Integration of Sequential Reactions in a Continuous Flow Droplet Reactor: A Route to Architecturally Defined Bimetallic Nanostructures

Microreactors for nanoparticle (NP) synthesis offer advantages over batch reactions in terms of scale‐up and integration with online analyses. Herein, two microreactors (i.e., a duo‐microreactor) are integrated to achieve sequential reactions for the synthesis of bimetallic NPs with architectural control. The generality of the duo‐microreactor is shown with the synthesis of branched Pd‐Pt NPs and core@shell Pd@Au NPs, both achieved by synthesizing Pd nanocubes in the first part of the duo‐microreactor and then using those nanocubes downstream as seeds for Pt or Au deposition. Control of the dimensions of these NPs is further demonstrated and achieved by tailoring metal precursor concentrations inline. This microreactor methodology is anticipated to be applicable to other bimetallic NP systems.     

Kinetics of the production of chain-end groups and methanol from the depolymerization of cellulose during the ageing of paper/oil systems. Part 1: Standard wood kraft insulation

Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)), similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol^?1 for methanol and scissions, respectively). Furthermore, a comparison of the rate constants $ \left( {k_{{{\text{CH}}_{ 3} {\text{OH}}}} /k_{\text{scissions}} } \right) Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)), similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol⁻¹ for methanol and scissions, respectively). Furthermore, a comparison of the rate constants shows approximately constant values indicating an apparent yield for the methanol of about one-third molecule per every scission for the tests under air (0.27 ± 0.04 for Clupak HD75 and 0.37 ± 0.14 for Munksj? TH70) and even lower for the ones under N₂ (0.12 ± 0.03 for Munksj? E.G.). As expected from a pseudo-zero order model, these values were shown to be consistent with a similar comparison of the amount of CH₃OH and chain-end groups produced under specific time–temperature ageing conditions (168 h at 120 °C). Finally, an additional test carried out with unaged cellulose in contact with a fresh solution of methanol in oil (cellulose/oil weight–volume ratio of 1:18) shows that at equilibrium, over 58% of the species is lost from the solution due to penetration into the fibres. Such results reveal the importance of the species partitioning in establishing the true correspondence between the molecules of CH₃OH produced and the scissions.     

Spectral-spatial classification of hyperspectral data based on a stochastic minimum spanning forest approach

In this paper, a new method for supervised hyperspectral data classification is proposed. In particular, the notion of stochastic minimum spanning forest (MSF) is introduced. For a given hyperspectral image, a pixelwise classification is first performed. From this classification map, M marker maps are generated by randomly selecting pixels and labeling them as markers for the construction of MSFs. The next step consists in building an MSF from each of the M marker maps. Finally, all the M realizations are aggregated with a maximum vote decision rule in order to build the final classification map. The proposed method is tested on three different data sets of hyperspectral airborne images with different resolutions and contexts. The influences of the number of markers and of the number of realizations M on the results are investigated in experiments. The performance of the proposed method is compared to several classification techniques (both pixelwise and spectral-spatial) using standard quantitative criteria and visual qualitative evaluation.     

Resonant shattering of neutron star crusts

The resonant excitation of neutron star (NS) modes by tides is investigated as a source of short gamma-ray burst (SGRB) precursors. We find that the driving of a crust-core interface mode can lead to shattering of the NS crust, liberating ～10{46}-10{47} erg of energy seconds before the merger of a NS-NS or NS-black-hole binary. Such properties are consistent with Swift/BAT detections of SGRB precursors, and we use the timing of the observed precursors to place weak constraints on the crust equation of state. We describe how a larger sample of precursor detections could be used alongside coincident gravitational wave detections of the inspiral by Advanced LIGO class detectors to probe the NS structure. These two types of observations nicely complement one another, since the former constrains the equation of state and structure near the crust-core boundary, while the latter is more sensitive to the core equation of state.     

CVD diamond films: from growth to applications

The present review provides an up-to-date report on the main potential of CVD diamond films for industrial applications as well as on recent basic research which seeks to understand diamond deposition microwave plasma reactors. This review includes firstly an overview of diamond film applications. Elements which explain variations in diamond film characteristics as a function of synthesis conditions are given. Also experimental results are reported which show variations in diamond characteristics (quality, microstructure, growth rate, growth mechanisms) as four plasma variables (pressure, power, percentage of methane, substrate temperature) are systematically changed. In the second part, we discuss the effects of these variables on local parameters such as electron temperature, gas temperature, carbon-containing species and H-atom densities. Finally, based on these results, relationships between key local parameters and diamond characteristics are established and discussed.     

Synthesis of 3,4-dihydrothioxanthene-1,9-dione analogs as potential antimalarial agents

7-Chloro-3-(2,4-dichlorophenyl)-3,4-dihydro-1H-thioxanthene-1,9 (2H)-dione (10), and a variety of analogs and derivatives were prepared as sulfur isosteric analogs of the acridinedione antimalarial agent, floxacrine. The compounds were devoid of antimalarial activity against P. berghei in mice.     

trans-α-Necrodyl isobutyrate, the sex pheromone of the grape mealybug, Pseudococcus maritimus

Headspace volatiles of virgin female grape mealybugs contained a single compound that elicitited responses from antennae of males in GC-electroantennogram analyses. The structure, identified as (R^∗,R^∗)-trans-(3,4,5,5-tetramethylcyclopent-2-en-1-yl)methyl 2-methylpropanoate, an irregular, non-head-to-tail monoterpenoid, was confirmed by synthesis.     

Bis-β-(diketonates) Zn(II) complexes substituted with thiophene: Electropolymerization,homogeneous and heterogeneous catalysis for ring opening polymerization of lactide

Two Bis-β-diketonate zinc (II) complexes were synthesized using 1-(thiophen-2-yl)butane-1,3-dione and 1-(thiophen-2-yl)-3-(thiophen-3-yl)propane-1,3-dione as ligands. By electropolymerization of their thiophenyl groups, the metallopolymers deposited on FTO electrodes were obtained. The main objective was to study the reactivity of these compounds as ROP catalysts for PLA synthesis, using directly the zinc complexes (homogeneous catalysis) and also the modified electrodes with metallopolymers (heterogeneous catalysis). The homogeneous catalysis studies allowed the optimization of the polymerization conditions, such as reaction time, catalyst concentration, and the use of benzyl alcohol as cocatalyst, as well as their influence on the conversion rate, average molecular weight and polydispersity of PLA, using rac-LA and L-LA as monomers. Also, the effect on tacticity and thermal properties were discussed. Finally, the ROP studies using immersed modified electrodes in the polymerization medium were carried out under optimized experimental conditions. These tests were positive for one of the studied compounds, reaching conversions of up to 67%. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 557–567