Modulation of DNA binding by reversible metal-controlled molecular reorganizations of scorpiand-like ligands.
DNA interaction with scorpiand azamacrocycles has been achieved through modulation of their binding affinities. Studies performed with different experimental techniques provided evidence that pH or metal-driven molecular reorganizations of these ligands regulate their ability to interact with calf thymus DNA (ctDNA) through an intercalative mode. Interestingly enough, metal-driven molecular reorganizations serve to increase or decrease the biological activities of these compounds significantly.
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, …
Metal Complexes as Receptors
The role played by metal complexes as receptors of different substrates is discussed. For this purpose, several relevant examples of the work performed by different research groups have been briefly discussed. The metal complexes have been organized attending to the molecular topology of the ligands employed. The article ends with the description of metallocages in which at least one of the metal ions constituting the cage framework binds the guest through coordinative bonds.
Ditopic Aza-Scorpiand Ligands Interact Selectively with ds-RNA and Modulate the Interaction upon Formation of Zn2+ Complexes
Nucleic acids are essential biomolecules in living systems and represent one of the main targets of chemists, biophysics, biologists, and nanotechnologists. New small molecules are continuously developed to target the duplex (ds) structure of DNA and, most recently, RNA to be used as therapeutics and/or biological tools. Stimuli-triggered systems can promote and hamper the interaction to biomolecules through external stimuli such as light and metal coordination. In this work, we report on the interaction with ds-DNA and ds-RNA of two aza-macrocycles able to coordinate Zn2+ metal ions and form binuclear complexes. The interaction of the aza-macrocycles and the Zn2+ metal complexes with duple…
In vitro activity of scorpiand-like azamacrocycle derivatives in promastigotes and intracellular amastigotes of Leishmania infantum and Leishmania braziliensis.
The activity of a family scorpiand-like azamacrocycles against Leishmania infantum and Leishmania braziliensis was studied using promastigotes, axenic and intracellular amastigotes forms. All the compounds are more active and less toxic than meglumine antimoniate (Glucantime). Moreover, the data on infection rates and amastigotes showed that compounds P2Py, PN and P3Py are the most active against both species of Leishmania. On the other hand, studies on the inhibitory effect of these compounds on SOD enzymes showed that while the inhibition of the Fe-SOD enzyme of the promastigote forms of the parasites is remarkable, the inhibition of human CuZn-SOD and Mn-SOD from Escherichia coli is negl…
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.
Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C—H Bonds with Stereoretention
An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [FeII(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol-1) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tande…
Dramatic selectivity differences in the association of DNA and RNA models with new ethylene- and propylene diamine derivatives and their copper complexes.
The affinities of polyamines consisting of ethylenediamine units equipped with either one or two terminal naphthyl-, anthryl-, or acridyl units towards PolyA.PolyU as an RNA model, and Poly(dA).Poly(dT) as a DNA model are screened by measuring the melting point changes (DeltaT(m)) of the double strands, and also partially by a fluorimetric binding assay using ethidium bromide. The larger aromatic moieties with long spacers between them allow bisintercalation; this leads to an increased preference for DNA in comparison to RNA, where ion pairing of the ammonium centers with the major RNA groove phosphates dominates. Allosteric affinity control by metalation is achieved e.g. with Cu(2+) ions, …
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
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…
A Metal-Based Receptor for Selective Coordination and Fluorescent Sensing of Chloride
A scorpionate Zn2+ complex, constituted by a macrocyclic pyridinophane core attached to a pendant arm containing a fluorescent pyridyl-oxadiazole-phenyl unit (PyPD), has been shown to selectively recognize chloride anions, giving rise to changes in fluorescence emission that are clearly visible under a 365 nm UV lamp. This recognition event has been studied by means of absorption, fluorescence, and NMR spectroscopy, and it involves the intramolecular displacement of the PyPD unit by chloride anions. Moreover, since the chromophore is not removed from the system after the recognition event, the fluorescence can readily be restored by elimination of the bound chloride anion.
