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51.
《Analytical letters》2012,45(11):1707-1719
A method based on piecewise direct standardization was developed to directly predict leaf chlorophyll concentrations by correction of near-infrared spectra to construct a robust calibration model. Chinar, camphor, and gingko leaves collected from two growth intervals were evaluated. Spectral pretreatment methods and wavelength selection were investigated. The first derivative combined with stability competitive adaptive reweighted sampling before piecewise direct standardization provided the best performance. Under the optimized parameters, the root mean square error of prediction was significantly reduced by using piecewise direct standardization. This study demonstrates that the calibration model may be used to rapidly characterize chlorophyll concentrations across species and growth intervals. 相似文献
52.
Abstract The linear and non-linear relationships of acute toxicity (as determined on five aquatic non-vertebrates and humans) to molecular structure have been investigated on 38 structurally-diverse chemicals. The compounds selected are the organic chemicals from the 50 priority chemicals prescribed by the Multicentre Evaluation of In Vitro Cytotoxicity (MEIC) programme. The models used for the evaluations are the best combination of physico-chemical properties that could be obtained so far for each organism, using the partial least squares projection to latent structures (PLS) regression method and backpropagated neural networks (BPN). Non-linear models, whether derived from PLS regression or backpropagated neural networks, appear to be better than linear models for describing the relationship between acute toxicity and molecular structure. BPN models, in turn, outperform non-linear models obtained from PLS regression. The predictive power of BPN models for the crustacean test species are better than the model for humans (based on human lethal concentration). The physico-chemical properties found to be important to predict both human acute toxicity and the toxicity to aquatic non-vertebrates are the n?octanol water partition coefficient (Pow) and heat of formation (HF). Aside from the two former properties, the contribution of parameters that reflect size and electronic properties of the molecule to the model is also high, but the type of physico-chemical properties differs from one model to another. In all of the best BPN models, some of the principal component analysis (PCA) scores of the 13C-NMR spectrum, with electron withdrawing/accepting capacity (LUMO, HOMO and IP) are molecular size/volume (VDW or MS1) parameters are relevant. The chemical deviating from the QSAR models include non-pesticides as well as some of the pesticides tested. The latter type of chemical fits in a number of the QSAR models. Outliers for one species may be different from those of other test organisms. 相似文献
53.
B.K. Sharma P. Singh M. Shekhawat K. Sarbhai Y.S. Prabhakar 《SAR and QSAR in environmental research》2013,24(3-4):365-383
54.
55.
Junia O. Alves Bruno G. Botelho Marcelo M. Sena Rodinei Augusti 《Journal of mass spectrometry : JMS》2013,48(10):1109-1115
Direct infusion electrospray ionization mass spectrometry in the positive ion mode [ESI(+)‐MS] is used to obtain fingerprints of aqueous–methanolic extracts of two types of olive oils, extra virgin (EV) and ordinary (OR), as well as of samples of EV olive oil adulterated by the addition of OR olive oil and other edible oils: corn (CO), sunflower (SF), soybean (SO) and canola (CA). The MS data is treated by the partial least squares discriminant analysis (PLS‐DA) protocol aiming at discriminating the above‐mentioned classes formed by the genuine olive oils, EV (1) and OR (2), as well as the EV adulterated samples, i.e. EV/SO (3), EV/CO (4), EV/SF (5), EV/CA (6) and EV/OR (7). The PLS‐DA model employed is built with 190 and 70 samples for the training and test sets, respectively. For all classes (1–7), EV and OR olive oils as well as the adulterated samples (in a proportion varying from 0.5 to 20.0% w/w) are properly classified. The developed methodology required no ions identification and demonstrated to be fast, as each measurement lasted about 3 min including the extraction step and MS analysis, and reliable, because high sensitivities (rate of true positives) and specificities (rate of true negatives) were achieved. Finally, it can be envisaged that this approach has potential to be applied in quality control of EV olive oils. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
56.
