Fast and massive characterization of quality attributes in tomatoes is a necessary step toward it... more Fast and massive characterization of quality attributes in tomatoes is a necessary step toward its improvement; for sensory attributes this process is time-consuming and very expensive, which causes its absence in routine phenotpying. We aimed to assess the feasibility of near infrared (NIR) spectroscopy as a fast and economical tool to predict both the chemical and sensory properties of tomatoes. We built partial least squares models from spectra recorded from tomato puree and juice in 53 genetically diverse varieties grown in two environments. Samples were divided in calibration (210 samples for chemical traits, 45 samples for sensory traits) and validation sets (60 and 10, respectively) using the Kennard Stone algorithm. Models from puree spectra gave validation r2 values higher than 0.97 for fructose, glucose, soluble solids content, and dry matter (relative standard error of prediction, RSEP% ranged 3.5–5.8), while r2 values for sensory properties were lower (ranging 0.702–0.91...
The new model of University bets not only by expertise but also by the development of skills or a... more The new model of University bets not only by expertise but also by the development of skills or abilities that students should acquire. In this work is proposed that students work and put together the knowledge acquired independently in a working group that supports and enhances collaborative learning based on experience. They have to awaken their critical thinking, reflective and creative in the resolution of the problems based on experience. To this end, professors have designed a team activity for students to use creative techniques to solve a physics problem experimentally.
Near infrared chemical imaging (NIR-CI) has recently emerged as an effective technique for extrac... more Near infrared chemical imaging (NIR-CI) has recently emerged as an effective technique for extracting spatial information from pharmaceutical products in an expeditious, non-destructive and non-invasive manner. These features have turned it into a useful tool for controlling various steps in drug production processes. Imaging techniques provide a vast amount of both spatial and spectral information that can be acquired in a very short time. Such a huge amount of data requires the use of efficient and fast methods to extract the relevant information. Chemometric methods have proved especially useful for this purpose. In this study, we assessed the usefulness of the correlation coefficient (CC) between the spectra of samples, the pure spectra of the active pharmaceutical ingredient (API) and we assessed the excipients to check for correct ingredient distribution in pharmaceutical binary preparations blended in the laboratory. Visual information about pharmaceutical component distribut...
The growing interest of the pharmaceutical industry in Near Infrared-Chemical Imaging (NIR-CI) is... more The growing interest of the pharmaceutical industry in Near Infrared-Chemical Imaging (NIR-CI) is a result of its high usefulness for quality control analyses of drugs throughout their production process (particularly of its non-destructive nature and expeditious data acquisition). In this work, the concentration and distribution of the major and minor components of pharmaceutical tablets are determined and the spatial distribution from the internal and external sides has been obtained. In addition, the same NIR-CI allowed the coating thickness and its surface distribution to be quantified. Images were processed to extract the target data and calibration models constructed using the Partial Least Squares (PLS) algorithms. The concentrations of Active Pharmaceutical Ingredient (API) and excipients obtained for uncoated cores were essentially identical to the nominal values of the pharmaceutical formulation. But the predictive ability of the calibration models applied to the coated tablets decreased as the coating thickness increased.
Near Infrared Chemical Imaging (NIR-CI) is demonstrating an increasing interest in pharmaceutical... more Near Infrared Chemical Imaging (NIR-CI) is demonstrating an increasing interest in pharmaceutical research since it meets the challenging analytical needs of pharmaceutical quality and may serve as a versatile adjunct to conventional NIR spectroscopy in many fields. The direct analysis of samples by using hyperspectral imaging techniques, which provide a NIR spectrum in each pixel of the image, generates a big amount of information from one sample. Focusing the interest in pharmaceutical research, several chemometric algorithms are demonstrating their usefulness extracting the relevant information (i.e. quantitative determination of the component in one sample) in tablets with only one sample and without damaging it. In this work, a quantitative method to analyze different commercial Acetylsalicylic acid tablets is proposed by using Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) method to the hyperspectral image and without any previous calibration model. For this purpose, a large concentration range of active pharmaceutical ingredient (ASA, Acetylsalicylic acid in this work), between 82% and 12%, was covered depending on the manufacturer. MCR-ALS allowed obtaining a concentration maps for acetylsalicylic acid and therefore, consequent analysis of the ASA distribution in the tablet was developed by using the histograms of the distribution of concentration. Results certified the good distribution of ASA despite the different origins of the tablets. Moreover, the obtained values of concentration showed a very good concordance with the nominal value of ASA. As a matter of fact, the quality of the results demonstrated the useful of encompassing NIR-CI techniques with MCR-ALS and, consequently, the well development on the production of Acetylsalicylic acid tablets.
