Thèses sur le sujet « Near-infrared technology »

A near-infrared spectrometer incorporating solid-state design applicable for industrial quantitative/qualitative process monitoring analysis is presented. The solid-state near-infrared spectrometer provides inherent wavelength stability necessary for long term calibration accuracy. The spectrometer consists of a 24 volt, 10 watt quartz-halogen-tungsten regulated source with optical feedback. Wavelength dispersion was accomplished using a 50 μm entrance slit, f/4, 0.25 meter spectrograph equipped with astigmatism correcting toroidal mirrors and a 300 gr/mm plane reflectance ruled grating blazed for 2000 nm peak efficiency. A 1024 element backside- illuminated Schottky-barrier PtSi photodiode array detector with wavelength response from 900-5000 nm and peak quantum efficiency of 8% at 1100 nm was operated using cryogenic cooling to reduce dark response. A readout rate of 31.25 kHz produced 41 msec integration time per array read. The readout was digitized to 16 bit resolution for subsequent data storage. This system demonstrated 1.5 nm spectral bandpass, 3 orders linear dynamic range and typical baseline rms noise level of 10⁻⁴ a.u. Using this system, quantitative/qualitative chemical analyses were performed focusing on industrial analytical chemical applications. Simultaneous quantitative multcomponent xylene isomer mixtures analysis was achieved using the solid-state near-infrared spectrometer coupled with partial least squares regression multivariate data treatment. The results demonstrate an absolute accuracy of ± 0.05, ±0.12 and ±0.09% w/v for o-, m- and p-xylene isomers respectively. In a separate chemical study, qualitative classification analysis of specially denatured alcohol mixtures was successfully performed on 53 validation samples using 35 reference samples belonging to 12 classes. The validation set included mixture sample types used for model calibration as well as others composed of compounds not used for model calibration. The multivariate cluster classification method using principal components was employed to correctly classify 100% of the validations samples analyzed. The solid-state near-infrared spectrometer was also applied for direct reaction monitoring of the O-H overtone absorption band at 1411 nm for the reaction between triisopropyl-chlorosilane and methanol. The results illustrated the utility of near-infrared functional group monitoring of reactions at relatively high concentrations for information elucidation concerning reaction initiation and completion.

Egg is a fragile component within the human diet. Important changes occur in egg during storage. Prediction of these changes is critical in order to grade the eggs upon their quality and freshness. The objectives of this study were to evaluate the application of visible and near infrared spectroscopy as a non-destructive method for the assessment of egg quality and freshness. Therefore, visible and near infrared transmittance spectral data ranging from 350 to 2500 nm was collected with the help of a radiospectrometer on 360 freshly laid eggs. A partial least squares model was built in order to link the spectral data with the most widely used destructive methods, namely Haugh Units and albumen pH in terms of egg quality and the number of storage days in terms of egg freshness. The ability of maximum R2 method to select the relevant wavelengths in order to build a partial least squares (PLS) predictive model was investigated in the first part of the study. The results showed that this method improved the predictive ability of the model. Coefficient of determination (R2) and root mean square error of cross validation (RMSECV) were calculated in order to select sets of wavelengths to build the model with the best predictive ability. The second part of the study was based on building calibration models for predicting egg freshness in terms of number of storage day and egg quality in terms of Haugh Units and albumen pH. The results showed that the models had good predictive ability and R2 for number of storage days, Haugh Units and albumen pH were 0.89, 0.79 and 0.90, respectively. RMSECV for these three parameters were 1.65, 5.05 and 0.06, respectively.
L'oeuf est un composant fragile dans le regime alimentaire humain. Des changements importants arrivent dans loeuf pendant le stockage. La prediction de ces changements eat ctitique pour classer les oeufs selon leur qualité et leur fraîcheur. Les objectifs de cette étude étaient d'évaluer l'application méthode basée sur la spectroscopie visible et infra-rouge proche comme une method non destructive pour l'évaluation de la qualité et la fraîcheur des oeufs. Donc, la transmission visible et infra rouge proche des données spectrales aux limites de 350 à 2500 nm ont été exécutées à l'aide d'un radiosectromètre sur 360 oeufs récemment pondus. Un modèle des moindres carrées partiels (MCP) a été construit afin de lier les données soectrakes avec les méthodes destructives les plus utilisées, à savoir Unité de Haugh at le pH d'albumen en termes de qualité d'oeufs et le nombre de jours de stoclage en termees de fraîcheur d'oeufs. La première étude a traité de la capacité de la méthode maximum R2 à choisir les longueurs d'onde appropriées afin d'établir un modèle des moindres carrés partiels (MCP). Les résultats ont révélé combien cette méthode a été un bon outil dans le choix des longueurs d'onde instructives et dans l'amélioration de la capacité prédictive du modèle. Le coefficient de détermination (R2) et les erreurs de la racine carrée moyenne (ERCM) ont été calculés afin de choisir des ensembles de longueurs d'onde, lesquels aident le mieux à construire le modèle qui possède la meilleure capacité prédictive. La seconde étude a visé l'établissement des modèles prédictifs de la fraîcheur d'oeufs en fonction du n

