Distinct Sustainable Carbon Nanodots Enable Free Radical Photopolymerization, Photo-ATRP and Photo-CuAAC Chemistry.

Carbon nanodots (CDs) originating from different biomass result in different activities to sensitize photo-ATRP and photo-CuAAC reaction protocols with visible light. Free radical polymerization of tri(propylene glycol)diacrylate also exhibited a good efficiency using CDs in combination with an iodonium salt employing LEDs emitting either at 405 nm, 525 nm or 660 nm. Photo-ATRP experiments confirmed controlled polymerization conditions using CuII at the ppm scale resulting in dispersities between 1.06 to 1.10. Chain end fidelity was successfully provided by chain extension and block copolymerization additionally approving the living feature of polymerization using a CD synthesized from lac dye comprising olefinic moieties in the originating biomass. By global analysis, time resolved fluorescence measurements indicated the appearance of several emitting species contributing to the reactivity of the excited states. Different cytotoxic response appeared following the answer of MCF-10A cells in a flow cytometry assay; that is 400 µg mL-1 . Thus, cell viability was greater 80 % in the case of CD-2-CD-5 while that of CD-1 was close to 70 %.

NIR Light-Induced ATRP for Synthesis of Block Copolymers Comprising UV-Absorbing Moieties.

NIR exposure at 790 nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [CuII /(TPMA)]Br2 (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol.

Carbon Dots as a Promising Green Photocatalyst for Free Radical and ATRP-Based Radical Photopolymerization with Blue LEDs.

Carbon dots (CDs) have been used for the first time as a sensitizer to initiate and activate free radical and controlled radical polymerization, respectively, based on an ATRP protocol with blue LEDs. Consideration of diverse heteroatom-doped CDs indicated that N-doped CDs could serve as an effective photocatalyst and photosensitizer in combination with LEDs emitting either at 405 nm or 470 nm. Free radical polymerization was initiated by combining the CDs with an iodonium or sulfonium salt in tri(propylene glycol) diacrylate. Polymerization of methyl methacrylate (MMA) by photo-induced ATRP was achieved with CDs and ethyl α-bromophenylacetate using CuII as catalyst in the ppm range. The polymers obtained showed temporal control, narrower dispersity ≲1.5, and chain-end fidelity. The first-order kinetics and ON/OFF experiments additionally gave evidence of the constant concentration of polymer radicals. No remarkable cytotoxic activity was observed for the CDs, underlining their biocompatibility.

Photophysics and photochemistry of NIR absorbers derived from cyanines: key to new technologies based on chemistry 4.0.

Cyanines derived from heptamethines were mainly discussed regarding their functionalization to broaden the solubility in different surroundings exhibiting either hydrophilic or hydrophobic properties and to tailor made the ΔG et photopysical properties with respect to absorption and fluorescence. Electrochemical properties were additionally considered for some selected examples. The cyanines chosen comprised as end groups either indolenine, benzo[e]- or benzo[cd]indolium pattern, which facilitated to shift the absorption between 750-1000 nm. This enabled their use in applications with light sources emitting in the near-infrared (NIR) region selected from high power LEDs or lasers with line-shaped focus. The absorbers considered were discussed regarding their function as sensitizer for applications related to Chemistry 4.0 standards. These were mainly photopolymer coatings, which can be found for applications in the graphic industry or to protect selected substrates. The huge release of heat on demand upon turning ON or OFF the NIR light source enables them for photothermal treatment in processes requesting heat to initiate either chemical (activated reactions) or physical (melting, evaporation) events.

Near-Infrared Sensitized Photoinduced Atom-Transfer Radical Polymerization (ATRP) with a Copper(II) Catalyst Concentration in the ppm Range.

NIR-sensitized photoinduced atom-transfer radical polymerization (ATRP) is possible by using ppm of CuII /tris(2-pyridylmethyl)amine (TPMA) as the catalyst, a polymethine as the photosensitizer, and α-bromophenylacetate as the alkyl halide initiator. Among the polymethines investigated with cationic, zwitterionic, or anionic structures, only the zwitterionic 2 exhibited sensitization activity under NIR light at room temperature resulting in the formation of polymers with controlled molecular weight characteristics and functionalities. The barbital group placed at the meso-position of 2 caused the activity in this photo-ATRP framework. The chain-end fidelity of the polymers was confirmed by chain extension and block copolymerization experiments. The polymerization system exhibits high photostability under NIR light exposure and irradiation dependency as demonstrated by light on/off experiments.