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Journal articles on the topic 'Free radical reaction'

Author: Grafiati

Published: 4 June 2021

Last updated: 1 February 2022

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1

Wu, Yuh-Wern, Hsu-Ting Huang, Yi-Jing Chen, and Jyh-Ferng Yang. "Free radical SH2′ reaction mechanism study by comparing free radical SH2′ reaction with free radical addition reaction." Tetrahedron 62, no. 25 (2006): 6061–64. http://dx.doi.org/10.1016/j.tet.2006.03.106.

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2

Mohammad, Mahboob, Muhammad Tariq, and Muhammad Tahir Soomro. "“Long-life” atom-free radical: Generation and reactions of bromine atom-free radical." Collection of Czechoslovak Chemical Communications 75, no. 11 (2010): 1061–74. http://dx.doi.org/10.1135/cccc2010066.

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In order to study the damaging or beneficial properties of bromine atom-free radical, reaction of the free radical (Br•) with some biologically important compounds were investigated. Br• was generated through electrochemical oxidation of bromide ion (Br–). First the reactivity of Br• atom-free radical vis a vis its dimerization to form Br2, was studied using cyclic voltammetry and spectroelectrochemistry. Through these techniques it was ascertained that the substrates understudy and the under experimental conditions used, underwent reactions with Br• and not with dibromine (Br2). The monitorin

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3

Chuang, Che-Ping, Sheng-Shu Hou, and Ru-Rong Wu. "Allylsulfone in Free Radical Reaction." Synthetic Communications 22, no. 3 (1992): 467–76. http://dx.doi.org/10.1080/00397919208055425.

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4

Davies, M. J., S. Fu, and R. T. Dean. "Protein hydroperoxides can give rise to reactive free radicals." Biochemical Journal 305, no. 2 (1995): 643–49. http://dx.doi.org/10.1042/bj3050643.

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Proteins damaged by free-radical-generating systems in the presence of oxygen yield relatively long-lived protein hydroperoxides. These hydroperoxides have been shown by e.p.r. spectroscopy to be readily degraded to reactive free radicals on reaction with iron(II) complexes. Comparison of the observed spectra with those obtained with free amino acid hydroperoxides had allowed identification of some of the protein-derived radical species (including a number of carbon-centred radicals, alkoxyl radicals and a species believed to be the CO2 radical anion) and the elucidation of novel fragmentation

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5

Li, Guoxiang, Zhongyang Luo, Wenbo Wang, and Jianmeng Cen. "A Study of the Mechanisms of Guaiacol Pyrolysis Based on Free Radicals Detection Technology." Catalysts 10, no. 3 (2020): 295. http://dx.doi.org/10.3390/catal10030295.

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In order to understand the reaction mechanism of lignin pyrolysis, the pyrolysis process of guaiacol (o-methoxyphenol) as a lignin model compound was studied by free radical detection technology (electron paramagnetic resonance, EPR) in this paper. It was proven that the pyrolysis reaction of guaiacol is a free radical reaction, and the free radicals which can be detected mainly by EPR are methyl radicals. This paper proposes a process in which four free radicals (radicals 1- C6H4(OH)O*, radicals 5- C6H4(OCH3)O*, methyl radicals, and hydrogen radicals) are continuously rearranged during the py

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6

Pinet, Sandra, Mathieu Pucheault, Virginie Liautard, and Mégane Debiais. "Radical Metal-Free Borylation of Aryl Iodides." Synthesis 49, no. 21 (2017): 4759–68. http://dx.doi.org/10.1055/s-0036-1588431.

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A simple metal-free borylation of aryl iodides mediated by a fluoride sp2–sp3 diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated in situ.

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7

Packer, JE, and RER Taylor. "Free-Radical Reductions of Arenediazonium Ions in Aqueous Solution. VI. On Iododediazoniation." Australian Journal of Chemistry 38, no. 6 (1985): 991. http://dx.doi.org/10.1071/ch9850991.

