• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1281-1281
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• 2001

Near-infrared (NIR) spectra have bean measured for high-density (HDPE), linear low-density (LLDPE), and low-density (LDPE) polyethylene in pellet or thin films. The obtained spectra have been analyzed by conventional spectroscopic analysis methods and chemometrics. By using the second derivative, principal component analysis (PCA), and two-dimensional (2D) correlation analysis, we could separate many overlapped bands in the NIR. It was found that the intensities of some bands are sensitive to density and crystallinity of PE. This may be the first time that such bands in the NIR region have ever been discussed. Correlations of such marker bands among the NIR spectra have also been investigated. This sort of investigation is very important not only for further understanding of vibration spectra of various of PE but also for quality control of PE by vibrational spectroscopy. Figure 1 (a) and (b) shows a NIR reflectance spectrum of one of the LLDPE samples and that of PE, respectively. Figure 2 shows a PC weight loadings plot of factor 1 for a score plot of PCA for the 16 kinds of LLDPE and PE based upon their 51 NIR spectra in the 1100-1900 nm region. The PC loadings plot separates the bands due to the $CH_3$ groups and those arising form the $CH_2$ groups, allowing one to make band assignments. The 2D correlation analysis is also powerful in band enhancement, and the band assignments based upon PCA are in good agreement with those by the 2D correlation analysis.(Figure omitted). We have made a calibration model, which predicts the density of LLDPE by use of partial least square (PLS) regression. From the loadings plot of regression coefficients for the model , we suggest that the band at 1542, 1728, and 1764 nm very sensitive to the changes in density and crystalinity.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1243-1243
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• 2001

During two consecutive years, it was developed global calibrations for the prediction of fatty acids on Iberian pig fat. These equations should analyse well samples of that animal fat because of their high accuracy (SECV/sub C16:0/ = 0.26%; SECV/sub C18:0/ = 0.28%; SECV/sub C18:1/ = 0.26%; SECV/sub C18:2/ = 0.15%) and their broad covering composition range. In some cases, when new samples are predicted H (Mahalanobis distance) values higher than 3 (recommended value for agricultural products by the ISI software) are obtained. However, there are not any obvious factors which tells that samples scanned are very different to the spectral mean of the calibration population. Furthermore, these samples are well predicted according to the SEP values. The objective of the present work is to deepen the understanding of the H statistic when analysing animal fats. Three different validation files were predicted with equations obtained from January '97 to April '98. The Set A has spectra of 20 samples not included on the calibration file and scanned in May of 1998. The Set B has spectra of 20 samples included on the calibration file and scanned again in November '99. The Set C contains 150 spectra of one sample representative of the mean values (for fatty acids composition) of the calibration file. This sample was analysed three times per week during June '99 to July '00. The H mean values for the Set A, Set B and Set C were respectively 1.35, 14.39 and 11.71. These anomalous values for the Set B and C make not sense because Set B contains replicate subsamples of the same samples scanned during calibration development and Set C only contains spectra of one sample which represent the mean spectrum of the calibration files. Results will be shown to demonstrate that small day to day variations are responsible of the high H values. When a PCA and LIB file are created with calibration samples and spectra of the Set C modelling day to day variations, the H values for Set A, Set B and Set C were respectively 1.83, 2.16 and 0.93.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1182-1182
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• 2001

