-Fridovich assay and in Escherichiacoli sodAsodB deficient bacterial cells. The three systems were tested as anti-inflammatory drugs in human macrophages measuring the accumulation of cyto…

Structural reorganisation in polytopic receptors revealed by kinetic studies.

One of the first kinetic studies of metal ion reorganisation between the different sites of a tritopic polyaza ligand reveals well defined pathways for the movement of the metal ion.

A Ferromagnetic [Cu3(OH)2]4+Cluster Formed inside a Tritopic Nonaazapyridinophane: Crystal Structure and Solution Studies

Paramagnetic Cobalt and Nickel Derivatives of Alcaligenes denitrificans Azurin and Its M121Q Mutant. A 1H NMR Study

Using cobalt or nickel to replace copper in native azurin allows one to fingerprint the metal coordination site of the protein. The metal sites of wild type Alcaligenes denitrificans azurin and its M121Q mutant are clearly distinguishable through the paramagnetic 1H NMR spectra of the Ni(II) and Co(II) derivatives. In the wild type azurin, Gly45 coordinates to nickel or cobalt, while Met121 appears as a weak metal ligand. On the contrary, in the M121Q azurin mutant, the metal exhibits a clear preference for the Gln121, which coordinates through the side chain carbonyl oxygen, and Gly45 is not a ligand. Changes in the isotropic shifts and relaxation properties of signals from the Cys112, His…

The Crystal Structure of Nickel(II)-Azurin

The nickel(II)-azurin metalloderivative has been crystallized and its structure solved at 0.205-nm resolution by X-ray diffraction. The overall structure is not modified by the metal exchange and the only differences with regard to the native copper(II)-azurin occur in the metal site region. These variations affect principally the axial ligands. Nickel co-ordinates more strongly to the carbonyl oxygen of Gly45 while its distance to the Met121 S4 enlarges up to 0.330 nm. The resulting metal center structure is intermediate between those of the Cu(II) and Zn(II) azurins, and can be described as distorted tetrahedral. However, the existence of contact interaction between Met121 and the nickel …

1H-NMR spectroscopic studies of paramagnetic superstructured iron(III) porphyrinsThis article is dedicated to the memory of Professor Michel Momenteau of Institut Curie.Abbreviations. 1D and 2D: one-dimensional and two-dimensional; COSY: correlated spectroscopy; NOESY: nuclear Overhauser effect spectroscopy; TPP: 5,10,15,20-tetraphenylporphyrinate dianion.

The electronic properties of several superstructured iron(III) porphyrins, in which the two faces of the porphyrin are protected by two chains linked at the opposite phenyl rings, have been investigated. The paramagnetic 1H NMR spectra of three iron(III) “basket-handle” porphyrins such as FeIII[e-BHP(C12)2], FeIII[a-BHP(C12)2] and FeIII[e-BHP(C12)(ImC11)] in organic solvent have been assigned. The 1H T1 values of the signals were measured and resonance assignments made based on NOESY and COSY experiments. The electronic structure of the iron(III) is discussed on the basis of the temperature dependence of the isotropic shifts and relaxation times. The hyperfine-shifted resonances in these sp…

Imidazolate bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) complexes of a terpyridinophane azamacrocycle: a solution and solid state study.

The dinuclear Cu2+ and Zn2+ as well as the mixed Cu2+-Zn2+ complexes of a 5,5''-pentaazaterpyridinophane ligand (L) are able to incorporate imidazolate (Im-) as a bridging ligand. The crystal structure of [Cu(2)L(Im)(Br)(H2O)](CF(3)SO(3))(2).3H2O (1) shows one copper coordinated by the three pyridine nitrogens of the terpyridine unit, one nitrogen of the imidazolate bridge (Im-) and one bromide anion occupying the axial position of a distorted square pyramid. The second copper atom is coordinated by the remaining imidazolate nitrogen, the three secondary nitrogens at the centre of the polyamine bridge and one water molecule that occupies the axial position. Magnetic measurements have been p…

