• Korean Chemical Engineering Research
• /
• v.48 no.6
• /
• pp.757-762
• /
• 2010

Since the quality and performance of medicinal products are heavily dependent upon the size, shape and polymorphism of active pharmaceutical ingredients(APIs), their crystallization has been regarded as one of the most important pharmaceutical processes. In this study, NIR-based inline measurements were employed to monitor key attributes of API particles real-time during the crystallization process. Principal component analysis(PCA) method was selected to correlate inline NIR spectra while the well-known aspirin was studied as a model drug. According to our characterization results, the ratio of ethanol to acetone did not cause any change in polymorphism, but resulted in a significant difference in the nucleation time, crystal growth and crystal shape. These phenomenological changes were well correlated with the PCA's implications. It turned out that the NIR-based inline monitoring technology can be employed well in observing and predicting key quality attributes such as crystal size during pharmaceutical crystallization processes.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
• /
• 2001.06a
• /
• pp.1154-1154
• /
• 2001

Near infra-red (NIR) spectroscopy has been used for the non-invasive assessment of intact fruit for eating quality attributes such as total soluble solids (TSS) content. However, little information is available in the literature with respect to the robustness of such calibration models validated against independent populations (however, see Peiris et al. 1998 and Guthrie et al. 1998). Many studies report ‘prediction’ statistics in which the calibration and prediction sets are subsets of the same population (e. g. a three year calibration validated against a set from the same population, Peiris et al. 1998; calibration and validation subsets of the same initial population, Guthrie and Walsh 1997 and McGlone and Kawano 1998). In this study, a calibration was developed across 84 melon fruit (R$^2$= 0.86$^{\circ}$Brix, SECV = 0.38$^{\circ}$Brix), which predicted well on fruit excluded from the calibration set but taken from the same population (n = 24, SEP = 0.38$^{\circ}$Brix with 0.1$^{\circ}$Brix bias), relative to an independent group (same variety and farm but different harvest date) (n = 24, SEP= 0.66$^{\circ}$ Brix with 0.1$^{\circ}$Brix bias). Prediction on a different variety, different growing district and time was worse (n = 24, SEP = 1.2$^{\circ}$Brix with 0.9$^{\circ}$Brix bias). Using an ‘in-line’ unit based on a silicon diode array spectrometer, as described in Walsh et al. (2000), we collected spectra from fruit populations covering different varieties, growing districts and time. The calibration procedure was optimized in terms of spectral window, derivative function and scatter correction. Performance of a calibration across new populations of fruit (different varieties, growing districts and harvest date) is reported. Various calibration sample selection techniques (primarily based on Mahalanobis distances), were trialled to structure the calibration population to improve robustness of prediction on independent sets. Optimization of calibration population structure (using the ISI protocols of neighbourhood and global distances) resulted in the elimination of over 50% of the initial data set. The use of the ISI Local Calibration routine was also investigated.

• Journal of The Korean Society of Grassland and Forage Science
• /
• v.37 no.2
• /
• pp.154-160
• /
• 2017

This study was conducted to find out an alternative way of rapid and accurate analysis of chemical composition of permanent pastures in hilly grazing area. Near reflectance infrared spectroscopy (NIRS) was used to evaluate the potential for predicting proximate analysis of permanent pastures in a vegetative stage. 386 pasture samples obtained from hilly grazing area in 2015 and 2016 were scanned for their visible-NIR spectra from 400~2,400nm. 163 samples with different spectral characteristics were selected and analysed for moisture, crude protein (CP), crude ash (CA), acid detergent fiber (ADF) and neutral detergent fiber (NDF). Multiple linear regression was used with wet analysis data and spectra for developing the calibration and validation mode1. Wavelength of 400 to 2500nm and near infrared range with different critical T outlier value 2.5 and 1.5 were used for developing the most suitable equation. The important index in this experiment was SEC and SEP. The $R^2$ value for moisture, CP, CA, CF, Ash, ADF, NDF in calibration set was 0.86, 0.94, 0.91, 0.88, 0.48 and 0.93, respectively. The value in validation set was 0.66, 0.86, 0.83, 0.71, 0.35 and 0.88, respectively. The results of this experiment indicate that NIRS is a reliable analytical method to assess forage quality for CP, CF, NDF except ADF and moisture in permanent pastures when proper samples incorporated into the equation development.

