Pharmaceutical fingerprinting in phase space. 2. Pattern recognition.

The current study introduces an approach for pattern recognition of drug manufacturers according to their HPLC trace impurity data. This method considers signals in phase space and accounts for two different types of noise: additive and perturbative. The pharmaceutical fingerprints are estimated as mean trajectories of HPLC trace impurity data and are used as reference models for recognition of new data by the minimal length classifier. The chromatographic trace organic impurity patterns collected from six different manufacturers of L-tryptophan are analyzed as an example. The prediction ability of the new method tested using three different cross-validation procedures remains about 95% even if the number of available data in the training sets decreases by 5 times. The accuracy of prediction in phase space is superior compared to results calculated using a Window Preprocessing method and artificial neural networks. The difference in performance between new and previous methods becomes more significant under particular conditions that are more adequate for practical application of the method. In addition, the current approach enables simple and comprehensive interpretation of the calculated results.     

Numerical analysis of fringe patterns recorded in holographic interferometry using high-order ambiguity function

This letter introduces a new approach for the demodulation of fringe patterns recorded in holographic interferometry using high-order ambiguity function (HAF). The proposed approach is capable of retrieving the phase from a single fringe pattern. The main advantage of this approach is that it directly provides an estimation of the continuous phase distribution and thereby avoids the necessity of using a cumbersome 2D phase unwrapping procedure. This method first computes the discrete-time analytic signal of the recorded fringe pattern. Then, by modelling this analytic signal as a polynomial phase signal embedded in additive complex white Gaussian noise, a parametric estimation procedure based on HAF is employed to directly estimate the unwrapped phase distribution. Numerical simulations and experimental results demonstrate the potential of the proposed approach.     

Split spectrum algorithms rely on instantaneous phase information-a geometrical approach [US NDE

Split spectrum algorithms for suppression of interference noise in ultrasonic nondestructive evaluation are known to work well when properly tuned. However, the algorithms are sensitive to certain parameter values and it is not clear how the algorithms use the phase and amplitude information available. This is partly because most split spectrum algorithms have been suggested heuristically without any detailed signal and noise model. A first step towards a model based approach to split spectrum is initiated. Based on a fairly detailed signal model, geometrical interpretations of the split spectrum concept are presented in an attempt to trace the phase and amplitude information utilized by the algorithms. In the light of gained theoretical knowledge, the conventional algorithms, polarity thresholding, minimization and geometric mean are evaluated. The geometrical approach is related to statistical pattern recognition and neural network approaches and the signal model is verified experimentally on real ultrasonic signals.     

Multiple signal classification technique for phase estimation from a fringe pattern

The paper introduces a multiple signal classification technique based method for fringe analysis. In the proposed method, the phase of a fringe pattern is locally approximated as a polynomial. The polynomial phase signal is then transformed to obtain signals comprising of only even- or odd-order polynomial coefficients. Subsequently, covariance matrix formulation is applied, and the two sets of coefficients are jointly estimated from the noise subspace of the covariance matrix using the multiple signal classification technique. The method allows simultaneous estimation of multiple coefficients and provides phase without the requirement of complex unwrapping algorithms. The effectiveness of the proposed method is validated through numerical simulation.     

Detection of signals at the output of gravity resonance antennas by estimation of the distribution parameters

The statistical problem of detection of a useful vector signal at the output of resonance spatially-separated gravitational antennas with overlapping directional patterns is considered. A method involving estimation of the distribution parameters of the additive noise at the output of an optimal linear system of whitewashing and matched filters is used to solve the problem. The additive noise is assumed to be a mixture of correlated Gaussian noise and rare random pseudo-gravitational signals (minimax detection criterion).     

基于超声相控技术的船舶吃水测量方法

为了解决内河船舶因超吃水引起的通航阻塞以及船舶安全问题,提出一种基于超声相控技术的船舶吃水测量方法。以超声相控技术为理论基础,通过控制一维线型超声相控阵列换能器发射聚焦声波,实现对目标船舶的相控扫描,获取各扫描点的回波信号;利用匹配滤波算法对回波信号进行滤波,改善信噪比;利用阈值法提取回波信号的时延;利用渡越时间法,计算出扫描点到各发射振元中心的距离,利用双曲交汇法计算出扫描点的空间坐标;分析回波信号幅值和扫描点位置坐标即可得到船舶吃水深度。为验证方法的可靠性,搭建了小比尺船模吃水测量实验系统,分析了110~140 mm不同吃水深度下的实验结果,计算了实际吃水与测量吃水间的相对误差。实验结果表明,使用匹配滤波法处理后的回波信号信噪比从15.26 dB提高至36.39 dB,实验时,最大相对误差出现在船舶实际吃水130 mm时,绝对误差为2.3 mm,相对误差为1.7%。     

