Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity?

Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors, and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF2, by ball milling it with BaF2, to create nanostructured Ba1–xCaxF2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including “simulating synthesis”, we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include structural disorder, excess volume, pseudovacancy arrays, and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba1–xCaxF2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [ Nature 2015, 521, 303] remarks that classical crystallography is inadequate to describe systems with correlated disorder, but that correlated disorder has clear crystallographic signatures. Here, we identify two possible crystallographic signatures of geometric frustration: excess volume and correlated “snake-like” ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013, 138, 12A538]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, and branching of the “snake” arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous, or liquid states and processes such as ionic conductivity, melting, and crystallization

The Enter-Vet Italian surveillance network: data on samples of pig origin from 2002 to 2005

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Tumour budding in pancreatic cancer revisited: validation of the ITBCC scoring system.

AIMS Pancreatic ductal adenocarcinoma (PDAC) is a highly lethal malignancy with rising incidence. Biomarkers that would help the prognostic stratification of patients are needed urgently. Although tumour budding (BD) is a strong and independent prognostic factor in PDAC it is not included in histopathology reports, due partly to the lack of a standardised scoring system. The aim of the present work is to assess the reliability and reproducibility of the BD scoring system proposed recently by the International Tumour Budding Consensus Conference (ITBCC) 2016 in a well-characterised PDAC cohort (n = 120) with complete clinicopathological and follow-up information. METHODS AND RESULTS BD was scored independently by two pathologists on haematoxylin and eosin-stained PDAC sections by assessing the densest budding area at ×20 magnification (one hot-spot, 0.785 mm ), regardless of intra- or peritumoural localisation, and assigned to four categories: BD0: no buds; BD1: one to four buds; BD2: five to nine buds; and BD3: ≥ 10 buds. Findings were correlated to patient and tumour characteristics and interobserver agreement was assessed. The weighted kappa value for BD category was 0.62 (0.5-0.73), indicating strong agreement. Increasing BD category (BD3 versus BD0-2) correlated with higher grade (P = 0.002) and shorter overall [OS, P < 0.0001, hazard ratio (HR) = 3.234, 95% confidence interval (CI) = 1.95-5.37] and disease-free survival (DFS, P = 0.0135, HR = 1.974, 95% CI = 1.15-3.39). BD (BD3 versus BD0-2) was an independent prognostic factor for OS and DFS, after adjusting for tumour-node-metastasis (TNM) stage by using both the 8th American Joint Committee on Cancer (AJCC) edition (OS: P = 0.0031, HR = 2.298, 95% CI = 1.32-0.99; DFS: P = 0.0458, HR = 1.713, 95% CI = 1.01-2.91) and the 7th AJCC edition (OS: P < 0.0001, HR = 2.795,95% CI = 1.71-4.57 and DFS: P = 0.00786, HR = 1.643, 95% CI = 0.95-2.86). CONCLUSIONS ITBCC scoring is a simple, reliable and reproducible method to evaluate BD in PDAC and facilitates its documentation in histopathology reports, allowing the prognostic stratification of PDAC patients

HIV infection in IVDU

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Exposure to cadmium through Italian rice (Oryza sativa L.): Consumption and implications for human health

Cd bioaccumulation was investigated in the most consumed rice varieties (Oryza sativa L.) in Italy to assess the health risk related to consumption of the cereal for Italian population. In addition, the health implications concerning to consumption of rice-based foods was evaluated for Italian infants. Cadmium was detected by Q-ICP-MS. Method was validated in compliance with UNI CEI EN ISO/IEC 17025. Cd concentrations were found below the Maximum Levels (MLs) established at the European Union level for rice (0.092 mg kg−1for brown rice and 0.062 mg kg−1for white rice). The Cd Estimated Weekly Intakes (EWIs) through brown rice and white rice consumption by total population accounted approximately for 6% and 4% of the TWI set by the European Food Safety Authority (2.5 μg kg−1body weight), respectively. The Cd EWIs through rice consumption by different population groups obtained in this survey did not show notable differences with those related to the total population except for child group that showed the highest EWIs of Cd. As regards to the Cd EWIs quantified for infants of four, six and eight month old considering the rice-based infant food consumption accounted for 22%, 38%, and 36% of the EFSA TWI, respectively

