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M C Lin

Publications and source records attributed to M C Lin.

At least 37 records · Page 2Linked to original sources
PubMed2005

Reactions of hydrazoic acid on TiO2 nanoparticles: an experimental and computational study.

This article reports the results of a computational and experimental study on the reaction of hydrazoic acid, HN3, adsorbed on 15-20 nm TiO2 particle films. Experimentally, FTIR spectra of HN3(a) have been measured by varying HN3 dosage, UV irradiation time and surface annealing temperature. Three sharp peaks, related to v(a)(NNN) of HN3(a) and N3(a) with different configurations in the 2000-2200 cm(-1) region, and a broad band absorption, related to associated and isolated HN(a) and HO(a) adsorptions in the 3000-3800 cm(-1) region, have been detected. Computationally, molecular structures, vibrational frequencies and adsorption energies of possible adsorbates including HN3 and its derivatives, N3, N2, NH, and H, have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. On the basis of the experimental and computational results, the peak appeared at 2075 cm(-1), which increases at a faster rate with HN3 exposure time, is attributed to a stable adsorbate, N3-Ti(a), with the predicted adsorption energy, E(ads) = 13 kcal/mol. The peak at 2118 cm(-1), which survives at the highest surface temperature in the heating experiment, is attributable to the most stable adsorbate, Ti-N2N(H)-O(a) with E(ads) = 36 kcal/mol. The peak at 2170 cm(-1), which vanishes most readily in all of the aforementioned experiments, is related to less stable molecular adsorbates, end-on HN3-Ti(a) with E(ads) = 5 kcal/mol and side-on HN(N2)-Ti(a) with E(ads) = 8 kcal/mol. A potential energy diagram for the formation of various absorbates with their transition states has been established for the HN3/TiO2 system. On the basis of the predicted desorption energies, the four most stable products of the HN3 reaction on TiO2 are H-O(a), 118 kcal/mol; HN-O(a), 85 kcal/mol; Ti-N2N(H)-O(a), 36 kcal/mol; and N3-O(a), 19 kcal/mol.

Journal Article↗
PubMed2005

Characteristics of patients suffering from tuberculous pleuritis with pleural effusion culture positive and negative for Mycobacterium tuberculosis, and risk factors for fatality.

SETTING: A 2500-bed hospital. OBJECTIVES: To clarify characteristics of tuberculous pleuritis (TP) with pleural effusion culture positive and negative for Mycobacterium tuberculosis (PECP-MT and PECN-MT) and to identify risk factors for fatality. PATIENTS AND METHODS: Retrospective analysis of TP patients with PECP-MT and PECN-MT, and review of medical charts of deceased patients. RESULTS: Of 126 patients enrolled (28 PECP-MT and 98 PECN-MT), those with PECP-MT had a higher prevalence of steroid use (SU) (14.3% vs. 2.0%; P = 0.022) and concurrent tuberculosis involving another site (7.2% vs. 0.0%; P = 0.048), increased neutrophils (36.4% vs. 16.6%; P = 0.020) and decreased glucose levels (mean 88.7 vs. 127.6 g/dl; P = 0.012) in pleural effusion, and a higher fatality rate (28.0% vs. 3.1%; P < 0.001). Deceased patients (n = 10) were older (mean 74.2 vs. 64.4 years; P = 0.047), had a higher incidence of acute renal failure (ARF) (50.0% vs. 11.7%; P = 0.007), and a higher prevalence of malignancy (40.0% vs. 6.3%; P = 0.006), history of stroke (30.0% vs. 7.2%; P = 0.048) and SU (20.0% vs. 1.8%; P = 0.034). CONCLUSION: SU, concurrent tuberculosis involving another site, increased neutrophils and decreased glucose levels in pleural effusion may be predictive factors for PECP-MT. Malignancy, ARF and SU, and perhaps being elderly or history of stroke, are risk factors for fatality in patients with TP.

Age Factors↗
PubMed2004

Ab initio studies of CIO, reactions: prediction of the rate constants of CIO + NO for the forward and reverse processes.