Georgina M. S. Alves Júlia M. C. S. Magalhães Roma Tauler Helena M. V. M. Soares 《Electroanalysis》2013,25(8):1895-1906
Simultaneous anodic stripping voltammetric determination of Pb and Cd is restricted on gold electrodes as a result of the overlapping of these two peaks. This work describes the quantitative determination of a binary mixture system of Pb and Cd, at low concentration levels (up to 15.0 and 10.0 µg L?1 for Pb and Cd, respectively) by differential pulse anodic stripping voltammetry (DPASV; deposition time of 30 s), using a green electrode (vibrating gold microwire electrode) without purging in a chloride medium (0.5 M NaCl) under moderate acidic conditions (HCl 1.0 mM), assisted by chemometric tools. The application of multivariate curve resolution alternating least squares (MCR‐ALS) for the resolution and quantification of both metals is shown. The optimized MCR‐ALS models showed good prediction ability with concentration prediction errors of 12.4 and 11.4 % for Pb and Cd, respectively. The quantitative results obtained by MCR‐ALS were compared to those obtained with partial least squares (PLS) and classical least squares (CLS) regression methods. For both metals, PLS and MCR‐ALS results are comparable and superior to CLS. For Cd, as a result of the peak shift problem, the application of CLS was unsuitable. MCR‐ALS provides additional advantage compared to PLS since it estimates the pure response of the analytes signal. Finally, the built up multivariate calibration models, based either in MCR‐ALS or PLS regression, allowed to quantify concentrations of Pb and Cd in surface river water samples, with satisfactory results. 相似文献
57.
The ripeness of grapes at the harvest time is one of the most important parameters for obtaining high quality red wines. Traditionally the decision of harvesting is to be taken only after analysing sugar concentration, titratable acidity and pH of the grape juice (technological maturity). However, these parameters only provide information about the pulp ripeness and overlook the real degree of skins and seeds maturities (phenolic maturity). Both maturities, technological and phenolic, are not simultaneously reached, on the contrary they tend to separate depending on several factors: grape variety, cultivar, adverse weather conditions, soil, water availability and cultural practices. Besides, this divergence is increasing as a consequence of the climate change (larger quantities of CO2, less rain, and higher temperatures). 相似文献
58.
Lorilee S.L. Arakaki Kenneth A. Schenkman Wayne A. Ciesielski Jeremy M. Shaver 《Analytica chimica acta》2013
We have developed a method to make real-time, continuous, noninvasive measurements of muscle oxygenation (Mox) from the surface of the skin. A key development was measurement in both the visible and near infrared (NIR) regions. Measurement of both oxygenated and deoxygenated myoglobin and hemoglobin resulted in a more accurate measurement of Mox than could be achieved with measurement of only the deoxygenated components, as in traditional near-infrared spectroscopy (NIRS). Using the second derivative with respect to wavelength reduced the effects of scattering on the spectra and also made oxygenated and deoxygenated forms more distinguishable from each other. Selecting spectral bands where oxygenated and deoxygenated forms absorb filtered out noise and spectral features unrelated to Mox. NIR and visible bands were scaled relative to each other in order to correct for errors introduced by normalization. Multivariate Curve Resolution (MCR) was used to estimate Mox from spectra within each data set collected from healthy subjects. A Locally Weighted Regression (LWR) model was built from calibration set spectra and associated Mox values from 20 subjects using 2562 spectra. LWR and Partial Least Squares (PLS) allow accurate measurement of Mox despite variations in skin pigment or fat layer thickness in different subjects. The method estimated Mox in five healthy subjects with an RMSE of 5.4%. 相似文献
59.
Aiming at the linear temperature compensation algorithm’s disadvantage of temperature measurement error in rotary kiln infrared scanning temperature measurement process, this paper proposes a precise nonlinear cubic polynomial fitting temperature compensation algorithm. The proposed algorithm compensates the temperature values of scanning points on rotary kiln surface by following steps: Calculating temperature difference between the real temperature value of rotary kiln and temperature value measured by infrared scanning temperature measurement system; Fitting the temperature difference data with cubic polynomial; Using the obtained function to compensate temperature. Experimental result shows that compared with the usual linear temperature compensation algorithm, the accuracy of proposed algorithm has raised about 2.25 times when cubic polynomial is used. 相似文献
60.
飞机飞行中,测量剩余油量是关乎飞行安全的重要工作。以往采用的查表法存在存储数据量过大的问题,而插值法的计算又过于复杂,为此,提出了一种基于多项式数据拟合的油箱剩余油量测量方法,该方法通过存储多项式系数减少数据存储量,通过将多元插值计算改为多项式计算降低运算量。实验中,首先通过地面实验数据拟合获取多项式参数,再利用飞机飞行中获取的测量数据进行计算,所得结果与油箱内剩余油量的实际测量结果相比较,测量误差满足使用要求。通过理论和实验分析,在多项式拟合的阶数选择上明确了使用三阶多项式的合理性。该方法有较好的实用性,已在实践中应用。 相似文献