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1.
Org Biomol Chem ; 21(26): 5424-5432, 2023 07 05.
Artículo en Inglés | MEDLINE | ID: mdl-37335019

RESUMEN

The synthesis, acid-base behaviour and anion recognition of neurotransmitters (dopamine, tyramine and serotonin) in aqueous solution of different aza-scorpiand ligands functionalized with hydroxyphenyl and phenyl moieties (L1-L3 and L4, respectively) have been studied by potentiometry, NMR, UV-Vis and fluorescence spectroscopy and isothermal titration calorimetry (ITC). The analysis of the potentiometric results shows the selective recognition of serotonin at physiological pH (Keff = 8.64 × 104) by L1. This selectivity has an entropic origin probably coming from a fine pre-organization of the interacting partners. Thus, the complementarity of the receptor and the substrate allows the reciprocal formation of hydrogen bonds, π-π and cation-π interactions, stabilizing the receptors and slowing the rate of oxidative degradation, and satisfactory results are obtained at acidic and neutral pH values. NMR and molecular dynamics studies reveal the rotation blockage in the neurotransmitter side chain once complexed with L1.


Asunto(s)
Serotonina , Agua , Ligandos , Agua/química , Aniones/química , Oxidación-Reducción
2.
Molecules ; 28(22)2023 Nov 20.
Artículo en Inglés | MEDLINE | ID: mdl-38005400

RESUMEN

Antibiotic resistance is now a first-order health problem, which makes the development of new families of antimicrobials imperative. These compounds should ideally be inexpensive, readily available, highly active, and non-toxic. Here, we present the results of our investigation regarding the antimicrobial activity of a series of natural and synthetic polyamines with different architectures (linear, tripodal, and macrocyclic) and their derivatives with the oxygen-containing aromatic functional groups 1,3-benzodioxol, ortho/para phenol, or 2,3-dihydrobenzofuran. The new compounds were prepared through an inexpensive process, and their activity was tested against selected strains of yeast, as well as Gram-positive and Gram-negative bacteria. In all cases, the conjugated derivatives showed antimicrobial activity higher than the unsubstituted polyamines. Several factors, such as the overall charge at physiological pH, lipophilicity, and the topology of the polyamine scaffold were relevant to their activity. The nature of the lipophilic moiety was also a determinant of human cell toxicity. The lead compounds were found to be bactericidal and fungistatic, and they were synergic with the commercial antifungals fluconazole, cycloheximide, and amphotericin B against the yeast strains tested.


Asunto(s)
Antibacterianos , Antiinfecciosos , Humanos , Antibacterianos/farmacología , Antibacterianos/química , Poliaminas/farmacología , Poliaminas/química , Saccharomyces cerevisiae , Bacterias Gramnegativas , Bacterias Grampositivas , Antiinfecciosos/farmacología , Antiinfecciosos/química , Pruebas de Sensibilidad Microbiana
3.
Inorg Chem ; 61(1): 368-383, 2022 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-34933551

RESUMEN

Polyiodide networks are currently of great practical interest for the preparation of new electronic materials. The participation of metals in the formation of these networks is believed to improve their mechanical performance and thermal stability. Here we report the results on the construction of polyiodide networks obtained using Cu(II) complexes of a series of pyridinol-based tetraazacyclophanes as countercations. The assembly of these crystalline polyiodides takes place from aqueous solutions on the basis of similar structural elements, the [CuL]2+ and [Cu(H-1L)]+ (L = L2, L2-Me, L2-Me3) complex cations, so that the peculiarities induced by the increase of N-methylation of ligands, the structural variable of ligands, can be highlighted. First, solution equilibria involving ligands and complexes were analyzed (potentiometry, NMR, UV-vis, ITC). Then, the appropriate conditions could be selected to prepare polyiodides based on the above complex cations. Single-crystal XRD analysis showed that the coordination of pyridinol units to two metal ions is a prime feature of these ligands, leading to polymeric coordination chains of general formula {[Cu(H-1L)]}nn+ (L = L2-Me, L2-Me3). In the presence of the I-/I2 couple, the polymerization tendency stops with the formation of [(CuL)(CuH-1L)]3+ (L = L2-Me, L2-Me3) dimers which are surrounded by polyiodide networks. Moreover, coordination of the pyridinol group to two metal ions transforms the surface charge of the ring from negative to markedly positive, generating a suitable environment for the assembly of polyiodide anions, while N-methylation shifts the directional control of the assembly from H-bonds to I···I interactions. In fact, an extended concatenation of iodine atoms occurs around the complex dimeric cations, the supramolecular I···I interactions become shorter and shorter, fading into stronger forces dominated by the orbital overlap, which is promising for effective electronic materials.