Noise properties of a quadrature phase tracker for interferometricoptical fiber sensors

The noise performance of an electronic quadrature phase-detection system for interferometric optical fiber sensors is presented. Three noise sources are discussed in this work, namely, synchronous detection-circuit noise, phase-perturbation noise; and additive amplitude noise. We determined the output signal-to-noise ratio (SNR) experimentally as a function of input phase power for each of the three noise sources. For uncorrelated synchronous detection-circuit noise the output SNR increases monotonically with input phase power. For correlated noise the output SNR has distinct peaks due to noise cancellation. System performance is limited by uncorrelated detection-circuit noise which exhibits a threshold behavior in output SNR at a phase shift of 25 mrad/Hz^½. The phase noise has a more conventional behavior in the sense that SNR gain occurs only at the expense of dynamic performance. Uncorrelated amplitude noise also displays noise cancellation at certain discrete values of input phase, as is the case for correlated synchronous detection-circuit noise. System insensitivity to correlated light-source amplitude noise is evident from the fact that the output SNR is more than 30 dB higher than the input SNR     

基于相空间重构与独立分量分析的局部独立投影降噪算法

针对故障分析信号中存在噪声问题,提出一种将相空间重构与独立分量分析相结合的局部独立投影降噪算法。其中相空间重构的目的在于从高维相空间中恢复混沌吸引子,独立分量分析能够找到信号的主流形,选择邻域是为了将特征相近的相点结合在一起。使用该方法对正弦仿真信号和Lorenz仿真信号进行降噪处理,结果表明局部独立投影降噪算法的降噪效果与局部独立分量分析算法降噪效果接近,但优于全局投影降噪算法。运用该方法对低速重载轴承振动信号进行分析,准确判断出轴承故障。     

Development of sandwich HPLC microcolumns for analyte adsorption on the millisecond time scale

A new class of columns is reported that uses only microgram quantities of active support and that provides for the retention of biological compounds and other analytes on the millisecond time scale. This was accomplished by packing standard HPLC supports into layers as small as 60 microm in length and using only 90 microg of support material. This provided columns with effective residence times in the millisecond time range when routine HPLC flow rates and pressures were used. The retention of analytes by such columns was examined under both adsorption- and diffusion-limited conditions. The RPLC adsorption of hemoglobin (a system with diffusion-limited retention) was found to give 95% binding in as little as 4 ms. The adsorption of fluorescein by an anti-fluorescein antibody column (an adsorption-limited system) gave 95% retention in 100-120 ms. One application examined for these columns was their use in a chromatographic-based competitive binding immunoassay. This used bovine serum albumin (BSA) as the model analyte, and fluorescein-labeled BSA was used for detection. The resulting approach had a contact time of 180 ms between the sample and an anti-BSA immunoaffinity microcolumn and provided a signal within 5-25 s after sample injection. The columns developed in this work should also be useful in other situations that involve a small amount of a stationary phase or that require short column residence times.     

Retention of Ionizable Compounds on HPLC. 2. Effect of pH, Ionic Strength, and Mobile Phase Composition on the Retention of Weak Acids

A new model that relates the retention of a weak acid in HPLC columns with the pH and ionic strength of the mobile phase is derived and tested for different benzoic acids in methanol-water mobile phases. The proposed model uses the pH value in the mobile phase instead of the pH value in water, takes into account the effect of the activity coefficients, and considers different holdup times for the neutral and ionic species. The dependence of the holdup time of the ionic species on the mobile phase properties (pH, solvent composition, and ionic strength) is evaluated. It is demonstrated that the holdup time of the neutral species does not depend on the mobile phase properties, but the holdup time of the ionic species depends on the particular buffer used. The proposed equations can be combined with previously derived equations that relate the retention with the solvent composition of the mobile phase to establish a general model that relates the retention of the solute with the significant mobile phase properties: composition, pH, and ionic strength.     

离子迁移谱检测仪信号处理方法研究

离子迁移谱（IMs）检测仪是对化学毒剂、有毒有害气体等化学物质进行痕量检测和分析的一种有效的快速现场检测仪器．介绍了离子迁移谱检测仪的组成结构和工作原理,先后讨论了几种信号处理方法,并对含噪IMS信号进行了处理．结果表明,数据平均、平滑、数字滤波有效消除了IMS信号中的噪声,本底扣除消除了信号基线的非线性特征,求导数法能准确地确定谱峰的峰位,确定了以约化离子迁移率为特征值的识别方法．这为实现IMS信号的准确识别奠定了基础．     

Measuring ultrashort optical pulses in the presence of noise: an empirical study of the performance of spectral phase interferometry for direct electric field reconstruction

We have measured the performance of a real spectral phase interferometry for direct electric field reconstruction (SPIDER) apparatus operating under suboptimal conditions. We analyzed the errors in SPIDER's measurements of the temporal phases and intensities of 50-fs ultrashort laser pulses as a function of the additive noise in the detected signal. It was found that SPIDER performs exceptionally well, particularly in the case of additive noise. Specifically, a signal with 10% noise yields a pulse that has a mere 2% error in its intensity profile and a phase that differs from the nominal value by 0.2 rad. Furthermore, we quantified SPIDER's performance with limited detector resolution and as a function of signal averaging.     

