Browsing by Author "Wang, Niann-Shiah"

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A comparative study on the production yield of H atom in the thermal decomposition of i-C4H10 and n-C4H10: Examination of the contribution of the roaming radical channels
(2018-01-01)
Chen, Wei-Yu
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Matsui, Hiroyuki
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Wang, Niann-Shiah
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應用化學系
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Department of Applied Chemistry
The yields of H atoms in the thermal decomposition of i-C4H10 -> products (1) and n-C4H10 -> products (2) are measured at 1470-1800 K behind reflected shock waves. A comparative method is used to evaluate the branching fractions for i-C4H10 -> CH3 + i-C3H7 (1a) and n-C4H10 -> 2C(2)H(5) (2b), where, C3H6 is used as a reference. The branching fractions for (1a) and (2b) are expressed by k(1a)/ k(1) = (0.64 +/- 0.14) (10 T-3/ K) - (0.06 +/- 0.23) and, k(2b)/ k(2) = (0.050 +/- 0.059)(10 T-3/ K) + (0.49 +/- 0.10), respectively. Contributions of the roaming channels are less than 12 and 5% for i-C4H10 -> CH4 + C3H6 (1b) and n-C4H10 -> CH4 + C3H6 (2c), respectively. (C) 2017 Elsevier B. V. All rights reserved.
Cellular uptake and phototoxicity of surface-modified fluorescent nanodiamonds
(2012-02-01)
Weng, Mao-Feng
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Chang, Bo-Jui
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Chiang, Su-Yu
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Wang, Niann-Shiah
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Niu, Huan
Bioconjugated fluorescent nanodiamonds (FNDs) show potential for effectively targeted imaging and the enhanced photokilling of cancer cells. In this study, we investigated the mechanisms involved in the cellular uptake of surface-modified 140 nm FNDs and evaluated their cytotoxicity and phototoxicity following particle internalization. Through an analysis of flow cytometry, the internalized FND-Tf and FND-NH2 particles reached their respective saturation values, with half-life times of approximately 0.8 h and 1.4 h. The determination indicated that the receptor-mediated endocytosis of FND-Tf particles was highly effective and nearly twice as efficient as the endocytic process of FND-NH2 particles mainly through surface electrostatic interactions. The cytotoxicity of internalized particles was evaluated using the MU assay, indicating that at saturation concentrations, the rate of proliferation of FND-treated cells decreases to less than half that of untreated cells. An examination of the phototoxicity of internalized FND-Tf particles under irradiation using a 532 nm laser revealed that the FND-treated cells could be killed using less than half the energy required for untreated cells. The enhanced cellular killing was attributed to FND particles converting light to thermal energy, with the support of Raman spectra of nanodiamond clusters that showed an increase in particle temperature under irradiation. Our results demonstrated that bioconjugated FNDs could be highly effective in the targeting of cancer cells for fluorescence imaging and photokilling with a minimum of collateral cell damage. (C) 2011 Elsevier B.V. All rights reserved.
