RESUMO

The receptor ability of diethyl N,N'-(1,3-phenylene)dicarbamate (1) to form host-guest complexes with theophylline (TEO) and caffeine (CAF) by mechanochemistry was evaluated. The formation of the 1-TEO complex (C12H16N2O4·C7H8N4O2) was preferred and involves the conformational change of one of the ethyl carbamate groups of 1 from the endo conformation to the exo conformation to allow the formation of intermolecular interactions. The formation of an N-H...O=C hydrogen bond between 1 and TEO triggers the conformational change of 1. CAF molecules are unable to form an N-H...O=C hydrogen bond with 1, making the conformational change and, therefore, the formation of the complex impossible. Conformational change and selective binding were monitored by IR spectroscopy, solid-state 13C nuclear magnetic resonance and single-crystal X-ray diffraction. The 1-TEO complex was characterized by IR spectroscopy, solid-state 13C nuclear magnetic resonance, powder X-ray diffraction and single-crystal X-ray diffraction.

RESUMO

The mol-ecular structure of 2-ferrocenyl-2-[(2-ferrocenylethen-yl)(morpholin-4-yl)meth-yl]-1,3-di-thiol-ane, [Fe2(C5H5)2(C19H21NOS2)] or C29H31Fe2NOS2, has the ferrocenyl fragments in a trans disposition with respect to the vinyl group. One of the methyl-ene groups is disordered over two sites with occupancies of 0.782 (13):0.218 (13). In the crystal, cyclo-penta-dienyl-C-H⋯O(morpholin-yl) inter-actions feature within helical chains parallel to the c-axis direction. The chains are connected by methyl-ene- and cyclo-penta-dienyl-C-H⋯O(cyclo-penta-dien-yl) inter-actions.

RESUMO

The aim to access linked tetravanadate [V4O12]4- anion with mixed copper(II) complexes, using α-amino acids and phenanthroline-derived ligands, resulted in the formation of four copper(II) complexes [Cu(dmb)(Gly)(OH2)]2[Cu(dmb)(Gly)]2[V4O12]·9H2O (1) [Cu(dmb)(Lys)]2[V4O12]·8H2O (2), [Cu(dmp)2][V4O12]·C2H5OH·11H2O (3), and [Cu(dmp)(Gly)Cl]·2H2O (4), where dmb = 4,4'-dimethioxy-2,2'-bipyridine; Gly = glycine; Lys = lysine; and dmp = 2,9-dimethyl-1,10-phenanthroline. The [V4O12]4- anion is functionalized with mixed copper(II) units in 1 and 2; while in 3, it acts as a counterion of two [Cu(dmp)]2+ units. Compound 4 crystallized as a unit that did not incorporate the vanadium cluster. All compounds present magnetic couplings arising from Cu⋯O/Cu⋯Cu bridges. Stability studies of water-soluble 3 and 4 by UV-Vis spectroscopy in cell culture medium confirmed the robustness of 3, while 4 appears to undergo ligand scrambling over time, resulting partially in the stable species [Cu(dmp)2]+ that was also identified by electrospray ionization mass spectrometry at m/z = 479. The in vitro cytotoxicity activity of 3 and 4 was determined in six cancer cell lines; the healthy cell line COS-7 was also included for comparative purposes. MCF-7 cells were more sensitive to compound 3 with an IC50 value of 12 ± 1.2 nmol. The tested compounds did not show lipid peroxidation in the TBARS assay, ruling out a mechanism of action via reactive oxygen species formation. Both compounds inhibited cell migration at 5 µM in wound-healing assays using MCF-7, PC-3, and SKLU-1 cell lines, opening a new window to study the anti-metastatic effect of mixed vanadium-copper(II) systems.

Assuntos

RESUMO

The structure of the title Fe complex, [Fe(C5H5)2(C17H16N4O)], was determined at 130 K, and has ortho-rhom-bic (Pna21) symmetry. It is of inter-est with respect to the class of triazine heterocyclic compounds: the triazine ring is substituted by two ferrocenyl and one morpholine groups. The crystal structure features C-H⋯O and C-H⋯N non-classical hydrogen bonds.