4.
Inorg Chem ; 61(30): 11592-11599, 2022 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-35857283

RESUMEN

A unique V-shaped "chiral" supramolecular scaffold, N-(4-pyridyl)-4-amino-1,8-naphthalimide Tröger's base (TBNap), was synthesized in good yield from a precursor N-(4-pyridyl)-4-amino-1,8-naphthalimide (Nap). TBNap was characterized using different spectroscopic methods and the molecular structure was elucidated by diffraction analysis. A new p-cymene-Ru(II)-curcumin conjugate (TB-Ru-Cur) was designed by reacting TBNap dipyridyl donor and ruthenium-curcuminato acceptor [RuCur = (p-cymene)Ru-(curcuminato)Cl] in the presence of silver triflate. TB-Ru-Cur was isolated in quantitative yield and characterized using Fourier transform infrared (FT-IR), NMR (1H, 13C, and 19F), and electrospray ionization mass spectrometry (ESI-MS), and the molecular structure has been predicted using a computational study. Both TBNap and TB-Ru-Cur exhibited intramolecular charge transfer (ICT)-based fluorescence emission. Furthermore, the anticancer properties of TBNap, Ru-Cur, and TB-Ru-Cur were assessed in different cancer cell lines. Gratifyingly, the conjugate TB-Ru-Cur displayed fast-cellular internalization and good cytotoxicity against HeLa, HCT-116, and HepG2 cancer cells and the estimated IC50 value was much lower than that of the precursors (TBNap and Ru-Cur) and the well-known chemotherapeutic drug cisplatin.


Asunto(s)
Antineoplásicos , Complejos de Coordinación , Curcumina , Rutenio , 1-Naftilamina/análogos & derivados , Antineoplásicos/química , Línea Celular Tumoral , Complejos de Coordinación/química , Curcumina/química , Curcumina/farmacología , Cimenos , Humanos , Naftalimidas , Quinolonas , Rutenio/química , Rutenio/farmacología , Espectroscopía Infrarroja por Transformada de Fourier
5.
Inorg Chem ; 61(4): 1982-1996, 2022 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-35034445

RESUMEN

The work represents a rare example of an aza-crown-based macrocyclic chemosensor, H2DTC (H2DTC = 1,16-dihydroxy-tetraaza-30-crown-8) for the selective detection of both Zn2+ and Cu2+ in HEPES buffer medium (pH 7.4). H2DTC exhibits a fluorescence response for both Zn2+ and Cu2+ ions. The reversibility of the chemosensor in its binding with Zn2+ and Cu2+ ions is also examined using a Na2EDTA solution. H2DTC exhibits a chelation-enhanced fluorescence (CHEF) effect in the presence of Zn2+ ions and a quenching effect (CHEQ) in the presence of paramagnetic Cu2+ ions. Furthermore, the geometry and spectral properties of H2DTC and the chemosensor bound to Zn2+ have been studied by DFT and TDDFT calculations. The limit of detection (LOD) values are 0.11 × 10-9 and 0.27 × 10-9 M for Cu2+ and Zn2+, respectively. The formation constants for the Zn2+ and Cu2+ complexes have been measured by pH-potentiometry in 0.15 M NaCl in 70:30 (v:v) water:ethanol at 298.1 K. UV-vis absorption and fluorometric spectral data and pH-potentiometric titrations indicate 1:1 and 2:1 metal:chemosensor species. In the solid state H2DTC is able to accommodate up to four metal ions, as proved by the crystal structures of the complexes [Zn4(DTC)(OH)2(NO3)4] (1) and {[Cu4(DTC)(OCH3)2(NO3)4]·H2O}n (2). H2DTC can be used as a potential chemosensor for monitoring Zn2+ and Cu2+ ions in biological and environmental media with outstanding accuracy and precision. The propensity of H2DTC to detect intracellular Cu2+ and Zn2+ ions in the triple negative human breast cancer cell line MDA-MB-468 and in HeLa cells has been determined by fluorescence cell imaging.


