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71.
Liu L Qiu S Wang B Zhang W Lu P Xie Z Hanif M Ma Y Shen J 《The journal of physical chemistry. B》2005,109(49):23366-23370
We have investigated the thermal degradation in air by Fourier transform infrared spectroscopy of a ladder-type copolymer containing fluorene units in the backbone (Me-LPF), to reveal the formation of the ketonic defects. As thermal treatment of Me-LPF film at 200 degrees C in air proceeds, a new group of complex absorption bands due to degradation products arises in the range between 1800 and 1600 cm(-1). The observed overlapping bands were separated and assigned by utilizing the second-derivative IR spectral analysis, which can narrow the peak width to one-third of the originals and thereby eases the analysis. The degraded products were assigned as fluorenone (1718 cm(-1)) and benzophenone (Ar-(C=O)-Ar) (1665 cm(-1)), formed by the oxidation of the backbone, and acylphenone (Ar-(C=O)-R) (1685 cm(-1)) from the side chain. The fluorenone was found to be the major component among the degraded products in the main chain, and the time and temperature dependence indicated that the oxidation is a kind of autocatalytic radical-chain process. The oxidation can reach a very high degree (approximately 30% for 6 h oxidation at 240 degrees C estimated by absorption of the alkyl). Our results suggest the possibility of the oxidation of the 9-bialkylfluorene sites. We propose that the degradation of the alkyl in the side chain can help the radicals to propagate in the chain reaction. 相似文献
72.
在恒定丙三醇质量分数x=0.1的条件下,测定了无液接电池(A)和电池(B)的电动势根据电池(A)电动势确定了丙三醇和水混合溶剂中的Ag-AgCl电极的标准电极电势,讨论了HCl的迁移性质;由电池(B)测得的电动势计算了HCl在该体系中的活度系数γA,计算的结果表明,对于所讨论的体系,在溶液中总离子强度保持恒定,HCl的活度系数服从Harned规则.在溶液组成恒定时,IgγA是温度倒数1/T的线性函数,讨论了混合物中HCl的相对偏摩尔焓及介质效应. 相似文献
73.
Tao-Min Huang Chun-Hui Deng Ying-Jia Yu Xiao-Wei Zheng Geng-Li Duan 《Chromatographia》2006,63(11-12):551-556
An accurate, simple and sensitive method based on reversed-phase high-performance liquid chromatography with UV detection has been developed for determination of tiopronin (TP) in human plasma. TP in plasma was reacted with p-bromophenacyl bromide (p-BPB) to give the TP-p-BPB adduct and this derivative was then extracted from the plasma on a silica gel cartridge. Potential interfering compounds were removed by washing with water, and the TP-p-BPB adduct was then eluted with acetonitrile. The organic phase obtained was evaporated to complete dryness under a stream of nitrogen. The residue was dissolved in acetonitrile and this solution was injected on to a reversed-phase ODS HPLC column. The mobile phase was usually the ternary mixture acetonitrile–water–trifluoroacetic acid, 40:59.88:0.12 (v/v). The retention times of TP-p-BPB and the internal standard adduct were 14.4 and 17.9 min, respectively. No interfering peaks were encountered in several blank plasma samples examined. The limit of detection for TP was 12 ng mL?1. Extraction recovery exceeded 70%. The calibration plot for the TP derivative was linear in the range 40?4000 ng mL?1, regression coefficient 0.9989, and the coefficient of the variation of the points of the calibration plot was below 10%. The method was validated appropriately and successfully applied to the determination of TP in human plasma. 相似文献
74.
Amperometric glucose biosensor based on electrodeposition of platinum nanoparticles onto covalently immobilized carbon nanotube electrode 总被引:6,自引:0,他引:6
A new amperometric biosensor for glucose was developed based on adsorption of glucose oxidase (GOx) at the gold and platinum nanoparticles-modified carbon nanotube (CNT) electrode. CNTs were covalently immobilized on gold electrode via carbodiimide chemistry by forming amide linkages between carboxylic acid groups on the CNTs and amine residues of cysteamine self-assembled monolayer (SAM). The fabricated GOx/Aunano/Ptnano/CNT electrode was covered with a thin layer of Nafion to avoid the loss of GOx in determination and to improve the anti-interferent ability. The immobilization of CNTs on the gold electrode was characterized by quartz crystal microbalance technique. The morphologies of the CNT/gold and Ptnano/CNT/gold electrodes have been investigated by scanning electron microscopy (SEM), and the electrochemical performance of the gold, CNT/gold, Ptnano/gold and Ptnano/CNT/gold electrodes has also been studied by amperometric method. In addition, effects of electrodeposition time of Pt nanoparticles, pH value, applied potential and electroactive interferents on the amperometric response of the sensor were discussed.
