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ObjectiveIn the management of patients with IBD, there is a need to identify prognostic markers and druggable biological pathways to improve mucosal repair and probe the efficacy of tumour necrosis factor alpha biologics. Vnn1 is a pantetheinase that degrades pantetheine to pantothenate (vitamin B5, a precursor of coenzyme A (CoA) biosynthesis) and cysteamine. Vnn1 is overexpressed by inflamed colonocytes. We investigated its contribution to the tolerance of the intestinal mucosa to colitis-induced injury.DesignWe performed an RNA sequencing study on colon biopsy samples from patients with IBD stratified according to clinical severity and modalities of treatment. We generated the VIVA mouse transgenic model, which specifically overexpresses Vnn1 on intestinal epithelial cells and explored its susceptibility to colitis. We developed a pharmacological mimicry of Vnn1 overexpression by administration of Vnn1 derivatives.ResultsVNN1 overexpression on colonocytes correlates with IBD severity. VIVA mice are resistant to experimentally induced colitis. The pantetheinase activity of Vnn1 is cytoprotective in colon: it enhances CoA regeneration and metabolic adaptation of colonocytes; it favours microbiota-dependent production of short chain fatty acids and mostly butyrate, shown to regulate mucosal energetics and to be reduced in patients with IBD. This prohealing phenotype is recapitulated by treating control mice with the substrate (pantethine) or the products of pantetheinase activity prior to induction of colitis. In severe IBD, the protection conferred by the high induction of VNN1 might be compromised because its enzymatic activity may be limited by lack of available substrates. In addition, we identify the elevation of indoxyl sulfate in urine as a biomarker of Vnn1 overexpression, also detected in patients with IBD.ConclusionThe induction of Vnn1/VNN1 during colitis in mouse and human is a compensatory mechanism to reinforce the mucosal barrier. Therefore, enhancement of vitamin B5-driven metabolism should improve mucosal healing and might increase the efficacy of anti-inflammatory therapy.

The sorting stage of mechanical recycling of post‐consumer polyolefins has severe challenges. Polypropylene (PP) is often contaminated with polyethylene (PE) and vice versa. To meet quality requirements, characterization of the recycled pellets is needed. To address this problem, fast characterization generating a statistical assessment of the content of the various batches from recycling is required. This investigation shows that the use of fast scanning rates (in a conventional Differential Scanning Calorimeter) in the successive self‐nucleation and annealing (SSA) protocol can reduce the thermal fractionation time, without losing resolution power, as long as the increase in heating/cooling rate is compensated by reducing sample mass. Using a “coupled SSA protocol” for polypropylene and polyethylene fractions at a rate of 10 °C/min, the measurement time is approximately 420 min. Implementing mass compensation, faster heating rates (i.e., 30 °C/min) and using a single‐fraction protocol, sufficient to determine the content of PP and high‐density PE, reduced the time of the measurement to 75 min. Examples of fractionations of commercial post‐consumer and post‐industrial recycled polyolefin blends conducted at a faster rate are provided. The derived polyolefin content is compared with the standard temperature rising elution fractionation analysis to assess the validity of the proposed method.

•Less pain and disability after hand therapy with a dynamic stabilization approach•Clients with unilateral thumb pain improved more than those with bilateral pain•Persons in early radiographic stages had more functional gains than late stages•Persons with higher pain levels improved more than those with lower pain levels

