Vinyl‐type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts

Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, ¹³C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). ¹³C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003     

Strengthening the Connection between Science,Society and Environment to Develop Future French and European Bioeconomies: Cutting-Edge Research of VAALBIO Team at UCCS

The development of the future French and European bioeconomies will involve developing new green chemical processes in which catalytic transformations are key. The VAALBIO team (valorization of alkanes and biomass) of the UCCS laboratory (Unité de Catalyse et Chimie du Solide) are working on various catalytic processes, either developing new catalysts and/or designing the whole catalytic processes. Our research is focused on both the fundamental and applied aspects of the processes. Through this review paper, we demonstrate the main topics developed by our team focusing mostly on oxygen- and hydrogen-related processes as well as on green hydrogen production and hybrid catalysis. The social impacts of the bioeconomy are also discussed applying the concept of the institutional compass.     

A mixed directed-undirected data structure for a parallel implementation of a domain decomposition algorithm

The choice of data structures influences the parallelization, efficiency and the manageability of a mesh refinement program. We introduce a mixed directed-undirected graph that combines both communication and scheduling needs. An inverted index is maintained for the directed graph to improve code performance and readability.This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.     

Associations between Neurocardiovascular Signal Entropy and Physical Frailty

In this cross-sectional study, the relationship between noninvasively measured neurocardiovascular signal entropy and physical frailty was explored in a sample of community-dwelling older adults from The Irish Longitudinal Study on Ageing (TILDA). The hypothesis under investigation was that dysfunction in the neurovascular and cardiovascular systems, as quantified by short-length signal complexity during a lying-to-stand test (active stand), could provide a marker for frailty. Frailty status (i.e., “non-frail”, “pre-frail”, and “frail”) was based on Fried’s criteria (i.e., exhaustion, unexplained weight loss, weakness, slowness, and low physical activity). Approximate entropy (ApEn) and sample entropy (SampEn) were calculated during resting (lying down), active standing, and recovery phases. There was continuously measured blood pressure/heart rate data from 2645 individuals (53.0% female) and frontal lobe tissue oxygenation data from 2225 participants (52.3% female); both samples had a mean (SD) age of 64.3 (7.7) years. Results revealed statistically significant associations between neurocardiovascular signal entropy and frailty status. Entropy differences between non-frail and pre-frail/frail were greater during resting state compared with standing and recovery phases. Compared with ApEn, SampEn seemed to have better discriminating power between non-frail and pre-frail/frail individuals. The quantification of entropy in short length neurocardiovascular signals could provide a clinically useful marker of the multiple physiological dysregulations that underlie physical frailty.     

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Can basic auditory and cognitive measures predict hearing-impaired listeners' localization and spatial speech recognition abilities?

This study aimed to clarify the basic auditory and cognitive processes that affect listeners' performance on two spatial listening tasks: sound localization and speech recognition in spatially complex, multi-talker situations. Twenty-three elderly listeners with mild-to-moderate sensorineural hearing impairments were tested on the two spatial listening tasks, a measure of monaural spectral ripple discrimination, a measure of binaural temporal fine structure (TFS) sensitivity, and two (visual) cognitive measures indexing working memory and attention. All auditory test stimuli were spectrally shaped to restore (partial) audibility for each listener on each listening task. Eight younger normal-hearing listeners served as a control group. Data analyses revealed that the chosen auditory and cognitive measures could predict neither sound localization accuracy nor speech recognition when the target and maskers were separated along the front-back dimension. When the competing talkers were separated along the left-right dimension, however, speech recognition performance was significantly correlated with the attentional measure. Furthermore, supplementary analyses indicated additional effects of binaural TFS sensitivity and average low-frequency hearing thresholds. Altogether, these results are in support of the notion that both bottom-up and top-down deficits are responsible for the impaired functioning of elderly hearing-impaired listeners in cocktail party-like situations.     

Stretching of polymer chains by fluctuating flow fields

We investigate polymer stretching by fluctuating flow fields via numerical solutions of the Brownian dynamics of multibead polymer chains taking into account nonlinear elasticity, hydrodynamic interactions and good solvent, excluded volume interaction effects. By varying the scaling exponent of the energy spectrum whilst keeping the same Reynolds and Deborah numbers, as well as microscale length and turnover times, we show that steeper spectra are associated with stronger stretching. We compute the probability density functions of chain length, and explain their main features by examining explicit molecular histories. We quantify the interaction between strain rate tensor structure and chain geometry as a means of understanding better the different stretching mechanisms in mild, moderate and strong polymer stretching regimes.     

Levels of mineral nutrients in fresh- and frozen bulk hydrated biological specimens: A comparison of EDS data collected in the environmental SEM and a conventional cryo-SEM

Energy-dispersive X-ray microanalysis (EDS) was compared in fresh- and frozen bulk hydrated tissues using the Environmental SEM (ESEM) and conventional cryo-SEM, respectively. Analyses of globoid inclusions of Eucalyptus calophylla seed from two soil types demontsrated that higher levels of cations (K, Ca, Mg, Al, Fe, Mn, Cu, Zn) occurred in seeds from soils containing higher levels of Al, while EDS-detectable levels of S and P were dependent upon the techniques utilised. Cumulative changes in ESEM-EDS-detectable levels of S and P were characterised by collecting cumulative spectra from nutrient standards and compared with those for K. Progressive increases in K occurred and were consistent with an enriching effect. Levels of S and P increased during early analysis (40–60 sec live time) and decreased thereafter. The semi-conductive nature of biological samples, the loss of anions and gain of cations from the net negatively-charged electron interaction volume contributed to an electrochemical bias. These local modifications in fluid chemistry were reversible. Dehydration effects also occurred in stable, “wet‘ samples. These differences indicated that EDS in ESEM may be limited to cations rather than anions, and that changes in fluid electrochemistry and dehydration may affect the level and distribution of elements.     

Applying Text Analytics for Studying Research Trends in Dependability

The dependability of systems and networks has been the target of research for many years now. In the 1970s, what is now known as the top conference on dependability—The IEEE/IFIP International Conference on Dependable Systems and Networks (DSN)—emerged gathering international researchers and sparking the interest of the scientific community. Although it started in niche systems, nowadays dependability is viewed as highly important in most computer systems. The goal of this work is to analyze the research published in the proceedings of well-established dependability conferences (i.e., DSN, International Symposium on Software Reliability Engineering (ISSRE), International Symposium on Reliable Distributed Systems (SRDS), European Dependable Computing Conference (EDCC), Latin-American Symposium on Dependable Computing (LADC), Pacific Rim International Symposium on Dependable Computing (PRDC)), while using Natural Language Processing (NLP) and namely the Latent Dirichlet Allocation (LDA) algorithm to identify active, collapsing, ephemeral, and new lines of research in the dependability field. Results show a strong emphasis on terms, like ‘security’, despite the general focus of the conferences in dependability and new trends that are related with ’machine learning’ and ‘blockchain’. We used the PRDC conference as a use case, which showed similarity with the overall set of conferences, although we also found specific terms, like ‘cyber-physical’, being popular at PRDC and not in the overall dataset.