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1.
J Hazard Mater ; 386: 121636, 2020 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-31753671

RESUMO

The elimination mechanisms and the dynamics of 2,5-dimethylbenzoquinone/2,6-dimethylbenzoquinone are performed by DFT under the presence of ·OH radical and TiO2-clusters. The rate coefficients, calculated within the atmospheric and combustion temperature range of 200-2000 K, agree well with the experimental data. The subsequent reactions including the bond cleavage of quinone ring, O2 addition or abstraction, the reactions of peroxy radical with NO yielding the precursor of organic aerosol are studied. Gaseous water molecule plays an important role in the transformation of alkoxy radical and exhibits a catalytic performance in the enol-ketone tautomerism. The lifetimes of 2,5-dimethylbenzoquinone/2,6-dimethylbenzoquinone are about 12.04-12.86 h at 298 K, which are in favor of the medium range transport of them in the atmosphere. Significantly, the water environment plays a negative role on the ·OH-degradation of dimethylbenzoquinone. Compared to the quinone ring, 2,5-dimethylbenzoquinone onto (TiO2)n clusters (n = 1-6) is easier to be absorbed by TiO2-clusters through its oxygen site because of its strong chemisorption, which indicates that TiO2-clusters are capable of trapping dimethylbenzoquinones effectively. The water environment could weaken the adsorption of 2,5-dimethylbenzoquinone onto (TiO2)n clusters (n = 1-6) by increasing the adsorption energy. This work reveals the removal of dimethylbenzoquinones and the formation of organic aerosol under polluted environments.

2.
Sci Total Environ ; 699: 134190, 2020 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-31670037

RESUMO

The initial reactions of organics with •OH are important to understand their transformations and fates in advanced oxidation processes in aqueous phase. Herein, the kinetics and mechanism of •OH-initiated degradation of ciprofloxacin (CIP), an antibiotic of fluoroquinolone class, are obtained using density functional and computational kinetics methods. All feasible mechanisms are considered, including H-abstraction, •OH-addition, and sequential electron proton transfer. Results showed that the H-abstraction is the dominant reaction pathway, and the product radicals P7H, P9H, and P10H are the dominating intermediates. The aqueous phase rate coefficients for the •OH-triggered reaction of ciprofloxacin are calculated from 273 K to 323 K to examine the temperature dependent effect, and the theoretical value of 6.07 × 109 M-1 s-1 at 298 K is close to the corresponding experimental data. Moreover, the intermediates P7H, P9H, and P10H could easily transform to several stable products in the presence of O2, HO2•, and •OH. The peroxy radical, which is generated from the incorporation of H-abstraction product radicals (P7H, P9H, and P10H) with O2, prefers to produce HO2• into the surrounding through direct concerted elimination rather than the indirect mechanism. In addition, the peroxy radical could react with HO2• via triplet and singlet routes, and the former is more favorable due to its smaller barrier compared with the latter. The hydroxyl-substituted CIP has higher activity than its parent compound in their reactions with •OH due to its lower barrier and faster rate. In addition, the -NHC(O)-containing compound IM3-P10-H-4 is harmful to aquatic fish and is the primary product in the •OH-rich environment according to the ecotoxicity assessment computations. This study can improve our comprehension on CIP transformation in complex water environments.