Usually, the nature of surface-induced nucleation in polymer blends is not easily disclosed. A novel approach for studying surface-induced crystallization in blends of semicrystalline polymers is proposed here. It consists of detecting variations in the crystallization kinetics of the dispersed phase with changing the crystalline state of the matrix through self-nucleation. It can be used only when the dispersed phase has a lower melting temperature than the matrix phase. As a case study, the crystallization behavior of dispersed polyethylene droplets in a polypropylene matrix was investigated. An enhancement of crystallization kinetics of polyethylene was achieved when the lamellar thickness of polypropylene increased, and it was proved by the formation of a transcrystalline layer of polyethylene at the interface, as observed by scanning electron microscopy. Compared to the self-nucleated neat polyethylene, the efficiency of the nucleating effect of polypropylene toward polyethylene was estimated around 140%. This result together with a very low value for the interfacial free energy difference as obtained from isothermal crystallization measurements is evidence that such surface-induced nucleation occurs through epitaxial growth. Moreover, a mechanism of polyethylene nuclei formation through epitaxy, which was proposed in the literature, was proved to be valid for blends of the two polymers through small- and wide-angle X-ray scattering structural analysis. While epitaxy between polyethylene and polypropylene was previously shown only for ideal systems such as thin-layered films, it is hereby reported for common melt mixed blends of the two polyolefins.

Nuclear magnetic resonance (NMR)-based metabolomic studies commonly involve the use of T2filter pulse sequences to eliminate or attenuate the broad signals from large molecules and improve spectral resolution. In this paper, we demonstrate that the T1ρfilter-based pulse sequence represents an interesting alternative because it allows the stability and the reproducibility needed for statistical analysis. The integrity of the samples and the stability of the instruments were assessed for different filter durations and amplitudes. We showed that the T1ρfilter pulse sequence did not induce sample overheating for a filter duration of up to 500 ms. The reproducibility was evaluated and compared with the T2filter in serum and liver samples. The implementation is relatively simple and provides the same statistical and analytical results as those obtained with the standard filters. Regarding tissues analysis, because the duration of the filter is the same as that of the spin-lock, the synchronization of the echo delays with the magic angle spinning (MAS) rate is no longer necessary as for T2filter-based sequences. The results presented in this article aim at establishing a new protocol to improve metabolomic studies and pave the way for future developments on T1ρalternative filters, in liquid and HR-MAS NMR experiments.

AbstractFungi are increasingly being used in criminal investigations as a source of data for crime scene and can be proposed as a forensic tool. There are very few forensic investigators trained in this discipline, which justifies the small amount of published data and most justice professionals are not aware of the contribution of fungi to these investigations. A wide variety of techniques derived from biology are used by forensic investigators to study the changes in the corpse and in the ground where the corpse decomposition occurs in order to solve a crime or find clandestine burials. We review the data available on the use of mycological evidence in criminal cases and as proofs before the justice. The first uses of fungi as evidence were restricted to cases associated with poisonous or psychotropic species. Currently, the objective of forensic mycology is to date the post-mortem and post-burial intervals using information from the fungal community found on the corpse surface or in the environment associated with a clandestine burial. The use of fungi as a forensic tool in different parts of the world has aroused the interest of forensic investigators, such as the members of the different Law Enforcements who deal with solving criminal cases.

Chirality, a foundational concept throughout science, may arise at ferromagnetic domain walls1and in related objects such as skyrmions2. However, chiral textures should also exist in other types of ferroic materials, such as antiferromagnets, for which theory predicts that they should move faster for lower power3, and ferroelectrics, where they should be extremely small and possess unusual topologies4,5. Here, we report the concomitant observation of antiferromagnetic and electric chiral textures at domain walls in the room-temperature ferroelectric antiferromagnet BiFeO3. Combining reciprocal and real-space characterization techniques, we reveal the presence of periodic chiral antiferromagnetic objects along the domain walls as well as a priori energetically unfavourable chiral ferroelectric domain walls. We discuss the mechanisms underlying their formation and their relevance for electrically controlled topological oxide electronics and spintronics.

The ongoing anthropogenic‐induced warming assessment requires a robust background from regional sea surface temperature (SST) reconstructions. Planktonic foraminifera have yielded valuable insights into late Quaternary SST dynamics, but the techniques to estimate SST from fossil assemblages have only rarely been used in very recent sedimentary records (the last 2,000 years). Here we use two transfer function methods, modern analog technique and artificial neural networks, to reconstruct SST variability in two cores from the Central Mediterranean Sea that span the last five centuries. Both cores show similar and considerable changes in the planktonic foraminifera assemblages. However, the inferred mean annual SSTs only varied in a narrow range, in agreement with instrumental data that go back to 1850 CE. Our reconstructions extend this time frame and indicate that SST variability did not exceed 1.5 °C over the past three centuries. Rather than temperature, we suggest that the changes in the assemblages reflect switches between sea surface winter/spring productivity and a deep winter mixed layer, due to the atmosphere/ocean interplay that governs different productivity modes in neighboring mesoscale gyres. Modern Analogue Technique and Artificial Neural Network SST reconstructions are tested on planktonic foraminifera of the last 500 yearsThe atmosphere/ocean interplay governs different water column configurations in neighboring mesoscale gyres at multidecadal scale