Thesis (Ph. D.)--West Virginia University, 2008.
Title from document title page. Document formatted into pages; contains xi, 98 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 47-52).

Classification of migraineur and healthy subjects using statistical pattern classifiers on functional Near Infrared Spectroscopy (NIRS) data is the main purpose of this study. Also a statistical comparison between trials that have different type of classifiers, classifier settings and feature sets is done. Features are extracted from raw light measurement data acquired with NIRS device, namely Niroxcope, during two separate previous studies, using Modified Beer-Lambert Law. After feature extraction, Naï
ve Bayes classifier and k Nearest Neighbor classifier are utilized with and with-out Principal Component Analysis in separate trials. Results obtained are compared within each other using statistical hypothesis tests namely Mc Nemar and Cochran Q.

The purpose of this research is to ascertain potential iris scan data variations from near infrared waves derived from fluorescent illumination. Prior studies of iris data variances from infrared wave interference of halogen, incandescent, and sunlight with iris cameras suggest that similar changes may exist under near infrared wavelengths from fluorescent light. The concern is that the fluorescent energy emission may interfere with the near infrared detection of an iris camera. An iris camera is used to measure human eye characteristics known as biometrics. If such infrared emission is statistically significant, then it can alter the validity of the iris scan data. The experiment utilized nine hundred forty-five (945) scans from sixty-three (63) subjects. Measured results showed increased heat from ambient fluorescent illumination does not statistically alter the biometric readings of human eyes. The test results fail to reject that data loss will not occur as heat is increased in the ambient fluorescent light source.

Introduction: Process analytical technologies are systems for the analysis and control of manufacturing processes to assure acceptable end-product quality. This is achieved by timely measurements of critical parameters and performance attributes of raw material and in-process material and processes. The introduction of process analytical technology using near infrared analysis was investigated in three areas, namely incoming raw material analysis, blend uniformity analysis and moisture determination in the fluid bed dryer. Methodology: Incoming raw material identification - The FOSS XDS rapid content analyzer was used for the development of a NIR method for the identification and material qualification of starch maize and lactose monohydrate. Blend uniformity analysis – The SP15 Laboratory Blender fitted with near infrared probe was utilized for the study. Two types of blend experiments were designed to monitor the distribution of magnesium stearate (lubricant) in the blend, namely, a powder blend utilizing lactose monohydrate and a granule blend utilizing Ridaq® granule. Software methods were developed to monitor the standard deviation of the absorbance at the wavelengths that were specific for lactose monohydrate, Ridaq® granule and magnesium stearate. To confirm the prediction of end-point using near infrared, results were verified using an atomic absorption method for magnesium stearate. The blends were sampled at the selected time intervals corresponding to three states of the blend, namely, before end-point, at end-point and after end-point using a sampling plan. An additional six blends were conducted for the granule blend and sampled when the standard deviation had reached a value below 3 x 10-6 at the magnesium stearate wavelength at four consecutive data points (standard deviation value extrapolated from blends carried out to predetermined time intervals). Moisture determination in the fluid bed dryer – Moisture values for two products (Product A and Product B) were retrospectively collected from past production batches. A process capability study was conducted on the moisture values to determine if the current process was in a state of control. Results and Discussion: Incoming raw material identification – The algorithms used for the spectral library were able to distinguish between the raw materials selected. The spectral library positively identified the starch maize and lactose monohydrate samples that were not present in the library. The negative challenge with pregelatinised starch and tablettose demonstrated that the spectral library was able to differentiate between closely related compounds. Blend uniformity analysis – Blends sampled at the predetermined time intervals demonstrated a homogeneous state when the standard deviation of the absorbance was low and a non-homogeneous state when the standard deviation of the absorbance was high, thus near infrared prediction on the state of the blend was confirmed by the standard analytical methods. The series of Ridaq® granule and magnesium stearate blends sampled when the standard deviation was below 3 x 10-6 were homogeneous with the exception of one blend that was marginally out of specification. Blend durations were significantly lower than the standard blend durations used in the facility and ranged from 112 to 198 seconds. Moisture determination in the fluid bed dryer – From the process capability study of the two products it was noted that Product A is stable but can still be optimized while Product B is at a desirable state. The statistical evaluation of the moisture values for Product A and Product B demonstrated that the use of the product temperature to monitor the moisture gave consistent results. The current process is stable and capable of producing repeatable results although near infrared provides a means for continuously monitoring the product moisture and allows one to take action to prevent over-drying or under-drying. Conclusion: From the investigations conducted, it can be seen that there is definitely a niche for process analytical technology at this pharmaceutical company. The implementation is a gradual process of change, which may take time, probably several years (Heinze & Hansen 2005).