• Journal of Korean Society of Forest Science
• /
• v.112 no.2
• /
• pp.145-156
• /
• 2023

In this study, Fourier-transform near-infrared (FT-NIR) spectra of Korean red pine seeds stored at -18℃ and 4℃ for 18 years were analyzed. To develop seed-germination prediction models, the performance of seven machine learning methods, namely XGBoost, Boosted Tree, Bootstrap Forest, Neural Networks, Decision Tree, Support Vector Machine, PLS-DA, were compared. The predictive performance, assessed by accuracy, misclassification, and area under the curve (0.9722, 0.0278, and 0.9735 for XGBoost, and 0.9653, 0.0347, and 0.9647 for Boosted Tree), was better for the XGBoost and decision tree models when compared with other models. The 54 wave-number variables of the two models were of high relative importance in seed-germination prediction and were grouped into six spectral ranges (811~1,088 nm, 1,137~1,273 nm, 1,336~1,453 nm, 1,666~1,671 nm, 1,879~2,045 nm, and 2,058~2,409 nm) for aromatic amino acids, cellulose, lignin, starch, fatty acids, and moisture, respectively. Use of the NIR spectral data and two machine learning models developed in this study gave >96% accuracy for the prediction of pine-seed germination after long-term storage, indicating this approach could be useful for non-destructive viability testing of stored seed genetic resources.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
• /
• 2001.06a
• /
• pp.1265-1265
• /
• 2001

The organic materials included in excreta of livestock are important resources for organic manure and for improving soil quality, although there is still far from effective using. One reason for this is still unclearly standard of quality for evaluation of manure made from excreta of livestock. Therefore, the objective of this study is to develop rapid and accurate analytical method for analyzing organic compositions of manure made from excreta of livestock, and to establish quality evaluation method based on the compositions predicted by near infrared reflectance spectroscopy (NIRS). Sixteen samples of manure, each eight samples prepared from two treatments, were used in this study. The manure samples were prepared by mixing 560 kg feces of swine,60 kg sawdust with moisture content was adjusted to be 65%. The mixture was then keep under two kinds of shelter, black and clear sheets, as a treatment on the effect of sunlight. Samples were taken in every week (form week-0 to 7) during the process of manure making. Samples were analyzed to determine neutral detergent fiber (NDF), acid detergent fiber (ADF) and acid detergent lignin (ADL) by detergent methods, and organic cell wall (OCW) and fibrous content of low digestibility in OCW (Ob) by enzymatic methods. Biological oxygen demand (BOD) was analyzed by coulometric respirometer method. These compositions were carbohydrateds and lignin that were hardly digested. Spectra of samples were scanned by NIR instrument model 6500 (Pacific Scientific) and read over the range of wavelength between 400 and 2500nm. Calibration equations were developed using eight manure samples collected from black sheet shelter, while prediction was conducted to the other eight samples from clear sheet shelter. Accuracy of NTRS prediction was evaluated by correlation coefficients (r), standard error of prediction (SEP) and ration of standard deviation of reference data in prediction sample set to SEP (RPD). The r, SEP and RPD value of forage were 0.99, 0.69 and 7.6 for ADL, 0.96, 1.03 and 4.1 for NDF, 0.98, 0.60 and 4.9 for ADF, 0.92, 1.24 and 2.6 for Ob, and 0.91, 1.02 and 7.3 for BOD, respectively. The results indicated that NIRS could be used to measure the organic composition of forage used in manure samples.

