Fats and Oils as a Sustainable Source of Photopolymerizable Monomers.

Bio-derived monomers and biobased building blocks obtained from natural sources, e.g., fats and oils, are attracting increasing attention mainly due to sustainability concerns.

Photocrosslinkable starch cinnamyl ethers as bioinspired bio-based polymers.

A novel starch-based ether bearing cinnamyl functionalities, conferring photo-crosslinking properties, is synthesised by reaction with cinnamyl chloride in the presence of sodium hydroxide. Natural yuca was selected as a sustainable source of starch. Three different molar equivalents of reagents are used, affording starch-cinnamyl ethers with different degrees of substitution, ranging from 0.

Structure of Starch-Sepiolite Bio-Nanocomposites: Effect of Processing and Matrix-Filler Interactions.

Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging.

Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with -hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO NPs.

Novel perfluoropolyalkylethers monomers: synthesis and photo-induced cationic polymerization.

Unlabelled: Several difunctional oligomers were synthesized by functionalizing perfluoropolyalkylether (PFPAE) chains with different vinyl ethers and epoxides end-groups. Due to their innate synthetic challenges and demanding purification protocols, the PFPAE derivatives were obtained in low yield and with an average functionality lower than 2. However, the functionalized PFPAE oligomers were successful in being used in photo-induced cationic polymerization processes, obtaining transparent and soft films.

Valorization of Byproducts of Hemp Multipurpose Crop: Short Non-Aligned Bast Fibers as a Source of Nanocellulose.

Nanocellulose was extracted from short bast fibers, from hemp ( L.) plants harvested at seed maturity, non-retted, and mechanically decorticated in a defibering apparatus, giving non-aligned fibers. A chemical pretreatment with NaOH and HCl allowed the removal of most of the non-cellulosic components of the fibers.

Photoinduced Processes as a Way to Sustainable Polymers and Innovation in Polymeric Materials.

Photoinduced processes have gained considerable attention in polymer science and have greatly implemented the technological developments of new products. Therefore, a large amount of research work is currently developed in this area: in this paper we illustrate the advantages of a chemistry driven by light, the present perspectives of the technology, and summarize some of our recent research works, honoring the memory of Prof. Aldo Priola who passed away in March 2021 and was one of the first scientists in Italy to contribute to the field.

Vinyl ethers and epoxides photoinduced copolymerization with perfluoropolyalkylether monomers.

New perfluoropolyalkylether (PFPAE) monomers, chain extended with different alkyl groups and functionalized with vinyl ether or epoxide end-groups, were employed, together with trimethylolpropane trivinyl ether or trimethylolpropane triglycidyl ether, to produce fluorinated copolymers. The photoinduced cationic polymerization was investigated, and the PFPAE-based copolymer properties were thoroughly characterized. Interesting surface properties and two different values of refractive index were observed: thus, these fluorinated copolymers can be suitable materials for the manufacture of self-cleaning coatings and optical waveguides.

Photoinduced Polymerization of Eugenol-Derived Methacrylates.

Biobased monomers have been used to replace their petroleum counterparts in the synthesis of polymers that are aimed at different applications. However, environmentally friendly polymerization processes are also essential to guarantee greener materials. Thus, photoinduced polymerization, which is low-energy consuming and solvent-free, rises as a suitable option.

Radical Aqueous Emulsion Copolymerization of Eugenol-Derived Monomers for Adhesive Applications.

Biobased monomers derived from eugenol were copolymerized by emulsion polymerization to produce latexes for adhesive applications. Stable latexes containing ethoxy dihydroeugenyl methacrylate and ethoxy eugenyl methacrylate with high total solids content of 50 wt % were obtained and characterized. Latexes synthesis was carried out using a semibatch process, and latexes with particle diameters in the range of 159-178 nm were successfully obtained.

Correction: Synthesis of α,β-unsaturated esters of perfluoropolyalkylethers (PFPAEs) based on hexafluoropropylene oxide units for photopolymerization.

[This corrects the article DOI: 10.1039/C8RA06354K.].

Edge Functionalized Graphene Layers for (Ultra) High Exfoliation in Carbon Papers and Aerogels in the Presence of Chitosan.

Ultra-high exfoliation in water of a nanosized graphite (HSAG) was obtained thanks to the synergy between a graphene layer edge functionalized with hydroxy groups and a polymer such as chitosan (CS). The edge functionalization of graphene layers was performed with a serinol derivative containing a pyrrole ring, serinol pyrrole (SP). The adduct between CS and HSAG functionalized with SP was formed simply with a mortar and pestle, then preparing water dispersions stable for months in the presence of acetic acid.

Photofabrication of polymeric biomicrofluidics: New insights into material selection.

We propose a versatile method to evaluate the suitability of polymers for the fabrication of microfluidic devices for biomedical applications, based on the concept that the selection and the design of convenient materials should involve different properties depending on the final microfluidic application. Here polymerase chain reaction (PCR) is selected as biological model and target microfluidic reaction. A class of photocured siloxanes is introduced as device building polymers and copolymerization is adopted as strategy to finely tune and optimize the final material properties.

Photocuring of Epoxidized Cardanol for Biobased Composites with Microfibrillated Cellulose.