The control of the esterification reaction for production of polyester saturated resins is follow... more The control of the esterification reaction for production of polyester saturated resins is followed usually by determination of the acid value (AV) and hydroxyl value (OHV).These parameters are determined by titrimetry, but these methods are slow, intensity working and produce waste. In this paper an alternative methodology is proposed, based in the construction of multivariate models on NIR spectroscopic data
Journal of Pharmaceutical and Biomedical Analysis, 2011
Near infrared chemical imaging (NIR-CI) is attracting growing interest in pharmaceutical analysis... more Near infrared chemical imaging (NIR-CI) is attracting growing interest in pharmaceutical analysis by virtue of its ability to provide a wealth of information from a single sample. Among others, NIR-CI has enabled the determination of the quantitative composition and distribution of acetylsalicylic (ASA) from the analysis of commercial tablets. In this work, we analyzed ASA commercial tablets of four different brands purchased at local chemists. The nominal ASA concentration for the brands was calculated from the nominal content and averaged weight of tablets. The tablets were found to span an ASA concentration range of 71-82%, and to differ in size and composition between brands. The API content and its homogeneity distribution were determined by applying quantitative algorithm to global hyperspectral image of ten tablets. Multivariate curve resolution-alternating least squares (MCR-ALS) is used to quantify each pixel in the images to obtain appropriate concentration maps. No prior calibration or reference data were needed for quantitation and results are close to the nominal content used as reference. Application to an image for 10 tablets and an individual tablet quantitation of the API allowed us to obtain the Accepted Value (AV) as defined by the European Pharmacopoeia. We conclude that all brands meet the pharmacopoeia specifications.
ABSTRACT This paper compares existing approaches to the monitoring of pharmaceutical blending pro... more ABSTRACT This paper compares existing approaches to the monitoring of pharmaceutical blending processes and the detection of their end-point by use of near infrared spectroscopy (NIRS). To this end, we examined homogenization in a pharmaceutical mixture containing a relatively low concentration (<4%) of an API that exhibits low absorption in the NIR region and is difficult to blend with excipients. The end-point of the process (viz. where a uniform distribution of the API in the mixture was reached) was determined by using various qualitative and quantitative spectral treatments for comparison. The results revealed the capabilities of different spectral treatments for establishing blend homogeneity, which can be especially useful with a view to optimizing their industrial use. API distribution uniformity in the final blend was confirmed by near infrared chemical imaging (NIR-CI) analysis.