Direct measurement of site-specific rates of reactions of H with C3H8, i-C4H10, and n-C4H10
(2017-08-14)
Lin, Chia-Chieh
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Chen, Wei-Yu
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Matsui, Hiroyuki
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Wang, Niann-Shiah
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應用化學系
We measured the rates of abstraction of a hydrogen atom from specific sites in propane C3H8, 2-methyl propane (i-C4H10), and butane (n-C4H10); the sites are a primary hydrogen of C3H8 and i-C4H10 and a secondary hydrogen of n-C4H10. The excellent reproducibility of conditions of a diaphragm-less shock tube enabled us to conduct comparative measurements of the evolution of H atoms in three mixtures-(i) 0.5 ppm C2H5I + Ar, (ii) 0.5 ppm C2H5I + 50-100 ppm alkane as C3H8 or i-C4H10 or n-C4H10 + Ar, and (iii) the same concentrations of alkane + Ar without C2H5I-in the temperature range 1000-1200 K and at a pressure of 2.0 bars. The net profile of rise and decay of H atoms in the C2H5I + alkane mixture was derived on subtracting the absorbance of (iii) from that of (ii). Measurements of the mixture (iii) are important because the absorption of alkanes at 121.6 nm is not negligible. In the temperature range 1000-1100 K, the rate of decomposition of C2H5I was evaluated directly on analyzing the exponential growth of H atoms in the mixture (i). The rate of decomposition of C2H5I is summarized as ln(k/s(-1)) = (33.12 +/- 1.4) - (25.23 +/- 1.5) 10(3)/T (T = 1000-1100 K, P = 2.0 bars); the broadening factor F(T) in the Lindemann-Hinshelwood formula was evaluated in the fall-off region. The site-specific rates of H + (C-3-C-4) alkanes are summarized as follows: H + C3H8 -> H-2 + 1-C3H7, ln(k(1a)) = -(21.34 +/- 0.86) - (5.39 +/- 0.93) 10(3)/T, H + i-C4H10 -> H-2 + i-C4H9, ln(k(2a)) = -(20.50 +/- 1.36) - (6.14 +/- 0.13) 10(3)/T, H + n-C4H10 -> H-2 + 2-C4H9, ln(k(3b)) = - (21.37 +/- 1.15) - (4.83 +/- 1.26) 10(3)/T. The present experimental results are compared with published results from quantum-chemical calculations of potential-energy surfaces and transition-state theory. The present experiments are consistent with those calculations for the reaction rates for the attack at the primary site for H + C3H8 and H + i-C4H10, but for the attack at the secondary site of n-C4H10, our results are substantially smaller than the computational prediction, which might indicate a hindrance by the C-H bonds of the primary sites that serves to decrease the rate of abstraction from the secondary site of n-C4H10. The influence on the total rates of reactions H + alkane and the group additivity rule are discussed. Published by AIP Publishing.
Experimental and Theoretical Study on the Thermal Decomposition of C3H6 (Propene)
(2015-02-26)
Hung, Wei-Chung
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Tsai, Chieh-Ying
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Matsui, Hiroyuki
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Wang, Niann-Shiah
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Miyoshi, Akira
Fluorescent nanodiamonds for specifically targeted bioimaging: Application to the interaction of transferrin with transferrin receptor
(2009-02-01)
Weng, Mao-Feng
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Chiang, Su-Yu
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Wang, Niann-Shiah
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Niu, Huan
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應用化學系
Fluorescent nanodiamonds (FND)as specifically targeted probes to image the interactions of transferrins (TF) with their receptors that were over-expressed on HeLa cells were studied in this work. The 100-nm diamonds were irradiated with a 2.5-MeV ion beam and thermally annealed to emit bright fluorescence in the region 550-800 nm upon excitation at 514.5 nm; accordingly, the interference of cellular autofluorescence at 520-650 nm was eliminated significantly on detecting fluorescence at >660 nm. FND-Tf bioconjugates were produced via the formation of an amide bond between carboxylated FND and transferrin and used to target transferrin receptors (TfR) on HeLa cells for activity testing. The receptor-mediated uptake of FND-Tf bioconjugates into HeLa cells was confirmed from confocal fluorescence images; in contrast, the uptake of FND-Tf bioconjugates on presaturated receptors or carboxylated FND on HeLa cells was unobserved. We measured also the fluorescence spectra and lifetimes of carboxylated FND, FND-Tf bioconjugates and FND-Tf-TfR complexes for characterization. Their measured lifetimes are 11.8 +/- 0.1, 11.6 +/- 0.1 and 12.+/- 0.1 ns, respectively. and fluorescence spectra are comparable except that the two zero-phonon lines of FND-Tf-TfR complexes become indistinct. Both results show that the surface effects of chemical interactions on the emission center of FND are negligible. (C) 2008 Elsevier B.V. All rights reserved.
