Spectrophotometric and chemometric studies on the simultaneous determination of two benzodiazepines in human plasma

A numerical simple, accurate and precise method based on spectrophotometric data coupled with multivariate calibration methods, PLS and MLR, combined with GA was developed for the simultaneous determination of two benzodiazepines, Clobazam and Flurazepam. A data set of absorption spectra obtained from a calibration set of mixtures containing the compounds was used to build GA-PLS and GA-MLR models. The models were tested using a dataset constructed from the compound synthetic solutions. The better model was also applied to plasma samples. The proposed method requires no preliminary separation steps and can be used for these drugs analysis in quality control laboratories.     

Effects of nonlinearities and uncorrelated or correlated errors in realistic simulated data on the prediction abilities of augmented classical least squares and partial least squares

Comparisons of prediction models from the new augmented classical least squares (ACLS) and partial least squares (PLS) multivariate spectral analysis methods were conducted using simulated data containing deviations from the idealized model. The simulated data were based on pure spectral components derived from real near-infrared spectra of multicomponent dilute aqueous solutions. Simulated uncorrelated concentration errors, uncorrelated and correlated spectral noise, and nonlinear spectral responses were included to evaluate the methods on situations representative of experimental data. The statistical significance of differences in prediction ability was evaluated using the Wilcoxon signed rank test. The prediction differences were found to be dependent on the type of noise added, the numbers of calibration samples, and the component being predicted. For analyses applied to simulated spectra with noise-free nonlinear response, PLS was shown to be statistically superior to ACLS for most of the cases. With added uncorrelated spectral noise, both methods performed comparably. Using 50 calibration samples with simulated correlated spectral noise, PLS showed an advantage in 3 out of 9 cases, but the advantage dropped to 1 out of 9 cases with 25 calibration samples. For cases with different noise distributions between calibration and validation, ACLS predictions were statistically better than PLS for two of the four components. Also, when experimentally derived correlated spectral error was added, ACLS gave better predictions that were statistically significant in 15 out of 24 cases simulated. On data sets with nonuniform noise, neither method was statistically better, although ACLS usually had smaller standard errors of prediction (SEPs). The varying results emphasize the need to use realistic simulations when making comparisons between various multivariate calibration methods. Even when the differences between the standard error of predictions were statistically significant, in most cases the differences in SEP were small. This study demonstrated that unlike CLS, ACLS is competitive with PLS in modeling nonlinearities in spectra without knowledge of all the component concentrations. This competitiveness is important when maintaining and transferring models for system drift, spectrometer differences, and unmodeled components, since ACLS models can be rapidly updated during prediction when used in conjunction with the prediction augmented classical least squares (PACLS) method, while PLS requires full recalibration.     

近红外光谱法测定茶多酚中总儿茶素含量

以高效液相色谱(HPLC)分析结果为参考值,建立了快速测量茶多酚中总儿茶素含量的近红外光谱定标模型.将48份茶多酚样品组成定标样品集,在1000～2500nm(4000～10000cm-1)的近红外漫反射光谱为定标波长范围内,光谱经一阶导数(Firstderivative)、二阶导数(Secondderivative)、标准归一化(Stan-dardnormalvariate,SNV)和多元散射校正(multiplicativesignalcorrection,MSC)处理后结合偏最小二乘回归(PLS)定标.经内部交叉验证表明,光谱经SNV处理后建模结果最佳.模型的相关系数Corr.Coeff=0.997,校正均方根RMSEC=1.71%.比较了经典最小二乘法(CLS)、偏最小二乘法(PLS)和主成分回归(PCR)等方法建模结果,以偏最小二乘回归建模效果最好.     

Redundancy allocation for multi-state systems using physical programming and genetic algorithms

This paper proposes a multi-objective optimization model for redundancy allocation for multi-state series–parallel systems. This model seeks to maximize system performance utility while minimizing system cost and system weight simultaneously. We use physical programming as an effective approach to optimize the system structure within this multi-objective optimization framework. The physical programming approach offers a flexible and effective way to address the conflicting nature of these different objectives. Genetic algorithm (GA) is used to solve the proposed physical programming-based optimization model due to the following three reasons: (1) the design variables, the number of components of each subsystems, are integer variables; (2) the objective functions in the physical programming-based optimization model do not have nice mathematical properties, and thus traditional optimization approaches are not suitable in this case; (3) GA has good global optimization performance. An example is used to illustrate the flexibility and effectiveness of the proposed physical programming approach over the single-objective method and the fuzzy optimization method.     

