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1.
P Rubin JP Williams PN Riggs S Bartos T Sarac R Pomerantz J Castano M Schell RM Green 《Canadian Metallurgical Quarterly》1998,40(4):929-941
BACKGROUND: Desflurane, enflurane and isoflurane can be degraded to carbon monoxide (CO) by carbon dioxide absorbents, whereas sevoflurane and halothane form negligible amounts of CO. Carbon monoxide formation is greater with drier absorbent, and with barium hydroxide, than with soda lime. The mechanism, role of absorbent composition and water, and anesthetic structures determining CO formation are unknown. This investigation examined sequential steps in anesthetic degradation to CO. METHODS: Carbon monoxide formation from anesthetics and desiccated barium hydroxide lime or soda lime was determined at equimole and equiMAC concentrations. Carbon monoxide formation from deuterium-substituted anesthetics was also quantified. Proton abstraction from anesthetics by strong base was determined by deuterium isotope exchange. A reactive chemical intermediate was trapped and identified by gas chromatography-mass spectrometry. The source of the oxygen in CO was identified by 18O incorporation. RESULTS: Desflurane,enflurane,andisoflurane(difluoromethylethyl ethers), but not sevoflurane (monofluoromethyl ether), methoxyflurane (methy-ethyl ether), or halothane (alkane) were degraded to CO. The amount of CO formed was desflurane > or = enflurane > isoflurane at equiMAC and enflurane > desflurane > isoflurane at equimole concentrations. Proton abstraction from the difluoromethoxy carbon was greater with potassium than with sodium hydroxide, but unmeasurable with barium hydroxide. Carbon monoxide formation was correlated (r = 0.95-1.00) with difluoromethoxy (enflurane > desflurane > isoflurane > or = methoxyflurane = sevoflurane = 0) but not ethyl carbon proton abstraction. Deuterium substitution on enflurane and desflurane diminished CO formation. Chemical trapping showed formation of a difluorocarbene intermediate from enflurane and desflurane. Incorporation of H2(18)O in barium hydroxide lime resulted in C18O formation from unlabeled enflurane and desflurane. CONCLUSIONS: A difluoromethoxy group is a structural requirement for haloether degradation to CO. Results are consistent with initial base-catalyzed difluoromethoxy proton abstraction (potassium > sodium hydroxide, thus greater CO formation with barium hydroxide lime vs. soda lime) forming a carbanion (reprotonated by water to regenerate the anesthetic, hence requirements for relatively dry absorbent), carbanion decomposition to a difluorocarbene, and subsequent difluorocarbene reaction to form CO. 相似文献
2.
采用热重分析法研究了H2-CO还原钛精粉的特征。热重、相组成和形貌分析表明:在纯H2基础上,配加CO还原钛精粉的热重曲线具有相似性,即质量分数首先随时间的延长而下降,达到平衡后维持一定时间,随后逐渐增加;在质量分数降低的过程中,失重率随H2含量的增加而增加;相反,在质量分数增加的过程中,增重率首先随CO含量的减小而增加,至80%CO时达到最大值,而后逐渐减小。要保证还原产物中铁元素主要以金属相、非渗碳体相形式存在的合理温度是1150℃;开始阶段由于氢气原子半径小、扩散能力强,H2含量高时,产物表面孔隙较多,利于气体传输,还原能力强,随后由于渗碳体参与还原反应,产生大量气体,产物破碎程度增强,增加了其比表面积。 相似文献
3.
