Complexes of Pd(II) and Pt(II) with 9-aminoacridine: reactions with DNA and study of their antiproliferative activity

Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO)2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.

Complexes of Pd(II) and Pt(II) with 9-aminoacridine: reactions with DNA and study of their antiproliferative activity

Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO)2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.

Complexes of Pd(II) and Pt(II) with 9-aminoacridine: reactions with DNA and study of their antiproliferative activity

Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO)2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.

Geology of the Cerro-Quema Au-Cu deposit (Azuero Peninsula, Panama)

The Cerro Quema district, located on the Azuero Peninsula, Panama, is part of a large regional hydrothermal system controlled by regional faults striking broadly E-W, developed within the Río Quema Formation. This formation is composed of volcanic, sedimentary and volcano-sedimentary rocks indicating a submarine depositional environment, corresponding to the fore-arc basin of a Cretaceous-Paleogene volcanic arc. The structures observed in the area and their tectono-stratigraphic relationship with the surrounding formations suggest a compressive and/or transpressive tectonic regime, at least during Late Cretaceous-Oligocene times. The igneous rocks of the Río Quema Formation plot within the calc-alkaline field with trace and rare earth element (REE) patterns of volcanic arc affinity. This volcanic arc developed on the Caribbean large igneous province during subduction of the Farallon Plate. Mineralization consists of disseminations of pyrite and enargite as well as a stockwork of pyrite and barite with minor sphalerite, galena and chalcopyrite, hosted by a subaqueous dacitic lava dome of the Río Quema Formation. Gold is present as submicroscopic grains and associated with pyrite as invisible gold. A hydrothermal alteration pattern with a core of advanced argillic alteration (vuggy silica with alunite, dickite, pyrite and enargite) and an outer zone of argillic alteration (kaolinite, smectite and illite) has been observed. Supergene oxidation overprinted the hydrothermal alteration resulting in a thick cap of residual silica and iron oxides. The ore minerals, the alteration pattern and the tectono-volcanic environment of Cerro Quema are consistent with a high sulfidation epithermal system developed in the Azuero peninsula during pre-Oligocene times.

Platinum (II) and palladium (II) complexes with (N,N') and (C,N,N') ligands derived from pyrazole as anticancer and antimalarial agents: synthesis, characterization and in vitro activities

The study of the reactivity of three 1-(2-dimethylaminoethyl)-1H-pyrazole derivatives of general formula [1-(CH2)2NMe2}-3,5-R2-pzol] {where pzol represents pyrazole and Rdouble bond; length as m-dashH (1a), Me (1b) or Ph (1c)} with [MCl2(DMSO)2] (Mdouble bond; length as m-dashPt or Pd) under different experimental conditions allowed us to isolate and characterize cis-[M{κ2-N,N′-{[1-(CH2)2NMe2}-3,5-R2-pzol])}Cl2] {MMdouble bond; length as m-dashPtPt (2a-2c) or Pd (3a-3c)} and two cyclometallated complexes [M{κ3-C,N,N′-{[1-(CH2)2NMe2}-3-(C5H4)-5-Ph-pzol])}Cl] {Mdouble bond; length as m-dashPt(II) (4c) or Pd(II) (5c)}. Compounds 4c and 5c arise from the orthometallation of the 3-phenyl ring of ligand 1c. Complex 2a has been further characterized by X-ray crystallography. Ligands and complexes were evaluated for their in vitro antimalarial against Plasmodium falciparum and cytotoxic activities against lung (A549) and breast (MDA MB231 and MCF7) cancer cellular lines. Complexes 2a-2c and 5c exhibited only moderate antimalarial activities against two P. falciparum strains (3D7 and W2). Interestingly, cytotoxicity assays revealed that the platinacycle 4c exhibits a higher toxicity than cisplatin in the three human cell lines and that the complex 2a presents a remarkable cytotoxicity and selectivity in lung (IC50 = 3 μM) versus breast cancer cell lines (IC50 > 20 μM). Thus, complexes 2c and 4c appear to be promising leads, creating a novel family of anticancer agents. Electrophoretic DNA migration studies in presence of the synthesized compounds have been performed, in order to get further insights into their mechanism of action.

Morfologia flexiva i flexió verbal catalana

La característisca més notable dels sistemes flexius és la resistència que ofereixen a la tasca lingüística d'establir relacions entre morfs i morfemes. En sistemes d'aquesta classe, en efecte, les relacions esmentades són molt complexes, i fugen de la biunicitat pròpia dels sistemes aglutinants. Aclarir aquestes relacions, il·lustrant-les des de l'angle del verb català, i suggerir mecanismes formals per tractar-les dins un esquema generatiu constitueixen, de fet, els dos objectius fonamentals del present article.