Asunto(s)
Fluorescencia
6.
Inorg Chem ; 59(10): 7306-7317, 2020 May 18.
Artículo en Inglés | MEDLINE | ID: mdl-32379437

RESUMEN

We report the synthesis and characterization of the macrocyclic ligand 2,2'-((2-(3,9-bis(carboxymethyl)-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane-6-yl)ethyl)azanediyl)diacetic acid (H4L) and several of its complexes with lanthanide ions. The structure of the free ligand was determined using X-ray diffraction measurements. Two N atoms of the pyclen moiety in the trans position are protonated in the solid state, together with the exocyclic N atom and one of the carboxylate groups of the ligand. The relaxivity of the Gd3+ complex was found to increase from 6.7 mM-1 s-1 at pH 8.6 to 8.5 mM-1 s-1 below pH ≈ 6.0. Luminescence lifetime measurements recorded from H2O and D2O solutions of the Eu3+ complex evidence the presence of a single complex species in solution at low pH (∼5.0) that contains two inner-sphere water molecules. DFT calculations suggest that the coordination environment of the Ln3+ ion is fulfilled by the four N atoms of the pyclen unit, two oxygen atoms of the macrocyclic acetate groups, and an oxygen atom of an exocyclic carboxylate group. The two inner-sphere water molecules complete coordination number nine around the metal ion. At high pH (∼9.3), the lifetime of the excited 5D0 level of Eu3+ displays a biexponential behavior that can be attributed to the presence of two species in solution with hydration numbers of q = 0 and q = 1. The 1H NMR and DOSY spectra recorded from solutions of the Eu3+ and Y3+ complexes reveal a structural change triggered by pH and the formation of small aggregates at high pH values.

7.
Chem Soc Rev ; 46(24): 7706-7756, 2017 Dec 11.
Artículo en Inglés | MEDLINE | ID: mdl-29177281

RESUMEN

Ruthenium(ii) [Ru(ii)] polypyridyl complexes have been the focus of intense investigations since work began exploring their supramolecular interactions with DNA. In recent years, there have been considerable efforts to translate this solution-based research into a biological environment with the intention of developing new classes of probes, luminescent imaging agents, therapeutics and theranostics. In only 10 years the field has expanded with diverse applications for these complexes as imaging agents and promising candidates for therapeutics. In light of these efforts this review exclusively focuses on the developments of these complexes in biological systems, both in cells and in vivo, and hopes to communicate to readers the diversity of applications within which these complexes have found use, as well as new insights gained along the way and challenges that researchers in this field still face.


Asunto(s)
Complejos de Coordinación/farmacocinética , Piridinas/farmacocinética , Rutenio/farmacocinética , Línea Celular , Complejos de Coordinación/síntesis química , Complejos de Coordinación/química , Humanos , Estructura Molecular , Piridinas/química , Rutenio/química
8.
Inorg Chem ; 56(8): 4400-4412, 2017 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-28338318

RESUMEN

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 spectra, respectively. The formation rate of [Fe(H-2L)]2+ in aqueous solutions containing Fe2+ and L (1:1 molar ratio) is strongly dependent on the pH, the process being completed in times that range from months in acid solutions to hours in basic conditions. However, detailed kinetic studies show that those differences are caused, at least in part, by the effect of pH on the rate of formation of the unoxidized [FeL]2+ complex. In this sense, the protonation of the donor atoms in the pendant arm of the scorpiand ligand leads to the formation of protonated species resistant to oxidative dehydrogenation. Complementary studies in acetonitrile solution indicate that the initial stage in the oxidative dehydrogenation process is the oxidation of the starting complex to form a [FeL]3+ complex, which then undergoes disproportionation into [Fe(H-2L)]2+ and [FeL]2+. Experiments starting with Fe(III) have allowed us to determine that disproportionation occurs with first order kinetics both in water and acetonitrile solutions. However, whereas a significant acceleration is observed in water when the pH is increased, no effect of the addition of acid or base on the rate of disproportionation is observed in acetonitrile. Oxidative dehydrogenation of the Fe(II) complex formed in experiments starting with an Fe(III) salt is slower than that occurring when an Fe(II) salt is used, an observation that can be explained in terms of the formation of two different Fe(III) complexes, one of them with a structure unable to evolve directly toward the product of oxidative dehydrogenation.

