1000 resultados para reaction microscope
Resumo:
The rate constant of very fast chemical reaction generally can be measured by electrochemical methods, but can not by the thin layer electrochemical methods because of the influence of diffusion effect. Long optical path length thin layer cell (LOPTLC) with large ratio of electrode area to solution volume can be used to monitor the fist chemical reaction in situ with high sensitivity and accuracy. It enable the adsorption spectra to be measured without the influence of diffusion effect. In the present paper, a fast chemical reaction of Alizarin Red S (ARS) with its oxidative state has been studied. The reaction equilibrium constant (K) under different potentials can be determined by single step potential-absorption spectra in LOPTLC. An equilibrium constant of 7.94 x 10(5) l.mol(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)'). Rate constant (k) under different potentials can be measured by single step potential-chronoabsorptiometry. A rate constant of 426.6 l.mol(-1).s(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)') with (E - E-1(0)') = 0.
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The C-phycocyanin (C-PC) trimmer was isolated from the blue-green alga Spirulina platensis, and scanning tunnelling microscope (STM) was used to investigate its structure, High resolution STM images of C-PC were obtained. From the STM images, it could be observed that the C-PC molecules were disk-like in shape and the subunits of C-PC arranged in ring-like pattern with a channel in the center. After filter treatment, the folding of the polypeptide chains could be. seen clearly. This is the first time to observe directly the topography of phycobiliprotein, and the results showed STM to be a powerful tool for the structural study of phycobiliproteins.
Resumo:
C-phycocyanin (C-PC) was isolated from blue-green alga spirulina platensis. A scanning tunneling microscope (STM) has been used to investigate its three-dimensional structure. The samples were dialyzed before the STM experiment, and then deposited on highly oriented pyrolytic graphite (HOPG). The measurement was carried out in ambient condition at room temperature. STM images showed that C-phycocyanin was uniformly distributed on solid-state substrate HOPG. The shape of C-phycocyanin is disklike with a channel in the center. It is concluded that STM has great potential to observe the structure of biliproteins and phycobilisomes.
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The electrochemical impedance spectroscopy (EIS) at different potentials has been used to study the oxygen reduction reaction (ORR) in 3.5% NaCl solution on glassy carbon (GC) electrode in this work. Results show that ORR consists of three two-electron reaction steps and both superoxide ion (O-2(-)) and hydrogen peroxide (H2O2), which are produced by ORR, obstruct the diffusion of oxygen to the surface of the electrode and make the EIS results change into a transmissive finite diffusion process with the real part contraction and a reflective finite diffusion process from a semi-infinite diffusion process. The values of electron transfer resistance (R-t) and diffusion resistance (R-d) were calculated from EIS. O-2(-) influenced strongly on the Rt values and induced a maximum at -0.45 V.
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Corrosion inhibition by some new triazole derivatives on mild steel in 1 M hydrochloric acid solutions has been investigated by weight loss test, electrochemical measurement, scanning electronic microscope analysis and quantum chemical calculations. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds following the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were calculated. (C) 2009 Published by Elsevier B.V.
Resumo:
Berberine was abstracted from coptis chinensis and its inhibition efficiency on corrosion of mild steel in 1 M H2SO4 was investigated through weight loss experiment, electrochemical techniques and scanning electronic microscope (SEM) with energy disperse spectrometer (EDS). The weight loss results showed that berbefine is an excellent corrosion inhibitor for mild steel immersed in 1M H2SO4. Potentiodynamic curves suggested that berbefine suppressed both cathodic and anodic processes for its concentrations higher than 1.0 x 10(-4) M and mainly cathodic reaction was suppressed for lower concentrations. The Nyquist diagrams of impedance for mild steel in 1 M H2SO4 containing berbefine with different concentrations showed one capacitive loop, and the polarization resistance increased with the inhibitor concentration rising. A good fit to Flory-Huggins isotherm was obtained between surface coverage degree and inhibitor concentration. The surface morphology and EDS analysis for mild steel specimens in sulfuric acid in the absence and presence of the inhibitor also proved the results obtained by the weight loss and electrochemical experiments. The correlation of inhibition effect and molecular structure of berberine was then discussed by quantum chemistry study. (c) 2005 Elsevier B.V. All rights reserved.
