Institut National des Sciences Appliquées Rouen Normandie

The present review is devoted to summarizing the recent advances (2015-2017) in the field of metal-catalysed group-directed C-H functionalisation. In order to clearly showcase the molecular diversity that can now be accessed by means of directed C-H functionalisation, the whole is organized following the directing groups installed on a substrate. Its aim is to be a comprehensive reference work, where a specific directing group can be easily found, together with the transformations which have been carried out with it. Hence, the primary format of this review is schemes accompanied with a concise explanatory text, in which the directing groups are ordered in sections according to their chemical structure. The schemes feature typical substrates used, the products obtained as well as the required reaction conditions. Importantly, each example is commented on with respect to the most important positive features and drawbacks, on aspects such as selectivity, substrate scope, reaction conditions, directing group removal, and greenness. The targeted readership are both experts in the field of C-H functionalisation chemistry (to provide a comprehensive overview of the progress made in the last years) and, even more so, all organic chemists who want to introduce the C-H functionalisation way of thinking for a design of straightforward, efficient and step-economic synthetic routes towards molecules of interest to them. Accordingly, this review should be of particular interest also for scientists from industrial R&D sector. Hence, the overall goal of this review is to promote the application of C-H functionalisation reactions outside the research groups dedicated to method development and establishing it as a valuable reaction archetype in contemporary R&D, comparable to the role cross-coupling reactions play to date.

International audience

ADVERTISEMENT RETURN TO ISSUEReviewNEXTUpdate 1 of: Asymmetric Fluorination, Trifluoromethylation, and Perfluoroalkylation ReactionsJun-An Ma† and Dominique Cahard*‡View Author Information Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China, and UMR 6014 CNRS, laboratoire COBRA de l'IRCOF (Institut de Recherche en Chimie Organique Fine), Université et INSA de Rouen, Rue Tesniere, F-76130 Mont Saint Aignan, France* To whom correspondence should be addressed. Fax: (33) 2 35 52 29 62. E-mail: [email protected]†Tianjin University.‡Université et INSA de Rouen.Cite this: Chem. Rev. 2008, 108, 9, PR1–PR43Publication Date (Web):September 10, 2008Publication History Received11 March 2008Published online10 September 2008Published inissue 10 September 2008https://pubs.acs.org/doi/10.1021/cr800221vhttps://doi.org/10.1021/cr800221vreview-articleACS PublicationsCopyright © 2008 American Chemical SocietyRequest reuse permissionsArticle Views13320Altmetric-Citations823LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Halogenation,Organic compounds,Reagents,Stereoselectivity,Trifluoromethylation Get e-Alerts

The isothermal tetragonal‐to‐monoclinic transformation of a 3Y‐TZP ceramic is investigated from 70° to 130°C in water and in steam by X‐ray diffraction and optical interferometer techniques. Aging kinetics followed by X‐ray diffraction are fitted by the Mehl‐Avrami‐Johnson law, suggesting nucleation and growth to be the key mechanisms for transformation. Optical interferometer observations of highly polished samples effectively reveal a nucleation and growth micromechanism for tetragonal‐to‐monoclinic transformation. A model based on surface change analysis is developed that fits closely to the X‐ray diffraction results.

Multi-modality is widely used in medical imaging, because it can provide multiinformation about a target (tumor, organ or tissue). Segmentation using multimodality consists of fusing multi-information to improve the segmentation. Recently, deep learning-based approaches have presented the state-of-the-art performance in image classification, segmentation, object detection and tracking tasks. Due to their self-learning and generalization ability over large amounts of data, deep learning recently has also gained great interest in multi-modal medical image segmentation. In this paper, we give an overview of deep learning-based approaches for multi-modal medical image segmentation task. Firstly, we introduce the general principle of deep learning and multi-modal medical image segmentation. Secondly, we present different deep learning network architectures, then analyze their fusion strategies and compare their results. The earlier fusion is commonly used, since it’s simple and it focuses on the subsequent segmentation network architecture. However, the later fusion gives more attention on fusion strategy to learn the complex relationship between different modalities. In general, compared to the earlier fusion, the later fusion can give more accurate result if the fusion method is effective enough. We also discuss some common problems in medical image segmentation. Finally, we summarize and provide some perspectives on the future research.