Production of H and O(P-3) Atoms in the Reaction of CH2 with O-2
(2012-09-20)
Lee, Pei-Fang
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Matsui, Hiroyuki
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Chen, Wei-Yu
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Wang, Niann-Shiah
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應用化學系
The reaction CH2 + O-2 -> 4 products has been studied by using atomic resonance absorption spectrometry (ARAS) of H and O(P-3) atoms behind reflected shock waves over 1850-2050 K and 2.1-1.7 atm. Measurements of [H] and [O] are conducted using mixtures of highly diluted CH2I2 (0.2 and 0.4 ppm) with excess O-2 (100 and 262 ppm) in Ar; comparative measurement of [H] in the 0.2 and 0.4 ppm CH2I2 + 300 ppm H-2 mixture has been conducted simultaneously to confirm the initial concentration of CH2. The apparent reaction rate of CH2 + O-2 (k(2)'), including the contributions of (CH2)-C-3 + O-2 -> products (2) and (CH2)-C-1 + O-2 -> products (3), has been measured from the evolutions of [H] and [O] and summarized as k(2)'/cm(3) molecule(-1) s(-1) = (1.90 +/- 0.31) x 10(-11). The contribution of (CH2)-C-1 + O-2 reaction on the measured k(2)' has been evaluated as 0.15 +/- 0.04, with an assumption that k(3) is independent of temperature and given by the result measured at room temperature [Langford, A. O.; Petek, H.; Moore, C. B. J. Chem. Phys. 1983, 78, 6650-6659]. The net rate for the (CH2)-C-3 + O-2 reaction is given as k(2)/cm(3) molecule(-1) s(-1) = (1.69 +/- 0.31) x 10(-11). The result on k(2) in this study is found to be consistent with the extrapolation of the previous work at lower temperature range of 295-600 K. [Vinckler, C.; Debruyn, W. J. Phys. Chem. 1979, 83, 2057-2062]; these results can be summarized as k(2)/cm(3) molecule(-1) s(-1) = 2.74 x 10(-11) exp(-874/T), (T = 295-2050 K). The apparent production yields of H and O atoms for the reaction channels (CH2)-C-1,3 + O-2 -> H + products (2a, 3a) and (1)'(CH2)-C-3 + O-2 -> O(P-3) + products (2h, 3b) have been evaluated as phi(2a)' = 0.59 +/- 0.06 and phi(2b)' = 0.23 +/- 0.06, respectively. The contributions of (CH2)-C-1 + O-2 reaction on measured phi(2a)' and phi(2b)' are indicated to be minor; the net branching fractions for the (CH2)-C-3+O-2 reaction are estimated as phi(2a) = 0.58 +/- 0.06 and phi(2b) = 0.25 +/- 0.06. No obvious temperature dependence is indicated in the measured rate constant nor in the branching fractions of H and 0 atoms. The mechanism of the reaction of CH2 with O-2 is discussed based on the result of the present study together with those of the previous theoretical/experimental studies.