Resumo:
The inhibition effect of nicotinic acid for corrosion of hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid was investigated using quantum chemistry analysis, weight loss test, electrochemical measurement, and scanning electronic microscope (SEM) analysis. Quantum chemistry calculation results showed that nicotinic acid possessed planar structure with a number of active centers, and the populations of the Mulliken charge, the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) were found mainly focused around oxygen and nitrogen atoms, and the cyclic of the benzene as well. The results of weight loss test and electrochemical measurement indicated that inhibition efficiency (IE%) increased with inhibitor concentration, and the highest inhibition efficiency was up to 96.7%. The corrosion inhibition of these coatings was discussed in terms of blocking the electrode reaction by adsorption of the molecules at the active centers on the electrode surface. It was found that the adsorption of nicotinic acid on coating surface followed Langmuir adsorption isotherm with single molecular layer, and nicotinic acid adsorbed on the coating surface probably by chemisorption. Nicotinic acid, therefore, can act as a good nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid solution. (c) 2007 Elsevier Ltd. All rights reserved.
Resumo:
Cyclic voltammetry, electrochemical impedance spectroscopy, and rotating disk electrode voltammetry have been used to study the effect of chloride ions on the dissolved oxygen reduction reaction (ORR) on Q235 carbon steel electrode in a 0.02 M calcium hydroxide (Ca(OH)(2)) solutions imitating the liquid phase in concrete pores. The results indicate that the cathodic process on Q235 carbon steel electrode in oxygen-saturated 0.02 M Ca(OH)(2) with different concentrations of chloride ions contain three reactions except hydrogen evolution: dissolved oxygen reduction, the reduction of Fe(III) to Fe(II), and then the reduction of Fe(II) to Fe. The peak potential of ORR shifts to the positive direction as the chloride ion concentration increases. The oxygen molecule adsorption can be inhibited by the chloride ion adsorption, and the rate of ORR decreases as the concentration of chloride ions increases. The mechanism of ORR is changed from 2e(-) and 4e(-) reactions, occurring simultaneously, to quietly 4e(-) reaction with the increasing chloride ion concentration.
Resumo:
In this experiment, we tested the hypothesis that males of root voles (Microtus oeconomus Pallas) of different social ranks display different behavioural strategies. To document behavioural differences between social ranks, we investigated patterns in the behavioural responses to urine cues from familiar and novel individu in a choice maze. Ten pairs of male voles were efectively used in this experiment. All behaviour was recorded with OBSERVER 5.0. When experiment was finished, video tapes were transformed into digital data. Then all data were analyzed by SPSS. The results showed that the approach latency of subordinates was shorter for familiar odours than novel ones, dominant individuals preferentially entered the strange odourant box, subordinates preferred familiar odours over novel ones, subordinates spent more time visiting familiar odours compared to the novel odours, dominants preferred novel odours to familiar ones, subordinates approached familiar odours more frequently than novel ones and self-groomed more often in the familiar odourant box than in the novel box, and dominant and subordinate individuals showed significantly different countermarking behaviours to familiar and novel odours. In conclusion, the dominants and subordinates displayed different behaviour patterns when faced to familiar and novel conspecific males' urine cues. The data support our hypothesis that differences in social rank induce differences in behavioural patterns.
Resumo:
The reaction of nitrone, N-methyl nitrone, and their hydroxylamine tautomers (vinyl-hydroxylamine and N-methyl vinyl-hydroxylamine) on the reconstructed Si(100)-2 x 1 surface has been investigated by means of hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The calculations predicted that both of the nitrones should react with the surface dimer via facile concerted 1,3-dipolar cycloaddition leading to 5-member-ring compounds. The reaction of hydroxylamine tautomers on the Si(100) surface follows pi-complex (intermediate) mechanism. For the reaction of N-methyl vinyl-hydroxylamine, the pi-complex intermediate undergoes [2+2] cycloaddition leading to a 4-member-ring compound. But in the reaction of vinyl-hydroxylamine, the intermediate undergoes H-migration reaction ("ene" reaction) resulting in the oxime-terminated Si surface. All the surface reactions result in the hydroxyl-terminated silicon surfaces, which are very useful for the further modification of the semiconductor.
Resumo:
To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.
