From thorium phosphate hydrogenphosphate hydrate to β\beta-thorium phosphate diphosphate: Structural evolution to a radwaste storage ceramic

$\beta$-Thorium phosphate diphosphate ($\beta$-TPD), considered as a very promising radwaste storage material, was obtained from thorium phosphate hydrogenphosphate hydrate (TPHPH) precursor through dehydration and hydrogen phosphate condensation. The structures of TPHPH, intermediate $\alpha$-thorium phosphate diphosphate ($\alpha$-TPD) and its hydrate ($\alpha$-TPDH) have been resolved ab initio by Rietveld analysis of their synchrotron diffraction patterns. All were found orthorhombic (space group Cmcm) and similarly composed of [ThPO$_4$]$_4^{4+}$ slabs alternating with disordered layers hosting either [HPO$_4$·H$_2$O]$_2^{4-}$ (TPHPH), [P$_2$O$_7$·2H$_2$O]$^{4-} ($\alpha$-TPDH), or [P$_2O_7$]$^{4-}$($\alpha$-TPD), unlike the 3D structure of$\beta$-TPD. The diphosphate groups of$\alpha$-TPD and$\alpha$-TPDH are strongly bent. The irreversible transition to the final$\beta$-TPD consists in a shearing of the slabs and a reduction of the interslabs cavities that explains the stability of this high-temperature form

Merging Copper Catalysis with Nitro Allyl and Allyl Sulfone Derivatives: Practical, Straightforward, and Scalable Synthesis of Diversely Functionalized Allyl Boranes

We report here the first example of a copper-catalyzed transformation involving nitro allyl derivatives. This borylation reaction, which exploits the high versatility of the aforementioned precursor, tolerates a variety of functional groups and allows practical, scalable, and highly straightforward access to diversely substituted allylboronic esters in high yields. The method was also extended to allyl sulfones, which provides a very complementary approach, offering additional structural diversity along with improved stereoselectivities. This new reactivity was further exploited to synthesize γ-fluoroallyl boronic esters as well as various synthetically useful building blocks through key post-functionalizations. Both the reaction mechanism and the chemoselectivity were rationalized experimentally and through DFT calculations

Catalytic living ring-opening metathesis polymerization

In living ring-opening metathesis polymerization (ROMP), a transition-metal–carbene complex polymerizes ring-strained olefins with very good control of the molecular weight of the resulting polymers. Because one molecule of the initiator is required for each polymer chain, however, this type of polymerization is expensive for widespread use. We have now designed a chain-transfer agent (CTA) capable of reducing the required amount of metal complex while still maintaining full control over the living polymerization process. This new method introduces a degenerative transfer process to ROMP. We demonstrate that substituted cyclohexene rings are good CTAs, and thereby preserve the ‘living’ character of the polymerization using catalytic quantities of the metal complex. The resulting polymers show characteristics of a living polymerization, namely narrow molecular-weight distribution, controlled molecular weights and block copolymer formation. This new technique provides access to well- defined polymers for industrial, biomedical and academic use at a fraction of the current costs and significantly reduced levels of residual ruthenium catalyst

A study protocol for applying the co-creating knowledge translation framework to a population health study

BACKGROUND: Population health research can generate significant outcomes for communities, while Knowledge Translation (KT) aims to expressly maximize the outcomes of knowledge producing activity. Yet the two approaches are seldom explicitly combined as part of the research process. A population health study in Port Lincoln, South Australia offered the opportunity to develop and apply the co-KT Framework to the entire research process. This is a new framework to facilitate knowledge formation collaboratively between researchers and communities throughout a research to intervention implementation process. DESIGN: This study employs a five step framework (the co-KT Framework) that is formulated from engaged scholarship and action research principles. By following the steps a knowledge base will be cumulatively co-created with the study population that is useful to the research aims. Step 1 is the initiating of contact between the researcher and the study contexts, and the framing of the research issue, achieved through a systematic data collection tool. Step 2 refines the research issue and the knowledge base by building into it context specific details and conducting knowledge exchange events. Step 3 involves interpreting and analysing the knowledge base, and integrating evidence to inform intervention development. In Step 4 the intervention will be piloted and evaluated. Step 5 is the completion of the research process where outcomes for improvement will be instituted as regular practice with the facilitation of the community. In summary, the model uses an iterative knowledge construction mechanism that is complemented by external evidence to design interventions to address health priorities within the community. DISCUSSION: This is a systematic approach that operationalises the translational cycle using a framework for KT practice. It begins with the local context as its foundation for knowledge creation and ends with the development of contextually applicable interventions. It will be of interest to those involved in KT research, participatory action research, population health research and health care systems studies. The co-KT Framework is a method for embedding the principles of KT into all stages of a community-based research process, in which research questions are framed by emergent data from each previous stage.Kathryn Powell, Alison Kitson, Elizabeth Hoon, Jonathan Newbury, Anne Wilson and Justin Beilb