Reaction Dynamics of O((1)D,(3)P) + OCS Studied with Time-Resolved Fourier Transform Infrared Spectroscopy and Quantum Chemical Calculations
(2009-11-26)
Chiang, Hung-Chu
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Wang, Niann-Shiah
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Tsuchiya, Soji
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Chen, Hsin-Tsung
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Lee, Yuan-Pern
Time-resolved infrared emission of CO(2) and OCS was observed in reactions O((1)P) + OCS and O((1)D) + OCS with a step-scan Fourier transform spectrometer. The CO(2) emission involves Delta nu(3) = -1 transitions from highly vibrationally excited states, whereas emission of OCS is mainly from the transition (0, 0 degrees, 1) (0, 0, 0); the latter derives its energy via near-resonant V-V energy transfer from highly excited CO(2). Rotationally resolved emission lines of CO (v <= 4 and J <= 30) were also observed in the reaction O((1)D) + OCS. For O((3)P) + OCS, weak emission Of CO(2) diminishes when Ar is added, indicating that O((3)P) is translationally hot to overcome the barrier for CO(2) formation. The band contour of CO(2) agrees with a band shape simulated on the basis of a Dunharn expansion model of CO(2); the average vibrational energy of CO(2) in this channel is 49% of the available energy. This vibrational distribution fits with that estimated through a statistical partitioning of energy E* congruent to 18 000 +/- 500 cm(-1) into all vibrational modes of CO(2). For the reaction of O((1)D) + OCS, approximately 51% of the available energy is converted into vibrational energy of CO(2), and a statistical prediction using E* congruent to 30 000 +/- 500 cm(-1) best fits the data. The mechanisms of these reactions are also investigated with the CCSD(T)/6-311+G(3df)//B3LYP/6-311+G(3df) method. The results indicate that the triplet O((3)P) + OCS(X(1)Sigma(+)) surface proceeds via direct abstraction and substitution channels with barriers of 27.6 and 36.4 kJ mol(-1), respectively, to produce SO(X(3)Sigma(-)) + CO(X(1)Sigma(+)) and S((3)P) + CO(2)(X(1)A(1)), whereas two intermediates, OSCO and SC(O)O, are formed from the singlet O((1)D) + OCS(X(1)Sigma(+)) surface without barrier, followed by decomposition to SO(a(1)Delta) + CO(X(1)Sigma(+)) and S((1)D) + CO(2)(X(1)A(1)), respectively. For the ground-state reaction O((3)P) + OCS(X(1)Sigma(+)), the singlet-triplet curve crossings play important roles in the observed kinetics and chemiluminescence.
Reaction Dynamics of O(D-1,P-3) + OCS Studied with Time-Resolved Fourier Transform Infrared Spectroscopy and Quantum Chemical Calculations
(2009-11-26)
Chiang, Hung-Chu
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Wang, Niann-Shiah
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Tsuchiya, Soji
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Chen, Hsin-Tsung
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Lee, Yuan-Pern
Time-resolved infrared emission of CO2 and OCS was observed in reactions O(P-1) + OCS and O(D-1) + OCS with a step-scan Fourier transform spectrometer. The CO2 emission involves Delta nu(3) = -1 transitions from highly vibrationally excited states, whereas emission of OCS is mainly from the transition (0, 0 degrees, 1) (0, 0, 0); the latter derives its energy via near-resonant V-V energy transfer from highly excited CO2. Rotationally resolved emission lines of CO (v <= 4 and J <= 30) were also observed in the reaction O(D-1) + OCS. For O(P-3) + OCS, weak emission Of CO2 diminishes when Ar is added, indicating that O(P-3) is translationally hot to overcome the barrier for CO2 formation. The band contour of CO2 agrees with a band shape simulated on the basis of a Dunharn expansion model of CO2; the average vibrational energy of CO2 in this channel is 49% of the available energy. This vibrational distribution fits with that estimated through a statistical partitioning of energy E* congruent to 18 000 +/- 500 cm(-1) into all vibrational modes of CO2. For the reaction of O(D-1) + OCS, approximately 51% of the available energy is converted into vibrational energy of CO2, and a statistical prediction using E* congruent to 30 000 +/- 500 cm(-1) best fits the data. The mechanisms of these reactions are also investigated with the CCSD(T)/6-311+G(3df)//B3LYP/6-311+G(3df) method. The results indicate that the triplet O(P-3) + OCS(X-1 Sigma(+)) surface proceeds via direct abstraction and substitution channels with barriers of 27.6 and 36.4 kJ mol(-1), respectively, to produce SO(X-3 Sigma(-)) + CO(X-1 Sigma(+)) and S(P-3) + CO2(X(1)A(1)), whereas two intermediates, OSCO and SC(O)O, are formed from the singlet O(D-1) + OCS(X-1 Sigma(+)) surface without barrier, followed by decomposition to SO(a(1)Delta) + CO(X-1 Sigma(+)) and S(D-1) + CO2(X(1)A(1)), respectively. For the ground-state reaction O(P-3) + OCS(X-1 Sigma(+)), the singlet-triplet curve crossings play important roles in the observed kinetics and chemiluminescence.