Thermodynamic and kinetic studies on the Cu2+ coordination chemistry of a novel binucleating pyridinophane ligandElectronic supplementary information (ESI) available: Table S1: observed rate constants for the acid-promoted decomposition of Cu2+ complexes with ligand L. Table S2: observed rate constants for the acid-promoted decomposition of Cu2+ complexes with macrocycle L1. Fig. S1: Variation of some selected 13C chemical shifts as a function of pH. See http://www.rsc.org/suppdata/dt/b2/b209013a/
The synthesis and coordination chemistry of the novel pyridine-functionalized ligand 2,6,9,12,16-pentaaza[17]-(2,6)pyridinophane (L1) is described. The compound behaves as a hexaprotic base in aqueous solution. NMR studies indicate a protonation pattern in which the sp2 pyridine nitrogen (N(py)) does not undergo a net protonation although it is involved in formation of hydrogen bonds. L1 forms mono and binuclear hydroxylated complexes. The crystal structure of [CuL1](ClO4)2 shows a square planar coordination for Cu2+ with the pyridine and the three central nitrogens of the chain forming the vertices of the square. The benzylic nitrogens could be occupying the axial positions of a strongly a…
Hydrogen and copper ion-induced molecular reorganizations in scorpionand-like ligands. A potentiometric, mechanistic, and solid-state study.
Two aza scorpionand-like macrocycles (L2 and L3) have been prepared. L2 consists of a tren amine with two of its arms cyclizized with a 2,6-bis(bromomethyl)pyridine. In L3, the remaining pendant arm has been further functionalized with a fluorophoric naphthalene group. X-ray data on the compounds [H(L3)]ClO4.H2O (1) and [H3(L3)](H2PO4)3.H2O (2) as well as solution studies (pH-metry, UV-vis, and fluorescence data) show the movement of the pendant arm as a result of the protonation degree of the macrocycles and of the formation of intramolecular hydrogen bonds. X-ray data on the complexes [Cu(L2)](ClO4)2]2.H2O (3) and [Cu(L3)](ClO4)2 (4) and solution studies on Cu2+ coordination show the impl…
Pb2+complexes of small-cavity azamacrocyclic ligands: thermodynamic and kinetic studies
The synthesis, acid-base behavior and Pb2+ coordination chemistry of the new aza-scorpiand like ligand 5-[2-(N-2-fluorenyl)ethylamino]-2,5,8-triaza[9]-2,6-pyridinophane (L1) have been studied by potentiometry, NMR and spectrofluorimetric titrations, and the results are compared with those obtained for the related compounds L2, lacking the fluorenyl group, and L3, the macrocycle lacking the pendant arm. The crystal structures obtained for complexes [PbL1][PbL1Cl](NO3)Cl2·4H2O (1) and [PbL3](ClO4)2 (2) reveal that the metal ion is located over the plane defined by the nitrogen atoms of the macrocyclic core due to its inability to accommodate the large Pb2+ ion in the macrocyclic cavity. For L…
A tetraazahydroxypyridinone derivative as inhibitor of apple juice enzymatic browning and oxidation
Abstract Enzymatic browning in fruits and vegetables can produce undesirable colour changes and adversely affect the taste, flavour, and nutritional value. This fact poses a challenge to the food industry to apply appropriate inhibitors to control enzymatic browning to maintain food quality. Accordingly, this study aims to evaluate the effect of small mazamacrocyclic compounds modified with a hydroxypyridinone similar to kojic acid on enzymatic browning, total polyphenols and antioxidant activity in apple juice. The results showed how these compounds interact with the tyrosinase enzyme in a complex interaction inhibiting its activity. The hydroxypyridinone attached to the macrocycle (I1) wa…
Hydrogen and Copper Ion Induced Molecular Reorganizations in Two New Scorpiand-Like Ligands Appended with Pyridine Rings
The synthesis of two new ligands constituted of a tris(2-aminoethyl)amine moiety linked to the 2,6 positions of a pyridine spacer through methylene groups in which the hanging arm is further functionalized with a 2-pycolyl (L1) or 3-pycolyl (L2) group is presented. The protonation of L1 and L2 and formation of Cu(2+) complexes have been studied using potentiometric, NMR, X-ray, and kinetic experiments. The results provide new information about the relevance of molecular movements in the chemistry of this kind of so-called scorpiand ligand. The comparison between these two ligands that only differ in the position of the substituent at the arm reveals important differences in both thermodynam…
Heterocyclic Diamines with Leishmanicidal Activity.
