快速傅立叶变换用于色谱噪声平滑及微弱信号的检测

应用快速傅立叶变换法（ＦＦＴ）对色谱噪声进行平滑处理及微弱信号检测,同时,也与其他数字滤波法进行了比较。结果表明,利用ＦＦＴ法可以很好地对噪声进行平滑处理,使信噪比提高１８倍,为更好地进行痕量组分的色谱微弱信号检测打下了基础。     

自适应中值滤波用于色谱信号去噪的研究

在分析化学领域中，如何从被干扰的信号中有效去除噪声并恢复有用信号，具有重要的意义。此文从中值滤波基本概念出发，针对经典中值滤波器滑动窗口长度固定对信号去噪的影响，提出了自适应中值滤波器，通过对某元素色谱曲线进行去噪处理，并与移动均值法和小波变换法进行比较表明，此方法不仅能有效地滤除脉冲和高斯噪声，而且使色谱峰的边缘得到良好保护，从而提高了色谱数据分析的精确性。     

毛细管电泳信号的小波平滑与去噪

比较了小波去噪与小波平滑方法对毛细管电泳信号处理的差别.结果表明,用平滑方法处理毛细管电泳信号会使峰变宽变低,而用去噪方法处理引起有用信号的变化极小.     

激光拉曼光谱解谱和处理的方法研究

研究一种拉曼光谱解谱和处理的方法。以化学计量学为基础,信号处理技术为工具,配合计算机算法的数据处理方法。具体为基线校正:对拉曼光谱原始信号进行基于自适应迭代重加权惩罚最小二乘法的基线校正;平滑:对进行完基线校正的拉曼光谱信号进行基于惩罚最小二乘法的平滑;峰检测:对进行完基线校正和平滑的信号进行基于连续小波变换的峰检测。这种基于惩罚最小二乘法的光谱平滑具有快速,可以连续控制平滑度并且可以进行交叉验证得到最客观的平滑值。改善了基于非对称最小二乘法的传统基线校正方法的两个缺陷。同时,基于连续小波变换的峰检测算法可以自动地并且同时考虑峰形和峰高对峰进行检测,最大限度地降低了峰检测假阳性的概率。     

基于分形维数的分析信号自适应中值滤波

提出一种面向分析仪器谱图信号处理的分形维自适应中值波方法（AMeFFD）。该法延拓运用分形理论，定义了相对点盒维数概念，由此建立建立判定脉冲型噪声的特异性指标，从而可自动调节中值滤波窗口宽度，有效地滤除脉冲型噪声及其它类噪声。对仿真色谱信号及实测色谱图的处理结果表明：AMeFFD法克服了经典中值滤波算法的缺陷，无论在信号的均方根偏差还是谱峰差等指标上，均明显优于后者，能在确保谱峰不畸变的同时更有效地滤除脉冲型常见噪声，是处理化学谱图信号的有力工具。     

计算机快速富里叶变换应用于气相色谱痕量分析

将计算机快速富里叶变换(FFT)应用于高分辨率气相色谱痕量分析中,以增加色谱峰的S/N比(信号与噪声比),提高分析精度.对S/N非常低的色谱峰采用的这种计算机快速富里叶变换平滑新方法,可以提取出几乎被噪声淹没的色谱信号,使S/N比提高12倍以上,而色谱峰面积误差非常小.     

基于微型计算机的1.5次微分极谱法

作者研制了一个实时钟控制的高精度数据采集和处理系统,用于采集和处理了双组分体系悬汞电极线性扫描伏安数据。原始数据经过九点最小二乘法平滑滤波,利用卷积变换算法程序处理,得到了半积分、半微分和1.5次微分极谱图。这种基于微型计算机的新极谱法与电子模拟仪器相比,能更好地消除噪声干扰,改善分析方法的灵敏度和分辨率。     

电感耦合等离子体原子发射光谱分析中导数光谱法研究——Ⅱ.数据平滑和扫描步长的影响

数据平滑和扫描步长是两个重要求导条件。本工作用五点三次多项式平滑技术对扫描数据进行平滑处理以消除随机噪音,但平滑次数增大会导致信号失真从而使导数光谱的分辨能力降低。扫描步长减小能提高导数光谱的分辨能力,但同时导致导数光谱灵敏度减小。导数光谱中干扰物等效浓度IEC的大小是上述因素的综合反映。本文以IEC为考察指标,讨论了平滑次数和扫描步长的优化。     

小波变换用于高效液相色谱的噪声滤除

根据小波变换将信号分频的性质，用Ｈａａｒ小波成功地解决了高效液相色谱中噪音的扣除问题，并应用于乳酸－稀土络合物体系的色谱数据，得到的色谱曲线平滑且峰位置不变，大葱旁氡群徒档土思觳庀蕖?     

