Hydration water and ionic aggregation in aqueous solutions of imidazolium-based protic ionic liquids

Water molecules, present as additive or as contaminant of Protic Ionic Liquids (PILs), can compete for the hydrogen bond sites leading to important modifications of the local order of these liquids and to the modulation of their physical–chemical properties. In this work, aqueous solutions of a set of N-methylimidazolium-based PILs [MIM][X] (X = NO3-- , TfO-- , HSO4-- , and Cl-- ) were investigated by deep UV Resonance Raman (UVRR) spectroscopy in the water-rich domain where ionic aggregates and bulk-like water coexist. A differential method was used to analyze the OH stretching profile to extract the so-called solute-correlated (SC) spectrum, which is particular informative of the hydration features of the PILs. Moreover, specific bands of the cation, sensitive to the hydrogen bonding, were comparatively investigated. The progressive evolution from solvent-separated ion pairs (SIP) and/or solvent-shared ion pairs (SSIP) to contact ion pairs (CIP) and/or larger ionic aggregates can be monitored as a function of the hydration level, in the water-rich domain. Our approach showed that, in the highly diluted regime, the hydration environment around the [MIM] cation does not depend on the type of anion. Moreover, [MIM][NO3] and [MIM][TfO] showed cation-water (ionic) H-bonds at the NH site stronger than the cation–anion (double-ionic) ones. The analysis of SC Raman spectra points out the formation of cation–anion Hbonds (through the CH ring groups), stronger than cation-water ones, upon PILs concentration increase, especially evident in the case of [MIM][Cl]. The H-bond strength between the anion and hydration water is found to decrease following the order: [Cl] ~ [HSO4] > [NO3] > [TfO]. Chloride ions tend to perturb a larger number of water molecules than the other anions. The number of perturbed water molecules decreases at increasing PIL concentration, showing a larger dependence for [MIM][Cl], consistently with its larger propensity to form ionic aggregates. The unique response of [MIM][Cl] to hydration found by analyzing SC-UVRR data is related to the synergy of different factors such as the anion reduced size (higher charge density), spherical symmetry, and high H-bond basicity

In-stent restenosis of superficial femoral artery: use all arrows in the quiver.

In-stent restenosis (ISR) is a common superficial femoral artery (SFA) stenting complication, occurring in more than one third of patients within 2-3 years after the index procedure. Moreover, there is no standard treatment for ISR, and although many options are available, there is still limited data regarding its optimal management. We report a paradigmatic case report of a patient complaining of symptomatic peripheral arterial disease, underwent multiple endovascular revascularizations for recurrent femoro-popliteal ISR. A step-by-step approach was followed. At the time of the first presentation, the ISR was treated by drug-eluting balloon (DEB) angioplasty. The repeated ISR was treated by laser debulking, achieving a good angiographic result. Finally, after the third repeated restenosis, a combined approach with laser debulking and DEB angioplasty guaranteed a good acute angiographic result. Long-term duplex-scan follow-up demonstrated the good patency of the femoro-popliteal target lesion

Study on lipid fractions of Streptococcus thermophilus by TLC, GC and GC/MS techniques

In this research the lipid fraction of two strains of Streptococcus thermophilus was studied. Lipids were extracted by applying Folch method and fractioned by thin layer chromatography (TLC). Fatty acid composition was determined both before TLC, on the total fat extracted, and after TLC on diacylglycerol and apolar fractions. Gas chromatographic analysis was performed by using both flame ionization (FID) and mass spectrometer (MS) detector. The main difference between the two strains was the presence of short and medium chain fatty acids in food-born S. thermophilus. Moreover one of the most important bacterial fatty acids, C19 cyclopropane, was detected only in diacylglycerols, which, as reported in literature, are formed transiently as intermediates in the biosynthesis of glycerophospholipids

Reddening, Absorption, and Decline Rate Corrections for a Complete Sample of Type Ia Supernovae leading to a Fully Corrected Hubble Diagram to v<30,000kms-1

Photometric BVI and redshift data corrected for streaming motions are compiled for 111 "Branch normal", 4 1991T-like, 7 1991bg-like, and 2 unusual SNe Ia. Color excesses E(B-V)host of normal SNe Ia, due to the absorption of the host galaxy, are derived by three independent methods leading to the intrinsic colors at maximum of (B-V)00=-0.024, and (V-I)00=-0.265 if normalized to a common decline rate of Dm_15=1.1. The strong correlation between redshift absolute magnitudes (based on Ho=60), corrected only for the extrinsic Galactic absorption, and the derived E(B-V)host leads to well determined, yet abnormal absorption-to-reddening ratios of R_BVI=3.65, 2.65, and 1.35. Comparison with the canonical Galactic values of 4.1, 3.1, 1.8 forces the conclusion that the law of interstellar absorption in the path length to the SN in the host galaxy is different from the local Galactic law. Improved correlations of the fully corrected absolute magnitudes with host galaxy type, decline rate, and intrinsic color are derived. The four peculiar 1991T-type SNe are significantly overluminous as compared to Branch-normal SNe Ia. The overluminosity of the seven 1999aa-like SNe is less pronounced. The seven 1991bg-types in the sample constitute a separate class of SNeIa, averaging in B two magnitudes fainter than the normal Ia. New Hubble diagrams in BVI are derived out to ~30,000kms-1 using the fully corrected magnitudes and velocities, corrected for streaming motions. Nine solutions for the intercept magnitudes in these diagrams show extreme stability at the 0.04 level using various subsamples of the data. The same precepts for fully correcting SN magnitudes we shall use for the luminosity recalibration of SNe Ia in the forthcoming final review of our HST Cepheid-SN experiment for the Hubble constant.Comment: 49 pages, 15 figures, 8 tables, accepted for publication in the Astrophysical Journa

