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1.
Experimental studies have been conducted to determine the rate coefficient and mechanism of the reaction between methylglyoxal (CH(3)COCHO, MGLY) and the OH radical over a wide range of temperatures (233-500 K) and pressures (5-300 Torr). The rate coefficient is pressure independent with the following temperature dependence: k(3)(T) = (1.83 +/- 0.48) x 10(-12) exp((560 +/- 70)/T) cm(3) molecule(-1) s(-1) (95% uncertainties). Addition of O(2) to the system leads to recycling of OH. The mechanism was investigated by varying the experimental conditions ([O(2)], [MGLY], temperature and pressure), and by modelling based on a G3X potential energy surface, rovibrational prior distribution calculations and master equation RRKM calculations. The mechanism can be described as follows: Addition of oxygen to the system shows that process (4) is fast and that CH(3)COCO completely dissociates. The acetyl radical formed from reaction (4) reacts with oxygen to regenerate OH radicals (5a). However, a significant fraction of acetyl radical formed by reaction (R4) is sufficiently energised to dissociate further to CH(3) + CO (R4b). Little or no pressure quenching of reaction (R4b) was observed. The rate coefficient for OD + MGLY was measured as k(9)(T) = (9.4 +/- 2.4) x 10(-13) exp((780 +/- 70)/T) cm(3) molecule(-1) s(-1) over the temperature range 233-500 K. The reaction shows a noticeable inverse (k(H)/k(D) < 1) kinetic isotope effect below room temperature and a slight normal kinetic isotope effect (k(H)/k(D) > 1) at high temperature. The potential atmospheric implications of this work are discussed.  相似文献   

2.
推荐了一个大学化学综合实验"9-(4-溴丁基)-9H-咔唑的相转移催化合成、表征及室温磷光性能研究"。实验利用相转移催化合成9-(4-溴丁基)-9H-咔唑分子,采用核磁共振、高分辨质谱和红外光谱对其分子结构进行表征,并利用紫外-可见吸收光谱、稳态/瞬态荧光光谱和密度泛函(DFT)理论计算对其室温磷光性能进行研究。本综合实验涵盖了有机化学、分析化学、物理化学、仪器分析以及理论化学的知识点,建议纳入化学专业高年级综合实验课程。  相似文献   

3.
Two photoproducts of DNA damage, i.e. cyclobutane pyrimidine dimers (CPDs) and 6-4 photoproducts (6-4PPs), induced by UV-B radiation in suspension-cultured tobacco cells were quantified by enzyme-linked immunosorbent assay (ELISA) with monoclonal antibodies. CPDs and 6-4PPs were induced in tobacco cells by UV-B radiation. Photorepair of CPDs was faster than that of 6-4PPs. UV-B radiation induces formation of CPDs and 6-4PPs even at 0 degrees C, but low temperature significantly decreases the UV-B-induced (in contrast to UV-C-induced) formation of CPDs and 6-4PPs. Low temperature also retarded the removal of CPDs and 6-4PPs under white light, and almost no photorepair of CPDs and 6-4PPs was detected at 0 degrees C. When purified DNA from tobacco cells grown in darkness was irradiated with UV-B, formation of CPDs and 6-4PPs took place at the same speed at different temperatures. It indicated that formation of CPDs and 6-4PPs induced by UV-B was temperature-independent in a non-cellular system. Based on our results for suspension-cultured tobacco cells, not only the photorepair but also UV-B-induced formation of CPDs and 6-4PPs are temperature-dependent.  相似文献   

