Summary) The abstract should follow the structure of the article (relevance, degree of exploration of the problem, the goal, the main results, conclusion) and characterize the theoretical and practical significance of the study results. The abstract should not contain wording echoing the title, cumbersome grammatical structures and abbreviations. The text should be written in scientific style. The volume of abstracts (summaries) depends on the content of the article, but should not be less than 250 words. All abbreviations must be disclosed in the summary (in spite of the fact that they will be disclosed in the main text of the article), references to the numbers of publications from reference list should not be made. The sentences of the abstract should constitute an integral text, which can be made by use of the words “consequently”, “for example”, “as a result”. Avoid the use of unnecessary introductory phrases (eg, “the author of the article considers...”, “The article presents...” and so on.)

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Ministry of Education and Science of the Russian Federation

Among the living radical polymerization techniques, reversible addition–fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347–5393, 2005

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/pola.20986

Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization

Exposure to ultraviolet (UV) radiation may cause the significant degradation of many materials. UV radiation causes photooxidative degradation which results in breaking of the polymer chains, produces free radical and reduces the molecular weight, causing deterioration of mechanical properties and leading to useless materials, after an unpredictable time. Polystyrene (PS), one of the most important material in the modern plastic industry, has been used all over the world, due to its excellent physical properties and low-cost. When polystyrene is subjected to UV irradiation in the presence of air, it undergoes a rapid yellowing and a gradual embrittlement. The mechanism of PS photolysis in the solid state (film) depends on the mobility of free radicals in the polymer matrix and their bimolecular recombination. Free hydrogen radicals diffuse very easily through the polymer matrix and combine in pairs or abstract hydrogen atoms from polymer molecule. Phenyl radical has limited mobility. They may abstract hydrogen from the near surrounding or combine with a polymer radical or with hydrogen radicals. Almost all synthetic polymers require stabilization against adverse environmental effects. It is necessary to find a means to reduce or prevent damage induced by environmental components such as heat, light or oxygen. The photostabilization of polymers may be achieved in many ways. The following stabilizing systems have been developed, which depend on the action of stabilizer: (1) light screeners, (2) UV absorbers, (3) excited-state quenchers, (4) peroxide decomposers, and (5) free radical scavengers; of these, it is generally believed that excited-state quenchers, peroxide decomposers, and free radical scavengers are the most effective. Research into degradation and ageing of polymers is extremely intensive and new materials are being synthesized with a pre-programmed lifetime. New stabilizers are becoming commercially available although their modes of action are sometimes not thoroughly elucidated. They target the many possible ways of polymer degradation: thermolysis, thermooxidation, photolysis, photooxidation, radiolysis etc. With the goal to increase lifetime of a particular polymeric material, two aspects of degradation are of particular importance: Storage conditions, and Addition of appropriate stabilizers. A profound knowledge of degradation mechanisms is needed to achieve the goal.

/pdf/photodegradation-and-photostabilization-of-polymers-2iaxe4qvtk.pdf

Photodegradation and photostabilization of polymers, especially polystyrene: review

More polyunsaturated fats in processed foods and fewer additives are a huge demand of public health agencies and consumers. Consequently, although foods have an enhanced tendency to oxidize, the usage of antioxidants, especially synthetic antioxidants, is restrained. An alternate solution is to better control the localization of reactants inside the food matrix to limit oxidation. This review establishes the state-of-the-art on lipid oxidation in oil-in-water (O/W) emulsions, with an emphasis on the role of the interfacial region, a critical area in the system in that respect. We first provide a summary on the essential basic knowledge regarding (i) the structure of O/W emulsions and interfaces and (ii) the general mechanisms of lipid oxidation. Then, we discuss the factors involved in the development of lipid oxidation in O/W emulsions with a special focus on the role played by the interfacial region. The multiple effects that can be attributed to emulsifiers according to their chemical structure and their location, and the interrelationships between the parameters that define the physicochemistry and structure of emulsions are highlighted. This work sheds new light on the interpretation of reported results that are sometimes ambiguous or contradictory.

