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1.
J Phys Chem A ; 128(2): 456-465, 2024 Jan 18.
Artículo en Inglés | MEDLINE | ID: mdl-38181389

RESUMEN

We interrogated C7H produced from reactions C4 + C3H2/C4H + C3H → C7H + H using both translational and photoionization spectroscopy. Reactants C3H, C3H2, C4, and C4H were synthesized in two crossed beams of 1% C2H2/He ignited by pulsed high-voltage discharge. The individual contributions of reactions C4 + C3H2 and C4H + C3H to product C7H were evaluated as 17:83 from reactant concentrations in both molecular beams. The translational energy distribution, the angular distribution, and the photoionization efficiency curve of product C7H were unraveled. C7H was identified as the most stable linear isomer by its photoionization efficiency curve that features two ionization thresholds corresponding to separate transitions to singlet and triplet states of l-C7H+. The quantum-chemical calculations indicate that the associations of C4 with C3H2 and C4H with C3H incur no entrance barriers, and the most favorable exit channel leads to product l-C7H + H. It is the first time demonstrating that C7H is producible from reactions 1,3C4 + 1C3H2 and 2C4H + 2C3H on the lowest-lying singlet and triplet potential energy surfaces of 1,3C7H2. This work implies that the reactions of C4 + C3H2 and C4H + C3H might have contributions to interstellar C7H to some extent as compared with the C + C6H2 reaction commonly adopted in an astrochemical model.

2.
J Chem Phys ; 160(4)2024 Jan 28.
Artículo en Inglés | MEDLINE | ID: mdl-38258925

RESUMEN

We interrogated C6H and C8H produced separately from the reactions C3 + C3H2/C3H + C3H/C3H2 + C3 → C6H + H and C4 + C4H2/C4H + C4H/C4H2 + C4 → C8H + H using product translational and photoionization spectroscopy. Individual contributions of the three reactions to the product C6H or C8H were evaluated with reactant concentrations. Translational-energy distributions, angular distributions, and photoionization efficiency curves of products C6H and C8H were unraveled. The product C6H (C8H) was recognized as the most stable linear isomer by comparing its photoionization efficiency curve with that of l-C6H (l-C8H), produced exclusively from the reaction C2 + C4H2 → l-C6H + H (C2 + C6H2 → l-C8H + H). The ionization threshold after deconvolution was determined to be 9.3 ± 0.1 eV for l-C6H and 8.9 ± 0.1 eV for l-C8H, which is in good agreement with theoretical values. Quantum-chemical calculations indicate that the reactions of C3 + C3H2 and C3H + C3H (C4 + C4H2 and C4H + C4H) incur no energy barriers that lie above the corresponding reactant and the most stable product l-C6H (l-C8H) with H on the lower-lying potential-energy surfaces. The theoretical calculation is in accord with the experimental observation. This work implies that the reactions of C3 + C3H2/C3H + C3H and C4 + C4H2/C4H + C4H need to be taken into account for the formation of interstellar C6H and C8H, respectively.

3.
Europace ; 25(12)2023 12 06.
Artículo en Inglés | MEDLINE | ID: mdl-38042981

RESUMEN

AIMS: This study aimed to investigate the effectiveness of closed-loop stimulation (CLS) pacing compared with the traditional DDD mode in patients with chronotropic incompetence (CI) using bicycle-based cardiopulmonary exercise testing (CPET). METHODS AND RESULTS: This single-centre, randomized crossover trial involved 40 patients with CI. Patients were randomized to receive either DDD-CLS or DDD mode pacing for 2 months, followed by a crossover to the alternative mode for an additional 2 months. Bicycling-based CPET was conducted at the 3- and 5-month follow-up visits to assess exercise capacity. Other cardiopulmonary exercise outcome measures and health-related quality of life (QoL) were also assessed. DDD-CLS mode pacing significantly improved exercise capacity, resulting in a peak oxygen uptake (14.8 ± 4.0 vs. 12.0 ± 3.6 mL/kg/min, P < 0.001) and oxygen uptake at the ventilatory threshold (10.0 ± 2.2 vs. 8.7 ± 1.8 mL/kg/min, P < 0.001) higher than those of the DDD mode. However, there were no significant differences in other cardiopulmonary exercise outcome measures such as ventilatory efficiency of carbon dioxide production slope, oxygen uptake efficiency slope, and end-tidal carbon dioxide between the two modes. Patients in the DDD-CLS group reported a better QoL, and 97.5% expressed a preference for the DDD-CLS mode. CONCLUSION: DDD-CLS mode pacing demonstrated improved exercise capacity and QoL in patients with CI, highlighting its potential as an effective pacing strategy for this patient population.