Shock Tube Study on the Thermal Decomposition of CH(3)OH
(2010-05-06)
Lu, Ku-We
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Matsui, Hiroyuki
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Huang, Ching-Liang
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Raghunath, P.
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Wang, Niann-Shiah
H atom produced in the thermal decomposition of CH(3)OH highly diluted in Ar (0.48-10 ppm) was monitored behind reflected shock waves by atomic resonance absorption spectrometry (ARAS) at fixed temperatures (and pressures), that is, 1660 (1.73 atm), 1760 (2.34 atm), 1860 (2.04 atm), 1950 (2.18 atm), and 2050 K (1.76 atm) (+/- 10 K, respectively). High sensitivity for the H atom has been attained by signal averaging of the ARAS signals down to the concentrations of similar to 1 x 10(11) atoms/cm(3) and enables us to determine the branching fraction for the direct H atom production channel, CH(3)OH -> CH(2)OH + H (channel 1c) in a mixture of 1 ppm CH(3)OH. Channel 1c is confirmed to be minor, that is, branching fraction for channel 1c is expressed by Log(k(1c)/k(1)) = (- 2.88 +/- 1.88) x 10(3)/T - (0.23 +/- 1.02), which corresponds to k(1c)/k(1) < 0.03 for the present temperature range. By using 0.48 and 1.0 ppm CH(3)OH with (100-1000) ppm H(2), the total decomposition rate k(1) for CH(3)OH -> products is measured from the time dependence of H atom, where the radical products of main channels 1a and 1b, that is, OH, CH(3), and CH(2), were converted rapidly into H atoms. The experimental result is summarized as Log(k(1)/cm(3)molecule(-1)s(-1)) = (-12.82 +/- 0.71) x 10(3)/T - (8.5 +/- 0.38). A theoretical study based on ab initio/TST calculations with high accuracy has been conducted for the reaction: (3)CH(2) + H(2) -> CH(3) + H (reaction 3). The rate is given by k(3)/cm(3)molecule(-1) s(-1) = (7.32 x 10(-19))T(2.3) exp (-3699/T). This result is used for numerical simulations to evaluate k(1). Present experimental results on the thermal decomposition rate of CH(3)OH are found to be consistent with previous works. It is also found that time dependence of [H] observed in the 10 ppm CH(3)OH in Ar can be reproduced very well by kinetic simulations by using a reaction mechanism composed of 36 elementary reactions.
Shock Tube Study on the Thermal Decomposition of CH3OH
(2010-05-06)
Lu, Ku-We
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Matsui, Hiroyuki
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Huang, Ching-Liang
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Raghunath, P.
