Neutral-ionic phase transition : a thorough ab-initio study of TTF-CA

The prototype compound for the neutral-ionic phase transition, namely TTF-CA, is theoretically investigated by first-principles density functional theory calculations. The study is based on three neutron diffraction structures collected at 40, 90 and 300 K (Le Cointe et al., Phys. Rev. B 51, 3374 (1995)). By means of a topological analysis of the total charge densities, we provide a very precise picture of intra and inter-chain interactions. Moreover, our calculations reveal that the thermal lattice contraction reduces the indirect band gap of this organic semi-conductor in the neutral phase, and nearly closes it in the vicinity of the transition temperature. A possible mechanism of the neutral-ionic phase transition is discussed. The charge transfer from TTF to CA is also derived by using three different technics.Comment: 11 pages, 9 figures, 7 table

First-principles molecular-dynamics simulations for neutral p-chloranil and its radical anion

APS copyright is acknowledged url = {http://link.aps.org/doi/10.1103/PhysRevB.53.12112}International audienceThe neutral p -chloranil ~ 2,3,5,6-tetrachloro- p -benzoquinone ! and its radical anion have been extensively studied using the Car-Parrinello projector augmented wave method, which is an all-electron electronic structure method for first-principles molecular dynamics based on the local density approximation of density functional theory. Frequencies and eigenmodes are derived by fitting a system of harmonic oscillators to the molecular- dynamics trajectories. The dependence of the bond lengths and vibrational frequencies on the molecular ionicity is discussed, and the electron affinity, Coulomb repulsion, and the spin-splitting parameter of p -chloranil are also derived

Targeting the Src Pathway Enhances the Efficacy of Selective FGFR Inhibitors in Urothelial Cancers with FGFR3 Alterations.

Selective FGFR inhibitors such as infigratinib (BGJ398) and erdafitinib (JNJ-42756493) have been evaluated in clinical trials for cancers with FGFR3 molecular alterations, particularly in urothelial carcinoma patients. However, a substantial proportion of these patients (up to 50%) display intrinsic resistance to these drugs and receive minimal clinical benefit. There is thus an unmet need for alternative therapeutic strategies to overcome primary resistance to selective FGFR inhibitors. In this study, we demonstrate that cells expressing cancer-associated activating FGFR3 mutants and the FGFR3-TACC3 fusion showed primary resistance to infigratinib in long-term colony formation assays in both NIH-3T3 and urothelial carcinoma models. We find that expression of these FGFR3 molecular alterations resulted in elevated constitutive Src activation compared to wildtype FGFR3 and that cells co-opted this pathway as a means to achieve intrinsic resistance to infigratinib. Targeting the Src pathway with low doses of the kinase inhibitor dasatinib synergistically sensitized multiple urothelial carcinoma lines harbouring endogenous FGFR3 alterations to infigratinib. Our data provide preclinical rationale that supports the use of dasatinib in combination with selective FGFR inhibitors as a means to overcome intrinsic drug resistance in the salvage therapy setting in urothelial cancer patients with FGFR3 molecular alterations

Observation of new quantum interference effect in solids

In order to achieve quantum interference of free electrons inside a solid, we have modified the geometry of the solid so that de Broglie waves interfere destructively inside the solid. Quantum interference of de Broglie waves leads to a reduction in the density of possible quantum states of electrons inside the solid and increases the Fermi energy level. This effect was studied theoretically within the limit of the quantum theory of free electrons inside the metal. It has been shown that if a metal surface is modified with patterned indents, the Fermi energy level will increase and consequently the electron work function will decrease. This effect was studied experimentally in both Au and SiO2 thin films of special geometry and structure. Work function reductions of 0.5 eV in Au films and 0.2 eV in SiO2 films were observed. Comparative measurements of work function were made using the Kelvin Probe method based on compensation of internal contact potential difference. Electron emission from the same thin films was studied by two independent research groups using Photoelectron Emission Microscopy (PEEM).Comment: 11 pages, 5 figure

Produção da cenoura e efeito na fertilidade do solo e nutrição decorrente da solarização do solo para controle da tiririca.