Relationship between pathological gambling, alcoholism and drug addiction

The aim of this survey was to evaluate the distribution of pathological gamblers treated in an alcohol or drug addiction treatment program run by the Italian National Health Service providing assistance to alcohol and drug abusers in Venice (North east Italy) from September 1 to December 31, 2001. Each drug- or alcohol-dependent patient retained for treatment for at least one month was administrated an anonymous precoded questionnaire to collect personal and socio-demographic features. The South Oaks Gambling Screen (SOGS) was used to measure pathological gambling and the Symptom Checklist-90-Revised (SCL-90-R) to measure psychological distress levels and psychiatric symptoms. Among the 113 enrolled subjects we found a greater prevalence of pathological gamblers among drug users than among alcoholics and drug abusers were younger than alcoholics; moreover, there was a prevalence of single status, low schooling, and a low-medium income despite full-time occupation. Only pathological gamblers revealed a significant positive correlation with a family history of gambling and reached positive scores (&gt;1.5) for some likely psychiatric symptoms. Abuse disorders and pathological gambling are frequently associated with multidependence personality traits. Preventing substance abuse may reduce the pathological gambling rates and better results can be obtained with educational campaigns beginning earlier in life

Tossicodipendenza e infezione da HIV

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B18: A core XAS spectroscopy beamline for Diamond

During the past twenty years, XAS has progressed from being a technique only suitable for specialists to become a widely applicable tool. This situation has resulted from the steady development of reliable spectrometers and new generations of software for data analysis. B18 will be a general purpose XAS beamline on Diamond. It will cover a wide energy range (2 to 35 keV), with a monochromator designed to carry out both conventional and QEXAFS measurements. The main design novelty is that the low and high energy optic branches will run in parallel and the appropriate branch for a given experiment will be selected by changing the position of the slits, instead of by moving the optical elements. This will allow us to develop a very high level of automation in the operation of the instrument. Detection systems will include transmission, fluorescence and electron yield. Experience shows that considerable value is added by combining techniques. Therefore provision has been made for wide angle X-ray diffraction studies to be incorporated into the beamline architecture. The instrument will offer a variety of sample environments and the flexibility to integrate set-ups designed by the users. Hence, B18 will be able to contribute to research programs across a wide range of scientific disciplines, e.g. solid state physics and materials, catalysis, chemistry, soft matter, surfaces and biomaterials. The instrument will open to first users in April 2010. © 2009 IOP Publishing Ltd

Integrated Genomic and Immunophenotypic Classification of Pancreatic Cancer Reveals Three Distinct Subtypes with Prognostic/Predictive Significance

Abstract Purpose: Current clinical classification of pancreatic ductal adenocarcinoma (PDAC) is unable to predict prognosis or response to chemo- or immunotherapy and does not take into account the host reaction to PDAC cells. Our aim is to classify PDAC according to host- and tumor-related factors into clinically/biologically relevant subtypes by integrating molecular and microenvironmental findings. Experimental Design: A well-characterized PDAC cohort (n = 110) underwent next-generation sequencing with a hot spot cancer panel while next-generation tissue microarrays were immunostained for CD3, CD4, CD8, CD20, PD-L1, p63, hyaluronan-mediated motility receptor (RHAMM), and DNA mismatch repair proteins. Previous data on FOXP3 were integrated. Immune cell counts and protein expression were correlated with tumor-derived driver mutations, clinicopathologic features (TNM 8th edition, 2017), survival, and epithelial–mesenchymal transition (EMT)–like tumor budding. Results: Three PDAC subtypes were identified: the “immune escape” (54%), poor in T and B cells and enriched in FOXP3+ regulatory T cells (Treg), with high-grade budding, frequent CDKN2A, SMAD4, and PIK3CA mutations, and poor outcome; the "immune rich" (35%), rich in T and B cells and poorer in FOXP3+ Tregs, with infrequent budding, lower CDKN2A and PIK3CA mutation rate, and better outcome and a subpopulation with tertiary lymphoid tissue (TLT), mutations in DNA damage response genes (STK11 and ATM), and the best outcome; and the "immune exhausted" (11%), with immunogenic microenvironment and two subpopulations—one with PD-L1 expression and a high PIK3CA mutation rate and a microsatellite-unstable subpopulation with a high prevalence of JAK3 mutations. The combination of low budding, low stromal FOXP3 counts, presence of TLTs, and absence of CDKN2A mutations confers significant survival advantage in patients with PDAC. Conclusions: Immune host responses correlate with tumor characteristics, leading to morphologically recognizable PDAC subtypes with prognostic/predictive significance. Clin Cancer Res; 24(18); 4444–54. ©2018 AACR. See related commentary by Khalil and O'Reilly, p. 4355</jats:p