Leishmaniasis is one of the world's most neglected diseases with a worldwide prevalence of 12 million people. There are no effective human vaccines for its prevention, and outdated drugs hamper treatment. Therefore, research aimed at developing new therapeutic tools to fight leishmaniasis remains a crucial goal today. With this purpose in mind, here, we present 10 new compounds made up by linking alkylated ethylenediamine units to pyridine or quinoline heterocycles with promising in vitro and in vivo efficacy against promastigote and amastigote forms of Leishmania infantum, Leishmania donovani, and Leishmania braziliensis species. Three compounds (2, 4, and 5) showed a selectivity index muc…
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…
Cation and anion recognition characteristics of open-chain polyamines containing ethylenic and propylenic chains
Abstract The interaction of the polyamines 4,7,10,13-tetraazahexadecane-1,16-diamine (L1) and 4,7,10-triazatridecane-1,13-diamine (L2) with H + , Cu 2+ , Zn 2+ , Co 2+ and the nucleotides ATP, ADP and AMP has been followed by NMR and potentiometric studies performed at 298.1 K in 0.15 mol dm −3 NaClO 4 . The influence of the different sequences of hydrocarbon chains and chelate rings present in the ligands on the values of the protonation constants, the stability of the metal ion complexes as well as in the co-ordination to nucleotides is analysed. The formation of mixed complexes has been investigated for the system Cu 2+ –L1–AMP.
Molecular Rearrangement of an Aza-Scorpiand Macrocycle Induced by pH: A Computational Study †
Rearrangements and their control are a hot topic in supramolecular chemistry due to the possibilities that these phenomena open in the design of synthetic receptors and molecular machines. Macrocycle aza-scorpiands constitute an interesting system that can reorganize their spatial structure depending on pH variations or the presence of metal cations. In this study, the relative stabilities of these conformations were predicted computationally by semi-empirical and density functional theory approximations, and the reorganization from closed to open conformations was simulated by using the Monte Carlo multiple minimum method Financial support by the Spanish Ministerio de Economía y Competitiv…
Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.
The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows …
Cu2+ Coordination Properties of a 2-Pyridine Heptaamine Tripod: Characterization and Binding Mechanism
The synthesis, protonation, and Cu(2+) coordination chemistry of a tripodal heptaamine ligand (L(1)) functionalized with 2-pyridine fragments at the ends of its three branches are reported. L(1) presents six relatively high protonation constants followed by much more reduced constant that as indicated by the UV-vis and NMR data, occur on the pyridine fragments. p[H]-metric, ESI/MS(+), EPR and UV-vis data show that L(1) is able to form mono-, di-, and trinuclear Cu(2+) complexes. Slippage movements and molecular reorganizations have been observed to occur as a function of p[H] in the 1:1 Cu(2+) complexes. The kinetic studies showed that the complex formation is fast and proceeds through a di…
<strong>Synthesis and Platinum (II) Complexes of Different Polyazacyclophane Receptors</strong>
During the last years, research on coordination chemistry of platinum has aroused great interest due to their potential biological applications. Herein, we report the interaction of PtCI42- with different polyazacyclophanes containing a pyridine unit as aromatic spacer. Formation of complexes has been studied by 1H and 195Pt NMR spectroscopy. Analysis of the recorded spectra of D2O solutions containing L and PtCl42- in a 1:1 molar ratio at acidic pH shows the evolution with time of the 1H and 195Pt signals. Different crystal structures have been solved by X-ray diffraction analysis. At acidic pHs, the metal ion is coordinated by the central amino group of the macrocyclic cavity and three ch…