3.
Phys Chem Chem Phys ; 21(31): 17378-17392, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31355843

RESUMO

The oxidation mechanisms and dynamics of 3-methoxy-3-methyl-1-butanol (3M3M1B) initiated by ˙OH radicals were assessed by the density functional theory and canonical variational transition state theory. The effects of ubiquitous water on the title reactions were analyzed by utilizing an implicit solvation model in the present system. The results suggested that aqueous water played a negative role in the ˙OH-initiated degradation of 3M3M1B with an increase in the Gibbs free barriers. Meanwhile, the barriers were almost independent when explicit water molecules were involved in the gaseous phase, which could reduce the rate constant by approximately 3 orders of magnitude. The kinetic calculations showed that the rate constants were smaller by about 15, 9, 8, and 8 orders of magnitude for hydroxyl-, ammonia-, formic acid-, and sulfur acid-participating reactions, respectively, than that from an unassisted reaction. The results indicated that water, hydroxyl, ammonia, formic acid, or sulfur acid could not facilitate the title reaction when performed in the atmosphere. The investigations of the subsequent oxidation processes of the alkyl radical CH3OC(CH3)2CH2C·HOH indicated that CH3OC(CH3)2CH2CHO was the most favorable product by eliminating an HO2˙ radical. Additionally, the HO2˙ radical could serve as a self-catalyst to affect the above reaction through a double proton transfer process. With the introduction of NO, CH3OC(CH3)2CH2COOH and HNO2 were found to be the main products, which may be regarded as the new source of atmospheric nitrous acid. In the NO2-rich environment, the peroxynitrate of CH3OC(CH3)2CH2CH(OONO2)OH could be formed via the reaction of the CH3OC(CH3)2CH2CH(OO˙)OH radical with NO2. The degradation mechanism of CH3OC(CH3)2CH2CH(OONO2)OH in the presence of water, ammonia, and methylamine was demonstrated, and it was shown that water, ammonia, and methylamine could promote the formation of nitric hydrate and nitrate aerosol. The main species detected in the experiment were confirmed by a theoretical study. The atmospheric lifetimes of 3M3M1B in the temperature range of 217-298 K and altitude of 0-12 km were within the range of 6.83-8.64 h. This study provides insights into the transformation of 3M3M1B in a complex environment.

4.
Chemosphere ; 229: 374-382, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31078895

RESUMO

Recently, UV/peroxymonosulfate (PMS) seems as a panacea for the treatment of recalcitrant organic pollutants; however, the presence of high concentration of chloride in saline wastewater indeed complicates this end-of-pipe technology. Here a negative case of UV/PMS for the treatment of one of secondary degradation byproducts of dyes (coumarin, COU) is demonstrated. The removal rate of COU is reduced by addition of Cl- (0-10 mM). Further increase in Cl- content favors a rapid COU degradation, whereas Cl- involvement seems to open a "Pandora's box": 1) a variety of chlorinated organic intermediates such as 4-chloroisocoumarin and 5-chloro-2-hydroxy-benzaldehyde are identified; 2) Accumulation and relative increase of absorbable organic halogen (AOX) with reaction time in the presence of high levels of chloride are observed; 3) the acute toxicity of the treated COU solution increases; 4) mineralization rate of COU decreases with the increasing [Cl-]. The fluorescence intensity in the UV/PMS/COU system declines with the addition of Cl-, implying the scavenging effects of chloride on hydroxyl radicals. The possible reaction pathways of COU are discussed. These findings highlight the imperativeness of minimizing auxiliary salt dosages in dyeing processes (i.e., source reduction) and developing new end-of-pipe technologies that can work in a saline environment.


Assuntos
Cloro/química , Corantes/química , Cumarínicos/química , Peróxidos/química , Águas Residuárias/química , Halogenação , Cloreto de Sódio , Raios Ultravioleta , Poluentes Químicos da Água/química
5.
Graefes Arch Clin Exp Ophthalmol ; 257(7): 1473-1480, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31079203

RESUMO

PURPOSE: To compare the anatomical effects on anterior segment by lens extraction (LE, phacoemulsification with posterior chamber intraocular lens implantation) and laser peripheral iridotomy (LPI) in primary angle closure suspect (PACS) eyes. METHODS: This prospective comparative cohort trial included a total of 122 consecutive patients identified as PACS aged 52 to 80 years. LE or LPI was performed based on each patient's choice. The anterior segment optical coherence tomography (ASOCT) and gonioscopy were conducted at baseline and 4 weeks post-operation. Outcome measures include percentage of residual angle closure, mean angle width (modified Shaffer grade), angle opening distance (AOD), trabecular iris angle (TIA), trabecular iris space area (TISA), anterior chamber depth (ACD), iris curvature (I-Curve), lens vault (LV), intraocular pressure (IOP), and best-corrected visual acuity (BCVA). RESULTS: All anterior angle parameters (AOD, TIA, and TISA) were significantly greater after LE than LPI (P < 0.001 for all). ACD (P < 0.001) increased, LV (P < 0.001) decreased, IOP (P < 0.001) decreased, and BCVA (P < 0.001) increased after LE. However, no significant changes were found in ACD (P = 0.782), LV (P = 0.616), IOP (P = 0.112), and BCVA (P = 0.131) after LPI. In both groups, I-Curve decreased after the operation, but the iris was flatter after LE than LPI (P < 0.001). Gonioscopically, the LE group achieved a larger post-operative angle width (modified Shaffer grade) than LPI (P < 0.001) and all anterior chamber angles were open (defined as posterior pigmented trabecular meshwork (PTM) visible with static gonioscopy) after operation. Nevertheless, after LPI, 12 eyes (20.0%) still had two or more quadrants and 32 eyes (53.3%) still had at least one quadrant in which the posterior PTM could not be observed. CONCLUSIONS: Compared with LPI, LE resulted in a wider anterior chamber angle, a deeper anterior chamber, and a lower IOP in PACS eyes. Moreover, no residual angle closure was observed after LE, which could morphologically prevent the progress of angle closure. TRIAL REGISTRATION: ChiCTR1800016511.