BACKGROUND: Halothane and isoflurane previously were reported to attenuate endothelium-derived relaxing factor/nitric oxide-mediated vasodilation and cyclic guanosine monophosphate (cGMP) formation in isolated rat aortic rings. Carbon monoxide has many chemical and physiologic similarities to nitric oxide. This study was designed to investigate the effects of halothane and isoflurane on carbon monoxide-induced relaxations and cGMP formation in the isolated rat aorta. METHODS: Isometric tension was recorded continuously from endothelium denuded rat aortic rings suspended in Krebs-filled organ baths. Rings precontracted with submaximal concentrations of norepinephrine were exposed to cumulative concentrations of carbon monoxide (26-176 microM). This procedure was repeated three times, with anesthetics delivered 10 min before the second procedure. Carbon monoxide responses of rings contracted with the same concentration of norepinephrine (10(-6) M and 2 x 10(-6) M) used in the anesthetic-exposed preparations also were examined. The concentrations of cGMP were determined in denuded rings using radioimmunoassay. The rings were treated with carbon monoxide (176 microM, 30 s) alone, or carbon monoxide after a 10-min incubation with halothane (0.34 mM or 0.72 mM). To determine whether the sequence of anesthetic delivery influenced results, vascular rings pretreated with halothane were compared with nonpretreated rings. RESULTS: Carbon monoxide (26-176 microM) caused a dose-dependent reduction of norepinephrine-induced tension, with a maximal relaxation of 1.51 +/- 0.07 g (85 +/- 7% of norepinephrine-induced contraction). Halothane (0.34 mM and 0.72 mM) significantly attenuated the carbon monoxide-induced relaxations, but only the highest concentration of isoflurane (0.53 mM) significantly attenuated the carbon monoxide-induced relaxations. Carbon monoxide (176 microM) significantly increased cGMP content (+88.1 +/- 7.1%) and preincubation of the aortic rings with halothane (0.34 mM and 0.72 mM) inhibited this increase (-70.7 +/- 6.8% and -108.1 +/- 10.6%, respectively). When aortic rings and carbon monoxide were added simultaneously to Krebs solution equilibrated with halothane (0.72 mM), no inhibition of cGMP formation occurred. CONCLUSION: Carbon monoxide-induced endothelium-independent relaxations of rat aortic rings were decreased by clinically relevant concentrations of halothane and isoflurane. The carbon monoxide-induced elevations of cGMP were attenuated by halothane only when the anesthetic was incubated with aortic rings before carbon monoxide treatment. The possible clinical significance of the actions of the anesthetics on this endogenous vasodilator is yet to be determined. 相似文献
4.
WP Farrar S Bech-Nielsen JC Gordon SM Reed CI Pretzman CW Kohn 《Canadian Metallurgical Quarterly》1993,34(4):345-353
A sulfate-reducing bacterium using trinitrotoluene (TNT) as the sole nitrogen source was isolated with pyruvate and sulfate as the energy sources. The organism was able to reduce TNT to triaminotoluene (TAT) in growing cultures and cell suspensions and to further transform TAT to still unknown products. Pyruvate, H2, or carbon monoxide served as the electron donors for the reduction of TNT. The limiting step in TNT conversion to TAT was the reduction of 2,4-diamino-6-nitrotoluene (2,4-DANT) to triaminotoluene. The reduction proceeded via 2,4-diamino-6-hydroxylaminotoluene (DAHAT) as an intermediate. The intermediary formation of DAHAT was only observed in the presence of carbon monoxide or hydroxylamine, respectively. The reduction of DAHAT to triaminotoluene was inhibited by both CO and NH2OH. The inhibitors as well as DANT and DAHAT significantly inhibited sulfide formation from sulfite. The data were taken as evidence for the involvement of dissimilatory sulfite reductase in the reduction of DANT and/or DAHAT to triaminotoluene. Hydrogenase purified from Clostridium pasteurianum and carbon monoxide dehydrogenase partially purified from Clostridium thermoaceticum also catalyzed the reduction of DANT in the presence of methyl viologen or ferredoxin, however, as the main reduction product DAHAT rather than triaminotoluene was formed. The findings could explain the function of CO as an electron donor for the DANT reduction (to DAHAT) and the concomitant inhibitory effect of CO on triaminotoluene formation (from DAHAT) by the inhibition of sulfite reductase.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
5.
Arne Landsberg C. L. Hoatson F. E. Block 《Metallurgical and Materials Transactions B》1972,3(2):521-527
Chlorination of zirconium dioxide, an important step in the commercial production of reactor grade zirconium metal, has been
studied using carbon and carbon monoxide as reductants. Zirconium tetrachloride was produced when the oxide was reacted with
chlorine alone above 1000°C; by introducing carbon the reaction temperatures could be lowered 200°C, and when carbon monoxide
was used the reaction temperatures necessary for similar rates were even lower. With carbon monoxide the chlorination of zirconium
dioxide is described by two regions differentiated by temperature and the dependence of reaction rate upon chlorine and carbon
monoxide pressures. 相似文献
6.
