Chirality in Bare and Passivated Gold Nanoclusters

Chiral structures have been found as the lowest-energy isomers of bare (Au$_{28}$ and Au$_{55}) and thiol-passivated (Au$_{28}(SCH$_{3})$_{16}$and Au$_{38}(SCH_{3})_{24}) gold nanoclusters. The degree of chirality existing in the chiral clusters was calculated using the Hausdorff chirality measure. We found that the index of chirality is higher in the passivated clusters and decreases with the cluster size. These results are consistent with the observed chiroptical activity recently reported for glutahione-passivated gold nanoclusters, and provide theoretical support for the existence of chirality in these novel compounds.Comment: 5 pages, 1 figure. Submitted to PR

Frizzled-8 integrates Wnt-11 and transforming growth factor-β signaling in prostate cancer

Wnt-11 promotes cancer cell migration and invasion independently of β-catenin but the receptors involved remain unknown. Here, we provide evidence that FZD8 is a major Wnt-11 receptor in prostate cancer that integrates Wnt-11 and TGF-β signals to promote EMT. FZD8 mRNA is upregulated in multiple prostate cancer datasets and in metastatic cancer cell lines in vitro and in vivo. Analysis of patient samples reveals increased levels of FZD8 in cancer, correlating with Wnt-11. FZD8 co-localizes and co-immunoprecipitates with Wnt-11 and potentiates Wnt-11 activation of ATF2-dependent transcription. FZD8 silencing reduces prostate cancer cell migration, invasion, three-dimensional (3D) organotypic cell growth, expression of EMT-related genes, and TGF-β/Smad-dependent signaling. Mechanistically, FZD8 forms a TGF-β-regulated complex with TGF-β receptors that is mediated by the extracellular domains of FZD8 and TGFBR1. Targeting FZD8 may therefore inhibit aberrant activation of both Wnt and TGF-β signals in prostate cancer

Structural and energetic properties of nickel clusters: 2≤N≤1502 \le N \le 150

The four most stable structures of Ni$_N$ clusters with $N$ from 2 to 150 have been determined using a combination of the embedded-atom method in the version of Daw, Baskes and Foiles, the {\it variable metric/quasi-Newton} method, and our own {\it Aufbau/Abbau} method. A systematic study of energetics, structure, growth, and stability of also larger clusters has been carried through without more or less severe assumptions on the initial geometries in the structure optimization, on the symmetry, or on bond lengths. It is shown that cluster growth is predominantly icosahedral with $islands$ of {\it fcc}, {\it tetrahedral} and {\it decahedral} growth. For the first time in unbiased computations it is found that Ni$_{147}$ is the multilayer (third Mackay) icosahedron. Further, we point to an enhanced ability of {\it fcc} clusters to compete with the icosahedral and decahedral structures in the vicinity of N=79. In addition, it is shown that conversion from the {\it hcp}/anti-Mackay kind of icosahedral growth to the {\it fcc}/Mackay one occurs within a transition layer including several cluster sizes. Moreover, we present and apply different analytical tools in studying structural and energetic properties of such a large class of clusters. These include means for identifying the overall shape, the occurrence of atomic shells, the similarity of the clusters with, e.g., fragments of the {\it fcc} crystal or of a large icosahedral cluster, and a way of analysing whether the $N$-atom cluster can be considered constructed from the $(N-1)$-atom one by adding an extra atom. In addition, we compare in detail with results from chemical-probe experiment. Maybe the most central result is that first for clusters with $N$ above 80 general trends can be identified.Comment: 37 pages, 11 figure

A major star formation region in the receding tip of the stellar Galactic bar. II. Supplementary information and evidence that the bar is not the same structure as the triaxial bulge previouly reported

This paper is the second part of Garzon et al. (1997: ApJ 491, L31) in which we presented an outline of the analysis of 60 spectra from a follow-up program to the Two Micron Galactic Survey (TMGS) project in the l=27 deg., b=0 deg. area. In this second part, we present a more detailed explanation of the analysis as well a library of the spectra for more complete information for each of the 60 stars, and further discussions on the implications for the structure of the Galaxy. This region contains a prominent excess in the flux distribution and star counts previously observed in several spectral ranges, notably in the TMGS. More than 50% of the spectra of the stars detected with m_K<5.0 mag, within a very high confidence level, correspond to stars of luminosity class I, and a significant proportion of the remainder are very late giants which must also be rapidly evolving. We make the case, using all the available evidence, that we are observing a region at the nearer end of the Galactic bar, where the Scutum spiral arm breaks away, and that this is powerful evidence for the presence of the bar. Alternative explanations do not give nearly such a satisfactory account of the observations. The space localization of one and, a fortiori, of both ends of the bar allows us to infer a position angle for the bar of around 75 deg. with respect to the Sun-Galactic centre line. The angle is different from that given by other authors for the bar and this, we think, is because they refer to the triaxial bulge and not to the bar as detected here.Comment: 21 pages, 1 table, 9 figures, accepted in A

