Spontaneous S–Si bonding of alkanethiols to Si(111)–H: towards Si–molecule–Si circuits

We report the synthesis of covalently linked self-assembled monolayers (SAMs) on silicon surfaces, using mild conditions, in a way that is compatible with silicon-electronics fabrication technologies. In molecular electronics, SAMs of functional molecules tethered to gold via sulfur linkages dominate, but these devices are not robust in design and not amenable to scalable manufacture. Whereas covalent bonding to silicon has long been recognized as an attractive alternative, only formation processes involving high temperature and/or pressure, strong chemicals, or irradiation are known. To make molecular devices on silicon under mild conditions with properties reminiscent of Au–S ones, we exploit the susceptibility of thiols to oxidation by dissolved O2, initiating free-radical polymerization mechanisms without causing oxidative damage to the surface. Without thiols present, dissolved O2 would normally oxidize the silicon and hence reaction conditions such as these have been strenuously avoided in the past. The surface coverage on Si(111)–H is measured to be very high, 75% of a full monolayer, with density-functional theory calculations used to profile spontaneous reaction mechanisms. The impact of the Si–S chemistry in single-molecule electronics is demonstrated using STM-junction approaches by forming Si–hexanedithiol–Si junctions. Si–S contacts result in single-molecule wires that are mechanically stable, with an average lifetime at room temperature of 2.7 s, which is five folds higher than that reported for conventional molecular junctions formed between gold electrodes. The enhanced “ON” lifetime of this single-molecule circuit enables previously inaccessible electrical measurements on single molecules

Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry

Predicting or manipulating charge-transfer at semiconductor interfaces, from molecular electronics to energy conversion, relies on knowledge generated from a kinetic analysis of the electrode process, as provided by cyclic voltammetry. Scientists and engineers encountering non-ideal shapes and positions in voltammograms are inclined to reject these as flaws. Here we show that non-idealities of redox probes confined at silicon electrodes, namely full width at half maximum <90.6 mV and anti-thermodynamic inverted peak positions, can be reproduced and are not flawed data. These are the manifestation of electrostatic interactions between dynamic molecular charges and the semiconductor's space-charge barrier. We highlight the interplay between dynamic charges and semiconductor by developing a model to decouple effects on barrier from changes to activities of surface-bound molecules. These findings have immediate general implications for a correct kinetic analysis of charge-transfer at semiconductors as well as aiding the study of electrostatics on chemical reactivity.This work was supported by grants from the Australian Research Council (ARC, DE160100732 (S.C.), DE160101101 (N.D.)). J.G.S. and A.M. greatly appreciate the financial support provided by the Fundación Séneca de la Región de Murcia (Projects 19887/GERM/15 and 18968/JLI/13) and by the Ministerio de Economía y Competitividad (projects CTQ-2015-65243-P and CTQ-2015-71955-REDT Network of excellence “Sensors and Biosensors”). L.Z., M.L.C., and G.G.W. acknowledge funding from the ARC Centre of Excellence Scheme (Project No. CE 140100012). J.J.G. and G.G.W. are under ARC Laureate Fellowships (FL150100060 and FL110100196)

The zCOSMOS 10k-Bright Spectroscopic Sample

We present spectroscopic redshifts of a large sample of galaxies with I_(AB) < 22.5 in the COSMOS field, measured from spectra of 10,644 objects that have been obtained in the first two years of observations in the zCOSMOS-bright redshift survey. These include a statistically complete subset of 10,109 objects. The average accuracy of individual redshifts is 110 km s^(–1), independent of redshift. The reliability of individual redshifts is described by a Confidence Class that has been empirically calibrated through repeat spectroscopic observations of over 600 galaxies. There is very good agreement between spectroscopic and photometric redshifts for the most secure Confidence Classes. For the less secure Confidence Classes, there is a good correspondence between the fraction of objects with a consistent photometric redshift and the spectroscopic repeatability, suggesting that the photometric redshifts can be used to indicate which of the less secure spectroscopic redshifts are likely right and which are probably wrong, and to give an indication of the nature of objects for which we failed to determine a redshift. Using this approach, we can construct a spectroscopic sample that is 99% reliable and which is 88% complete in the sample as a whole, and 95% complete in the redshift range 0.5 < z < 0.8. The luminosity and mass completeness levels of the zCOSMOS-bright sample of galaxies is also discussed

Lyman-alpha Forest Tomography from Background Galaxies: The First Megaparsec-Resolution Large-Scale Structure Map at z>2