To test the hypothesis that carbon monoxide transfer across the placenta is, in part, a facilitated process, we have looked for evidence of saturation kinetics for carbon monoxide. In eight pregnant ewes, fetal to maternal carbon monoxide transfer was examined in a preparation in which the fetal side of the placenta was perfused with blood. The carboxyhemoglobin concentrations on the fetal side of the placenta were varied from 4.8 to 70% in 23 measurements. At increased carbon monoxide tensions, the transfer from fetus to mother always decreased. The slope of log rate of carbon monoxide transfer vs. log partial pressure gradient across the placenta was significantly different from 1. Placental membrane diffusing capacity was calculated separately from total placental diffusing capacity which includes hemoglobin reaction rates and erythrocyte membrane diffusion. Placental membrane diffusing capacity decreased at increased carbon monoxide tensions. Placental permeability for urea did not change with increasing carbon monoxide tensions. These results are consistent with the hypothesis that carbon monoxide diffusion in the placenta is, in part, carrier mediated. 相似文献
7.
Iron oxide slags are subjected to reduction at 1550 °C with the use of various reducing agents. The experiments with carbon monoxide are subdivided into series of top-blowing, injection or bottom-blowing experiments. Moreover, solid carbon is employed for further experiments. As a result of the necessary addition of Al2O3 – because of the corrosivity of FeOn towards the crucible material during experiments – reaction-inhibiting barrier layers precipitate in the form of spinels during reduction. Foams containing COn exert the same effect. From the experimental results, it can be concluded that the reduction of liquid oxides by carbon monoxide or by solid carbon does not consistently obey any law of reaction during the entire process sequence. The essential, decisive parameter for the carbon monoxide blowing experiments is the blowing rate. The experiments performed with the use of solid carbon exhibit the highest reduction rates, on the whole. For the purpose of elucidating the reaction mechanisms, only the experiments conducted by blowing carbon monoxide onto the melt yield clearcut results. After a possible initial steep rise, a reaction of first order is then established, as a first approximation. The further course of the experiment is characterized by covering of the blowing trough. Mass transfer can then proceed only through the spinel layer near the surface, or through the channels between the spinels. 相似文献
8.
N Bec AC Gorren C Voelker B Mayer R Lange 《Canadian Metallurgical Quarterly》1998,273(22):13502-13508
The reaction of reduced NO synthase (NOS) with molecular oxygen was studied at -30 degreesC. In the absence of substrate, the complex formed between ferrous NOS and O2 was sufficiently long lived for a precise spectroscopic characterization. This complex displayed similar spectral characteristics as the oxyferrous complex of cytochrome P450 (lambda max = 416.5 nm). It then decomposed to the ferric state. The oxidation of the flavin components was much slower and could be observed only at temperatures higher than -20 degreesC. In the presence of substrate (L-arginine), another, 12-nm blue-shifted, intermediate spectrum was formed. The breakdown of the latter species resulted in the production of Nomega-hydroxy-L-arginine in a stoichiometry of maximally 52% per NOS heme. This product formation took place also in the absence of the reductase domain of NOS. Both formation of the blue-shifted intermediate and of Nomega-hydroxy-L-arginine required the presence of tetrahydrobiopterin (BH4). We propose that the blue-shifted intermediate is the result of reductive activation of the oxygenated complex, and the electron is provided by BH4. These observations suggest that the reduction of the oxyferroheme complex may be the main function of BH4 in NOS catalysis. 相似文献
9.
