A Fluctuation Equation of State for Prediction of High-Pressure Densities of Ionic Liquids

International audienceDuring this work, we demonstrate, for the first time, that the volumetric properties of pure ionic liquids could be truly predicted as a function of temperature from 219 K to 473 K and pressure up to 300 MPa. This has been achieved by using only density and isothermal compressibility data at atmospheric pressure through the Fluctuation Theory-based Tait-like Equation of State (FT-EoS). The experimental density data of 80 different ionic liquids, described in the literature by several research groups as a function of temperature and pressure, was then used to provide comparisons. Excellent predictive capability of FT-EoS was observed with an overall relative absolute average deviation close to 0.14% for the 15,298 data points examined during this work

Treatment of a groin lymphatic fistula with negative pressure wound therapy.

peer reviewed[en] INTRODUCTION: Groin lymphatic fistulas are a troublesome finding after limb revascularization surgery. Its management represents a difficult task for the clinician. REPORT: We report our experience in the treatment of such a condition with negative-pressure wound therapy (NPWT) in a 70-year-old man which benefited from extra-anatomic prosthetic axillofemoral bypass. After a week of treatment, the fistula dried up and closure was obtained with simple suture under local anaesthesia. Follow-up at 9 months showed stable coverage without any sign of leakage. DISCUSSION: This study depicts NPWT as an effective non-invasive treatment in the management of groin lymphocutaneous fistula

Onecut-dependent Nkx6.2 transcription factor expression is required for proper formation and activity of spinal locomotor circuits.

In the developing spinal cord, Onecut transcription factors control the diversification of motor neurons into distinct neuronal subsets by ensuring the maintenance of Isl1 expression during differentiation. However, other genes downstream of the Onecut proteins and involved in motor neuron diversification have remained unidentified. In the present study, we generated conditional mutant embryos carrying specific inactivation of Onecut genes in the developing motor neurons, performed RNA-sequencing to identify factors downstream of Onecut proteins in this neuron population, and employed additional transgenic mouse models to assess the role of one specific Onecut-downstream target, the transcription factor Nkx6.2. Nkx6.2 expression was up-regulated in Onecut-deficient motor neurons, but strongly downregulated in Onecut-deficient V2a interneurons, indicating an opposite regulation of Nkx6.2 by Onecut factors in distinct spinal neuron populations. Nkx6.2-null embryos, neonates and adult mice exhibited alterations of locomotor pattern and spinal locomotor network activity, likely resulting from defective survival of a subset of limb-innervating motor neurons and abnormal migration of V2a interneurons. Taken together, our results indicate that Nkx6.2 regulates the development of spinal neuronal populations and the formation of the spinal locomotor circuits downstream of the Onecut transcription factors

Making Sense of Family Deaths in Urban Senegal: Diversities, Contexts, and Comparisons

Despite calls for cross-cultural research, Minority world perspectives still dominate death and bereavement studies, emphasizing individualized emotions and neglecting contextual diversities. In research concerned with contemporary African societies, on the other hand, death and loss are generally subsumed within concerns about AIDS or poverty, with little attention paid to the emotional and personal significance of a death. Here, we draw on interactionist sociology to present major themes from a qualitative study of family deaths in urban Senegal, theoretically framed through the duality of meanings-in-context. Such themes included family and community as support and motivation; religious beliefs and practices as frameworks for solace and (regulatory) meaning; and material circumstances as these are intrinsically bound up with emotions. Although we identify the experience of (embodied, emotional) pain as a common response across Minority and Majority worlds, we also explore significant divergencies, varying according to localized contexts and broader power dynamics

Contrasted photochromic and luminescent properties in dinuclear Pt(II) complexes linked through a central dithienylethene unit

We disclose two unprecedented complexes built with a central dithienylethene photochrome connecting two cyclometalated Pt(ii) moieties either on the reactive carbon atoms or on the lateral non-reactive carbon atoms of the photochrome. The two systems show vastly different properties that are rationalised thanks to quantum-chemical calculations

Spectroscopy with random and displaced random ensembles

Due to the time reversal invariance of the angular momentum operator J^2, the average energies and variances at fixed J for random two-body Hamiltonians exhibit odd-even-J staggering, that may be especially strong for J=0. It is shown that upon ensemble averaging over random runs, this behaviour is reflected in the yrast states. Displaced (attractive) random ensembles lead to rotational spectra with strongly enhanced BE2 transitions for a certain class of model spaces. It is explained how to generalize these results to other forms of collectivity.Comment: 4 pages, 4 figure