We present the first observations of foreground Lyman-$\alpha$ forest absorption from high-redshift galaxies, targeting 24 star-forming galaxies (SFGs) with $z\sim 2.3-2.8$ within a $5' \times 15'$ region of the COSMOS field. The transverse sightline separation is $\sim 2\,h^{-1}\mathrm{Mpc}$ comoving, allowing us to create a tomographic reconstruction of the 3D Ly$\alpha$ forest absorption field over the redshift range $2.20\leq z\leq 2.45$. The resulting map covers $6\,h^{-1}\mathrm{Mpc} \times 14\,h^{-1}\mathrm{Mpc}$ in the transverse plane and $230\,h^{-1}\mathrm{Mpc}$ along the line-of-sight with a spatial resolution of $\approx 3.5\,h^{-1}\mathrm{Mpc}$, and is the first high-fidelity map of large-scale structure on $\sim\mathrm{Mpc}$ scales at $z>2$. Our map reveals significant structures with $\gtrsim 10\,h^{-1}\mathrm{Mpc}$ extent, including several spanning the entire transverse breadth, providing qualitative evidence for the filamentary structures predicted to exist in the high-redshift cosmic web. Simulated reconstructions with the same sightline sampling, spectral resolution, and signal-to-noise ratio recover the salient structures present in the underlying 3D absorption fields. Using data from other surveys, we identified 18 galaxies with known redshifts coeval with our map volume enabling a direct comparison to our tomographic map. This shows that galaxies preferentially occupy high-density regions, in qualitative agreement with the same comparison applied to simulations. Our results establishes the feasibility of the CLAMATO survey, which aims to obtain Ly$\alpha$ forest spectra for $\sim 1000$ SFGs over $\sim 1 \,\mathrm{deg}^2$ of the COSMOS field, in order to map out IGM large-scale structure at $\langle z \rangle \sim 2.3$ over a large volume $(100\,h^{-1}\mathrm{Mpc})^3$.Comment: Accepted for publication in Astrophysical Journal Letters; 8 pages and 5 figure

Antibiotic resistance and host immune evasion in Staphylococcus aureus mediated by a metabolic adaptation

Staphylococcus aureus is a notorious human bacterial pathogen with considerable capacity to develop antibiotic resistance. We have observed that human infections caused by highly drug-resistant S. aureus are more prolonged, complicated, and difficult to eradicate. Here we describe a metabolic adaptation strategy used by clinical S. aureus strains that leads to resistance to the last-line antibiotic, daptomycin, and simultaneously affects host innate immunity. This response was characterized by a change in anionic membrane phospholipid composition induced by point mutations in the phospholipid biosynthesis gene, cls2, encoding cardiolipin synthase. Single cls2 point mutations were sufficient for daptomycin resistance, antibiotic treatment failure, and persistent infection. These phenotypes were mediated by enhanced cardiolipin biosynthesis, leading to increased bacterial membrane cardiolipin and reduced phosphatidylglycerol. The changes in membrane phospholipid profile led to modifications in membrane structure that impaired daptomycin penetration and membrane disruption. The cls2 point mutations also allowed S. aureus to evade neutrophil chemotaxis, mediated by the reduction in bacterial membrane phosphatidylglycerol, a previously undescribed bacterial-driven chemoattractant. Together, these data illustrate a metabolic strategy used by S. aureus to circumvent antibiotic and immune attack and provide crucial insights into membrane-based therapeutic targeting of this troublesome pathogen

pH-dependent interactions of coacervate-forming histidine-rich peptide with model lipid membranes

Peptide-based liquid droplets (coacervates) produced by spontaneous liquid-liquid phase separation (LLPS), have emerged as a promising class of drug delivery systems due to their high entrapping efficiency and the simplicity of their formulation. However, the detailed mechanisms governing their interaction with cell membranes and cellular uptake remain poorly understood. In this study, we investigated the interactions of peptide coacervates composed of HBpep—peptide derived from the histidine-rich beak proteins (HBPs) of the Humboldt squid—with model cellular membranes in the form of supported lipid bilayers (SLBs). We employed quartz crystal microbalance with dissipation monitoring (QCM-D), neutron reflectometry (NR) and atomistic molecular dynamics (MD) simulations to reveal the nature of these interactions in the absence of fluorescent labels or tags. HBpep forms small oligomers at pH 6 whereas it forms µm-sized coacervates at physiological pH. Our findings reveal that both HBpep oligomers and HBpep-coacervates adsorb onto SLBs at pH 6 and 7.4, respectively. At pH 6, when the peptide carries a net positive charge, HBpep oligomers insert into the SLB, facilitated by the peptide’s interactions with the charged lipids and cholesterol. Importantly, however, HBpep coacervate adsorption at physiological pH, when it is largely uncharged, is fully reversible, suggesting no significant lipid bilayer rearrangement. HBpep coacervates, previously identified as efficient drug delivery vehicles, do not interact with the lipid membrane in the same manner as traditional cationic drug delivery systems or cell-penetrating peptides. Based on our findings, HBpep coacervates at physiological pH cannot cross the cell membrane by a simple passive mechanism and are thus likely to adopt a non-canonical cell entry pathway

