Vibrational spectrum of solid picene (C_22H_14)

Recently, Mitsuhashi et al., have observed superconductivity with transition temperature up to 18 K in potassium doped picene (C22H14), a polycyclic aromatic hydrocarbon compound [Nature 464 (2010) 76]. Theoretical analysis indicate the importance of electron-phonon coupling in the superconducting mechanisms of these systems, with different emphasis on inter- and intra-molecular vibrations, depending on the approximations used. Here we present a combined experimental and ab-initio study of the Raman and infrared spectrum of undoped solid picene, which allows us to unanbiguously assign the vibrational modes. This combined study enables the identification of the modes which couple strongly to electrons and hence can play an important role in the superconducting properties of the doped samples

Generation of Alkyl Radicals:From the Tyranny of Tin to the Photon Democracy

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides to the point that "flight from the tyranny of tin"in radical processes was considered for a long time an unavoidable issue. This review summarizes the main alternative approaches for the generation of unstabilized alkyl radicals, using photons as traceless promoters. The recent development in photochemical and photocatalyzed processes enabled the discovery of a plethora of new alkyl radical precursors, opening the world of radical chemistry to a broader community, thus allowing a new era of photon democracy

Simulations of primary beam effects on the cosmic bispectrum phase observed with the Hydrogen Epoch of Reionization Array

The 21~cm transition from neutral Hydrogen promises to be the best observational probe of the Epoch of Reionisation. The main difficulty in measuring the 21 cm signal is the presence of bright foregrounds that require very accurate interferometric calibration. Closure quantities may circumvent the calibration requirements but may be, however, affected by direction dependent effects, particularly antenna primary beam responses. This work investigates the impact of antenna primary beams affected by mutual coupling on the closure phase and its power spectrum. Our simulations show that primary beams affected by mutual coupling lead to a leakage of foreground power into the EoR window, which can be up to $\sim4$ orders magnitude higher than the case where no mutual coupling is considered. This leakage is, however, essentially confined at $k < 0.3$~$h$~Mpc$^{-1}$ for triads that include 29~m baselines. The leakage magnitude is more pronounced when bright foregrounds appear in the antenna sidelobes, as expected. Finally, we find that triads that include mutual coupling beams different from each other have power spectra similar to triads that include the same type of mutual coupling beam, indicating that beam-to-beam variation within triads (or visibility pairs) is not the major source of foreground leakage in the EoR window

DAYENU: a simple filter of smooth foregrounds for intensity mapping power spectra

We introduce DPSS Approximate lazY filtEriNg of foregroUnds (DAYENU), a linear, spectral filter for H I intensity mapping that achieves the desirable foreground mitigation and error minimization properties of inverse co-variance weighting with minimal modelling of the underlying data. Beyond 21-cm power-spectrum estimation, our filter is suitable for any analysis where high dynamic-range removal of spectrally smooth foregrounds in irregularly (or regularly) sampled data is required, something required by many other intensity mapping techniques. Our filtering matrix is diagonalized by Discrete Prolate Spheroidal Sequences which are an optimal basis to model band-limited foregrounds in 21-cm intensity mapping experiments in the sense that they maximally concentrate power within a finite region of Fourier space. We show that DAYENU enables the access of large-scale line-of-sight modes that are inaccessible to tapered discrete Fourier transform estimators. Since these modes have the largest SNRs,DAYENU significantly increases the sensitivity of 21-cm analyses over tapered Fourier transforms. Slight modifications allow us to use DAYENU as a linear replacement for iterative delay CLEAN ing (DAYENUREST). We refer readers to the Code section at the end of this paper for links to examples and code

Hydrogen Epoch of Reionization Array (HERA)

The Hydrogen Epoch of Reionization Array (HERA) is a staged experiment to measure 21 cm emission from the primordial intergalactic medium (IGM) throughout cosmic reionization ($z=6-12$), and to explore earlier epochs of our Cosmic Dawn ($z\sim30$). During these epochs, early stars and black holes heated and ionized the IGM, introducing fluctuations in 21 cm emission. HERA is designed to characterize the evolution of the 21 cm power spectrum to constrain the timing and morphology of reionization, the properties of the first galaxies, the evolution of large-scale structure, and the early sources of heating. The full HERA instrument will be a 350-element interferometer in South Africa consisting of 14-m parabolic dishes observing from 50 to 250 MHz. Currently, 19 dishes have been deployed on site and the next 18 are under construction. HERA has been designated as an SKA Precursor instrument. In this paper, we summarize HERA's scientific context and provide forecasts for its key science results. After reviewing the current state of the art in foreground mitigation, we use the delay-spectrum technique to motivate high-level performance requirements for the HERA instrument. Next, we present the HERA instrument design, along with the subsystem specifications that ensure that HERA meets its performance requirements. Finally, we summarize the schedule and status of the project. We conclude by suggesting that, given the realities of foreground contamination, current-generation 21 cm instruments are approaching their sensitivity limits. HERA is designed to bring both the sensitivity and the precision to deliver its primary science on the basis of proven foreground filtering techniques, while developing new subtraction techniques to unlock new capabilities. The result will be a major step toward realizing the widely recognized scientific potential of 21 cm cosmology.Comment: 26 pages, 24 figures, 2 table

