Idalina M.M. de Carvalho

Self-assembled monolayers formed by [M(CN)5(pyS)]4−(M = Fe, Ru) on gold: a comparative study on stability and efficiency to assess the cyt c heterogeneous electron transfer reaction

A comparative study involving SAMs formed by [(CN)5M(pyS)]4− inorganic complexes (M = Fe, Ru; pyS = 4-mercaptopyridine) on gold (MpySAu) has been performed. The characterization data for these complexes suggests that the ruthenium complex exhibit a greater π-back-bonding effect that more strongly stabilizes the MpyC–S bond, thus anticipating its application as a SAM that would better enhance the gold adlayer stability than the iron complex. The MpySAu electrodes were characterized by SERS and electrochemical (LSV) techniques. The ex situ SERS spectra data for both SAMs suggest a σ interaction between the gold and sulfur atom of the complexes, inducing a perpendicular arrangement in relation to the surface. The spectra performed for freshly prepared MpySAu adlayers did not show any significant changes that would reflect the degradation of the adlayer. The LSV desorption curves of the SAMs indicate a better enhancement in the C–S bond strength of the pyS ligand when coordinated to the [Ru(CN)5]3− moiety. Comparatively to the data obtained for the desorption process of the pyS monolayer, the reductive desorption potentials, Erd, present shifts of −170 and −110 mV for the Ru and Fe complexes, respectively. The voltammetric curves of cytochrome c (cyt c) performed with the MpySAu electrodes showed electrochemical parameters consistent with that reported for the native protein. These results taken together reinforce that the π back-bonding effect from the [M(CN)5]3− metal center [Ru (4d) > Fe (3d)] strongly affects the MpySAu adlayer stability, reflecting the adlayer performance on the assessment of the cyt c hET reaction.

A novel and simple synthetic route for a piperazine derivative

Um novo derivado da piperazina, 5-oxopiperazinio-3-sulfonato monohidratado, foi produzido a partir de uma rota sintetica simples como resultado da adicao do ion bisulfito, HSO3-, ao anel e do ataque nucleofilico de moleculas de agua a moleculas de pirazina. O material isolado foi caracterizado por RMN, espectrometria de massa, infravermelho e difracao de raios-X.

Tetraammine ruthenate complexes: cationic SAMs for cytochrome c recognition

The redox process of the cyt c metalloprotein was assessed by the cationic SAMs formed with [Ru(CNPy)(NH3)4(1,4-dt)]2+ and [Ru(CNPy)(NH3)4(pyS)]2+ complexes on gold, where CNPy = 4-cyanopyridine, pyS = 4-mercaptopyridine and 1,4-dt = dithiane. The observed cyt c redox potentials are indicative of the native protein form. The voltammograms, however, were observed to be affected by the conformation of the modifiers, determined by SERS spectroscopy. The [Ru(CNPy)(NH3)4(pyS)]2+ complex, which exhibits trans conformation on the surface, presented a well-defined voltammogram. On the other hand, the gauche conformation of the [Ru(CNPy)(NH3)4(1,4-dt)]2+ SAM seems to make the assessment of the cyt c hET reaction difficult. The reductive desorption potentials, at -0.52 and -0.64 V vs Ag|AgCl|Cl- for the [Ru(CNPy)(NH3)4(1,4-dt)]2+ and [Ru(CNPy)(NH3)4(pyS)]2+ SAMs, respectively, are indicative of the bonding mode with the surface and the p withdrawing capability of the CNpy ligand.

Thermal isomerization of cis-[Fe(cyclam)Cl2]Cl·H2O complex in the solid state

Abstract The solid state thermal isomerization of cis -[Fe(cyclam)Cl 2 ]Cl·H 2 O (cyclam is 1,4,8,11-tetraazacyclotetradecane), is investigated by TG/DSC, electrochemical and vibrational spectroscopic methods. The thermal isomerization of this complex was found to be water dependent and endothermic. An aquation–anation pathway that precedes the macrocyclic ligand stereochemical rearrangement in the complex is proposed.

Aryl-Substituted Ruthenium(II) Complexes: A Strategy for Enhanced Photocleavage and Efficient DNA Binding

Ruthenium polypyridine complexes have shown promise as agents for photodynamic therapy (PDT) and tools for molecular biology (chromophore-assisted light inactivation). To accomplish these tasks, it is important to have at least target selectivity and great reactive oxygen species (ROS) photogeneration: two properties that are not easily found in the same molecule. To prepare such new agents, we synthesized two new ruthenium complexes that combine an efficient DNA binding moiety (dppz ligand) together with naphthyl-modified (1) and anthracenyl-modified (2) bipyridine as a strong ROS generator bound to a ruthenium complex. The compounds were fully characterized and their photophysical and photochemical properties investigated. Compound 2 showed one of the highest quantum yields for singlet oxygen production ever reported (ΦΔ= 0.96), along with very high DNA binding (log Kb = 6.78). Such photochemical behavior could be ascribed to the lower triplet state involving the anthracenyl-modified bipyridine, which is associated with easier oxygen quenching. In addition, the compounds exhibited moderate selectivity toward G-quadruplex DNA and binding to the minor groove of DNA, most likely driven by the pendant ligands. Interestingly, they also showed DNA photocleavage activity even upon exposure to a yellow light-emitting diode (LED). Regarding their biological activity, the compounds exhibited an exciting antibacterial action, particularly against Gram-positive bacteria, which was enhanced upon blue LED irradiation. Altogether, these results showed that our strategy succeeded in producing light-triggered DNA binding agents with pharmacological and biotechnological potential.