The mechanisms for ClO+NO and its reverse reactions were investigated by means of ab initio molecular orbital and statistical theory calculations. The species involved were optimized at the B3LYP/6-311 +G(3df) level, and their energies were refined at the CCSD(T)/6-311+ G(3df)//B3LYP/6-311 + G(3df) level. Five isomers and the transition states among them were located. The relative stability of these isomers is ClNO2 > cis-ClONO > trans-ClONO > cis-OClNO>trans-OClNO. The heats of formation of the three most-stable isomers were predicted using isodesmic reactions by different methods. The predicted bimolecular reaction rate constant shows that, below 100 atm, the formation of Cl+NO2 is dominant and pressure-independent. The total rate constant can be expressed as: k(ClO+NO)= 1.43 x 10(-9)T(-083)exp(92/ T) cm3 molecule(-1)s(-1) in the temperature range of 200-1000 K, in close agreement with experimental data. For the reverse reaction, Cl+NO2-->ClNO2 and ClONO (cis and trans isomers), the sum of the predicted rate constants for the formation of the three isomers and their relative yields also reproduce the experimental data well. The predicted total third-order rate constants in the temperature range of 200-1000 K can be represented by: k0(He) = 4.89 x 10(-6)T(-5.85) exp(-796/T) cm6 molecule(-1)s(-1) and k0(N2) =5.72 x 10(-15)T(-5.80) exp(-814/T) cm6 molecule(-1)s(-1). The predicted high- and low-pressure limit decomposition rates of CINO2 in Ar in the temperature range 400-1500 K can be expressed, respectively, by: k-(ClNO2) = 7.25 x 10(19)T(-1.89) exp(-16875/T) s(-1) and kd(ClNO2) = 2.51 x 10(38)T(-6.8) exp(-18409/T) cm3 molecule(-1) s(-1). The value of k0(ClNO2) is also in reasonable agreement with available experimental data.

Journal Article↗
PubMed2004

Experimental and theoretical investigations of rate coefficients of the reaction S(3P)+O2 in the temperature range 298-878 K.

Rate coefficients of the reaction S+O(2) with Ar under 50 Torr in the temperature range 298-878 K were determined with the laser photolysis technique. S atoms were generated by photolysis of OCS with a KrF excimer laser at 248 nm; their concentration was monitored via resonance fluorescence excited by atomic emission of S produced from microwave-discharged SO(2). Our measurements show that k(298 K)=(1.92+/-0.29)x10(-12) cm(3) molecule(-1) s(-1), in satisfactory agreement with previous reports. New data determined for 505-878 K show non-Arrhenius behavior; combining our results with data reported at high temperatures, we derive an expression k(T)=(9.02+/-0.27)x10(-19)T(2.11+/-0.15) exp[(730+/-120)/T] cm(3) molecule(-1) s(-1) for 298< or =T< or =3460 K. Theoretical calculations at the G2M (RCC2) level, using geometries optimized with the B3LYP/6-311+G(3df) method, yield energies of transition states and products relative to those of the reactants. Rate coefficients predicted with multichannel RRKM calculations agree satisfactorily with experimental observations; the reaction channel via SOO(1A') dominates at T<500 K, whereas channels involving formation of SOO(3A") followed by isomerization to SO(2) before dissociation, and formation of SOO(1A") followed by direct dissociation, become important at high temperatures, accounting for the observed rapid increase in rate coefficient.

Journal Article↗
PubMed2004

Kinetics and mechanism of the C6H5 + CH3CHO reaction: experimental measurement and theoretical prediction of the reactivity toward four molecular sites.

The kinetics and mechanism of the reaction of C6H5 with CH3CHO have been investigated experimentally and theoretically. The total rate constant for the reaction has been measured by means of the cavity ring-down spectrometry (CRDS) in the temperature range 299-501 K at pressures covering 20-75 Torr. The overall bimolecular rate constant can be represented by the expression k = (2.8 +/- 0.2) x 10(11) exp[-(700 +/- 30)/T] cm3 mol-1 s-1, which is slightly faster than for the analogous C6H5 + CH2O reaction determined with the same method in the same temperature range. The reaction mechanism for the C6H5 + CH3CHO reaction was also explored with quantum-chemical calculations at various hybrid density functional theories (DFTs) and using ab initio high-level composite methods. The theories predict that the reaction may occur by two hydrogen-abstraction and two addition channels with the aldehydic hydrogen-abstraction reaction being dominant. The rate constant calculated by the transition state theory for the aldehydic hydrogen-abstraction reaction is in good agreement with the experimental result after a very small adjustment of the predicted reaction barrier (+0.3 kcal mol-1). Contributions from other product channels are negligible under our experimental conditions. For combustion applications, we have calculated the rate constants for key product channels in the temperature range of 298-2500 K under atmospheric-pressure conditions; they can be represented by the following expressions in units of cm 3mol-1 s-1: k1,cho = 8.8 x 10(3)T2.6 exp(-90/T), k2,ch3 = 6.0 x 10(1)T3.3 exp(-950/T), k3a(C6H5COCH3 + H) = 4.2 x 10(5)T0.6 exp(-410/T) and k3b(C6H5CHO + CH3) = 6.6 x 10(9)T-0.5 exp(-310/T).