Assuntos
Segmento Anterior do Olho/diagnóstico por imagem , Glaucoma de Ângulo Fechado/cirurgia , Pressão Intraocular/fisiologia , Iridectomia/métodos , Terapia a Laser/métodos , Facoemulsificação/métodos , Tomografia de Coerência Óptica/métodos , Idoso , Idoso de 80 Anos ou mais , Feminino , Seguimentos , Glaucoma de Ângulo Fechado/diagnóstico , Glaucoma de Ângulo Fechado/fisiopatologia , Gonioscopia , Humanos , Lasers de Estado Sólido/uso terapêutico , Lentes Intraoculares , Masculino , Pessoa de Meia-Idade , Segmento Posterior do Olho , Estudos Prospectivos , Resultado do Tratamento , Acuidade Visual
6.
BMC Ophthalmol ; 19(1): 94, 2019 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-31014258

RESUMO

BACKGROUND: The exact pathogenesis of idiopathic choroidal neovascularization (ICNV) remains unclear. Cytokine-mediated inflammation has been thought to be involved in the pathophysiology of ICNV. The purpose of this study was to investigate serum cytokine profiles in patients with ICNV and to explore the relationship between serum cytokine levels and ICNV severity. METHODS: This case-control study was conducted in 32 ICNV patients and 30 healthy volunteers. Clinical and demographic information was obtained from the medical data platform and the serum was analysed with a multiplex assay to determine the levels of seven cytokines: interleukin (IL)-2, IL-10, IL-15, IL-17, basic fibroblast growth factor (basic FGF), granulocyte-macrophage colony-stimulating factor (GM-CSF), and vascular endothelial growth factor (VEGF). RESULTS: Serum levels of IL-2, IL-10, IL-17, basic FGF, and VEGF were elevated in ICNV patients compared to controls. Serum GM-CSF levels were positively related to central retinal thickness, and serum IL-17 levels were positively related to CNV lesion area. CONCLUSION: Serum inflammatory cytokines were significantly elevated in ICNV patients compared to controls. This suggests that systemic inflammation may play a critical role in the physiopathology of ICNV.


Assuntos
Neovascularização de Coroide/sangue , Citocinas/sangue , Adulto , Biomarcadores/sangue , Estudos de Casos e Controles , Neovascularização de Coroide/fisiopatologia , Feminino , Humanos , Inflamação/fisiopatologia , Masculino , Pessoa de Meia-Idade , Retina/patologia , Acuidade Visual/fisiologia
7.
Environ Sci Pollut Res Int ; 26(3): 2345-2352, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30467745

RESUMO

Using quantum chemistry methods, mechanisms and products of the CHBr2O2 + HO2 reaction in the atmosphere were investigated theoretically. Computational result indicates that the dominant product is CHBr2OOH + O2 formed on the triplet potential energy surface (PES). While CBr2O + OH + HO2 produced on the singlet PES is subdominant to the overall reaction under the typical atmospheric condition below 300 K. Due to higher energy barriers surmounted, other products including CBr2O2 + H2O2, CBr2O + HO3H, CH2O + HO3Br, CHBrO + HO3 + Br, and CHBr2OH + O3 make minor contributions to the overall reaction. In the presence of OH radical, CHBr2OOH generates CHBr2O2 and CBr2O2 + H2O subsequently, which enters into new Br-cycle in the atmosphere. The substitution effect of alkyl group and halogens plays negligible roles to the dominant products in the RO2 + HO2 (X = H, CH3, CH2OH, CH2F, CH2Cl, CH2Br, CH2Cl, and CH2Br) reactions in the atmosphere.