Dentre os desafios do cultivo orgânico de hortaliças destaca-se o controle de plantas daninhas, devido à proibição do uso de herbicidas. Entre as invasoras, a tiririca (Cyperus rotundus L.) é de difícil controle pela sua alta competitividade. A solarização é uma alternativa para desinfestação do solo, a qual consiste em cobri-lo com plástico transparente, com bons resultados no controle da tiririca. A fim de avaliar a influência do preparo e do revolvimento do solo sobre a eficiência da solarização no controle da tiririca, bem como seu posterior efeito sobre o cultivo da cenoura, foi realizado um experimento na Fazendinha Agroecológica, em Seropédica (RJ). O experimento foi disposto em blocos ao acaso com três repetições, em arranjo fatorial 2 x 3 mais uma testemunha adicional, sendo: 1) solo solarizado, preparado (com grade aradora) e revolvido 30 dias após a solarização (manualmente com auxílio de uma enxada); 2) solo solarizado, preparado e revolvido aos 60 dias; 3) solo solarizado, preparado e não revolvido; 4) solo solarizado, não preparado e revolvido aos 30 dias; 5) solo solarizado, não preparado e revolvido aos 60 dias; 6) solo solarizado, não preparado e não revolvido; solo não solarizado, não preparado e não revolvido (testemunha). A solarização iniciou-se em 29/1/2002, e durou cem dias. A solarização reduziu em 86% a infestação de tiririca no cultivo da cenoura. Até 10 cm de profundidade, a temperatura do solo foi superior nas parcelas solarizadas, porém a 5 cm, a solarização foi mais eficiente quando associada ao preparo do solo, não havendo efeito do revolvimento. A solarização aumentou os valores da biomassa microbiana e dos teores de Ca, Mg e P do solo. O desenvolvimento da cenoura foi influenciado pela solarização que resultou em maior produtividade

The effect of unfiltered coffee on potential biomarkers for colonic cancer risk in healthy volunteers: a randomized trial

Background: Epidemiologic studies suggest that coffee use might protect against colorectal cancer. Inconsistencies as to the effect of coffee use and colorectal cancer between epidemiologic studies might be related to the type of coffee brew. Objective: We studied the effect of unfiltered coffee consumption on putative biomarkers for colonic cancer risk. Design: A total of 64 healthy volunteers (31 men and 33 women), with a mean age of 43 ± 11 years were randomly assigned to two groups in a crossover design, with two intervention periods of 2 weeks separated by a washout period of 8 weeks. Treatments were 1 L of cafetiere (French press) coffee daily or no coffee. At the end of each intervention period, fasting blood samples, colorectal biopsies and 48 h faeces were collected. Results: No effect of coffee on colorectal cell proliferation, assayed by estimating the Proliferating Cell Nuclear Antigen labelling index, was seen. Additionally, no effects were seen on the concentrations of faecal soluble bile acids and colorectal mucosal glutathione S-transferase activity. However, unfiltered coffee significantly increased the glutathione content in the colorectal mucosa by 8% and in plasma by 15%. Other aminothiols in plasma also increased on coffee. Conclusion: Unfiltered coffee does not influence the colorectal mucosal proliferation rate, but might increase the detoxification capacity and anti-mutagenic properties in the colorectal mucosa through an increase in glutathione concentration. Whether this effect indeed contributes to a lower colon cancer risk remains to be established

Training the Trainers in Embedding Assessment Literacy into Module Design: A Case Study of a Collaborative Transcreation Project