Aldehydes↗
PubMed2004

Thermal decomposition of ethanol. III. A computational study of the kinetics and mechanism for the CH3+C2H5OH reaction.

The mechanism for the CH3+C2H5OH reaction has been investigated by the modified Gaussian-2 method based on the geometric parameters of the stationary points optimized at the B3LYP/6-311+G(d,p) level of theory. Five transition states have been identified for the production of CH4+CH3CHOH (TS1), CH4+CH3CH2O (TS2), CH4+CH2CH2OH (TS3), CH3OH+CH3CH2 (TS4), and CH3CH2OCH3+H (TS5) with the corresponding barriers 12.0, 13.2, 16.0, 44.7, and 49.9 kcal/mol, respectively. The predicted rate constants and branching ratios for the three lower-energy H-abstraction reactions were calculated using the conventional and variational transition state theory with quantum-mechanical tunneling corrections for the temperature range 300-3000 K. The predicted total rate constant, kt=8.36 x 10(-76) T(20.00) exp(5258/T) cm3 mol(-1) s(-1) (300-600 K) and 6.10 x 10(-25) T(4.10)exp(-4058/T) cm3 mol(-1) s(-1) (600-3000 K), agrees closely with existing experimental data in the temperature range 403-523 K. Similarly, the predicted rate constants for CH3+CH3CD2OH and CD3+C2H5OD are also in reasonable agreement with available low temperature kinetic data.

Journal Article↗
PubMed2004

Ab initio studies of alkyl radical reactions: Combination and disproportionation reactions of CH3 with C2H5, and the decomposition of chemically activated C3H8.

This paper reports the first quantitative ab initio prediction of the disproportionation/combination ratio of alkyl+alkyl reactions using CH3+C2H5 as an example. The reaction has been investigated by the modified Gaussian-2 method with variational transition state or Rice-Ramsperger-Kassel-Marcus calculations for several channels producing (1) CH4+CH2CH2, (2) C3H8, (3) CH4CH3CH, (4) H2+CH3CHCH2, (5) H2+CH3CCH3, and (6) C2H6+CH2 by H-abstraction and association/decomposition mechanisms through singlet and triplet potential energy paths. Significantly, the disproportionation reaction (1) producing CH4+C2H4 was found to occur primarily by the lowest energy path via a loose hydrogen-bonding singlet molecular complex, H3CHC2H4, with a 3.5 kcal/mol binding energy and a small decomposition barrier (1.9 kcal/mol), instead of a direct H-abstraction process. Bimolecular reaction rate constants for the formation of the above products have been calculated in the temperature range 300-3000 K. At 1 atm, formation of C3H8 is dominant below 1200 K. Over 1200 K, the disproportionation reaction becomes competitive. The sum of products (3)-(6) accounts for less than 0.3% below 1500 K and it reaches around 1%-4% above 2000 K. The predicted rate constant for the disproportionation reaction with multiple reflections above the complex well, k1=5.04 x T(0.41) exp(429/T) at 200-600 K and k1=1.96 x 10(-20) T(2.45) exp(1470/T) cm3 molecule(-1) s(-1) at 600-3000 K, agrees closely with experimental values. Similarly, the predicted high-pressure rate constants for the combination reaction forming C3H8 and its reverse dissociation reaction in the temperature range 300-3000 K, k2(infinity)=2.41 x 10(-10) T(-0.34) exp(259/T) cm3 molecule(-1) s(-1) and k(-2)(infinity)=8.89 x 10(22) T(-1.67)exp(-46 037/T) s(-1), respectively, are also in good agreement with available experimental data.

Journal Article↗
PubMed2004

Kinetics and mechanisms for the reactions of phenyl radical with ketene and its deuterated isotopomer: an experimental and theoretical study.

Kinetics and mechanism for the reaction of phenyl radical (C6H5) with ketene (H2C beta=C alpha=O) were studied by the cavity ring-down spectrometric (CRDS) technique and hybrid DFT and ab initio molecular orbital calculations. The C6H5 transition at 504.8 nm was used to detect the consumption of the phenyl radical in the reaction. The absolute overall rate constants measured, including those for the reaction with CD2CO, can be expressed by the Arrhenius equation k = (5.9 +/- 1.8) x 10(11) exp[-(1160 +/- 100)/T] cm3 mol-1 s-1 over a temperature range of 301-474 K. The absence of a kinetic isotope effect suggests that direct hydrogen abstraction forming benzene and ketenyl radical is kinetically less favorable, in good agreement with the results of quantum chemical calculations at the G2MS//B3LYP6-31G(d) level of theory for all accessible product channels, including the above abstraction and additions to the C alpha, C beta, and O sites. For application to combustion, the rate constants were extrapolated over the temperature range of 298-2500 K under atmospheric pressure by using the predicted transition-state parameters and the adjusted entrance reaction barriers E alpha = E beta = 1.2 kcal mol-1; they can be represented by the following expression in units of cm3 mol-1 s-1: k alpha = 6.2 x 10(19)T-23 exp[-7590/T] and k beta = 3.2 x 10(4)T2.4 exp[-246/T].