Increasing evidence suggests that S-nitrosothiols (thionitrites) might represent naturally occurring nitric oxide surrogates and function as intermediates in nitrogen monoxide metabolism. A facile, sensitive, and selective micromethod has been developed and validated for quantification of S-nitrosothiols as their mercury-displaceable nitrogen monoxide content. In this method, brief (5-min), room-temperature pretreatment of S-nitrosothiol with a molar excess of aqueous mercuric chloride was used to liberate into solution, quantitatively, the nitrogen monoxide moiety, which rapidly and quantitatively converted to its stable solution end-product, nitrite. Solution nitrite was reduced back to nitric oxide with vanadium(III), and the nitric oxide was detected by gas-phase chemiluminescence after reaction with ozone in a commercial nitric oxide analyzer. A linear relationship was observed between S-nitrosothiol-bound nitrogen monoxide and ozone-chemiluminescent detector response over a wide range (16.3-3500 pmol) of nitric oxide, as generated by reaction of vanadium(III) with either nitrite standard or mercury-treated S-nitrosothiol. Assay response was quantitatively identical for equivalent amounts of nitrite and S-nitrosothiol-bound nitrogen monoxide. The method displayed 96% selectivity for nitrite vs. nitrate and negligible (<2%) interference by nitrosated compounds bearing nitrogen monoxide moieties bound to either nitrogen or carbon. The lower limits of quantitative sensitivity and qualitative detection were below 50 and 20 pmol S-nitrosothiol-bound nitrogen monoxide-equivalents, respectively. The intraday and interday coefficients of variation did not exceed 8%. This technique has been applied to quantify structurally diverse natural and synthetic S-nitrosothiols with quantitative recovery from complex biological samples such as culture media and plasma at levels of nitrogen monoxide-equivalents undetectable by the popular Saville colorimetric method. 相似文献
10.
Carbon footprint is the mass of carbon formed in the full cycle of manufacturing one kind or another product. This carbon is included in greenhouse gases. During production of iron and steel are generated carbon monoxide and greenhouse gases: methane, and carbon dioxide. Methane and carbon monoxide burn to carbon dioxide by secondary energy resources. By this means, the carbon footprint by the production of iron and steel has determined by the weight of carbon dioxide formed in this production. As results of analysis of the processes of manufacture of iron and steel, it has revealed that the tandem of blast furnace with electric arc furnace is characterized by a lower value of integrated emissions of CO2 than the tandem of blast furnace with an oxygen converter. It was proposed to process of the cast iron made by one blast furnace, then in the oxygen converter, and, at last, in one or more electric arc furnaces. Moreover, the electric arc furnace is loaded by 30% of iron produced in blast furnace, and the remaining 70% are complemented by metal scrap. In the oxygen converter is loaded, the part of cast iron (75–85%), that remained after processing in the arc furnace. The converter is applied the metal scrap for full loading. Calculations of total emission of carbon dioxide for different triads of these units are made. Simultaneous use of oxygen converter with electric arc furnaces for cast iron smelting (obtained from one blast furnace) helps to reduce reliably the emission of carbon dioxide to 20% as it is follows from these calculations. This suggests that such a triad of used units conforms to green technology. Example of the use of mentioned triad is for a full load of the converter applied to metal scrap. The calculations total emissions of carbon dioxide for different triads of these units were performed. From these calculations it follows that the simultaneous use of oxygen converters after electric arc furnaces for smelting iron (obtained from one blast furnace), it helps to reduce the emission of carbon dioxide to 20%. This suggests that this triad of used units conforms to green technology. An example of using this triad is in the Magnitogorsk Iron and Steel Works, where along with the oxygen converter, electric arc furnaces with the use of locally produced electricity at burning fuel of secondary energy resources from units, in which the fuel is burnt. This practice can be recommended for a number of other metallurgical enterprises. 相似文献
11.
Y Shichida T Okada H Kandori Y Fukada T Yoshizawa 《Canadian Metallurgical Quarterly》1993,32(40):10832-10838
The photobleaching process of iodopsin (a chicken red-sensitive cone visual pigment) purified in a detergent system containing CHAPS and phosphatidylcholine was investigated by means of nanosecond laser photolysis at room temperature. Excitation of iodopsin with a nanosecond laser pulse (wavelength, 560 nm; pulse width, 17 ns) resulted in the formation of at least four intermediates on the nanosecond to millisecond time scale. The earliest intermediate detected had an absorption maximum at 571 nm, which was very close to that of original iodopsin (lambda max = 567 nm), and remarkably blue-shifted as compared with that of bathoiodopsin [lambda max = 625 nm; Kandori et al. (1990) Proc. Natl. Acad. Sci. U.S.A. 87, 8908-8912]. The intermediate, named BL-iodopsin, converted to the next intermediate, lumiiodopsin (lambda max = 535 nm), with a time constant of 130 ns. The BL intermediate had an absorption maximum just between batho- and lumiiodopsins, and an extinction coefficient comparable with these intermediates. These properties are different from those of the corresponding intermediate of rhodopsin [BL(BSI)-rhodopsin], suggesting that the binding of chloride to iodopsin, but not to rhodopsin, has an influence upon changes of the chromophore-opsin interaction in the early stage of photobleaching of iodopsin. Lumiiodopsin converted to metaiodopsin I (lambda max < 500 nm) with a time constant of 230 microseconds, and then to metaiodopsin II (lambda max = 390 nm) with a time constant of 6 ms. A thermal equilibrium between metaiodopsin I and II was established, but unlike meta intermediates of rhodopsin, they showed little temperature dependence. 相似文献
12.