We propose some new methods for evaluating variable subset relevance in a purpose of variable selection . Relevance criteria are derived from Support Vector Machines and are based on the sensitivity of the weight vector kwk or the upper bounds of generalization error with respect to a variable. Experiments on linear and non-linear toy problem were ran and real-world datasets have also been used to assess the eectiveness of these criteria.

We present a theoretical description of the scattering of a Gaussian beam by a spherical, homogeneous, and isotropic particle. This theory handles particles with arbitrary size and nature having any location relative to the Gaussian beam. The formulation is based on the Bromwich method and closely follows Kerker’s formulation for plane-wave scattering. It provides expressions for the scattered intensities, the phase angle, the cross sections, and the radiation pressure.

This paper is devoted to difference of convex functions (d.c.) optimization: d.c. duality, local and global optimality conditions in d.c. programming, the d.c. algorithm (DCA), and its application to solving the trust-region problem. The DCA is an iterative method that is quite different from well-known related algorithms. Thanks to the particular structure of the trust-region problem, the DCA is very simple (requiring only matrix-vector products) and, in practice, converges to the global solution. The inexpensive implicitly restarted Lanczos method of Sorensen is used to check the optimality of solutions provided by the DCA. When a nonglobal solution is found, a simple numerical procedure is introduced both to find a feasible point having a smaller objective value and to restart the DCA at this point. It is shown that in the nonconvex case, the DCA converges to the global solution of the trust-region problem, using only matrix-vector products and requiring at most 2m+2 restarts, where m is the number of distinct negative eigenvalues of the coefficient matrix that defines the problem. Numerical simulations establish the robustness and efficiency of the DCA compared to standard related methods, especially for large-scale problems.

Severe plastic deformation (SPD) is effective in producing bulk ultrafine-grained and nanostructured materials with large densities of lattice defects. This field, also known as NanoSPD, experienced a significant progress within the past two decades. Beside classic SPD methods such as high-pressure torsion, equal-channel angular pressing, accumulative roll-bonding, twist extrusion, and multi-directional forging, various continuous techniques were introduced to produce upscaled samples. Moreover, numerous alloys, glasses, semiconductors, ceramics, polymers, and their composites were processed. The SPD methods were used to synthesize new materials or to stabilize metastable phases with advanced mechanical and functional properties. High strength combined with high ductility, low/room-temperature superplasticity, creep resistance, hydrogen storage, photocatalytic hydrogen production, photocatalytic CO2 conversion, superconductivity, thermoelectric performance, radiation resistance, corrosion resistance, and biocompatibility are some highlighted properties of SPD-processed materials. This article reviews recent advances in the NanoSPD field and provides a brief history regarding its progress from the ancient times to modernity. Abbreviations: ARB: Accumulative Roll-Bonding; BCC: Body-Centered Cubic; DAC: Diamond Anvil Cell; EBSD: Electron Backscatter Diffraction; ECAP: Equal-Channel Angular Pressing (Extrusion); FCC: Face-Centered Cubic; FEM: Finite Element Method; FSP: Friction Stir Processing; HCP: Hexagonal Close-Packed; HPT: High-Pressure Torsion; HPTT: High-Pressure Tube Twisting; MDF: Multi-Directional (-Axial) Forging; NanoSPD: Nanomaterials by Severe Plastic Deformation; SDAC: Shear (Rotational) Diamond Anvil Cell; SEM: Scanning Electron Microscopy; SMAT: Surface Mechanical Attrition Treatment; SPD: Severe Plastic Deformation; TE: Twist Extrusion; TEM: Transmission Electron Microscopy; UFG: Ultrafine Grained. © 2022 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.

Brain-computer interface P300 speller aims at helping patients unable to activate muscles to spell words by means of their brain signal activities. Associated to this BCI paradigm, there is the problem of classifying electroencephalogram signals related to responses to some visual stimuli. This paper addresses the problem of signal responses variability within a single subject in such brain-computer interface. We propose a method that copes with such variabilities through an ensemble of classifiers approach. Each classifier is composed of a linear support vector machine trained on a small part of the available data and for which a channel selection procedure has been performed. Performances of our algorithm have been evaluated on dataset II of the BCI Competition III and has yielded the best performance of the competition.