In this study, the newly constructed optical measurement system, which was mainly composed of a parametric tunable laser and a near infrared photoelectric multiplier, was introduced to clarify the optical characteristics of wood as discontinuous body with anisotropic cellular structure from the viewpoint of the time-of-flight near infrared spectroscopy (TOF-NIRS). The combined effects of the cellular structure of wood sample, the wavelength of the laser beam λ, and the detection position of transmitted light on the time resolved profiles were investigated in detail. The variation of the attenuance of peak maxima At, the time delay of peak maxima Δt and the variation of full width at half maximum Δw were strongly dependent on the feature of cellular structure of a sample and the wavelength of the laser beam. The substantial optical path length became about 30 to 35 times as long as sample thickness except the absorption band of water. Δt ${\times}$ Δw representing the light scattering condition increased exponentially with the sample thickness or the distance between the irradiation point and the end of sample. Around the λ=900-950 nm, there may be considerable light scattering in the lumen of tracheid, which is multiple specular reflection and easy to propagate along the length of wood fiber. Such tendency was remarkable for soft wood with the aggregate of thin layers of cell walls. When we apply TOF-NIRS to the cellular structural materials like wood, it is very important to give attention to the difference in the light scattering within cell wall and the multiple specular-like reflections between cell walls. We tried to express the characteristics of the time resolved profile on the basis of the optical parameters for light propagation determined by the previous studies, which were absorption coefficient K and scattering coefficient S from Kubelka-Munk theory and n from nth power cosine model of radiant intensity. The wavelength dependency of the product of K/S and n, which expressed the light-absorbing and -scattering condition and the degree of anisotropy, respectively, was similar to that of the time delay of peak maxima Δt. The variation of the time resolved profile is governed by the combination of these parameters. So, we can easily find the set of parameters for light propagation synthetically from Δt.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1527-1527
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• 2001

Glucose, fructose and sucrose being the main sugars that can be found in natural fruit juice. Many instrumental methods, such as GC, LC, electrochemical or spectrometric methods provide information about both the total content of sugars and the specific concentration of each carbohydrate[1]. The simplicity of sample handling and measurement in the near IR(NIR) wavelength region, which allows the use of long pathlength, optical glass cells and optical fibers, makes NIR a good alternative for sugar determination [2]. In the present study, six varieties of persian grapes were harvested at intervals through august to october and analysed for sugars by NIR. The results were processed by principal component regression (PCR) and partial least squares (PLS) analysis. Sample juice was prepared by squeezing through gauze from crashed grape. This solution was treated by zinc ferrocyanide prior to analysis in order to eliminate colored compounds and all optically active nonsugar substances. For glucose and fructose the most characteristic wavelengths were 1456nm corresponding to the first harmonic O-H stretching and the second at 2062nm corresponding to O-H stretching and deformation; secondary characteristic combination bands were also seen at 2265 nm (O-H and C-C stretching) and at 2240 nm (C-H and C-C stretching). However these spectra were taken over a wavelength range from 1100-2500nm at room temperature of 25-$30^{\circ}C$. To test the accuracy of the described procedure, samples of six varieties of grape were analysed by the proposed NIR and a standard method[2]. Good agreement were found between these two sets of the results. To perform the recovery studies , samples of grape juices previously analysed by the proposed method, were spiked with known amounts of each individual sugars and then analysed again. Relative standard deviations varied from 1.4 to 1.8% for six independent measurements of individual and total sugar concentration. In the analysis of real and synthetic samples, precise and accurate results were obtained , providing accuracy errors lower than 1.9% in all cases. Average recoveries of ${97}{\pm}{4%}$ for total sugar and between ${95}{\pm}{5%}$ and ${99}{\pm}{2%}$ for sing1e sugars demonstrate the applicability of the methodology developed to the direct analysis of grape Juice.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1526-1526
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• 2001

