Heterogenized water oxidation catalysts prepared by immobilizing Klaui-type organometallic precursors

An efficient heterogenized water oxidation catalyst (2_TiO2) has been synthesized by immobilizing the Kläui-type organometallic precursor [Cp*Ir{P(O)(OH)2}3]Na (2, Cp*=1,2,3,4,5-pentamethylcyclopentadienyl ligand) onto rutile TiO2. Iridium is homogeneously distributed at the molecular and atomic/small cluster level in 2_TiO2 and 2'_TiO2 (solid catalyst recovered after the first catalytic run), respectively, as indicated by STEM-HAADF (scanning transmission electron microscopy - high angle annular dark field) studies. 2'_TiO2 exhibits TOF values up to 23.7 min-1 in the oxidation of water to O2 driven by NaIO4 at nearly neutral pH, and a TON only limited by the amount of NaIO4 used, as indicated by multiple run experiments. Furthermore, while roughly 40¿% leaching is observed during the first catalytic run, 2'_TiO2 does not undergo any further leaching even when in contact with strongly basic solutions and completely maintains its activity for thousands of cycles. NMR studies, in combination with ICP-OES (inductively coupled plasma optical emission spectrometry), indicate that the activation of 2_TiO2 occurs through the initial oxidative dissociation of PO43-, ultimately leading to active centers in which a 1:1 P/Ir ratio is present (derived from the removal of two PO43- units) likely missing the Cp* ligand.Peer ReviewedPostprint (author's final draft

Enumeration and Structure of Trapezoidal Words

Trapezoidal words are words having at most $n+1$ distinct factors of length $n$ for every $n\ge 0$. They therefore encompass finite Sturmian words. We give combinatorial characterizations of trapezoidal words and exhibit a formula for their enumeration. We then separate trapezoidal words into two disjoint classes: open and closed. A trapezoidal word is closed if it has a factor that occurs only as a prefix and as a suffix; otherwise it is open. We investigate open and closed trapezoidal words, in relation with their special factors. We prove that Sturmian palindromes are closed trapezoidal words and that a closed trapezoidal word is a Sturmian palindrome if and only if its longest repeated prefix is a palindrome. We also define a new class of words, \emph{semicentral words}, and show that they are characterized by the property that they can be written as $uxyu$, for a central word $u$ and two different letters $x,y$. Finally, we investigate the prefixes of the Fibonacci word with respect to the property of being open or closed trapezoidal words, and show that the sequence of open and closed prefixes of the Fibonacci word follows the Fibonacci sequence.Comment: Accepted for publication in Theoretical Computer Scienc

Comprehensive multi-omics analysis uncovers a group of TGF-β-regulated genes among lncRNA EPR direct transcriptional targets

Abstract Long non-coding RNAs (lncRNAs) can affect multiple layers of gene expression to control crucial cellular functions. We have previously demonstrated that the lncRNA EPR, by controlling gene expression at different levels, affects cell proliferation and migration in cultured mammary gland cells and impairs breast tumor formation in an orthotopic transplant model in mice. Here, we used ChIRP-Seq to identify EPR binding sites on chromatin of NMuMG mammary gland cells overexpressing EPR and identified its trans binding sites in the genome. Then, with the purpose of relating EPR/chromatin interactions to the reshaping of the epitranscriptome landscape, we profiled histone activation marks at promoter/enhancer regions by ChIP-Seq. Finally, we integrated data derived from ChIRP-Seq, ChIP-Seq as well as RNA-Seq in a comprehensive analysis and we selected a group of bona fide direct transcriptional targets of EPR. Among them, we identified a subset of EPR targets whose expression is controlled by TGF-β with one of them—Arrdc3—being able to modulate Epithelial to Mesenchymal Transition. This experimental framework allowed us to correlate lncRNA/chromatin interactions with the real outcome of gene expression and to start defining the gene network regulated by EPR as a component of the TGF-β pathway