Blank augmentation protocol for improving the robustness of multivariate calibrations

An updating procedure is described for improving the robustness of multivariate calibration models based on near-infrared spectroscopy. Employing a single blank sample containing no analyte, repeated spectra are acquired during the instrumental warm-up period. These spectra are used to capture the instrumental profile on the analysis day in a way that can be used to update a previously computed calibration model. By augmenting the original spectra of the calibration samples with a group of spectra collected from the blank sample, an updated model can be computed that incorporates any instrumental drift that has occurred. This protocol is evaluated in the context of an analysis of physiological levels of glucose in a simulated biological matrix designed to mimic blood plasma. Employing data of calibration and prediction samples acquired over approximately six months, procedures are studied for implementing the algorithm in conjunction with calibration models based on partial least squares (PLS) regression. Over the range of 1-20 mM glucose, the final algorithm achieves a standard error of prediction (SEP) of 0.79 mM when the augmented PLS model is applied to data collected 176 days after the collection of the calibration spectra. Without updating, the original PLS model produces a seriously degraded SEP of 13.4 mM.     

The effect of flow rate, accelerometer location and temperature in acoustic chemometrics on liquid flow: Spectral changes and robustness of the prediction models

Prediction of chemical composition of flowing liquids using passive acoustic measurements and multivariate regression (acoustic chemometrics) has been reported as a promising in-line measurement method. However, the passive acoustic measurement results are also affected directly or indirectly by other factors than composition of the liquid, i.e. physical conditions of the flow and equipment/pipe properties. The present study focuses on the effects of flow rate, accelerometer location and temperature on the acoustic spectra and prediction of composition of liquids. The studied liquids were two-component mixtures of sucrose and water, and three-component mixtures of ethanol, sucrose and water. Multivariate models were estimated using both local and global calibration on full spectra, and augmented frequency and amplitude matrices derived from full spectra. Flow rate and accelerometer location had the most pronounced effect on acoustic spectra and prediction results from recalibrated local models. Temperature had a minor effect on the acoustic spectra and prediction results. The prediction error for determination of ethanol, sucrose and water increased with increasing flow rate. Changes in flow rate resulted in considerable spectral variations, causing the resultant local calibration model to perform poorly predicting the new samples taken at other flow conditions. Global models performed well on prediction of liquid composition at all studied flow and temperature levels. The global models, however, needed higher number of PLS factors and led to higher prediction errors compared to local models. Using the augmented frequency and amplitude matrices in PLS/PPLS global regression models led to higher prediction errors compared to full spectra models. However, the augmented frequency and amplitude models were more parsimonious (4–6 PLS factors) compared to the full spectra models (10–12 PLS factors).     

Sparse partial least-squares regression and its applications to high-throughput data analysis

The partial least-squares (PLS) method is designed for prediction problems where the number of predictors is larger than the number of training samples. PLS is based on latent components that are linear combinations of all of the original predictors, so it automatically employs all predictors regardless of their relevance. This will potentially compromise its performance, but it will also make it difficult to interpret the result. In this paper, we propose a new formulation of the sparse PLS (SPLS) procedure to allow both sparse variable selection and dimension reduction. We use the standard L₁-penalty and the unbounded penalty of [1]. We develop a computing algorithm for SPLS by modifying the nonlinear iterative partial least-squares (NIPALS) algorithm, and illustrate the method with an analysis of a cancer dataset. Through the numerical studies we find that our SPLS method generally performs better than the standard PLS and other existing methods in variable selection and prediction.     

Extracting coal ash content from laser-induced breakdown spectroscopy (LIBS) spectra by multivariate analysis

Laser-induced breakdown spectroscopy (LIBS) combined with partial least squares (PLS) analysis has been applied for the quantitative analysis of the ash content of coal in this paper. The multivariate analysis method was employed to extract coal ash content information from LIBS spectra rather than from the concentrations of the main ash-forming elements. In order to construct a rigorous partial least squares regression model and reduce the calculation time, different spectral range data were used to construct partial least squares regression models, and then the performances of these models were compared in terms of the correlation coefficients of calibration and validation and the root mean square errors of calibration and cross-validation. Afterwards, the prediction accuracy, reproducibility, and the limit of detection of the partial least squares regression model were validated with independent laser-induced breakdown spectroscopy measurements of four unknown samples. The results show that a good agreement is observed between the ash content provided by thermo-gravimetric analyzer and the LIBS measurements coupled to the PLS regression model for the unknown samples. The feasibility of extracting coal ash content from LIBS spectra is approved. It is also confirmed that this technique has good potential for quantitative analysis of the ash content of coal.     

