A Kinetic Study of the n-Propyl Radical Decomposition Reaction

Calvert, Jack G.; Sleppy, W. C.

doi:10.1021/ja01516a006

Cited by 16 publications

(12 citation statements)

References 2 publications

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“…The rate constant for the decomposition of n ‐propyl radical to form ethylene and a methyl radical (Table V) has been determined from the reverse addition reaction via microscopic reversibility. This value of 9.24 × 10 10 T 0.87 exp(−30,460 cal mol −1 / RT ) s −1 is plotted as a function of inverse temperature together with experimentally determined values 45, 46, 54–59 (Fig. 8), a summary of which is provided in Table IX.…”

Section: Alkyl Radical Decompositionmentioning

confidence: 99%

Screen for genes differentially expressed during regeneration of the zebrafish caudal fin

Padhi¹,

Joly²,

Tellis

et al. 2004

Developmental Dynamics

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The zebrafish caudal fin constitutes an important model for studying the molecular basis of tissue regeneration. The cascade of genes induced after amputation or injury, leading to restoration of the lost fin structures, include those responsible for wound healing, blastema formation, tissue outgrowth, and patterning. We carried out a systematic study to identify genes that are up-regulated during "initiation" (1 day) and "outgrowth and differentiation" (4 days) of fin regeneration by using two complementary methods, suppression subtraction hybridization (SSH) and differential display reverse transcriptase polymerase chain reaction (DDRT-PCR). We obtained 298 distinct genes/sequences from SSH libraries and 24 distinct genes/sequences by DDRT-PCR. We determined the expression of 54 of these genes using in situ hybridization. In parallel, gene expression analyses were done in zebrafish embryos and early larvae. The information gathered from the present study provides resources for further investigations into the molecular mechanisms of fin development and regeneration.

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Section: Alkyl Radical Decompositionmentioning

confidence: 99%

Screen for genes differentially expressed during regeneration of the zebrafish caudal fin

Padhi¹,

Joly²,

Tellis

et al. 2004

Developmental Dynamics

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“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] For the n-propyl radical, the most energetically favored dissociation channel was found to be C-C bond cleavage to CH 3 + ethylene, [4][5][6][7][8][13][14][15]17,20 while the energetically less favored C-H bond fission to H + propene may compete with C-C bond cleavage at higher temperature, 17 n-C 3 H 7 → C 2 H 4 + CH 3 , ∆H = 23.7 kcal/mol, → C 3 H 6 + H, ∆H = 32.0 kcal/mol. The decomposition rate constant was investigated extensively, [4][5][6][7][13][14][15]19 decomposition of the n-C 3 H 7 radical showed general agreements between the experimental and theoretical activation energies and rate constants. 9,18 For the i-propyl radical, previous studies indicated that the dominant dissociation pathway was the lowest energy channel C-H bond fission to H + propene, [11][12][13][14][15][16][17]20 i-C 3 H 7 → C 3 H 6 + H, ∆H = 34.3 kcal/mol.…”

Section: Introductionmentioning

confidence: 99%

Ultraviolet photodissociation dynamics of the n-propyl and i-propyl radicals

Song

Zheng

Zhou

et al. 2015

The Journal of Chemical Physics

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Ultraviolet (UV) photodissociation dynamics of jet-cooled n-propyl (n-C3H7) radical via the 3s Rydberg state and i-propyl (i-C3H7) radical via the 3p Rydberg states are studied in the photolysis wavelength region of 230-260 nm using high-n Rydberg atom time-of-flight and resonance enhanced multiphoton ionization techniques. The H-atom photofragment yield spectra of the n-propyl and i-propyl radicals are broad and in good agreement with the UV absorption spectra. The H + propene product translational energy distributions, P(E(T))'s, of both n-propyl and i-propyl are bimodal, with a slow component peaking around 5-6 kcal/mol and a fast one peaking at ∼50 kcal/mol (n-propyl) and ∼45 kcal/mol (i-propyl). The fraction of the average translational energy in the total excess energy, 〈f(T)〉, is 0.3 for n-propyl and 0.2 for i-propyl, respectively. The H-atom product angular distributions of the slow components of n-propyl and i-propyl are isotropic, while that of the fast component of n-propyl is anisotropic (with an anisotropy parameter ∼0.8) and that of i-propyl is nearly isotropic. Site-selective loss of the β hydrogen atom is confirmed using the partially deuterated CH3CH2CD2 and CH3CDCH3 radicals. The bimodal translational energy and angular distributions indicate two dissociation pathways to the H + propene products in the n-propyl and i-propyl radicals: (i) a unimolecular dissociation pathway from the hot ground-state propyl after internal conversion from the 3s and 3p Rydberg states and (ii) a direct, prompt dissociation pathway coupling the Rydberg excited states to a repulsive part of the ground-state surface, presumably via a conical intersection.

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“…The work relates to a study by Lin and Laidler (6) of the decomposition of propane sensitized by azomethane. One matter of particular concern in the present investigation was the establishment of a reliable value for the activation energy for the decomposition of the n-propyl radical into CH, + C,H,, seven previous studies (6)(7)(8)(9)(10)(11)(12) having given values ranging from 20 to 35 kcal mol-'.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of the Mercury-Photosensitized Decomposition of Propane. Part I. The Overall Mechanism

Papic¹,

Laidler²

1971

Can. J. Chem.

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The mercury-photosensitized decomposition of propane was investigated from 250 to 350 "C, and at pressures from 5 to 700 Torr. The following products were identified and their initial rates of formation measured: Hz, CH4, CzH4, C2H6, (CH3)2C,HCH(CH3)2, (CH3)2CHCH2CH2CH3, and n-C6H14. The results lead to conclusions about the mechanism. The pressure dependence of the rates were determined and interpreted in terms of a simplified steady-state treatment based on the mechanism.

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A Kinetic Study of the n-Propyl Radical Decomposition Reaction

Cited by 16 publications

References 2 publications

Screen for genes differentially expressed during regeneration of the zebrafish caudal fin

Screen for genes differentially expressed during regeneration of the zebrafish caudal fin

Ultraviolet photodissociation dynamics of the n-propyl and i-propyl radicals

Kinetics of the Mercury-Photosensitized Decomposition of Propane. Part I. The Overall Mechanism

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