Synthesis and Cu(II) coordination of two new hexaamines containing alternated propylenic and ethylenic chains: Kinetic studies on pH-driven metal ion slippage movements
Abstract The synthesis of the open-chain and cyclic polyamines, 1,5,8,12,15,19-hexaazaheptadecane (L1) and 2,6,9,13,16,20-hexaaza[21]-(2,6)-pyridinophane (L2), are described. The protonation constants and interaction constants with Cu(II) have been determined by potentiometric measurements carried out at 298.1 K in 0.15 mol dm −3 NaClO 4 . The values obtained are discussed as a function of the open-chain or cyclic nature of the ligands and compared with analogous polyamines containing different sets of hydrocarbon chains between the nitrogen donors. Kinetic studies on the acid-promoted dissociation of the Cu(II) complexes indicate that the mono and binuclear complexes of L1 decompose with d…
Equilibrium and Kinetic Properties of Cu II Cyclophane Complexes: The Effect of Changes in the Macrocyclic Cavity Caused by Changes in the Substitution at the Aromatic Ring
The o-B232, m-B232 and p-B232 cyclophanes result from attaching the terminal amine groups of 1,4,8,11-tetraazaundecane (232) to the benzylic carbons of the corresponding o-, m- or p-xylanes. The cavity size of these cyclophanes changes moderately as a consequence of the substitution at the aromatic ring. The effects caused by these changes on the equilibrium constants for protonation and CuII complex formation of the cyclophanes are analyzed and compared with those of the noncyclic 232 polyamine. All three cyclophanes form mononuclear complexes, but only o-B232 is able to coordinate to CuII through the four amine groups simultaneously, whereas m-B232 and p-B232 can only use three nitrogen d…
CO2 Fixation by Cu2+ and Zn2+ complexes of a terpyridinophane aza receptor. Crystal structures of Cu2+ complexes, pH-metric, spectroscopic, and electrochemical studies.
The synthesis of the terpyridinophane-type polyamine 2,6,9,12,16-pentaaza[17]-(5,5' ')-cyclo-(2,2':6',2' ')-terpyridinophane heptahydrobromide tetrahydrate (L.7HBr.4H2O) is described. L presents six protonation constants with values in the range 9.21-3.27 logarithmic units. L interacts with Cu2+ and Zn2+ forming in both cases, neutral, protonated, and hydroxylated mono- and binuclear complexes whose constants have been calculated by potentiometry in 0.15 M NaClO4 at 298.1 K. The crystal structures of the compounds [Cu(HL-carb)(H2O)](ClO4)3.2H2O (1) and [Cu2(H2L)(CO3)]2(ClO4)8.9H2O (2) have been solved by X-ray diffraction. In 1, the metal center presents square pyramidal geometry. The base …
A thermodynamic insight into the recognition of hydrophilic and hydrophobic amino acids in pure water by aza-scorpiand type receptors.
Interactions of different hydrophilic (His, Asp, Glu,) and hydrophobic (Ala, Phe, Tyr, Trp) amino acids in water with a scorpiand aza-macrocycle (L1) containing a pyridine group in the ring and its derivative (L2) bearing a naphthalene group in the tail have been analysed by potentiometric and calorimetric measurements. Theoretical calculations corroborate that major attractive forces that hold the adduct together are hydrogen bonds and salt-bridges, even though other interactions such as π-stacking or NH(+)⋯π may contribute in the case of hydrophobic amino acids and L2. Calorimetric measurements indicate that the interactions between L1 and the different amino acids are principally driven …
Hydrogen-ion driven molecular motions in Cu2+-complexes of a ditopic phenanthrolinophane ligand
One of the first kinetic evaluations of a metal ion interchange between the two coordination sites of a ditopic macrocycle is presented. Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es ; Soriano Soto, Concepción, Concepcion.Soriano@uv.es ; Verdejo Viu, Begoña, Begona.Verdejo@uv.es
CO2 Fixation by Copper(II) Complexes of a Terpyridinophane Aza Receptor
CO2 is fixed by a Cu2+ complex of a macrocyclic terpyridinophane ligand forming a carbamate group. Several features of the structure mimic the enzyme rubisco.