9.
Chemistry ; 22(28): 9709-23, 2016 Jul 04.
Artículo en Inglés | MEDLINE | ID: mdl-27258206

RESUMEN

Here we have investigated the influence of the antenna group position on both the formation of chiral amphiphilic Eu(III) -based self-assemblies in CH3 CN solution and, on the ability to form monolayers on the surface of quartz substrates using the Langmuir-Blodgett technique, by changing from the 1-naphthyl (2(R), 2(S)) to the 2-naphthyl (1(R), 1(S)) position. The evaluation of binding constants of the self- assemblies in CH3 CN solution was achieved using conventional techniques such as UV/Visible and luminescence spectroscopies along with more specific circular dichroism (CD) spectroscopy. The binding constants obtained for EuL, EuL2 and EuL3 species in the case of 2-naphthyl derivatives were comparable to those obtained for 1-naphthyl derivatives. The analysis of the changes in the CD spectra of 1(R) and 1(S) upon addition of Eu(III) not only allowed us to evaluate the values of the binding constants but the resulting recalculated spectra may also be used as fingerprints for assignment of the chiral self-assembly species formed in solution. The obtained monolayers were predominantly formed from EuL3 (≈85 %) with the minor species present in ≈15 % EuL2 .

10.
Angew Chem Int Ed Engl ; 55(31): 8938-43, 2016 07 25.
Artículo en Inglés | MEDLINE | ID: mdl-27295556

RESUMEN

We report the remarkable ability of 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) compounds 2 with appended olefin amide arms to self-template the formation of interlocked [2]catenane structures 3 in up to 50 % yield when subjected to olefin ring-closing metathesis in CH2 Cl2 . X-ray diffraction crystallography enabled the structural characterization of both the [2]catenane 3 a and the non-interlocked macrocycle 4 a. These [2]catenanes showed selective triazolyl hydrogen-bonding interactions with the tetrahedral phosphate anion when screened against a range of ions; 3 a,b are the first examples of selective [2]catenane hosts for phosphate.

11.
Org Biomol Chem ; 13(3): 843-50, 2015 Jan 21.
Artículo en Inglés | MEDLINE | ID: mdl-25406915

RESUMEN

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 by entropy, often associated with solvation/desolvation processes.


Asunto(s)
Aminoácidos/análisis , Compuestos Corona/química , Receptores Artificiales/química , Calorimetría , Compuestos Corona/síntesis química , Enlace de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Modelos Moleculares , Potenciometría , Receptores Artificiales/síntesis química , Soluciones , Termodinámica , Agua
12.
Angew Chem Int Ed Engl ; 54(15): 4566-70, 2015 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-25693755

RESUMEN

The design and synthesis of tripodal ligands 1-3 based upon the N-methyl-1,3,5-benzenetricarboxamide platform appended with three aryl urea arms is reported. This ligand platform gives rise to highly preorganized structures and is ideally suited for binding SO4 (2-) and H2 PO4 (-) ions through multiple hydrogen-bonding interactions. The solid-state crystal structures of 1-3 with SO4 (2-) show the encapsulation of a single anion within a cage structure, whereas the crystal structure of 1 with H2 PO4 (-) showed that two anions are encapsulated. We further demonstrate that ligand 4, based on the same platform but consisting of two bis-urea moieties and a single ammonium moiety, also recognizes SO4 (2-) to form a self-assembled capsule with [4:4] SO4 (2-) :4 stoichiometry in which the anions are clustered within a cavity formed by the four ligands. This is the first example of a self-sorting self-assembled capsule where four tetrahedrally arranged SO4 (2-) ions are embedded within a hydrophobic cavity.