Thesis (Ph. D.)--University of Kentucky, 2006.
Title from document title page (viewed on August 22, 2006). Document formatted into pages; contains: xvi, 229 p. : ill. (some col.). Includes abstract and vita. Includes bibliographical references (p. 213-227).

L’elaboració de formatge es pot considerar un “procés controlat d’eliminació d’aigua de la llet”. Aquest procés concentra la proteïna, el greix i altres nutrients de la llet, augmentant la seva vida útil. La fabricació de formatge consta de diverses etapes d’entre les quals, dues de les més importants, tenen lloc en el tanc de formatgeria: la coagulació de la llet i la sinèresi de la quallada. La monitorització a temps real de la coagulació de la llet i l’enduriment del gel lacti, així com la predicció del temps de tall, són essencials per la producció de formatge ja que aquests factors exerceixen un impacte substancial tant en el rendiment formatger com en la qualitat del formatge final. Hi ha nombrosos factors que afecten el procés de fabricació de formatge mitjançant la modificació de la quantitat, la qualitat i les propietats tecnològiques de la llet. Si bé la majoria d’aquests factors són ben coneguts, alguns no han estat suficientment estudiats. L’objectiu general d’aquesta tesi fou avaluar l’impacte de la mescla de llet (i. e., diferents proporcions de llet de cabra, ovella i vaca) i la llet de baixa qualitat (i. e., llet d’animals amb mastitis subclínica) en la predicció del temps de coagulació, del temps de tall, de la velocitat d’eliminació del sèrum i de diversos altres índexs de producció formatgera, mitjançant la monitorització de la coagulació i la sinèresi amb vàries tecnologies de sensors de dispersió de llum d’infraroig proper: sensor de coagulació de laboratori CoAguLAb; sensor de coagulació CoAguLite i sensor de sinèresi LFV. Els dos darrers, instal·lats en la paret d’un tanc de formatgeria de deu litres a escala de planta pilot. El paràmetre de dispersió tmax i diversos altres paràmetres òptics de temps es correlacionaren significativament amb els temps visual i reològics de coagulació i de tall, així com amb els rendiments de sèrum i formatge i amb el recompte de cèl·lules somàtiques. Es va observar que les mescles de llet i la raça dels animals no tingueren un efecte significatiu (P ≥ 0,05) en els indicadors òptics ni reològics del temps de coagulació, mentre que la concentració d’enzim, la temperatura de coagulació i la infecció subclínica tingueren un efecte significatiu sobre tots els índexs, tant òptics com reològics, relacionats amb el temps de coagulació i la velocitat d’acoblament del gel lacti (i. e., agregació micel·lar i enduriment del gel). La mastitis subclínica, la mescla de llet, la temperatura i la raça tingueren un efecte significatiu sobre la sinèresi de la quallada, mentre que el rendiment formatger es veié afectat per la mastitis subclínica i la raça (cal fer notar que els efectes de la concentració d’enzim, la temperatura i la mescla de llet no foren avaluats directament). S’obtingueren models de predicció pels temps de coagulació i de tall, tant visuals com reològics, l’angle de fase (tgδ) en el moment de tall, la velocitat de sinèresi i diversos indicadors de rendiment formatger. Els nostres resultats confirmen la utilitat de la monitorització a temps real mitjançant dispersió de llum d’infraroig proper tant de la coagulació de llet com de l’eliminació de sèrum de la quallada, amb la finalitat de millorar el control d’aquestes dues etapes crítiques de l’elaboració del formatge. Els resultats obtinguts demostren que l’impacte de factors com la mescla de llets i la mastitis subclínica s’ha de tenir en consideració en les operacions de control de processos de l’elaboració de formatge.
La elaboración de queso puede considerarse como un "proceso controlado de eliminación de agua de la leche". Este proceso concentra la proteína, grasa y otros nutrientes de la leche, aumentando su vida útil. La fabricación de queso consta de varias etapas, de entre las cuales dos de las más importantes tienen lugar en la cuba quesera: la coagulación de la leche y la sinéresis de la cuajada. La monitorización a tiempo real de la coagulación de la leche y el endurecimiento del gel láctico, así como la predicción del tiempo de corte es esencial para la producción de queso ya que dichos factores ejercen un impacto sustancial tanto en el rendimiento quesero como en la calidad del queso final. Existen numerosos factores que afectan al proceso de fabricación de queso mediante la modificación de la cantidad, calidad y propiedades tecnológicas de la leche. Si bien la mayoría de dichos factores son bien conocidos, algunos no han sido suficientemente estudiados. El objetivo general de esta tesis fue evaluar el impacto de la mezcla de leche (i.e., diferentes proporciones de cabra, oveja y vaca) y la leche de baja calidad (i.e., leche de animales con mamitis subclínica) en la predicción del tiempo de coagulación, del tiempo de corte, de la velocidad de desuerado y de varios otros índices de producción quesera, mediante la monitorización de la coagulación