Surgical interventions for the spastic upper extremity aim to correct the common deformities of elbow flexion, forearm pronation, wrist flexion and ulnar deviation, and thumb-in-palm deformity. One goal is achieving optimal function and improved limb positioning. Aesthetics of the limb have a profound impact on self-esteem and satisfaction. Surgical deformity correction has not reliably been shown to improve sensory function such as stereognosis. Validated outcome measures are used to present outcomes after surgical treatment of the spastic upper extremity as it relates to motor function and limb positioning, sensory function, and self-esteem.

ABSTRACTCadavers are an abundant source of organic matter. During their decomposition, a variety of organisms – insects, bacteria, and fungi – can feed on them. Within the ambit of forensic science, fungi have thus far received little attention. Nevertheless, the current study found that forensic mycology can be developed as a tool that provides useful evidence for case resolution. The fungal biota found growing on the surface of two cadavers with different post-mortem intervals (PMI) was examined and identified. The fungal samples were cultured and identified by morphology and molecular genetics. Fungal species such as Arthrinium arundinis, Aspergillus niger, Aspergillus terreus, Candida guillermondii, Candida lypolitica, Cladosporium cladosporioides, Chrysosporium merdarium, and Scopulariopsis brevicauliswere registered. These findings are the first contributions to forensic mycology from Argentine research. In combination with the joint investigations of forensic researchers worldwide, these results should contribute in the discussion of the use of mycology as a valid forensic tool in which fungi can provide evidence in complex cases.

Hafnium oxide and Nb doped HfO2 were grown by anodizing sputtering-deposited Hf and Hf-4at.%Nb. Photoelectrochemical characterization was carried out in order to estimate solid state properties such as band gap, flat band potential and electrons internal photoemission threshold energy as a function of thickness and composition of anodic oxides. Impedance measurements were performed in a wide range of electrode potentials in order to study the response of the anodic oxides under anodic and cathodic polarization and to estimate their dielectric constants.

The polymorphism of isotactic polypropylene (iPP) in combination with the strong response of this polymer to nucleation can be utilized for expanding the application range of this versatile polymer. Based on three “case studies” related to ß-iPP pressure pipes, ethylene-propylene (EP) random copolymers for thin-wall injection molding and transparency and sterilization resistance of cast films we demonstrate ways of combining polymer composition, nucleation and process settings to achieve the desired application performance. The importance of considering interactions between polymer design, nucleation and processing parameters for designing application properties is highlighted.

The morphologic features of Talaromyces udagawaeStolk and Samson are here described and illustrated. This teleomorphic Ascomycota fungus was isolated from soil obtained in Buenos Aires province (Argentina) from beneath a human cadaver in an advanced state of decomposition. After washing and serial dilution of the soil along with moist-chamber techniques for fungal cultivation, T. udagawaeformed very restricted colonies of bright yellow color on different growth media with 8-ascospored asci. The ascospores were ellipsoidal and ornamented. The anamorphic state was not observed. Molecular-genetic techniques identified the species. The present record is the first of the species in Argentina, pointing it as a tool to identify soils where cadaver decomposition occurs.