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γ-Irradiation of aqueous solutions of p-ClC6H4N2+BF4- and KI initiates a chain reaction in which dichloroazobenzene is the major product. When iodine is also present the chain reaction is longer and the major product is chloroiodobenzene . The reaction � �� I2-·+ArN2+ → I2+Ar·+N2 is suggested to be propagation step in both reactions, with Ar · reacting with I3- in the presence of iodine and with ArN2+ in its absence. The relevance of these reactions to iododediazoniation is discussed.

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8

Goodman, B. A. "The involvement of oxygen-derived free radicals in plant–pathogen interactions." Proceedings of the Royal Society of Edinburgh. Section B. Biological Sciences 102 (1994): 479–93. http://dx.doi.org/10.1017/s0269727000014500.

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SynopsisPlants have evolved a multiplicity of defence mechanisms against pathogen attack. Their modes of action may be to (i) kill the pathogen directly, (ii) block the action of enzymes required for infection, or (iii) erect barriers to pathogen growth. Some of these reactions proceed via free radical intermediates and make use of either atmospheric oxygen or reactive oxygen species. This paper reviews the various types of reaction involving oxygen-derived free radicals that are initiated in plant tissue when it is invaded by pathogenic organisms. Both the production of free radicals by plant

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9

Fletcher, R. J., and J. A. Murphy. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 88 (1991): 83. http://dx.doi.org/10.1039/oc9918800083.

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10

Hewlins, S. A., and J. A. Murphy. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 89 (1992): 75. http://dx.doi.org/10.1039/oc9928900075.

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11

Caddick, S. "Chapter 4. Reaction mechanisms Part (ii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 90 (1993): 81. http://dx.doi.org/10.1039/oc9939000081.

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12

Caddick, S., and K. Aboutayab. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 91 (1994): 103. http://dx.doi.org/10.1039/oc9949100103.

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13

Caddick, Stephen, and Kerry Jenkins. "Chapter 3. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 92 (1995): 51. http://dx.doi.org/10.1039/oc9959200051.

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14

Caddick, Stephen, Vern M. Delisser, and Craig L. Shering. "Chapter 3. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 93 (1996): 55. http://dx.doi.org/10.1039/oc9969300055.

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15

Caddick, S., V. M. Delisser, and C. L. Shering. "Chapter 3. Reaction Mechanisms . Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 93 (1997): 55. http://dx.doi.org/10.1039/oc093055.

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16

E. Falvey, Daniel. "Chapter 9. Reaction mechanisms . Part (iv) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 94 (1998): 321. http://dx.doi.org/10.1039/oc094321.

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17

Griller, D. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 82 (1985): 75. http://dx.doi.org/10.1039/oc9858200075.

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18

Crich, D. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 83 (1986): 65. http://dx.doi.org/10.1039/oc9868300065.

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19

Crich, D. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 84 (1987): 81. http://dx.doi.org/10.1039/oc9878400081.

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20

Crich, D. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 85 (1988): 71. http://dx.doi.org/10.1039/oc9888500071.

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21

Griffiths, J., and J. A. Murphy. "Chapter 4. Reaction mechanisms. Part (iii) Free-radical reactions." Annual Reports Section "B" (Organic Chemistry) 87 (1990): 85. http://dx.doi.org/10.1039/oc9908700085.

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22

Monroe, Manus, and Karl Abrams. "Chain reaction wheel: An approach to free radical reactions." Journal of Chemical Education 62, no. 6 (1985): 467. http://dx.doi.org/10.1021/ed062p467.

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23

CADDICK, S., and K. JENKINS. "ChemInform Abstract: Reaction Mechanisms. Part 3. Free-Radical Reactions." ChemInform 28, no. 14 (2010): no. http://dx.doi.org/10.1002/chin.199714275.

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24

GRIFFITHS, J., and J. A. MURPHY. "ChemInform Abstract: Reaction Mechanisms. Part 3. Free-Radical Reactions." ChemInform 25, no. 9 (2010): no. http://dx.doi.org/10.1002/chin.199409305.

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25

FLETCHER, R. J., and J. A. MURPHY. "ChemInform Abstract: Reaction Mechanisms. Part 3. Free-Radical Reactions." ChemInform 25, no. 11 (2010): no. http://dx.doi.org/10.1002/chin.199411308.