Asunto(s)
Benzamidas/química , Fosfatos/química , Sulfatos/química , Urea/análogos & derivados , Sitios de Unión , Enlace de Hidrógeno , Ligandos , Metilación , Modelos Moleculares
13.
Chemistry ; 20(13): 3730-41, 2014 Mar 24.
Artículo en Inglés | MEDLINE | ID: mdl-24574302

RESUMEN

The detection of nucleotides is of crucial importance because they are the basic building blocks of nucleic acids. Scorpiand-based polyamine receptors functionalized with pyridine or anthracene units are able to form stable complexes with nucleotides in water, based on coulombic, π-π stacking, and hydrogen-bonding interactions. This behavior has been rationalized by means of an exploration with NMR spectroscopy and DFT calculations. Binding constants were determined by potentiometry. Fluorescence spectroscopy studies have revealed the potential of these receptors as sensors to effectively and selectively distinguish guanosine-5'-triphosphate (GTP) from adenosine-5'-triphosphate (ATP).


Asunto(s)
Adenosina Trifosfato/química , Guanosina Trifosfato/química , Nucleótidos/química , Agua/química , Enlace de Hidrógeno , Modelos Teóricos , Estructura Molecular , Resonancia Magnética Nuclear Biomolecular , Espectrometría de Fluorescencia/métodos
14.
Dalton Trans ; 2024 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-38973348

RESUMEN

The Cu2+ complexes of three [1 + 1] azacyclophane macrocycles having the 1H-pyrazole ring as the spacer and the pentaamine 1,5,8,11,15-pentaazadecane (L1) or hexaamines 1,5,8,12,15,19-hexaazanonadecane (L2) and 1,5,9,13,17,21-hexaazaheneicosane (L3) as bridges show endo- coordination of the pyrazolate bridge giving rise to discrete monomeric species. Previously reported pyrazolacyclophanes evidenced, however, exo-coordination with the formation of dimeric species of 2 : 2, 3 : 2 or even 4 : 2 Cu2+ : L stoichiometry. The complexes have been characterized in solution using potentiometric studies, UV-Vis spectroscopy, paramagnetic NMR, cyclic voltammetry and mass spectrometry. The measurements show that all three ligands have as many protonation steps in water as secondary amines are in the bridge, while they are able to form both mono- and binuclear Cu2+ species. The crystal structures of the complexes [Cu(HL1)Br]Br(1+x)(ClO4)(1-x)·yH2O (1) and [Cu2(H-1L2)Cl(ClO4)](ClO4)·H2O·C2H5OH (2) have been solved by X-ray diffraction studies. In 1 the metal ion lies at one side of the macrocyclic cavity being coordinated by one nitrogen of the pyrazolate moiety and the three consecutive nitrogen atoms of the polyamine bridge. The other nitrogen of the pyrazole ring is hydrogen-bonded to an amine group. In 2 the two metal ions are interconnected by a pyrazolate bis(monodentate) moiety and complete their coordination spheres with three amines and either a bromide or a perchlorate anion, which occupy the axial positions of distorted square pyramid geometries. Paramagnetic NMR studies of the binuclear complexes confirm the coordination pattern observed in the crystal structures. Cyclic voltamperommetry data show potentials within the adequate range to exhibit superoxide dismutase (SOD) activity. The IC50 values calculated by McCord-Fridovich enzymatic assays show that the binuclear Cu2+ complexes of L2 and L3 have SOD activities that rank amongst the highest ones reported so far.

15.
RSC Adv ; 14(28): 19787-19793, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38903672

RESUMEN

Two rhenium compounds: cis-tetrachlorotetrabenzimidazoldirhenium(iii) chloride - I and tetrabenzimidazoldioxorhenium(v) - II have been synthesized and characterized. X-ray data are presented for the new complex II. I and II show strong emission that has been used to investigate their interaction with several non-canonical DNA structures. Both compounds have a quenching effect on the fluorescence intensity upon addition of the investigated oligonucleotides; I was more selective for binding G4-than II. Association constant values obtained for I and II with G-quadruplexes reached 106 M-1, which suggests a strong interaction between both complexes and these sequences. FRET-melting assays show that I and II have a rather high level of stabilization of ckit1 and ckit2 quadruplexes. I is toxic against macrophages RAW267.7 only in high concentrations, while complex II shows no toxicity against these cells. I and II accumulate inside cells in different degrees. Molecular dynamic simulation studies have provided insights into the binding modes of II with ckit1 and ckit2 G-quadruplexes. The results obtained show the DNA binding activity of the rhenium complexes and their ability to be players in the anti-cancer fight since they can bind to non-canonical DNA forms in oncogene promoters, accumulate in some cancer cells, and influence the cancer cells microenvironment.