Assuntos
Atmosfera/química , Radicais Livres/química , Halogênios/química , Modelos Químicos , Brometos/química , Ozônio , Trialometanos/química
8.
Environ Sci Pollut Res Int ; 25(25): 24939-24950, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-29931646

RESUMO

The hydroxyl radical, as the most important oxidant, controls the removal of some volatile organic compounds (VOCs) in the atmosphere. In this work, the atmospheric oxidation processes of acrylic acid by OH radical have been investigated by density functional theory (DFT). The energetic routes of the reaction of CH2CHCOOH with OH radical have been calculated accurately at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level. It is implicated that the oxidation has five elementary reaction pathways mostly hinging on how hydroxyl radical approaches to the carbon skeleton of acrylic acid. The atmospheric degradation mechanisms of the CH2CHCOOH by OH radical are the formation of reactive intermediates IM1 and IM2. Meanwhile, the further oxidation mechanisms of IM1 and IM2 by O3 and NO are also investigated. The rate coefficients have been computed using tight transition state theory of the variflex code. The calculated rate coefficient is 2.3 × 10-11 cm3 molecule-1 s-1 at standard pressure and 298 K, which is very close to the laboratory data (1.75 ± 0.47 × 10-11 cm3 molecule-1 s-1). Moreover, the atmospheric lifetime of acrylic acid is about 6 h at 298 K and 1 atm, implying that the fast sinks of acrylic acid by hydroxyl radical.


Assuntos
Acrilatos/química , Atmosfera/química , Radical Hidroxila/química , Teoria Quântica , Cinética , Oxirredução
9.
Molecules ; 23(6)2018 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-29799497

RESUMO

In this work, feasible mechanisms and pathways of the C2H5O2 + BrO reaction in the atmosphere were investigated using quantum chemistry methods, i.e., QCISD(T)/6-311++G(2df,2p)//B3LYP/6-311++G(2df,2p) levels of theory. Our result indicates that the title reaction occurs on both the singlet and triplet potential energy surfaces (PESs). Kinetically, singlet C2H5O3Br and C2H5O2BrO were dominant products under the atmospheric conditions below 300 K. CH3CHO2 + HOBr, CH3CHO + HOBrO, and CH3CHO + HBrO2 are feasible to a certain extent thermodynamically. Because of high energy barriers, all products formed on the triplet PES are negligible. Moreover, time-dependent density functional theory (TDDFT) calculation implies that C2H5O3Br and C2H5O2BrO will photolyze under the sunlight.


Assuntos
Atmosfera/química , Compostos de Bromo/química , Etilenoglicol/química , Óxidos/química , Cinética , Fotólise , Teoria Quântica , Luz Solar , Termodinâmica
10.
Chemosphere ; 197: 367-374, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29407807

RESUMO

This study reports that the redox reactions between weak electron donors and Cr(VI) can be significantly accelerated by many environmentally occurring or industrially produced polycarboxylates (PolyCAs). The results demonstrate that oxalic acid (OA) can act as a redox mediator to accelerate the reduction of Cr(VI) by As(III) in pH range of 2.0-5.0, as well as a reductant donating electron for Cr(VI) reduction at pH < 4.0. Density functional theory calculation results indicate that the coordination of OA with Cr(VI) can remarkably enhance the reactivity of the CrO bond in HCrO4- toward oxygen atom transfer or the protonation of oxo groups during Cr(VI) reduction. Moreover, the ligand field effect can also cause instability in the tetrahedral Cr(VI) species, which probably lowers the reaction barrier in the transformation of tetrahedral Cr(VI) to octahedral Cr(III), and therefore favors the reduction of Cr(VI) to Cr(III). Similar to OA, other aliphatic and amino PolyCAs can also accelerate the reduction of Cr(VI), which depends significantly on both the electron transfer capabilities of PolyCAs and their abilities to coordinate chromium species. In general, our findings indicate the novel effect of the interplay between PolyCAs and chromium species on Cr(VI) reduction and provide significant information to develop remediation strategies for Cr(VI) contamination.