Near-infrared spectroscopy (NIRS) has been widely used in the pharmaceutical field because of its... more Near-infrared spectroscopy (NIRS) has been widely used in the pharmaceutical field because of its ability to provide quality information about drugs in nearreal time. In practice, however, the NIRS technique requires construction of multivariate models in order to correct collinearity and the typically poor selectivity of NIR spectra. In this work, a new methodology for constructing simple NIR calibration models has been developed, based on the spectrum for the target analyte (usually the active principle ingredient, API), which is compared with that of the sample in order to calculate a correlation coefficient. To this end, calibration samples are prepared spanning an adequate concentration range for the API and their spectra are recorded. The model thus obtained by relating the correlation coefficient to the sample concentration is subjected to least-squares regression. The API concentration in validation samples is predicted by interpolating their correlation coefficients in the straight calibration line previously obtained. The proposed method affords quantitation of API in pharmaceuticals undergoing physical changes during their production process (e.g. granulates, and coated and non-coated tablets). The results obtained with the proposed methodology, based on correlation coefficients, were compared with the predictions of PLS1 calibration models, with which a different model is required for each type of sample. Error values lower than 1-2% were obtained in the analysis of three types of sample using the same model; these errors are similar to those obtained by applying three PLS models for granules, and non-coated and coated samples. Based on the outcome, our methodology is a straightforward choice for constructing calibration models affording expeditious prediction of new samples with varying physical properties. This makes it an effective alternative to multivariate calibration, which requires use of a different model for each type of sample, depending on its physical presentation.
Determining homogeneity of a mixture using hyperspectral-imaging (HSI) techniques is at this mome... more Determining homogeneity of a mixture using hyperspectral-imaging (HSI) techniques is at this moment an interesting research subject in pharmaceutical industry. A new methodology based in the macropixel analysis technique for the homogeneity assessment in powder blend mixtures has been developed. The appropriate selection of the macropixel size for evaluation of the homogeneity is a topic under discussion. We propose that the macropixel size selection would be based in a statistical criterion called "representative sample size" criterion. Moreover, it has been demonstrated that the macropixel size should be a function of the particle size and, thus, the particle size has been included in the formula to calculate the macropixel size. The proposed equations allow to accurately calculate the homogeneity index (H% Poole). By means of using simulated chemical images, a relationship between the H% Poole index and the controlled homogeneity was established. The method has been applied to determine the homogeneity of binary and ternary powder blends mixtures of different pharmaceuticals discriminating between homogeneous and non-homogeneous samples.
The control of the esterification reaction for production of polyester saturated resins is follow... more The control of the esterification reaction for production of polyester saturated resins is followed usually by determination of the acid value (AV) and hydroxyl value (OHV).These parameters are determined by titrimetry, but these methods are slow, intensity working and produce waste. In this paper an alternative methodology is proposed, based in the construction of multivariate models on NIR spectroscopic data
ABSTRACT The use of industrial paraffin depends of the properties which are strongly influenced b... more ABSTRACT The use of industrial paraffin depends of the properties which are strongly influenced by the composition but also affected by the oil content. Since paraffin is a by-product of lubricant oils in the petrochemical industry, there is inherently a certain amount of oil difficult to be completely removed. The determination of oil content in paraffin is described by American Society for Testing and Materials (ASTM) method, which involves the oil extraction with methyl ethyl ketone (MEK) at very low temperature (- 32ºC). However, this method is slow and scarcely precise. In this work, we characterized the main components of industrial paraffin (de-oiled paraffin and extracted oil) by gas chromatography in combination with mass spectrometry (GC/MS) and nuclear magnetic resonance (NMR) spectroscopy. Also, we developed two methods for the determination of the oil content in paraffin. The first method measures total iso-paraffins content by GC. The second method uses near infrared (NIR) spectroscopy in order to quantify the content of MEK-removable oil. The results obtained with the NIR-based method were quite consistent with those of the official, extraction-based method. NIR spectroscopy therefore provides an effective alternative to the ASTM method with the added advantage of substantially greater expeditiousness and reproducibility.
