Orbital redistribution in molecular nanostructures mediated by metal-organic bonds

Dicyanovinyl-quinquethiophene (DCV5T-Me) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/STS) and atomic force microscopy (AFM). We find that DCV5T-Me self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal-ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites

The coexistence of peace and conflict in South America: toward a new conceptualization of types of peace

South America's predominant democratic regimes and its increasing interdependence on regional trade have not precluded the emergence of militarized crises between Colombia and Venezuela or the revival of boundary claims between Chile and Peru. This way, how can we characterize a zone that, in spite of its flourishing democracy and dense economic ties, remain involved in territorial disputes for whose resolution the use of force has not yet been discarded? This article contends that existing classifications of zones of peace are not adequate to explain this unusual coexistence. Thus, its main purpose is to develop a new analytical category of regional peace for assessing this phenomenon: the hybrid peace. It aims to research the evolution of security systems in South America during the previous century and build a new, threefold classification of peace zones: negative peace zones, hybrid peace zones, and positive peace zones

A Mitosis Block Links Active Cell Cycle with Human Epidermal Differentiation and Results in Endoreplication

How human self-renewal tissues co-ordinate proliferation with differentiation is unclear. Human epidermis undergoes continuous cell growth and differentiation and is permanently exposed to mutagenic hazard. Keratinocytes are thought to arrest cell growth and cell cycle prior to terminal differentiation. However, a growing body of evidence does not satisfy this model. For instance, it does not explain how skin maintains tissue structure in hyperproliferative benign lesions. We have developed and applied novel cell cycle techniques to human skin in situ and determined the dynamics of key cell cycle regulators of DNA replication or mitosis, such as cyclins E, A and B, or members of the anaphase promoting complex pathway: cdc14A, Ndc80/Hec1 and Aurora kinase B. The results show that actively cycling keratinocytes initiate terminal differentiation, arrest in mitosis, continue DNA replication in a special G2/M state, and become polyploid by mitotic slippage. They unambiguously demonstrate that cell cycle progression coexists with terminal differentiation, thus explaining how differentiating cells increase in size. Epidermal differentiating cells arrest in mitosis and a genotoxic-induced mitosis block rapidly pushes epidermal basal cells into differentiation and polyploidy. These observations unravel a novel mitosis-differentiation link that provides new insight into skin homeostasis and cancer. It might constitute a self-defence mechanism against oncogenic alterations such as Myc deregulation

Orbital redistribution in molecular nanostructures mediated by metal-organic bonds

Dicyanovinyl-quinquethiophene (DCV5T-Me) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/STS) and atomic force microscopy (AFM). We find that DCV5T-Me self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal-ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites

Laparoscopic cholecystectomy in the treatment of biliary lithiasis: outpatient surgery or short stay unit?

Objective: analysis of clinical and surgical factors in a series of patients subjected to laparoscopic cholecystectomy in an outpatient unit and their relationship with time of discharge and patient acceptance. Patients and method: eighty one consecutive patients underwent to elective laparoscopic cholecystectomy during year 2002 within S.A.S. (Andalusian Health Service) from a surgical waiting list. Retrospective and comparative study between two groups: group A includes patients discharged between 24 and 48 hours after intervention; group B includes patients discharged in less than 24 hours. We analyse the clinical and surgical characteristics and post-operative outcome of both groups of patients. Results: group A was composed of 53 patients and group B of 28 patients. Factors of clinical significance which determined discharge after 24 hours included: early post-surgical incidences or complications (p = 0.017), inability to tolerate oral diet (p = 0.002), and doubts and feelings insecurity of patients regarding discharge by traditional means 62.3% (p = 0.0003). Conclusions: outpatient laparoscopic cholecystectomy is a safe and reliable procedure with a high acceptance rate and few complications. Perhaps traditional culture has to be changed to obtain better results