The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for glucose in the absence of a mediator. The linear range was from 0.5 to 17.5 mM with correction coefficient of 0.996. The biosensor had good reproducibility and stability for the determination of glucose. 相似文献
75.
Effects of Calcination Temperature on the Acidity and Catalytic Performances of HZSM-5 Zeolite Catalysts for the Catalytic Cracking of n-Butane
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The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature (excluding 800 ℃). The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature.The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking. 相似文献
76.
Yuan Zhihao Wang Yuhong Sun Yongchang Wang Jing Bie Lijian Duan Yueqing 《中国科学B辑(英文版)》2006,49(1):67-74
A nanocomposite photocatalyst composed of AlFeO3 and TiO2 is prepared, and characterized through X-ray diffraction. Application of the nanocomposite for the photodegradations of eosin
dye and methyl orange gives an improved photoactivity compared with TiO2-only nanomaterials. The optimal concentration of AlFeO3 in the composite is about 1.0 wt% under UV excitation, and 9.0 wt% under sunlight excitation for the improved photoactivity.
Furthermore, this nanocomposite is more active for eosin photodegradation if natural sunlight rather than UV is used. This
may be due to the reason that adding AlFeO3 nanoparticles into TiO2 matrix can promote the separation of photogener-ated charge carriers, and extend the photoresponse of TiO2 toward visible region, which results in an increase in the solar energy utilization efficiency. 相似文献
77.
Hu Chuanjiang Duan Chunying Meng Qingjin Liu Yongjiang Lu Changsheng Reng Xiaoming Chen Yijun Cao Mi 《Transition Metal Chemistry》2000,25(2):141-144
The mixed-valence molybdovanadate compound Na2(NH4)4[VIVVV
8Mo)O28] · 10H2O [Vanadata(6-)tetradeca--oxotetra-3-oxodi-6-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH2OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO6 octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4. 相似文献
78.
Mukhopadhyay I Duan YB Wu XT Takagi K 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2000,(1):19-28
In this work, we have extended our previous analysis of the Hamiltonian of 13C substituted methanol to include a large number of spectral lines involving the second excited torsional state using an improved model. The data set consisted of 2529 Fourier transform and microwave transitions with the rotational angular momentum J < or = 10, K < or = 6 and n < or = 2 (with 336 MW lines). The data set was fitted with the new Hamiltonian model to derive the molecular parameters. The results indicate that the model developed for the other methanol species (CH3OH, CH3(18)OH and CH3OD) is also valid for the C-13 substituted species. The results will allow the energy levels of the molecule to be calculated for higher torsional levels above the internal rotational barrier with improved precision and allow the analysis to be carried out for more excited torsional states. 相似文献
79.
Xin-ping Duan Tianyi Chen Tianxiang Chen Lele Huang Li Ye Benedict T. W. Lo Youzhu Yuan Shik Chi Edman Tsang 《Chemical science》2021,12(25):8791
Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts. However, owing to their low melting point, poor thermal stability remains a major obstacle towards their application under reaction conditions. It is a common practice to use porous inorganic templates such as mesoporous silica SBA-15 to disperse Ag nanoparticles (NPs) against aggregation but their stability is far from satisfactory. Here, we show that the catalytic activity for hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) over Ag NPs dispersed on SBA-15 silica can be further promoted by incorporation of alkali metal ions at small loading, which follows the inverse order of their cationic size: Li+ > Na+ > K+ > Rb+. Among these, 5Ag1–Li0.05/SBA-15 can double the MG yield compared to pristine 5Ag/SBA-15 under identical conditions with superior thermal stability. Akin to the effect of an ionic surfactant on stabilization of a micro-emulsion, the cationic charge of an alkali metal ion can maintain dispersion and modulate the surface valence of Ag NPs. Interstitial Li in the octahedral holes of the face center packed Ag lattice is for the first time confirmed by X-ray pair distribution function and electron ptychography. It is believed that this interstitial-stabilization of coinage metal nanoparticles could be broadly applicable to multi-metallic nanomaterials for a broad range of C–O bond activating catalytic reactions of esters.Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts. 相似文献
80.
连续一级反应的热动力学研究 总被引:1,自引:0,他引:1
本文把时间比法引入热动力学研究,建立了连续一级反应的热动力学研究法,并用来研究了一个连续反应体系的热动力学,验证了该方法的正确性. 相似文献