Refined Structure of Metastable Ice XVII from Neutron Diffraction Measurements

The structure of the recently identified metastable ice XVII, obtained by release of hydrogen from the C$_0$ D$_2$O-H$_2$ compound (filled ice), has been accurately measured by neutron powder diffraction. The diffraction pattern is indexed with a hexagonal cell and can be refined with space group $P6_122$ so to obtain accurate values of the oxygen and deuterium positions. The values of the lattice constants at three temperatures between 25 to 100 K are reported, and their behavior is compared with that of ice Ih. Ice XVII is a porous solid that, if exposed to H$_2$ gas, may adsorb a substantial amount of it. Monitoring this effect at a constant temperature of 50 K, we have observed that the two lattice constants show opposite behavior, $a$ increases and $c$ decreases, with the volume showing a linear increase. At temperatures higher than 130 K the metastability of this form of porous ice is lost and the sample transforms into ice Ih

Quantum calculation of inelastic neutron scattering spectra of a hydrogen molecule inside a nanoscale cavity based on rigorous treatment of the coupled translation-rotation dynamics

We present a quantum methodology for the calculation of the inelastic neutron scattering (INS) spectra of an ${\mathrm{H}}_{2}$ molecule confined in a nanoscale cavity. Our approach incorporates the coupled five-dimensional translation-rotation (TR) energy levels and wave functions of the guest molecule. The computed INS spectra are highly realistic and reflect in full the complexity of the coupled TR dynamics on the anisotropic potential energy surfaces of the confining environment. Utilizing this methodology, we simulate the INS spectra of $p$- and $o$-H${}_{2}$ in the small cage of the structure II clathrate hydrate and compare them with the experimental data

Iatrogenic Hypoglycemia Induced by Valproic Acid in an Adult Patient

Literature on antiepileptic induced iatrogenic hypoglycemia is scanty. Due to its broad spectrum of activity and mechanisms of action, valproic acid (VPA), a fatty acid, is the most widely prescribed epilepsy treatment worldwide.Herein, we describe an adult epileptic patient, where persistent, otherwise unexplained hypoglycemia, was most likely induced by VPA, as suggested by the VPA time course and glucose blood levels. Indeed, no further hypoglycemic episodes occurred after VPA discontinuation and the diagnostic work-up ruled out other possible causes of hypoglycemia.This case supports the hypothesis that VPA may induce hypoglycemia, due to still not well-defined metabolic mechanisms of action. Moreover, it emphasizes the fact that an iatrogenic pathogenesis should be considered if an apparently unexplained hypoglycemia occurs in a patient on chronic therapy with antiepileptics, even at a therapeutical dosage

Optimization of an analytical method based on SPME-Arrow and chemometrics for the characterization of the aroma profile of commercial bread

A SPME-Arrow GC-MS approach, coupled with chemometrics, was used to thoroughly investigate the impact of different types of yeast (sourdough, bear's yeast and a mixture of both) and their respective leaving time (one, three and five hours) on VOCs of commercial bread samples. This aspect is of paramount importance for the baking industry to adjust recipe modifications and production parameters, as well as to meet consumer needs in formulating new products. A deep learning approach, PARADISe (PARAFAC2-based deconvolution and identification system), was used to analyse the obtained chromatograms in an untargeted manner. In particular, PARADISe, was able to perform a fast deconvolution of the chromatographic peaks directly from raw chromatographic data to allow a putatively identification of 66 volatile organic compounds, including alcohols, esters, carboxylic acids, ketones, aldehydes. Finally, Principal Component Analysis, applied on the areas of the resolved compounds, showed that bread samples differentiate according to their recipe and highlighted the most relevant volatile compounds responsible for the observed differences

Upgrading grape pomace contained ethanol into hexanoic acid, fuel additives and a sticky polyhydroxyalkanoate: an effective alternative to ethanol distillation