Assuntos
Cromo/química , Oxalatos/química , Espectroscopia de Ressonância de Spin Eletrônica , Transporte de Elétrons , Elétrons , Concentração de Íons de Hidrogênio , Oxirredução , Oxigênio/química
11.
J Hazard Mater ; 343: 1-9, 2018 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-28934687

RESUMO

The reductive detoxification of Cr(VI) by sulfite is known as the prevailing strategy and can be successfully implemented for the treatment of Cr(VI)-contaminated waters. However, this method inevitably faces the challenges of excessive consumption of sulfite due to the generations of highly oxidative OH and SO4- during the process of sulfite reducing Cr(VI). In this study, we find that a small quantity of thiocyanate (SCN) can catalytically enhance the process efficiency of Cr(VI) reduction by sulfite and effectively prevent the excessive consumption of sulfite. Specifically, when adding 5µM SCN into 100µM Cr(VI) + 600µM sulfite reaction system at pH 3.5, Cr(VI) reduction amount and [sulfite]oxidation/[Cr(VI)]reduction ratio value were approximately 2 and 0.45, respectively, times those in the SCN-free case. The maximum Cr(VI) reduction amount can be achieved at an initial [SCN]/[Cr(VI)] molar ratio of 2.0. Electron spin resonance measurement, combined with the fluorescence spectrum detection, verified that the process of sulfite reducing Cr(VI) mediated by SCN probably proceeds via the non-radical pathway, avoiding the formation of OH and SO4- under aerobic condition.

12.
Sci Rep ; 7(1): 14128, 2017 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-29074989

RESUMO

Corneal endothelium morphological abnormalities result in fluid imbalance, stromal swelling, and loss of transparency, thus impairing visual function. Recently, growing number of studies have focused on diabetic corneal abnormalities after cataract surgery and its comparison with non-diabetic patients, the results remain conflicting. Thus, to evaluate the effect of phacoemulsification on the corneal properties in diabetic and non-diabetic patients, prospective studies were comprehensively searched through PubMed, EMBASE, and Cochrane databases updated to Jan 2017. A meta-analysis of the 13 identified studies was performed using weighted mean difference (WMD) and 95% confidence interval (CI). For the dynamic changes between preoperative and postoperative values, significant differences were identified between the two groups in endothelial cell density (ECD) and hexagon cells (HC%) at 1 day, 1 week, 1 month, and 3 months postoperatively, in central corneal thickness (CCT) at 1 month postoperatively, and in coefficient variation (CV) at 1 week and 1 month postoperatively. However, no significant differences were observed in CCT at 1 day, 1 week and 3 months postoperatively or in CV at 1 day and 3 months postoperatively. Diabetic corneas are more vulnerable to stress and trauma, resulting in greater morphological abnormalities and longer recovery time.


Assuntos
Catarata/tratamento farmacológico , Catarata/patologia , Córnea/efeitos dos fármacos , Córnea/patologia , Complicações do Diabetes/tratamento farmacológico , Complicações do Diabetes/patologia , Emulsões , Humanos
13.
J Phys Chem A ; 121(26): 5045-5055, 2017 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-28587451

RESUMO

Methyl iodine (CH3I) and carbon tetrachloride (CCl4) are both important volatile precursors for atmospheric ozone destruction. CH3I and CCl4 can act as halogen bond donors to form molecular complexes with atmospheric organic species, such as 2,5-dihydrofuran, tetrahydrofuran, and acetone. This study characterized the halogen bonds in the CH3I and CCl4 complexes using matrix isolation infrared spectroscopy and density functional theory calculations. With the combination of vibrational frequencies in spectra and the calculated interaction energies, frequencies and atoms-in-molecules analyses, we confirmed the formation of halogen-bonded complexes. CH3I as a halogen-bond donor is comparable or slightly weaker than CCl4, and furans involving ether oxygens are better halogen acceptors than acetone. The results help to understand the possibilities of formation of atmospheric molecular complexes that may influence the atmospheric chemical activities and enhance the aerosol formation.