Cu2+and AMP complexation of enlarged tripodal polyamines

The synthesis, characterization, Cu2+ coordination and interaction with AMP of three tripodal polyamines are reported. The polyamines are based on the structure of the tetraamine (tren) which has been enlarged with three propylamino functionalities (TAL), with a further anthrylmethyl fragment at one of its terminal primary nitrogens (ATAL) or with naphthylmethyl fragments at its three ends (N3TAL). The protonation constants of all three polyamines show that at pH 6, all six primary and secondary nitrogen atoms in the arms are protonated. The interaction with Cu2+ and AMP (adenosine-5′-monophosphate) has been studied by potentiometric, UV-Vis, ESI-MS spectroscopy and NMR techniques. pH-Metri…

CCDC 1953932: Experimental Crystal Structure Determination

Related Article: Alberto Lopera, Ariadna Gil-Martínez, Javier Pitarch-Jarque, Begoña Verdejo, Salvador Blasco, M. Paz Clares, Hermas R. Jiménez, Enrique García-España|2020|Dalton Trans.|49|8614|doi:10.1039/D0DT01056A

CCDC 1521794: Experimental Crystal Structure Determination

Related Article: M. Paz Clares, Laura Acosta-Rueda, Carmen E. Castillo, Salvador Blasco, Hermas R. Jiménez, Enrique García-España, and Manuel G. Basallote|2017|Inorg.Chem.|56|4400|doi:10.1021/acs.inorgchem.6b03070

CCDC 1953930: Experimental Crystal Structure Determination

Related Article: Alberto Lopera, Ariadna Gil-Martínez, Javier Pitarch-Jarque, Begoña Verdejo, Salvador Blasco, M. Paz Clares, Hermas R. Jiménez, Enrique García-España|2020|Dalton Trans.|49|8614|doi:10.1039/D0DT01056A

CCDC 1990725: Experimental Crystal Structure Determination

Related Article: Alberto Lopera, Ariadna Gil-Martínez, Javier Pitarch-Jarque, Begoña Verdejo, Salvador Blasco, M. Paz Clares, Hermas R. Jiménez, Enrique García-España|2020|Dalton Trans.|49|8614|doi:10.1039/D0DT01056A

CCDC 1994847: Experimental Crystal Structure Determination

Related Article: Javier Pitarch-Jarque, Hermas R. Jiménez, Elina Kalenius, Salvador Blasco, Alberto Lopera, M. Paz Clares, Kari Rissanen, Enrique García-España|2021|Dalton Trans.|50|9010|doi:10.1039/D1DT01302E

CCDC 1953929: Experimental Crystal Structure Determination

Related Article: Alberto Lopera, Ariadna Gil-Martínez, Javier Pitarch-Jarque, Begoña Verdejo, Salvador Blasco, M. Paz Clares, Hermas R. Jiménez, Enrique García-España|2020|Dalton Trans.|49|8614|doi:10.1039/D0DT01056A

CCDC 1994844: Experimental Crystal Structure Determination

Related Article: Javier Pitarch-Jarque, Hermas R. Jiménez, Elina Kalenius, Salvador Blasco, Alberto Lopera, M. Paz Clares, Kari Rissanen, Enrique García-España|2021|Dalton Trans.|50|9010|doi:10.1039/D1DT01302E

CCDC 1994845: Experimental Crystal Structure Determination

Related Article: Javier Pitarch-Jarque, Hermas R. Jiménez, Elina Kalenius, Salvador Blasco, Alberto Lopera, M. Paz Clares, Kari Rissanen, Enrique García-España|2021|Dalton Trans.|50|9010|doi:10.1039/D1DT01302E

CCDC 1994846: Experimental Crystal Structure Determination

Related Article: Javier Pitarch-Jarque, Hermas R. Jiménez, Elina Kalenius, Salvador Blasco, Alberto Lopera, M. Paz Clares, Kari Rissanen, Enrique García-España|2021|Dalton Trans.|50|9010|doi:10.1039/D1DT01302E

CCDC 1953933: Experimental Crystal Structure Determination

Related Article: Alberto Lopera, Ariadna Gil-Martínez, Javier Pitarch-Jarque, Begoña Verdejo, Salvador Blasco, M. Paz Clares, Hermas R. Jiménez, Enrique García-España|2020|Dalton Trans.|49|8614|doi:10.1039/D0DT01056A