Assessing the bibliometric productivity of forest scientists in Italy

Since 2010, the Italian Ministry of University and Research issued new evaluation protocols to select candidates for University professorships and assess the bibliometric productivity of Universities and Research Institutes based on bibliometric indicators, i.e. scientific paper and citation numbers and the h-index. Under this framework, the objective of this study was to quantify the bibliometric productivity of the Italian forest research community during the 2002-2012 period. We examined the following productivity parameters: (i) the bibliometric productivity under the Forestry subject category at the global level; (ii) compared the aggregated bibliometric productivity of Italian forest scientists with scientists from other countries; (iii) analyzed publication and citation temporal trends of Italian forest scientists and their international collaborations; and (iv) characterized productivity distribution among Italian forest scientists at different career levels. Results indicated the following: (i) the UK is the most efficient country based on the ratio between Gross Domestic Spending (GDS) on Research and Development (R&D) and bibliometric productivity under the Forestry subject category, followed by Italy; (ii) Italian forest scientist productivity exhibited a significant positive time trend, but was characterized by high inequality across authors; (iii) one-half of the Italian forest scientist publications were written in collaboration with foreign scientists; (iv) a strong relationship exists between bibliometric indicators calculated by WOS and SCOPUS, suggesting these two databases have the same potential to evaluate the forestry research community; and (v) self-citations did not significantly affect the rank of Italian forest scientists

Clinical expression of facioscapulohumeral muscular dystrophy in carriers of 1-3 D4Z4 reduced alleles: Experience of the FSHD Italian National Registry

OBJECTIVES: Facioscapulohumeral muscular dystrophy type 1 (FSHD1) has been genetically linked to reduced numbers ( 64 8) of D4Z4 repeats at 4q35. Particularly severe FSHD cases, characterised by an infantile onset and presence of additional extra-muscular features, have been associated with the shortest D4Z4 reduced alleles with 1-3 repeats (1-3 DRA). We searched for signs of perinatal onset and evaluated disease outcome through the systematic collection of clinical and anamnestic records of de novo and familial index cases and their relatives, carrying 1-3 DRA. SETTING: Italy. PARTICIPANTS: 66 index cases and 33 relatives carrying 1-3 DRA. OUTCOMES: The clinical examination was performed using the standardised FSHD evaluation form with validated inter-rater reliability. To investigate the earliest signs of disease, we designed the Infantile Anamnestic Questionnaire (IAQ). Comparison of age at onset was performed using the non-parametric Wilcoxon rank-sum or Kruskal-Wallis test. Comparison of the FSHD score was performed using a general linear model and Wald test. Kaplan-Meier survival analysis was used to estimate the age-specific cumulative motor impairment risk. RESULTS: No patients had perinatal onset. Among index cases, 36 (54.5%) showed the first signs by 10 years of age. The large majority of patients with early disease onset (26 out of 36, 72.2%) were de novo; whereas the majority of patients with disease onset after 10 years of age were familial (16, 53.3%). Comparison of the disease severity outcome between index cases with age at onset before and over 10 years of age, failed to detect statistical significance (Wald test p value=0.064). Of 61 index cases, only 17 (27.9%) presented extra-muscular conditions. Relatives carrying 1-3 DRA showed a large clinical variability ranging from healthy subjects, to patients with severe motor impairment. CONCLUSIONS: The size of the D4Z4 allele is not always predictive of severe clinical outcome. The high degree of clinical variability suggests that additional factors contribute to the phenotype complexity

Radiological Protection in Industries Involving NORM: A (Graded) Methodological Approach to Characterize the Exposure Situations

The interest in radiation protection in industrial sectors involving Naturally Occurring Radioactive Materials (NORM) is increasingly growing. This is due also to the recent implementation of the European Council Directive 59/2013/Euratom which in Italy and in the other European Union Member States extends the field of application to industrial sectors never involved before. This paper reports main results of a research project on radiation protection in industries involving NORM carried out in Italy aimed to provide useful tools for stakeholders to comply new legal obligations. The project activities were mainly focused on different aspects relevant to the NORM involving industries, accounting for the positive list reported in the Italian law. Firstly, the inventory of the industries currently operating in Italy in order to identify the industrial sectors with an important radiological impact on population and workers was updated. Based on this information, a general methodology was elaborated taking into account a graded approach. The first phase consists in the identification and characterization of the most critical exposure scenarios and of the radiological content of NORMs involved in the different phases of the industrial processes. In the second phase calculation methods were developed for dose estimation for workers and members of public. These tools require the use of existing and well tested calculation codes, and the development of a dedicated user-friendly software