4.
The solid-phase extraction (SPE) method for the preconcentration of trace amounts of cadmium using synthetic zeolite A-4 and its determination by graphite furnace atomic absorption spectrometry (GFAAS) was investigated. The preconcentration conditions, such as the optimum pH range of the sample solution for the adsorption of cadmium and the kind of acid solution for dissolving the cadmium-adsorbed synthetic zeolite A-4, as well as the measurement conditions for the determination of cadmium by GFAAS, e.g., the ashing and atomizing temperature, were investigated. Quantitative recovery of cadmium onto zeolite A-4 from the sample solution over the pH range 2.0 - 9.0 was achieved by the batch method. After the solid-phase (cadmium-adsorbed zeolite A-4) was separated from the sample solution by a membrane filter, it was dissolved in 2.0 cm(3) of 2.0 mol dm(-3) nitric acid. An aliquot of the resulting solution was injected into the graphite furnace. In GFAAS measurements an alternate gas (Ar, 90%; O(2), 10%) was used as a sheath gas, and the ashing temperature and atomizing temperature were 400 degrees C and 1600 degrees C, respectively. The detection limit (3 sigma) for cadmium was 0.002 microg dm(-3). The relative standard deviation at 0.010 microg dm(-3) was 3.5 - 4.5% (n = 5). The proposed method has been successfully applied to the analysis of trace cadmium in environmental water samples.  相似文献   

5.
Using a recently-developed chemiluminescence technique for monitoring O(1D), the rate coefficient, k1, of the important atmospheric reaction O(1D) + CH4 --> products has been determined over a wide temperature range, 227 to 450 K. The rate coefficient was shown to be independent of temperature, having a value of (1.91 +/- 0.08) x 10(-10) cm3 s(-1); the quoted uncertainties are with 95% confidence. This highly precise value, based on an extended set of determinations with very low scatter, is significantly greater, 26%, than current recommended values. Secondly, the fraction of O(1D) quenched to O(3P) by CH4, k(1q)/k1, was precisely determined from chemiluminescence decays over the temperature range 236 to 340 K. A temperature independent value for k(1q)/k1 of 0.002 +/- 0.003 was found. Finally, LIF detection of OH has been applied to accurately determine the product branching fraction to OH of O(1D) + CH4 at room temperature. Our value, k(1a)/k1 = 0.76 +/- 0.08 (95% confidence), is in line with recent determinations by other groups.  相似文献   

6.
The Synthesis of 3,3′-bis(4-[3-ethynylphenoxy]phenyl)-7,7′-bis(phenylethynyl)-2,2′-diphenyl-6,6′-biquinoxaline (I) was accomplished by the reaction of 2,2′-bis(phenylethynyl)-5,5′-diaminobenzidine (II) and 4-(3-ethynylphenoxy)benzil. Thermal analysis of I indicated a softening temperature of 107°C, followed by an exotherm above 150°C that corresponded to a independent crosslinking reaction of the terminal acetylene groups and an intramolecular cycloaddition (IMC) reaction of the 2,2′-bis(phenylethynyl)biphenyl moieties. In the synthetic work substantial improvements were made in the synthesis of II. The sample of I was cured at 200°C and the maximum partially cured transition temperature attained was 280°C. A sample of 3,3′-bis(4,[3-ethynylphenoxy]phenyl)-2,2′-diphenyl-6,6′-biquinoxaline (IV) was similarly tested as a model without IMC capability and its corresponding value was 250°C. The difference between these two values is discussed briefly.  相似文献   

7.
为解决非线性光学活性有机分子透明性差及熔点低的问题,设计合成了2-(4-N-硝基,N-甲基氨基苯基)-(4-硝基苯基)-5-(2,4,6-三硝基苯基)噻唑化合物,并研究了其热性能及光学性质。根据实验结果得出由于杂环的引入,提高了化合物的裂解温度,并较好地改善了有机分子的透明性。  相似文献   

8.
异丁烷高温热解反应动力学和机理   总被引:2,自引:0,他引:2  
用激波管激光纹影技术测定了异丁烷高温热解反应信号,对热解过程中重要单分子反应的降变行为作了理论计算,建立了由五十个基元反应组成的反应机理并进行了计算机模拟,本文得到引发反应i-C_4H_(10)→CH_3+i-C_3H_7在温度为1500-1850 K,压1.00×10~4-2.00×10~4 Pa时的速率常数为k_1=6.22×10~(11) exp(-457000/RT)±50%(S~(-1)).这一结果与降变理论计算符合得很好.  相似文献   