Cardanol is a natural alkylphenolic compound derived from Cashew NutShell Liquid (CNSL), a non-food annually renewable raw material extracted from cashew nutshells. In the quest for sustainable materials, the curing of biobased monomers and prepolymers with environmentally friendly processes attracts increasing interest. Photopolymerization is considered to be a green technology owing to low energy requirements, room temperature operation with high reaction rates, and absence of solvents.

Tuning Porosity and Functionality of Electrospun Rubber Nanofiber Mats by Photo-Crosslinking.

The present work proposes a versatile and efficient method to fabricate rubber nanofiber membranes with a controlled morphology and tailored functionality, based on the application of photoinduced thiol-ene cross-linking reactions to electrospun mats. Besides preventing the polymer cold flow and freezing the structure obtained by electrospinning, the photocuring step finely controls the morphology of the nanofiber mats, in terms of the fiber diameter up to the nanometer range and of the membrane porosity. Nanofiber membranes are also made chemically resistant, while retaining their flexibility.

Photo-crosslinking of chitosan/poly(ethylene oxide) electrospun nanofibers.

Photo-crosslinked nanofiber mats containing chitosan were obtained through the versatile and promising technology of electrospinning. Due to the challenging processability of chitosan by electrospinning because of its stiffness and polycationic nature, it was blended with easily-spinnable poly(ethylene oxide). The optimum conditions for electrospinning of chitosan/poly(eyhylene oxide) (CS/PEO) blends were selected for further characterization and investigation: the composition of CS/PEO 70/30 mass fraction was chosen as it allowed to produce uniform and defect free electrospun mats formed by fibers with an average diameter of 270 nm.

Domino Reaction for the Sustainable Functionalization of Few-Layer Graphene.

The mechanism for the functionalization of graphene layers with pyrrole compounds was investigated. Liquid 1,2,5-trimethylpyrrole (TMP) was heated in air in the presence of a high surface area nanosized graphite (HSAG), at temperatures between 80 °C and 180 °C. After the thermal treatments solid and liquid samples, separated by centrifugation, were analysed by means of Raman, Fourier Transform Infrared (FT-IR) spectroscopy, X-Rays Photoelectron Spectroscopy (XPS) and ¹H-Nuclear Magnetic Resonance (¹H NMR) spectroscopy and High Resolution Transmission Electron Microscopy (HRTEM).

Synthesis of α,β-unsaturated esters of perfluoropolyalkylethers (PFPAEs) based on hexafluoropropylene oxide units for photopolymerization.

α,β-unsaturated esters are usually synthesized for polymer applications. However, the addition of maleate (configuration) to a fluorinated moiety is challenging due to its potential isomerization during esterification. Various synthetic routes were attempted and led to very low conversion or side-products.

3D Printing: 3D Printing of Conductive Complex Structures with In Situ Generation of Silver Nanoparticles (Adv. Mater. 19/2016).

On page 3712, E. Fantino, A. Chiappone, and co-workers fabricate conductive 3D hybrid structures by coupling the photo-reduction of metal precursors with 3D printing technology.

3D Printing of Conductive Complex Structures with In Situ Generation of Silver Nanoparticles.

Coupling the photoreduction of a metal precursor with 3D-printing technology is shown to allow the fabrication of conductive 3D hybrid structures consisting of metal nanoparticles and organic polymers shaped in complex multilayered architectures. 3D conductive structures are fabricated incorporating silver nitrate into a photocurable oligomer in the presence of suitable photoinitiators and exposing them to a digital light system.

Oxygen-Inhibition Lithography for the Fabrication of Multipolymeric Structures.

The oxygen inhibition of UV curable polymers is exploited in novel technology for the fabrication of patterns and closed devices. Multiscale structures with thicknesses ranging from few micro-meters to millimeters are rapidly fabricated. Multipolymeric and multifunctional structures are also prepared: adequately choosing the material of each layer, a set of different properties is arranged in the same device.

Electrodes/electrolyte interfaces in the presence of a surface-modified photopolymer electrolyte: application in dye-sensitized solar cells.

Since hundreds of studies on photoanodes and cathodes show that the electrode/electrolyte interfaces represent a key aspect at the base of dye-sensitized solar cell (DSSC) performances, it is reported here that these interfaces can be managed by a smart design of the spatial composition of quasi-solid electrolytes. By means of a cheap, rapid, and green process of photoinduced polymerization, composition-tailored polymer electrolyte membranes (PEMs) with siloxane-enriched surfaces are prepared, and their properties are thoroughly described. When assembled in DSSCs, the interfacial action promoted by the composition-tailored PEMs enhances the photocurrent and fill factor values, thus increasing the global photovoltaic conversion efficiency with respect to the non-modified PEMs.

Visible Light Curable Restorative Composites for Dental Applications Based on Epoxy Monomer.

A cationic photo-curable cycloaliphatic epoxy resin has been investigated as reactive monomer in blue light crosslinking process. We have demonstrated that camphorquinone is able to abstract labile hydrogen from the epoxy monomer, giving rise to the formation of carbon-centered radicals that are oxidized by the onium salt; a complete epoxy group conversion was reached after 50 s of irradiation. The presence of water up to 1 wt% was tolerated without any important detrimental effect on the kinetics of light-curing.