Unusual DNA binding modes for metal anticancer complexes

DNA is believed to be the primary target for many metal-based drugs. For example, platinum-based anticancer drugs can form specific lesions on DNA that induce apoptosis. New platinum drugs can be designed that have novel modes of interaction with DNA, such as the trinuclear platinum complex BBR3464. Also it is possible to design inert platinum(IV) pro-drugs which are non-toxic in the dark, but lethal when irradiated with certain wavelengths of light. This gives rise to novel DNA lesions which are not as readily repaired as those induced by cisplatin, and provides the basis for a new type of photoactivated chemotherapy. Finally, newly emerging ruthenium(II) organometallic complexes not only bind to DNA coordinatively, but also by H-bonding and hydrophobic interactions triggered by the introduction of extended arene rings into their versatile structures. Intriguingly osmium (the heavier congener of ruthenium) reacts differently with DNA but can also give rise to highly cytotoxic organometallic complexes

The nature of correlations in the insulating states of twisted bilayer graphene

The recently observed superconductivity in twisted bilayer graphene emerges from insulating states believed to arise from electronic correlations. While there have been many proposals to explain the insulating behaviour, the commensurability at which these states appear suggests that they are Mott insulators. Here we focus on the insulating states with $\pm 2$ electrons or holes with respect to the charge neutrality point. We show that the theoretical expectations for the Mott insulating states are not compatible with the experimentally observed dependence on temperature and magnetic field if, as frequently assumed, only the correlations between electrons on the same site are included. We argue that the inclusion of non-local (inter-site) correlations in the treatment of the Hubbard model can bring the predictions for the magnetic and temperature dependencies of the Mott transition to an agreement with experiments and have consequences for the critical interactions, the size of the gap, and possible pseudogap physics. The importance of the inter-site correlations to explain the experimental observations indicates that the observed insulating gap is not the one between the Hubbard bands and that antiferromagnetic-like correlations play a key role in the Mott transition.Comment: 8 pages (including appendix), 5 figure

Caracteres preimaginales y aspectos bionómicos de Gyriosomus luczotii Laporte, 1840 (Coleoptera, Tenebrionidae)

Se describe la morfología y microestructura coriónica del huevo y la morfología del primer estadio larvario de Gyriosomus luczotii Laporte, 1840 (Coleoptera, Tenebrionidae, Nycteliini). También se exponen antecedentes bionómicos y distribucionales de la especie. Para la obtención de huevos y larvas, se recolectaron parejas en el terreno que fueron mantenidas en cajas de cria hasta la ovoposición y posterior eclosión. La estructura y ornamentación del exocorion del huevo y características morfológicas externas de la larva fueron analizadas mediante microscopía electrónica de barrido. Los resultados muestran que los huevos de G. luczotii presentan un micropilo redondeado y exocorion liso, con células hexagonales sin aeropilos. Las larvas de G. luczotii presentan características morfológicas adaptativas para la vida edáfica del tipo Pedobionta: cápsula cefálica con gran cantidad de sensillas, patas protorácicas de función cavadora, y pigopodio bien desarrollado. Se analiza la importancia de algunos caracteres morfológicos de la larva de primer estadio como criterio de diagnóstico específico y se establece que las diferencias interespecíficas referidas a las sensillas frontales, la forma del clípeo y el margen anterior del labro tienen valor taxonómico y probablemente filogenético. Palabras clave: Tenebrionidae, Gyriosomus, Morfología, Estadios preimaginales, Desierto costero, Chile.Preimaginal characters and bionomical aspects of Gyriosomus luczotii Laporte, 1840 (Coleoptera, Tenebrionidae) We describe the morphology and microstructure of the egg chorion, and the morphology of the first instar larva of Gyriosomus luczotii Laporte, 1840 (Coleoptera, Tenebrionidae, Nycteliini). Bionomical and distributional data on this species are also provided. To obtain eggs and larvae, couples were collected in the field and kept in rearing cages until oviposture and ecclosion. The structure and adornment of the egg exochorion, and the exterior morphological features of larvae were examined with electron scanning microscopy. The eggs of G. luczotii showed a rounded micropyle and a smooth exochorion, composed of hexagonal cells without aeropyles. The larvae of G. luczotii showed morphological characteristics suited for an edaphic life similar to that of Pedobionta: digging prothoracic legs, cephalic capsule with abundant sensilla, and well–developed pygopodium. We analysed the importance of larval morphology as an element for specific diagnosis and found that interspecific differences regarding frontal sensilla, clypeus shape, and anterior part of labrum, had a taxonomic value and possibly a phylogenetic value. Key words: Tenebrionidae, Gyriosomus, Morphology, Preimaginal stages, Coastal desert, Chile.Se describe la morfología y microestructura coriónica del huevo y la morfología del primer estadio larvario de Gyriosomus luczotii Laporte, 1840 (Coleoptera, Tenebrionidae, Nycteliini). También se exponen antecedentes bionómicos y distribucionales de la especie. Para la obtención de huevos y larvas, se recolectaron parejas en el terreno que fueron mantenidas en cajas de cria hasta la ovoposición y posterior eclosión. La estructura y ornamentación del exocorion del huevo y características morfológicas externas de la larva fueron analizadas mediante microscopía electrónica de barrido. Los resultados muestran que los huevos de G. luczotii presentan un micropilo redondeado y exocorion liso, con células hexagonales sin aeropilos. Las larvas de G. luczotii presentan características morfológicas adaptativas para la vida edáfica del tipo Pedobionta: cápsula cefálica con gran cantidad de sensillas, patas protorácicas de función cavadora, y pigopodio bien desarrollado. Se analiza la importancia de algunos caracteres morfológicos de la larva de primer estadio como criterio de diagnóstico específico y se establece que las diferencias interespecíficas referidas a las sensillas frontales, la forma del clípeo y el margen anterior del labro tienen valor taxonómico y probablemente filogenético. Palabras clave: Tenebrionidae, Gyriosomus, Morfología, Estadios preimaginales, Desierto costero, Chile