L'Agricultura baixempordanesa a mitjan segle XIX: Producció agrària i usos del sòl

El paisatge agrari -entès en termes físics- és una construcció humana fruit d'una activitat productiva -la practica de l'agricultura- a traves de la qual s'imprimeix conscientment una determinada forma als espais naturals tot cercant l'adaptació dels objectius productius a les variades condicions del medi. Els elements que componen un paisatge agrari són múltiples i abasten des del tipus de poblament fins a la forma de les parcel•les, passant pel sistema hidrogràfic, el mode d'apropiació dels espais, les característiques de l'explotació ramadera i les formes d'aprofitament del sòl. En aquest article ens ocuparem d'un dels components del paisatge agrari de la comarca del Baix Empordà, concretament dels usos del d l i de les principals línies productives que caracteritzaven l'agricultura baixempordanesa a mitjan segle XIX. La primera qüestió que tractarem serà la de la paralització del procés d'expansió de l'àrea conreada just després de les dècades centrals del segle, aspecte de gran interès tant per la seva precocitat en el context català i espanyol, com pel fet que revela un canvi en l'evolució del sector estretament relacionat amb una remarcable disminució de la pressió demogràfica. En segon lloc, a partir de la contrastació de fonts documentals de naturalesa diversa (amillaraments, estadístiques provincials, interrogatoris municipals i comptabilitats privades), realitzarem un intent de quantificar el pes dels diversos aprofitaments i la seva distribució geogràfica. I, finalment, plantejarem la qüestió de la intensificació de l'ús del sòl a través del retrocés del guaret blanc i la difusió de rotacions complexes, qüestió clau en l'avaluació de l'eficiència econòmica del sistema agrari baixempordanès

Contribución al conocimiento de la geología del depósito de Au-Cu de La Pava (Península de Azuero, Panamá)

The «La Pava» Au-Cu deposit is hosted by a vulcanosedimentary sequence, named Ocú Formation,developed in an island arc environment that resulted from the subduction of the Nazca Plate beneath the Caribbean Plate during the Cretaceous times. The deposit consists of disseminations and stockworks of pyrite and chalcopyrite accompanied by barite, quartz and carbonates. Three hydrothermal alteration zones have been recognized: silicic, argillic and propilityc, typical of gold-related high sulfidation systems. A supergenic alteration overprints the hydrothermal alterations developing a cap rich in silica and Feoxides. The detailed study of the Ocú Fm. indicates that the sulfides and the accompanying gold was formed in a submarine environment. Therefore we suggest that «La Pava» represents an Au-Cu hybrid deposit between high sulphidation epithermal and VMS types, which are found in volcanogenic massive sulphide environments.

Traducció i adopció a l'Índia: Hindu Adoptions And Maintenance Act, 1956

L’objectiu principal d’aquest treball de fi de grau és fer-se càrrec d’una traducció jurídica amb tot el què això implica: documentar-se a través de fonts fiables, emprar les eines adequades, lliurar-lo dins el termini establert, entre d’altres. En aquest cas, és una traducció de les lleis que regulen les adopcions a l’Índia. A més, en aquest treball també s’explica breument el dret civil a Catalunya i es compara amb el de l’Índia, ja que es basen en idees molt diferents. Aquests tipus de traduccions exigeixen precisió i claredat perquè els conceptes i les estructures sintàctiques acostumen a ser molt complexes. A continuació, hi ha detallat cada pas que s’ha seguit per tal d’assolir l’objectiu principal.

Adquisició de les codes complexes finals del català per part d'alumnat panjabi: el mètode experimental

En aquest treball estudiem l’adquisició del català per part de parlants que tenen el panjabi com a primera llengua, concretament en relació amb les codes complexes de final de mot, per a aprenents d’un nivell inicial de català

Building complexity in O2-binding copper complexes : site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand

A novel unsymmetric dinucleating ligand (LN3N4) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. LN3N4 is able to discriminate between CuI and a complementary metal (M′ = CuI, ZnII, FeII, CuII, or GaIII) so that pure heterodimetallic complexes with a general formula [CuIM′(LN3N4)]n+ are synthesized. Reaction of the dicopper(I) complex [CuI 2(LN3N4)]2+ with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and TP) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM′(LN3N4)]n+ with O2 at low temperature is used as a tool to determine the final position of the CuI center in the system because only one of the two Cu2O2 species is formed