Asunto(s)
Estimulación Cardíaca Artificial , Calidad de Vida , Humanos , Estimulación Cardíaca Artificial/métodos , Dióxido de Carbono , Ciclismo , Tolerancia al Ejercicio , Estudios Cruzados , Prueba de Esfuerzo , Oxígeno , Frecuencia Cardíaca/fisiología
4.
J Chem Phys ; 151(14): 141101, 2019 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-31615217

RESUMEN

UV-excited aromatic molecules with N-H/O-H moieties often possess an important nonradiative relaxation pathway, from an optically bright ππ* state to a dark dissociative πσ* state. We apply a new time-selected photofragment translational spectroscopy method to disclose a previously unknown triplet-mediated N-H dissociation of aniline prevented by the multiphoton dissociative ionization in conventional methods. We further determined the branching fractions of aniline dissociated in the πσ*, triplet, and ground states at 248 nm. Additionally, we selectively captured the population changes in the singlet and triplet states with ionization from different laser wavelengths, 355 or 266 nm, in time-resolved photoion yields. The combination of experimental data enables us to uniquely determine the relative ionization cross sections of the singlet and triplet states at an ionization laser wavelength of 266 nm and allows us to extensively measure the rate constants of intersystem crossing and the branching fractions at various excitation wavelengths.

5.
J Chem Phys ; 148(7): 074306, 2018 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-29471658

RESUMEN

Phenol is an important model molecule for the theoretical and experimental investigation of dissociation in the multistate potential energy surfaces. Recent theoretical calculations [X. Xu et al., J. Am. Chem. Soc. 136, 16378 (2014)] suggest that the phenoxyl radical produced in both the X and A states from the O-H bond fission in phenol can contribute substantially to the slow component of photofragment translational energy distribution. However, current experimental techniques struggle to separate the contributions from different dissociation pathways. A new type of time-resolved pump-probe experiment is described that enables the selection of the products generated from a specific time window after molecules are excited by a pump laser pulse and can quantitatively characterize the translational energy distribution and branching ratio of each dissociation pathway. This method modifies conventional photofragment translational spectroscopy by reducing the acceptance angles of the detection region and changing the interaction region of the pump laser beam and the molecular beam along the molecular beam axis. The translational energy distributions and branching ratios of the phenoxyl radicals produced in the X, A, and B states from the photodissociation of phenol at 213 and 193 nm are reported. Unlike other techniques, this method has no interference from the undissociated hot molecules. It can ultimately become a standard pump-probe technique for the study of large molecule photodissociation in multistates.