https://onlinelibrary.wiley.com/doi/pdf/10.1111/1541-4337.12097

Lipid Oxidation in Oil‐in‐Water Emulsions: Involvement of the Interfacial Layer

Kilogram-Scale Production of Corannulene

Preface. Symbols and Abbreviations. PART I: INITIATORS. Chapter 1. Mechanism of Decomposition of Initiators. 1.1 Introduction. 1.2 Nonconcerted Unimolecular Decomposition. 1.3 Concerted Fragmentation of Initiators. 1.4 Anchimerically Assisted Decomposition of Peroxides. 1.5 Decay of Initiators to Free Radicals and Molecular Products. 1.6 Chain Decomposition of Initiators. References. Chapter 2. Cage Effect. 2.1 Introduction. 2.2 Experimental Evidence for the Cage Effect. 2.3 Mechanistic Schemes of Cage Effect. 2.4 Cage Effect in Solid Polymers. References. Chapter 3. Methods of Study of Initiator Decomposition and Free Radical Generation. 3.1 Kinetic Decay of Initiator (KDI). 3.2 Kinetic Product Formation (KPF). 3.3 Acceptors of Free Radicals (AFR). 3.4 Kinetic Chain Initiated Reaction (KIR). 3.5 Chemiluminescence (CL) Method. References. Chapter 4. Dialkyl Peroxides and Hydroperoxides. 4.1 Dialkyl Peroxides. 4.2 Hydroperoxides and Peracids. References. Chapter 5. Diacyl Peroxides, Peroxy Esters, Polyatomic, and Organometallic Peroxides. 5.1 Diacyl Peroxides. 5.2 Peroxy Esters. 5.3 Decomposition of Polyatomic Peroxides. 5.4 Organometallic Peroxides. References. Chapter 6. Organic Polyoxides. 6.1 Dialkyl Trioxides. 6.2 Hydrotrioxides. 6.3 Tetroxides. References. Chapter 7. Azo Compounds. 7.1 Synthesis and Structure of Azo Compounds. 7.2 Thermochemistry of Azo Compounds. 7.3 Decomposition of Azo Compounds. References. Chapter 8. Compounds with Weak C-C, N-N, C-N and N-O Bonds. 8.1 Polyphenylhydrocarbons. 8.2 Substituted Hydrazines. 8.3 Alkoxyamines. 8.4 Nitro Compounds. 8.5 Nitrates and Nitrites. 8.6 Disulfides and Polysulfides. 8.7 Organometallic Compounds. References. PART II: BIMOLECULAR REACTIONS OF FREE RADICAL GENERATION. Chapter 9. Parabolic Model of Bimolecular Homolytic Reaction. 9.1 Introduction. 9.2 Principles for the Parabolic Model of Bimolecular Homolytic Reaction. 9.3 Parameters of Bimolecular Homolytic Reaction in the Parabolic Model. References. Chapter 10. Bimolecular and Trimolecular Reactions of Free Radical Generation by Dioxygen. 10.1 Reaction of Dioxygen with C-H Bonds of Organic Compounds. 10.2 Reaction of Dioxygen with the Double Bond of Olefins. 10.3 Trimolecular Reaction of Radical Initiation by Dioxygen. References. Chapter 11. Bimolecular Reactions of Free Radical Generation by Ozone. 11.1 Initiation of Radicals by Ozone Reactions. 11.2 Chain Reactions of Ozone Decomposition. References. Chapter 12. Bimolecular Reactions of Hydroperoxides with Free Radical Generation. 12.1 Bimolecular Decomposition of Hydroperoxides. 12.2 Bimolecular Reactions of Hydroperoxides with a pi-Bond to Olefins. 12.3 Bimolecular Reactions of Hydroperoxides with C-H, N-H, and O-H Bonds of Organic Compounds. 12.4 Acid Catalysis for Homolytic Reactions of Hydroperoxides. 12.5 Reaction of Peroxides with Amines. References. Chapter 13. Free Radical Generation by Olefins. 13.1 Reactions of Retrodisproportionation. 13.2 Chain Initiation in Thermal Radical Polymerization. References. Chapter 14. Free Radicals Generation by Haloid Molecules and Nitrogen Dioxide. 14.1 Reactions of Fluorine Compounds. 14.2 Reactions of Dichlorine and Other Chlorine Compounds. 14.3 Initiation by Nitrogen Dioxide. References. Chapter 15. Free Radical Generation by Reactions of Ions with Molecules. 