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Wang, Niann-Shiah
H atom produced in the thermal decomposition of CH3OH highly diluted in Ar (0.48-10 ppm) was monitored behind reflected shock waves by atomic resonance absorption spectrometry (ARAS) at fixed temperatures (and pressures), that is, 1660 (1.73 atm), 1760 (2.34 atm), 1860 (2.04 atm), 1950 (2.18 atm), and 2050 K (1.76 atm) (+/- 10 K, respectively). High sensitivity for the H atom has been attained by signal averaging of the ARAS signals down to the concentrations of similar to 1 x 10(11) atoms/cm(3) and enables us to determine the branching fraction for the direct H atom production channel, CH3OH -> CH2OH + H (channel 1c) in a mixture of 1 ppm CH3OH. Channel 1c is confirmed to be minor, that is, branching fraction for channel 1c is expressed by Log(k(1c)/k(1)) = (- 2.88 +/- 1.88) x 10(3)/T - (0.23 +/- 1.02), which corresponds to k(1c)/k(1) < 0.03 for the present temperature range. By using 0.48 and 1.0 ppm CH3OH with (100-1000) ppm H-2, the total decomposition rate k(1) for CH3OH -> products is measured from the time dependence of H atom, where the radical products of main channels 1a and 1b, that is, OH, CH3, and CH2, were converted rapidly into H atoms. The experimental result is summarized as Log(k(1)/cm(3)molecule(-1)s(-1)) = (-12.82 +/- 0.71) x 10(3)/T - (8.5 +/- 0.38). A theoretical study based on ab initio/TST calculations with high accuracy has been conducted for the reaction: (CH2)-C-3 + H-2 -> CH3 + H (reaction 3). The rate is given by k(3)/cm(3)molecule(-1) s(-1) = (7.32 x 10(-19))T-2.3 exp (-3699/T). This result is used for numerical simulations to evaluate k(1). Present experimental results on the thermal decomposition rate of CH3OH are found to be consistent with previous works. It is also found that time dependence of [H] observed in the 10 ppm CH3OH in Ar can be reproduced very well by kinetic simulations by using a reaction mechanism composed of 36 elementary reactions.
Shock Tube Study on the Thermal Decomposition of Ethanol
(2011-07-21)
Wu, Chih-Wei
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Matsui, Hiroyuki
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Wang, Niann-Shiah
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Lin, M. C.
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應用化學系
The thermal decomposition of C(2)H(5)OH highly diluted in Ar (1 and 3 ppm) has been studied by monitoring H atoms using the atomic resonance absorption spectrometry (ARAS) technique behind reflected shock waves over the temperature range 1450-1760 K at fixed pressure: 1, 1.45, and 2 atm. The rate constant and the product branching fractions have been determined by analyzing temporal profiles of H atoms; the effect of the secondary reactions on the results has been examined by using a detailed reaction mechanism composed of 103 elementary reactions. The apparent rate constant of ethanol decomposition can be expressed as k(1)/s(-1) = (5.28 +/- 0.14) x 10(10) exp[-(23 530 +/- 980)/T] (T = 1450-1670 K, P = 1-2 atm) without a detectable pressure dependence within the tested pressure range of this study. Branching fractions for producing CH(3) + CH(2)OH (1a) and H(2)O + C(2)H(4) (1b) have been examined by a quantitative measurement of H atoms produced in the successive decompositions of the products CH(2)OH (1a): the pressure dependence of the branching fraction for channel 1a is obtained by a linear least-squares analysis of the experimental data and can be expressed as phi(1a) = (0.71 +/- 0.07) - (826 +/- 116)/T, (0.92 +/- 0.04) (1108 +/- 70)/T, and (1.02 +/- 0.10) (1229 +/- 168)/T for T = 1450-1760 K, at P = 0.99, 1.45, and 2.0 atm, respectively. The rate constant obtained in this study is found to be consistent with previous theoretical and experimental results; however, the pressure dependence of the branching fraction obtained in this study is smaller than those of previous theoretical works. Modification of the parameters for the decomposition rate in the falloff region is suggested to be important to improve the practical modeling of the pyrolysis and combustion of ethanol
Study on the Reaction of CH2 with H-2 at High Temperature
(2012-03-01)
Lee, Pei-Fang