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26

CADDICK, S., and K. ABOUTAYAB. "ChemInform Abstract: Reaction Mechanisms. Part 3. Free-Radical Reactions." ChemInform 27, no. 29 (2010): no. http://dx.doi.org/10.1002/chin.199629260.

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27

HEWLINS, S. A., and J. A. MURPHY. "ChemInform Abstract: Reaction Mechanisms. Part 3. Free-Radical Reactions." ChemInform 25, no. 38 (2010): no. http://dx.doi.org/10.1002/chin.199438297.

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28

CADDICK, S. "ChemInform Abstract: Reaction Mechanisms. Part 2. Free-Radical Reactions." ChemInform 26, no. 28 (2010): no. http://dx.doi.org/10.1002/chin.199528281.

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29

Falvey, Daniel E. "ChemInform Abstract: Reaction Mechanisms Part 4. Free-Radical Reactions." ChemInform 31, no. 18 (2010): no. http://dx.doi.org/10.1002/chin.200018285.

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30

Murphy, John A. "Free radicals in synthesis. Clean reagents affording oxidative or reductive termination." Pure and Applied Chemistry 72, no. 7 (2000): 1327–34. http://dx.doi.org/10.1351/pac200072071327.

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Neurotoxic organotin reagents currently play a key role in radical chemistry. As a result, this is an important area for development of new clean replacement reactions. The pharmaceutical industry in particular has had to avoid use of radical methodology for the formation of carbon_carbon bonds for this reason. With the current dawn in green chemistry, a host of new clean radical methods is beginning to flourish. Our aim has been to develop new nontoxic methodology for carbon_carbon bond formation by radical chemistry, which would provide either reductive termination (giving a hydrogen atom to

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31

Elliot, A. John, Shahsultan Padamshi, and Jana Pika. "Free-radical redox reactions of uranium ions in sulphuric acid solutions." Canadian Journal of Chemistry 64, no. 2 (1986): 314–20. http://dx.doi.org/10.1139/v86-053.

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The radiolytic reduction of uranyl ions in degassed sulphuric acid solutions containing various organic solutes was studied. It was shown that while ĊOOH, CO2−, and α-hydroxy-alkyl radicals reduced uranyl ions, the β-hydroxy-alkyl radicals and those derived from gluconic acid could not affect the reduction. The oxidation of uranium(IV) by hydrogen peroxide at pH 0.7 involves hydroxyl radicals in a chain mechanism but at pH 2.0 the oxidation proceeds by a non-radical reaction pathway. From the enhancement of the rate of oxidation of uranium(IV) by oxygen in the presence of 2-propanol, a mechani

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32

Khudyakov, Igor, Peter Levin, and Aleksei Efremkin. "Cage Effect under Photolysis in Polymer Matrices." Coatings 9, no. 2 (2019): 111. http://dx.doi.org/10.3390/coatings9020111.

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Photoinduced elementary reactions of low-MW compounds in polymers is an area of active research. Cured organic polymer coatings often undergo photodegradation by free-radical paths. Besides practical importance, such studies teach how the polymer environment controls elementary free-radical reactions. Presented here is a review of recent literature which reports such studies by product analysis and by a time-resolve technique of photochemical reaction inside the cage of a polymer and in the bulk of a polymer. It was established that application of moderate external magnetic field allows the co

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33

ROTA, Cristina, P. David BARR, V. Martha MARTIN, F. Peter GUENGERICH, Aldo TOMASI, and P. Ronald MASON. "Detection of free radicals produced from the reaction of cytochrome P-450 with linoleic acid hydroperoxide." Biochemical Journal 328, no. 2 (1997): 565–71. http://dx.doi.org/10.1042/bj3280565.