Near-infrared spectroscopy chemical imaging (NIR-CI) is a powerful tool for providing a great dea... more Near-infrared spectroscopy chemical imaging (NIR-CI) is a powerful tool for providing a great deal of information on pharmaceutical samples, since the NIR spectrum can be measured for each pixel of the image over a wide range of wavelengths.Joining NIR-CI with chemometric algorithms (e.g., Principal Component Analysis, PCA) and using correlation coefficients, cluster analysis, classical least-square regression (CLS) and multivariate curve
Fast and massive characterization of quality attributes in tomatoes is a necessary step toward it... more Fast and massive characterization of quality attributes in tomatoes is a necessary step toward its improvement; for sensory attributes this process is time-consuming and very expensive, which causes its absence in routine phenotpying. We aimed to assess the feasibility of near infrared (NIR) spectroscopy as a fast and economical tool to predict both the chemical and sensory properties of tomatoes. We built partial least squares models from spectra recorded from tomato puree and juice in 53 genetically diverse varieties grown in two environments. Samples were divided in calibration (210 samples for chemical traits, 45 samples for sensory traits) and validation sets (60 and 10, respectively) using the Kennard Stone algorithm. Models from puree spectra gave validation r2 values higher than 0.97 for fructose, glucose, soluble solids content, and dry matter (relative standard error of prediction, RSEP% ranged 3.5–5.8), while r2 values for sensory properties were lower (ranging 0.702–0.91...
The new model of University bets not only by expertise but also by the development of skills or a... more The new model of University bets not only by expertise but also by the development of skills or abilities that students should acquire. In this work is proposed that students work and put together the knowledge acquired independently in a working group that supports and enhances collaborative learning based on experience. They have to awaken their critical thinking, reflective and creative in the resolution of the problems based on experience. To this end, professors have designed a team activity for students to use creative techniques to solve a physics problem experimentally.
Near infrared chemical imaging (NIR-CI) has recently emerged as an effective technique for extrac... more Near infrared chemical imaging (NIR-CI) has recently emerged as an effective technique for extracting spatial information from pharmaceutical products in an expeditious, non-destructive and non-invasive manner. These features have turned it into a useful tool for controlling various steps in drug production processes. Imaging techniques provide a vast amount of both spatial and spectral information that can be acquired in a very short time. Such a huge amount of data requires the use of efficient and fast methods to extract the relevant information. Chemometric methods have proved especially useful for this purpose. In this study, we assessed the usefulness of the correlation coefficient (CC) between the spectra of samples, the pure spectra of the active pharmaceutical ingredient (API) and we assessed the excipients to check for correct ingredient distribution in pharmaceutical binary preparations blended in the laboratory. Visual information about pharmaceutical component distribut...
The growing interest of the pharmaceutical industry in Near Infrared-Chemical Imaging (NIR-CI) is... more The growing interest of the pharmaceutical industry in Near Infrared-Chemical Imaging (NIR-CI) is a result of its high usefulness for quality control analyses of drugs throughout their production process (particularly of its non-destructive nature and expeditious data acquisition). In this work, the concentration and distribution of the major and minor components of pharmaceutical tablets are determined and the spatial distribution from the internal and external sides has been obtained. In addition, the same NIR-CI allowed the coating thickness and its surface distribution to be quantified. Images were processed to extract the target data and calibration models constructed using the Partial Least Squares (PLS) algorithms. The concentrations of Active Pharmaceutical Ingredient (API) and excipients obtained for uncoated cores were essentially identical to the nominal values of the pharmaceutical formulation. But the predictive ability of the calibration models applied to the coated tablets decreased as the coating thickness increased.
Near Infrared Chemical Imaging (NIR-CI) is demonstrating an increasing interest in pharmaceutical... more Near Infrared Chemical Imaging (NIR-CI) is demonstrating an increasing interest in pharmaceutical research since it meets the challenging analytical needs of pharmaceutical quality and may serve as a versatile adjunct to conventional NIR spectroscopy in many fields. The direct analysis of samples by using hyperspectral imaging techniques, which provide a NIR spectrum in each pixel of the image, generates a big amount of information from one sample. Focusing the interest in pharmaceutical research, several chemometric algorithms are demonstrating their usefulness extracting the relevant information (i.e. quantitative determination of the component in one sample) in tablets with only one sample and without damaging it. In this work, a quantitative method to analyze different commercial Acetylsalicylic acid tablets is proposed by using Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) method to the hyperspectral image and without any previous calibration model. For this purpose, a large concentration range of active pharmaceutical ingredient (ASA, Acetylsalicylic acid in this work), between 82% and 12%, was covered depending on the manufacturer. MCR-ALS allowed obtaining a concentration maps for acetylsalicylic acid and therefore, consequent analysis of the ASA distribution in the tablet was developed by using the histograms of the distribution of concentration. Results certified the good distribution of ASA despite the different origins of the tablets. Moreover, the obtained values of concentration showed a very good concordance with the nominal value of ASA. As a matter of fact, the quality of the results demonstrated the useful of encompassing NIR-CI techniques with MCR-ALS and, consequently, the well development on the production of Acetylsalicylic acid tablets.