• Korean Journal of Soil Science and Fertilizer
• /
• v.37 no.4
• /
• pp.259-265
• /
• 2004

A quicker method was developed for foliar analysis in diagnosis of nitrogen in apple trees based on multivariate calibration procedure using partial least squares regression (PLSR) and principal component regression (PCR) to establish the relationship between reflectance spectra in the near infrared region and nitrogen content of fresh- and dry-leaf. Several spectral pre-processing methods such as smoothing, mean normalization, multiplicative scatter correction (MSC) and derivatives were used to improve the robustness and performance of the calibration models. Norris first derivative with a seven point segment and a gap of six points on MSC gave the best result of partial least squares-1 PLS-1) model for dry-leaf samples with root mean square error of prediction (RMSEP) equal to $0.699g\;kg^{-1}$, and that the Savitzky-Golay first derivate with a seven point convolution and a quadratic polynomial on MSC gave the best results of PLS-1 model for fresh-samples with RMSEP of $1.202g\;kg^{-1}$. The best PCR model was obtained with Savitzky-Golay first derivative using a seven point convolution and a quadratic polynomial on mean normalization for dry leaf samples with RMSEP of $0.553g\;kg^{-1}$, and obtained with the Savitzky-Golay first derivate using a seven point convolution and a quadratic polynomial for fresh samples with RMSEP of $1.047g\;kg^{-1}$. The results indicate that nitrogen can be determined by the near infrared reflectance (NIR) technology for fresh- and dry-leaf of apple.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
• /
• 2001.06a
• /
• pp.1246-1246
• /
• 2001

The quality of meat is highly variable in many properties. This variability originates from both animal production and meat processing. At the pre-slaughter stage, animal factors such as breed, sex, age contribute to this variability. Environmental factors include feeding, rearing, transport and conditions just before slaughter (Hildrum et al., 1995). Meat can be presented in a variety of forms, each offering different opportunities for adulteration and contamination. This has imposed great pressure on the food manufacturing industry to guarantee the safety of meat. Tissue and muscle speciation of flesh foods, as well as speciation of animal derived by-products fed to all classes of domestic animals, are now perhaps the most important uncertainty which the food industry must resolve to allay consumer concern. Recently, there is a demand for rapid and low cost methods of direct quality measurements in both food and food ingredients (including high performance liquid chromatography (HPLC), thin layer chromatography (TLC), enzymatic and inmunological tests (e.g. ELISA test) and physical tests) to establish their authenticity and hence guarantee the quality of products manufactured for consumers (Holland et al., 1998). The use of Near Infrared Reflectance Spectroscopy (NIRS) for the rapid, precise and non-destructive analysis of a wide range of organic materials has been comprehensively documented (Osborne et at., 1993). Most of the established methods have involved the development of NIRS calibrations for the quantitative prediction of composition in meat (Ben-Gera and Norris, 1968; Lanza, 1983; Clark and Short, 1994). This was a rational strategy to pursue during the initial stages of its application, given the type of equipment available, the state of development of the emerging discipline of chemometrics and the overwhelming commercial interest in solving such problems (Downey, 1994). One of the advantages of NIRS technology is not only to assess chemical structures through the analysis of the molecular bonds in the near infrared spectrum, but also to build an optical model characteristic of the sample which behaves like the “finger print” of the sample. This opens the possibility of using spectra to determine complex attributes of organic structures, which are related to molecular chromophores, organoleptic scores and sensory characteristics (Hildrum et al., 1994, 1995; Park et al., 1998). In addition, the application of statistical packages like principal component or discriminant analysis provides the possibility to understand the optical properties of the sample and make a classification without the chemical information. The objectives of this present work were: (1) to examine two methods of sample presentation to the instrument (intact and minced) and (2) to explore the use of principal component analysis (PCA) and Soft Independent Modelling of class Analogy (SIMCA) to classify muscles by quality attributes. Seventy-eight (n: 78) beef muscles (m. longissimus dorsi) from Hereford breed of cattle were used. The samples were scanned in a NIRS monochromator instrument (NIR Systems 6500, Silver Spring, MD, USA) in reflectance mode (log 1/R). Both intact and minced presentation to the instrument were explored. Qualitative analysis of optical information through PCA and SIMCA analysis showed differences in muscles resulting from two different feeding systems.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
• /
• 2001.06a
• /
• pp.1519-1519
• /
• 2001