Background: The use of web-based monitoring for lung cancer patients is growing in interest because of promising recent results suggesting improvement in cancer and resource utilization outcomes. It remains an open question whether the overall survival (OS) in these patients could be improved by using a web-mediated follow-up rather than classical scheduled follow-up and imaging. Methods: Advanced-stage lung cancer patients without evidence of disease progression after or during initial treatment were randomly assigned in a multicenter phase III trial to compare a web-mediated follow-up algorithm (experimental arm), based on weekly self-scored patient symptoms, with routine follow-up with CT scans scheduled every three to six months according to the disease stage (control arm). In the experimental arm, an alert email was automatically sent to the oncologist when self-scored symptoms matched predefined criteria. The primary outcome was OS. Results: From June 2014 to January 2016, 133 patients were enrolled and 121 were retained in the intent-to-treat analysis; 12 deemed ineligible after random assignment were not subsequently followed. Most of the patients (95.1%) had stage III or IV disease. The median follow-up was nine months. The median OS was 19.0 months (95% confidence interval [CI] = 12.5 to noncalculable) in the experimental and 12.0 months (95% CI = 8.6 to 16.4) in the control arm (one-sided P = .001) (hazard ratio = 0.32, 95% CI = 0.15 to 0.67, one-sided P = .002). The performance status at first detected relapse was 0 to 1 for 75.9% of the patients in the experimental arm and for 32.5% of those in the control arm (two-sided P < .001). Optimal treatment was initiated in 72.4% of the patients in the experimental arm and in 32.5% of those in the control arm (two-sided P < .001). Conclusions: A web-mediated follow-up algorithm based on self-reported symptoms improved OS due to early relapse detection and better performance status at relapse.

Constructal theory is the view that the generation of flow configuration is a physics phenomenon that can be based on a physics principle (the constructal law): “For a finite-size flow system to persist in time (to survive) its configuration must evolve in such a way that it provides an easier access to the currents that flow through it” [A. Bejan, Advanced Engineering Thermodynamics, 2nd ed. (Wiley, New York, 1997); Int. J. Heat Mass Transfer, 40, 799 (1997)]. This principle predicts natural configuration across the board: river basins, turbulence, animal design (allometry, vascularization, locomotion), cracks in solids, dendritic solidification, Earth climate, droplet impact configuration, etc. The same principle yields new designs for electronics, fuel cells, and tree networks for transport of people, goods, and information. This review describes a paradigm that is universally applicable in natural sciences, engineering and social sciences.

The multifunctional nature of Alzheimer's disease calls for MTDLs (multitarget-directed ligands) to act on different components of the pathology, like the cholinergic dysfunction and amyloid aggregation. Such MTDLs are usually on the basis of cholinesterase inhibitors (e.g. tacrine or huprine) coupled with another active molecule aimed at a different target. To aid in the design of these MTDLs, we report the crystal structures of hAChE (human acetylcholinesterase) in complex with FAS-2 (fasciculin 2) and a hydroxylated derivative of huprine (huprine W), and of hBChE (human butyrylcholinesterase) in complex with tacrine. Huprine W in hAChE and tacrine in hBChE reside in strikingly similar positions highlighting the conservation of key interactions, namely, π-π/cation-π interactions with Trp86 (Trp82), and hydrogen bonding with the main chain carbonyl of the catalytic histidine residue. Huprine W forms additional interactions with hAChE, which explains its superior affinity: the isoquinoline moiety is associated with a group of aromatic residues (Tyr337, Phe338 and Phe295 not present in hBChE) in addition to Trp86; the hydroxyl group is hydrogen bonded to both the catalytic serine residue and residues in the oxyanion hole; and the chlorine substituent is nested in a hydrophobic pocket interacting strongly with Trp439. There is no pocket in hBChE that is able to accommodate the chlorine substituent.

A tri-ing transformation: The increasingly high demand for trifluoromethylated arenes and heteroarenes is a major challenge that has been addressed through the development of trifluoromethylation reactions. Several effective approaches for late-stage trifluoromethylation, as well as the use of practical and cheap trifluoromethylation reagents, are highlighted.

The design and development of new high-performance catalysts for applications in asymmetric catalytic reactions is of ongoing interest in organic chemistry. The combination of a Lewis acid and a Lewis base working in concert is now considered state of the art in stereoselective syntheses. The synergistic activation by two or more reactive centers allows high reaction rates and excellent transfer of stereochemical information. Despite the self-quenching reaction between Lewis acids and Lewis bases that might lead to an inactive catalyst, considerable effort has been directed towards the development of the dual-activation concept. The ultimate goal is to mimic nature by the discovery of catalytic systems analogous to enzymatic processes that involve metal-ion cocatalysts. With this aim, the dual activation concept greatly broadens the range of artificial catalysts. The most efficient catalytic systems are reviewed, and the mechanisms of action are discussed.