结合CO2的高温反应特性,针对性地制定了CO2冶炼工艺,并对转炉顶吹CO2比例对终点磷、氮和碳氧浓度积的影响进行了工业试验研究。结果表明:随着转炉冶炼前中期CO2顶吹比例由4.84%逐渐提高到9.68%,转炉终点磷的质量分数先下降后基本不变,氮的质量分数逐渐下降,碳氧浓度积与渣中TFe变化趋势基本相同,均为先降低后增加,对于不同指标最佳顶吹CO2比例不同。试验转炉终点磷、氮的质量分数、碳氧浓度积与渣中TFe均下降,下降比例最高分别为20.4%、34.3%、12.92%和8.89%。 相似文献
13.
The chemical feasibility of reducing nickel sulfide with carbon and lime, without emitting sulfur-containing gases, has been
investigated. A reaction mixture of nickel sulfide particles intimately mixed with carbon and lime (used as a sulfur scavenger)
was prepared. The thermodynamics of reacting this mixture in an inert atmosphere, producing carbon dioxide and carbon monoxide,
was examined and found favorable. The rate of this reaction was measured in the temperature range 800 to 1124 °C ( 1073 to
1397 K). The effects of particle size and relative amounts of solid reactants were determined. The possibility of recovering
the product nickel by carbonylation was also investigated.
Formarly Graduate Student in Metallurgy at the University of Utah, 相似文献
14.
《钢铁冶炼》2013,40(2):170-176
AbstractA numerical model for the process of reduction and meltdown of iron ore-carbon pellets has been developed. The model covers the devolatilisation of coal, a set of gaseous reduction reactions by carbon monoxide and hydrogen and reactions for the formation of reducing gases. Carburisation of reduced iron and its subsequent meltdown is an important high temperature feature of the model. Transport of heat and gases is included, the latter using a specific isobaric approach. Model computations have been applied to a number of test cases with variable ore-reductant combinations and temperatures. Computed results match reasonably well with the results of laboratory tests. The reactions are found to occur in a complex sequence with main steps as follows: devolatilisation and gas evolution, gaseous reduction and Boudouard reaction, carburisation of solid iron and finally formation of liquid iron. The limits and potential use of the model are discussed. 相似文献
15.
MT Kleinman DA Leaf E Kelly V Caiozzo K Osann T O'Niell 《Canadian Metallurgical Quarterly》1998,53(6):388-397
Seventeen men with stable angina pectoris who resided at or near sea level performed cardiopulmonary exercise stress tests after they were exposed to either carbon monoxide (3.9%), carboxyhemoglobin, or clean air. Investigators conducted the tests at sea level, and they simulated 2.1-km altitudes (i.e., reduced arterial oxygen saturation by approximately 4%) in a randomized double-blind experiment in which each subject acted as his or her own control. The duration of symptom-limited exercise, heart rate, indicators of cardiac ischemia and arrhythmia, blood pressure, and respiratory gas exchange were measured. Analyses of variance showed that both independent variables-altitude and carbon monoxide-significantly (p < or = .01) reduced total duration of exercise for the group as a whole (n=17) and reduced the time to onset of angina for a subset of 13 subjects who experienced angina during all four test conditions (p < .05). Time to onset of angina was reduced either after exposure to sea-level carbon monoxide (9%) or to simulated high-altitude clean-air exposures (11%), compared with clean air at sea level. Joint exposure to carbon monoxide at a simulated high altitude reduced the time to onset of angina, relative to clean air, by 18% (p < .05). Other cardiological, hemodynamic, and respiratory physiological parameters were also affected adversely by altitude and carbon monoxide exposures. None of the parameters measured were associated significantly with either altitude or carbon monoxide, indicating that the effects of carbon-monoxide-induced and high-altitude-induced hypoxia were additive. The results of this study suggest that high-altitude conditions exacerbate the effects of carbon monoxide exposures in unacclimatized individuals who have coronary artery disease. 相似文献
16.
