Self-Healing Transparent Poly(dimethyl)siloxane with Tunable Mechanical Properties: Toward Enhanced Aging Materials for Space Applications.

When exposed to the geostationary orbit, polymeric materials tend to degrade on their surface due to the appearance of cracks. Implementing the self-healing concept in polymers going to space is a new approach to enhancing the lifespan of materials that cannot be replaced once launched. In this study, the elaboration of autonomous self-healing transparent poly(dimethylsiloxane) (PDMS) materials resistant to proton particles is presented. The PDMS materials are functionalized with various compositions of urea and imine moieties, forming dynamic covalent and/or supramolecular networks. The hydrogen bonds induced by the urea ensure the formation of a supramolecular network, while the dynamic covalent imine bonds are capable of undergoing exchange reactions. Materials with a broad range of mechanical properties were obtained depending on the composition and structure of the PDMS networks. As coating applications in a spatial environment were mainly targeted, the surface properties of the polymer are essential. Thus, percentages of scratch recovery were determined by AFM. From these data, self-healing kinetics were extracted and rationalized based on the polymer structures. The obtained data were in good agreement with the relaxation times determined by rheology in stress relaxation experiments. Moreover, the accelerated aging of materials under proton irradiation, simulating a major part of the geostationary environment, revealed a strong limitation or disappearance of cracks while keeping the transparency of the PDMS. These promising results open routes to prepare new flexible autonomous polymeric materials for space applications.

Surface Functionalization of Silicon, HOPG, and Graphite Electrodes: Toward an Artificial Solid Electrolyte Interface.

Electrografting of diazonium salts containing a protected alkyne moiety was used for the first functionalization of silicon and highly ordered pyrolytic graphite model surfaces. After deprotection with tetrabutylammonium fluoride, further layers were added by the thiol-yne click chemistry. The composition of each layer was characterized via X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. The same approach was then used to functionalize graphite powder electrodes, which are classically used as negative electrode in lithium-ion batteries. The effect of the coating on the formation of the solid electrolyte layer was investigated electrochemically by cyclovoltammetry and galvanostatic measurements. The modified graphite electrodes showed different reduction peaks in the first cycle, indicating reduced and altered decomposition processes of the components. Most importantly, the electrochemical investigations show a remarkable reduction of irreversible capacity loss of the battery.

An Update on Isocyanide-Based Multicomponent Reactions in Polymer Science.

Developments and progress in polymer science are often inspired by organic chemistry. In recent years, multicomponent reactions-especially the Passerini and Ugi reactions-have become very important tools for macromolecular design, mainly due to their modular character. In this review, the versatility of the Passerini and Ugi reactions in polymer science is highlighted by discussing recent examples of their use for monomer synthesis, as polymerization techniques, and for postpolymerization modification, as well as their suitability for architecture control, sequence control, and sequence definition.

Renewability is not Enough: Recent Advances in the Sustainable Synthesis of Biomass-Derived Monomers and Polymers.

Taking advantage of the structural diversity of different biomass resources, recent efforts were directed towards the synthesis of renewable monomers and polymers, either for the substitution of petroleum-based resources or for the design of novel polymers. Not only the use of biomass, but also the development of sustainable chemical approaches is a crucial aspect for the production of sustainable materials. This review discusses the recent examples of chemical modifications and polymerizations of abundant biomass resources with a clear focus on the sustainability of the described processes. Topics such as synthetic methodology, catalysis, and development of new solvent systems or greener alternative reagents are addressed. The chemistry of vegetable oil derivatives, terpenes, lignin, carbohydrates, and sugar-based platform chemicals was selected to highlight the trends in the active field of a sustainable use of renewable resources.

High Glass Transition Temperature Renewable Polymers via Biginelli Multicomponent Polymerization.

A novel and straightforward one-pot multicomponent polycondensation method was established in this work. The Biginelli reaction is a versatile multicomponent reaction of an aldehyde, a ß-ketoester (acetoacetate) and urea, which can all be obtained from renewable resources, yielding diversely substituted 3,4-dihydropyrimidin-2(1H)-ones (DHMPs). In this study, renewable diacetoacetate monomers with different spacer chain lengths (C3, C6, C10, C20) were prepared via simple transesterification of renewable diols and commercial acetoacetates. The diacetoacetate monomers were then reacted with renewable dialdehydes, i.e., terephthalaldehyde and divanillin in a Biginelli type step-growth polymerization. The obtained DHMP polymers (polyDHMPs) displayed high molar masses, high glass transition temperatures (Tg) up to 203 °C and good thermal stability (Td5%) of 280 °C. The Tg of the polyDHMPs could be tuned by variation of the structure of the dialdehyde or the diacetoacetate component.

From Lignin-derived Aromatic Compounds to Novel Biobased Polymers.

Nowadays, the synthesis of (semi)aromatic polymers from lignin derivatives is of major interest, as aromatic compounds are key intermediates in the manufacture of polymers and lignin is the main source of aromatic biobased substrates. Phenols with a variety of chemical structures can be obtained from lignin deconstruction; among them, vanillin and ferulic acid are the main ones. Depending on the phenol substrates, different chemical modifications and polymerization pathways are developed, leading to (semi)aromatic polymers covering a wide range of thermomechanical properties. This review discusses the synthesis and properties of thermosets (vinyl ester resins, cyanate ester, epoxy, and benzoxazine resins) and thermoplastic polymers (polyesters, polyanhydrides, Schiff base polymers, polyacetals, polyoxalates, polycarbonates, acrylate polymers) prepared from vanillin, ferulic acid, guaiacol, syringaldehyde, or 4-hydroxybenzoic acid.

Applications of vectorized gold nanoparticles to the diagnosis and therapy of cancer.

This critical review focuses on the anti-cancer fight using gold nanoparticles (AuNPs) functionalized with chemotherapeutic drugs in so-called "complexes" (supramolecular assemblies) and "conjugates" (covalent assemblies) as vectors. There is a considerable body of recent literature on various tumor-imaging techniques using the surface plasmon band (SPB) and the "passive" and "active" vectorization of anti-cancer drugs. This article reviews the main concepts and the most recent literature data with emphasis on AuNP preparation, cytotoxicities and use in selective targeting of cancer cells with over-expressed receptors for diagnosis and therapy (108 references).