高效阴离子交换色谱-脉冲电化学检测方法和应用

评述了高效阴离子交换色谱和脉冲电化学检测方法。内容包括：色谱柱和流动相;糖和氨基酸在色谱柱上的保留行为;脉冲安培法(PAD)和积分脉冲安培法(IPAD);方法在糖和氨基酸分析中的应用。     

Quality and limits of a thermokinetic method to study gas—solid interactions

In order to test the qualities and limits of a thermokinetic method for the determination of adsorption rates, the adsorption of separate doses of oxygen on an initially nearly stoichiometric nickel oxide was studied at 473 K by two independent methods: calorimetry and pressure measurements.The calorimetric curves were corrected for instrumental distortion and compared with the results based on pressure curves. The following aspects of the correction procedure are discussed: determination of the instrument response function, smoothing procedure, influence of the ratio of the velocities of the instrument response and of the reaction under study.     

Nickel induces secretion of IFN-�� by splenic natural killer cells

Although nickel hypersensitivity is known as a delayed-type hypersensitivity mediated by nickel-specific T cells, it is greatly influenced by other immune cells. Here we show that splenic natural killer cells (NK cells) directly or indirectly respond to nickel by secretion of IFN-γ. Using enzyme-linked immunosorbent spot (ELISPOT) assays, we found that nickel-reactive cells readily secreted IFN-γ when splenocytes were cultured in the presence of varying concentrations of nickel sulfate (NiSO₄) for 24 h. However, nickel-reactive IL-2- or IL- 4-secreting cells were infrequent during the 24-h culture with NiSO₄. Immune responses to nickel were innate, not adaptive, in nature since the frequency of nickel-reactive IFN-γ-secreting cells did not increase upon previous exposure to NiSO₄ and recombination activating gene (RAG)-1-deficient mice contained nickel-reactive IFN-γ-secreting cells. The involvement of NK cells in the innate response to NiSO₄ was confirmed since we could observe a significant reduction of the frequency of nickel-reactive cells in NK cell-depleted mice. Furthermore, the number of IFN-γ secreting cells was significantly reduced in the ELISPOT assays when NKG2D was blocked by anti-NKG2D antibody. These results suggest that there is an early and rapid innate immune response to nickel, which is mediated by NK cells and the NKG2D receptor. The significance of the innate response to nickel is that it may contribute to development of the late T cell-mediated delayed type hypersensitivity against nickel.     

纳米二氧化硅对镍电沉积影响及在复合镀层中的化学键合状态

用线性扫描伏安法和电位阶跃法研究了n-SiO2/Ni复合电刷镀体系的电化学响应,探讨了纳米颗粒的影响;用X射线光电子谱研究了复合镀层中n-SiO2/Ni颗粒表面与基质金属间的相互作用．结果表明纳米颗粒使金属沉积过电位显著降低,电流效率、金属成核率及晶体生长速度增加,纳米颗粒对金属镍电结晶有明显的催化效应;n-SiO2/Ni表面氧的不饱和化学键与表面扩散过程中吸附态金属Ni原子键合形成Ni-O键,纳米颗粒与基质镍以化学键方式结合．     

Application of a Partial Least Squares Regression for the Determination of Nanomolar Concentrations of Scandium in the Presence of Nickel by Adsorptive Stripping Voltammetry

This paper presents the methodology of a very sensitive determination of scandium in excess of nickel by adsorptive stripping voltammetry on a mercury film electrode and PLS regression. A calibration set consisting of binary mixtures containing 5, 15, 25, 35 or 45×10^?9 M Sc(III) and simultaneously 0.5–50×10^?7 M of Ni(II) was used to develop the chemometric PLS calibrations. An external set containing synthetic mixtures of 10, 20, 30, 40×10^?9 M Sc(III) and the same Ni(II) concentration as mentioned above was used to validate the model and evaluate predictive ability. The application of data pretreatment techniques involving baseline correction, smoothing, range‐scaling, mean‐centering and their influence on the PLS model complexity, were also investigated. In the effect, the model for Sc(III), including 6 latent variables, was constructed. The model fulfills validation criteria and is characterized by a good prediction ability (majority of the prediction errors are lower than 10%). This work shows significant progress in the development of a very sensitive analytical technique for the determination of scandium in the presence of different concentrations of nickel by application of multivariate calibration tools.     

Non-aqueous sol–gel preparation of carbon-supported nickel nanoparticles

This work addresses the novel non-aqueous sol–gel process preparation of carbon-supported nickel nanoparticles. In the sol–gel process, ethanol, nickel nitrate or nickel (П) acetylacetonate, and citric acid were used as solvent, source of metallic element, and chelating agent, respectively. Hexadecylamine (HDA), oleic acid and oleylamine were used as surfactants. The calcination process was performed under protecting Ar or N₂ flowing. Carbon supported nickel nanoparticles can be prepared by this sol–gel process. Moreover, no grain growth occurs in a temperature range of 200 K, meaning that the grain size of the nickel nanoparticles can be controlled in this sol–gel process. The nickel nanoparticles can display typical superparamagnetic behavior at room temperature when HDA has been used. This novel method is expected to have wide applications in the field of metallic nanoparticles.     