Abstract Blended cements, where Portland cement clinker is partially replaced by supplementary cementitious materials (SCMs), provide the most feasible route for reducing carbon dioxide emissions associated with concrete production. However, lowering the clinker content can lead to an increasing risk of neutralisation of the concrete pore solution and potential reinforcement corrosion due to carbonation. carbonation of concrete with SCMs differs from carbonation of concrete solely based on Portland cement (PC). This is a consequence of the differences in the hydrate phase assemblage and pore solution chemistry, as well as the pore structure and transport properties, when varying the binder composition, age and curing conditions of the concretes. The carbonation mechanism and kinetics also depend on the saturation degree of the concrete and CO 2 partial pressure which in turn depends on exposure conditions (e.g. relative humidity, volume, and duration of water in contact with the concrete surface and temperature conditions). This in turn influence the microstructural changes identified upon carbonation. This literature review, prepared by members of RILEM technical committee 281-CCC carbonation of concrete with supplementary cementitious materials, working groups 1 and 2, elucidates the effect of numerous SCM characteristics, exposure environments and curing conditions on the carbonation mechanism, kinetics and structural alterations in cementitious systems containing SCMs.

Motion capture setups are used in numerous fields. Studies based on motion capture data can be found in biomechanical, sport or animal science. Clinical science studies include gait analysis as well as balance, posture and motor control. Robotic applications encompass object tracking. Today's life applications includes entertainment or augmented reality. Still, few studies investigate the positioning performance of motion capture setups. In this paper, we study the positioning performance of one player in the optoelectronic motion capture based on markers: Vicon system. Our protocol includes evaluations of static and dynamic performances. Mean error as well as positioning variabilities are studied with calibrated ground truth setups that are not based on other motion capture modalities. We introduce a new setup that enables directly estimating the absolute positioning accuracy for dynamic experiments contrary to state-of-the art works that rely on inter-marker distances. The system performs well on static experiments with a mean absolute error of 0.15 mm and a variability lower than 0.025 mm. Our dynamic experiments were carried out at speeds found in real applications. Our work suggests that the system error is less than 2 mm. We also found that marker size and Vicon sampling rate must be carefully chosen with respect to the speed encountered in the application in order to reach optimal positioning performance that can go to 0.3 mm for our dynamic study.

Heat release effects on laminar flame propagation in partially premixed flows are studied. Data for analysis are obtained from direct numerical simulations of a laminar mixing layer with a uniformly approaching velocity field. The structure that evolves under such conditions is a triple flame, which consists of two premixed wings and a trailing diffusion flame. Heat release increases the flame speed over that of the corresponding planar premixed flame. In agreement with previous analytical work, reductions in the mixture fraction gradient also increase the flame speed. The effects of heat release and mixture fraction gradients on flame speed are not independent, however; heat release modifies the effective mixture fraction gradient in front of the flame. For very small mixture fraction gradients, scaling laws that determine the flame speed in terms of the density change are presented.

Major challenges must be tackled for brain-computer interfaces to mature into an established communications medium for VR applications, which will range from basic neuroscience studies to developing optimal peripherals and mental gamepads and more efficient brain-signal processing techniques.

Ecological Footprint accounting quantifies the supply and demand of Earth’s biocapacity. The National Footprint Accounts (NFA) are the most widely used Ecological Footprint (EF) dataset, and provide results for most countries and the world from 1961 to 2014, based primarily on publicly available UN datasets. Here, we review the evolution of the NFA, describe and quantify the effects of improvements that have been implemented into the accounts since the 2012 edition, and review the latest global trends. Comparing results over six editions of NFAs, we find that time-series trends in world results remain stable, and that the world Ecological Footprint for the latest common year (2008) has increased six percent after four major accounting improvements and more than thirty minor improvements. The latest results from the NFA 2018 Edition for the year 2014 indicate that humanity’s Ecological Footprint is 1.7 Earths, and that global ecological overshoot continues to grow. While improved management practices and increased agricultural yields have assisted in a steady increase of Earth’s biocapacity since 1961, humanity’s Ecological Footprint continues to increase at a faster pace than global biocapacity, particularly in Asia, where the total and per capita Ecological Footprint are increasing faster than all other regions.