RESUMO

A new Cu(II) paddle-wheel-like complex with 4-vinylbenzoate was synthesized using acetonitrile as the solvent. The complex was characterized by X-ray crystal diffraction, FT-IR, diffuse reflectance spectroscopy, thermogravimetric, differential scanning calorimetric, magnetic susceptibility, and electronic paramagnetic resonance analyses. The X-ray crystal diffraction analysis indicated that each copper ion was bound at an equatorial position to four oxygen atoms from the carboxylate groups of the 4-vinylbenzoate ligand in a square-based pyramidal geometry. The distance between the copper ions was 2.640(9) Å. The acetonitrile molecules were coordinated at the axial position to the copper ions. Exposure of the Cu(II) complex to humid air promoted the gradual replacement of the coordinated acetonitrile by water molecules, but the complex structure integrity remained. The EPR spectra exhibited signals attributed to the presence of a mixture of the monomeric (S = ½) and dimeric (S = 1) copper species in a possible 3:1 ratio. The magnetic studies revealed a peak at 50-100 K, which could be associated with the oxygen absorption capacity of the Cu(II)-vba complex.

RESUMO

We present the synthesis and characterization of organic Salphen compounds containing bromine substituents at the para/ortho-para positions, in their symmetric and non-symmetric versions, and describe the X-ray structure and full characterization for the new unsymmetrical varieties. We report for the first time antiproliferative activity in metal-free brominated Salphen compounds, by evaluations in four human cancer cell lines, cervix (HeLa), prostate (PC-3), lung (A549) and colon (LS 180) and one non-cancerous counterpart (ARPE-19). We assessed in vitro cell viability against controls using the MTT assay ((3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide)) and determined the concentration required for 50 % growth inhibition (IC50 ), together with their selectivity vs. non-cancerous cells. We found promising results against prostate (9.6 µM) and colon (13.5 µM) adenocarcinoma cells. We also found a tradeoff between selectivity (up to 3-fold vs. ARPE-19) and inhibition, depending upon the symmetry and bromine-substitution of the molecules, showing up to 20-fold higher selectivity vs. doxorubicin controls.

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RESUMO

The novel [Cuphen(VBA)2H2O] complex (phen: phenanthroline, VBA: vinylbenzoate) was prepared and used as a functional monomer to preorganize a new ion-imprinted polymer (IIP). By leaching the Cu(II) from the molecular imprinted polymer (MIP), [Cuphen(VBA)2H2O-co-EGDMA]n (EGDMA: ethylene glycol dimethacrylate), the IIP was obtained. A non-ion-imprinted polymer (NIIP) was also prepared. The crystal structure of the complex and some physicochemical, spectrophotometric techniques were also used for the MIP, IIP, and NIIP characterization. The results showed that the materials are nonsoluble in water and polar solvents, which are the main features of polymers. The surface area of the IIP is higher than the NIIP demonstrated by the blue methylene method. The SEM images show monoliths and particles smoothly packed together on spherical and prismatic-spherical surfaces in the morphology of MIP and IIP, respectively. Moreover, the MIP and IIP could be considered as mesoporous and microporous materials, shown by the size of the pores determined by the BET and BJH methods. Furthermore, the adsorption performance of the IIP was studied using copper(II) as a contaminant heavy metal. The maximum adsorption capacity of IIP was 287.45 mg/g at 1600 mg/L Cu2+ ions with 0.1 g of IIP at room temperature. The Freundlich model was found to best describe the equilibrium isotherm of the adsorption process. The competitive results indicate that the stability of the Cu-IIP complex is higher than the Ni-IIP complex with a selectivity coefficient of 1.61.