9.
Soluble aromatic polyamides containing phthalazinone moieties were prepared. Those polymers were obtained from the solution polymerization of a new diacid containing phthalazinone moieties with various diamines. The new monomer, 2-(4-carboxyphenyl)-4-(4-carboxyphenoxy)phenyl-1(2H)phthalazinone(Ⅳ) was synthesized in a two-step reaction sequence. 2-(4-Cyanophenyl)-4-(4-cyanophenoxy)phenyl-1(2H)phthalazinone (Ⅲ) was prepared via the condensation reaction of 4-(4-hydroxyphenyl)-1(2H)phthalazinone (Ⅰ) with p-chlorobenzonitrile (Ⅱ). After (Ⅲ) was hydrolyzed, (Ⅳ) was acquired. The synthesized polyamides were characterized by means of viscosimetry, DSC, FT-IR, 1H NMR and EA. The polyamides have a high glass transition temperature which can be as high as 316 ℃. The polyamides also have good solubilities in some organic solvents.  相似文献   

10.
彭红  龚跃法 《有机化学》2004,24(5):516-520
报道了以苯酚和三氟丙酮酸乙酯为起始原料,在温和条件下合成高产率的2-(4-羟基苯基)-3,3,3-三氟丙酸乙酯的一条新途径.该途径包括无水碳酸钾催化的苯酚与三氟丙酮酸乙酯间的亲电取代反应、由此形成的产物的选择性侧连羟基的氯代反应和随后的硼氢化钠还原反应.  相似文献   

11.
Dimethytin(IV) S(+)-2-(4-isobutylphenyl)propanoate was synthesized and characterized by elemental analysis and IR and variable temperature NMR spectroscopy. Variable temperature NMR analysis was performed to see the effect of temperature on coordination geometry of organotin complexes in non-coordinating solvent. Spectral data has shown that temperature change does not alter the coordination geometry of the complex, and that it remains greater than four at variable temperatures as well as at room temperature in solution state. This text was submitted by the authors in English.  相似文献   

12.
Wang X  Huang Q  Deng J  Yu R  Chen J  Xing X 《Inorganic chemistry》2011,50(6):2685-2690
Two phase transformations of TaVO(5) were observed by DSC and/or dilatometry measurements in the studied temperature range. X-ray diffraction and neutron powder diffraction structure refinements indicated a phase transformation at -14 °C from a monoclinic symmetry with space group P2(1)/c to an orthorhombic symmetry with space group Pnma above this temperature. The rigid TaO(6) octahedron in orthorhombic phase becomes nonregular at -14 °C, which results in the transition from Pnma to P2(1)/c. TaVO(5) was found to be a negative thermal expansion material above room temperature. The calculated volumetric thermal expansion coefficients (TECs) are -8.92 × 10(-6) °C(-1) in the range of 20-600 °C, and -2.19 × 10(-5) °C(-1) above 600 °C, respectively. The negative thermal expansion behavior is accounted for by the tilt of the TaO(6) and VO(4) polyhedra, where the shrinkage of the VO(4) tetrahedra result in the increase of Ta-O-V angles on heating, while the angle of Ta-O1-Ta maintains at 180° in the framework.  相似文献   

13.
New measurements have been made of rate constants for electron attachment to c-C(4)F(8) (octafluorocyclobutane) and thermal electron detachment from the parent anion, c-C(4)F(8) (-), over the temperature range 298-400 K in 133 Pa of He gas in a flowing-afterglow Langmuir-probe apparatus. From these data the electron affinity for c-C(4)F(8) was determined, EA(c-C(4)F(8))=0.63+/-0.05 eV. The motivation was to resolve a discrepancy between our earlier EA estimate and a higher value (EA=1.05+/-0.10 eV) reported from a recent experiment of Hiraoka et al. [J. Chem. Phys. 116, 7574 (2002)]. The electron attachment rate constant is 9.3+/-3.0x10(-9) cm(3) s(-1) at 298 K. The electron detachment rate constant is negligible at room temperature but climbs to 1945+/-680 s(-1) at 400 K. G3(MP2) calculations were carried out for the neutral (D(2d), (1)A(1)) and anion (D(4h), (2)A(2u)) and yielded EA(c-C(4)F(8) (-))=0.595 eV. Bond energies were also calculated for loss of F from c-C(4)F(8) and loss of F or F(-) from c-C(4)F(8) (-). From these, dissociative electron attachment is found to be endothermic by at least 1.55 eV.  相似文献   