14.
J Mol Graph Model ; 76: 521-534, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28629707

RESUMO

Catalytic dehydration and dehydrogenation reactions of ethanol have been investigated systematically using the ab initio quantum chemistry methods The catalysts include water, hydrogen peroxide, formic acid, phosphoric acid, hydrogen fluoride, ammonia, and ethanol itself. Moreover, a few clusters of water and ethanol were considered to simulate the catalytic mechanisms in supercritical water and supercritical ethanol. The barriers for both dehydration and dehydrogenation can be reduced significantly in the presence of the catalysts. It is revealed that the selectivity of the catalytic dehydration and dehydrogenation depends on the acidity and basicity of the catalysts and the sizes of the clusters. The acidic catalyst prefers dehydration while the basic catalysts tend to promote dehydrogenation more effectively. The calculated water-dimer catalysis mechanism supports the experimental results of the selective oxidation of ethanol in the supercritical water. It is suggested that the solvent- and catalyst-free self-oxidation of the supercritical ethanol could be an important mechanism for the selective dehydrogenation of ethanol on the theoretical point of view.


Assuntos
Etanol/química , Modelos Teóricos , Oxirredução , Água/química , Algoritmos , Catálise , Hidrogênio , Cinética , Modelos Moleculares
15.
Chemosphere ; 111: 545-53, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-24997964

RESUMO

Mechanisms for the atmospheric degradation reaction of BrCH2O2+HO2 were investigated using quantum chemistry methods. The result indicates that the dominant product is BrCH2OOH+O2((3)Σ). While CH2O+HBr+O3, BrCHO+OH+HO2 and CH2O+Br+HO3 will be competitive to a certain extent in the atmosphere. Meanwhile, the nascent product - BrCH2OOH reacts easily with OH radicals leading to BrCH2O2 again under the atmospheric conditions. Moreover, OH radicals could act as a catalyst in the net reaction of BrCH2OOH→BrCHO+H2O. Thus the proposed product BrCHO+H2O+O2 in the experiment might be generated from the subsequent reaction of BrCH2OOH with extra OH radicals. Comparisons indicate that halogen substitution effect makes minor contributions to the XCH2O2 (X=H, F, Cl and Br)+HO2 reactions in the atmosphere.


Assuntos
Atmosfera/química , Hidrocarbonetos Bromados/química , Radical Hidroxila/química , Modelos Moleculares , Oxigênio/química , Água/química
16.
J Comput Chem ; 35(22): 1646-56, 2014 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-24995629

RESUMO

The reaction of propargyl alcohol with hydroxyl radical has been studied extensively at CCSD(T)/aug-cc-pVTZ//MP2/cc-pVTZ level. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. Two reaction mechanisms were revealed, namely addition/elimination and hydrogen abstraction mechanism. The reaction mechanism confirms that OH addition to C≡C triple bond forms the chemically activated adducts, IM1 (·CHCOHCH2OH) and IM2 (CHOH·CCH2OH), and the hydrogen abstraction pathways (-CH2OH bonded to the carbon atom and alcohol hydrogen) may occur via low barriers. Harmonic model of Rice-Ramsperger-Kassel-Marcus theory and variational transition state theory are used to calculate the overall and individual rate constants over a wide range of temperatures and pressures. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with Ar as bath gas, IM1 (·CHCOHCH2OH) and IM2 (CHOH·CCH2OH) formed by collisional stabilization are dominant in the low temperature range. The production of CHCCHOH + H2O via hydrogen abstraction becomes dominate at higher temperature. The fraction of IM3 (CH2COHCH2·O) is very significant over the moderate temperature range.