The control of the esterification reaction for production of polyester saturated resins is follow... more The control of the esterification reaction for production of polyester saturated resins is followed usually by determination of the acid value (AV) and hydroxyl value (OHV).These parameters are determined by titrimetry, but these methods are slow, intensity working and produce waste. In this paper an alternative methodology is proposed, based in the construction of multivariate models on NIR spectroscopic data
Journal of Pharmaceutical and Biomedical Analysis, 2011
Near infrared chemical imaging (NIR-CI) is attracting growing interest in pharmaceutical analysis... more Near infrared chemical imaging (NIR-CI) is attracting growing interest in pharmaceutical analysis by virtue of its ability to provide a wealth of information from a single sample. Among others, NIR-CI has enabled the determination of the quantitative composition and distribution of acetylsalicylic (ASA) from the analysis of commercial tablets. In this work, we analyzed ASA commercial tablets of four different brands purchased at local chemists. The nominal ASA concentration for the brands was calculated from the nominal content and averaged weight of tablets. The tablets were found to span an ASA concentration range of 71-82%, and to differ in size and composition between brands. The API content and its homogeneity distribution were determined by applying quantitative algorithm to global hyperspectral image of ten tablets. Multivariate curve resolution-alternating least squares (MCR-ALS) is used to quantify each pixel in the images to obtain appropriate concentration maps. No prior calibration or reference data were needed for quantitation and results are close to the nominal content used as reference. Application to an image for 10 tablets and an individual tablet quantitation of the API allowed us to obtain the Accepted Value (AV) as defined by the European Pharmacopoeia. We conclude that all brands meet the pharmacopoeia specifications.
ABSTRACT This paper compares existing approaches to the monitoring of pharmaceutical blending pro... more ABSTRACT This paper compares existing approaches to the monitoring of pharmaceutical blending processes and the detection of their end-point by use of near infrared spectroscopy (NIRS). To this end, we examined homogenization in a pharmaceutical mixture containing a relatively low concentration (<4%) of an API that exhibits low absorption in the NIR region and is difficult to blend with excipients. The end-point of the process (viz. where a uniform distribution of the API in the mixture was reached) was determined by using various qualitative and quantitative spectral treatments for comparison. The results revealed the capabilities of different spectral treatments for establishing blend homogeneity, which can be especially useful with a view to optimizing their industrial use. API distribution uniformity in the final blend was confirmed by near infrared chemical imaging (NIR-CI) analysis.