Sudden cardiac death after robbery: Homicide or natural death?

Tako-Tsubo is one of a number of rare acquired cardiomyopathies that are characterized by left ventricular dyskinesia and symptomatology typical of acute myocardial infarction (AMI). The most important feature is that the clinical features are triggered by a severe physical or emotional stress. The authors describe the story of a woman, who was brutally assaulted by two men during a house robbery and died from sudden heart failure 8 hours later, after being taken to hospital. External examination revealed no macroscopic alteration of the inner organs, whereas microscopy showed contraction bands with myocardial necrosis, subendocardial and interstitial neutrophil infiltration and fibrosis. These findings were consistent with death due to stress cardiomyopathy even in the absence of previous heart disease. The robbers were convicted of homicide and sentenced to eighteen years in prison

Synthesis of Enantioenriched Amines by Iron-Catalysed Amination of Alcohols Employing at Least One Achiral Substrate

The synthesis of a broad range of enantioenriched amines by the direct Fe-catalysed coupling of amines with alcohols through the borrowing hydrogen strategy, while at least one of these substrates is achiral is reported. When starting from α-chiral amines and achiral alcohols, a wide range of enantioenriched amine products, including N-heterocyclic moieties can be obtained with complete retention of stereochemistry and the power of this method is demonstrated in the one-step synthesis of known pharmaceuticals from commercially available, simple enantiopure primary amines and achiral alcohols. It was also found that the use of β-branched enantioenriched primary alcohols and achiral amines as reaction partners leads to a partial loss of stereochemical integrity in the final product, however, a systematic optimization enabled partial retention of enantiopurity and possible parameters effecting for racemization were identified.</p

Audio-Tactile Integration in Congenitally and Late Deaf Cochlear Implant Users

Several studies conducted in mammals and humans have shown that multisensory processing may be impaired following congenital sensory loss and in particular if no experience is achieved within specific early developmental time windows known as sensitive periods. In this study we investigated whether basic multisensory abilities are impaired in hearing-restored individuals with deafness acquired at different stages of development. To this aim, we tested congenitally and late deaf cochlear implant (CI) recipients, age-matched with two groups of hearing controls, on an audio-tactile redundancy paradigm, in which reaction times to unimodal and crossmodal redundant signals were measured. Our results showed that both congenitally and late deaf CI recipients were able to integrate audio-tactile stimuli, suggesting that congenital and acquired deafness does not prevent the development and recovery of basic multisensory processing. However, we found that congenitally deaf CI recipients had a lower multisensory gain compared to their matched controls, which may be explained by their faster responses to tactile stimuli. We discuss this finding in the context of reorganisation of the sensory systems following sensory loss and the possibility that these changes cannot be "rewired" through auditory reafferentation

Atp bioluminescence for rapid and selective detection of bacteria and yeasts in wine

Microbial contamination may represent a loss of money for wine producers as several defects can arise due to a microorganism’s growth during storage. The aim of this study was to implement a bioluminescence assay protocol to rapidly and simultaneously detect bacteria and yeasts in wines. Different wines samples were deliberately contaminated with bacteria and yeasts at different concentrations and filtered through two serial filters with decreasing mesh to separate bacteria and yeasts. These were resuscitated over 24 h on selective liquid media and analyzed by bioluminescence assay. ATP measurements discriminated the presence of yeasts and bacteria in artificially contaminated wine samples down to 50 CFU/L of yeasts and 1000 CFU/L of bacteria. The developed protocol allowed to detect, rapidly (24 h) and simultaneously, bacteria and yeasts in different types of wines. This would be of great interest for industries, for which an early detection and discrimination of microbial contaminants would help in the decision‐making proces

Primjena Sponheuerovog i Blakeovog modela pri procjeni seizčkog hazarda: Slučaj Mesinskog tjesnaca

Attenuation is fundamental in the description of a seismic event, determining the spatial distribution of intensity associated with it. Knowing the influence of the attenuation coefficients on the values of the maximum expected intensity for North-Eastern Sicily, the necessity arises to quantify the “weight” of the attenuation models and of the respective coefficients on the intensity estimates. The first evaluation is presented here using the Sponheuer and Blake models. The comparison of the maps of expected intensity, obtained from the cross-use of the laws allows the first critical estimate, showing the greater adaptability of the Sponheuer model to describe the attenuation of intensity for the investigated area