Porphyrin-silver acetylide cluster catalysts with dual active sites for the electrochemical reduction of CO.

A one-step synthesis of porphyrin-silver acetylide clusters from tetra alkyne-substituted porphyrin is described. The solid-state properties of three 2D-like compounds were fully characterised using XPS and XRD while their catalytic properties under CO electroreduction reaction conditions were assessed and their faradaic efficiency quantified.

Selectivity of a Copper Oxide CO Reduction Electrocatalyst Shifted by a Bioinspired pH-Sensitive Polymer.

A bioinspired polymeric membrane capable of shifting the selectivity of a copper oxide electrocatalyst in the CO reduction reaction is described. The membrane is deposited on top of copper oxide thin films from wet deposition techniques under controlled conditions of humidity and self-assembles into an arranged network of micrometer-sized pores throughout the polymer cross-section. The membrane was composed of a block copolymer with a precisely controlled ratio of poly-4-vinylpyridine and poly(methyl methacrylate) blocks (PMMA--P4VP).

Evaporative Drying Induced Self-Assembly of Epicuticular Wax: A Biomimetic Approach in Tuning Surface Roughness.

Epicuticular wax is an example of a naturally created functional material that forms a layer on the outermost surface of plants with the objective to protect them from adverse environmental conditions, such as UV-solar radiation, uncontrolled water loss, microbial attacks, and so forth. Their functionalities are often attributed to the chemical composition of the wax as well as the physical structuration formed by the wax crystals on the surface. With this work, we present a simple, one-step biomimetic approach to replicate similar surface structures, on model substrate, using wax extracted from ( wax).

Synthetic styrene-based bioinspired model of the [FeFe]-hydrogenase active site for electrocatalytic hydrogen evolution.

Integration of molecular catalysts inside polymeric scaffolds has gained substantial attention over the past decade, as it provides a path towards generating systems with enhanced stability as well as enzyme-like morphologies and properties. In the context of solar fuels research and chemical energy conversion, this approach has been found to improve both rates and energy efficiencies of a range of catalytic reactions. However, system performance still needs to be improved to reach technologically relevant currents and stability, parameters that are heavily influenced by the nature of the incorporated molecular catalyst.

Low performance of interferon gamma release assay Quantiferon-TB gold coupled or not with Pst1/3/lipoglycan humoral detection to predict Mycobacterium tuberculosis complex disease in a low-burden area.

Whole T cell interferon gamma release assays such as QuantiFERON-TB Gold Plus (QTF-TB) are used to evaluate Mycobacterium tuberculosis complex (MTC) exposure but fail to discriminate latent tuberculosis infection (LTBI) from active disease. In this study conducted in a low-burden area, 1215 patients presenting MTC risk and tested both for QTF-TB and mycobacterial infection (microscopy, culture, and/or PCR) were selected, as well as 1298 controls screened with QTF-TB before medical recruitment. The humoral response (LIODetect®TB-ST) was further evaluated in 199 selected patients.

Water-borne synthesis of multi-responsive and biodegradable chitosan-crosslinked microgels: Towards self-assembled films with adaptable properties.

The present study aims in the synthesis of new biodegradable stimuli-responsive microgels with controllable microstructure and with the ability to form cohesive films. Such self-assembled films by water evaporation at ambient conditions without any chemicals but just physical entanglements between soft colloid shell, present adaptable mechanical, adhesive and mechano-electrical properties. For that, oligo(ethylene glycol)-based stimuli-responsive microgels have been synthesized using biodegradable chitosan-methacrylates (Chi-MAs) with different degree of substitution (DS) as unique cross-linking agents by precipitation polymerization in water, for the first time.

Key hydraulic traits control the dynamics of plant dehydration in four contrasting tree species during drought.

Trees are at risk of mortality during extreme drought, yet our understanding of the traits that govern the timing of drought-induced hydraulic failure remains limited. To address this, we tested SurEau, a trait-based soil-plant-atmosphere model designed to predict the dynamics of plant dehydration as represented by the changes in water potential against those observed in potted trees of four contrasting species (Pinus halepensis Mill., Populus nigra L.