6.
J Phys Chem A ; 121(51): 9687-9697, 2017 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-29232517

RESUMEN

The reactions of C3H and C4H radicals with C6H2 were investigated for the first time. Reactants C3H, C4H, and C6H2 were synthesized in two beams of C2H2 diluted with helium by pulsed high-voltage discharge. We measured translational-energy distributions, angular distributions, and photoionization-efficiency spectra of C9H2 and C10H2 produced from the title reactions in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet photoionization. The C3H (C4H) + C6H2 reaction releases 42% (33%) of available energy into the translational degrees of freedom of product C9H2 (C10H2) + H and scatters products into a nearly isotropic angular distribution. The photoionization-efficiency spectrum of C9H2 (C10H2) is in good agreement with that of C9H2 (C10H2) produced from the C7H (C8H) + C2H2 reaction. The ionization threshold, after deconvolution, was determined as 8.0 ± 0.1 eV for C9H2 and 8.8 ± 0.1 eV for C10H2. The combination of measurements of product translational-energy release and photoionization-efficiency spectra indicates productions of 3HC9H/c-1HC3(C)C5H/c-1HC7(C)CH + H and 1HC10H + H in the two title reactions, which are supported also by quantum-chemical calculations. Ratios branching to the three isomers of C9H2 remain unknown. This work demonstrates that long carbon-chain molecules (e.g., C9H2 and C10H2) can be synthesized from reactions of CmH (e.g., m = 3 and 4) radicals with polyynes (e.g., HC6H) and gives some valuable implications to planetary, interstellar, and combustion chemistry.

7.
J Phys Chem A ; 121(36): 6732-6741, 2017 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-28862852

RESUMEN

We used crossed laser-molecular beam scattering to study the primary photodissociation channels of chloroacetaldehyde (CH2ClCHO) at 157 nm. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence two other photodissociation channels: HCl photoelimination and C-C bond fission. This is the first direct evidence of the C-C bond fission channel in chloroacetaldehyde, and we found that it significantly competes with the C-Cl bond fission channel. We determined the total primary photodissociation branching fractions for C-Cl fission:HCl elimination:C-C fission to be 0.65:0.07:0.28. The branching between the primary channels suggests the presence of interesting excited state dynamics in chloroacetaldehyde. Some of the vinoxy radicals from C-Cl photofission and most of the ketene cofragments formed in HCl photoelimination have enough internal energy to undergo secondary dissociation. While our previous velocity map imaging study on the photodissociation of chloroacetaldehyde at 157 nm focused on the barrier for the unimolecular dissociation of vinoxy to H + ketene, this work shows that the HCl elimination channel contributed to the high kinetic energy portion of the m/z = 42 signal in that study.

8.
J Phys Chem A ; 121(33): 6262-6268, 2017 Aug 24.
Artículo en Inglés | MEDLINE | ID: mdl-28806080

RESUMEN

These experiments report the dissociative photoionization of vinoxy radicals to m/z = 15 and 29. In a crossed laser-molecular beam scattering apparatus, we induce C-Cl bond fission in 2-chloroacetaldehyde by photoexcitation at 157 nm. Our velocity measurements, combined with conservation of angular momentum, show that 21% of the C-Cl photofission events form vinoxy radicals that are stable to subsequent dissociation to CH3 + CO or H + ketene. Photoionization of these stable vinoxy radicals, identified by their velocities, which are momentum-matched with the higher-kinetic-energy Cl atom photofragments, shows that the vinoxy radicals dissociatively photoionize to give signal at m/z = 15 and 29. We calibrated the partial photoionization cross section of vinoxy to CH3+ relative to the bandwidth-averaged photoionization cross section of the Cl atom at 13.68 eV to put the partial photoionization cross sections on an absolute scale. The resulting bandwidth-averaged partial cross sections are 0.63 and 1.3 Mb at 10.5 and 11.44 eV, respectively. These values are consistent with the upper limit to the cross section estimated from a study by Savee et al. on the O(3P) + propene bimolecular reaction. We note that the uncertainty in these values is primarily dependent on the signal attributed to C-Cl primary photofission in the m/z = 35 (Cl+) time-of-flight data. While the value is a rough estimate, the bandwidth-averaged partial photoionization cross section of vinoxy to HCO+ calculated from the signal at m/z = 29 at 11.53 eV is approximately half that of vinoxy to CH3+. We also present critical points on the potential energy surface of the vinoxy cation calculated at the G4//B3LYP/6-311++G(3df,2p) level of theory to support the observation of dissociative ionization of vinoxy to both CH3+ and HCO+.