Synthesis, Protonation and Cu II Complexes of Two Novel Isomeric Pentaazacyclophane Ligands: Potentiometric, DFT, Kinetic and AMP Recognition Studies
The synthesis and coordination chemistry of two novel ligands, 2,6,9,12,16-pentaaza[17]metacyclophane (L1) and 2,6,9,12,16-pentaaza[17]paracyclophane (L2), is described. Potentiometric studies indicate that L1 and L2 form a variety of mononuclear complexes the stability constants of which reveal a change in the denticity of the ligand when moving from L1 to L2, a behaviour that can be qualitatively explained by the inability of the paracyclophanes to simultaneously use both benzylic nitrogen atoms for coordination to a single metal centre. In contrast, the formation of dinuclear hydroxylated complexes is more favoured for the paraL2 ligand. DFT calculations have been carried out to compare …
Inhibitory Effect of Azamacrocyclic Ligands on Polyphenol Oxidase in Model and Food Systems
[EN] Enzymatic browning is one of the main problems faced by the food industry due to the enzyme polyphenol oxidase (PPO) provoking an undesirable color change in the presence of oxygen. Here, we report the evaluation of 10 different azamacrocyclic compounds with diverse morphologies as potential inhibitors against the activity of PPO, both in model and real systems. An initial screening of 10 ligands shows that all azamacrocyclic compounds inhibit to some extent the enzymatic browning, but the molecular structure plays a crucial role on the power of inhibition. Kinetic studies of the most active ligand (L2) reveal a S-parabolic I-parabolic noncompetitive inhibition mechanism and a remarkab…
Equilibrium, Kinetic, and Computational Studies on the Formation of Cu2+ and Zn2+ Complexes with an Indazole-Containing Azamacrocyclic Scorpiand: Evidence for Metal-Induced Tautomerism
Cu(2+) and Zn(2+) coordination chemistry of a new member of the family of scorpiand-like macrocyclic ligands derived from tris(2-aminoethyl)amine (tren) is reported. The new ligand (L1) contains in its pendant arm not only the amine group derived from tren but also a 6-indazole ring. Potentiometric studies allow the determination of four protonation constants. UV-vis and fluorescence data support that the last protonation step occurs on the indazole group. Equilibrium measurements in the presence of Cu(2+) and Zn(2+) reveal the formation of stable [ML1](2+), [MHL1](3+), and [ML1(OH)](+) complexes. Kinetic studies on the acid-promoted decomposition of the metal complexes were carried out usi…
Tritopic phenanthroline and pyridine tail-tied aza-scorpiands
The synthesis of two new tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties have been linked with 2,6-dimethylpyridine (L1) or 2,9-dimethylphenanthroline (L2) units is reported for the first time. Their acid-base behaviour and Zn(2+) coordination chemistry have been studied by pH-metric titrations, molecular dynamic calculations, NMR, UV-Vis and steady-state fluorescence techniques. L1 and L2 behave, respectively, as hexaprotic and heptaprotic bases in the experimental conditions used (298.1 +/- 0.1 K, 0.15 mol dm(-3) NaCl, pH range under study 2.0-11.0). These ligands are able to form mono-, bi- and trinuclear Zn(2+) co…
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…
About the relevance of anion-π interactions in water.
Anion-π interactions are emerging as exotic features with potential applications in chemistry. In the last years, their relevance in living systems has been outlined, and so far there is no concluding significant evidence recognized about the participation of anion-π interactions in water because anion-π sensors contain large aromatic hydrophobic surfaces with limited solubility. By transforming a neutral heterocycle (for example quinoline) into its corresponding salt (quinolinium), we have been able to overcome these solubility issues, and new cationic water-soluble fluorophores have been prepared. Herein, we used N-alkylated heterocycles as π-acidic surfaces to shed light on the nature of…
Manganese(II) complexes of scorpiand-like azamacrocycles as MnSOD mimics.
Mn(II) complexes of scorpiand-type azamacrocycles constituted by a tretrazapyridinophane core appended with an ethylamino tail including 2- or 4-quinoline functionalities show very appealing in vitro SOD activity. The observed behaviour is related to structural and electrochemical parameters.
Stability and kinetics of the acid-promoted decomposition of Cu(II) complexes with hexaazacyclophanes: kinetic studies as a probe to detect changes in the coordination mode of the macrocycles.