The management of grape pomace (GP), the main winery solid residue, is presently supported by government subsidies, promoting the energetically expensive recovery of ethanol by distillation. This work proposes and assesses a novel sustainable alternative GP valorisation strategy: chain elongation fermentation. Besides, the proof-of-concept of a multipurpose cascading scheme is presented based on experimental data for each step on the laboratory scale. The new cascading biorefinery scheme includes: (1) the ethanol upgrade into highly concentrated (ca. 900 g L−1) n-hexanoic acid (C6) by anaerobic acidogenic fermentation and a simple downstream; the exploitation of the obtained C6 as (2) a reagent for obtaining an ester-alcohol mixture as well as (3) a substrate for the production of medium chain length polyhydroxylalkanoates (mcl-PHAs), and (4) the complementary biomethanization of the solids leftovers from the acidogenic step. Specifically, the identified fermentation conditions (pH 7, 37 °C and P > Patm) allowed obtaining the highest C6 titer (22 g L−1) and productivity (6.2 g L−1 d−1) ever achieved from non pre-treated biowaste and without the need of either exogenus ethanol or methanization inhibitor or expensive in-line extraction methods. Such titer, allowed employing a cheap easy-direct C6 downstream leading to 54% C6 recovery (87% purity) at potentially competitive overall costs. Although a preliminary assessment showed that this partial valorisation could be economically sustainable in itself for GP-management, the exploitation of the highly concentrated GP-derived C6 was demonstrated for the first time. Heterogenous catalytic hydrogenation (180 °C and 115 bar), with pre-reduced commercial catalyst Re/C 5 wt%, allowed the conversion of the obtained C6 into a mixture of 1-hexanol and hexyl-hexanoate (molar yield of 75%), which represents a promising blendstock for both diesel and biodiesel fuels. On the other hand, a fed-batch culture system, carried out on a bench-top bioreactor, allowed obtaining 60% PHA content with a yield of 0.30 g g−1. The recovered sticky bioelastomer was mainly composed of 3-hydroxyhexanoate (90%). Complementarily, ca. 200 N-L kgVS−1 of biomethane was obtained from GP leftover solids

Cell-Mediated Assembly of Phototherapeutics

Light-activatable drugs offer the promise of controlled release with exquisite temporal and spatial resolution. However, light sensitive pro-drugs are typically converted to their active forms using short wavelengths, which display poor tissue penetrance. We report herein erythrocyte-mediated assembly of long wavelength-sensitive phototherapeutics. The activating wavelength of the constructs is readily pre-assigned by using fluorophores with the desired λex. Drug release from the erythrocyte carrier was confirmed by standard analytical tools and by the expected biological consequences of the liberated drugs in cell culture: methotrexate, binding to intracellular dihydrofolate reductase; colchicine, inhibition of microtubule polymerization; dexamethasone, induced nuclear migration of the glucocorticoid receptor

ER stress protein AGR2 precedes and is involved in the regulation of pancreatic cancer initiation

The work was supported by a grant A12008 from CR-UK (L. Dumartin, N.R. Lemoine and T. Crnogorac-Jurcevic)

Long-acting bronchodilators improve Health Related Quality of Life in patients with COPD

Summary Background Long-acting bronchodilators are first-line treatment for chronic obstructive pulmonary disease (COPD), and their efficacy on lung function and clinical parameters is recognized. Objective To explore the available evidence about the effects of long acting bronchodilators on Health Related Quality of Life (HRQoL) and Health Status (HS) in clinical research. Methods Randomized controlled trials published till December 2012 evaluating HRQoL/HS in COPD by means of validated questionnaires were analysed. Results Fifty-one trials on Long acting β 2 agonist (LABA) and Long acting Anticholinergic (LAMA) met the inclusion criteria. A total of 37,225 moderate-severe COPD patients testing 6 drugs, 12 different devices and 22 different dosages, with a study duration ranging from 4 weeks to 4 years were studied. A statistical significant HRQoL/HS improvement was reached in 93% of the studies. Nevertheless, the Minimal Important Difference (MID) was reached in 70,6% of the studies considering the difference between baseline and end of the study, and in 50% when comparing active treatment and placebo. Conclusions The data coming from the review support the efficacy of long acting bronchodilators in improving HRQoL/HS of COPD patients. Further research evaluating HRQoL/HS as primary outcome and according to guidelines on Patient Reported Outcomes is needed