P. M. Prasad T. R. Mankhand P. Surya Prakash Rao S. N. Singh A. J. K. Prasad 《Metallurgical and Materials Transactions B》2002,33(3):345-354
Kinetic studies were conducted on the carbon monoxide reduction of molybdenite in the presence of lime. Contrary to the expectation
that the MoS2 (s)+CaO (s)+CO (g) reaction will result in metal formation, molycarbide was found to form and no Mo was detected in the product.
This is explained on the basis of thermochemical considerations, which indicate that the Mo2C formation is more feasible by eight orders of magnitude. The effects of quantity of lime in the charge, CO flow rate, temperature
(1123 to 1298 K), and time of reduction have been studied. Kinetic analysis reveals that the results on the MoS2 (s) conversion to Mo2C (s) fit into a modified parabolic rate law. Based on the thermochemical calculations and experimental findings, the probable
reaction scheme has been identified. Molycarbide appears to form by a three-successive solid-gas reaction path consisting
of (1) metal formation by the MoS2 (s)+CO (g) reaction followed by (2) in-situ carburization of Mo metal by CO (g), and finally (3) the scavenging of the COS (g) by lime, resulting in CaS (s). The latter
two reactions drive the overall reaction forward. Further, out of these three consecutive reactions, progress of the overall
MoS2+CaO+CO reaction seems to be governed by the intrinsic kinetics of the first one. Calcium molybdate, which forms as a transitory phase, plays a significant role by modifying the linear
kinetics of the MoS2 (s)+CO (g) to one of parabolic nature. 相似文献
17.
18.
Catalytic effect of iron on decomposition of carbon monoxide: I. carbon deposition in H2-CO Mixtures
Hematite ore reduced with hydrogen was used as a catalyst in the present investigation of the rate of decomposition of carbon monoxide in H2-CO mixtures. It was found that the amount of carbon deposited from purified carbon monoxide was directly proportional to the amount of porous iron catalyst present in the system. However, this simple relation did not hold for H2-CO mixtures. During carbon deposition the porous iron granules dis-integrated and were dispersed evenly in the carbon deposit. The deposit consisted of graphite, cementite and iron, with cementite/iron ratio increasing as more soot accumulated. When most of the iron was converted to cementite, carbon deposition ceased. A small amount of hydrogen enhanced markedly the rate of decomposition of carbon monoxide. Indications are that hydrogen adsorbed on iron catalyzes the decomposition of carbon monoxide, 2CO → C + CO2, in addition to the occurrence of the second reaction H2 + CO → C + H2O. 相似文献
19.
The reaction of iron and chromium oxides with carbon is considered. The decomposition of carbon monoxide is an important source of carbon at the surface of the iron oxides. In the reaction of Cr2O3 with carbon, the first stage includes dissociation of the oxides, with the liberation of atomic and molecular oxygen, and the formation of carbon oxides. Rapid reduction of chromium is ensured by the reaction of Cr2O3 with C3O2 and elementary carbon, which is produced from oxides. 相似文献
20.
The reaction of SiO(g) with carbon saturated iron plays an important role in silicon transfer in the iron blast furnace. In
the tuyere zone SiO(g) is generated from the reaction of coke with its ash, and the SiO(g) reacts with carbon saturated iron
droplets as they pass through the furnace. This reaction may also play a role as a gaseous intermediate reaction for the reduction
of SiO2 from slags by carbon dissolved in iron. The rate and controlling mechanism for the SiO reaction with carbon dissolved in
liquid iron was determined in the temperature range 1823 to 1923 K. A constant pressure of SiO(g) was generated by the reaction
of CO with SiO2; the reaction of carbon with SiO2 gave higher but decreasing pressures of SiO with time. The SiO(g) generated was then reacted with carbon saturated iron under
conditions for which the gas phase mass transfer conditions are clearly defined. By a systematic variation of the appropriate
variables it was demonstrated that the rate was controlled by gas phase transfer of SiO to the gas-metal interface. The rate
changed with gas diffusional distance but was not a strong function of temperature or of melt composition. The rate calculated
for gas phase mass transfer was in good agreement with the experimental results.
An erratum to this article is available at . 相似文献