Marcos Martínez-García

Synthesis of 5-aryl-1,4-benzodiazepine derivatives attached in resorcinaren-PAMAM dendrimers and their anti-cancer activity.

A series of resorcinaren-PAMAM dendrimers with benzodiazepines in the periphery were synthesized and their anticancer properties studied. The synthesized dendrimers showed potential anticancer activities, which were enhanced in the presence of a chloro-substituent in the second ring of the 5-aryl-1,4-benzodiazepine. The dendrimers were characterized by IR, (1)H and (13)C NMR, UV-vis absorption, electrospray (ES) and/or MALDI-TOF mass spectrometries.

Dendrimers containing ferrocene and porphyrin moieties: synthesis and cubic non-linear optical behavior.

Dendrons with ferrocenyl ended groups joined by styryl moieties were attached to a porphyrin core. All the dendrons used for dendrimer synthesis showed trans configuration. The chemical structure of the first generation dendron was confirmed by X-ray crystallographic studies. The structure of the synthesized dendrimers was confirmed by 1H- and 13C-NMR, electrospray mass spectrometry and elemental analysis. Cubic non-linear optical behavior of the ferrocene and porphyrin-containing dendrimers was studied in solid thin films by THG Maker-Fringe technique at 1,260 nm.

Synthesis and X-ray characterization of new 1-[μ-dithio-bis-(tricarbonyliron)]-2-(p-R-benzoyl)ethane complexes

Diiron nonacarbonyl reacts with the para- substituted derivatives 1a – d of 3,3-dithio-1-( p -substituted phenyl)-2-propen-1-one affording surprisingly the new dinuclear Fe(0) complexes 2a – d with a σ - S coordination instead of the attended η 2 or η 4 π -coordination upon the α , β -unsaturated system of the ligands. The complexes 2a – c were characterized by mass spectrometry, IR and 1 H- and 13 C-NMR spectroscopies and their structures were fully confirmed by single-crystal X-ray analysis. Such structural studies revealed as the main feature an ideal C 2v (mm 2 ) symmetry with the carbonyl groups in an eclipsed configuration of the Se 2 Fe 2 (CO) 6 moiety.

Synthesis of porphyrin-dendrimers with a pyrene in the periphery and their cubic nonlinear optical properties.

Dendrons of pyrene derivatives were attached to a porphyrin core. A marked effect in solution for the dendrimers was observed in the absorption spectra. All the compounds obtained were characterized by 1H-, 13C-NMR, FTIR, UV-vis, MALDI-TOF or FAB+ mass spectrometry and elemental analysis. The cubic nonlinear optical behavior of some the synthesized compounds was tested via Z-Scan measurements in spin-coated film samples.

Synthesis of 2-Aminobenzophenone Derivatives and Their Anticancer Activity

Abstract A number of 2-aminobenzophenones have been synthesized by acylation of para-chloroaniline with different 2-, 3-, 4-chloro- or fluorobenzoyl chloride in solid state via the Friedel–Crafts reaction. Synthesized compounds were characterized by 1H and 13C NMR, Fourier transform–infrared, ultraviolet–visible spectroscopy, mass spectrometry, and elemental analysis. Evaluation of biological activity in vitro showed that the selected compounds 9, 10, and 13 have potential anticancer activity. The presence of one chlorine atom in the second aromatic ring of the benzophenone molecule makes it more active. GRAPHICAL ABSTRACT

High Fluorescent Porphyrin-PAMAM-Fluorene Dendrimers

Two new classes of dendrimers bearing 8 and 32 fluorene donor groups have been synthesized. The first and second generations of these porphyrin-PAMAM-fluorene dendrimers were characterized by 1H-NMR, 13C-NMR, FTIR, UV-vis spectroscopy, elemental analyses and MALDI-TOF mass spectrometry. The UV-vis spectra showed that the individual properties of donor and acceptor moieties were preserved, indicating that the new dendrimers could be used as photosynthetic antennae. Furthermore, for fluorescent spectroscopy, these dendrimers showed good energy transfer.