Translator trainers are being asked to respond in their course and module design to a variety of changing requirements, including institutional, professional and pedagogical ones. This paper proposes a way that translator trainers can respond to two sets of these new requirements. The first are those for a widening conception of translation brought about by the rapid globalisation of markets and the needs for intercultural mediators (Katan, 2016; Massey et al., 2017; Massey & Wieder, 2019). Indeed, Katan finishes the paper with the startling statement ‘There is really no question about it: if T/Is are going to survive they must make the transcreational turn’ (ibid.: 378). The second set of requirements comes from the process of articulating what attributes a graduate should possess and how these attributes are developed (Hughes, 2010). As the Higher Education Academy (HEA, 2012; see also Elkington, 2016) state, one way to ensure that the graduate skills are developed is through new assessment practices based on assessment for learning and assessment literacy. New assessment practices mean that assessment ‘does not just contribute to learning at university, but develops learning and evaluative skills essential for employment and lifelong learning’ (ibid.: 10). This paper offers translation trainers an approach to module design which can address both these sets of demands. The module is designed with a collaborative transcreation project at its core and has incorporated assessment literacy into the design. The study is supported with quantitative and qualitative data gained from a survey of participating students. By introducing the case study of our module design and linking the design to the underlying theories which informed it, the paper provides trainers with a set of concepts which could be applied to their own curricula needs in order to future proof their students in the changing employment market

The fatty acid compositions of erythrocyte and plasma polar lipids in children with autism, developmental delay or typically developing controls and the effect of fish oil intake

The erythrocyte and plasma fatty acid compositions of children with autism were compared in a case-control study with typically developing (TD) children and with children showing developmental delay (DD). Forty-five autism subjects were age-matched with TD controls and thirty-eight with DD controls. Fatty acid data were compared using paired t tests. In addition, blood fatty acids from treatment-naive autism subjects were compared with autism subjects who had consumed fish oil supplements by two-sample t tests. Relatively few differences were seen between erythrocyte fatty acids in autism and TD subjects although the former had an increased arachidonic acid (ARA):EPA ratio. This ratio was also increased in plasma samples from the same children. No changes in n-3 fatty acids or ARA:EPA ratio were seen when comparing autism with DD subjects but some SFA and MUFA were decreased in the DD subjects, most notably 24 : 0 and 24 : 1, which are essential components of axonal myelin sheaths. However, if multiple comparisons are taken into account, and a stricter level of significance applied, most of these values would not be significant. Autism subjects consuming fish oil showed reduced erythrocyte ARA, 22 : 4n-6, 22 : 5n-6 and total n-6 fatty acids and increased EPA, 22 : 5n-3, 22 : 6n-3 and total n-3 fatty acids along with reduced n-6:n-3 and ARA:EPA ratios. Collectively, the autism subjects did not have an underlying phospholipid disorder, based on erythrocyte fatty acid compositions, although the increased ARA:EPA ratio observed suggested that an imbalance of essential highly unsaturated fatty acids may be present in a cohort of autism subjects

Copeptin for risk stratification in non-traumatic headache in the emergency setting: a prospective multicenter observational cohort study

In the emergency setting, non-traumatic headache is a benign symptom in 80% of cases, but serious underlying conditions need to be ruled out. Copeptin improves risk stratification in several acute diseases. Herein, we investigated the value of copeptin to discriminate between serious secondary headache and benign headache forms in the emergency setting.; Patients presenting with acute non-traumatic headache were prospectively enrolled into an observational cohort study. Copeptin was measured upon presentation to the emergency department. Primary endpoint was serious secondary headache defined by a neurologic cause requiring immediate treatment of the underlying disease. Secondary endpoint was the combination of mortality and hospitalization within 3 months. Two board-certified neurologist blinded to copeptin levels verified the endpoints after a structured 3-month-telephone interview.; Of the 391 patients included, 75 (19%) had a serious secondary headache. Copeptin was associated with serious secondary headache (OR 2.03, 95%CI 1.52-2.70, p < 0.0001). Area under the curve (AUC) for copeptin to identify the primary endpoint was 0.70 (0.63-0.76). After adjusting for age > 50, focal-neurological abnormalities, and thunderclap onset of symptoms, copeptin remained an independent predictive factor for serious secondary headache (OR 1.74, 95%CI 1.26-2.39, p = 0.001). Moreover, copeptin improved the AUC of the multivariate logistic clinical model (p-LR-test < 0.001). Even though copeptin values were higher in patients reaching the secondary endpoint, this association was not significant in multivariate logistic regression.; Copeptin was independently associated with serious secondary headache as compared to benign headaches forms. Copeptin may be a promising novel blood biomarker that should be further validated to rule out serious secondary headache in the emergency department.; Study Registration on 08/02/2010 as NCT01174901 at clinicaltrials.gov