To improve the accuracy of sweetness sensor in automated sorting operations, it is necessary to clarify unevenness of the sugar content distribution within fruits. And it is expected that the technique to evaluate the content distribution in fruits contribute to the development of the near-infrared (NIR) imaging spectroscopy. Sugiyama (1999) had succeeded to visualize the distribution of the sugar content on the surface of a half-cut green fresh melon. However, this method cannot be applied to red flesh melons because it depends on information of the absorption band of chlorophyll (676 nm), which is affected by the color of the fresh. The objective of this study was to develop the universal visualization method depends on the absorption band of sugar, which can be applied to various kinds of melons and other fruits. The relationship between the sugar contents and absorption spectra of both green and red fresh melons were investigated by using a NIR spectrometer to determine the absorption band of sugar. The combination of 2$\^$nd/ derivative absorbances at 902 nm and 874 nm was highly correlated with the sugar contents. The wavelength of 902 nm is attributed to the absorption band of sugar. A cooled charge-coupled device (CCD) imaging camera which has 16 bit (65536 steps) A/D resolution was equipped with rotating band-pass filter wheel and used to capture the spectral absorption images of the flesh of a vertically half-cut red fresh melon. The advantage of the high A/D resolution in this research is that each pixel of the CCD is expected to function as a detector of the NIR spectrometer for quantitative analysis. Images at 846 nm, 874 nm, 902 nm and 930 nm were acquired using this CCD camera. Then the 2$\^$nd/ derivative absorbances at 902 nm and 874 nm at each pixel were calculated using these four images. On the other hand, parts of the same melon were extracted for capturing the images and squeezed for the measurement of sugar content. Then the calibration curve between the combination of 2$\^$nd/ derivative absorbances at 902 nm and 874 nm and sugar content was developed. The calibration method based on NIR spectroscopy techniques was applied to each pixel of the images to convert the 2$\^$nd/ derivative absorbances into the Brix sugar content. Mapping the sugar content value of each pixel with linear color scale, the distribution of the sugar content was visualized. As a result of the visualization, it was quantitatively confirmed that the Brix sugar contents are low at the near of the skin and become higher towards the seeds. This result suggests that the visualization technique by the NIR imaging spectroscopy could become a new useful method fer quality evaluation of melons.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1042-1042
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• 2001

In linear discriminant analysis there are two important properties concerning the effectiveness of discriminant function modeling. The first is the separability of the discriminant function for different classes. The separability reaches its optimum by maximizing the ratio of between-class to within-class variance. The second is the stability of the discriminant function against noises present in the measurement variables. One can optimize the stability by exploring the discriminant variates in a principal variation subspace, i. e., the directions that account for a majority of the total variation of the data. An unstable discriminant function will exhibit inflated variance in the prediction of future unclassified objects, exposed to a significantly increased risk of erroneous prediction. Therefore, an ideal discriminant function should not only separate different classes with a minimum misclassification rate for the training set, but also possess a good stability such that the prediction variance for unclassified objects can be as small as possible. In other words, an optimal classifier should find a balance between the separability and the stability. This is of special significance for multivariate spectroscopy-based classification where multicollinearity always leads to discriminant directions located in low-spread subspaces. A new regularized discriminant analysis technique, the principal discriminant variate (PDV) method, has been developed for handling effectively multicollinear data commonly encountered in multivariate spectroscopy-based classification. The motivation behind this method is to seek a sequence of discriminant directions that not only optimize the separability between different classes, but also account for a maximized variation present in the data. Three different formulations for the PDV methods are suggested, and an effective computing procedure is proposed for a PDV method. Near-infrared (NIR) spectra of blood plasma samples from daily monitoring of two Japanese cows have been used to evaluate the behavior of the PDV method in comparison with principal component analysis (PCA), discriminant partial least squares (DPLS), soft independent modeling of class analogies (SIMCA) and Fisher linear discriminant analysis (FLDA). Results obtained demonstrate that the PDV method exhibits improved stability in prediction without significant loss of separability. The NIR spectra of blood plasma samples from two cows are clearly discriminated between by the PDV method. Moreover, the proposed method provides superior performance to PCA, DPLS, SIMCA md FLDA, indicating that PDV is a promising tool in discriminant analysis of spectra-characterized samples with only small compositional difference.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1141-1141
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• 2001