9.
J Chem Phys ; 147(6): 064307, 2017 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-28810763

RESUMEN

Synchrotron radiation VUV-photoionization based photofragment translational spectroscopy was used to identify the primary and secondary photodissociation reactions of methyl azide (CH3N3) at 157 nm under collision-free conditions. Two primary dissociation channels are identified, leading to CH3 + N3 (the radical channel) and CH3N + N2 (the molecular elimination channel). The last channel is the major dissociation pathway, but unlike work at longer photolysis wavelengths, here, the radical channel exclusively produces the higher energy isomer cyclic-N3. Product time-of-flight data for both channels were obtained and compared with earlier work on methyl azide photochemistry at 193 nm based on electron impact ionization, allowing us to estimate a product branching ratio ΦCH3-N3 ΦCH3N-N2 =2.3%±0.6%97.7%±0.6%.

10.
J Chem Phys ; 147(1): 013904, 2017 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-28688420

RESUMEN

The original ion imaging technique has low velocity resolution, and currently, photodissociation is mostly investigated using velocity map ion imaging. However, separating signals from the background (resulting from undissociated excited parent molecules) is difficult when velocity map ion imaging is used for the photodissociation of large molecules (number of atoms ≥ 10). In this study, we used the photodissociation of phenol at the S1 band origin as an example to demonstrate how our multimass ion imaging technique, based on modified spatial map ion imaging, can overcome this difficulty. The photofragment translational energy distribution obtained when multimass ion imaging was used differed considerably from that obtained when velocity map ion imaging and Rydberg atom tagging were used. We used conventional translational spectroscopy as a second method to further confirm the experimental results, and we conclude that data should be interpreted carefully when velocity map ion imaging or Rydberg atom tagging is used in the photodissociation of large molecules. Finally, we propose a modified velocity map ion imaging technique without the disadvantages of the current velocity map ion imaging technique.

11.
Acta Cardiol Sin ; 33(4): 377-383, 2017 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-29033508

RESUMEN

BACKGROUND: Some difficulties and variations remain associated with the care of elderly patients with non-ST elevation acute coronary syndrome (NSTE-ACS). METHODS: We included 1470 patients from a Taiwan nationwide registry who fulfilled the criteria of NSTE-ACS, and stratified these patients by age and evaluated the treatment, complications and outcomes in different age groups. Furthermore, we analyzed risk factors and standards of care to determine the predictors of mortality. RESULTS: Patients ≥ 75 years of age (n = 396) had significantly higher incidences of 90-day mortality [odd ratio (OR) = 4.5 (1.2-16.3), p = 0.023] and 1-year mortality [OR = 4.9 (2.0-12.3), p = 0.001] compared with those patients 45-64 years of age (n = 595). In the patients ≥ 75 years of age, previous myocardial infarction (MI) [OR = 3.3 (1.1-9.8), p = 0.035], statins [OR = 0.35 (0.1-0.9), p = 0.037], left ventricular ejection fraction (LVEF) < 35% [OR = 3.9 (1.5-10.4), p = 0.006] were associated with 90-day mortality. Furthermore, previous MI [OR = 4.0 (1.3-12.6), p = 0.019] was an independent predictor of 90-day mortality. Age [OR = 1.1 (1.03-1.2), p = 0.002], previous MI [OR = 2.2 (1.1-4.4), p = 0.034], angiotensin-converting enzyme inhibitor or angiotensin receptor blocker [OR = 0.5 (0.3-0.9), p = 0.028], and LVEF < 35% [OR = 4.3 (1.9-9.5), p < 0.001] were associated with 1-year mortality. Furthermore, previous MI [OR = 2.6 (1.1-6.5), p = 0.037], LVEF < 35% [OR = 4.7 (1.5-14.4), p = 0.007] and percutaneous coronary intervention(PCI) or not [OR = 0.3 (0.1-0.9), p = 0.021] were independent predictors of 1-year mortality. CONCLUSIONS: Previous MI, LVEF < 35% and PCI or not could predict 1-year mortality in advanced elderly patients with NSTE-ACS. Despite their elevated morbidities and complications, PCI was still beneficial for these patients.

