Polymer and organic molecules ordered via epitaxy: geometrical and molecular interactions

Control of structural order at the molecular level for both conventional linear polymers and conjugated polymers with valuable opto‐electronic properties has major consequence on the macroscopic properties of these polymers. Though the traditional means of orientation of polymer was mechanical deformation, presently extensive works are concerned with a more controlled way of orientation: epitaxial crystallisation. Most of the first documented examples of epitaxial growth of conventional polymers on single crystals followed the well‐established geometrical rules of best matching. However, recent examples show off more subtle rules of selection. Analogous cases, following or breaking the matching rules, have been observed for diacetylenes ordered via epipolymerisation on single crystals. Hereafter, representative examples of the structural matching rules are depicted first, and then recent examples, which depart from the simple geometrical fitting, are described. The analysis of the former leads to define the subtle matching rules applying for polymers linked to their conformational adaptability. The analysis of the latter gives the opportunity to discuss the relative influence of geometrical and molecular interactions between the deposit and the substrate.     

Parallel ab initio and molecular mechanics investigation of polycoordinated Zn(II) complexes with model hard and soft ligands: Variations of binding energy and of its components with number and charges of ligands

In this study we compare the binding energies of polycoordinated complexes of Zn²⁺ within cavities composed of model “hard” (H₂O, OH⁻) or “soft” (CH₃SH, CH₃S⁻) ligands. Ab initio supermolecule computations are performed at the HF and MP2 levels using extended basis sets to determine the binding energies and their components as a function of: the number of ligands, ranging from three to six; the net charge of the cavity; and the “hard” versus “soft” character of the ligands. These ab initio computations are used to test the reliability of the SIBFA molecular mechanics procedure, originally formulated and calibrated on the basis of ab initio computations, for such charged systems. The SIBFA intermolecular interaction energies match the corresponding ab initio values using a coreless effective potential split‐valence basis set with a relative error of ≤3%. Extensions to binuclear Zn²⁺ complexes, such as those that occur in the Zn‐binding sites of Gal4 and β‐lactamase proteins, are performed to test the applicability of the methodology for such systems. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1011–1039, 2000     

Aqueous Chemistry of Zirconium(IV) in Carbonate Media

The interactions between carbonate ions and zirconium oxychloride are studied by potentiometry, dialysis, and ¹³C‐ and ¹⁷O‐NMR spectroscopy in aqueous media. The nature of the soluble carbonatohydroxo complexes depends on the proportions of hydrogencarbonate and carbonate ions in solution before the addition of zirconium oxychloride. Carbonate media lead to polynuclear entities containing no more than two complexed carbonate ions per Zr⁴⁺. The presence of hydrogencarbonate favors the formation of less condensed and more carbonated complexes such as [Zr(CO₃)₄]⁴⁻. The polycondensation degree of the species decreases when the number of carbonates linked per Zr⁴⁺ increases. In all complexes, the carbonate is bidentate, and the metal atoms are linked via hydroxo bridges. The complexation of carbonate with Zr⁴⁺ occurs for a total carbonate concentration higher than 0.1M . Consequently, in natural medium, the speciation of this metal is governed only by the formation of hydroxo complexes.     

Analysis of a Prototypical Multiscale Method Coupling Atomistic and Continuum Mechanics： the Convex Case

In order to describe a solid which deforms smoothly in some region,but non smoothly in someother region,many multiscale methods have been recently proposed that aim at coupling an atomistic model(discrete mechanics) with a macroscopic model (continuum mechanics).We provide here a theoretical basis forsuch a coupling in a one-dimensional setting,in the case of convex energy.     

Comparative Metabolomic Analysis of Four Fabaceae and Relationship to In Vitro Nematicidal Activity against Xiphinema index

The grapevine fanleaf virus (GFLV), responsible for fanleaf degeneration, is spread in vineyards by the soil nematode Xiphinema index. Nematicide molecules were used to limit the spread of the disease until they were banned due to negative environmental impacts. Therefore, there is a growing interest in alternative methods, including plant-derived products with antagonistic effects to X. index. In this work, we evaluated the nematicidal potential of the aerial parts and roots of four Fabaceae: sainfoin (Onobrychis viciifolia), birdsfoot trefoil (Lotus corniculatus), sweet clover (Melilotus albus), and red clover (Trifolium pratense), as well as that of sainfoin-based commercial pellets. For all tested plants, either aerial or root parts, or both of them, exhibited a nematicidal effect on X. index in vitro, pellets being as effective as freshly harvested plants. Comparative metabolomic analyses did not reveal molecules or molecule families specifically associated with antagonistic properties toward X. index, suggesting that the nematicidal effect is the result of a combination of different molecules rather than associated with a single compound. Finally, scanning electron microscope observations did not reveal the visible impact of O. viciifolia extract on X. index cuticle, suggesting that alteration of the cuticle may not be the primary cause of their nematicidal effect.     

