Tris-benzo[cd]indole Cyanine Enables the NIR-photosensitized Radical and Thiol-ene Polymerizations at 940†nm.

A near-infrared-absorbing heptamethine (HM+ ) incorporating three bulky benzo[cd]indole heterocycles was designed to efficiently prevent self-aggregation of the dye, which results in a strong enhancement of its photoinitiating reactivity as compared to a parent bis-benzo[cd]indole heptamethine (HMCl+ ) used as a reference system. In this context, we highlight an efficient free-radical NIR-polymerization up to a 100 % acrylates C=C bonds conversion even under air conditions. Such an important initiating performance was obtained by incorporating our NIR-sensitizer into a three-component system leading to its self-regeneration. This original photoredox cycle was thoroughly investigated through the identification of each intermediary species using EPR spectroscopy.

Biobased polymer resources and essential oils: a green combination for antibacterial applications.

To fight nosocomial infections, the excessive use of antibiotics has led to the emergence of multidrug-resistant microorganisms, which are now considered a relevant public health threat by the World Health Organization. To date, most antibacterial systems are based on the use of petro-sourced polymers, but the global supplies of these resources are depleting. Besides, silver NPs are widely accepted as the most active biocide against a wide range of bacterial strains but their toxicity is an issue. The growing interest in natural products has gained increasing interest in the last decade. Therefore, the design of functional antibacterial materials derived from biomass remains a significant challenge for the scientific community. Consequently, attention has shifted to naturally occurring substances such as essential oils (EOs), which are classified as Generally Recognized as Safe (GRAS). EOs can offer an alternative to the common antimicrobial agents as an inner solution or biocide agent to inhibit the resistance mechanism. Herein, this review not only aims at providing developments in the antibacterial modes of action of EOs against various bacterial strains and the recent advances in genomic and proteomic techniques for the elucidation of these mechanisms but also presents examples of biobased polymer resource-based EO materials and their antibacterial activities. Especially, we describe the antibacterial properties of biobased polymers, e.g. cellulose, starch, chitosan, PLA PHAs and proteins, associated with EOs (cinnamon (CEO), clove (CLEO), bergamot (BEO), ginger (GEO), lemongrass (LEO), caraway (CAEO), rosemary (REO), Eucalyptus globulus (EGEO), tea tree (TTEO), orange peel (OPEO) and apricot (Prunus armeniaca) kernel (AKEO) essential oils). Finally, we discuss the influence of EOs on the mechanical strength of bio-based materials.

Lawsone Derivatives as Efficient Photopolymerizable Initiators for Free-Radical, Cationic Photopolymerizations, and Thiol-Ene Reactions.

Two new photopolymerizable vinyl (2-(allyloxy) 1,4-naphthoquinone, HNQA) and epoxy (2-(oxiran-2yl methoxy) 1,4-naphthoquinone, HNQE) photoinitiators derived from lawsone were designed in this paper. These new photoinitiators can be used as one-component photoinitiating systems for the free-radical photopolymerization of acrylate bio-based monomer without the addition of any co-initiators. As highlighted by the electron paramagnetic resonance (EPR) spin-trapping results, the formation of carbon-centered radicals from an intermolecular H abstraction reaction was evidenced and can act as initiating species. Interestingly, the introduction of iodonium salt (Iod) used as a co-initiator has led to (1) the cationic photopolymerization of epoxy monomer with high final conversions and (2) an increase of the rates of free-radical polymerization of the acrylate bio-based monomer; we also demonstrated the concomitant thiol-ene reaction and cationic photopolymerizations of a limonene 1,2 epoxide/thiol blend mixture with the HNQA/Iod photoinitiating system.