y la sinéresis con varias tecnologías de sensores de dispersión de luz de infrarrojo próximo: sensor de coagulación de laboratorio CoAguLAb; sensor de coagulación CoAguLite y sensor de sinéresis LFV. Los dos últimos, instalados en la pared de una cuba de quesería de diez litros a escala de planta piloto. El parámetro de dispersión tmax y varios otros parámetros ópticos de tiempo se correlacionaron significativamente con los tiempos visuales y reológicos de coagulación y de corte así como con los rendimientos de suero y queso; y con el recuento de células somáticas. Se observó que las mezclas de leche y la raza de los animales no tienen un efecto significativo (P ≥ 0,05) ni en los indicadores ópticos ni en los reológicos del tiempo de coagulación, mientras que la concentración de enzima, la temperatura de coagulación, y la infección subclínica tuvieron un efecto significativo sobre todos los índices tanto ópticos como reológicos relacionados con el tiempo de coagulación y la velocidad de ensamblado del gel láctico (i.e., agregación micelar y endurecimiento del gel). La mastitis subclínica, la mezcla de leche, la temperatura y la raza tuvieron un efecto significativo sobre la sinéresis de la cuajada, mientras que el rendimiento quesero se vio afectado por la mastitis subclínica y la raza (nótese que el efecto de la concentración de enzima, la temperatura y la mezcla de leche no fue evaluado directamente). Se obtuvieron modelos de predicción para los tiempos de coagulación y de corte tanto visuales como reológicos, el ángulo de fase (tgδ) en el momento del corte, la velocidad de sinéresis y varios indicadores de rendimiento quesero. Nuestros resultados confirman la utilidad de la monitorización a tiempo real tanto de la coagulación de leche como del desuerado de la cuajada mediante dispersión de luz de infrarrojo próximo, a fin de mejorar el control de esas dos etapas críticas de elaboración de queso. Los resultados obtenidos demuestran que el impacto de factores tales como la mezcla de leches y la mastitis subclínica debe ser tenido en consideración en las operaciones de control de procesos de la elaboración de queso.
Cheese making is the “controlled process of removing water from milk”. This process concentrates the milk protein, fat and other nutrients and increases its shelf life. Cheese manufacture consists of two main steps occurring in the cheese vat, milk coagulation and curd syneresis. Real-time monitoring of milk coagulation, curd firming and syneresis as well as inline prediction of cutting time is essential for cheese making as those factors exert a substantial impact in both cheese yield and quality. Many factors affect the cheese manufacturing process by modifying the quantity, quality, and processing properties of the produced milk. The general objective of this dissertation was to evaluate the impact of milk mixture (i.e., different proportions of goat, sheep and cow milk) and low quality milk (i.e., milk from animals with subclinical mammary infections) in the prediction of clotting time, cutting time, syneresis rate and several other cheese making indexes based on monitoring milk coagulation and syneresis using NIR light backscatter sensor technologies. Several optical devices: a lab-scale coagulation tester (CoAguLab), an inline coagulation sensor and an inline large field of view (LFV) syneresis sensor were used to monitor milk coagulation, cutting time, and whey separation during Manchego cheese manufacture. Optical parameter tmax and several other time-based light backscatter parameters were highly correlated with visually- and rheologically-derived clotting and cutting times as well as cheese yield, yield of whey and SCC. It was observed that milk mixtures and animal breed did not have a significant (P ≥ 0.05) effect on optical and rheological time parameters related to clotting time, while different enzyme concentrations, coagulation temperatures, and subclinical infection had a significant effect on all optical and rheological parameters related to milk clotting time, and gel assembly rate (i.e., aggregation and firming rates). Subclinical mastitis, milk mixtures, temperature, and breed had a significant effect on curd syneresis while cheese yield was affected by subclinical mastitis and breed (note that syneresis effect of enzyme concentration, temperature and milk mixtures was not directly evaluated). Prediction models using light backscatter parameters alone or in combination with protein/solids concentration were successfully obtained for visually determined clotting and cutting times, rheologically derived gelation and cutting times, tanδ at cutting, syneresis rate constant and several cheese yield indicators. Our results confirm the usefulness of light backscatter inline monitoring of milk coagulation and curd syneresis for improved process control of those two critical cheese making steps. The results obtained show that the impact of factors such as milk mixtures and subclinical mastitis in cheese manufacture needs to be considered on cheese making process control operations.