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The ESR spin-trapping technique was employed to investigate the reaction of rabbit cytochrome P-450 1A2 (P450) with linoleic acid hydroperoxide. This system was compared with chemical systems where FeSO4 or FeCl3 was used in place of P450. The spin trap 5,5ʹ-dimethyl-1-pyrroline N-oxide (DMPO) was employed to detect and identify radical species. The DMPO adducts of hydroxyl, O2-•, peroxyl, methyl and acyl radicals were detected in the P450 system. The reaction did not require NADPH-cytochrome P-450 reductase or NADPH. The same DMPO-radical adducts were detected in the FeSO4 system. Only DMPO-•

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34

Mitrohina, Natal'ya. "Oxidative stress in animals: role in oncogenesis from pathomorphologist view." Russian veterinary journal 2020, no. 5 (2020): 27–30. http://dx.doi.org/10.32416/2500-4379-2020-5-27-30.

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Oxidative stress is a pathological accumulation of free radicals that contribute to the launch of intracellular damaging action mechanisms. Free radical is an atom possessing free or missing electron, and seeking to restore the lost electron, taking it from other molecules ― as a result a new free radical is formed. The mechanism is chain reaction-based. Hypoxia acts as an additional stimulus to the appearance of oxygen free radicals. Cell hypoxia develops following any type of cell damage: mechanical, bacteriological, chemical, etc. Cell hypoxia inevitably leads to the development of an infla

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35

Goez, Martin, Isabell Frisch, and Ingo Sartorius. "Electron and hydrogen self-exchange of free radicals of sterically hindered tertiary aliphatic amines investigated by photo-CIDNP." Beilstein Journal of Organic Chemistry 9 (February 26, 2013): 437–46. http://dx.doi.org/10.3762/bjoc.9.46.

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The photoreactions of diazabicyclo[2,2,2]octane (DABCO) and triisopropylamine (TIPA) with the sensitizers anthraquinone (AQ) and xanthone (XA) or benzophenone (BP) were investigated by time-resolved photo-CIDNP (photochemically induced dynamic nuclear polarization) experiments. By varying the radical-pair concentration, it was ensured that these measurements respond only to self-exchange reactions of the free amine-derived radicals (radical cations DH • + or α-amino alkyl radicals D • ) with the parent amine DH; the acid–base equilibrium between DH • + and D • also plays no role. Although the

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36

Beltrán, Fernando J., Manuel Checa, Javier Rivas, and Juan F. García-Araya. "Modeling the Mineralization Kinetics of Visible Led Graphene Oxide/Titania Photocatalytic Ozonation of an Urban Wastewater Containing Pharmaceutical Compounds." Catalysts 10, no. 11 (2020): 1256. http://dx.doi.org/10.3390/catal10111256.

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In a water ozonation process, dissolved organics undergo two reactions at least: direct ozone attack and oxidation with hydroxyl radicals generated from the ozone decomposition. In the particular case of urban wastewater contaminated with pharmaceuticals, competition between these two reactions can be studied through application of gas–liquid reaction kinetics. However, there is a lack in literature about kinetic modeling of ozone processes in water specially in photocatalytic ozonation. In this work, lumped reactions of ozone and hydroxyl radicals with total organic carbon have been proposed.

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37

Das, Suresh, and Clemens von Sonntag. "The Oxidation of Trimethylamine by OH Radicals in Aqueous Solution, as Studied by Pulse Radiolysis, ESR, and Product Analysis. The Reactions of the Alkylamine Radical Cation, the Aminoalkyl Radical, and the Protonated Aminoalkyl Radical." Zeitschrift für Naturforschung B 41, no. 4 (1986): 505–13. http://dx.doi.org/10.1515/znb-1986-0418.

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Hydroxyl radical reactions with trimethylamine in aqueous solution lead to the formation of the aminoalkyl radical (CH3)2NCH2 (A) and its conjugated acid (CH3)2HN+CH2 (AH+) as well as to the alkylamine radical cation (CH3)3N+(N+). These radicals are transform ed into each other by hydrolytic reactions, e.g.[xxx]Radicals AH+ are more acidic (pKa ≈ 3.6) than the radicals N+(pKa ≈ 8.0). Consequently, N+ predom inate over AH+ under quasi equilibrium conditions (e.g. in the presence of phosphate buffer) and are the only species observed by ESR in acid solutions. Reacting with the protonated amine.