Journal Article↗
PubMed2004

Quantitative three-dimensional power Doppler ultrasound predicts the outcome of placental chorioangioma.

The relationship of large and vascularized chorioangiomas to adverse pregnancy outcome is well recognized. We present a patient with a large placental tumor and signs of impending fetal cardiac failure. The angioarchitecture of the tumor depicted by three-dimensional (3D) power Doppler ultrasound enabled us to accurately diagnose a placental chorioangioma. During the follow-up period, quantitative flow data obtained using 3D power Doppler indicated altered hemodynamics in the tumor and concomitant improvement in the condition of the fetus, enabling us to manage the mother conservatively. Spontaneous delivery occurred at 38 weeks without any complications. This report demonstrates the potential value of 3D power Doppler in prenatal diagnosis and monitoring of pregnancies complicated by large, vascularized chorioangioma.

Adult↗
PubMed2003

Reaction of phenyl radicals with acetylene: quantum chemical investigation of the mechanism and master equation analysis of the kinetics.

The mechanism of the C(6)H(5) + C(2)H(2) reaction has been investigated by various quantum chemical methods. Electrophilic addition to the CC triple bond is found to be the only important mode of phenyl radical attack on acetylene. The initially formed chemically activated C(6)H(5)C(2)H(2) adducts may follow several isomerization pathways in competition with collisional stabilization and H-elimination. Thermochemistry of various decomposition and isomerization channels is evaluated by the G2M method. For key intermediates, the following standard enthalpies of formation have been deduced from isodesmic reactions: 94.2 +/- 2.0 kcal/mol (C(6)H(5)CHCH), 86.4 +/- 2.0 kcal/mol (C(6)H(5)CCH(2)), and 95.5 +/- 1.8 kcal/ mol (o-C(6)H(4)C(2)H(3)). The accuracy of theoretical predictions was examined through extensive comparisons with available experimental and theoretical data. The kinetics and product branching of the C(6)H(5) + C(2)H(2) reaction have been evaluated by weak collision master equation/Rice-Ramsperger-Kassel-Marcus (RRKM) analysis of the truncated kinetic model including only kinetically important transformations of the isomeric C(8)H(7) radicals. Available experimental kinetic data can be quantitatively reproduced by calculation with a minor adjustment of the C(6)H(5) addition barrier from 3.7 to 4.1 kcal/mol. Our predicted total rate constant, k(R1) = (1.29 x 10(10))T(0.834) exp(-2320/T) cm(3) mol(-)(1) s(-)(1), is weakly dependent on P and corresponds to the phenylation process under combustion conditions (T > 1000 K).

Journal Article↗
PubMed2003

Gene therapy for new bone formation using adeno-associated viral bone morphogenetic protein-2 vectors.

Previous reports have suggested that bone morphogenetic protein (BMP) gene therapy could be applied for in vivo bone regeneration. However, these studies were conducted either using immunodeficient animals because of immunogenicity of adenovirus vectors, or using ex vivo gene transfer technique, which is much more difficult to handle. Adeno-associated virus (AAV) is a replication-defective virus without any association with immunogenicity and human disease. This study was conducted to investigate whether orthotopic new bone formation could be induced by in vivo gene therapy using AAV-based BMP2 vectors. To test the feasibility of this approach, we constructed an AAV vector carrying human BMP2 gene. Mouse myoblast cells (C2C12) transduced with this vector could produce and secrete biologically active BMP2 protein and induce osteogenic activity, which was confirmed by ELISA and alkaline phosphatase activity assay. For in vivo study, AAV-BMP2 vectors were directly injected into the hindlimb muscle of immunocompetent Sprague-Dawley rats. Significant new bone under X-ray films could be detected as early as 3 weeks postinjection. The ossification tissue was further examined by histological and immunohistochemical analysis. This study is, to our knowledge, the first to establish the feasibility of AAV-based BMP2 gene therapy for endochondral ossification in immunocompetent animals.

Animals↗
PubMed2002

Rates and characteristics of lower limb amputations in Taiwan, 1997.