Experiments were conducted to assess the feasibility of determining the quality attributes of tomato (Lycopersicon esculentum Mill cv 'DRK 453' and 'Trust') based upon visible/near-infrared reflectance (VIS/NIR) spectroscopy. A partial least squares regression (PLS) method was used to build prediction models. Excellent prediction performance was achieved for lycopene content (LC), colour value a*/b* ratio, tomato colour index (TCI), and firmness. Coefficient of determination (R2) for each of the parameters was respectively 0.96, 0.99, 0.99, and 0.97. All these R2 were significant at 1% level. The root mean square errors of prediction (RMSEP) for all the parameters were low indicating the high quality of the fit of the prediction models. The values were 2.15, 0.06, 1.52, and 1.44 for LC, a*/b* ratio, TCI, and firmness, respectively. However, the models for prediction of titratable acidity, soluble solids content (SSC) and acid-Brix ratio showed relatively poor reliability, with R2 value of 0.49, 0.03 and 0.65, and RMSEP of 0.43, 0.15 and 0.08, respectively. Further, a model built by the PLS2 method showed good performance in simultaneously predicting a*/b* ratio, TCI, firmness, and LC of tomato, with R2 values of 0.99, 0.99, 0.97, and 0.92, and RMSEP of 0.06, 1.75, 1.44, and 3.03, respectively. Once again here all the R2 values were significant at 1% level.
Des essais visant à évaluer la faisabilité d'utiliser la spectroscopie de réflectance dans le visible et le proche infrarouge (VIS/PIR) pour déterminer certaines caractéristiques contribuant à la qualité de la tomate (Lycopersicon esculentum Mill. cv. 'DRK 453' et 'Trust') ont été menés. Une analyse de régression partielle par les moindres carrés a servi à bâtir des modèles de prédiction. D'excellentes prédictions ont été obtenues pour la teneur en lycopène (TL), la valeur chromatique a*/b*, l'indice de couleur de la tomate (ICT), et la fermeté. Les coefficients de détermination (R2) pour chacun de ces paramètres ont été de 0.96, 0.99, 0.99 et 0.97. Tous ces R2 ont été significatifs à un niveau de 1%. L'erreur-type de prédiction (ETP) a été petite pour tous ces paramètres, indiquant un très bon degré d'ajustement des modèles. Des valeurs d'ETP de 2.15, 0.06, 1.52 et 1.44 ont respectivement été obtenues pour le TL, le rapport a*/b*, l'ICT, et la fermeté. Cependant, les modèles visant à prédire l'acidité totale, la teneur en solides solubles et le rapport acide-Brix se sont montrés peu fiables avec des valeurs respectives de R2 de 0.49, 0.03 et 0.65 et de ETP de 0.43, 0.15 et 0.08. De plus, un modèle multivariable bâti par une méthode de régression partielle par des moindres carrés (PLS2) s'est montrée très performant pour la prédiction simultanée du rapport a*/b*, de l'ICT, de la fermeté et de la TL avec des valeurs respectives de R2 de 0.99, 0.99, 0.97 et 0.92 et de ETP de 0.06, 1.75, 1.44 et 3.03. Comme auparavant toutes les valeurs de R2 ont été significatives à un niveau de 1%.