Resumo:
The Ultrahigh Pressure Metamorphic (UHPM) eclogite, which was resulted from deep subduction of crustal continent, is very significant due to its continental dynamic implications. Further more, this kind of rocks experienced great P-T, fluid and stresses changes during its forming and exhumation, causing mineral reactions occur intensively, which resulted in a lot of fantastic micro-texture. The micro-texture was preserved duo to a rapid exhumation of the eclogite. This PhD dissertation takes such micro-textures in 10 Donghai eclogite samples South Sulu UHPM terrene, as research object to reveal the transformation of the eclogite to amphibolite. Microscope and Scanning Electron Microscope were employed to observe the micro-texture. Basing on microprobe analysis of minerals, the ACF projections and iso-con analysis were used to uncover the mineral reactions during the transformation. Micro-texture observation (both of Microcopy and Electron Scanning Microscope), demonstrated: l.The peak mineral assemblage of the researched Donghai eclogites is garnet + omphacite + rutile (+ kyanite + aptite +coesite). 2.The transformation of the Donghai eclogite to amphibolite can be divided into two stages: The earlier one is Symplectization, resulting in the forming of diopside + albite (+magnetite) symplectite that occurred only along the boundary between two adjacent omphacite grains. Other minerals were not involved in such reaction. The latter stage is Fluid-Infiltration of the eclogite, which was caused by fluid-intrusion. The infiltration is demonstrated by amphibolization of the symplectite, decomposition of garnet and the forming of some hydrous minerals such as phengite and epidote, and resulted in an amphibole + plagioclase + phengite + epidote or ziosite assemblage. Basing on microprobe analysis of the minerals, ACF projections indicated: In the ACF diagrams, the two joint lines of peak Grt + Omp and Dio + Ab crossed at Omp projection-point, indicating that the garnet had not taken part in the forming reaction of the Dio + Ab symplectite, just like that had been pointed out by micro-texture observation. In the ACF diagrams, the hornblende + plagioclase + epidote + phengite quadrilateral intersected with Dio + Ab + Grt triangle, demonstrating that the hydrous mineral assemblage was formed by fluid infiltration through garnet, diopside and albite. Iso-con (mass-balance) analysis of the symplectization and infiltration reveals: 1.The symplectization of the omphacite has a very complex mass exchange: Some symplectite gained only silicon from its surroundings; and some one requires Ca, but provides Na to its surroundings; while other symplectite provides Ca, Mg and Fe to its surroundings. 2.The infiltration cause variable mass exchanges occurring among the garnet, diopside and albite: In some eclogite sample, no mass, except H2O, exchange occurred during the infiltration. Meanwhile, there was not any hydrous mineral except hornblende formed in the sample accordingly. In some samples, the mass exchange among the three minerals is complex: amphibolization of the diopside in a symplectite gained Al from garnet, and provided Si and Ca to its surrounding, resulting in a Si, Ca and Al-rich fluid. Correspondingly, there was a lot of phengite and ziosite occurred in the sample. In other samples, the amphibolization of a symplectite provided Fe and Mg besides Si and Ca to its surrounding while gained Al. In such kind of sample, epidote occurred within the hydrous mineral assemblage. Synthesizing the micro-texture observation, ACF analysis and iso-con analysis, we deduced the transformation procedure as following: 1. A symplectite after an omphacite was resulted by one, or two, or all of following mineral reactions together: Jd (Ca-Tsch) +SiO2=Ab (An) (1) 4NaA IS i.A+CaO=2NaAlS i308+Na20+CaAl2S 1208 (2) 2NaAlSi2OB (Jd in Omp)+CaMgSi;,0B(Dio in Omp)-2NaAlSi:,O"(Ab)+Ca0+Mg0 (3) 2(CaAl2Si0fi) (Ca-tsch in Omp)+CaFeSi2O6(Hed in 0mp)-H>2CaAl2Si208(An)+Ca0 + FeO (4) A CO2-rich fluid is suggested as cataclysm for the above reactions, which largely increased the mobility of Ca, Mg and Na resulted from reaction (2), (3) and (4). The immobile product Fe2* combined with rutile to form ilmenite, resulting in rutile + ilmenite symplectite. Or, the Fe was precipitated as hematite locally. A procedure of the fluid infiltration as following is suggested: I .A hydrous fluid intruded into the eclogite, and reacted first with garnet to form hornblende and extra Al, resulting in a hornblende film around the garnet grain and an Al-rich fluid. 2.The Al-rich fluid infiltrated through the symplectite, OH" and part of the Al in the fluid combined with Dio while some Si and Ca in the Dio were dissolved made the Dio transferred to amphibole. Meanwhile, plagioclase-type cation exchange occurred between the fluid and plagioclase in the symplectite, making the plagioclase have a higher An-content. 3.Above infiltration and cation exchange resulted in an Al, Si, Ca (and K, providing the primary hydrous fluid contain K)-rich fluid. 4.Under suitable conditions, the solute in the fluid precipitated to form phengite firstly. After the K element in the fluid was consumed up, ziosite or epidote was formed. If the fluid did not contain any K. element, only ziosite or epidote was precipitated. For those eclogites, where all omphacite had been replaced by symplectite before infiltration, neither element exchange occurred, nor did phengite or epidote form during the infiltration. At the last stage, the garnet was oxidized and breakdown: garnet + H2O = epidote + hornblende + hematite, due to more and more fluid intruding into the eclogite. At this time, all the peak minerals were replaced by amphibolite-phase ones, and the eclogite transformed to an amphibolite completely. Tentative pressure calculation indicates that the infiltration occurred at 3-6kbar (about 10-20km depth), where the deformation mechanics transformed from brittle to ductile yield. At such depth, the surface water can permeate the rocks through fault system, causing a rapid cooling.