RESUMO

Sulfamethazine [N1-(4,6-dimethylpyrimidin-2-yl)sulfanilamide] is an antimicrobial drug that possesses functional groups capable of acting as hydrogen-bond donors and acceptors, which make it a suitable supramolecular building block for the formation of cocrystals and salts. We report here the crystal structure and solid-state characterization of the 1:1 salt piperidinium sulfamethazinate (PPD+·SUL-, C5H12N+·C12H13N4O2S-) (I). The salt was obtained by the solvent-assisted grinding method and was characterized by IR spectroscopy, powder X-ray diffraction, solid-state 13C NMR spectroscopy and thermal analysis [differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)]. Salt I crystallized in the monoclinic space group P21/n and showed a 1:1 stoichiometry revealing proton transfer from SUL to PPD to form salt I. The PPD+ and SUL- ions are connected by N-H+...O and N-H+...N interactions. The self-assembly of SUL- anions displays the amine-sulfa C(8) motif. The supramolecular architecture of salt I revealed the formation of interconnected supramolecular sheets.

RESUMO

We synthesize and characterize nine copper(II) compounds. Four with general formula [Cu(NNO)(NO3)] and five mixed chelates [Cu(NNO)(N-N)]+, where NNO corresponds to asymmetric salen ligands (E)-2-((2-(methylamino)ethylimino)methyl)phenolate (L1) and (E)-3-((2-(methylamino)ethylimino)methyl)naphthalenolate (LN1); and their hydrogenated derivatives 2-((2-(methylamino)ethylamino)methyl)phenolate (LH1) and 3-((2-(methylamino)ethylamino)methyl)naphthalenolate (LNH1); and N-N correspond to 4,4'-dimethyl-2,2'-bipiridyne(dmbpy) or 1,10-phenanthroline (phen). Using EPR, the geometries of the compounds in solution in DMSO were assigned, [Cu(LN1)(NO3)] and [Cu(LNH1)(NO3)] a square-planar, [Cu(L1)(NO3)], [Cu(LH1)(NO3)], [Cu(L1)(dmby)]+ and [Cu(LH1)(dmby)]+ a square-based pyramid; and [Cu(LN1)(dmby)]+, [Cu(LNH1)(dmby)]+ and [Cu(L1)(phen)]+ and elongated octahedral. By X-ray it was observed that [Cu(L1)(dmby)]+ and. [Cu(LN1)(dmby)]+ presented a square-based pyramidal, and [Cu(LN1)(NO3)]+ a square-planar geometry. The electrochemical study showed that copper reduction process is a quasi-reversible system, where the complexes with hydrogenated ligands were less oxidizing. The cytotoxicity of the complexes was tested by MTT assay, all the compounds showed biological activity in HeLa cell line, the mixed compounds were the more active ones. Naphthalene moiety, imine hydrogenation and aromatic diimine coordination, increased biological activity. A structure-activity relationships were found: Log(IC50) =  - 1.01(Epc) - 0.35(Conjugated Rings) + 0.87, for Schiff base complexes and Log(IC50) = 0.078(Epc) - 0.32(Conjugated Rings) + 1.94, for hydrogenated complexes; the less oxidizing species with a great number of conjugated rings presented the best biological activity. Complexes-DNA binding constants were obtained by uv-vis studies using CT-DNA, the results suggested that the complexes can interact through the grooves, except the phenanthroline mixed complex that intercalate with DNA. Gel electrophoresis study with pBR 322 showed that compounds can produce changes in the form of DNA and some complexes can cleave DNA in the presence of H2O2.

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RESUMO

Two novel Iron (II) complexes featuring tetrapodal bis(benzimidazole)amino thio- and selenoether ligands (LS and LSe) were synthesized, characterized, and tested as electrocatalysts for the hydrogen evolution reaction. The bromide complexes [Fe(LS,LSe)Br2] (1-2) are highly insoluble, but their DMSO solvates were characterized by single crystal X-ray diffraction, revealing an octahedral coordination environment that does not feature coordination of the chalcogen atoms. The corresponding triflate derivatives [Fe(LS,LSe)(MeCN)3]OTf2 (1c-2c) were employed for electrocatalytic proton reduction, with 1c exhibiting higher activity, thus suggesting that the thioether may participate as a more competent pendant ligand for proton transfer.

Assuntos