We report on the observation of intersubband absorption in GaN/AlN quantum well superlattices grown on (112)-oriented GaN. The absorption is tuned in the 1.5–4.5 μm wavelength range by adjusting the well thickness. The semipolar samples are compared with polar samples with identical well thickness grown during the same run. The intersubband absorption of semipolar samples shows a significant red shift with respect to the polar ones due to the reduction of the internal electric field in the quantum wells. The experimental results are compared with simulations and confirm the reduction of the polarization discontinuity along the growth axis in the semipolar case. The absorption spectral shape depends on the sample growth direction: for polar quantum wells the intersubband spectrum is a sum of Lorentzian resonances, whereas a Gaussian shape is observed in the semipolar case. This dissimilarity is explained by different carrier localization in these two cases.

Funding Agencies|EC FET-OPEN project Unitride|233950|EU ERC-StG under project TeraGaN|278428|French National Research Agency under project COSNI|ANR-08-BLAN-0298-01|

This thesis focuses on the investigation and application of functional Data Analysis methodologies to address calibration challenges of spectroscopic data. Of particular interest is the area of calibration of near-infrared spectral data. Different strategies to construct functional linear calibration methodologies and a number of functional linear calibration approaches are initially discussed. A novel approach is then proposed to compare functional linear calibration methodologies with a well established and widely used methodology in the chemometrics area, Partial Least Squares (PLS). From this perspective, a common framework can be established to investigate the similarities and differences between these two methodologies. It is shown that the model structures of these two methodologies are similar but the difference is the selection of basis function to represent the original spectral data. As opposed to the loadings of PLS, B-splines capture local features of the data.

Current practices for routine milk composition determination employ commercial infrared systems. The use of SW-NIR and NIR FT-Raman spectra coupled with conductivity and refractive index could lead to more frequent and less costly analysis of fat, lactose and protein in milk.
The present study examines the potential of both SW-NIR absorbance spectrophotometry and NIR FT-Raman spectrophotometry to develop a model to estimate fat, lactose, and protein in whole milk of cows. To accomplish this, 79 milk standards, spanning the range of composition seen in practice, were obtained. Acquisition of NIR spectra over the wavelength range of 700 nm to 1018 nm was conducted. Between 0 and 3700 cm-1, NIR FT-Raman spectrophotometric measurements of the milk samples were made using a 1064 nm Nd: YAG laser source. Conductivity and refractive index measurements were also obtained for the milk standards.
A partial least squares calibration with leave-N-out cross validation was made using spectra with conductivity and refractive index to estimate fat, lactose and protein contents. Calibrations were developed using 75% of the milk standards. Models were further validated using an independent test set comprised of the remaining 25% of the data that had been excluded from calibration. A second calibration was conducted using a genetic algorithm approach. (Abstract shortened by UMI.)