Rule extraction from an optimized neural network for traffic crash frequency modeling

This study develops a neural network (NN) model to explore the nonlinear relationship between crash frequency and risk factors. To eliminate the possibility of over-fitting and to deal with the black-box characteristic, a network structure optimization algorithm and a rule extraction method are proposed. A case study compares the performance of the trained and modified NN models with that of the traditional negative binomial (NB) model for analyzing crash frequency on road segments in Hong Kong. The results indicate that the optimized NNs have somewhat better fitting and predictive performance than the NB models. Moreover, the smaller training/testing errors in the optimized NNs with pruned input and hidden nodes demonstrate the ability of the structure optimization algorithm to identify the insignificant factors and to improve the model generalization capacity. Furthermore, the rule-set extracted from the optimized NN model can reveal the effect of each explanatory variable on the crash frequency under different conditions, and implies the existence of nonlinear relationship between factors and crash frequency. With the structure optimization algorithm and rule extraction method, the modified NN model has great potential for modeling crash frequency, and may be considered as a good alternative for road safety analysis.     

Near-infrared spectroscopic measurement of urea in dialysate samples collected during hemodialysis treatments

Single-beam spectra were collected over the combination region of the near-infrared spectrum for 80 samples collected from 15 people over a two-week period. Partial least-squares (PLS) regression was used to generate an optimized calibration model for urea. PLS calibration models accurately measure urea in the spent dialysate matrix. Prediction errors are on the order of 0.15 mM, which is sufficient for the clinical assessment of the dialysis process. In addition, the feasibility of a global calibration model is demonstrated by generating a calibration model from samples and spectra obtained from 12 people to predict the level of urea in samples collected from 3 different people. In this case, the standard error of prediction is 0.09 mM. Spectra were modified in order to systematically examine the impact of resolution and noise. Little impact is observed by altering the spectral resolution from 4 to 32 cm-1. Spectral noise, however, plays an important role in the accuracy of these calibration models. Increasing the magnitude of the spectral noise increases the prediction errors and increases the width of the spectral range necessary for extracting the analytical information. The utility of the method is demonstrated by analyzing dialysate samples collected during actual dialysis treatments. In addition, the necessary resolution and spectral quality necessary for reliable on-line urea monitoring is identified. These findings indicate that a dedicated, on-line urea spectrometer must posses a resolution of 16 cm-1 coupled with a sample thickness of 1.5 mm and spectral noise levels on the order of 25 micro-absorbance units when measured as the root-mean-square (RMS) noise of 100% lines.     

Effect on the partial least-squares prediction of yarn properties combining raman and infrared measurements and applying wavelength selection

The combination of Raman and infrared spectroscopy on the one hand and wavelength selection on the other hand is used to improve the partial least-squares (PLS) prediction of seven selected yarn properties. These properties are important for on-line quality control during production. From 71 yarn samples, the Raman and infrared spectra are measured and reference methods are used to determine the selected properties. Making separate PLS models for all yarn properties using the Raman and infrared spectra, prior to wavelength selection, reveals that Raman spectroscopy outperforms infrared spectroscopy. If wavelength selection is applied, the PLS prediction error decreases and the correlation coefficient increases for all properties. However, a substantial wavelength selection effect is present for the infrared spectra compared to the Raman spectra. For the infrared spectra, wavelength selection results in PLS prediction errors comparable with the prediction performance of the Raman spectra prior to wavelength selection. Concatenating the Raman and infrared spectra does not enhance the PLS prediction performance, not even after wavelength selection. It is concluded that an infrared spectrometer, combined with a wavelength selection procedure, can be used if no (suitable) Raman instrument is available.     

Multi-objective hierarchical genetic algorithms for multilevel redundancy allocation optimization

Multilevel redundancy allocation optimization problems (MRAOPs) occur frequently when attempting to maximize the system reliability of a hierarchical system, and almost all complex engineering systems are hierarchical. Despite their practical significance, limited research has been done concerning the solving of simple MRAOPs. These problems are not only NP hard but also involve hierarchical design variables. Genetic algorithms (GAs) have been applied in solving MRAOPs, since they are computationally efficient in solving such problems, unlike exact methods, but their applications has been confined to single-objective formulation of MRAOPs. This paper proposes a multi-objective formulation of MRAOPs and a methodology for solving such problems. In this methodology, a hierarchical GA framework for multi-objective optimization is proposed by introducing hierarchical genotype encoding for design variables. In addition, we implement the proposed approach by integrating the hierarchical genotype encoding scheme with two popular multi-objective genetic algorithms (MOGAs)—the strength Pareto evolutionary genetic algorithm (SPEA2) and the non-dominated sorting genetic algorithm (NSGA-II). In the provided numerical examples, the proposed multi-objective hierarchical approach is applied to solve two hierarchical MRAOPs, a 4- and a 3-level problems. The proposed method is compared with a single-objective optimization method that uses a hierarchical genetic algorithm (HGA), also applied to solve the 3- and 4-level problems. The results show that a multi-objective hierarchical GA (MOHGA) that includes elitism and mechanism for diversity preserving performed better than a single-objective GA that only uses elitism, when solving large-scale MRAOPs. Additionally, the experimental results show that the proposed method with NSGA-II outperformed the proposed method with SPEA2 in finding useful Pareto optimal solution sets.     