Soft Self-Assembled Mechanoelectrical Transducer Films from Conductive Microgel Waterborne Dispersions.

The present study aims in the developing of new soft transducers based on sophisticated stimuli-responsive microgels that exhibit spontaneous self-assembly forming cohesive films with conductive and mechanoelectrical properties. For that, oligo(ethylene glycol)-based stimuli-responsive microgels have been synthesized using bio-inspired catechol cross-linkers by one-step batch precipitation polymerization in aqueous media. Then, 3,4-ethylene dioxyyhiophene (EDOT) has been directly polymerized onto stimuli-responsive microgels using catechol groups as the unique dopant.

Electrode-modified block copoly-ionic liquid boosting the CO reduction toward CO in water-based media.

Coupling polymer and ionic liquids with electrodes for catalysis is a promising tool for optimization of electrocatalytic CO reduction reaction (CORR). Here, block copolymer ionic liquids BCPILs were synthesized controlled radical polymerization and nucleophilic post-substitution to introduce imidazole moieties. We show that, thanks to these PIL functionalities, the BCPIL/Re@HPC/GDL electrode can keep the selectivity toward CO when a higher amount of water is present in the electrolyte than the raw Re@HPC/GDL system.

Selenium-decorated biocompatible honeycomb films with redox-switchable surface for controlling cell adhesion/detachment.

Hypothesis: Selenium (Se)-containing compound is sensitive to redox stimulation, showing hydrophobic-hydrophilic reversible transition. Introduction of such compound into honeycomb film could confer on it redox-switchable surface wettability, which is expected to control cell adhesion/detachment behavior.

Experiments: Didodecyl selenide was designed and mixed with polystyrene to prepare honeycomb films using "breath figure" method.

Photoswitchable assembly of long-lived azobenzenes in water using visible light.

Hypothesis: Switchable assemblies relevant for bio-applications may be accessed from water-soluble tetra-ortho-substituted azobenzenes that reversibly self-assemble and form complexes with β-cyclodextrin under visible light.

Experiments: Two azobenzenes bearing either four fluorines or two chlorines and two fluorines in the ortho positions were synthesised with short poly(ethylene oxide) tails for water solubility. Photophysical properties were determined by UV-vis and H NMR spectroscopies, complexation with β-cyclodextrin was assessed by H NMR spectroscopy, and self-assembly in water was investigated by static and dynamic light scattering.

Non-Covalent Integration of a [FeFe]-Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution.

Surface integration of molecular catalysts inspired from the active sites of hydrogenase enzymes represents a promising route towards developing noble metal-free and sustainable technologies for H production. Efficient and stable catalyst anchoring is a key aspect to enable this approach. Herein, we report the preparation and electrochemical characterization of an original diironhexacarbonyl complex including two pyrene groups per catalytic unit in order to allow for its smooth integration, through π-interactions, onto multiwalled carbon nanotube-based electrodes.

Heterogenised Molecular Catalysts for Sustainable Electrochemical CO Reduction.

There has been a rapid rise in interest regarding the advantages of support materials to protect and immobilise molecular catalysts for the carbon dioxide reduction reaction (CO RR) in order to overcome the weaknesses of many well-known catalysts in terms of their stability and selectivity. In this Review, the state of the art of different catalyst-support systems for the CO RR is discussed with the intention of leading towards standard benchmarking for comparison of such systems across the most relevant supports and immobilisation strategies, taking into account these multiple pertinent metrics, and also enabling clearer consideration of the necessary steps for further progress. The most promising support systems are described, along with a final note on the need for developing more advanced experimental and computational techniques to aid the rational design principles that are prerequisite to prospective industrial upscaling.

Spontaneously Self-Assembled Microgel Film as Co-Delivery System for Skincare Applications.

Nowadays, the design of innovative delivery systems is driving new product developments in the field of skincare. In this regard, serving as potential candidates for on-demand drug delivery and fulfilling advanced mechanical and optical properties together with surface protection, spontaneously self-assembled microgel films can be proposed as ideal smart skincare systems. Currently, the high encapsulation of more than one drug simultaneously in a film is a very challenging task.