The principal aim of this research was to assess at-line Near Infrared Spectroscopy (NIRS) to support Process Analytical Technology (PAT) applications within solid dosage form manufacturing. The history of PAT was traced from implementation of process analytical applications prior to the 2003 United States, Food and Drug Administration PAT initiative through to current time. The use of NIRS within the PAT context was reviewed, highlighting two areas in solid dosage manufacturing where further research of at-line NIRS is warranted; material testing and finished dosage form analysis. Novel applications of at-line NIRS were investigated and developed aligned with the PAT philosophy, to establish an innovative system of analysis that combined chemometrics and spectral analysis with statistical process control (SPC). In particular, various chemometric algorithms were explored to enable rapid monitoring of global spectral quality as well as the quality of specific critical-to-process material attributes within a SPC framework. Novel approaches to within and between batch SPC for tablet quality conformance were also developed including the adaption of distribution profile control charts typically applied to particle size measurement. These were quick to develop with greatly reduced reliance on reference analysis. It provided an opportunity for extensive process monitoring and in-depth process understanding. The work highlighted gaps in currently available chemometric and SPC capabilities within NIR instrument control software and provided insight into a new direction for NIRS analysis in the future. The new conformance methodology was demonstrated to provide business value and critical science based understanding of the pharmaceutical formulation and processes with successful application of the methodology at a commercial Pfizer facility. This methodology is in the process of rolling out worldwide. The approach was found to be approachable for plant operators through to quality analysts, and is broadly applicable with the potential to extend beyond the solid dosage form studied.

Thesis (Ph. D.)--Harvard-MIT Division of Health Sciences and Technology, 2011.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 199-217).
In vivo multimodal, multiplexed microscopy allows real-time observation of hematopoietic cells, their stem and progenitor cells and metastatic cancer cells in their native bone marrow (BM) environment. Multiplexing has made possible detailed studies of the BM's microarchitecture, which helps define the niche of these cells; it has nonetheless been limited by the paucity of suitable probes fluorescent in the near-infrared spectrum that is favored by tissue optics. This project attempts to address this problem by developing cellular and vascular fluorescent imaging probes comprised of semiconductor nanocrystals, or quantum dots (QDs), with tunable fluorescence between 65o-8oonm and exhibiting photostability, robust quantum yield and narrow fluorescence profiles that are critical for such applications. The synthesis of alloyed CdTexSe1 x QDs will be detailed in the thesis. Reproducibility and workability in subsequent steps are emphasized in the methods. Special attention is also paid to the difference between working with alloyed versus single semiconductor QDs, especially the need to achieve physical and spectral uniformity when composition and its gradient are also variable. The steps for creating biological probes from these QD fluorophores are also described. They include overcoating, water solubilization and functionalization for cellular uptake and vascular retention. Finally, the thesis returns to its motivation and reports novel methods, developed using NIR QD vascular imaging probes, for visualizing in vivo 3-D imaging data of the murine BM and characterizing the tissue's architecture. Measuring the Euclidean distance between BM osteoblasts and blood vessels is presented to exemplify a potential platform for describing the geographic relationships between cells, molecules and structural components in any tissue.
by Juwell Wendy Wu.
Ph.D.