14.
A new dialdehyde 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane (BBMPC) was synthesized starting from cyclopentanone and O-cresol to give 1,1-bis(4-hydroxy-3-methyl phenyl)cyclopentane (BHMPC); followed by reaction with 4-fluorobenzaldehyde in N, N-dimethyl formamide (DMF), containing anhydrous potassium carbonate. New series of poly(ether-azomethine)s were synthesized from (BBMPC) with different diamines such as 4,4′- diamino diphenyl ether (ODA); 4,4′-diaminodiphenyl methane (MDA); 4-aminophenyl sulfone (SDA); p-phenylene diamines (p-PDA), etc. in N, N’- dimethyl acetamide (DMAc) with 5 wt% LiCl by the solution polycondensation method. Inherent viscosities of these polymers were in the range 0.20 to 0.38 dL/g indicating formation of moderate molecular weights. These polymers exhibited good solubility in various polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), DMAc, DMF, etc. However some polymers showed partial solubility in DMF and DMAc. X-Ray diffraction pattern of polymers showed amorphous nature. Thermal stability was assessed by 10% weight loss temperature and the degradation temperature of the resultant polymers falls in the ranges from 444-501°C in nitrogen. The glass transition temperature was in the range of 155-205°C. The structure-property correlation among these polyazomethines were studied; in view of their potential applications as high performance polymers.  相似文献   

15.
SO2-4/ZrO2/Fe3O4/Al2O3磁性固体超强酸的制备与表征   总被引:5,自引:0,他引:5  
用化学共沉淀法制备了一系列SO2-4/ZrO2/Fe3O4/Al2O3磁性固体超强酸, 利用XRD、IR、TG-DSC、VSM、TEM及HRTEM等手段对样品结构进行了表征. 结果表明, 引入一定量的Fe3O4和Al2O3有利于四方晶相ZrO2(t)结构的稳定;Fe3O4超细粒子的引入, 使固体超强酸具备了超顺磁性;HRTEM 结果显示ZrO2晶体生长趋向于ZrO2(t)的[101]方向,其(101)晶面间距为d(101)=0.29 nm, 与XRD 衍射结果一致. Hammett 指示剂测得样品SZA-20-200-800酸强度(H0<-13.8)最强, 酸性大于浓硫酸(H0=-11.9).  相似文献   

16.
The new ligand, tris(5-methylpyrazolyl)methane (1), has been prepared by the reaction of n-butyl lithium with tris(pyrazolyl)methane followed by trimethylation of the tetralithiated species with methyl iodide. The BF(4)(-), ClO(4)(-), and BPh(3)CN(-) salts of the Fe(II) complex of this ligand were also synthesized. The X-ray crystal structure of the BF(4)(-) complex (2) at 100 K had Fe-N bond lengths of 1.976 ?, indicative of a low spin Fe(II) complex, while at room temperature, the structure of this complex had a Fe-N bond distance close to 2.07 ?, indicative of an admixture of approximately 50% low-spin and 50% high-spin. The solid-state structure of the complex with a ClO(4)(-) counterion was determined at 5 different temperatures between 173 and 293 K, which allowed the thermodynamic parameters for the spin-crossover to be estimated. M?ssbauer spectra of the BF(4)(-) complex further support spin-state crossover in the solid state with a transition temperature near 300 K. UV-visible spectroscopy and (1)H NMR studies of 2 show that the transition temperature in solution is closer to 400 K. No spin-crossover was observed for [Fe(1)(2)](2+)·2BPh(3)CN(-). The results allow the separation of effects of groups in the 3-position from those in the 5-position on tpm ligands, and also point toward a small cooperative effect in the spin-crossover for the Fe(II) complex.  相似文献   

