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81.
玻璃药瓶中的氧气残留对瓶中药品的无菌特性造成了严重的威胁。采用波长调制光谱(Wavelength Modulated Spectrum, WMS)技术解调得到的二次谐波信号峰高值作为氧浓度反演的基础。然而,在用二次谐波信号测量气体浓度时,由于调制深度的变化会导致二次谐波峰值的变化,这通常会给系统带来误差,进而降低浓度的反演精度。而调制深度受调制电流波动、温度和压强变化等因素的影响不能直接计算获得进而修正。针对这一问题,本文成功地将调制深度与二次谐波峰高的关系转换为二次谐波峰宽和峰高的关系。然后,利用峰宽校正后的谐波峰高对气体浓度进行反演。初步实验表明,利用峰宽校正后的谐波峰高对瓶内气体浓度进行预测的准确性提高了2.1%,且系统的整体鲁棒性也得以提升。本文提出的校正方法不需要系统参数信息与气体成分信息,可以直接从谐波信号本身出发对调制深度进行校正,十分适合于工业现场的在线氧气浓度预测。 相似文献
82.
梳理基于等待门限判决的脉冲位置键控系统相关文献资料,发现文献给出的误比特率(BER)理论公式不能准确描述系统误比特率,尤其是在低信噪比情况下一些理论公式计算的误比特率已经高于0.5,超过了通信系统误比特率上限,不符合通信理论。分析了各文献资料误比特率理论公式推导过程中的问题所在,推导得到了一个新的误比特率理论公式。进行了数值仿真,结果表明,新的误比特率理论公式与仿真吻合良好,能够准确描述系统误比特率,并且在低噪比下计算的误比特率不高于0.5,符合通信理论。在新的误比特率理论公式基础上,分析了基于等待门限判决的脉冲位置键控系统能量效率,并与二进制相移键控(BPSK)系统进行了比较,表明基于等待门限判决的脉冲位置键控系统是一种具有较高能量效率的系统,在一定条件下甚至优于BPSK系统。 相似文献
83.
84.
示差脉冲伏安法测定黄酒中的酪氨酸 总被引:3,自引:0,他引:3
本文研究了硼砂介质中镍与酪氨酸络合物的示差脉冲吸附伏安特性,实验了仪器参数对示差脉冲阴极吸附伏安法的影响,在最佳条件下络合物峰电流与酪氨酸浓度在2.0×10^-7~4.0×10^-5mol.L^-1范围内有线性关系,并以此法测定了黄酒中酪氨酸的含量。 相似文献
85.
《Electroanalysis》2006,18(22):2225-2231
The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10?8 to 5×10?6 M with a detection limit of 1×10?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity. 相似文献
86.
Anna B. DenisovaVyacheslav Ya. Sosnovskikh Wim Dehaen Suzanne ToppetLuc Van Meervelt Vasiliy A. Bakulev 《Journal of fluorine chemistry》2002,115(2):183-192
Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c. 相似文献
87.
~~Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative@赵红卫$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@江致勤$Department of Chemistry, Tongji Unviersity!Shanghai 200092,China
@窦大营$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@吴铁一$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@王文锋$Shanghai… 相似文献
88.
The present paper deals with the speciation of selenium in potatoes (enriched or not in selenium). The study was carried out by using differential pulse cathodic stripping voltammetry (DPCSV) for quantifying selenium. Results obtained provide evidence that the selenium content in the protein fraction is rather independent from the selenium added to the plants during their growth. On the contrary, the amount of Se in the non-protein fraction (water and starch) in Se-enriched sample is significantly higher than in non-enriched one, suggesting that it is the main selenium-storing site. In this fraction the Se(VI)/Se(IV) ratio seems independent from selenium application but it may be related to the redox conditions. The accumulation of selenium in the non-protein fraction is tentatively ascribed to the “Se–starch interaction” that should be able to modulate both the Se absorption into proteins and, possibly, its toxic effect for the plant itself. 相似文献
89.
Voltammetric behaviour and determination of moxifloxacin in pharmaceutical products and human plasma
Erk N 《Analytical and bioanalytical chemistry》2004,378(5):1351-1356
The oxidative behaviour of moxifloxacin was studied at a glassy carbon electrode in different buffer systems using cyclic, differential pulse, and Osteryoung square-wave voltammetry. The oxidation process was shown to be irreversible over the entire pH range studied (2.0–10.0) and was diffusion-controlled. The methods were performed in Britton–Robinson buffer and the corresponding calibration graphs were constructed and statistical data were evaluated. When the proposed methods were applied at pH 6.0 linearity was achieved from 4.4×10–7 to 1.0×10–5 mol L–1. Applicability to tablets and human plasma analysis was illustrated. Furthermore, a high-performance liquid chromatographic method with diode-array detection was developed. A calibration graph was established from 4.0×10–6 to 5.0×10–5 mol L–1 moxifloxacin. The described methods were successfully employed with high precision and accuracy for estimation of the total drug content of human plasma and for pharmaceutical dosage forms of moxifloxacin. 相似文献
90.
《Electroanalysis》2004,16(5):355-359
Water present in undiluted acetic acid can be monitored in situ with Pt and Au microelectrodes using differential pulse and square‐wave voltammetries. Both reduction and oxidation peaks can be obtained. The best quantitative analytical results were obtained for the anodic peak, the Pt microelectrode, and differential pulse voltammetry. The anodic water peak is located at +1.55 V vs. the quasi reference Pt electrode. The voltammetric peak obtained at Pt electrode is apparently not a diffusional one, however, the calibration plot obtained by employing this peak is linear over a wide concentration range, up to 4 mol dm?3. The detection limit has been estimated as 2.3 mM or 0.0043 v/v%. The developed method may be particularly useful, since the Karl Fischer method can not be used to determine water in glacial acetic acid due to the estrification reaction of acetic acid with methanol. A voltammetric wave of undiluted acetic acid could not be obtained in the positive and negative ranges of potential. 相似文献