Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area of organic chemistry. Fluorine present in a molecule largely determines its specific chemical and biological properties. This thematic issue covers the trends of organofluorine chemistry that have been actively developed in Russia the last 15 – 20 years. The review describes nucleophilic substitution and heterocyclization reactions involving fluorinated arenes and quinones and skeletal cationoid rearrangements in the polyfluoroarene series. The transformations involving CF3-substituted carbocations and radical cations are considered. Heterocyclization and oxidative addition reactions of trifluoroacetamide derivatives and transformations of the organic moiety in polyfluorinated organoboranes and borates with retention of the carbon – boron bond are discussed. Particular attention is devoted to catalytic olefination using freons as an efficient synthetic route to fluorinated compounds. The application of unsymmetrical fluorine-containing N-heterocyclic carbene ligands as catalysts for olefin metathesis is demonstrated. A variety of classes of organofluorine compounds are considered, in particular, polyfluorinated arenes and 1,2-diaminobenzenes, 1-halo-2-trifluoroacetylacetylenes, α-fluoronitro compounds, fluorinated heterocycles, 2-hydrazinylidene-1,3-dicarbonyl derivatives, imines and silanes. The potential practical applications of organofluorine compounds in fundamental organic chemistry, materials science and biomedicine are outlined. The bibliography includes 1019 references.
Silicon quantum dots (SiQDs) are semiconductor Si nanoparticles ranging from 1 to 10 nm that hold great applicative potential as optoelectronic devices and fluorescent bio-marking agents due to their ability to fluoresce blue and red light. Their biocompatibility compared to conventional toxic Group II-VI and III-V metal-based quantum dots makes their practical utilization even more attractive to prevent environmental pollution and harm to living organisms. This work focuses on their possible use for light-emitting diode (LED) manufacturing. Summarizing the main achievements over the past few years concerning different Si quantum dot synthetic methods, LED formation and characteristics, and strategies for their stabilization by microencapsulation and modification of their surface by specific ligands, this work aims to provide guidance en route to the development of the first stable Si-based light-emitting diodes.
The Diels–Alder (DA) reaction is a promising tool for obtaining covalently crosslinked hydrogels due to its reaction bioorthogonality, the absence of by-products, and the application of mild conditions without a catalyst. The resulting hydrogels are in demand for use in various fields of materials science and biomedicine. While the dynamic nature of the cycloaddition of diene and dienophile has previously been used extensively for the fabrication of self-healing materials, it has only recently spread to the expansion of the functional properties of polymer gels for bioapplications. This review describes strategies and recent examples of obtaining hydrogels based on the DA reaction, demonstrating that the emerging functional properties go beyond self-healing. The types of classifications of hydrogels are listed, depending on the type of reaction and the nature of the components. Examples of obtaining hydrogels based on the normal and inverse electron-demand DA reaction, as well as the application of hydrogels for cell culture, drug delivery, injectable gels, and wound dressings, are considered. In conclusion, possible developmental directions are discussed, including the use of diene–dienophile pairs with a low temperature for the reversal of DA reaction, the modification of nanoparticles by diene and/or dienophile fragments, and new applications such as ink for 3D printing, sensing hydrogels, etc.
In an attempt to improve the mechanical and thermal properties of poly(ionic liquid)s (PILs), a new synthetic method for the modification of polyimides is reported here for the first time. The proposed methodology consists of the transformation of polyimides into their ionic forms via subsequent N-alkylation and quaternization of benzimidazole or quinuclidine moieties. Finally, an ion exchange reaction was also carried out in order to prepare polymers bearing the bis(trifluoromethylsulfonyl)imide anion. The elaboration of optimal conditions for the reactions afforded the preparation of high molecular weight (Mn = 2.2–9.7 × 104) cationic polyelectrolytes with a degree of quaternization as high as 96%. Among the unique features of these new PILs are the preservation of excellent mechanical and thermal properties inherent in polyimides, the adjustable surface wettability with variable water contact angles from 70.5 to 94.3°, the enhanced hydrolytic stability (up to 9 h in boiling water) and improved gas transport properties (CO2 permeability up to 28.9 Barrer for a neat film and 85.0 Barrer for a filled membrane at 20 °C and 100 kPa).
This review covers the mechanisms of formation, properties, characterization, and a broad range applications of nanocolloidal gels that are an evolving class of soft matter materials in which nanoparticles act as a building block of a network.