Near-infrared spectroscopy (NIRS) has been widely used in the pharmaceutical field because of its... more Near-infrared spectroscopy (NIRS) has been widely used in the pharmaceutical field because of its ability to provide quality information about drugs in nearreal time. In practice, however, the NIRS technique requires construction of multivariate models in order to correct collinearity and the typically poor selectivity of NIR spectra. In this work, a new methodology for constructing simple NIR calibration models has been developed, based on the spectrum for the target analyte (usually the active principle ingredient, API), which is compared with that of the sample in order to calculate a correlation coefficient. To this end, calibration samples are prepared spanning an adequate concentration range for the API and their spectra are recorded. The model thus obtained by relating the correlation coefficient to the sample concentration is subjected to least-squares regression. The API concentration in validation samples is predicted by interpolating their correlation coefficients in the straight calibration line previously obtained. The proposed method affords quantitation of API in pharmaceuticals undergoing physical changes during their production process (e.g. granulates, and coated and non-coated tablets). The results obtained with the proposed methodology, based on correlation coefficients, were compared with the predictions of PLS1 calibration models, with which a different model is required for each type of sample. Error values lower than 1-2% were obtained in the analysis of three types of sample using the same model; these errors are similar to those obtained by applying three PLS models for granules, and non-coated and coated samples. Based on the outcome, our methodology is a straightforward choice for constructing calibration models affording expeditious prediction of new samples with varying physical properties. This makes it an effective alternative to multivariate calibration, which requires use of a different model for each type of sample, depending on its physical presentation.
Determining homogeneity of a mixture using hyperspectral-imaging (HSI) techniques is at this mome... more Determining homogeneity of a mixture using hyperspectral-imaging (HSI) techniques is at this moment an interesting research subject in pharmaceutical industry. A new methodology based in the macropixel analysis technique for the homogeneity assessment in powder blend mixtures has been developed. The appropriate selection of the macropixel size for evaluation of the homogeneity is a topic under discussion. We propose that the macropixel size selection would be based in a statistical criterion called "representative sample size" criterion. Moreover, it has been demonstrated that the macropixel size should be a function of the particle size and, thus, the particle size has been included in the formula to calculate the macropixel size. The proposed equations allow to accurately calculate the homogeneity index (H% Poole). By means of using simulated chemical images, a relationship between the H% Poole index and the controlled homogeneity was established. The method has been applied to determine the homogeneity of binary and ternary powder blends mixtures of different pharmaceuticals discriminating between homogeneous and non-homogeneous samples.
The control of the esterification reaction for production of polyester saturated resins is follow... more The control of the esterification reaction for production of polyester saturated resins is followed usually by determination of the acid value (AV) and hydroxyl value (OHV).These parameters are determined by titrimetry, but these methods are slow, intensity working and produce waste. In this paper an alternative methodology is proposed, based in the construction of multivariate models on NIR spectroscopic data
ABSTRACT The use of industrial paraffin depends of the properties which are strongly influenced b... more ABSTRACT The use of industrial paraffin depends of the properties which are strongly influenced by the composition but also affected by the oil content. Since paraffin is a by-product of lubricant oils in the petrochemical industry, there is inherently a certain amount of oil difficult to be completely removed. The determination of oil content in paraffin is described by American Society for Testing and Materials (ASTM) method, which involves the oil extraction with methyl ethyl ketone (MEK) at very low temperature (- 32ºC). However, this method is slow and scarcely precise. In this work, we characterized the main components of industrial paraffin (de-oiled paraffin and extracted oil) by gas chromatography in combination with mass spectrometry (GC/MS) and nuclear magnetic resonance (NMR) spectroscopy. Also, we developed two methods for the determination of the oil content in paraffin. The first method measures total iso-paraffins content by GC. The second method uses near infrared (NIR) spectroscopy in order to quantify the content of MEK-removable oil. The results obtained with the NIR-based method were quite consistent with those of the official, extraction-based method. NIR spectroscopy therefore provides an effective alternative to the ASTM method with the added advantage of substantially greater expeditiousness and reproducibility.
Near-infrared spectroscopy chemical imaging (NIR-CI) is a powerful tool for providing a great dea... more Near-infrared spectroscopy chemical imaging (NIR-CI) is a powerful tool for providing a great deal of information on pharmaceutical samples, since the NIR spectrum can be measured for each pixel of the image over a wide range of wavelengths.Joining NIR-CI with chemometric algorithms (e.g., Principal Component Analysis, PCA) and using correlation coefficients, cluster analysis, classical least-square regression (CLS) and multivariate curve
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Papers by Jordi Cruz