Multivariate Optimization: A Powerful Tool for the Systematic Control of Quantum Dots Properties.

In this chapter, we present some chemometric tools used in the area of experimental design and multivariate optimization. To make the subject more understandable, a didactic example employing colloidal aqueous synthesis of quantum dots is employed. We start with the factorial design that is very useful in screening which factors are important to the response of interest.

Low-frequency Raman spectrophotometer with wide laser illumination on the sample: A tool for pharmaceutical analytical analysis.

This work describes an optical configuration for a Raman spectrophotometer, which permits variation of the laser spot size from 3 to 3000 μm, maintaining a high Raman photons throughput and allowing acquisitions with a short integration time. In addition, the instrument can acquire spectra from the low to middle frequency vibrational range (10 to 2000 cm), on the Stokes and anti-Stokes sides. One of the features of this new optical configuration is the non-use of beam splitters to redirect the scattered light to the detector, which would sacrifice the laser power.

Authenticity assessment of banknotes using portable near infrared spectrometer and chemometrics.

Spectra recorded using a portable near infrared (NIR) spectrometer, Soft Independent Modeling of Class Analogy (SIMCA) and Linear Discriminant Analysis (LDA) associated to Successive Projections Algorithm (SPA) models were applied to identify counterfeit and authentic Brazilian Real (R$20, R$50 and R$100) banknotes, enabling a simple field analysis. NIR spectra (950-1650nm) were recorded from seven different areas of the banknotes (two with fluorescent ink, one over watermark, three with intaglio printing process and one over the serial numbers with typography printing). SIMCA and SPA-LDA models were built using 1st derivative preprocessed spectral data from one of the intaglio areas.

Portable near-infrared instruments: Application for quality control of polymorphs in pharmaceutical raw materials and calibration transfer.

This work presents an evaluation of the analytical performance of three different portable near-infrared (NIR) instruments (denominated Port.1, Port.2 and Port.

Comprehensive near infrared study of Jatropha oil esterification with ethanol for biodiesel production.

This work presents a comprehensive near infrared study for in-line monitoring of the esterification reaction of high acid oils, such as Jatropha curcas oil, using ethanol. Parallel reactions involved in the process were carried out to select a spectral region that characterizes the evolution of the esterification reaction. Using absorbance intensities at 5176cm(-1), the conversion and kinetic behaviors of the esterification reaction were estimated.

Using near-infrared overtone regions to determine biodiesel content and adulteration of diesel/biodiesel blends with vegetable oils.

This work evaluates the use of near-infrared (NIR) overtone regions to determine biodiesel content, as well potential adulteration with vegetable oil, in diesel/biodiesel blends. For this purpose, NIR spectra (12,000-6300 cm(-1)) were obtained using three different optical path lengths: 10 mm, 20 mm and 50 mm. Two strategies of regression with variable selection were evaluated: partial least squares (PLS) with significant regression coefficients selected by Jack-Knife algorithm (PLS/JK) and multiple linear regression (MLR) with wavenumber selection by successive projections algorithm (MLR/SPA).

Screening analysis to detect adulteration in diesel/biodiesel blends using near infrared spectrometry and multivariate classification.

This paper proposes an analytical method to detect adulteration of diesel/biodiesel blends based on near infrared (NIR) spectrometry and supervised pattern recognition methods. For this purpose, partial least squares discriminant analysis (PLS-DA) and linear discriminant analysis (LDA) coupled with the successive projections algorithm (SPA) have been employed to build screening models using three different optical paths and the following spectra ranges: 1.0mm (8814-3799 cm(-1)), 10mm (11,329-5944 cm(-1) and 5531-4490 cm(-1)) and 20mm (11,688-5952 cm(-1) and 5381-4679 cm(-1)).

A modification of the successive projections algorithm for spectral variable selection in the presence of unknown interferents.

This work proposes a modification to the successive projections algorithm (SPA) aimed at selecting spectral variables for multiple linear regression (MLR) in the presence of unknown interferents not included in the calibration data set. The modified algorithm favours the selection of variables in which the effect of the interferent is less pronounced. The proposed procedure can be regarded as an adaptive modelling technique, because the spectral features of the samples to be analyzed are considered in the variable selection process.

A flow system for generation of concentration perturbation in two-dimensional correlation near-infrared spectroscopy: application to variable selection in multivariate calibration.

A flow system is proposed to produce a concentration perturbation in liquid samples, aiming at the generation of two-dimensional correlation near-infrared spectra. The system presents advantages in relation to batch systems employed for the same purpose: the experiments are accomplished in a closed system; application of perturbation is rapid and easy; and the experiments can be carried out with micro-scale volumes. The perturbation system has been evaluated in the investigation and selection of relevant variables for multivariate calibration models for the determination of quality parameters of gasoline, including ethanol content, MON (motor octane number), and RON (research octane number).

Determination of Se(IV) by anodic stripping voltammetry using gold electrodes made from recordable CDs.

This work presents a simple, reproducible and low cost method, employing differential pulse anodic stripping voltammetry, for determination of selenium(IV). A gold electrode obtained from recordable compact disks (CD-R) was used to evaluate the voltammetric behavior of the metallic ion in 0.1molL(-1) HClO(4).

Near-infrared spectropolarimetry based on acousto-optical tunable filters.

A new approach to near-infrared (NIR) spectropolarimetry is described, in which the properties of a noncollinear acousto-optical tunable filter (AOTF) made of an anisotropic crystal of TeO2 is employed to produce a novel instrument that precludes or reduces significantly the use of mechanical parts and simplifies the acquisition of optical rotation spectra of absorbing species in the NIR region. In essence, the instrument is based on the measurement of the relative beam intensities produced when a 45 degrees plane polarized beam of radiation passes through a sample cell and is directed to the entrance window of the AOTF. Because of the crystal anisotropy, two planar and orthogonally polarized beams will leave the AOTF, angularly split from the nondiffracted beam, after the acousto-optical interaction has occurred.

A comparative study of calibration transfer methods for determination of gasoline quality parameters in three different near infrared spectrometers.

This work presents a comparative study of calibration transfer among three near infrared spectrometers for determination of naphthenes and RON (Research Octane Number) in gasoline. Seven transfer methods are compared: direct standardization (DS), piecewise direct standardization (PDS), orthogonal signal correction (OSC), reverse standardization (RS), piecewise reverse standardization (PRS), slope and bias correction (SBC) and model updating (MU). Two pre-treatment procedures, namely standard normal variate (SNV) and multiplicative scatter correction (MSC), are also investigated.