E. Rodrı́guez-Fernández

Thiourea derivatives and their nickel(II) and platinum(II) complexes: antifungal activity

We have synthesized two thiourea derivatives of methyl anthranilate (1, 2) and their complexes with nickel (3) and platinum(II) (4). We have also prepared the complexes of nickel(II) with two benzoylthiourea derivatives (5, 6). The obtained compounds were characterized by elemental analysis, spectroscopic methods (FT-IR, UV-vis, NMR), mass spectrometry and thermal analysis. Compound 1, C(20)H(23)N(3)O(2)S, crystallizes in monoclinic space group P21/n, with Z=4, and unit cell parameters, a=8.8042(4) A, b=7.6608(3) A, c=28.834(2) A, alpha=gamma=90 degrees, beta=90.94(1) degrees. Compound 2, C(20)H(21)N(3)O(3)S, crystallizes in monoclinic space group P21/c, with Z=4, and unit cell parameters, a=7.7345(4) A, b=8.6715(4) A, c=29.113(2) A, alpha=gamma=90 degrees, beta=90.67(1) degrees. Compound 5, C(24)H(30)N(4)NiO(2)S(2), crystallizes in monoclinic space group P21/n, with Z=4, and unit cell parameters, a=10.4317(8) A, b=18.517(2) A, c=13.299(1) A, alpha=gamma=90 degrees, beta=104.53(1) degrees. Compound 6, C(25)H(28)Cl(2)N(4)NiO(4)S(2), crystallizes with a molecule of CH(2)Cl(2) in triclinic space group P-1, with Z=2, and unit cell parameters, a=10.362(1) A, b=11.849(2) A, c=12.536(2) A, alpha=90.04(2) degrees, beta=84.73(1) degrees, gamma=113.43(2) degrees. Compounds 1 and 2 show antifungal activity against the major pathogens responsible for important plant diseases (Botrytis cinerea, Colletotrichum fragariae, Fusarium oxysporum and Phoma betae). The antifungal activity is practically the same for morpholine and ethyl derivatives.

Thiourea derivatives of α-aminoacids. Synthesis and characterization of Ni(II), Cu(II) and Pt(II) complexes with l-valinate derivatives. Antifungal activity

Abstract The preparation of metal complexes with 2-[(3,3′-diethylthioureido)phenylmethylamino]-3-methylbutyric acid methyl ester, Hetv, or 3-methyl-2′-{[morpholine-4-carbothioylimino)phenylmethyl]amino}-butyric acid methyl ester, Hmtv, has been achieved. The complexes obtained with formulae of Ni(etv)2, Cu(mtv)2·2H2O and Pt(Hmtv)Cl2, were studied and characterized by elemental analysis, electrical conductivity in solution, IR and UV–VIS spectra, FAB+ and electron impact (EI) mass spectrometry, 1H- and 13C-NMR, ESR, magnetic susceptibility, atomic absorption spectrometry and thermal analysis. Their antifungal activity was studied against the plant pathogenic fungi Colletotrichum fragariae, Rhizoctonia solani and Phoma betae.

Chloride and ethyl ester morpholine thiourea derivatives and their Ni(II) complexes. Crystal and molecular structures of the thiourea derivative L-leucine methyl ester and its complexes with Cu(II) and Pt(II). Growth of the pathogenic fungus Botrytis cinerea.

We have synthesized a series of ligands (1, 3, 4, 6 and 7) and some of their complexes with Ni(II), Cu(II) and Pt(II) (2, 5, 8 and 9). These compounds were studied and characterized by elemental analysis, IR and UV-Vis spectra, conductivity measurements in solution, FAB+/MS, 1H and 13C NMR, ESR, etc. Compound 7 crystallized in the orthorhombic space group P2(1)2(1)2(1), with Z = 4. Unit cell parameters were as follows: a = 21.307(2) A, alpha = 90 degrees, b = 12.498(1) A, beta = 90 degrees, c = 7.7232(4) A, gamma = 90 degrees. For seven of these compounds, the antifungal activity of a major pathogen responsible for important crop damage was studied. In general, inhibition by the ligands was higher than that of the complexes. When the thiourea was linked to some diethyl groups, the compounds showed higher antifungal activity than the morpholine groups. Compound 3 achieved total inhibition (100%).

New organotropic compounds. Synthesis, characterization and reactivity of Pt(II) and Au(III) complexes with bile acids: DNA interactions and 'in vitro' anticancer activity.

Based on the ability of bile acids to vectorialize the cytostatic activity of other agents, we have designed and synthesized a new series of platinum and gold complexes. These compounds were studied and characterized by elemental analysis, FT-IR, FAB(+)/MS, 1H, 13C and 195Pt NMR, UV-Vis spectroscopy and conductivity measurements in solution, among other techniques. Kinetic studies carried out in aqueous solution and in the presence of different NaCl concentrations: 4 mM (similar to cytoplasmic concentration), 150 mM (similar to plasmatic concentration). The effects on the electrophoretic mobility of the pUC18 plasmid, the DNA denaturation temperature, and ethidium bromide (EtBr) binding to DNA were studied. The complexes are able to inter-react with DNA to inhibit DNA synthesis and hence, to reduce cell proliferation. The complexes were evaluated for in vitro cytostatic activity against human colon adenocarcinoma, mouse hepatoma, human hepatoma, mouse leukemia, etc. The antitumor effect of some of the compounds prepared was similar to that of cisplatin. However, other compounds had lower cytostatic activity. This different behavior can be accounted for by the structure/activity relationship (SAR), although other factors, such as uptake and the different kinetic behavior in solution, may be responsible for these differences.