16.
Anal Chim Acta ; 1303: 342476, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38609256

RESUMEN

Defining the distribution of the chemical species in a multicomponent system is a task of great importance with applications in many fields. To clarify the identity and the abundance of the species that can be formed by the interaction of the components of a solution, it is fundamental to know the formation constants of those species. The determination of equilibrium constants is mainly performed through the analysis of experimental data obtained by different instrumental techniques. Among them, potentiometry is the elective technique for this purpose. As such, a survey was run within the NECTAR COST Action - Network for Equilibria and Chemical Thermodynamics Advanced Research, to identify the most used software for the analysis of potentiometric data and to highlight their strengths and weaknesses. The features and the calculation processes of each software were analyzed and rationalized, and a simulated titration dataset of a hypothetic hexaprotic acid was processed by each software to compare and discuss the optimized protonation constants. Moreover, further data analysis was also carried out on the original dataset including some systematic errors from different sources, as some calibration parameters, the total analytical concentration of reagents and ionic strength variations during titrations, to evaluate their impact on the refined parameters. Results showed that differences on the protonation constants estimated by the tested software are not significant, while some of the considered systematic errors affect results. Overall, it emerged that software commonly used suffer from many limitations, highlighting the urgency of new dedicated and modern tools. In this context, some guidelines for data generation and treatment are also given.

17.
Inorg Chem ; 52(19): 10795-803, 2013 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-24041115

RESUMEN

The synthesis of a novel cyclophane (L1) consisting of a 1H-pyrazole moiety linked through methylene groups to a 1,5,9,13-tetraazadecane chain is described. As far as we know, this is one of the first reported syntheses of a [1 + 1] condensation 1H-pyrazole azamacrocyclic ligand. The crystal structures of the complexes [Cu2(H(H(-1)L1))(H(-1)L1)](ClO4)3·3.75H2O (1) and ([Cu2(H(H(-1)L1))(0.5)(H(-1)L1)(1.5)]2(ClO4)3Br2·4.2H2O (2) show that Cu(2+) coordination leads to formation of 2:2 Cu(2+):L dinuclear dimeric complexes in which the 1H-pyrazole units lose a proton behaving as bis(monodentate) bridging ligands. Unlike previously reported complexes of [2 + 2] pyrazole azamacrocycles, the pyrazolate units in 1 are pointing outward from the macrocyclic cavity to bind the Cu(2+) ions. Inner coordination with formation of 1:1 Cu(2+):L complexes is however observed in [1 + 1] pyridine azamacrocycles as shown by the crystal structure here presented of the complex [CuL2](ClO4)2 (3). Crystals of [Cu3(H(-1)L1)2(CO3)(H2O)](ClO4)2·8H2O (4) grown by evaporating aqueous solution at pH 9 containing Cu(2+) and L1 in 3:2 molar ratio show the presence of a further Cu(2+) coordinated to the two free amine groups found in structures 1 and 2. The metal ion fills its coordination sphere capturing atmospheric CO2 as a η(1),η(2)-bidentate carbonate anion placed in the equatorial position and an axial water molecule. pH-metric data, UV-vis spectroscopic data, EPR measurements, and HR-ESI-MS data support that the outer coordination mode with formation of 2:2 dinuclear dimeric and 3:2 trinuclear complexes is preserved in aqueous solution.


Asunto(s)
Compuestos Aza/química , Dióxido de Carbono/química , Compuestos Macrocíclicos/química , Pirazoles/química , Complejos de Coordinación/síntesis química , Complejos de Coordinación/química , Cristalografía por Rayos X , Modelos Moleculares
18.
ACS Omega ; 8(8): 7479-7491, 2023 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-36873024

