High-Performance UV-Vis Light Induces Radical Photopolymerization Using Novel 2-Aminobenzothiazole-Based Photosensitizers

The popularity of using the photopolymerization reactions in various areas of science and technique is constantly gaining importance. Light-induced photopolymerization is the basic process for the production of various polymeric materials. The key role in the polymerization reaction is the photoinitiator. The huge demand for radical and cationic initiators results from the dynamic development of the medical sector, and the optoelectronic, paints, coatings, varnishes and adhesives industries. For this reason, we dealt with the subject of designing new, highly-efficient radical photoinitiators. This paper describes novel photoinitiating systems operating in UV-Vis light for radical polymerization of acrylates. The proposed photoinitiators are composed of squaraine (SQ) as a light absorber and various diphenyliodonium (Iod) salts as co-initiators. The kinetic parameters of radical polymerization of trimethylolpropane triacrylate (TMPTA), such as the degree of double bonds conversion (C%), the rate of photopolymerization (Rp), as well as the photoinitiation index (Ip) were calculated. It was found that 2-aminobenzothiazole derivatives in the presence of iodonium salts effectively initiated the polymerization of TMPTA. The rates of polymerization were at about 2 × 10−2 s−1 and the degree of conversion of acrylate groups from 10% to 36% were observed. The values of the photoinitiating indexes for the most optimal initiator concentration, i.e., 5 × 10−3 M were in the range from 1 × 10−3 s−2 even to above 9 × 10−3 s−2. The photoinitiating efficiency of new radical initiators depends on the concentration and chemical structure of used photoinitiator. The role of squaraine-based photoinitiating systems as effective dyeing photoinitiators for radical polymerization is highlighted in this article.

Vanadium(V) Complexes with Siderophore Vitamin E-Hydroxylamino-Triazine Ligands

Novel vitamin E chelate siderophore derivatives and their VV and FeIII complexes have been synthesised and the chemical and biological properties have been evaluated. In particular, the α- and δ-tocopherol derivatives with bis-methyldroxylamino triazine (α-tocTHMA) and (δ-tocDPA) as well their VV complexes, [V2VO3(α-tocTHMA)2] and [V2IVO3(δ-tocTHMA)2], have been synthesised and characterised by infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and ultra violet-visible (UV-Vis) spectroscopies. The dimeric vanadium complexes in solution are in equilibrium with their respefrctive monomers, H2O + [V2VO2(μ-O)]4+ = 2 [VVO(OH)]2+. The two amphiphilic vanadium complexes exhibit enhanced hydrolytic stability. EPR shows that the complexes in lipophilic matrix are mild radical initiators. Evaluation of their biological activity shows that the compounds do not exhibit any significant cytotoxicity to cells.

Reactivity of substrates with multiple competitive reactive sites toward NBS under neat reaction conditions promoted by visible light

Regioselectivity of visible-light-induced transformations of a range of (hetero)aryl alkyl-substituted ketones bearing several competitive reactive sites (α-carbonyl, benzyl and aromatic ring) with N-bromosuccinimide (NBS) was studied under solvent-free reaction conditions (SFRC) and in the absence of inert-gas atmosphere, radical initiators and catalysts. An 8-W energy-saving household lamp was used for irradiation. Heterogeneous reaction conditions were dealt with throughout the study. All substrates were mono- or dibrominated at the α-carbonyl position, and additionally, some benzylic or aromatic bromination was observed in substrates with benzylic carbon atoms or electron-donating methoxy groups, respectively. Surprisingly, ipso-substitution of the acyl group with a bromine atom took place with (4-methoxynaphthyl) alkyl ketones. While the addition of the radical scavenger TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy) decreased the extent of α- and ring bromination, it completely suppressed the benzylic bromination and α,α-dibromination with NBS under SFRC.

Diacyl peroxides, practical reagents as aryl and alkyl radical sources

Diacyl peroxides, which can be easily synthesized from corresponding carboxylic acids, are commonly utilized as radical initiators and one electron oxidants. Under thermal, transition-metal catalysis or irradiation conditions the cleavage...

Effect of ethane and ethylene on catalytic non oxidative coupling of methane

Ethane and ethylene are radical initiators in non-oxidative coupling of methane at high temperature, without adverse effect on product selectivity, when compared to the Fe/SiO2 catalyst.

Aryl Radical Initiators Accumulated within Layered Silicates Realize Polystyrene with Directly- and Regioselectively-bonded Aryl-terminal Groups

Arbitrary design of a terminal group of polymers exploits the still-veiled functions of polymers with potential for applications in fields such as drug delivery systems, photonics, and energy conversions. Here...

Oxidation of cycloalkene using supported ruthenium catalysts under solvent-free conditions

The present paper employs supported ruthenium nanoparticles alongside catalytic quantities of the radical initiator, which are proven to be capable of cyclooctene oxidation with green conditions, in the absence of solvent, with air as the main oxidant and without sacrificial reductant. The paper examines the effects of a range of radical initiators and how the products are distributed over time. Furthermore, the paper addresses the reaction pathways to the epoxides and allylic alcohol, the latter being the primary by-product, whilst also analysing the impact of the technique of synthesis, reaction time, and various supports. Catalyst activity can be markedly improved by adopting a sol-immobilization technique to synthesise the catalysts, with retention of selectivity to the epoxide.