Rough-Fuzzy-GA-based design of Al alloys having superior cryogenic performance

Multi-objective genetic algorithm (GA) is employed for the optimal design of novel heat-treatable aluminum alloys with superior performance at cryogenic temperatures. Existing database on age-hardenable aluminum alloys is utilized to create a learning model. Composition and processing parameters of the alloys are considered as the inputs, whereas mechanical properties, viz. YS (Yield Strength), UTS (Ultimate Tensile Strength) and %Elongation tested at subzero temperatures, are used as the outputs, which characterize the performance of the alloy. Data-driven models are developed using the hybrid rough-fuzzy approach. While rough set brings out the most significant variables and formulates if-then rules to explain the relationships between inputs and outputs, fuzzy inference system (FIS) serves as the predictive model. Strength and ductility of the Al alloys at low temperature being conflicting in nature are simultaneously optimized using multi-objective GA to design alloys having an optimal blend of the two properties.     

Parallel genetic algorithm co-optimization of spectral pre-processing and wavelength selection for PLS regression

Spectral pre-processing and variable selection are often used to produce PLS regression models with better prediction abilities.We proposed here to optimize simultaneously the spectral pre-processing and the variable selection for PLS regression. The method is based on parallel genetic algorithm with a unique chromosome coding both for pre-processing and variable selections. A pool of 31 pre-processing functions with various settings is tested. In the same chromosome several pre-processing steps can be combined.Three near infrared spectroscopic datasets have been used to evaluate the methodology. The efficacy of the co-optimization is evaluated by comparing the prediction ability of the PLS models with those after pre-processing optimization only. The effect of the number of successive pre-processing steps has been also tested.Concerning the different datasets used here, one can observe two different behaviors. In a first case the GA co-optimization procedure is found to perform well, leading to important improvement of the prediction ability especially when three consecutive pre-processing techniques are applied. In a second case, only the preprocessing optimization is enough to obtain an optimal model. All these models are optimal and more accurate compared to the classical models (build with the “trial and error” methods).     

Predicting motor vehicle collisions using Bayesian neural network models: an empirical analysis

Statistical models have frequently been used in highway safety studies. They can be utilized for various purposes, including establishing relationships between variables, screening covariates and predicting values. Generalized linear models (GLM) and hierarchical Bayes models (HBM) have been the most common types of model favored by transportation safety analysts. Over the last few years, researchers have proposed the back-propagation neural network (BPNN) model for modeling the phenomenon under study. Compared to GLMs and HBMs, BPNNs have received much less attention in highway safety modeling. The reasons are attributed to the complexity for estimating this kind of model as well as the problem related to "over-fitting" the data. To circumvent the latter problem, some statisticians have proposed the use of Bayesian neural network (BNN) models. These models have been shown to perform better than BPNN models while at the same time reducing the difficulty associated with over-fitting the data. The objective of this study is to evaluate the application of BNN models for predicting motor vehicle crashes. To accomplish this objective, a series of models was estimated using data collected on rural frontage roads in Texas. Three types of models were compared: BPNN, BNN and the negative binomial (NB) regression models. The results of this study show that in general both types of neural network models perform better than the NB regression model in terms of data prediction. Although the BPNN model can occasionally provide better or approximately equivalent prediction performance compared to the BNN model, in most cases its prediction performance is worse than the BNN model. In addition, the data fitting performance of the BPNN model is consistently worse than the BNN model, which suggests that the BNN model has better generalization abilities than the BPNN model and can effectively alleviate the over-fitting problem without significantly compromising the nonlinear approximation ability. The results also show that BNNs could be used for other useful analyses in highway safety, including the development of accident modification factors and for improving the prediction capabilities for evaluating different highway design alternatives.     

