João A. Lopes

Optimized Bidding of a EV Aggregation Agent in the Electricity Market

An electric vehicle (EV) aggregation agent, as a commercial middleman between electricity market and EV owners, participates with bids for purchasing electrical energy and selling secondary reserve. This paper presents an optimization approach to support the aggregation agent participating in the day-ahead and secondary reserve sessions, and identifies the input variables that need to be forecasted or estimated. Results are presented for two years (2009 and 2010) of the Iberian market, and considering perfect and naïve forecast for all variables of the problem.

Bioreactor monitoring with spectroscopy and chemometrics: a review.

Biotechnological processes are crucial to the development of any economy striving to ensure a relevant position in future markets. The cultivation of microorganisms in bioreactors is one of the most important unit operations of biotechnological processes, and real-time monitoring of bioreactors is essential for effective bioprocess control. In this review, published material on the potential application of different spectroscopic techniques for bioreactor monitoring is critically discussed, with particular emphasis on optical fiber technology, reported for in situ bioprocess monitoring. Application examples are presented by spectroscopy type, specifically focusing on ultraviolet–visible, near-infrared, mid-infrared, Raman, and fluorescence spectroscopy. The spectra acquisition devices available and the major advantages and disadvantages of each spectroscopy are discussed. The type of information contained in the spectra and the available chemometric methods for extracting that information are also addressed, including wavelength selection, spectra pre-processing, principal component analysis, and partial least-squares. Sample handling techniques (flow and sequential injection analysis) that include transport to spectroscopic sensors for ex-situ on-line monitoring are not covered in this review.

A Review on the Applications of Portable Near-Infrared Spectrometers in the Agro-Food Industry

Industry has created the need for a cost-effective and nondestructive quality-control analysis system. This requirement has increased interest in near-infrared (NIR) spectroscopy, leading to the development and marketing of handheld devices that enable new applications that can be implemented in situ. Portable NIR spectrometers are powerful instruments offering several advantages for nondestructive, online, or in situ analysis: small size, low cost, robustness, simplicity of analysis, sample user interface, portability, and ergonomic design. Several studies of on-site NIR applications are presented: characterization of internal and external parameters of fruits and vegetables; conservation state and fat content of meat and fish; distinguishing among and quality evaluation of beverages and dairy products; protein content of cereals; evaluation of grape ripeness in vineyards; and soil analysis. Chemometrics is an essential part of NIR spectroscopy manipulation because wavelength-dependent scattering effects, instrumental noise, ambient effects, and other sources of variability may complicate the spectra. As a consequence, it is difficult to assign specific absorption bands to specific functional groups. To achieve useful and meaningful results, multivariate statistical techniques (essentially involving regression techniques coupled with spectral preprocessing) are therefore required to extract the information hidden in the spectra. This work reviews the evolution of the use of portable near-infrared spectrometers in the agro-food industry.

Application of Fourier transform infrared spectroscopy and chemometrics for differentiation of Salmonella enterica serovar Enteritidis phage types

ABSTRACT Fourier transform infrared (FT-IR) spectroscopy and chemometric techniques were used to discriminate five closely related Salmonella enterica serotype Enteritidis phage types, phage type 1 (PT1), PT1b, PT4b, PT6, and PT6a. Intact cells and outer membrane protein (OMP) extracts from bacterial cell membranes were subjected to FT-IR analysis in transmittance mode. Spectra were collected over a wavenumber range from 4,000 to 600 cm−1. Partial least-squares discriminant analysis (PLS-DA) was used to develop calibration models based on preprocessed FT-IR spectra. The analysis based on OMP extracts provided greater separation between the Salmonella Enteritidis PT1-PT1b, PT4b, and PT6-PT6a groups than the intact cell analysis. When these three phage type groups were considered, the method based on OMP extract FT-IR spectra was 100% accurate. Moreover, complementary local models that considered only the PT1-PT1b and PT6-PT6a groups were developed, and the level of discrimination increased. PT1 and PT1b isolates were differentiated successfully with the local model using the entire OMP extract spectrum (98.3% correct predictions), whereas the accuracy of discrimination between PT6 and PT6a isolates was 86.0%. Isolates belonging to different phage types (PT19, PT20, and PT21) were used with the model to test its robustness. For the first time it was demonstrated that FT-IR analysis of OMP extracts can be used for construction of robust models that allow fast and accurate discrimination of different Salmonella Enteritidis phage types.