The aim of the study was to evaluate the performance of 3 calibration methods, modified partial least squares (MPLS), local PLS (LOCAL) and artificial neural network (ANN) on the prediction of chemical composition of forages, using a large NIR database. The study used forage samples (n=25,977) from Australia, Europe (Belgium, Germany, Italy and Sweden) and North America (Canada and U.S.A) with information relative to moisture, crude protein and neutral detergent fibre content. The spectra of the samples were collected with 10 different Foss NIR Systems instruments, which were either standardized or not standardized to one master instrument. The spectra were trimmed to a wavelength range between 1100 and 2498 nm. Two data sets, one standardized (IVAL) and the other not standardized (SVAL) were used as independent validation sets, but 10% of both sets were omitted and kept for later expansion of the calibration database. The remaining samples were combined into one database (n=21,696), which was split into 75% calibration (CALBASE) and 25% validation (VALBASE). The chemical components in the 3 validation data sets were predicted with each model derived from CALBASE using the calibration database before and after it was expanded with 10% of the samples from IVAL and SVAL data sets. Calibration performance was evaluated using standard error of prediction corrected for bias (SEP(C)), bias, slope and R2. None of the models appeared to be consistently better across all validation sets. VALBASE was predicted well by all models, with smaller SEP(C) and bias values than for IVAL and SVAL. This was not surprising as VALBASE was selected from the calibration database and it had a sample population similar to CALBASE, whereas IVAL and SVAL were completely independent validation sets. In most cases, Local and ANN models, but not modified PLS, showed considerable improvement in the prediction of IVAL and SVAL after the calibration database had been expanded with the 10% samples of IVAL and SVAL reserved for calibration expansion. The effects of sample processing, instrument standardization and differences in reference procedure were partially confounded in the validation sets, so it was not possible to determine which factors were most important. Further work on the development of large databases must address the problems of standardization of instruments, harmonization and standardization of laboratory procedures and even more importantly, the definition of the database population.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1523-1523
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• 2001

The wine industry requires practical methods for objectively measuring the composition of both red wine grapes on the vine to determine optimal harvest time; and of freshly harvested grapes for efficient allocation to vinery process streams for particular red wine products, and to determine payment of contract grapegrowers. To be practical for industry application these methods must be rapid, inexpensive and accurate. In most cases this restricts the analyses available to measurement of TSS (total soluble solids, predominantly sugars) by refractometry and pH by electropotentiometry. These two parameters, however, do not provide a comprehensive compositional characterization for the purpose of winemaking. The concentration of anthocyanin pigment in red wine grapes is an accepted indicator of potential wine quality and price. However, routine analysis for total anthocyanins is not considered as a practical option by the wider wine industry because of the high cost and slow turnaround time of this multi-step wet chemical laboratory analysis. Recent work by this ${group}^{l,2}$ has established the capability of near infrared (NIR) spectroscopy to provide rapid, accurate and simultaneous measurement of total anthocyanins, TSS and pH in red wine grapes. The analyses may be carried out equally well using either research grade scanning spectrometers or much simpler reduced spectral range portable diode-array based instrumentation. We have recently expanded on this work by collecting thousands of red wine grape samples in Australia. The sample set spans two vintages (1999 and 2000), five distinct geographical winegrowing regions and three main red wine grape varieties used in Australia (Cabernet Sauvignon, Shiraz and Merlot). Homogenized grape samples were scanned in diffuse reflectance mode on a FOSE NIR Systems6500 spectrometer and subject to laboratory analysis by the traditional methods for total anthocyanins, TSS and pH. We report here an analysis of the correlations between the NIR spectra and the laboratory data using standard chemometric algorithms within The Unscrambler software package. In particular, various subsets of the total data set are considered in turn to elucidate the effects of vintage, geographical area and grape variety on the measurement of grape composition by NIR spectroscopy. The relative ability of discrete calibrations to predict within and across these differences is considered. The results are then used to propose an optimal calibration strategy for red wine grape analysis.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1131-1131
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• 2001