Anodic films were grown to 5 V (Ag/AgCl) on mechanically polished Hf in 0.1 M ammonium biborate and 0.1 M NaOH. Independent of the anodizing conditions, the photoelectrochemical characterization allowed the observation of optical transitions at 3.25 eV, i.e. at photon energy lower than the bandgap of HfO2. They are attributed to localized states inside the gap of the oxide induced by the presence of oxygen vacancies. From the cathodic photocurrent spectra, it was possible to estimate an energy threshold of [?]2.15 eV for internal electron photoemission phenomena. The impedance measurements proved the formation of insulating oxides with e = 19. The anodizing occurs under a high field regime with an activation energy of 1.1 eV and an activation distance of 3.8 A.

The formation of the NLRP3inflammasome in the heart during acute myocardial infarction amplifies the inflammatory response and mediates further damage. Glyburide has NLRP3inhibitory activity in vitro but requires very high doses in vivo, associated with hypoglycemia. The aim of this study was to measure the effects on the NLRP3inflammasome of 16673-34-0, an intermediate substrate free of the cyclohexylurea moiety, involved in insulin release.

Protein resistant polymer brushes of poly(diethylene glycol methylether methacrylate) (DEGMA) are synthesized by surface‐initiated polymerization (SIP) on gold and are thoroughly characterized with particular attention to the nanomechanical properties. Compared to the well known brushes of poly(oligoethylene glycol methylether methacrylate) (POEGMA) on gold, PDEGMA brushes grow faster and yield higher final brush heights. In confocal fluorescence microscopy experiments it is shown that both types of brushes possess similar low non‐specific adsorption levels of labeled bovine serum albumin (BSA) from buffer. While the surface stiffness evaluated by depth sensing indentation in the dry state suggests that side chain crystallization imparts high stiffness to the POEGMA brush, PDEGMA brushes behave similar to poly(methyl methacrylate) (PMMA) brushes of comparable thickness. In the wet state PDEGMA brushes are shown to possess an elastic modulus of 800 kPa, as estimated by AFM nanoindentation, which is smaller than that of POEGMA (3 000 kPa). Expanding these brushes to end‐functional polymers with recently developed block copolymer brush approaches, tailored soft biointerfaces can be generated for cell ‐ surface interaction and cell culture studies.

The performance of a novel rapid‐scanning (20 000 amu/s) quadrupole mass spectrometer (qMS) has been evaluated in the comprehensive 2‐D gas chromatography (GC×GC) analysis of pesticides contained in water. Analyte extraction was performed by using direct solid‐phase microextraction (SPME). The MS system was operated using a rather wide m/z50–450 mass range and a 33 Hz spectral production rate, a frequency which was found sufficient for reliable quantification. The qMS performance was evaluated considering: (i) number of data points per peak, (ii) mass spectral quality, (iii) extent of peak skewing, and (iv) consistency of retention times. Seven‐point calibration curves (external calibration) were constructed for 28 pesticides over the limit of quantification range of 100 μg/L (1, 5, 10, 25, 50, and 100 μg/L). The solid‐phase microextraction‐GC×GC‐qMS method was validated by calculating limits of detection and quantification, intraday peak area precision, accuracy, and intraday retention‐time precision. A series of tap water samples were subjected to analysis, fortunately giving negative results.

Tertiary geological processes and Quaternary climatic oscillations significantly contributed in determining plant species ranges in the Mediterranean basin, making it difficult to distinguish between relative influence of habitat fragmentation and long-distance dispersal in shaping actual species distribution across disjointed regions. We studied the phylogeographic structure of Anacamptis longicornu, a Western Mediterranean orchid species spanning over the main continental islands (Sicily, Sardinia, Corsica, Balearic Islands) and North Africa. We aimed to answer the question whether the highly disjointed distribution of this orchid was determined by: (1) recent over-sea dispersion after the last glacial phase; (2) range fragmentation after the refilling of Mediterranean basin at the end of the Messinian Salinity Crisis (MSC); (3) ancient dispersal events linked to the insurgence of favourable bioclimatic conditions in the basin. Haplotype differentiation, haplotype network, and mismatch analysis support the hypothesis that the current distribution of A. longicornuis more likely explained by allopatric separation and restricted gene flow in connection with fragmentation of a continuous range or a series of ancient dispersal events, after the MSC but before the most recent glaciations. Recent over-sea dispersion, if occurring, must have played a marginal role.