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38

Nikolić-Kokić, Aleksandra, Duško Blagojević, and Mihajlo Spasić. "Complexity of free radical Metabolism in human Erythrocytes." Journal of Medical Biochemistry 29, no. 3 (2010): 189–95. http://dx.doi.org/10.2478/v10011-010-0018-7.

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Complexity of free radical Metabolism in human ErythrocytesThe auto-oxidation of oxyhaemoglobin to methaemoglobin generating superoxide anion radical (O2.-) represents the main source of free radicals in the erythro-cytes. Hydrogen peroxide is produced by O2.-dismutation or originates from the circulation. Human erythrocytes are also exposed to the prooxidative actions of nitric oxide (NO) from circulation. Free radicals that may induce reactions with direct dangerous consequences to erythrocytes are also preceded by the reaction of O2.-and NO producing peroxynitrite. In physiological settings

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39

Wiegel, Aaron A., Matthew J. Liu, William D. Hinsberg, Kevin R. Wilson, and Frances A. Houle. "Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols." Physical Chemistry Chemical Physics 19, no. 9 (2017): 6814–30. http://dx.doi.org/10.1039/c7cp00696a.

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40

Ramirez, Dario C., Sandra E. Gomez-Mejiba, Jean T. Corbett, Leesa J. Deterding, Kenneth B. Tomer, and Ronald P. Mason. "Cu,Zn-superoxide dismutase-driven free radical modifications: copper- and carbonate radical anion-initiated protein radical chemistry." Biochemical Journal 417, no. 1 (2008): 341–53. http://dx.doi.org/10.1042/bj20070722.

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The understanding of the mechanism, oxidant(s) involved and how and what protein radicals are produced during the reaction of wild-type SOD1 (Cu,Zn-superoxide dismutase) with H2O2 and their fate is incomplete, but a better understanding of the role of this reaction is needed. We have used immuno-spin trapping and MS analysis to study the protein oxidations driven by human (h) and bovine (b) SOD1 when reacting with H2O2 using HSA (human serum albumin) and mBH (mouse brain homogenate) as target models. In order to gain mechanistic information about this reaction, we considered both copper- and C

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41

Bulgakov, V. G., V. F. Tatarinov, and N. S. Gavryushenko. "Tribochemical Component of Oxidative Stress Development at Artificial Joints Implantation. Part 5. Pro-oxidative Properties and Interrelation of Titanium and Non-Metallic Orthopaedic Material Wear Particles with Antioxidants." N.N. Priorov Journal of Traumatology and Orthopedics 22, no. 3 (2015): 41–44. http://dx.doi.org/10.17816/vto201522341-44.

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Radical-forming ability of artificial wear particles of BT6 titanium alloy and nonmetallic materials was studied using modelling reaction of cumene oxidation. It was stated that alloy particles initiate formation of radicals and consecutive repeated cumene oxidation by metallic particles took place with significantly higher rate of radicals’ formation. Particles of nonmetallic materials (polyethylene, corundum ceramics, carbon nanocomposite) are inert and do not possess radical-forming ability that ensures their advantage in prevention of possible development of adverse free radical reactions

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42

Bulgakov, V. G., V. F. Tatarinov, and N. S. Gavryushenko. "Tribochemical Component of Oxidative Stress Development at Artificial Joints Implantation. Part 5. Pro-oxidative Properties and Interrelation of Titanium and Non-Metallic Orthopaedic Material Wear Particles with Antioxidants." Vestnik travmatologii i ortopedii imeni N.N. Priorova, no. 3 (September 30, 2015): 41–44. http://dx.doi.org/10.32414/0869-8678-2015-3-41-44.

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Radical-forming ability of artificial wear particles of BT6 titanium alloy and nonmetallic materials was studied using modelling reaction of cumene oxidation. It was stated that alloy particles initiate formation of radicals and consecutive repeated cumene oxidation by metallic particles took place with significantly higher rate of radicals’ formation. Particles of nonmetallic materials (polyethylene, corundum ceramics, carbon nanocomposite) are inert and do not possess radical-forming ability that ensures their advantage in prevention of possible development of adverse free radical reactions

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43

Flitter, W. D., and R. P. Mason. "The spin trapping of pyrimidine nucleotide free radicals in a Fenton system." Biochemical Journal 261, no. 3 (1989): 831–39. http://dx.doi.org/10.1042/bj2610831.