To develop a nondestructive quality evaluation technique of fruits, a K-mean algorism is applied to near infrared (NIR) spectroscopy of apples. The K-mean algorism is one of neural network partition methods and the goal is to partition the set of objects O into K disjoint clusters, where K is assumed to be known a priori. The algorism introduced by Macqueen draws an initial partition of the objects at random. It then computes the cluster centroids, assigns objects to the closest of them and iterates until a local minimum is obtained. The advantage of using neural network is that the spectra at the wavelengths having absorptions against chemical bonds including C-H and O-H types can be selected directly as input data. In conventional multiple regression approaches, the first wavelength is selected manually around the absorbance wavelengths as showing a high correlation coefficient between the NIR $2^{nd}$ derivative spectrum and Brix value with a single regression. After that, the second and following wavelengths are selected statistically as the calibration equation shows a high correlation. Therefore, the second and following wavelengths are selected not in a NIR spectroscopic way but in a statistical way. In this research, the spectra at the six wavelengths including 900, 904, 914, 990, 1000 and 1016nm are selected as input data for K-mean analysis. 904nm is selected because the wavelength shows the highest correlation coefficients and is regarded as the absorbance wavelength. The others are selected because they show relatively high correlation coefficients and are revealed as the absorbance wavelengths against the chemical structures by B. G. Osborne. The experiment was performed with two phases. In first phase, a reflectance was acquired using fiber optics. The reflectance was calculated by comparing near infrared energy reflected from a Teflon sphere as a standard reference, and the $2^{nd}$ derivative spectra were used for K-mean analysis. Samples are intact 67 apples which are called Fuji and cultivated in Aomori prefecture in Japan. In second phase, the Brix values were measured with a commercially available refractometer in order to estimate the result of K-mean approach. The result shows a partition of the spectral data sets of 67 samples into eight clusters, and the apples are classified into samples having high Brix value and low Brix value. Consequently, the K-mean analysis realized the classification of apples on the basis of the Brix values.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.4101-4101
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• 2001

Information of body composition (fat and protein) in living animal is important to determine the nutrients requirement. Deuterium oxide (D2O) dilution techniques, as one of isotope dilution techniques have been useful for the prediction of body composition. However, the determination of D2O concentration is time consuming and complicated. Therefore this study was conducted to develop a new method to predict D2O concentration in plasma using near infrared spectroscopy technique (NIRS). Four dairy cows in early lactation were used. They were fed total mixed ration containing conr silage, timothy hay, and concentrates to make 17.0%CP and 14.0 MJDE/kgDM. Dosing D2O was at week 1,3 and 5 after parturition. After dosing D2O, the blood was collected from hour 0 to 72. Blood samples were then centrifuge at 3,000 rpm for 10 minutes to obtain plasma. D2O concentration was analyzed by gas chromatograph (deuterium oxide analyzable system, HK102, Shokotsusyou) after extracted from plasma by liophilization. Plasma sample was scanned by NIRS using Pacific Scientific (Neotec) model 6500 (Perstorp Analytical, Silver Spring, MD) in the range of wavelength from 1100 to 2500 nm. Calibration equation was developed using multiple linear regression. Sample from one animal (cow #550; n: 74) was used for developing the calibration while the rest three animals were used for validating the equation. The range, R and SEC of the calibration set samples were 135-925 ppm, 0.93 and 48.1 ppm, respectively. Validation of the calibration equation for three individual cows was done and the average of NIR predicted value of D2O at each collection time from three weeks injection showed a high correlation. The range, r and 53 of plasma from cow #474 were 322-840 ppm,0.93 and 53.1; cow #478 were 146-951 ppm,0.95 and 39.8; cow #942 were 313-885 ppm,0.95 and 37.2, respectively. Judgement of accuracy based on ratio of standard deviation and standard error in validation set samples (RPD) for cow #474, #478 and #942 were 2.2,4.3 and 3.4, respectively. The error in application due to the variation between individual was considered smaller than the bias from collection period, however, this prediction can be overcome with correction of standard zero-minute concentration of blood. The results of this preliminary study on the use of NIRS for determination of D2O in plasma showed very promising as shown by a convenient and satisfy accuracy. Further study on various physiological stage of animal should be done.