Internal screening and dielectric engineering in magic-angle twisted bilayer graphene

Magic-angle twisted bilayer graphene (MA-tBLG) has appeared as a tunable testing ground to investigate the conspiracy of electronic interactions, band structure, and lattice degrees of freedom to yield exotic quantum many-body ground states in a two-dimensional Dirac material framework. While the impact of external parameters such as doping or magnetic field can be conveniently modified and analyzed, the all-surface nature of the quasi-2D electron gas combined with its intricate internal properties pose a challenging task to characterize the quintessential nature of the different insulating and superconducting states found in experiments. We analyze the interplay of internal screening and dielectric environment on the intrinsic electronic interaction profile of MA-tBLG. We find that interlayer coupling generically enhances the internal screening. The influence of the dielectric environment on the effective interaction strength depends decisively on the electronic state of MA-tBLG. Thus, we propose the experimental tailoring of the dielectric environment, e.g. by varying the capping layer composition and thickness, as a promising pursuit to provide further evidence for resolving the hidden nature of the quantum many-body states in MA-tBLG.Comment: 9 pages, 3 figures, supplemental material included (8 figures

Photoactivation of trans diamine platinum complexes in aqueous solution and effect on reactivity towards nucleotides

We show that UVA irradiation (365 nm) of the Pt-IV complex trans,trans,trans-[(PtCl2)-Cl-IV(OH)(2)(dimethylamine) (isopropylamine)] (1), induces reduction to Pt-II photoproducts. For the mixed amine Pt-II complex, trans[(PtCl2)-Cl-II(isopropylamine)(methylamine)] (2), irradiation at 365 nm increases the rate and extent of hydrolysis, triggering the formation of diaqua species. Additionally, irradiation increases the extent of reaction of complex 2 with guanosine-5'-monophosphate and affords mainly the bis-adduct, while reactions with adenosine-5'-monophosphate and cytidine-5'-monophosphate give rise only to mono-nucleotide adducts. Density Functional Theory calculations have been used to obtain insights into the electronic structure of complexes 1 and 2, and their photophysical and photochemical properties. UVA-irradiation can contribute to enhanced cytotoxic effects of diamine platinum drugs with trans geometry

Photodegradation of nimodipine and felodipine in microheterogeneous systems

Indexación: Web of Science; ScieloThe photochemical behavior of nimodipine (NIMO) and felodipine (FELO), photolabile drugs widely used as antihypertensive calcium channel blockers, is studied in constrained media. Specifically, we are interested in the kinetic analysis of 4-aryl-1,4-dihydropyridine photodegradation processes when they are incorporated in biological-mimicking systems like micelles or liposomes. In order to establish if the nature of the head of surfactant (ionic or nonionic) could be important modulating the photo-reactivity of these drugs, we studied the photodegradation of NIMO and FELO incorporated in micelles formed with sodium dodecyl sulfate (SDS, anionic), dodecyl-pyridinium chloride (DPC, cationic) and mono lauryl sucrose ester (MLS, nonionic) as surfactants. Additionally, the results of the photodegradation of these compounds in liposomes were also included. The results clearly indicate that both dihydropyridines studied, NIMO and FELO, are located near to the interface, but the surface charge of micelles does not affect neither, the photodegradation rate constant nor the photodegradation products profile. The absence of singlet oxygen generation in micellar media is consistent with the proposition of these 4-aryl-1,4-dihidropyridines located near to the interface of the micelle, where a polar environment is sensed. In addition, the ethanol preferential location on membranes and dihydropyridine enhanced photodegradation by alcohol presence are interesting results to consider in future research.http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072012000300025&nrm=is

Synthesis, physicochemical and photophysical characterization of 4-(1-Pyrenyl)-Butyl-α-d-mannopyranoside

Indexación: Web of Science; Scopus; Scielo.Glycolipids are biomolecules composed of a lipid chain (lipophilic) and a monosaccharide or oligosaccharide as hydrophilic group. Their chemical structure and biological role make them undoubtedly good candidates for a large and continuously growing number of biotechnological applications. Mannose is a carbohydrate present on membrane glycolipids of a wide number of pathogenic microorganisms (bacteria, fungi, protozoa, and viruses) and specifically recognized by several lectins. We synthesized a mannose derivative linked through a short methylene chain to a pyrene moiety which behaves as a surfactant, able to aggregate, and retains the photophysical properties of pyrene: showing comparable absorption and emission spectra, having lower fluorescence quantum yield and the ability to form excimer, and finally the ability to produce O-2((1)Delta(g)) with high quantum yields. Thus, this novel molecule would open future applications for detection (fluorescence) or inactivation (singlet oxygen) of bacterial pathogens, viruses, tumor cells, or particular cells.http://ref.scielo.org/pcn4d