Mass and environment as drivers of galaxy evolution in SDSS and zCOSMOS and the origin of the Schechter function

We explore the inter-relationships between mass, star-formation rate and environment in the SDSS, zCOSMOS and other surveys. The differential effects of mass and environment are completely separable to z ~ 1, indicating that two distinct processes are operating, "mass-quenching" and "environment-quenching". Environment-quenching, at fixed over-density, evidently does not change with epoch to z ~ 1, suggesting that it occurs as large-scale structure develops in the Universe. The observed constancy of the mass-function shape for star-forming galaxies, demands that the mass-quenching of galaxies around and above M*, must be proportional to their star-formation rates at all z < 2. We postulate that this simple mass-quenching law also holds over a much broader range of stellar mass and epoch. These two simple quenching processes, plus some additional quenching due to merging, then naturally produce (a) a quasi-static Schechter mass function for star-forming galaxies with a value of M* that is set by the proportionality between the star-formation and mass-quenching rates, (b) a double Schechter function for passive galaxies with two components: the dominant one is produced by mass-quenching and has exactly the same M* as the star-forming galaxies but an alpha shallower by +1, while the other is produced by environment effects and has the same M* and alpha as the star-forming galaxies, and is larger in high density environments. Subsequent merging of quenched galaxies modifies these predictions somewhat in the denser environments, slightly increasing M* and making alpha more negative. All of these detailed quantitative relationships between the Schechter parameters are indeed seen in the SDSS, lending strong support to our simple empirically-based model. The model naturally produces for passive galaxies the "anti-hierarchical" run of mean ages and alpha-element abundances with mass.Comment: 66 pages, 19 figures, 1 movie, accepted for publication in ApJ. The movie is also available at http://www.exp-astro.phys.ethz.ch/zCOSMOS/MF_simulation_d1_d4.mo

Role of Bcl-2 as a prognostic factor for survival in lung cancer: a systematic review of the literature with meta-analysis

The role of the anti-apoptotic protein Bcl-2 in lung cancer remains controversial. In order to clarify its impact on survival in small and non-small cell lung cancer (NSCLC), we performed a systematic review of the literature. Trials were selected for further analysis if they provided an independent assessment of Bcl-2 in lung cancer and reported analysis of survival data according to Bcl-2 status. To make it possible to aggregate survival results of the published studies, their methodology was assessed using a quality scale designed by the European Lung Cancer Working Party (including study design, laboratory methods and analysis). Of 28 studies, 11 identified Bcl-2 expression as a favourable prognostic factor and three linked it with poor prognosis; 14 trials were not significant. No differences in scoring measurement were detected between the studies, except that significantly higher scores were found in the trials with the largest sample sizes. Assessments of methodology and of laboratory technique were made independently of the conclusion of the trials. A total of 25 trials, comprising 3370 patients, provided sufficient information for the meta-analysis. The studies were categorised according to histology, disease stage and laboratory technique. The combined hazard ratio (HR) suggested that a positive Bcl-2 status has a favourable impact on survival: 0.70 (95% confidence interval 0.57-0.86) in seven studies on stages I-II NSCLC; 0.50 (0.39-0.65) in eight studies on surgically resected NSCLC; 0.91 (0.76-1.10) in six studies on any stage NSCLC; 0.57 (0.41-0.78) in five studies on squamous cell cancer; 0.75 (0.61-0.93) and 0.71 (0.61-0.83) respectively for five studies detecting Bcl-2 by immunohistochemistry with Ab clone 100 and for 13 studies assessing Bcl-2 with Ab clone 124; 0.92 (0.73-1.16) for four studies on small cell lung cancer; 1.26 (0.58-2.72) for three studies on neuroendocrine tumours. In NSCLC, Bcl-2 expression was associated with a better prognosis. The data on Bcl-2 expression in small cell lung cancer were insufficient to assess its prognostic value.Journal ArticleMeta-AnalysisResearch Support, Non-U.S. Gov'tReviewinfo:eu-repo/semantics/publishe

The data acquisition system for the ANTARES neutrino telescope

The ANTARES neutrino telescope is being constructed in the Mediterranean Sea. It consists of a large three-dimensional array of photo-multiplier tubes. The data acquisition system of the detector takes care of the digitisation of the photo-multiplier tube signals, data transport, data filtering, and data storage. The detector is operated using a control program interfaced with all elements. The design and the implementation of the data acquisition system are described.Comment: 20 pages, 6 figures, accepted for publication in Nucl. Instrum. Meth.