Stereoselective synthesis of both stereoisomers of β-fluorostyrene derivatives from a common intermediate

The stereoselective synthesis of both cis- and trans-β-fluorostyrene derivatives from a common intermediate, (Z)-1-aryl-2-fluoro-1-(trimethylsilyl)ethenes, is described. The trans isomers are obtained by a stereospecific replacement of the silyl group in the presence of water and a fluoride source, whereas the preparation of the cis isomers is achieved by a bromination/desilicobromination sequence followed by reduction of the newly created C-Br bond. A stereoselective transformation of both stereoisomers of β-fluorostyrene is also presented.     

Detection of Frozen–Thawed Duck Fatty Liver by MALDI-TOF Mass Spectrometry: A Chemometrics Study

The marketing of poultry livers is only authorized as fresh, frozen, or deep-frozen. The higher consumer demand for these products for a short period of time may lead to the marketing of frozen–thawed poultry livers: this constitutes fraud. The aim of this study was to design a method for distinguishing frozen–thawed livers from fresh livers. For this, the spectral fingerprint of liver proteins was acquired using Matrix-Assisted Laser Dissociation Ionization-Time-Of-Flight mass spectrometry. The spectra were analyzed using the chemometrics approach. First, principal component analysis studied the expected variability of commercial conditions before and after freezing–thawing. Then, the discriminant power of spectral fingerprint of liver proteins was assessed using supervised model generation. The combined approach of mass spectrometry and chemometrics successfully described the evolution of protein profile during storage time, before and after freezing-thawing, and successfully discriminated the fresh and frozen–thawed livers. These results are promising in terms of fraud detection, providing an opportunity for implementation of a reference method for agencies to fight fraud.     

Single- and Multi-Objective Cooperation for the Flexible Docking Problem

In this article, the impact of single-objective methods as intensification factors in a multi-objective approach is presented for the flexible docking problem. Based on a novel tri-objective model, a parallel multi-objective genetic algorithm has been designed. However, due to the high variability of the energy objective, intensification methods focused on this objective have been also included in order to improve the convergence speed of the genetic algorithm and the quality of the results. The corresponding approach, combining single- and multi-objective methods, has been proved efficient according to the tested instances and the quality criterion used.     

Low-temperature H2 sensing in self-assembled organotin thin films

Self-assembled nanoporous tin-based hybrid thin films prepared by the sol-gel method from organically-bridged ditin hexaalkynides detect hydrogen gas from 50 to 200 °C at the 200-10,000 ppm level. This finding opens a fully new class of gas-sensing materials as well as a new opportunity to integrate organic functionality in gas sensing metal oxides.     

Cis and trans selective 1,4-addition of a lithium dithioester enolate to 4-O-TBS-2-cyclohexenone

The 1,4-addition of the lithium enolate of methyldithioacetate (LMDTA) to (+/-)-4-O-TBS-2-cyclohexenone (3) can be varied from being highly 3,4-trans selective to being highly 3,4-cis selective simply by varying the reaction temperature. This stereodivergency allows expedient syntheses of the corresponding trans and cis methyl esters 6t and 6c and derived bicyclic ketolactones 7t and 7c.     

Fitness Landscape Analysis and Metaheuristics Efficiency

Landscape analysis has been identified as a promising way to develop efficient optimization methods. Nevertheless, the links between properties of the landscape and efficiency of methods is not easy to understand. In this article, we propose to give a contribution in this field using a vehicle routing problem as an illustration. Metaheuristics use a neighborhood operator that connects solutions of the search space. Thus, this operator acts on the dynamics of the search and impacts metaheuristics efficiency. Therefore, we characterize two landscapes differenciated by their neighborhood function and then, we analyze the performance of classical metaheuristics using one or the other neighborhood operator. Finally, a discussion provides insights on the relations between results of the landscape analysis and results of methods performance.     

On the structure of multiobjective combinatorial search space: MNK-landscapes with correlated objectives

The structure of the search space explains the behavior of multiobjective search algorithms, and helps to design well-performing approaches. In this work, we analyze the properties of multiobjective combinatorial search spaces, and we pay a particular attention to the correlation between the objective functions. To do so, we extend the multiobjective NK-landscapes in order to take the objective correlation into account. We study the co-influence of the problem dimension, the degree of non-linearity, the number of objectives, and the objective correlation on the structure of the Pareto optimal set, in terms of cardinality and number of supported solutions, as well as on the number of Pareto local optima. This work concludes with guidelines for the design of multiobjective local search algorithms, based on the main fitness landscape features.     

Enhanced Controllability of Low Reynolds Number Swimmers in the Presence of a Wall

Swimming, i.e., being able to advance in the absence of external forces by performing cyclic shape changes, is particularly demanding at low Reynolds numbers which is the regime of interest for micro-organisms and micro-robots. We focus on self-propelled stokesian robots composed of assemblies of balls and we prove that the presence of a wall has an effect on their motility. To rest on what has been done in Alouges et al. (Discrete Contin. Dyn. Syst., Ser. B 18(5):1189–1215, 2013) for such systems swimming on R ³, we demonstrate that a controllable swimmer remains controllable in a half space whereas the reachable set of a non fully controllable one is increased by the presence of a wall.     

Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: Spectrometric Evidence for Pt-Catalysed Decarboxylation at Anode-Relevant Potentials

The carbon oxidation reaction (COR) is a critical issue in proton-exchange membrane fuel cells (PEMFCs), as carbon in various forms is the most used electrocatalyst support material. The COR is thermodynamically possible above the C/CO₂ standard potential, but its rate becomes significantly important only at high overpotential (e. g. PEMFC cathode potential). Herein, using on-line differential electrochemical mass spectrometry, we show that oxygen-containing carbon surface groups present on high-surface aera carbon, Vulcan XC72 or reinforced graphite are oxidized at PEMFC anode-relevant potential (E=0.1 V vs. the reversible hydrogen electrode, RHE), but not at E=0.4 V vs. RHE. We rationalized our findings by considering a Pt-catalysed decarboxylation mechanism in which Pt nanoparticles provide adsorbed hydrogen species to the oxygen-containing carbon surface groups, eventually leading to evolution of carbon dioxide and carbon monoxide. These results shed fundamental light on an unexpected degradation mechanism and facilitate the understanding of the long-term stability of PEMFC anode nanocatalysts.