12.
Phys Chem Chem Phys ; 18(3): 2120-9, 2016 Jan 21.
Artículo en Inglés | MEDLINE | ID: mdl-26691183

RESUMEN

The Cm+2H2 family can be classified into two categories - C2n+1H2 and C2n+2H2. Cm+2H2 are important intermediates in the syntheses of large carbonaceous molecules. An understanding of the formation mechanisms of both odd and even carbon-numbered Cm+2H2 is beneficial to atmospheric, astronomical, and combustion chemistry. HC2n+2H (polyynes) are believed to be producible from C2nH + C2H2 and C2H + C2nH2 reactions but C2n+1H2 (n≥ 2) attract less attention to their formation mechanisms. In the present study, we make up for the lack of knowledge on C2n+1H2 formation mechanisms by investigating the reactions C2n-1H + C2H2→ C2n+1H2 + H with n = 1-4. The dynamics of reactions of C2n-1H radicals with C2H2 are explored in crossed molecular beams using products C2n+1H2. The translational-energies and angular distributions of the hydrogen-loss channels of products are unraveled by measuring time-of-flight spectra and photoionization-efficiency spectra of C2n+1H2 with tunable synchrotron vacuum-ultraviolet ionization. The C2n+1H2 product includes two isomers, c-(1)HC2n-1(C)CH and (3)HC2n+1H, which are identified by the maximal translational-energy release and the photoionization threshold. Furthermore, quantum-chemical calculations indicate that the title reactions incur a small or negligible entrance barrier and are nearly isoergic except for the barrierless exothermic reaction CH + C2H2→ C3H2 + H. We demonstrate for the first time that C5H2, C7H2, and C9H2 are producible from the title reactions. In conjunction with studies on the C2nH + C2H2 reactions, a brief picture for the CmH (m = 1-8) + C2H2→ Cm+2H2 + H reactions can be outlined.

13.
J Phys Chem A ; 120(27): 4973-87, 2016 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-27124098

RESUMEN

We first characterize the dissociation pathways of BrCH2CH2ONO, a substituted alkyl nitrite, upon photoexcitation at 193 nm under collision-free conditions, in a crossed laser-molecular beam scattering apparatus using vacuum ultraviolet photoionization detection. Three primary photodissociation pathways occur: photoelimination of HNO, leading to the products HNO + BrCH2CHO; C-Br bond photofission, leading to Br + CH2CH2ONO; and O-NO bond photofission, leading to NO + BrCH2CH2O. The data show that alkyl nitrites can eliminate HNO via a unimolecular mechanism in addition to the commonly accepted bulk disproportionation mechanism. Some of the products from the primary photodissociation pathways are highly vibrationally excited, so we then probe the product branching from the unimolecular dissociation of these unstable intermediates. Notably, the vibrationally excited CH2CH2ONO radicals undergo two channels predicted by statistical transition-state theory, and an additional non-intrinsic reaction coordinate channel, HNO elimination. CH2CH2ONO is formed with high rotational energy; by employing rotational models based on conservation of angular momentum, we predict, and verify experimentally, the kinetic energies of stable CH2CH2ONO radicals and the angular distribution of dissociation products. The major dissociation pathway of CH2CH2ONO is NO2 + ethene, and some of the NO2 is formed with sufficient internal energy to undergo further photodissociation. Nascent BrCH2CHO and CH2Br are also photodissociated upon absorption of a second 193 nm photon; we derive the kinetic energy release of these dissociations based on our data, noting similarities to the analogous photodissociation of ClCH2CHO and CH2Cl.

