Photo-cycloaddition reactions of vinyldiazo compounds.

Heterocyclic rings are important structural scaffolds encountered in both natural and synthetic compounds, and their biological activity often depends on these motifs. They are predominantly accessible via cycloaddition reactions, realized by either thermal, photochemical, or catalytic means. Various starting materials are utilized for this purpose, and, among them, diazo compounds are often encountered, especially vinyldiazo compounds that give access to donor-acceptor cyclopropenes which engage in [2+n] cycloaddition reactions. Herein, we describe the development of photochemical processes that produce diverse heterocyclic scaffolds from multisubstituted oximidovinyldiazo compounds. High chemoselectivity, good functional group tolerance, and excellent scalability characterize this methodology, thus predisposing it for broader applications. Experimental and computational studies reveal that under light irradiation these diazo reagents selectively transform into cyclopropenes which engage in cycloaddition reactions with various dipoles, while under thermal conditions the formation of pyrazole from vinyldiazo compounds is favored.

Unlocking the reactivity of diazo compounds in red light with the use of photochemical tools.

Structurally diversified diazoalkanes can be activated under red light irradiation relying on direct photolysis, photosensitization or photoredox catalysis.

Porphyrins as Promising Photocatalysts for Red-Light-Induced Functionalizations of Biomolecules.

Red-light enables deeper material penetration, which is important for biological applications and has consequences for chemical synthesis. Therefore, the search for new photocatalysts that absorb in this region is crucial. Despite the undeniable utility of porphyrins in blue- and green-light-induced energy- and electron-transfer processes, they are also perfectly suited for red-light applications. Herein, we describe free-base porphyrins as photoredox catalysts for red-light-induced organic transformations. They can act as both photooxidants and photoreductants and can accomplish the synthesis of biaryls once merged with Pd-catalysis. The developed methodology holds promise for broader applications, as the heme-based protoporphyrin is used as a photocatalyst and reactions can be realized in aqueous conditions.

Impact of Plasma Pre-Treatment on the Tribological Properties of DLC Coatings on PDMS Substrates.

The processes of the deposition of carbon coatings on PDMS (polydimethylsiloxane) substrates using plasma techniques are widely used in a large number of studies, in applications ranging from electronic to biological. That is why the potential improvement of their functional properties, including tribological properties, seems very interesting. This paper presents an analysis of the impact of plasma pre-treatment on the properties of the produced diamond-like carbon (DLC) coatings, including changes in the coefficients of friction and wear rates. The initial modification processes were performed using two different techniques based on low-pressure plasma (RF PACVD, radio-frequency plasma-assisted chemical vapour deposition) and dielectric barrier discharge (DBD) plasma. The effects of the above-mentioned treatments on the geometric structure of the PDMS surface and its water contact angles and stability over time were determined. The basic properties of the DLC coatings produced on unmodified substrates were compared to those of the coatings subjected to plasma pre-treatment. The most interesting effects in terms of tribological properties were achieved after the DBD process and production of DLC coatings, achieving a decrease in wear rates to 2.45 × 10-8 mm3/Nm. The tests demonstrate that the cross-linking of the polymer substrate occurs during plasma pre-treatment.