Enhanced cytotoxic activity of bile acid cisplatin derivatives by conjugation with gold nanoparticles

This article explores the potential cytotoxic activity of bile-acid cisplatin derivatives like bisursodeoxycholate(ethylenediamine)platinum(II), PtU2, when conjugated with gold nanoparticles, being a promising alternative to cisplatin in the treatment of cancer due to their lower toxicity. For our purpose we analyzed the intracellular delivery ability of these compounds after conjugation with 20-nm gold nanoparticles (PtU2-AuNPs) in the MG63 (osteosarcoma) cell line. Same platinum uptake after incubation with PtU2 and PtU2-AuNPs-derivatives is associated with a higher cytotoxic activity in case of the platinum-gold nanoparticle conjugate, the overall IC50 of PtU2 being reduced more than 10 fold for these new conjugates. When conjugated with gold nanoparticles, this bile-acid derivative is more efficient than the platinum compound alone in terms of their cytotoxic activity.

Bisursodeoxycholate(ethylenediamine)platinum(II): a new autofluorescent compound. Cytotoxic activity and cell cycle analysis in ovarian and hematological cell lines.

The present paper describes for the first time an intrinsic fluorescent square-planar platinum(II) complex carrying two ursodeoxycholate ligands ([Pt(UDC)2(en)], where UDC(-) = ursodeoxycholate), that emits at room temperature once free in solution. Kinetic studies were carried out in aqueous solution and in the presence of different NaCl concentrations: 4 mM (similar to cytoplasmic concentration) and 150 mM (similar to plasmatic concentration). This novel compound was synthesized from a [PtCl2(en)] complex and shows increased cytotoxic activity against both resting and cycling HeLa cells, with no toxicity for cell lines derived from neoplastic haematopoietic cells.

Procedures for Controlling the Size, Structure and Optical Properties of CdS Quantum Dots during Synthesis in Aqueous Solution

We report an easy approach for the synthesis of CdS Quantum Dots (CdS QDs) with high luminescence and temporal stability through the reaction of Cd2+ and S2- in the presence of mercaptoacetic acid (MAA) as a capping reagent in aqueous medium, under normal pressure and room temperature. The influence of several experimental variables, including temperature, pH, the Cd/S ratio and the Cd/MAA ratio, on the optical properties of the QDs obtained was studied systematically. The experimental results indicate that these variables play an important role in determining the size and state of the surface of the nanoparticles, and hence their luminescent properties and temporal stability. The general aspects of nanocrystal nucleation and growth in the synthesis of nanocrystals were studied. The best conditions for the synthesis of nanoparticles of high quality are also reported. The CdS nanocrystals obtained exhibited a narrow PL band, with reproducible room-temperature quantum yields.

A novel approach to the fabrication of cdse quantum dots in aqueous solution: procedures for controlling size, fluorescence intensity, and stability over time

This paper report a straightforward approach for the synthesis of CdSe quantum dots (CdSe QDs) in aqueous solution. This method, performed in homogeneous phase, affords optimal sizes and high quantum yields for each application desired. It is an a la carte procedure for the synthesis of nanoparticles aimed at their later application. By controlling the experimental conditions, CdSe QDs of sizes ranging between 2 and 6 nm can be obtained. The best results were achieved in an ice-bath thermostated at 4°C, using mercaptoacetic acid as dispersant. Under these conditions, a slow growth of quantum nanocrystals was generated and this was controlled kinetically by the hydrolysis of SeSO32- to generate Se2- in situ, one of the forming species of the nanocrystal. The organic dispersant mercaptoacetate covalently binds to the Cd2+ ion, modifying the diffusion rate of the cation, and plays a key role in the stabilization of CdSe QDs. In optimum conditions, when kept in their own solution CdSe QDs remain dispersed over 4 months. The NPs obtained under optimal conditions show high fluorescence, which is a great advantage as regards their applications. The quantum efficiency is also high, owing to the formation under certain conditions of a nanoshell of Cd(OH)2, values of 60% being reached.

Platinum complexes for multi-parametric assays using microarray systems

Here, we present a two novel fluorescent dyes ethylenediaminechlorocholylglycinateplatinum(II), [Pt(CG)Cl(en)] complex 1 and bisursodeoxycholate(ethylenediamine)platinum(II), [Pt(UDC)(2)(en)] complex 2 based on well-known cis-platin chemistry. These platinum complexes contain cholylglycinate (CG) and ursodeoxycholate (UDC) as ligands. These compounds enable qualitative detection of double-helix DNA and quantitative detection (from pg to μg). These novel compounds have absorption and emission spectra in a difference range as the common ones (for example: cyanine dyes such as Cy3, Cy5, Cy7,…); therefore, it could allow the multi-parametric detection of DNA arrays, incrementing the capacity of experimental performance per one single array. As a consequence, it will increase the amount of data info obtained per chip. The combination of the intrinsic property of this compounds with the optical properties in different fluorescence channels, can allow introducing a new molecule with a wide range of possible applications in DNA arrays.