A New Method to Resolve Overlapped Voltammetric Peaks

A new method called spline convolution (SC) for resolving overlapped peaks was proposed in this paper. The differential pulse voltammetric overlapped peaks of mixtures of Pb(Ⅱ） and T1(I) were investigated by this method, and satisfactory results were obtained. The results show excellent correlation between peak areas of the processed signals and the concentrations.     

Compact program resolves overlapping voltammetric peaks

A simple self-contained program designed to separate overlapping peaks from electrochemical analyses is presented. Combining an original interactive way to define initial parameter estimates with nonlinear curve fitting based on the simplex method of optimization, it allows the user to resolve voltammograms consisting of 2 to 5 analytical peaks raised on a straight base line. The program provides highly intuitive interface, easy operation, and straightforward result documentation. A free package including the program, three data files and user instructions is available on request.     

Resolution of overlapping capillary electrophoresis peaks by using chemometric analysis: quantification of the components in compound reserpine tablets

The application of multivariate curve resolution with alternating least squares (MCR-ALS) methods to second-order data from capillary electrophoresis with diode array detector (CE-DAD) is reported. Initial qualitative solutions obtained by evolving factor analysis (EFA) and pure-variable detection method can be further optimized by a simultaneous analysis of multiple electrophoresis run data with ALS regression. While unknown samples are analyzed simultaneously against the corresponding standards in different composition ratios, the exact amounts of common components in different CE runs can be determined by the traditional calibration curve method, and quantification can thus be achieved. The above methods are applied to the determination of the components in compound reserpine tablets in overlapping peaks from CE. The quantification results are compared with those of the first derivative of the electropherogram method and artificial neural network (ANN) method.     

Unknown biological mixtures evaluation using STR analytical quantification

Allelic quantification of STRs, where the presence of three or more alleles represents mixtures, provides a novel method to identify mixtures from unknown biological sources. The allelic stutters resulting in slightly different repeat containing products during fragment amplification can be mistaken for true alleles complicating a simple approach to mixture analysis. An algorithm based on the array of estimated stutters from known samples was developed and tuned to maximize the identification of true non-mixtures through the analysis of three pentanucleotide STRs. Laboratory simulated scenarios of needle sharing generated 58 mixture and 38 non-mixture samples that were blinded for determining the number of alleles. Through developing and applying an algorithm that additively estimates stuttering around the two highest peaks, mixtures and non-mixtures were characterized with sensitivity of 77.5, 82.7 and 58% while maintaining the high specificity of 100, 97.4 and 100 for the W, X, and Z STRs individually. When all three STRs were used collectively, the resulting sensitivity and specificity was 91.4 and 97.4%, respectively. The newly validated approach of using multiple STRs as highly informative biomarkers in unknown sample mixture analyses has potential applications in genetics, forensic science, and epidemiological studies.     

Chalcogen-doped zinc oxide nanoparticles for photocatalytic degradation of Rhodamine B under the irradiation of ultraviolet light

In the present work, the chalcogen (Se²⁺)-doped ZnO nanoparticles (SeZO-NPs) were synthesized using sol-gel precipitation method and tested for photocatalytic degradation of Rhodamine B (RhB). X-ray diffraction pattern of SeZO-NPs showed the hexagonal wurtzite crystal structure regardless of Se concentration. The band edge and defect-level emissions of SeZO-NPs were determined by using the photoluminescence spectra with the excitation source of 370 nm. The bandgap, E_g, of SeZO-NPs was measured from diffused reflectance spectroscopy, which increased from 3.22 to 3.26 eV as Se concentration increased from 0 to 10 wt.%. The highest specific surface area and lowest pore size of 5-SeZO-NPs were observed to be 36.42 m²/g and 13.48 nm, respectively. The photocatalytic degradation of SeZO-NPs was measured under the illumination of ultraviolet (UV) light. The double donor (Se) played an important role toward photodegradation of RhB via reducing the recombination of charge carriers. The highest photocatalytic degradation (98.23%) and mineralization were achieved for the sample 5-SeZO (Se: 5 wt.%). The improved photocatalytic performance of 5-SeZO was attributed to the optimum Se dopant concentration for the production of more reactive oxygen species because of effective separation of charge carriers in UV light.     