14.
Circ J ; 78(4): 922-8, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-24562675

RESUMEN

BACKGROUND: Spectral analysis of the left atrium can identify high dominant frequency (DF) sites, which might play a role in the perpetuation of atrial fibrillation (AF). Furthermore, the role of the cardiac autonomic nervous system (CANS) in the genesis of AF has been demonstrated. The relationship between CANS and the high-DF sites (AF nest) was the aim of the investigation. METHODS AND RESULTS: In 12 dogs, high frequency stimulation was applied to locate 4 major left atrial (LA) ganglionated plexi (GPs). An Ensite Array and a mapping catheter were delivered into the left atrium for electroanatomical mapping. During sinus rhythm, spectral analysis was performed on the bipolar electrograms in the left atrium before and after epicardial GP ablation. The majority of AF nests were close to the GPs (52±18% of total AF nests). After GP ablation, the mean LA DF values decreased from 54±7Hz to 49±4Hz (P=0.023), and DF values of the AF nest decreased from 93±2Hz to 87±4Hz (P=0.001). Most of the previous AF nest sites close to the GPs disappeared (85±23%). The surface area of the AF nest decreased from 9±5cm(2) to 3±2cm(2) (P=0.001). CONCLUSIONS: Catheter ablation of the GP decreased the DF values, AF nest areas and diminished the number of AF nests; particularly those close to the GPs, indicating that the CANS might play an important role in the mechanism of the AF nest.


Asunto(s)
Fibrilación Atrial/fisiopatología , Electrofisiología Cardíaca , Sistema de Conducción Cardíaco/fisiopatología , Animales , Fibrilación Atrial/patología , Perros , Técnicas Electrofisiológicas Cardíacas/métodos , Atrios Cardíacos/patología , Atrios Cardíacos/fisiopatología , Sistema de Conducción Cardíaco/patología
15.
J Phys Chem A ; 118(26): 4707-22, 2014 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-24947044

RESUMEN

These experiments investigate the decomposition mechanisms of geminal dinitro energetic materials by photolytically generating two key intermediates: 2-nitropropene and 2-nitro-2-propyl radicals. To characterize the unimolecular dissociation of each intermediate, we form them under collision-free conditions using the photodissociation of 2-bromo-2-nitropropane; the intermediates are formed at high internal energies and undergo a multitude of subsequent unimolecular dissociation events investigated herein. Complementing our prior work on this system, the new data obtained with a crossed-laser molecular beam scattering apparatus with VUV photoionization detection at Taiwan's National Synchrotron Radiation Research Center (NSRRC) and new velocity map imaging data better characterize two of the four primary 193 nm photodissociation channels. The C-Br photofission channel forming the 2-nitro-2-propyl radicals has a trimodal recoil kinetic energy distribution, P(ET), suggesting that the 2-nitro-2-propyl radicals are formed both in the ground electronic state and in two low-lying excited electronic states. The new data also revise the HBr photoelimination P(ET) forming the 2-nitropropene intermediate. We then resolved the multiple competing unimolecular dissociation channels of each photoproduct, confirming many of the channels detected in the prior study, but not all. The new data detected HONO product at m/e = 47 using 11.3 eV photoionization from both intermediates; analysis of the momentum-matched products allows us to establish that both 2-nitro-2-propyl → HONO + CH3CCH2 and 2-nitropropene → HONO + C3H4 occur. Photoionization at 9.5 eV allowed us to detect the mass 71 coproduct formed in OH loss from 2-nitro-2-propyl; a channel missed in our prior study. The dynamics of the highly exothermic 2-nitro-2-propyl → NO + acetone dissociation is also better characterized; it evidences a sideways scattered angular distribution. The detection of some stable 2-nitropropene photoproducts allows us to fit signal previously assigned to H loss from 2-nitro-2-propyl radicals. Overall, the data provide a comprehensive study of the unimolecular dissociation channels of these important nitro-containing intermediates.