This study aims to describe the national incidence rate and characteristics of lower limb amputations (LLA) in 1997 from an island-wide database of the national health insurance programme in Taiwan. Some 117,647 discharge records from a sampled database (1 in 20) of the National Health Insurance Research Database were analysed. This study included records (n=171) containing LLA procedures. The LLA procedure rates were obtained by multiplying the number of identified procedures by 20 as the numerator and mid-year total population of Taiwan in 1997 as the denominator. Each procedure was further analysed according to the demographic characteristics of the patients, cause and level of amputation. Summarised gender ratios of LLA procedure rates were obtained by Poisson regression analysis. The crude LLA procedure rate was 18.1 per 100,000 population per year and the crude major LLA procedure rate was 8.8 per 100,000 population per year in Taiwan in 1997. The major cause of LLA procedures was peripheral vascular disease (72%), and the toe was most frequently amputated (48%). The LLA procedure rates, which increased logarithmically with age of patients, were significantly higher in men with a summarised male to female rate ratio of 1.65. The age-standardised LLA procedure rate in Taiwan was lower than that reported in the United States, Finland, the Netherlands, the United Kingdom (Leeds, Middlesborough, and Newcastle), but higher than Spain, Italy, and Japan. The trend of an increasing proportion of PVD-related LLA procedures will prompt the health professionals to develop strategies for LLA prevention.

Adolescent↗
PubMed2001

Increased risk of preterm delivery in areas with air pollution from a petroleum refinery plant in Taiwan.

The petrochemical and petroleum industries are among the main sources of industrial air pollution in Taiwan. Data in this study concern outdoor air pollution and the health of individuals living in communities in close proximity to a petroleum refinery plant. The prevalence of delivery of preterm birth infants was significantly higher in mothers living in a petroleum refinery area compared to controls in Taiwan. After controlling for several possible confounders (including maternal age, season, marital status, maternal education, and infant sex), the adjusted odds ratio was 1.41 (95% CI = 1.08-1.82) for delivery of preterm infants in the polluted region. Data support the view that air pollution can affect the outcome of pregnancy.

Adult↗
PubMed2001

Functional p53 is required for triptolide-induced apoptosis and AP-1 and nuclear factor-kappaB activation in gastric cancer cells.

Triptolide, a major component in the extract of Chinese herbal plant Tripterygium wilfordii Hook f (TWHf), has potential anti-neoplastic effect. In the present study we investigated the potential therapeutic effects and mechanisms of triptolide against human gastric cancer cells. Four gastric cancer cell lines with different p53 status, AGS and MKN-45 (wild type p53); MKN-28 and SGC-7901 (mutant p53) were observed as to cell growth inhibition and induction of apoptosis in response to triptolide treatment. We showed that triptolide inhibited cell growth, induced apoptosis and suppressed NK-kappaB and AP-1 transactivation in AGS cells with wild-type p53. Triptolide induced apoptosis by stimulating the expressions of p53, p21(waf1/cip1), bax protein, and increased the activity of caspases. In addition, it caused cell cycle arrest in the G(0)/G(1) phase. To examine the role of p53 in these functions, we showed that suppression of p53 level with antisense oligonucleotide abrogated triptolide-induced apoptosis and over-expression of dominant negative p53 abolished the inhibitory effect on NF-kappaB activation. Furthermore, we demonstrated that triptolide had differential effects on gastric cancer cells with different p53 status. We showed that triptolide also inhibited cell growth and induced apoptosis in MKN-45 with wild-type p53, whereas it had no significant growth-inhibition and apoptosis induction effects on the MKN-28 and SGC-7901 cells with mutant p53. Our data suggest that triptolide exhibits anti-tumor and anti-inflammatory effects by inhibiting cell proliferation, inducing apoptosis and inhibiting NF-kappaB and AP-1 transcriptional activity. However, a functional p53 is required for these proapoptotic, anti-inflammatory and anti-tumor effects.

Apoptosis↗
PubMed2001

Adverse pregnancy outcome in a petrochemical polluted area in Taiwan.

The petrochemical industry is the main source of industrial air pollution in Taiwan. Reported here are the results from an ongoing study of outdoor air pollution and the health of individuals living in a community in close proximity to petrochemical industrial complexes. The prevalences of term low birth weight (LBW) in the petrochemical municipality and control municipality were 3.22%, and 1.84%, respectively. After controlling for several possible confounders (including maternal age, season, marital status, maternal education, and infant sex), the adjusted odds ratio was 1.767 (1.002-3.116) for term LBW in the petrochemical municipality. Data provide further support for the hypothesis that air pollution can affect the outcome of pregnancy.

Adolescent↗