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The reaction of the hydroxyl radical, generated by a Fenton system, with pyrimidine deoxyribonucleotides was investigated by using the e.s.r. technique of spin trapping. The spin trap t-nitrosobutane was employed to trap secondary radicals formed by the reaction of the hydroxyl radical with these nucleotides. The results presented here show that hydroxyl-radical attack on thymidine, 2-deoxycytidine 5-monophosphate and 2-deoxyuridine 5-monophosphate produced nucleotide-derived free radicals. The results indicate that .OH radical attack occurs predominantly at the carbon-carbon double bond of th

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44

Chuang, Che-Ping. "Free Radical Cyclization Reaction of 1,6-Dienes." Synlett 1990, no. 09 (1990): 527–28. http://dx.doi.org/10.1055/s-1990-21153.

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45

Matsumoto, Ken-ichiro, Minako Nyui, Masato Kamibayashi, Toshihiko Ozawa, Ikuo Nakanishi, and Kazunori Anzai. "Temperature-dependent free radical reaction in water." Journal of Clinical Biochemistry and Nutrition 50, no. 1 (2011): 40–46. http://dx.doi.org/10.3164/jcbn.10-145.

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46

Semrád, Hugo, Ctibor Mazal, and Markéta Munzarová. "Free Radical Isomerizations in Acetylene Bromoboration Reaction." Molecules 26, no. 9 (2021): 2501. http://dx.doi.org/10.3390/molecules26092501.

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The experimentally motivated question of the acetylene bromoboration mechanism was addressed in order to suggest possible radical isomerization pathways for the syn-adduct. Addition–elimination mechanisms starting with a bromine radical attack at the “bromine end” or the “boron end” of the C=C bond were considered. Dispersion-corrected DFT and MP2 methods with the SMD solvation model were employed using three all-electron bases as well as the ECP28MWB ansatz. The rate-determining, elimination step had a higher activation energy (12 kcal mol−1) in case of the “bromine end” attack due to interme

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47

Xu, Jun, William J. Cooper, and Weihua Song. "Free radical destruction of haloacetamides in aqueous solution." Water Supply 14, no. 2 (2013): 212–19. http://dx.doi.org/10.2166/ws.2013.184.

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Haloacetamides are disinfection byproducts (DBPs) formed through chlorine/chloramine disinfection processes in drinking waters and have been recently highlighted in the US national Reconnaissance Survey. These species occur at low concentrations, but have been determined to have high cytotoxicity and mutagenicity and therefore may represent a human health hazard. Advanced oxidation/reduction processes (AO/RPs) which utilize free radical reactions are new alternatives to degrade these species. This study reports the absolute bimolecular reaction rate constants for 12 haloacetamides with •OH rad

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48

Kobayashi, Michio, Michiko Gotoh, and Masato Yoshida. "Radical Switch Reaction. A Novel Reaction between Two Free Radicals in a Solvent Cage." Bulletin of the Chemical Society of Japan 60, no. 1 (1987): 295–99. http://dx.doi.org/10.1246/bcsj.60.295.

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49

Gansäuer, Andreas, Meriam Seddiqzai, Tobias Dahmen, Rebecca Sure, and Stefan Grimme. "Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines." Beilstein Journal of Organic Chemistry 9 (August 8, 2013): 1620–29. http://dx.doi.org/10.3762/bjoc.9.185.

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The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum c

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50

Silaev, M. M. "Competition Kinetics of the Nonbranched-Chain Addition of Free Radicals to Olefins, Formaldehyde, and Oxygen." International Journal of Chemical Engineering 2011 (2011): 1–19. http://dx.doi.org/10.1155/2011/830610.

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Five reaction schemes are suggested for the initiated nonbranched-chain addition of free radicals to the multiple bonds of alkenes, formaldehyde, and oxygen. The schemes include reactions competing with chain propagation through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them— , , , , or —is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the suggested schemes, nine rate equations containing one to three parameters to be determined directly are set up using

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