2nd-order spline wavelet convolution method in resolving chemical overlapped peaks

A 2nd-order spline wavelet convolution method in resolving overlapped peaks is developed. It determines the number of peaks, peak positions and width through wavelet's convolution, then uses spline function to construct the resoluter, which is used to resolve overlapped peaks. Theoretical proof is given, and the selections of wavelets and parameters are discussed. It is proven that baseline separation can be achieved after processed, the relative errors of peak position and area are less than 0.2% and 4.0% respectively. It can be directly applied to seriously overlapped signals, noisy signals and multi-component signals, and the results are satisfactory. It is a novel effective method for resolution.     

含间位取代苯基聚醚酮酮的结晶与晶体结构研究

通过差示扫描法（ＤＳＣ）及广角Ｘ-射线衍射（ＷＡＸＤ）技术研究了含间位取代苯基聚醚酮酮（ＰＥＫｍＫ）的结晶行为与晶体结构．Ｘ-射线结果表明,从熔融态及玻璃态结晶时,ＰＥＫｍＫ只有一种晶型,其晶胞参数为：ａ＝０.７６７２ｎｍ,ｂ＝０.６１４９ｎｍ,ｃ＝１.５９９ｎｍ．ＤＳＣ结果表明,ＰＥＫｍＫ热分析曲线都出现了熔融双峰,低熔融峰（ＤＯＷｎ）热焓占总热焓４～７％,它源于初始结晶形成的同一晶型不同厚度片晶．低熔融峰在２５０℃以上结晶转化成高熔融峰（Ｉ）,ＰＥＫｍＫ平衡熔点为２９５℃.     

噻菌灵农药的表面增强拉曼光谱分析

利用表面增强拉曼光谱技术(SERS)分析噻菌灵农药的拉曼特征峰。采用微波法制备银溶胶表面增强基底,利用激光显微共焦拉曼光谱仪分别采集514.5和785 nm激发波长下的噻菌灵农药拉曼光谱,解析不同激发波长下的拉曼特征峰并进行比较。结果表明：不同激发波长下噻菌灵的拉曼峰强度和拉曼频移差异较大,514.5 nm激发波长下的782和1 012 cm-1最强,是C—H变形振动较强特征峰,而785 nm激发波长下的1 284,1 450和1 592 cm-1最强,是环振动和CN伸缩振动较强特征峰。对比分析各个激发波长下噻菌灵的SERS谱图,找到了噻菌灵农药的5个较强特征拉曼峰：782,1 012,1 284,1 450和1 592 cm-1。这些特征峰可作为食品及农产品中噻菌灵农药残留定性定量判别的依据。     

基于多适应度量子遗传算法的X射线荧光重叠峰分解

智能算法在对谱峰重叠严重的复杂地质样品进行分析时,往往存在计算量过大、弱峰误差较大、收敛于局部极小值或不收敛等问题。量子遗传算法因其具有良好的收敛性,可用于X射线荧光光谱重叠峰的分解。针对X射线荧光分析过程中经常遇到的谱峰重叠问题,提出了一种基于元素关联高斯混合模型（GMM-ER）和多适应度量子遗传算法的重叠峰分解方法。首先介绍了基于元素K系和L系特征X射线的重叠峰GMM-EB模型。然后基于X射线荧光光谱的物理特性,对传统量子遗传算法进行了改进,引入了多适应度函数。由锰、铁、钴和镍的特征X射线产生一段谱峰严重重叠的模拟光谱,然后基于GMM-EB模型,分别用传统量子遗传算法和改进的多适应度量子遗传算法对模拟光谱进行了10次解析。实验结果显示,改进后的量子遗传算法的重叠峰分解精度平均提高了32.1%,最佳分解精度提高了73.9%。应用改进量子遗传算法进行分解时,含量比例低的元素分解精度得到较大改善,最佳情况下元素分解的相对误差范围缩小了64.5%。并且,改进算法收敛速度快于传统算法。该方法适合严重重叠谱峰的分解,且对弱峰有较高的分解精度。