15.1 Decomposition of Hydrogen Peroxide Catalyzed by Transition Metal Ions. 15.2 Catalysis by Ions and Complexes of Transition Metals in Liquid-Phase Oxidation of Organic Compounds. 15.3 Reactions of Free Radicals with Transition Metal Ions. 15.4 Oxidation of Transition Metal Ions by Dioxygen. 15.5 Oxidation of Organic Compounds by Transition Metal Ions. 15.6 Reduction of Peroxides by Radical Anions. References. PART III: REACTIONS OF FREE RADICALS. Chapter 16. Isomerization and Decomposition of Free Radicals. 16.1 Intramolecular Abstraction of Hydrogen Atom. 16.2 Cyclization of Free Radicals. 16.3 Decyclization of Cyclic Radicals. 16.4 Fragmentation of Free Radicals. References. Chapter 17. Free Radical Abstraction Reactions. 17.1 Classification of Radical Abstraction Reactions. 17.2 Enthalpy of Reaction. 17.3 Force Constants of Reacting Bonds. 17.4 Triplet Repulsion. 17.5 Electron Affinity of Atoms in Reaction Center. 17.6 Repulsion of Atoms Forming the Reaction Center. 17.7 Influence of pi-Bonds in the Vicinity of the Reaction Center. 17.8 Steric Effect. 17.9 Polar Effect in Radical Reactions. 17.10 Effect of Multidipole Interaction. 17.11 Solvating Effect. References. Chapter 18. Free Radical Reactions of Hydrogen Transfer and Substitution. 18.1 Reactions of Hydrogen Atom Transfer from a Free Radical to a Molecule. 18.2 Free Radical Substitution Reactions. 18.3 Reaction of Peroxides with Ketyl Radicals. References. Chapter 19. Free Radical Addition. 19.1 Enthalpy and Entropy of Free Radical Addition. 19.2 Empirical Correlation Equations. 19.3 Quantum Chemical Calculations for the Activation Energy. 19.4 Parabolic Model of Radical Addition. 19.5 Contribution of Enthalpy for an Addition Reaction to Its Activation Energy. 19.6 Force Constants of Reacting Bonds. 19.7 Triplet Repulsion in the Transition State of Addition Reactions. 19.8 Influence of Neighboring pi-Bonds on the Activation Energy of Radical Addition. 19.9 Role of the Radius of the Atom Bearing the Free Valence. 19.10 Interaction of Two Polar Groups. 19.11 Multidipole Interaction in Addition Reactions. 19.12 Steric Hindrance. 19.13 Addition of Alkyl Radicals to Dioxygen. References. Chapter 20. Recombination and Disproportionation of Free Radicals. 20.1 Alkyl Radicals. 20.2 Macroradicals. 20.3 Peroxyl Radicals. References. Index.

Handbook of Free Radical Initiators

Handbook of Free Radical Initiators: Denisov/Handbook Initiators

The Intersecting Parabolas Model as a Semi-Empirical Method for the Estimation of Activation Energies of Free Radical Reactions Kinetics of Chain Oxidation of Organic Compounds. Mechanisms of the Actions of Antioxidants Bond Dissociation Energies and Thermodynamic Functions of Antioxidants Reactions of Antioxidants with RO2, O2 O3, NO2, and ROOH Reactions of Phenoxyl, Aminyl, and Nitroxyl Radicals Phosphorus- and Sulfur-Containing Antioxidants Decomposing Hydroperoxides Antioxidants with Cyclic Mechanisms of Chain Termination Oxidation and Stabilization of Polymers Bioantioxidants References Index.

T. G. Denisova

Papers

Handbook of Free Radical Initiators

Handbook of Free Radical Initiators: Denisov/Handbook Initiators

Handbook of antioxidants : bond dissociation energies, rate constants, activation energies, and enthalpies of reactions

Diacyl Peroxides, Peroxy Esters, Polyatomic, and Organometallic Peroxides

Dialkyl Peroxides and Hydroperoxides