Errors and uncertainties in the measurement of ultrasonic wave attenuation and phase velocity

This paper presents an analysis of the error generation mechanisms that affect the accuracy of measurements of ultrasonic wave attenuation coefficient and phase velocity as functions of frequency. In the first stage of the analysis we show that electronic system noise, expressed in the frequency domain, maps into errors in the attenuation and the phase velocity spectra in a highly nonlinear way; the condition for minimum error is when the total measured attenuation is around 1 Neper. The maximum measurable total attenuation has a practical limit of around 6 Nepers and the minimum measurable value is around 0.1 Neper. In the second part of the paper we consider electronic noise as the primary source of measurement error; errors in attenuation result from additive noise whereas errors in phase velocity result from both additive noise and system timing jitter. Quantization noise can be neglected if the amplitude of the additive noise is comparable with the quantization step, and coherent averaging is employed. Experimental results are presented which confirm the relationship between electronic noise and measurement errors. The analytical technique is applicable to the design of ultrasonic spectrometers, formal assessment of the accuracy of ultrasonic measurements, and the optimization of signal processing procedures to achieve a specified accuracy.     

Sub-threshold signal processing in arrays of non-identical nanostructures

Weak input signals are routinely processed by molecular-scaled biological networks composed of non-identical units that operate correctly in a noisy environment. In order to show that artificial nanostructures can mimic this behavior, we explore theoretically noise-assisted signal processing in arrays of metallic nanoparticles functionalized with organic ligands that act as tunneling junctions connecting the nanoparticle to the external electrodes. The electronic transfer through the nanostructure is based on the Coulomb blockade and tunneling effects. Because of the fabrication uncertainties, these nanostructures are expected to show a high variability in their physical characteristics and a diversity-induced static noise should be considered together with the dynamic noise caused by thermal fluctuations. This static noise originates from the hardware variability and produces fluctuations in the threshold potential of the individual nanoparticles arranged in a parallel array. The correlation between different input (potential) and output (current) signals in the array is analyzed as a function of temperature, applied voltage, and the variability in the electrical properties of the nanostructures. Extensive kinetic Monte Carlo simulations with nanostructures whose basic properties have been demonstrated experimentally show that variability can enhance the correlation, even for the case of weak signals and high variability, provided that the signal is processed by a sufficiently high number of nanostructures. Moderate redundancy permits us not only to minimize the adverse effects of the hardware variability but also to take advantage of the nanoparticles' threshold fluctuations to increase the detection range at low temperatures. This conclusion holds for the average behavior of a moderately large statistical ensemble of non-identical nanostructures processing different types of input signals and suggests that variability could be beneficial for signal processing. We demonstrate also that circuits composed of coupled non-identical nanoparticles can act as elementary nano-oscillators that show synchronization properties for sub-threshold stimuli. The results obtained should be of conceptual interest for the design of reliable signal processing schemes with non-identical nanostructures.     

隧道爆破振动信号混沌分形特征研究

为了分析隧道延时爆破时滞信号动力系统的非线性特征,在对新悬泉寺隧道爆破信号准确采集的基础上,运用混沌理论研究了经频率切片小波变换后各频带重构子信号的混沌动力学行为.通过子信号吸引子相轨迹特征对隧道爆破信号系统状态进行了直观描述和定量分析.结果表明:隧道爆破振动信号具有混沌特征,不同频带子信号吸引子在二维相空间一定区域内...     

隧道爆破振动信号混沌分形特征研究

为了分析隧道延时爆破时滞信号动力系统的非线性特征,在对新悬泉寺隧道爆破信号准确采集的基础上,运用混沌理论研究了经频率切片小波变换后各频带重构子信号的混沌动力学行为。通过子信号吸引子相轨迹特征对隧道爆破信号系统状态进行了直观描述和定量分析。结果表明:隧道爆破振动信号具有混沌特征,不同频带子信号吸引子在二维相空间一定区域内具有特定层次结构且永不封闭椭圆形轨迹。随着频率的增大,混沌吸引子在相空间的形态表现为椭圆轨迹的长/短轴之比逐渐减小,混沌吸引子在相空间沿长轴方向收缩,沿短轴扩展并最终趋于稳定,信号高频噪声具有弱混沌特征。混沌吸引子形态的演化过程有助于爆破信号幅值、能量信息的精确提取和主频有效判别,为隧道爆破信号非线性特征提取提供了新的思路。     