A major star formation region in the receding tip of the stellar Galactic bar

We present an analysis of the optical spectroscopy of 58 stars in the Galactic plane at $l=27$\arcdeg, where a prominent excess in the flux distribution and star counts have been observed in several spectral regions, in particular in the Two Micron Galactic Survey (TMGS) catalog. The sources were selected from the TMGS, to have a $K$ magnitude brighter than +5 mag and be within 2 degrees of the Galactic plane. More than 60% of the spectra correspond to stars of luminosity class I, and a significant proportion of the remainder are very late giants which would also be fast evolving. This very high concentration of young sources points to the existence of a major star formation region in the Galactic plane, located just inside the assumed origin of the Scutum spiral arm. Such regions can form due to the concentrations of shocked gas where a galactic bar meets a spiral arm, as is observed at the ends of the bars of face-on external galaxies. Thus, the presence of a massive star formation region is very strong supporting evidence for the presence of a bar in our Galaxy.Comment: 13 pages (latex) + 4 figures (eps), accepted in ApJ Let

Stiff monatomic gold wires with a spinning zigzag geometry

Using first principles density functional calculations, gold monatomic wires are found to exhibit a zigzag shape which remains under tension, becoming linear just before breaking. At room temperature they are found to spin, what explains the extremely long apparent interatomic distances shown by electron microscopy.The zigzag structure is stable if the tension is relieved, the wire holding its chainlike shape even as a free-standing cluster. This unexpected metallic-wire stiffness stems from the transverse quantization in the wire, as shown in a simple free electron model.Comment: 4 pages, latex, 5 figures, submitted to PR

Plasmin activity in Manchega ewe milk: The effect of lactation, parity and health of the udder, and its influence on milk composition and rennet coagulation

Milk from 40 Manchega ewes was collected monthly and analysed during a complete lactation (5 months). Milk samples were classified by their origin in 3 categories, termed PR (primiparous ewes), M1 (multiparous ewes with no damage of the udder in the previous lactation) and M2 (multiparous ewes with udder damage in the previous lactation). The influence on plasmin of several factors as stage of lactation, parity, somatic cell count and udder health status was studied, as well as the effect of plasmin activity on milk composition and rennet coagulation. Plasmin activity decreased throughout lactation but was not affected by parity or somatic cell count (P > 0.05). A strong negative correlation was found between plasmin activity and protein (especially casein), presumably due to the proteolysis of ß-casein. Plasmin also worsened rennet coagulation, increasing rennet clotting time (RCT) and negatively affecting curd firmness (A60), especially in multiparous ewes. However, the good health condition in the herd may have camouflaged some effects of plasmin over renneting

A QM/MM approach for the study of monolayer-protected gold clusters

We report the development and implementation of hybrid methods that combine quantum mechanics (QM) with molecular mechanics (MM) to theoretically characterize thiolated gold clusters. We use, as training systems, structures such as Au25(SCH2-R)18 and Au38(SCH2-R)24, which can be readily compared with recent crystallographic data. We envision that such an approach will lead to an accurate description of key structural and electronic signatures at a fraction of the cost of a full quantum chemical treatment. As an example, we demonstrate that calculations of the 1H and 13C NMR shielding constants with our proposed QM/MM model maintain the qualitative features of a full DFT calculation, with an order-of-magnitude increase in computational efficiency.Comment: Journal of Materials Science, 201

Granzyme A inhibition reduces inflammation and increases survival during abdominal sepsis

Aims: Peritonitis is one of the most common causes of sepsis, a serious syndrome characterized by a dysregulated systemic inflammatory response. Recent evidence suggests that Granzyme A (GzmA), a serine protease mainly expressed by NK and T cells, could act as a proinflammatory mediator and could play an important role in the pathogenesis of sepsis. This work aims to analyze the role and the therapeutic potential of GzmA in the pathogenesis of peritoneal sepsis. Methods: The level of extracellular GzmA as well as GzmA activity were analyzed in serum from healthy volunteers and patients with confirmed peritonitis and were correlated with the Sequential Organ Failure Assessment (SOFA) score. Peritonitis was induced in C57Bl/6 (WT) and GzmA-/- mice by cecal ligation and puncture (CLP). Mice were treated intraperitoneally with antibiotics alone or in combination serpinb6b, a specific GzmA inhibitor, for 5 days. Mouse survival was monitored during 14 days, levels of some proinflammatory cytokines were measured in serum and bacterial load and diversity was analyzed in blood and spleen at different times. Results: Clinically, elevated GzmA was observed in serum from patients with abdominal sepsis suggesting that GzmA plays an important role in this pathology. In the CLP model GzmA deficient mice, or WT mice treated with an extracellular GzmA inhibitor, showed increased survival, which correlated with a reduction in proinflammatory markers in both serum and peritoneal lavage fluid. GzmA deficiency did not influence bacterial load in blood and spleen and GzmA did not affect bacterial replication in macrophages in vitro, indicating that GzmA has no role in bacterial control. Analysis of GzmA in lymphoid cells following CLP showed that it was mainly expressed by NK cells. Mechanistically, we found that extracellular active GzmA acts as a proinflammatory mediator in macrophages by inducing the TLR4-dependent expression of IL-6 and TNFa. Conclusions: Our findings implicate GzmA as a key regulator of the inflammatory response during abdominal sepsis and provide solid evidences about its therapeutic potential for the treatment of this severe pathology

An upper limit on hypertriton production in collisions of Ar(1.76 AGeV)+KCl

A high-statistic data sample of Ar(1.76 AGeV)+KCl events recorded with HADES is used to search for a hypertriton signal. An upper production limit per centrality-triggered event of $1.04$ x $10^{-3}$ on the $3\sigma$ level is derived. Comparing this value with the number of successfully reconstructed $\Lambda$ hyperons allows to determine an upper limit on the ratio $N_{_{\Lambda}^3H}/N_{\Lambda}$, which is confronted with statistical and coalescence-type model calculations