CO-Triggered ON/OFF Wettability Switching on Bioinspired Polylactic Acid Porous Films for Controllable Bioadhesion.

Bioinspired honeycomb-like porous films with switchable properties have drawn much attention recently owing to their potential application in scenarios in which the conversion between two opposite properties is required. Herein, the CO-gas-triggered ON/OFF switching wettability of biocompatible polylactic acid (PLA) honeycomb porous films is fabricated. Highly ordered porous films with diameters between 2.

Microgels self-assembly at liquid/liquid interface as stabilizers of emulsion: Past, present & future.

The most recent developments on Pickering emulsions deal with the design of responsive emulsions able to undergo fast destabilization under the effect of an external stimulus. In this scenario, soft colloidal particles like microgels are considered novel class suitable emulsifiers. Microgels particles self-assemblies are highly deformable at interfaces covering higher surfaces than hard particles and their interfacial behavior strongly depends on external-stimuli.

Bio-Inspired Silica Films Combining Block Copolymers Self-Assembly and Soft Chemistry: Paving the Way toward Artificial Exosqueleton of Seawater Diatoms.

This review is in line with the principles of bio-inspiration and biomimicry in order to envisage a softer and more environmentally friendly chemistry. Here, the source of inspiration is a microalga from the oceans with the ability to build an exoskeleton of silica under ambient conditions. Following this model, this review is interested in different ways of creating porous silica films with a hierarchical porosity similar to diatoms.

Immobilization of a Molecular Re Complex on MOF-derived Hierarchical Porous Carbon for CO Electroreduction in Water/Ionic Liquid Electrolyte.

The development of molecular catalysts for CO electroreduction within electrolyzers requests their immobilization on the electrodes. While a variety of methods have been explored for the heterogenization of homogeneous complexes, a novel approach using a hierarchical porous carbon material, derived from a metal-organic framework, is reported as a support for the well-known molecular catalyst [Re(bpy)(CO) Cl] (bpy=2,2'-bipyridine). This cathodic hybrid material, named Re@HPC (HPC=hierarchical porous carbon), has been tested for CO electroreduction using a mixture of an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, EMIM) and water as the electrolyte.

Microstructure-driven self-assembly and rheological properties of multi-responsive soft microgel suspensions.

Hypotheses: The deformation and swelling ability of microgels is influenced by the crosslinking distribution. Varying microgels microstructure is expected to obtain suspensions with different flow behavior and thereby, different rheological properties.

Experiments: Different multi-responsive microgels were synthesized using two different crosslinkers and varying their amounts: N,N-methylene bis-acrylamide (MBA) and oligo(ethylene glycol) diacrylate (OEGDA).

Microwave-Assisted Ultrafast RAFT Miniemulsion Polymerization of Biobased Terpenoid Acrylates.

There is a growing preference to move away from traditional petrochemical-based polymers toward biobased alternatives. Here, we report the microwave-assisted RAFT polymerization of several terpenoid acrylates (tetrahydrogeraniol, cyclademol, nopol, and citronellol). These biobased monomers give polymers with a broad range of glass transition temperatures and are excellent candidates to substitute oil-based (meth)acrylates in applications such as coatings and adhesives.

When a pH-triggered nanopatterned shape transition drives the wettability of a hierarchically self-organized film: A bio-inspired effect of "sea Anemone".

Hypothesis: Hierarchically structured surfaces including sensitive materials presents the advantage to exalt wettability variation due to the combination of micro structure effect directed by Cassie Baxter and/or Wenzel behaviour which is tuned by the surface energy variation of sensitive polymer films.

Experiments: Herein is reported the synthesis and the hierarchical structuration of a pH sensitive diblock copolymer P(S-stat-MMA)-b-P4VP with a pH-sensitive Poly 4-vinylpyridine P4VP block. Applying the Breath Figure method casting (minute time scale process), this diblock copolymer allows to obtain a micro porous honeycomb film while a wall nano-structuration due to self-assembly of diblock copolymer is observed.