RESUMEN

Metal bound macrocyclic compounds found in biological systems inspired us to design and synthesize two Robson-type macrocyclic Schiff-base chemosensors, H 2 L1 (H 2 L1=1,11-dimethyl-6,16-dithia-3,9,13,19-tetraaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1,11-diol) and H 2 L2 (H 2 L2=1,11-dimethyl-6,16-dioxa-3,9,13,19-tetraaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1,11-diol). Both the chemosensors have been characterized with different spectroscopic techniques. They act as multianalyte sensor and exhibit "turn-on" fluorescence toward different metal ions in 1X PBS (Phosphate Buffered Saline) solution. In presence of Zn2+, Al3+, Cr3+ and Fe3+ ions, H 2 L1 exhibits ∼6-fold enhancement of emission intensity, while H 2 L2 shows ∼6-fold enhancement of emission intensity in the presence of Zn2+, Al3+ and Cr3+ ions. The interaction between the different metal ion and chemosensor have been examined by absorption, emission, and 1H NMR spectroscopy as well as by ESI-MS+ analysis. We have successfully isolated and solved the crystal structure of the complex [Zn(H 2 L1)(NO3)]NO3 (1) by X-ray crystallography. The crystal structure of 1 shows 1:1 metal:ligand stoichiometry and helps to understand the observed PET-Off-CHEF-On sensing mechanism. LOD values of H 2 L1 and H 2 L2 toward metal ions are found to be ∼10-8 and ∼10-7 M, respectively. Large Stokes shifts of the probes against analytes (∼100 nm) make them a suitable candidate for biological cell imaging studies. Robson type phenol based macrocyclic fluorescence sensors are very scarce in the literature. Therefore, the tuning of structural parameters as the number and nature of donor atoms, their relative locations and presence of rigid aromatic groups can lead to the design of new chemosensors, which can accommodate different charged/neutral guest(s) inside its cavity. The study of the spectroscopic properties of this type of macrocyclic ligands and their complexes might open a new avenue of chemosensors.

19.
Dalton Trans ; 52(17): 5478-5485, 2023 May 02.
Artículo en Inglés | MEDLINE | ID: mdl-37000570

RESUMEN

Metal complexes have gained a huge interest in the biomedical research in the last decade because of the access to unexplored chemical space with regards to organic molecules and to present additional functionalities to act simultaneously as diagnostic and therapeutic agents. Herein, we evaluated the interaction of two polytopic polyaza ligands and their zinc complexes with DNA and RNA by UV thermal denaturation, fluorescence and circular dichroism spectroscopic assays. The zinc coordination was investigated by X-ray diffraction and afforded the structure of the binuclear zinc complex of PYPOD. Thermal denaturation of DNA and RNA and fluorimetry analysis revealed preferential binding of the zinc-PHENPOD complexes towards GC-containing DNA in contrast to the free ligands. On the other hand, PYPOD metal complexes, compared to the free ligand, stabilized AT-based DNA (B-form) better than AU-RNA (A-form). With regards to single stranded RNA, the binuclear complex of PHENPOD and the free ligand can efficiently identify polyadenylic acid (poly A) among other RNA sequences by circular dichroism spectroscopy. The antimicrobial activity in S. aureus and E. coli bacteria showed the highest activity for the free ligands and their trinuclear zinc complexes. This work can provide valuable insights into the impact of the nuclearity of polytopic polyaza ligands in the binding to DNA/RNA and the antimicrobial effect.


Asunto(s)
Antiinfecciosos , Complejos de Coordinación , ADN de Cadena Simple , ARN/química , Complejos de Coordinación/química , Zinc/química , Ligandos , Escherichia coli , Staphylococcus aureus , ADN/química , Antiinfecciosos/química
20.
J Am Chem Soc ; 134(23): 9644-56, 2012 Jun 13.
Artículo en Inglés | MEDLINE | ID: mdl-22594493

RESUMEN

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.


Asunto(s)
Antineoplásicos/química , Antineoplásicos/farmacología , ADN/metabolismo , Sustancias Intercalantes/química , Sustancias Intercalantes/farmacología , Metales/metabolismo , Animales , Bovinos , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Dicroismo Circular , Humanos , Compuestos Macrocíclicos/química , Compuestos Macrocíclicos/farmacología , Modelos Moleculares , Neoplasias/tratamiento farmacológico , Neoplasias/metabolismo , Desnaturalización de Ácido Nucleico/efectos de los fármacos , Protones , Espectrofotometría Ultravioleta
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