Probing the photoreactivity of aryl chlorides with oxygen

Molecular oxygen was used to probe the mechanism of the phototransformation of chlorobenzene and 4-chloroanisole in organic solvents. Laser. ash photolysis, electron paramagnetic resonance and product distribution studies clarified the reaction mechanisms of these compounds under a wide range of conditions. The main primary photochemical reaction step is the homolytic cleavage of the C-Cl bond to produce a triplet radical pair in the solvent cage. In non-polar solvents hydrogen abstraction, after radical diffusion, leads to reduction. In polar solvents, in addition to H-abstraction, electron transfer within the caged radical pair occurs and leads to an ion pair (phenyl cation and Cl(-)). In the presence of oxygen, phenyl radicals can form phenylperoxyl radicals which have a bathochromically shifted absorption, thus making the homolytic cleavage visible by. ash photolysis. The peroxyl radicals can couple, leading to more polar compounds, or undergo back reaction to the phenyl radical. For concentrations of the aryl chlorides of higher than 10(-3) M, dimerization becomes an important transformation process and occurs after reaction of the transients with ground state molecules. In addition, excimer formation is postulated to be involved in the dimerization process

Differential effects of age, cytomegalovirus-seropositivity and end-stage renal disease (ESRD) on circulating T lymphocyte subsets

The age- and cytomegalovirus (CMV)-seropositivity-related changes in subsets and differentiation of circulating T cells were investigated in end-stage renal disease (ESRD) patients (n = 139) and age-matched healthy individuals. The results show that CMV-seropositivity is associated with expansion of both CD4+ and CD8+ memory T cells which is already observed in young healthy individuals. In addition, CMV-seropositive healthy individuals have a more differentiated memory T cell profile. Only CMV-seropositive healthy individuals showed an age-dependent decrease in CD4+ naïve T cells. The age-related decrease in the number of CD8+ naïve T cells was CMV-independent. In contrast, all ESRD patients showed a profound naïve T-cell lymphopenia at every decade. CMV-seropositivity aggravated the contraction of CD4+ naïve T cells and increased the number of differentiated CD4+ and CD8+ memory T cells. In conclusion, CMV-seropositivity markedly alters the homeostasis of circulating T cells in healthy individuals and aggravates the T cell dysregulation observed in ESRD patients

Photoinduced energy- and electron-transfer from a photoactive coordination cage to bound guests.

In a coordination cage which contains an array of twelve naphthyl chromophores surrounding a central cavity, photoinduced energy or electron-transfer can occur from the chromophore array to the bound guest in supramolecular host/guest complexes

Epidemiological and clinical features, response to HAART, and survival in HIV-infected patients diagnosed at the age of 50 or more

BACKGROUND: Over the last years, the mean age of subjects with HIV infection and AIDS is increasing. Moreover, some epidemiological and clinical differences between younger and older HIV-infected individuals have been observed. However, since introduction of HAART therapy, there are controversial results regarding their response to HAART. The aim of the present study is to evaluate epidemiological and clinical features, response to HAART, and survival in elderly HIV-infected patients with regard to younger HIV-infected patients. METHODS: A prospective cohort study (1998–2003) was performed on patients from Sabadell Hospital, in Northeast of Spain. The cohort includes newly attended HIV-infected patients since January 1, 1998. For the purpose of this analysis, data was censured at December 31, 2003. Taking into account age at time of diagnosis, it was considered 36 HIV-positive people aged 50 years or more (Group 1, G1) and 419 HIV-positive people aged 13–40 years (Group 2, G2). Epidemiological, clinical, biological and therapy data are recorded. Statistical analysis was performed using Chi-squared test and Fisher exact test, Mann-Whitney U test, Kaplan-Meier, Log Rank test, and Two-Way ANOVA from random factors. RESULTS: G1 showed higher proportion of men than G2. The most common risk factors in G1 were heterosexual transmission (P = 0.01) and having sex with men or women (P < 0.001). G1 and G2 show parallel profiles through the time regarding immunological response (P = 0.989) and virological response (P = 0.074). However, older people showed lower CD4 cell counts at first clinic visit (P < 0.001) and, eventually, they did not achieve the same counts as G2. G1 presented faster progression to AIDS (P < 0.001) and shorter survival (P < 0.001). CONCLUSION: Older patients have different epidemiological features. Their immunological and virological responses are good. However, older patients do not achieve the same CD4 cell counts likely due to they have lower counts at first clinic visit. Thus, it is essential physicians know older HIV-infected patients features to consider the possibility of HIV infection in these patients with the aim of treatment would not be delayed