The aim of this work was to test the feasibility of NIRS in analysing textural characteristics of “Pasta Filata” cheese during the shelf-life. For this purpose, 128 samples of “Pasta Filata” cheese, subdivided into two sets on the basis of the wax used to avoid mechanical damages (paraffin, biodegradable wax), were analysed by using an InfraAlyzer 500 (Bran+Luebbe). Analyses were performed at room temperature. Samples were cut into small cylinders (D=3.2 cm, height = 1 cm), in agreement with literature information. Data were processed by using Sesame Software (Bran+Luebbe). Samples were analysed, during the shelf-life, at 90 and 120 days. In parallel, textural characteristics were detected carrying out a compression method by using an Universal Testing Machine Instron model 4301 (Instron Corporation, Canton, Massachusetts). As compression probe was used a cylinder (D = 5.8 cm, height = 3.7 cm) and a speed rate of 20mm/min was applied. The load at 20 mm of compression was recorded on sample cylinders of 1.7 cm (D) by 2 cm (height). Qualitative analysis of full spectra showed the possibility to gather samples on the basis of the days of shelf-life. The textural characteristics of cheese during the shelf-life was evaluated by comparing NIRS data with rheological results. The best correlation was obtained applying MLR to the first derivative of normalized absorbance values at seven wavelengths. Load values were plotted against the NIR prediction values based on first derivatives. NIRS proved to be an useful tool in classifying samples on the basis of the shelf-life period as well as in predicting their textural characteristics ($R^2$= 0.916, SEC = 0.192, SEP = 0.248, SEV = 0.345).

• Journal of Biosystems Engineering
• /
• v.38 no.1
• /
• pp.48-54
• /
• 2013

Purpose: This study evaluated the feasibility of using a discrete wavelet transform (DWT) method as a preprocessing tool for visible/near-infrared spectroscopy (VIS/NIRS) with a spectroscopic transmittance dataset for predicting the internal quality of cherry tomatoes. Methods: VIS/NIRS was used to acquire transmittance spectrum data, to which a DWT was applied to generate new variables in the wavelet domain, which replaced the original spectral signal for subsequent partial least squares (PLS) regression analysis and prediction modeling. The DWT concept and its importance are described with emphasis on the properties that make the DWT a suitable transform for analyzing spectroscopic data. Results: The $R^2$ values and root mean squared errors (RMSEs) of calibration and prediction models for the firmness, sugar content, and titratable acidity of cherry tomatoes obtained by applying the DWT to a PLS regression with a set of spectra showed more enhanced results than those of each model obtained from raw data and mean normalization preprocessing through PLS regression. Conclusions: The developed DWT-incorporated PLS models using the db5 wavelet base and selected approximation coefficients indicate their feasibility as good preprocessing tools by improving the prediction of firmness and titratable acidity for cherry tomatoes with respect to $R^2$ values and RMSEs.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
• /
• 2001.06a
• /
• pp.1041-1041
• /
• 2001

Removal of variability in spectra data before the application of chemometric modeling will generally result in simpler (and presumably more robust) models. Particularly for sparsely sampled data, such as typically encountered in diode array instruments, the use of Savitzky-Golay (S-G) derivatives offers an effective method to remove effects of shifting baselines and sloping or curving apparent baselines often observed with scattering samples. The application of these convolution functions is equivalent to fitting a selected polynomial to a number of points in the spectrum, usually 5 to 25 points. The value of the polynomial evaluated at its mid-point, or its derivative, is taken as the (smoothed) spectrum or its derivative at the mid-point of the wavelength window. The process is continued for successive windows along the spectrum. The original paper, published in 1964 [1] presented these convolution functions as integers to be used as multipliers for the spectral values at equal intervals in the window, with a normalization integer to divide the sum of the products, to determine the result for each point. Steinier et al. [2] published corrections to errors in the original presentation [1], and a vector formulation for obtaining the coefficients. The actual selection of the degree of polynomial and number of points in the window determines whether closely situated bands and shoulders are resolved in the derivatives. Furthermore, the actual noise reduction in the derivatives may be estimated from the square root of the sums of the coefficients, divided by the NORM value. A simple technique to evaluate the actual convolution factors employed in the calculation by the software will be presented. It has been found that some software packages do not properly account for the sampling interval of the spectral data (Equation Ⅶ in [1]). While this is not a problem in the construction and implementation of chemometric models, it may be noticed in comparing models at differing spectral resolutions. Also, the effects on parameters of PLS models of choosing various polynomials and numbers of points in the window will be presented.