16.
J Chem Phys ; 141(19): 194305, 2014 Nov 21.
Artículo en Inglés | MEDLINE | ID: mdl-25416889

RESUMEN

The reaction C2 + C6H2 → C8H + H was investigated for the first time. Reactant C2 (C6H2) was synthesized from 1% C3F6/He (5% C2H2/He) by pulsed high-voltage discharge. We measured the translational-energy distribution, the angular distribution, and the photoionization spectrum of product C8H in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. This reaction released average translational energy of 8.5 kcal mol(-1) corresponding to a fraction of 0.37 in translation. C8H was identified as octatetranyl based on the maximal translational-energy release 23 ± 2 kcal mol(-1) and the ionization threshold 8.9 ± 0.2 eV. Kinematic constraints can qualitatively account for the nearly isotropic angular distribution. The quantum-chemical calculations indicate that the exothermic reactions C2 (X (1)Σg (+)/a (3)Πu) + HC6H → C8H + H can proceed without entrance and exit barriers, implying the importance in the cold interstellar medium. This work verifies that interstellar C8H can be formed through the C2 + C6H2 reaction.

17.
J Chem Phys ; 141(12): 124314, 2014 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-25273444

RESUMEN

The reaction C3(a(3)Πu) + C2H2 → C5H + H was investigated at collision energy 10.9 kcal mol(-1) that is less than the enthalpy of ground-state reaction C3(X(1)Σg (+)) + C2H2 → C5H + H. C3(a(3)Πu) radicals were synthesized from 1% C4F6/He by pulsed high-voltage discharge. The title reaction was conducted in a crossed molecular-beam apparatus equipped with a quadrupole-mass filter. Product C5H was interrogated with time-of-flight spectroscopy and synchrotron vacuum-ultraviolet ionization. Reactant C3(a(3)Πu) and product C5H were identified using photoionization spectroscopy. The ionization thresholds of C3(X(1)Σg(+)) and C3(a(3)Πu) are determined as 11.6 ± 0.2 eV and 10.0 ± 0.2 eV, respectively. The C5H product is identified as linear pentynylidyne that has an ionization energy 8.4 ± 0.2 eV. The title reaction releases translational energy 10.6 kcal mol(-1) in average and has an isotropic product angular distribution. The quantum-chemical calculation indicates that the C3(a(3)Πu) radical attacks one of the carbon atoms of C2H2 and subsequently a hydrogen atom is ejected to form C5H + H, in good agreement with the experimental observation. As far as we are aware, the C3(a(3)Πu) + C2H2 reaction is investigated for the first time. This work gives an implication for the formation of C5H from the C3(a(3)Πu) + C2H2 reaction occurring in a combustion or discharge process of C2H2.

18.
Acta Cardiol Sin ; 30(4): 274-83, 2014 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-27122800

RESUMEN

BACKGROUND: Studies have reported that women with ST elevation myocardial infarction (STEMI) have worse short- and long-term outcomes than men. It has not yet been confirmed whether these differences reflect differences in age between men and women. METHODS: We retrospectively enrolled 1035 consecutive STEMI patients treated with primary percutaneous coronary intervention (PCI). Baseline clinical characteristics, coronary anatomy, and outcome were compared between young (< 65 years old) and older patients (≥ 65 years old) of both sexes. RESULTS: Younger women presented with a lower incidence of typical angina (83% vs. 93%, p = 0.03), single-vessel disease (21% vs. 35%, p = 0.03), and total occlusion of infarct-related artery (65% vs. 83%, p = 0.001) than younger men, with no gender difference noted in the older group. Younger women in the study had a higher incidence of reinfarction, heart failure requiring admission, or mortality (23% vs. 6%, p < 0.001) during follow-up, compared with younger men, with no gender difference in the older group. Using the Kaplan-Meier analysis, younger women had lower rates of event-free survival (p < 0.001 by log-rank test) than younger men, with no gender difference in the older group. In multivariate analysis, age could predict long-term outcome in men (Hazard ratio 4.43, 95% confidence interval: 2.89-6.78, p < 0.001) but not in women. CONCLUSIONS: In STEMI patients receiving primary PCI, sex-related long-term outcome differences were age-dependent, with younger women likely to have a worse long-term outcome when compared with younger men. KEY WORDS: Coronary heart disease; Gender; Myocardial infarction.

