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41.
In this study, preparation of novel pH-sensitive N-doped carbon dots (NCDs) using glucose and urea is reported. The prepared NCDs present strong excitation-dependent fluorescence changes towards the pH that is a new behavior from these nanomaterials. By taking advantage of this unique behavior, two separated ratiometric pH sensors using emission spectra of the NCDs for both acidic (pH 2.0 to 8.0) and basic (pH 7.0 to 14.0) ranges of pH are constructed. Additionally, by considering the entire Excitation–Emission Matrix (EEM) of NCDs as analytical signal and using a suitable multivariate calibration method, a broad range of pH from 2.0 to 14.0 was well calibrated. The multivariate calibration method was independent from the concentration of NCDs and resulted in a very low average prediction error of 0.067 pH units. No changes in the predicted pH under UV irradiation (for 3 h) and at high ionic strength (up to 2 M NaCl) indicated the high stability of this pH nanosensor. The practicality of this pH nanosensor for pH determination in real water samples was validated with good accuracy and repeatability. 相似文献
42.
Mathematical deconvolution methods can separate co-eluting peaks in samples for which (chromatographic) separation fail. However, these methods often heavily rely on manual user-input and interpretation. This is not only time-consuming but also error-prone and automation is needed if such methods are to be applied in a routine manner. 相似文献
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This article proposes a global, chaos-based procedure for the discretization of functionals of Brownian motion into functionals of a Poisson process with intensity . Under this discretization we study the weak convergence, as the intensity of the underlying Poisson process goes to infinity, of Poisson functionals and their corresponding Malliavin-type derivatives to their Wiener counterparts. In addition, we derive a convergence rate of for the Poisson discretization of Wiener functionals by combining the multivariate Chen–Stein method with the Malliavin calculus. Our proposed sufficient condition for establishing the mentioned convergence rate involves the kernel functions in the Wiener chaos, yet we provide examples, especially the discretization of some common path dependent Wiener functionals, to which our results apply without committing the explicit computations of such kernels. To the best our knowledge, these are the first results in the literature on the universal convergence rate of a global discretization of general Wiener functionals. 相似文献
45.
The obtained results by soft modeling multivariate curve resolution methods often are not unique and are questionable because of rotational ambiguity. It means a range of feasible solutions equally fit experimental data and fulfill the constraints. Regarding to chemometric literature, a survey of useful constraints for the reduction of the rotational ambiguity is a big challenge for chemometrician. It is worth to study the effects of applying constraints on the reduction of rotational ambiguity, since it can help us to choose the useful constraints in order to impose in multivariate curve resolution methods for analyzing data sets. In this work, we have investigated the effect of equality constraint on decreasing of the rotational ambiguity. For calculation of all feasible solutions corresponding with known spectrum, a novel systematic grid search method based on Species-based Particle Swarm Optimization is proposed in a three-component system. 相似文献
46.
In this paper, a modified single-index signal regression (mSISR) method is proposed to construct a nonlinear and practical model with high-accuracy. The mSISR method defines the optimal penalty tuning parameter in P-spline signal regression (PSR) as initial tuning parameter and chooses the number of cycles based on minimizing root mean squared error of cross-validation (RMSECV). mSISR is superior to single-index signal regression (SISR) in terms of accuracy, computation time and convergency. And it can provide the character of the non-linearity between spectra and responses in a more precise manner than SISR. Two spectra data sets from basic research experiments, including plant chlorophyll nondestructive measurement and human blood glucose noninvasive measurement, are employed to illustrate the advantages of mSISR. The results indicate that the mSISR method (i) obtains the smooth and helpful regression coefficient vector, (ii) explicitly exhibits the type and amount of the non-linearity, (iii) can take advantage of nonlinear features of the signals to improve prediction performance and (iv) has distinct adaptability for the complex spectra model by comparing with other calibration methods. It is validated that mSISR is a promising nonlinear modeling strategy for multivariate calibration. 相似文献
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Elisa Salvatore Marina Cocchi Andrea Marchetti Federico Marini Anna de Juan 《Analytica chimica acta》2013
This work proposes a fast and simple method for detection and quantification of phenolic compounds in PDO Lambrusco wines using HPLC-DAD and chemometric techniques. Samples belonging to three different varieties of Lambrusco (Grasparossa, Salamino and Sorbara) were analyzed to provide a methodology appropriate for routine analysis. Given the high complexity of the sample and the coelution among chromatographic peaks, the use of chemometric techniques to extract the information of the individual eluting compounds was needed. Multivariate curve resolution-alternating least squares (MCR-ALS) allowed the resolution of the chromatographic peaks obtained and the use of this information for the quantification of the phenolic analytes in the presence of interferences. Use of multiset analysis and local rank/selectivity information was proven to be crucial for the correct resolution and quantification of compounds. The quantitative data provided by MCR-ALS about the phenolic targets and additional compounds present in the samples analyzed provided wine composition profiles, which were afterwards used to distinguish among wine varieties. Principal component analysis applied to the wine profiles allowed characterizing the wines according to their varieties. 相似文献
49.
This study focuses on the development and extension of Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) to the analysis of four-way datasets. The proposed extension of the MCR-ALS method with non-negativity and the newly developed quadrilinear constraints can be exploited to summarize and manage huge multidimensional datasets and resolve their four way component profiles. In this study, its application is demonstrated by analyzing a four-way data set obtained in a long term environmental monitoring study (15 sampling sites × 9 variables × 12 months × 7 years) belonging to the Yamuna River, one of the most polluted rivers of India and the largest tributary of the Ganges river. MCR-ALS resolved pollution profiles described appropriately the major observed changes on pH, organic pollution, bacteriological pollution and temperature, along with their spatial and temporal distribution patterns for the studied stretch of Yamuna River. Results obtained by MCR-ALS have also been compared with those obtained by another multi-way method, PARAFAC. The methodology used in this study is completely general and it can be applied to other multi-way datasets. 相似文献
50.