Double Molecular Antenna Pyrene - Bridge - Fullerene C60

C60 pyrene anthrylvinylene triads were synthesized with good yields by an O-alkylation reaction of pyrene an- thracene chloride derivatives and functionalized fullerene C60. The presence of lateral butoxy chains imparts good solubil- ity. The NMR data indicate the formation of only the trans isomers. After C60 cyclopropanation, the UV-Vis spectra show the pyrene electronic transition with an absorption band extending from 400 to 800 nm due to the combination of the  electronic transition of the antrylvinylene moiety and the C60 band, regardless the extension of the anthrylvinylene moiety. However, the emission is almost mirror-like with respect to the absorption bands of pyrene, suggesting that the HOMO and LUMO are more localized on this substituent. All the obtained compounds were characterized by 1 H and 13 C NMR,

(C-rac-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)(nicotinato-O,O′)nickel(II) perchlorate

In the title compound, [Ni(C(6)H(4)NO(2))(C(16)H(36)N(4))]ClO(4), the macrocyclic unit adopts a folded conformation, allowing the two carboxyl O atoms to occupy two neighbouring coordination sites and thus form an additional four-membered chelate ring. The less crowded side of the macrocycle (that with the two asymmetric C-H groups) is directed towards the nicotinate anion and the asymmetric C-CH(3) groups are directed away from it. The macrocyclic NH groups neighbouring the C-CH(3) groups are also directed away from the nicotinate anion, while those NH groups which are near to the geminal methyl groups are directed towards the nicotinate anion. Although the complex does not include water molecules, three types of hydrogen bond were found, involving NH groups of the macrocyclic ligand, pyridine N atoms and O atoms of the perchlorate anions.

Synthesis, Characterization, and Nanomedical Applications of Conjugates between Resorcinarene-Dendrimers and Ibuprofen

Ibuprofen has been reported to possess anticancer activity. In the present work, four ibuprofen conjugates of resorcinarene-Polyamidoamine PAMAM-dendrimers were synthesized with eight or 16 ibuprofen moieties. The ibuprofen was released from the dendrimers in a dependent manner. The drug-conjugated nanoresorcinarene-dendrimers showed higher cellular uptake than free ibuprofen. In vitro cytotoxicity studies were performed with free ibuprofen and with the synthesized conjugates in U251, PC-3, K-562, HCT-15, MCF-7, SKLU-1, and MDA U251 (human glioblastoma), PC-3 (human prostatic adenocarcinoma), K-562 (human chronic myelogenous leukemia cells), HCT-15 (human colorectal adenocarcinoma), MCF-7 (human mammary adenocarcinoma), SKLU-1 (human lung adenocarcinoma), and MDA-MB-231 (human mammary adenocarcinoma) cancer cell lines by different cytotoxicity assays. Ibuprofen conjugates of the first and second generations showed significant cytotoxic effects towards the human glioblastoma (U251) and human mammary adenocarcinoma (MCF-7, MDA) cell lines. Moreover, the ibuprofen conjugates improved cytotoxicity compared to free ibuprofen. Increased therapeutic efficacy was observed with specific ibuprofen conjugates of the second generation using low doses.

Electrical Properties of Multi-Pyrene/Porphyrin-Dendrimers

Dendrimers bearing pyrene donor groups have been obtained and act as efficient light-harvesting antennae capable of transferring light energy through space from their periphery to their core. The light-harvesting ability increases with each generation due to an increase in the number of peripheral pyrenes. In order to evaluate the photovoltaic properties of the compounds, thermal evaporated thin films were produced and the voltage response in the presence of visible light was obtained. The energy transfer efficiency was found to be almost quantitative for the first and second generations. The dendrimers have the potential to become integral components of molecular photonic devices.