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Matsui, Hiroyuki
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Wang, Niann-Shiah
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應用化學系
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Department of Applied Chemistry
Thermal decomposition of CH2I2 [sequential C-I bond fission processes, CH2I2 + Ar -> CH2I + I + Ar (1a) and CH2I + Ar -> (CH2)-C-3 + I + Ar (1b)], and the reactions of (CH2)-C-3 + H-2 -> CH3 H (2) and (CH2)-C-1 + H-2 -> CH3 + H (3) have been studied by using atomic resonance absorption spectrometry (ARAS) of I and H atoms behind reflected shock waves. Highly diluted CH2I2 (0.1-0.4 ppm) with/without excess H-2 (300 ppm) in Ar has been used so that the effect of the secondary reactions can be minimized. From the quantitative measurement of I atoms in the 0.1 ppm CH2I2 + Ar mixture over 1550-2010 K, it is confirmed that two-step sequential C-I bond fission processes of CH2I2, (la) and (1b), dominate over other product channels. The decomposition step (1b) is confirmed to be the rate determining process to produce 3CH2 and the least-squares analysis of the measured rate gives, In(k(1b)/cm(3) molecule(-1) s(-1)) = -(17.28 +/- 0.79) - (30.17 +/- 1.40) x 10(3)/T. By utilizing this result, we examine reactions 2 and 3 by monitoring evolution of H atoms in the 0.2-0.4 ppm CH2I2 + 300 ppm H2 mixtures over 18502040 K. By using a theoretical result on k(2) (Lu, K. W.; Matsui, H.; Huang, C.-L.; Raghunath, P.; Wang, N.-S.; Lin, M. C. J. Phys. Chem. A 2010, 114, 5493), we determine the rate for (3) as k(3)/cm(3) molecule(-1) s(-1) = (1.27 +/- 0.36) x 10(-10). The upper limit of k(3) (k(3max)) is also evaluated by assuming k(2) = 0, i.e., k(3max)/cm(3) molecule(-1) s(-1) = (2.26 +/- 0.59) x 10(-10). The present experimental results on k(3) and k(3max) is found to agree very well with the previous frequency modulation spectroscopy study (Friedrichs, G.; Wagner, H. G. Z. Phys. Chem. 2001, 215, 1601); i.e., the importance of the contribution of (CH2)-C-1 in the reaction of CH2 with H-2 at elevated temperature range is reconfirmed.
Thermal Decomposition and Oxidation of CH3OH
(2013-01-24)
Lee, Pei-Fang
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Matsui, Hiroyuki
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Xu, Ding-Wei
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Wang, Niann-Shiah
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應用化學系
Thermal decomposition of CH3OH diluted in Ar has been studied by monitoring H atoms behind reflected shock waves of 100 ppm CH3OH + Ar. The total decomposition rate k(1) for CH3OH + M -> products obtained in this study is expressed as, ln(k(1)/cm(3) molecule(-1) s(-1)) = -(14.81 +/- 1.22) - (38.86 +/- 1.82) X 10(3)/T, over 1359-1644 K. The present result on k(1) is indicated to be substantially smaller than the extrapolation of the most of the previous experimental data but consistent with the published theoretical results [Faraday Discuss. 2002, 119, 191-205 and J. Phys. Chem. A 2007, 111, 3932-3950]. Oxidation of CH3OH has been studied also by monitoring H atoms behind shock waves of (0.35-100) ppm CH3OH + (100-400) ppm O-2 + Ar. For the low concentration CH3OH (below 10 ppm) + O-2 mixtures, the initial concentration of CH3OH is evaluated by comparing evolutions of H atoms in the same concentration of CH3OH with addition of 300 ppm H-2 diluted in Ar. The branching fraction for CH3OH + Ar -> (CH2)-C-1 + H2O + Ar has been quantitatively evaluated from this comparative measurements with using recent experimental result on the yield of H atoms in the reaction of (CH2)-C-1,3 + O-2 [J. Phys. Chem. A 2012, 116, 9245-9254]; i.e., the branching fraction for the above reaction is evaluated as, phi(1a) = 0.20 +/- 0.04 at T = 1880-2050 K, in the 1.3 and 3.5 ppm CH3OH + 100 ppm O-2 samples. An extended reaction mechanism for the pyrolysis and oxidation of CH3OH is constructed based on the results of the present study combined with the oxidation mechanism of natural gas [GRI-Mech 3.0]; evolution of H atoms can be predicted very well with this new reaction scheme over a wide concentration range for the pyrolysis (0.36-100 ppm CH3OH), and oxidation (0.36-100 ppm CH3OH + 100/400 ppm O-2) of methanol.