Evaluation of green coffee beans quality using near infrared spectroscopy: A quantitative approach

Characterisation of coffee quality based on bean quality assessment is associated with the relative amount of defective beans among non-defective beans. It is therefore important to develop a methodology capable of identifying the presence of defective beans that enables a fast assessment of coffee grade and that can become an analytical tool to standardise coffee quality. In this work, a methodology for quality assessment of green coffee based on near infrared spectroscopy (NIRS) is proposed. NIRS is a green chemistry, low cost, fast response technique without the need of sample processing. The applicability of NIRS was evaluated for Arabica and Robusta varieties from different geographical locations. Partial least squares regression was used to relate the NIR spectrum to the mass fraction of defective and non-defective beans. Relative errors around 5% show that NIRS can be a valuable analytical tool to be used by coffee roasters, enabling a simple and quantitative evaluation of green coffee quality in a fast way.

Particle sizing measurements in pharmaceutical applications: comparison of in-process methods versus off-line methods.

It has been previously described that when a samples particle size is determined using different sizing techniques, the results can differ considerably. The purpose of this study was to review several in-process techniques for particle size determination (Spatial Filtering Velocimetry, Focused Beam Reflectance Measurements, Photometric Stereo Imaging, and the Eyecon® technology) and compare them to well-known and widespread off-line reference methods (laser diffraction and sieve analysis). To start with, a theoretical explanation of the working mechanism behind each sizing technique is presented, and a comparison between them is established. Secondly, six batches of granules and pellets (i.e., spherical particles) having different sizes were measured using these techniques. The obtained size distributions and related D10, D50, and D90 values were compared using the laser diffraction wet dispersion method as reference technique. As expected, each technique provided different size distributions with different D values. These dissimilarities were examined and explained considering the measurement principles behind each sizing technique. The particle property measured by each particle size analyzer (particle size or chord length) and how it is measured as well as the way in which size information is derived and calculated from this measured property and how results are presented (e.g., volume or mass distributions) are essential for the interpretation of the particle size data.

Analysis of natural red dyes (cochineal) in textiles of historical importance using HPLC and multivariate data analysis

AbstractA new analytical approach based on high-performance liquid chromatography with diode array detector (HPLC-DAD) and multivariate data analysis was applied and assessed for analyzing the red dye extracted from cochineal insects, used in precious historical textiles. The most widely used method of analysis involves quantification of specific minor compounds (markers), using HPLC-DAD. However, variation in the cochineal markers concentration, use of aggressive dye extraction methods and poor resolution of HPLC chromatograms can compromise the identification of the precise insect species used in the textiles. In this study, a soft extraction method combined with a new dye recovery treatment was developed, capable of yielding HPLC chromatograms with good resolution, for the first time, for historical cochineal-dyed textiles. After principal components analysis (PCA) and mass spectrometry (MS), it was possible to identify the cochineal species used in these textiles, in contrast to the accepted method of analysis. In order to compare both methodologies, 7 cochineal species and 63 historical cochineal insect specimens were analyzed using the two approaches, and then compared with the results for 15 historical textiles in order to assess their applicability to real complex samples. The methodology developed here was shown to provide more accurate and consistent information than the traditional method. Almost all of the historical textiles were dyed with Porphyrophora sp. insects. These results emphasize the importance of adopting the proposed methodology for future research on cochineal (and related red dyes). Mild extraction methods and HPLC-DAD/MSn analysis yield distinctive profiles, which, in combination with a PCA reference database, are a powerful tool for identifying red insect dyes. FigureIn pursuit of a precious red dye! A new methodology has been developed for determining the precise cochineal dye used in historical textiles. Mild extraction methods and HPLC-DAD yield distinctive profiles that, in combination with a dye reference database based on PCA, creates a powerful tool for identifying the precise red dye used. Surprisingly, almost all of the historical textiles analysed were not dyed with American cochineal.