Smoothing and differentiation of thermogravimetric data of biomass materials

Due to the experimental errors, the chemical effect of minor reactions, and some physical effects of heat and mass transfer, there usually exists much noise in the mass loss data resulted from thermal decomposition experiments, and thus high quality smoothing algorithm plays an important role in obtaining reliable derivative thermogravimetric (DTG) curves required for differential kinetic analysis. In this paper three smoothing methods, i.e. Moving Average smoothing, Gaussian smoothing, and Vondrak smoothing, are investigated in detail for pre-treatment of biomass decomposition data to obtain the DTG curves, and the smoothing results are compared. It is concluded that by choosing reasonable smoothing parameters based on the spectrum analysis of the data, the Gaussian smoothing and Vondrak smoothing can be reliably used to obtain DTG curves. The kinetic parameters calculated from the original TG curves and smoothed DTG curves have excellent agreement, and thus the Gaussian and Vondrak smoothing algorithms can be used directly and accurately in kinetic analysis.This work was sponsored by National Natural Science Foundation of China under Grants 50346038 and 50323005, the China NKBRSF project (No. 2001CB409600), the Anhui Excellent Youth Scientist Fundation (2004–2005), the Specialized Research Fund for the Doctoral Program of Higher Education and the National Key Technologies R&D Programme (2001BA510B09-03).     

漆原镍催化剂用于苯酚催化加氢

利用锌粉将NiCl₂液相还原制备漆原镍催化剂,考察了碱/酸活化方法、锌粉用量、还原温度、添加载体等条件下漆原镍催化苯酚加氢反应的性能。结果表明,锌粉还原的漆原镍催化剂可用NaOH或者乙酸活化处理,NaOH的效果优于乙酸。与不添加载体的催化剂相比,添加载体组分明显提高了金属镍的分散性和利用率。γ-Al₂O₃、CaCO₃、MgO均可作为漆原镍催化剂载体组分,而γ-Al₂O₃效果最好。还原剂锌粉用量、载体加入量过少或过多,都会造成催化剂活性降低,这与其影响金属镍的可接近性及分散性相关。无载体或加入载体的漆原镍催化剂均可在120~160 ℃催化苯酚加氢反应,主要产物为环己醇和环己酮,并以环己醇为主。     

Effect of the crosslinking degree and the nickel salt load on the thermal decomposition of poly(2-hydroxyethyl methacrylate) hydrogels and on the metal release from them

Polymeric matrices of poly(2-hydroxyethyl methacrylate) (PHEMA) crosslinked with different percentages of ethylene glycol dimethacrylate (EGDMA) as well as different loads of nickel salt were synthesized. Nickel release from the polymeric systems, and their thermal stability were analyzed. A high percentage of the nickel loaded was released, although strong interactions between the polymeric matrices and the nickel ion must be established since a total nickel release did not take place. The values of the diffusion coefficients showed that nickel release depended on the amount of nickel salt loaded in the polymeric matrix and also on the crosslinking degree of the gels. On the other hand, the presence of nickel salt induced an evident thermal instability in the polymeric matrices, although all the polymeric systems can be considered thermally stable.     

Pulsed Current Electrochemical Synthesis of Nickel Nanoclusters and Application as Catalyst for Hydrogen and Oxygen Revolution

The main objective of this research is to prepare nickel nanoparticles with more porous structure by the pulsed current electrochemical method. A nickel optimized nanopowder was synthesized by using nickel chloride (0.005 M) as precursor, silver nitrate as a nucleation agent (at 0.5% mole of nickel salt in the starting solution), polyvinyl pyrrolidone (PVP) as structure director (with PVP/Ni = 1.7 g/g), ammonia (2 M), and hydrazine as reduction agent (with Hydrazine/Ni = 16 g/g) by pulsed current of 58 mA cm⁻² with a frequency of 12 Hz. The morphology and particle size of each synthesized sample was studied by scanning electron microscopy (SEM). The obtained results showed that temperature has no considerable effect on the morphology and particle size of nickel nanopowder. The nickel nanopowder synthesized in optimum conditions has excellent uniform and a more porous structure including nanoclusters with a particle size of approximately 10–20 nm. The obtained results indicate that the pulsed current electrochemical method can be used as a confident and controllable method for the preparation of nickel nanoparticles. Optimized nickel nanoclusters were used as catalyst for hydrogen and oxygen revolutions. Cyclic Voltammetry results showed that the synthesized nanoclusters can facilitate hydrogen reduction and increase hydrogen and oxygen revolution rates.