Performance of Bearing Ball Defect Classification Based on the Fusion of Selected Statistical Features

Among the existing bearing faults, ball ones are known to be the most difficult to detect and classify. In this work, we propose a diagnosis methodology for these incipient faults’ classification using time series of vibration signals and their decomposition. Firstly, the vibration signals were decomposed using empirical mode decomposition (EMD). Time series of intrinsic mode functions (IMFs) were then obtained. Through analysing the energy content and the components’ sensitivity to the operating point variation, only the most relevant IMFs were retained. Secondly, a statistical analysis based on statistical moments and the Kullback–Leibler divergence (KLD) was computed allowing the extraction of the most relevant and sensitive features for the fault information. Thirdly, these features were used as inputs for the statistical clustering techniques to perform the classification. In the framework of this paper, the efficiency of several family of techniques were investigated and compared including linear, kernel-based nonlinear, systematic deterministic tree-based, and probabilistic techniques. The methodology’s performance was evaluated through the training accuracy rate (TrA), testing accuracy rate (TsA), training time (Trt) and testing time (Tst). The diagnosis methodology has been applied to the Case Western Reserve University (CWRU) dataset. Using our proposed method, the initial EMD decomposition into eighteen IMFs was reduced to four and the most relevant features identified via the IMFs’ variance and the KLD were extracted. Classification results showed that the linear classifiers were inefficient, and that kernel or data-mining classifiers achieved 100% classification rates through the feature fusion. For comparison purposes, our proposed method demonstrated a certain superiority over the multiscale permutation entropy. Finally, the results also showed that the training and testing times for all the classifiers were lower than 2 s, and 0.2 s, respectively, and thus compatible with real-time applications.     

Lead Isotopic Constraints on the Provenance of Antarctic Dust and Atmospheric Circulation Patterns Prior to the Mid-Brunhes Event (~430 kyr ago)

A lead (Pb) isotopic record, covering the two oldest glacial–interglacial cycles (~572 to 801 kyr ago) characterized by lukewarm interglacials in the European Project for Ice Coring in Antarctica Dome C ice core, provides evidence for dust provenance in central East Antarctic ice prior to the Mid-Brunhes Event (MBE), ~430 kyr ago. Combined with published post-MBE data, distinct isotopic compositions, coupled with isotope mixing model results, suggest Patagonia/Tierra del Fuego (TdF) as the most important sources of dust during both pre-MBE and post-MBE cold and intermediate glacial periods. During interglacials, central-western Argentina emerges as a major contributor, resulting from reduced dust supply from Patagonia/TdF after the MBE, contrasting to the persistent dominance of dust from Patagonia/TdF before the MBE. The data also show a small fraction of volcanic Pb transferred from extra-Antarctic volcanoes during post-MBE interglacials, as opposed to abundant transfer prior to the MBE. These differences are most likely attributed to the enhanced wet removal efficiency with the hydrological cycle intensified over the Southern Ocean, associated with a poleward shift of the southern westerly winds (SWW) during warmer post-MBE interglacials, and vice versa during cooler pre-MBE ones. Our results highlight sensitive responses of the SWW and the associated atmospheric conditions to stepwise Antarctic warming.     

Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads

Three face-to-face linked porphyrin-corrole dyads were investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. The same three compounds were also investigated as to their ability to catalyze the electroreduction of dioxygen in aqueous 1 M HClO4 or HCl when adsorbed on a graphite electrode. The characterized compounds are represented as (PCY)H2Co, where P = a porphyrin dianion; C = a corrole trianion; and Y = a biphenylenyl, 9,9-dimethylxanthenyl, or anthracenyl spacer, which links the two macrocycles in a face-to-face arrangement. An axial binding of one or two Cl- ligands to the cobalt center of the corrole is observed for singly and doubly oxidized (PCY)H2Co, with the exact stoichiometry of the reaction depending upon the spacer size and the concentration of Cl- added to solution. No Cl- binding occurs for the neutral or reduced forms of the dyad, which contrasts with what is seen for the monocorrole, (Me4Ph5Cor)Co, where a single Cl- ligand is added to the Co(III) corrole in PhCN. The Co(III) form of the corrole in (PCY)H2Co also appears to be the catalytically active species in the electroreduction of dioxygen, which occurs at potentials associated with the Co(IV)/Co(III) reaction, that is, 0.35 V in 1 M HClO4 as compared to 0.31-0.42 V for the same three dyads in PhCN and 0.1 M TBAP. The potential for the catalytic electroreduction of O2 in HCl shifts negatively by 60 to 70 mV as compared to E(1/2) values in 1 M HClO4, consistent with the binding of Cl- to the Co(IV) form of the corrole and its rapid dissociation after electroreduction to Co(III) at the electrode surface.