Noncommutative Switching of Double Spiropyrans

The spiropyran family of photochromes are key components in molecular-based responsive materials and devices, e.g., as multiphotochromes, covalently coupled dyads, triads, etc. This attention is in no small part due to the change in properties that accompany the switch between spiropyran and merocyanine forms. Although the spiropyran is a single structural isomer, the merocyanine form represents a family of isomers (TTT, TTC, CCT, etc.) and protonation states. Combining two spiropyrans into one compound increases the number of possible structures dramatically and the interaction between the units determines, which are impeded due to intramolecular quenching of excited states. Here, we show that the coupling of two spiropyran photochromes through their phenol units yields favorable interactions (crosstalk) between the components that provides access to species inaccessible with the component monospiropyran alone. Specifically, the ring opening of one spiropyran unit, which is thermally stable at-30 °C, prevents ring opening of the second spiropyran unit. Furthermore, whereas protonated E-and Z-monomerocyanines were previously shown to undergo thermal-and photo-equilibration, the corresponding protonated E-and Z-bimerocyanines are thermally stable and show one-way photoisomerization from the Z,Z-to an emissive E,E-bimerocyanine form. Subsequent deprotonation at room temperature resets the system to the bispiro ring-closed form, but deprotonation at-30 °C yields the otherwise inaccessible bimerocyanine form. This form is photochemically inert but undergoes a two-step thermal relaxation via the merocyanine-spiropyran form, showing that the connection at the phenol units provides sufficient intramolecular interaction to fine-tune the complex isomerization pathways of spiropyrans and demonstrating noncommutability in photo-and pH-regulated multistep isomerization pathways

Isobaric and Isochoric Heat Capacities of Imidazolium-Based and Pyrrolidinium-Based Ionic Liquids as Function of Temperature: Modeling of Isobaric Heat Capacity

International audienceThe isobaric and isochoric heat capacities of seven 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides, two 1-alkyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides, and two bis(1-alkyl-3-methylimidazolium) tetrathiocyanatocobaltates were determined at atmospheric pressure in the temperature range from 293.15 to 323.15 K. The isobaric heat capacities were determined by means of differential scanning calorimetry, whereas isochoric heat capacities were determined along with isothermal compressibilities indirectly by means of the acoustic method from the speed of sound and density measurements. Based on the experimental data, as expected, the isobaric heat capacity increases linearly with increasing alkyl chain length in the cation of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides and no odd and even carbon number effect is observed. After critical comparison of the obtained data with the available literature data, the most reliable values are recommended. It has been also shown that, although the COSMOthermX calculations underestimated the isobaric heat capacity values whatever the temperature and the ionic liquid structure, the approach used during this work may be applied to estimate physical properties of non-single-charged ions as well. Additionally, based on the speeds of sound the thermal conductivities were calculated using a modified Bridgman relation

Reference materials for phase equilibrium studies. 1. Liquid–liquid equilibria (IUPAC Technical Report)

This article is the first of three projected IUPAC Technical Reports resulting from IUPAC Project 2011-037-2-100 (Reference Materials for Phase Equilibrium Studies). The goal of this project is to select reference systems with critically evaluated property values for the validation of instruments and techniques used in phase equilibrium studies of mixtures. This report proposes seven systems for liquid–liquid equilibrium studies, covering the four most common categories of binary mixtures: aqueous systems of moderate solubility, non-aqueous systems, systems with low solubility, and systems with ionic liquids. For each system, the available literature sources, accepted data, smoothing equations, and estimated uncertainties are given

Cross-sectional associations between air pollution and chronic bronchitis: an ESCAPE meta-analysis across five cohorts

BACKGROUND: This study aimed to assess associations of outdoor air pollution on prevalence of chronic bronchitis symptoms in adults in five cohort studies (Asthma-E3N, ECRHS, NSHD, SALIA, SAPALDIA) participating in the European Study of Cohorts for Air Pollution Effects (ESCAPE) project. METHODS: Annual average particulate matter (PM10, PM2.5, PMabsorbance, PMcoarse), NO2, nitrogen oxides (NOx) and road traffic measures modelled from ESCAPE measurement campaigns 2008-2011 were assigned to home address at most recent assessments (1998-2011). Symptoms examined were chronic bronchitis (cough and phlegm for ≥3 months of the year for ≥2 years), chronic cough (with/without phlegm) and chronic phlegm (with/without cough). Cohort-specific cross-sectional multivariable logistic regression analyses were conducted using common confounder sets (age, sex, smoking, interview season, education), followed by meta-analysis. RESULTS: 15 279 and 10 537 participants respectively were included in the main NO2 and PM analyses at assessments in 1998-2011. Overall, there were no statistically significant associations with any air pollutant or traffic exposure. Sensitivity analyses including in asthmatics only, females only or using back-extrapolated NO2 and PM10 for assessments in 1985-2002 (ECRHS, NSHD, SALIA, SAPALDIA) did not alter conclusions. In never-smokers, all associations were positive, but reached statistical significance only for chronic phlegm with PMcoarse OR 1.31 (1.05 to 1.64) per 5 µg/m(3) increase and PM10 with similar effect size. Sensitivity analyses of older cohorts showed increased risk of chronic cough with PM2.5abs (black carbon) exposures. CONCLUSIONS: Results do not show consistent associations between chronic bronchitis symptoms and current traffic-related air pollution in adult European populations