Assuntos
Alquinos/química , Gases/química , Radical Hidroxila/química , Modelos Químicos , Propanóis/química
17.
J Phys Chem A ; 118(28): 5279-88, 2014 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-24949666

RESUMO

Quantum chemical methods were used to investigate the OH initiated atmospheric degradation of methanimine, CH2═NH, the major primary product in the atmospheric photo-oxidation of methylamine, CH3NH2. Energies of stationary points on potential energy surfaces of reaction were calculated using multireference perturbation theory and coupled cluster theory. The results show that hydrogen abstraction dominates over the addition route in the CH2═NH + OH reaction, and that the major primary product is HCN, while HNC and CHONH2 are minor primary products. HNC is found to react with OH exclusively via addition to the carbon atom followed by O-H scission leading to HNCO; N2O is not a product in the atmospheric photo-oxidation of HNC. Additional G4 calculations of the CH2═NH + O3 reaction show that this is too slow to be of importance at atmospheric conditions. Rate coefficients for the CH2═NH + OH and HNC + OH reactions were calculated as a function of temperature and pressure using a master equation model based on the coupled cluster theory results. The rate coefficients for OH reaction with CH2═NH and HNC at 1000 mbar and room temperature are calculated to be 3.0 × 10(-12) and 1.3 × 10(-11) cm(3) molecule(-1) s(-1), respectively. The atmospheric fate of CH2═NH is discussed and a gas phase photo-oxidation mechanism is presented.

18.
J Phys Chem A ; 118(19): 3450-62, 2014 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-24766577

RESUMO

The rates of CH3NHNO2 and (CH3)2NNO2 reaction with OH radicals were determined relative to CH3OCH3 and CH3OH at 298 ± 2 K and 1013 ± 10 hPa in purified air by long path FTIR spectroscopy, and the rate coefficients were determined to be k(OH+CH3NHNO2) = (9.5 ± 1.9) × 10(-13) and k(OH+(CH3)2NNO2) = (3.5 ± 0.7) × 10(-12) (2σ) cm(3) molecule(-1) s(-1). Ozone was found to react very slowly with the two nitramines, k(O3+nitramine) < 10(-21) cm(3) molecule(-1) s(-1). Product formation in the photo-oxidation of CH3NHNO2 and (CH3)2NNO2 was studied by FTIR, PTR-ToF-MS, and quantum chemistry calculations; the major products in the OH-initiated degradation are the corresponding imines, CH2═NH and CH3N═CH2, and N-nitro amides, CHONHNO2 and CHON(CH3)NO2. Atmospheric degradation mechanisms are presented.


Assuntos
Compostos de Anilina/química , Atmosfera/química , Dimetilaminas/química , Radical Hidroxila/química , Metilaminas/química , Nitrobenzenos/química , Teoria Quântica , Ozônio/química
19.
Phys Chem Chem Phys ; 15(16): 5936-44, 2013 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-23493819

RESUMO

The mechanisms and reaction pathways for the CF3O2 + IO reaction have been investigated by quantum chemistry methods. It has been found that the title reaction takes place on both the singlet and triplet potential energy surfaces (PES). On the singlet PES, the most important products include CF3OOOI, CF3OOIO, CF3OIO2, and CF2O + FIO2, while other products such as CF2O + FOIO, CF2O + FOOI, CF3OOI + O((3)P), CF3OI + O2 ((1)Δ and (3)Σ), and CF3O + OIO are negligible due to high barriers or unstable formations. On the triplet PES, CF3O + OIO is the dominant product with a lower barrier. As for FIO2 and it isomers, the most stable one is FIO2. TDDFT (Time Dependent Density Functional Theory) calculation indicates that CF3OOOI, CF3OOIO and CF3OIO2 undergo photolysis easily under sunlight. Moreover, a minor contribution relative to hydrogen is found in the CX3O2 + IO (X = H and F) reactions.

20.
J Phys Chem A ; 117(1): 126-32, 2013 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-23186368

RESUMO

The reactions of CH(3)CH(2)NH and (CH(3)CH(2))(2)N radicals with NO have been studied using quantum chemistry methods. The results show that formation of the nitrosamines CH(3)CH(2)NHNO and (CH(3)CH(2))(2)NNO is similar and that both isolated molecules are thermally stable. The nitrosamine formation reaction is highly exothermic, and the hot CH(3)CH(2)NHNO may undergo isomerization and subsequent reaction with O(2) to form the corresponding imine, CH(3)CH═NH. Time-dependent density functional theory (TDDFT) calculations show little difference of the vertical excitation energy between the π* ← n transitions in CH(3)CH(2)NHNO and (CH(3)CH(2))(2)NNO, and both will readily photolyze under sunlight conditions.

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