17.
A simple and rapid reversed-phase high-performance liquid-chromatographic method for the separation and determination of process-related impurities of celecoxib (CXB) in bulk drugs and pharmaceuticals was developed. The separation of impurities viz., 4-methylacetophenone (I), 1-(4-methylphenyl)-4,4,4-trifluorobutane-1,3-dione (II), 4-hydrazinobenzene sulfonamide (III) and a regio-specific isomer [3-(4-methylphenyl)-5-trifluoromethyl-1H-pyrazole-1-yl]-benzenesulfonamide (IV), was accomplished on an Inertsil ODS-3 column dynamically coated with 0.1% hexamethyldisilazane (HMDS) in acetonitrile:water (55:45 v/v) as a mobile phase and detection at 242 nm using PDA at ambient temperature. The chromatographic conditions were optimized by studying the effects of HMDS, an organic modifier, time of silanization and column temperature. The method was validated and found to be suitable not only for monitoring the synthetic reactions, but also to evaluate the quality of CXB.  相似文献   

18.
涂敷15%(wt)三(4-甲基苯甲酸)纤维素酯于大孔硅胶担体上,制备手性固定相,以此手性固定相作填料,湿法装填液相色谱柱,直接分离(±)-曲美布汀对映体。确定对映体在固定相与洗脱液之间分配的自由能变之差值、焓变之差值和熵变之差值,考察洗脱液正己烷-异丙醇(v/v)中异丙醇含量在色谱分离对映体性能方面的影响。当洗脱液中异丙醇含量增加时,对映体的容量因子逐渐降低,分离因子变化不大,分离度逐渐降低。  相似文献   

19.
Wei H  Sun JJ  Wang YM  Li X  Chen GN 《The Analyst》2008,133(11):1619-1624
A disposable heated screen-printed carbon electrode (HSPCE) is successfully fabricated. It demonstrates rapid responses to electrical heating and is easily elevated above the water boiling point by a high frequency alternating current. The temperature rise at the HSPCE was found to be strongly dependent on the square of the heating current and the electrode width. Carbofuran (CAF) could be rapidly hydrolyzed to carbofuran phenol at the HSPCE with raised temperature, and then determined at the same electrode at room temperature by differential potential voltammetry (DPV). The factors influencing the detection were examined, including pH, hydrolytic temperature and heating time. Under the optimum conditions, the detection linear range of CAF was from 4.0 x 10(-7) to 4.0 x 10(-4) mol L(-1) and the detection limit was 5.0 x 10(-8) mol L(-1) (S/N = 3). This method was successfully applied to the analysis of CAF residues in real samples (spiked water, soil and vegetables), and satisfactory recoveries were obtained.  相似文献   

20.
The structurally chiral [7-(2'-pyridyl)-7,8-nido-C(2)B(9)H(11)](-), [](-), anion was prepared by a partial degradation reaction of 1-(2'-pyridyl)-1,2-closo-C(2)B(10)H(11). From this anion a protonated specie, H[7-(2'-pyridyl)-7,8-nido-C(2)B(9)H(11)] , and a tetramethylammonium salt, [NMe(4)][7-(2'-pyridyl)-7,8-nido-C(2)B(9)H(11)], [NMe(4)][] can be obtained. The (1)H{(11)B} DNMR study on in the temperature range from 298 to 203 K identified the weakly basic nitrogen atom in the pyridine ring as the proton accepting site in solid state and low temperature and revealed pronounced weakening of the nitrogen-proton interaction while the temperature increases. Capillary electrophoresis and X-ray diffraction confirmed the pyridine nitrogen atom as the proton binding site. Separation of the electrophoretically pure racemic [7-(2'-pyridyl)-7,8-nido-C(2)B(9)H(11)](-) ion into two peaks by the chiral selector beta-cyclodextrine has been achieved.  相似文献   

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