19.
Circ J ; 77(2): 383-9, 2013.
Artículo en Inglés | MEDLINE | ID: mdl-23131722

RESUMEN

BACKGROUND: Currently, the door-to-balloon (D2B) times observed in clinical practice in Taiwan are different from those recommended by evidence-based guidelines. D2B Alliance, a countrywide initiative for quality supported by the Taiwan Joint Commission on Hospital Accreditation, sought to achieve the goal of administering treatment to 75% of patients with ST-elevation myocardial infarction (STEMI) within 90min of hospital presentation. METHODS AND RESULTS: The current study was designed to be prospective, national, and multicenter. We conducted a longitudinal study of the D2B times recorded in 15 primary percutaneous coronary intervention centers and examined the changes caused by implementing the D2B Alliance strategies. A total of 1,726 patients were enrolled in the D2B Alliance and implementation of the D2B Alliance strategies resulted in a significant decrease in the average D2B times (128.8 ± 42.9 min vs. 83.2 ± 16.2 min; P<0.001) from those at baseline. By the end of the year-long study, the percentage of patients treated under 90 min had increased from 46.2% to 80.1% in the hospitals enrolled in the D2B Alliance. CONCLUSIONS: Over the 1 year, hospitals enrolled in the D2B Alliance achieved the goal of reducing the D2B times of 75% of STEMI patients to less than 90 min.


Asunto(s)
Angioplastia Coronaria con Balón , Servicios Médicos de Urgencia/estadística & datos numéricos , Infarto del Miocardio/epidemiología , Infarto del Miocardio/terapia , Tiempo de Tratamiento/estadística & datos numéricos , Electrocardiografía , Servicios Médicos de Urgencia/normas , Hospitales/normas , Hospitales/estadística & datos numéricos , Humanos , Estudios Longitudinales , Infarto del Miocardio/diagnóstico , Estudios Prospectivos , Mejoramiento de la Calidad/estadística & datos numéricos , Sistema de Registros/estadística & datos numéricos , Población Rural/estadística & datos numéricos , Taiwán/epidemiología , Tiempo de Tratamiento/normas , Población Urbana/estadística & datos numéricos
20.
Circ J ; 2013 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-23778183

RESUMEN

Background: Renal dysfunction is associated with a higher rate of atrial fibrillation in clinical practice. This study investigated the associations between renal function, left ventricular (LV) diastolic dysfunction, and postoperative atrial fibrillation (POAF). Methods and Results: A total of 265 consecutive patients who underwent cardiac surgery were prospectively enrolled in the study. Echocardiography was performed before cardiac surgery. The patients were divided into 3 groups based on estimated glomerular filtration rate (eGFR) (group 1, ≥90ml·min-1·1.73m-2; group 2, 60-90ml·min-1·1.73m-2; and group 3, <60ml·min-1·1.73m-2). POAF occurred in 83 of 265 patients (31.3%). The rate of new-onset POAF increased from 15.2% (12/79) in group 1 to 27.8% (27/97) in group 2 and 49.4% (44/89) in group 3 (P<0.001). Further, with increasing renal dysfunction from groups 1 to 3, the rate of LV diastolic dysfunction - defined as E/e' >15 - also increased (group 1, 19.0%; group 2, 38.1%; and group 3, 48.3%; P<0.001). Absolute eGFR was significantly correlated with E/e' ratio (r=-0.39, P<0.001). Renal function remained as the independent predictor of POAF on multivariate analysis (odds ratio, 1.90; 95% confidence interval: 1.26-2.87; P=0.002). Conclusions: In patients undergoing cardiac surgery, decreased eGFR was associated with an increased rate of LV diastolic dysfunction with a subsequent increase in the rate of POAF.

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