Substrate-Selective C-H Functionalization for the Preparation of Organosulfur Compounds from Crude Oil-Derived Components

The direct utilization of a natural feedstock in organic synthesis is an utmost challenge because the selective production of one product from a mixture of starting materials requires unprecedented substrate selectivity. In the present study, a simple and convenient procedure is evaluated for the substrate-selective alkenylation of a single component in a mixture of organosulfur compounds. Pd-catalyzed alkenylation of two-, three-, four-, and five-component mixtures of crude oil-derived sulfur species led to the exclusive C–H functionalization of only one compound. The observed remarkable substrate selectivity opens new opportunities for sustainable organic synthesis

Evaluation of phytotoxicity and cytotoxicity of industrial catalyst components (Fe, Cu, Ni, Rh and Pd): A case of lethal toxicity of a rhodium salt in terrestrial plants

Until recently, chemical derivatives of platinum group metals have not been in a systematic direct contact with living organisms. The situation has changed dramatically due to anthropogenic activity, which has led to significant redistribution of these metals in the biosphere. Millions of modern cars are equipped with automotive catalytic converters, which contain rhodium, palladium and platinum as active elements. Everyday usage of catalytic technologies promotes the propagation of catalyst components in the environment. Nevertheless, we still have not accumulated profound information on possible ecotoxic effects of these metal pollutants. In this study, we report a case of an extraordinarily rapid development of lethal toxicity of a rhodium (III) salt in the terrestrial plants Pisum sativum, Lupinus angustifolius and Cucumis sativus. The growth stage, at which the exposure occurred, had a crucial impact on the toxicity manifestation: at earlier stages, RhCl3 killed the plants within 24 h. In contrast, the salt was relatively low-toxic in human fibroblasts. We also address phytotoxicity of other common metal pollutants, such as palladium, iron, nickel and copper, together with their cytotoxicity. None of the tested compounds exhibited phytotoxic effects comparable with that of RhCl3. These results evidence the crucial deficiency in our knowledge on environmental dangers of newly widespread metal pollutants

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

The first example of an intermolecular thiol–yne–ene coupling reaction is reported for the one-pot construction of C−S and C−C bonds. Thiol–yne–ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via C−S three-electron σ-bond formation). Investigation of the reaction mechanism by combining online ESI-UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern–Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical-involving stages. As a result, previously unavailable products of the thiol–yne–ene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3-dienes

Plausible role of nanoparticle contamination in the synthesis and properties of organic electronic materials

Traceless transition metal catalysis (Pd, Ni, Cu, etc.) is very difficult to achieve. Metal contamination in the synthesized products is unavoidable and the most important questions are: How to control metal impurities? What amount of metal impurities can be tolerated? What is the influence of metal impurities? In this brief review, the plausible origins of nanoparticle contamination are discussed in the framework of catalytic synthesis of organic electronic materials. Key factors responsible for increasing the probability of contamination are considered from the point of view of catalytic reaction mechanisms. The purity of the catalyst may greatly affect the molecular weight of a polymer, reaction yield, selectivity and several other parameters. Metal contamination in the final polymeric products may induce some changes in the electric conductivity, charge transport properties, photovoltaic performance and other important parameters

Organic–Inorganic Hybrid Nanomaterials

The paramount progress in the field of organic–inorganic hybrid nanomaterials was stimulated by numerous applications in chemistry, physics, life sciences, medicine, and technology. Currently, in the field of hybrid materials, researchers may choose either to mimic complex natural materials or to compete with nature by constructing new artificial materials. The deep mechanistic understanding and structural insight achieved in recent years will guide a new wave in the design of hybrid materials at the atomic and molecular levels

Defects in 3D Printing and Strategies to Enhance Quality of FFF Additive Manufacturing. A Review

Additive manufacturing technologies (or 3D printing) have emerged as potent tools in the creation of a diverse array of objects, promising a paradigm shift in production methodologies across industries. However, the benefits of these technologies can be diminished by the use of suboptimal parameters or inferior materials, leading to defects that significantly degrade the quality and functionality of the resulting products. An incomplete understanding of defect formation keeps under the formulation of effective preventative strategies. In light of this, our review provides a comprehensive exploration of defects that arise during the Fused Filament Fabrication (FFF)—one of the most prevalent 3D printing methods. The defects are systematically classified according to several key characteristics, including size, type, mode of occurrence, and location. Each common defect is extensively discussed, detailing its external manifestation, root causes, the impact on the properties of printed parts, and potential preventative measures. Our findings unveil the complex interplay of material properties, printing parameters, and cooling dynamics in the defect formation process. This classification holds significant practical relevance, providing a solid foundation for the development of strategies for defect minimization and quality improvement in 3D printed products. It offers valuable insights for a broad audience, including researchers exploring additive manufacturing technologies, 3D printing engineers, 3D printer operators, and quality assurance (QA) engineers involved in production quality control. Furthermore, our review delineates the path for future research in this domain. There is a crucial need for the development of advanced machine learning and artificial intelligence models that can predict defect formation based on given printing parameters and material properties. Future investigations should also focus on the discovery of novel materials and refining of printing parameters to achieve superior quality of FFF 3D printed products. This review serves as a cornerstone for these future advancements, promoting a deeper understanding of defect formation and prevention in additive manufacturing

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

International audienceThis review highlights recent progress in the synthesis and application of vinyl ethers (VEs) as monomers for modern homo- and co-polymerization processes. VEs can be easily prepared using a number of traditional synthetic protocols including a more sustainable and straightforward manner by reacting gaseous acetylene or calcium carbide with alcohols. The remarkably tunable chemistry of VEs allows designing and obtaining polymers with well-defined structures and controllable properties. Both VE homopolymerization and copolymerization systems are considered, and specific emphasis is given to the novel initiating systems and to the methods of stereocontrol