Incorporation of single-wall carbon nanotubes into an organic polymer monolithic stationary phase for mu-HPLC and capillary electrochromatography

Single-wall carbon nanotubes (SWNT) were incorporated into an organic polymer monolith containing vinylbenzyl chloride (VBC) and ethylene dimethacrylate (EDMA) to form a novel monolithic stationary phase for high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The retention behavior of neutral compounds on this poly(VBC-EDMA-SWNT) monolith was examined by separating a mixture of small organic molecules using micro-HPLC. The result indicated that incorporation of SWNT enhanced chromatographic retention of small neutral molecules in reversed-phase HPLC presumably because of their strongly hydrophobic characteristics. The stationary phase was formed inside a fused-silica capillary whose lumen was coated with covalently bound polyethyleneimine (PEI). The annular electroosmotic flow (EOF) generated by the PEI coating allowed peptide separation by CEC in the counterdirectional mode. Comparison of peptide separations on poly(VBC-EDMA-SWNT) and on poly(VBC-EDMA) with annular EOF generation revealed that the incorporation of SWNT into the monolithic stationary phase improved peak efficiency and influenced chromatographic retention. The structures of pretreated SWNT and poly(VBC-EDMA-SWNT) monolith were examined by high-resolution transmission electron microscopy, Raman spectroscopy, scanning electron microscopy, and multipoint BET nitrogen adsorption/desorption.     

Chiral separations performed by enhanced-fluidity liquid chromatography on a macrocyclic antibiotic chiral stationary phase

The use of enhanced-fluidity liquid chromatography (EFLC) for chiral separations was demonstrated on a macrocyclic antibiotic column, Chirobiotic-V. This technique was compared to high performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) for the separation of chiral compounds in normal-phase mode. The highest resolution was always observed for EFLC condition. Higher efficiency and shorter retention time were also observed for most separations with portions of CO(2) in the range of 0-50 mol %. Larger amounts of CO(2) caused efficiency to decrease and retention time to be prolonged. For some separations, the temperature was elevated to bring the mobile phase to the supercritical condition. Improved efficiency was obtained in SFC, whereas resolution and selectivity were worse. The use of EFLC in reversed-phase chiral separations was also tested. Enantiomer resolution improved under the EFLC condition. For the tested methanol/H(2)O mixture, fluoroform provided more significant improvements in chromatographic performance than CO(2) when used as a fluidity enhancing liquid. The use of EFLC instead of HPLC also caused a markedly lower pressure drop across the column for commonly used flow rates. The low-pressure drop will allow the use of longer columns or multiple columns to increase the total efficiency of the separation. Since chiral columns are often inefficient, this attribute may be very important for chiral separations.     

离散频谱分析比值校正法幅值和相位的抗噪性分析

谐波信号离散频谱分析的比值校正法(内插法)在无噪声时是一种准确的校正方法,只存在计算时的舍入误差,但在包含噪声尤其信噪比较低时,校正精度会有所下降,甚至误差很大.研究了比值校正法的幅值与相位加不同的窗函数及加性高斯白噪声时的统计方差公式,并通过不同信噪比下的仿真验证了其准确性.建议避免在归一化频率误差较低的情况下使用加矩形窗的比值校正法来校正相位.     

Performance of monolithic silica capillary columns with increased phase ratios and small-sized domains

Monolithic silica capillary columns for HPLC were prepared from tetramethoxysilane to have smaller sized domains and increased phase ratios as compared to previous materials, and their performance was evaluated. The monolithic silica columns possessed an external porosity of 0.65-0.76 and a total porosity of 0.92-0.95 and showed considerably higher performance and greater retention factors in a reversed-phase mode after chemical modification than columns previously reported. An octadecylsilylated monolithic silica column with the smallest domain size (through-pores of approximately 1.3 microm and silica skeletons of approximately 0.9 microm) showed a plate height of less than 5 microm at optimum linear velocities (u) of 2-3 mm/s in 80% acetonitrile for a solute having retention factors of approximately 1, and approximately 7 microm at u = 8 mm/s. With a permeability similar to that of a column packed with 5-microm particles, the monolithic silica columns were able to attain column efficiencies comparable to that of particulate columns packed with 2-2.5-microm particles, and showed performance in the "forbidden region" for the previous columns. The performance of the monolithic column can be compared favorably with that of a particle-packed column when 15,000-30,000 or more theoretical plates are desired at a pressure drop of 20-40 MPa or lower. The increased homogeneity of the co-continuous structures, in addition to the small-sized domains, contributed to the higher performance as compared to previous monolithic silica columns.