The synthesis, protonation and Cu(II) coordination features of the novel azacyclophane type receptors 2,6,10,13,17,21-hexaza[22]-(2,6)-pyridinophane (L2), 2,6,9,12,15,19-hexaza[20]-(2,6)-pyridinophane (L5) and 2,6,9,12,15,19-hexaza[20]metacyclophane (L6) are presented. The protonation and Cu(II) constants are analysed and compared with the previously reported open-chain polyamines 4,8,11,15-tetrazaoctadecane-1,18-diamine (L1) and 4,7,10,13-tetraazahexadecane-1,16-diamine (L4) and of the cyclophane 2,6,10,13,17,21-hexaaza[22]paracyclophane (L3). All the systems form mono- and dinuclear complexes whose stability and pH range of existence depend on the type of hydrocarbon chains and molecular …
Stabilization of polyiodide networks with Cu(ii) complexes of small methylated polyazacyclophanes: shifting directional control from H-bonds to I⋯I interactions
Ordered polyiodide networks have recently gathered considerable attention as electronic materials, a topic historically dominated by metals. Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials? Herein we present a first principles study featuring three analogous polyazacyclophanes (L, L-Me, L-Me3), differing only in the extent of N-methylation. We demonstrate (potentiometry, ITC) how they all form the same CuL2+ (L = L, L-Me, L-Me3) complex as prevalent species in solution, so that a level playing field exists where only N-methylation distinguishes them. Then we use them as count…
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…
Extended structures of copper(II) complexes with 2-di1H-2-imidazolylmethylmalonate (DIMMAL), a versatile bis(imidazole)–bis(carboxylate) ligand: Solution studies, crystal structures and spectroscopic characterization
Abstract Copper(II) complexes of 2-di1H-2-imidazolylmethylmalonate (DIMMAL) have been studied by potentiometric methods. The data revealed that the CuHL 2 - and CuL 2 2 - species are prevalent in the studied pH range. Moreover, this paper reports the synthesis, structure solution and spectroscopic characterization of two new DIMMAL containing complexes, (NH4)2[Cu(DIMMAL)2] · 4H2O (1) and [Cu(DIMMAL)(en)(H2O)] · 5H2O (2). The structure of compound 1 consists of centrosymmetric mononuclear anionic [Cu(DIMMAL)2]2− units, NH 4 + cations and lattice water molecules, in which DIMMAL2− acts as a tridentate ligand through two imidazole nitrogen atoms and one oxygen atom from a carboxylate group. Th…
Hybrid GMP–polyamine hydrogels as new biocompatible materials for drug encapsulation
Here we present the preparation and characterization of new biocompatible materials for drug encapsulation. These new gels are based on positively charged [1+1] 1H-pyrazole-based azamacrocycles which minimise the electrostatic repulsions between the negatively charged GMP molecules. Rheological measurements confirm the electroneutral hydrogel structure as the most stable for all the GMP-polyamine systems. Nuclear magnetic resonance (NMR) was employed to investigate the kinetics of the hydrogel formation and cryo-scanning electron microscopy (cryo-SEM) was used to obtain information about the hydrogel morphology, which exhibited a non-homogeneous structure with a high degree of cross-linking…
Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics
Two polytopic aza-scorpiand-like ligands, 6-[7-(diaminoethyl)-3,7-diazaheptyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L1) and 6-[6′-[3,6,9-triaza-1-(2,6-pyridina)cyclodecaphan-6-yl]-3-azahexyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L2), have been synthesized. The acid–base behavior and Cu2+, Zn2+, and Cu2+/Zn2+ mixed coordination have been analyzed by potentiometry, cyclic voltammetry, and UV–vis spectroscopy. The resolution of the crystal structures of [Cu2L2Cl2](ClO4)2·1.67H2O (1), [Cu2HL2Br2](ClO4)3·1.5H2O (2), and [CuZnL2Cl2](ClO4)2·1.64H2O (3) shows, in agreement with the solution data, the formation of homobinuclear Cu2+/Cu2+ and heterobinuclear Cu2+/Zn2+ complexes. The m…
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 1939485: Experimental Crystal Structure Determination
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CCDC 1990725: Experimental Crystal Structure Determination
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CCDC 1446018: Experimental Crystal Structure Determination
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CCDC 2017311: Experimental Crystal Structure Determination
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