On the correlation between electronic intramolecular delocalization and Au-S bonding strength of ruthenium tetraammine SAMs

Trans-[Ru(L)(NH3)4(L’)](PF6)n type complexes, where L = 4-cyanopyridine (CNpy), NCS-, CN-, and L’ = CNpy, 1,4-dithiane (1,4-dt), 4-mercaptopyridine (pyS) and thionicotinamide (tna), were synthesized and characterized. SAMs on gold of the complexes containing sulfur were studied by reductive desorption and SERS spectroscopy. Depending on the nature of L’, the withdrawing capability of the CNpy ligand is strong enough to partially oxidize the ruthenium atom and, as a consequence, delocalize the s electronic density from the trans located ligand. The reductive desorption results showed that the stability of the SAMs is directly related to this effect.

Self-Organization of porphyrin-peptide units by metal-mediated peptide assembly

The polypeptide H21(30-mer) folds into a two-stranded coiled-coil in which two solvent-exposed histidine residues reside on opposite sides of its surface. This peptide was allowed to react with cobalt(III) protoporphyrin IX, Co(ppIX), to produce [Co(ppIX){(H21(30-mer)}2], as determined by UV-Vis spectroscopy. This bis-axial ligation thus positions a potential coiled-coil oligomerization domain onto each face of the cobalt porphyrin ring. Circular dichroism spectroscopy and high performance size exclusion chromatography provide evidence for the solution-phase self-assembly of these porphyrin-peptide units. Evaporation of the porphyrin-peptide solution on a solid support results in the formation of long rod-like materials having millimeter-scale lengths and micron-scale diameters. The presence of Co(ppIX) in these materials was confirmed by Raman microscopy. However, they were formed only from phosphate buffer, and not from organic buffers or pure water, indicating that their formation might involve a more complicated process than originally anticipated.

Thiocarbonyl-bound metallonitrosyl complexes with visible-light induced DNA cleavage and promising vasodilation activity

Nitric oxide has been involved in many key biological processes such as vasodilation, platelet aggregation, apoptosis, memory function, and this has drawn attention to the development of exogenous NO donors. Metallonitrosyl complexes are an important class of these compounds. Here, two new ruthenium nitrosyl complexes containing a thiocarbonyl ligand, with the formula cis-[Ru(phen)2(L)(NO)](PF6)3 (phen = phenantroline, L = thiourea or thiobenzamide), were synthesized and characterized by electronic spectroscopy, FTIR, NMR, mass spectrometry and voltammetric techniques. Theoretical calculations using Density Functional Theory (DFT) and Time-dependent Density Functional Theory (TD-DFT) were also used and further supported the characterizations of these complexes. An efficient release of nitric oxide by blue light was validated using a NO/HNO probe: 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, known as cPTIO. Interestingly, the complex containing thiourea cleaved DNA even in the dark, while both complexes showed great DNA photocleavage activity in blue light. This process might work mainly through NO and hydroxyl radical production. Additionally, these complexes showed promising vasodilator activity, whose mechanism of action was investigated using N-Nitro-l-arginine methyl ester hydrochloride (L-NAME) and 1H-[1,2,4]Oxadiazolo[4,3-a]quinoxalin-1-one (ODQ) and compared to sodium nitroprusside. Both compounds were indeed NO-mediated heme-dependent activators of soluble guanylate cyclase. Additionally, they did not show any significant cytotoxicity against cancer cell lines U87 and GBM02. Altogether, these results supported both complexes having potential pharmacological applications that deserve further studies.

Crystal structure, electrochemical and spectroscopic properties of the trans-K{[FeCl(NO0)(cyclam)]·[FeCl(NO+)(cyclam)]2}(PF6)6 complex

The trans-K{[FeCl(NO0)(cyclam)]·[FeCl(NO+)(cyclam)]2}(PF6)6 complex was prepared from the reaction of trans-[Fe(cyclam)Cl2]Cl and nitric oxide. The molecular structure of the complex was determined by X-ray diffraction (space group P21/c; a = 10.3560(3) A; b = 17.7110(6) A; c = 17.9480(6) A; β = 91.052(2)°). Crystal and spectroscopic evidence indicates the existence of two independent complexes with participation of different forms of nitric oxide: NO+ and NO0. The IR spectrum shows the presence of two ν(NO) stretching modes at 1863 and 1610 cm−1 which are characteristic of these NO species, respectively. Upon reduction by zinc amalgam, the ν(NO+) band at 1863 cm−1 disappears and the band at 1610 cm−1 becomes more intense. The EPR measurements indicate the presence of the NO0 group. No signal for paramagnetic species of Fe(III) was observed.