The use of net analyte signal (NAS) in near infrared spectroscopy pharmaceutical applications: Interpretability and figures of merit

Near infrared spectroscopy (NIRS) has been extensively used as an analytical method for quality control of solid dosage forms for the pharmaceutical industry. Pharmaceutical formulations can be extremely complex, containing typically one or more active product ingredients (API) and various excipients, yielding very complex near infrared (NIR) spectra. The NIR spectra interpretability can be improved using the concept of net analyte signal (NAS). NAS is defined as the part of the spectrum unique to the analyte of interest. The objective of this work was to compare two different methods to estimate the APIs NAS vector of different pharmaceutical formulations. The main difference between the methods is the knowledge of API free formulations NIR spectra. The comparison between the two methods was assessed in a qualitative and quantitative way. Results showed that both methods produced good results in terms of the similarity between the NAS vector and the pure API spectrum, as well as in the ability to predict the API concentration of unknown samples. Moreover, figures of merit such as sensitivity, selectivity, and limit of detection were estimated in a straightforward manner.

Strategic funding priorities in the pharmaceutical sciences allied to Quality by Design (QbD) and Process Analytical Technology (PAT)

Substantial changes in Pharmaceutical R&D strategy are required to address existing issues of low productivity, imminent patent expirations and pressures on pricing. Moves towards personalized healthcare and increasing diversity in the nature of portfolios including the rise of biopharmaceuticals however have the potential to provide considerable challenges to the establishment of cost effective and robust supply chains. To guarantee product quality and surety of supply for essential medicines it is necessary that manufacturing science keeps pace with advances in pharmaceutical R&D. In this position paper, the EUFEPS QbD and PAT Sciences network make recommendations that European industry, academia and health agencies focus attention on delivering step changes in science and technology in a number of key themes. These subject areas, all underpinned by the sciences allied to QbD and PAT, include product design and development for personalized healthcare, continuous-processing in pharmaceutical product manufacture, quantitative quality risk assessment for pharmaceutical development including life cycle management and the downstream processing of biopharmaceutical products. Plans are being established to gain commitment for inclusion of these themes into future funding priorities for the Innovative Medicines Initiative (IMI).

Determination of flow properties of pharmaceutical powders by near infrared spectroscopy.

The physical properties of pharmaceutical powders are of upmost importance in the pharmaceutical industry. The knowledge of their flow properties is of critical significance in operations such as blending, tablet compression, capsule filling, transportation, and in scale-up operations. Powders flow properties are measured using a number of parameters such as, angle of repose, compressibility index (Carrs index) and Hausner ratio. To estimate these properties, specific and expensive equipment with time-consuming analysis is required. Near infrared spectroscopy is a fast and low-cost analytical technique thoroughly used in the pharmaceutical industry in the quantification and qualification of products. To establish the potential of this technique to determine the parameters associated with the flow properties of pharmaceutical powders, blended powders based on paracetamol as the active pharmaceutical ingredient were constructed in pilot scale. Spectra were recorded on a Fourier-transform near infrared spectrometer in reflectance mode. The parameters studied were the angle of repose, aerated and tapped bulk density. The correlation between the reference method values and the near infrared spectrum was performed by partial least squares and optimized in terms of latent variables using cross-validation. The near infrared based properties predictions were compared with the reference methods results. Prediction errors, which varied between 2.35% for the angle of repose, 2.51% for the tapped density and 3.18% for the aerated density, show the potential of NIR spectroscopy in the determination of physical properties affecting the flowability of pharmaceutical powders.