Antiinflammatory Therapy with Canakinumab for Atherosclerotic Disease

Background: Experimental and clinical data suggest that reducing inflammation without affecting lipid levels may reduce the risk of cardiovascular disease. Yet, the inflammatory hypothesis of atherothrombosis has remained unproved. Methods: We conducted a randomized, double-blind trial of canakinumab, a therapeutic monoclonal antibody targeting interleukin-1β, involving 10,061 patients with previous myocardial infarction and a high-sensitivity C-reactive protein level of 2 mg or more per liter. The trial compared three doses of canakinumab (50 mg, 150 mg, and 300 mg, administered subcutaneously every 3 months) with placebo. The primary efficacy end point was nonfatal myocardial infarction, nonfatal stroke, or cardiovascular death. RESULTS: At 48 months, the median reduction from baseline in the high-sensitivity C-reactive protein level was 26 percentage points greater in the group that received the 50-mg dose of canakinumab, 37 percentage points greater in the 150-mg group, and 41 percentage points greater in the 300-mg group than in the placebo group. Canakinumab did not reduce lipid levels from baseline. At a median follow-up of 3.7 years, the incidence rate for the primary end point was 4.50 events per 100 person-years in the placebo group, 4.11 events per 100 person-years in the 50-mg group, 3.86 events per 100 person-years in the 150-mg group, and 3.90 events per 100 person-years in the 300-mg group. The hazard ratios as compared with placebo were as follows: in the 50-mg group, 0.93 (95% confidence interval [CI], 0.80 to 1.07; P = 0.30); in the 150-mg group, 0.85 (95% CI, 0.74 to 0.98; P = 0.021); and in the 300-mg group, 0.86 (95% CI, 0.75 to 0.99; P = 0.031). The 150-mg dose, but not the other doses, met the prespecified multiplicity-adjusted threshold for statistical significance for the primary end point and the secondary end point that additionally included hospitalization for unstable angina that led to urgent revascularization (hazard ratio vs. placebo, 0.83; 95% CI, 0.73 to 0.95; P = 0.005). Canakinumab was associated with a higher incidence of fatal infection than was placebo. There was no significant difference in all-cause mortality (hazard ratio for all canakinumab doses vs. placebo, 0.94; 95% CI, 0.83 to 1.06; P = 0.31). Conclusions: Antiinflammatory therapy targeting the interleukin-1β innate immunity pathway with canakinumab at a dose of 150 mg every 3 months led to a significantly lower rate of recurrent cardiovascular events than placebo, independent of lipid-level lowering. (Funded by Novartis; CANTOS ClinicalTrials.gov number, NCT01327846.

Analysis and Improvement of the Random Delay Countermeasure of CHES 2009

Random delays are often inserted in embedded software to protect against side-channel and fault attacks. At CHES 2009 a new method for generation of random delays was described that increases the attacker's uncertainty about the position of sensitive operations. In this paper we show that the CHES 2009 method is less secure than claimed. We describe an improved method for random delay generation which does not suffer from the same security weakness. We also show that the paper's criterion to measure the security of random delays can be misleading, so we introduce a new criterion for random delays which is directly connected to the number of acquisitions required to break an implementation. We mount a power analysis attack against an 8-bit implementation of the improved method verifying its higher security in practice

Experimental and theoretical investigations on the polymorphism and metastability of BiPO4

In this work we report the metastability and the energetics of the phase transitions of three different polymorphs of BiPO4, namely trigonal (Phase-I, space group P3(1)21), monoclinic monazite-type (Phase-II, space group P2(1)/n) and SbPO4-type monoclinic (Phase-III, space group P2(1)/m) from ambient and non-ambient temperature powder XRD and neutron diffraction studies as well as ab initio density functional theory (DFT) calculations. The symmetry ambiguity between P2(1) and P2(1)/m of the high temperature polymorph of BiPO4 has been resolved by a neutron diffraction study. The structure and vibrational properties of these polymorphs of the three polymorphs have also been reported in detail. Total energy calculations have been used to understand the experimentally observed metastable behavior of trigonal and monazite-type BiPO4. Interestingly, all of the three phases were found to coexist after heating a single phasic trigonal BiPO4 to 773 K. The irreversible nature of these phase transitions has been explained by the concepts of the interplay of the structural distortion, molar volume and total energy.This study was supported by the Spanish government MEC under grants no: MAT2010-21270-C04-01/04, by MALTA Consolider Ingenio 2010 project (CSD2007-00045), and by the Vicerrectorado de Investigacion y Desarrollo of the Universidad Politecnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). S. N. A. acknowledges the support provided by Universitat de Valencia during his visit to it. A. M. and P. R.-H. acknowledge the computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster.Achary, SN.; Errandonea, D.; Muñoz, A.; Rodríguez Hernández, P.; Manjón Herrera, FJ.; Krishna, PSR.; Patwe, SJ.... (2013). Experimental and theoretical investigations on the polymorphism and metastability of BiPO4. Dalton Transactions. 42:14999-15015. https://doi.org/10.1039/c3dt51823jS14999150154

Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3

A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers

Horizontal Side-Channel Attacks and Countermeasures on the ISW Masking Scheme

International audienceA common countermeasure against side-channel attacks consists in using the masking scheme originally introduced by Ishai, Sahai and Wagner (ISW) at Crypto 2003, and further generalized by Rivain and Prouff at CHES 2010. The countermeasure is provably secure in the probing model, and it was showed by Duc, Dziembowski and Faust at Eurocrypt 2014 that the proof can be extended to the more realistic noisy leakage model. However the extension only applies if the leakage noise σ increases at least linearly with the masking order n, which is not necessarily possible in practice. In this paper we investigate the security of an implementation when the previous condition is not satisfied, for example when the masking order n increases for a constant noise σ. We exhibit two (template) horizontal side-channel attacks against the Rivain-Prouff's secure multiplication scheme and we analyze their efficiency thanks to several simulations and experiments. Eventually, we describe a variant of Rivain-Prouff's multiplication that is still provably secure in the original ISW model, and also heuristically secure against our new attacks