基于性能衰退评估的轴承寿命状态识别方法研究

针对滚动轴承退化性能难以评估、寿命状态难以识别的难题,提出一种基于性能衰退评估的轴承寿命状态识别新方法,该方法基于卷积自编码器(convolutional autoencoder,CAE)与多维尺度分析(multidimensional scaling,MDS)算法构建轴承性能衰退指标,再根据构建指标和改进卷积神经网络(convolutional neural network,CNN)建立轴承寿命状态识别模型,实现轴承寿命状态识别。将轴承信号样本输入CAE,实现轴承寿命状态特征的自动提取与表达,再将所提取的特征通过MDS算法进行约简获得低维特征,在低维特征空间构造欧氏距离作为轴承性能衰退指标,依据指标实现轴承数据标签化。使用标签化的轴承数据训练CNN,建立轴承寿命状态识别模型。在训练过程中,为抑制过拟合,对原始训练样本进行加噪处理,为提高模型抗干扰能力,将Leaky ReLU(LReLU)函数和dropout作为激活函数。运用轴承全寿命试验数据对识别模型进行检验,通过对比验证,结果表明所提出的轴承寿命状态识别方法能更准确的实现轴承寿命状态识别。     

基于遗传算法的碳纤维增强树脂复合材料层合板单搭胶接结构的多目标优化

基于遗传算法对碳纤维增强树脂复合材料(CFRP)层合板单搭胶接结构进行了多目标优化,以提高其结构性能.首先,通过三维Hashin准则和三角形内聚力模型建立三维有限元模型来预测CFRP层内损伤过程、层间失效和胶层损伤过程,并通过试验验证其有效性.其次,利用拉丁超立方抽样(LHS)方法和二次多项式响应面法(RSM),基于搭...     

遗传神经网络在木塑复合材料力学性能预测中的应用

利用遗传算法(GA)和神经网络对木塑复合材料力学性能进行预测。首先利用神经网络构建木塑复合板材主要工艺参数热压时间(T)、马来酸酐(MA)和废旧塑料聚丙烯(PP)与材料力学性能内结合强度(IB)、静曲强度(MOR)、弹性模量(MOE)和吸收厚度膨胀率(TS)之间的关系模型,然后利用遗传算法对模型进行优化和训练;最后利用训练好模型对材料的力学性能进行预测以及模型验证。结合显示优化模型预测的板材的MOE的误差范围分别为2%～15.5%、9%～38%和4%～70%,远小于未优化模型的预测误差8%～1491%、2.8%～1950%和15%～128%;对IB、MOR和TS的预测也有相似的结果。     

Cyclic subspace regression with analysis of wavelength-selection criteria

Common methods of building linear calibration models are principal component regression (PCR), partial least squares (PLS), and least squares (LS). Recently, the method of cyclic subspace regression (CSR) has been presented and shown to provide PCR, PLS, LS and other related intermediate regressions with one algorithm. When forming a linear model with spectral data for quantitative analysis, prediction results can be adversely affected by responses that do not conform well to the linear model proposed. Wavelength selection can be used to eliminate wavelengths where such problem responses occur. It has recently been reported that CSR regression vectors can be formed by summing weighted eigenvectors where weights are determined from the hat matrix, singular values, and eigenvectors characterizing the sample space. Investigation of these weights shows that wavelength selection based on loading vectors can be misleading. Specifically, by using CSR it is shown that a small weight for an eigenvector can annihilate a large peak in a loading vector. In this study, correlograms are used with CSR regression vectors and eigenvector weights as wavelength-selection criteria. It is demonstrated that even though a model generated by LS for a wavelength subset produces substantially reduced prediction errors relative to PCR and PLS, CSR weight plots show that the LS model overfits and should not be used. Simulated situations containing spectral regions with excess noise or nonlinear responses are examined to study the effectiveness of wavelength selection based on the previously listed criteria. Near infrared spectra of gasoline samples with several known properties are also studied.     

Using sine wave histograms to estimate analog-to-digital converterdynamic error functions

This paper describes a new method for developing analog-to-digital converter (ADC) error function models using modified sinewave histogram methods. The error models may be used to digitally compensate for nonlinearities introduced by the converter. The histogram modification involves sorting of converter output samples based upon an estimated associated input derivative signal. This error model is based upon a previously unpublished result which shows that sinewave histograms yield distinctly different expected errors for each state based upon input signal slope associated with each output sample. This result thus provides a dynamic dependence for expected errors measured by means of histogram methods. Sorted sinewave histograms are used to estimate slope dependent expected errors at each ADC output state (code). The method provides improved error representation by providing error basis functions for every output code. Simulated results prove that this method removes all slope dependent errors for complex ADC architectures while experimental results for an 8-bit 200 MSPS ADC yielded more than 10 dB improvement in spurious-free-dynamic-range (SFDR) over the full Nyquist band. The new method is thus shown to possess wideband dynamic error character