In the present research, a split‐flow comprehensive 2‐D GC‐quadrupole MS (qMS) method was developed using: a primary apolar 30 m×0.25 mm id×0.25 μm dfcapillary linked, viaa T‐union, to a secondary polar 1.0 m×0.05 mm id×0.05 μm dfcapillary and to a 0.10 m×0.05 mm id×0.05 μm dfuncoated column segment. The GC×GC‐qMS instrument was equipped with two GC ovens and a loop‐type modulator. The polar column was connected to the MS, whereas the uncoated column directed most of the first‐dimension effluent to waste and enabled the generation of optimum gas velocities in both dimensions, namely circa20 and 80 cm/s in the first and second dimensions, respectively. The rapid‐scanning qMS was operated at a scan speed of 10 000 amu/s, a 25‐Hz data acquisition frequency (scan time+interscan time: 40 ms), and with a normal GC mass range (m/z40–360). Chromatography bands at the second‐dimension outlet were never less than 360 ms wide (6σ), enabling the acquisition of at least 10 spectra/peak.

The bacteria fatty acid profile has been extensively studied for taxonomic classification purposes, since bacteria, in general, contain particular and rare fatty acids, compared with animal and plant tissues. As for any real‐world sample type, the development of rapid and reliable methods for (i) sample identification (in this case, bacterium type), and (ii) constituent identification (in this instance, the fatty acid profile) is desirable. In this research, a half‐an‐hour procedure, to analyze bacteria, was developed: a 2‐min one‐step sample preparation step was followed by a relatively fast comprehensive 2D GC‐MS separation (25 min). Furthermore, dedicated MS libraries were constructed for the identification of bacteria and fatty acids. Finally, data processing, only qualitative at this stage, was carried out with the support of a novel comprehensive 2D GC software.

Cold‐pressed mandarin essential oils are products of great economic importance in many parts of the world and are used in perfumery, as well as in food products. Reconstituted mandarin oils are easy to find on the market; useful information on essential oil authenticity, quality, extraction technique, geographic origin and biogenesis can be attained through high‐resolution GC of the volatile fraction, or enantioselective GC, using different chiral stationary phases. Stable isotope ratio analysis has gained considerable interest for the unveiling of citrus oil adulteration, detecting small differences in the isotopic carbon composition and providing plenty of information concerning the discrimination among products of different geographical origin and the adulteration of natural essential oils with synthetic or natural compounds. In the present research, the authenticity of several mandarin essential oils was assessed through the employment of GC hyphenated to isotope ratio MS, conventional GC flame ionization detector, enantioselective GC and HPLC. Commercial mandarin oils and industrial natural (declared as such) mandarin essential oils, characterized by different harvest periods and geographic origins, were subjected to analysis. The results attained were compared with those of genuine cold‐pressed Italian mandarin oils, obtained during the 2008–2009 harvest season.

In the present work, carried out in relation to the European and American Directives on the quality of petrol and diesel fuels, the simultaneous determination of the oxygenate compounds and BTEX in gasoline was achieved through the use of a multidimensional GC (MDGC)/MS system, employing a Deans switch‐based transfer system, with an innovative configuration; the latter enabled multiple heart‐cut transfers with no hint of retention time shift, a phenomenon that can occur in MDGC, providing the possibility to achieve more then 20 different heart‐cuts for the compounds of interest. In this study, 20 selected compounds were quantitatively transferred with 12 heart‐cuts, from a first to a secondary column, in order to resolve primary column co‐elutions. Analyte quantification and identification was achieved through a fast‐scanning quadrupole mass analyzer, operated in full scan mode, in order to evaluate also the interfering compounds transferred together with the compounds of interest. The multidimensional method developed was subjected to validation. All attained data were in excellent correlation with results obtained through the UNI‐EN 12177:2000, ASTM D 5580‐02 and ASTM D 4815‐04 MDGC methods, for the determination of benzene, BTEX and oxygenate compounds in gasoline, respectively.