La mise en place de la démarche PAT (Process Analytical Technology), initiée par la FDA (Food and Drug Administration) s’est développée au cours de ces dernières années, au sein de l’industrie pharmaceutique. Grâce à des contrôles en continu au coeur des procédés de fabrication, elle permet une meilleure compréhension et une maîtrise de la formulation et du procédé, afin d’assurer la qualité finale des médicaments.A travers ce travail, nous avons mis en place un suivi en temps réel, par spectroscopie proche infrarouge, d’une opération d’enrobage suite à l’intégration d’une sonde à l’intérieur d’une turbine d’enrobage. La quantité d’enrobage, déterminée par une simple et rapide pesée mais néanmoins soumise à la variabilité de la masse des comprimés nus, ainsi que l’épaisseur du film, obtenue avec précision par imagerie térahertz ont servi de valeurs de référence pour calibrer l’information spectrale. Dans les deux cas, ces deux attributs qualité critiques ont été prédits avec de faibles erreurs de prédiction, qui se sont révélées être similaires. Par ailleurs, la prédiction en temps réel des propriétés de dissolution de comprimés prêts à être libérés, à partir de spectres acquis in-line, a permis de déterminer l’arrêt optimal de l’opération d’enrobage.Suite à un enrobage réalisé à partir d’une dispersion aqueuse de polymère une étape supplémentaire de traitement thermique ou curing est généralement nécessaire afin de stabiliser le film d’enrobage. Un travail de caractérisation mené à partir de techniques innovantes a permis d’apporter un nouvel éclairage sur la compréhension des phénomènes impliqués dans la formation du film au cours du curing. La caractérisation approfondie de la structure d’enrobage de comprimés soumis à un curing en turbine (conditions dynamiques) a mis en évidence la diminution de la porosité, couplée à l’évaporation de l’eau et à une meilleure organisation des chaînes de polymère au cours du curing. L’étude de comprimés soumis à un curing de référence en étuve durant 24 h (conditions statiques) a confirmé l’obtention d’un film stable après 4 h de curing dynamique. De nouveaux phénomènes, indépendants du curing, liés à la cristallisation et à la migration de l’alcool cétylique, couplée à la migration du lauryl sulfate de sodium, au sein de la couche d’enrobage ont été détectés au cours de la conservation des comprimés enrobés
Implementation of PAT (Process Analytical Technology) approach has recently been promoted by the FDA (Food and Drug Administration) within the pharmaceutical industry. A desired goal of the PAT framework is to enhance understanding and control of the manufacturing process through timely measurements, during processing, to ensure final product quality. Real-time monitoring of a coating operation was performed from in-line Near Infrared (NIR) measurements inside a pan coater. Mass of coating materials, determined by simple and fast weighing but depending on core tablet weight uniformity, and film coating thickness, obtained from accurate and non-destructive Terahertz Pulsed Imaging (TPI) measurements, were used as reference values to calibrate NIR spectral information. In both cases, these two critical quality attributes were predicted with low predictive errors, which were found to be similar. In addition, real-time predictions of drug release from cured tablets were carried out by in-line NIR measurements. The coating operation was successfully stopped when desired dissolution criteria were achieved. A post-coating thermal treatment, known as curing, is generally required to stabilize film coating from aqueous polymer dispersion. Innovative techniques were jointly used to elucidate the underlying mechanisms of film formation along the curing process. This study provided a new insight into the tablet coating structure, highlighting a reduced internal coating porosity, a decrease in water content and showing a better structural rearrangement of polymer chains, with dynamic curing. All investigated techniques confirmed that a stabilized state was reached after a 4 h dynamic curing in comparison with a reference curing carried out in an oven for 24 h. Interestingly even prior to curing, new findings were pointed out, during coated tablets storage, related to the crystallisation and the upward migration of cetyl alcohol, coupled to the downward migration of sodium lauryl sulfate within the coating layer

Spectroscopy and other optical methods can often be employed with limited or no sample preparation, making them well suited for in situ and in vivo analysis. This dissertation focuses on the use of a near-infrared spectroscopy (NIRS) and polarized light scatter for two such applications: the assessment of cardiovascular disease, and the validation of cleaning processes for pharmaceutical equipment.There is a need for more effective in vivo techniques for assessing intravascular disorders, such as aortic aneurysms and vulnerable atherosclerotic plaques. These, and other cardiovascular disorders, are often associated with structural remodeling of vascular walls. NIRS has previously been demonstrated as an effective technique for the analysis of intact biological samples. In this research, traditional NIRS is used in the analysis of aortic tissue samples from a murine knockout model that develops abdominal aortic aneurysms (AAAs) following infusion of angiotensin II. Effective application of NIRS in vivo, however, requires a departure from traditional instrumental principles. Toward this end, the groundwork for a fiber optic-based catheter system employing a novel optical encoding technique, termed molecular factor computing (MFC), was developed for differentiating cholesterol, collagen and elastin through intervening red blood cell solutions. In MFC, the transmission spectra of chemical compounds are used to collect measurements directly correlated to the desired sample information.Pharmaceutical cleaning validation is another field that can greatly benefit from novel analytical methods. Conventionally cleaning validation is accomplished through surface residue sampling followed by analysis using a traditional analytical method. Drawbacks to this approach include cost, analysis time, and uncertainties associated with the sampling and extraction methods. This research explores the development of in situ cleaning validation methods to eliminate these issues. The use of light scatter and polarization was investigated for the detection and quantification of surface residues. Although effective, the ability to discriminate between residues was not established with these techniques. With that aim in mind, the differentiation of surface residues using NIRS and MFC was also investigated.

Questo lavoro di tesi risponde al bisogno dell’industria lattiero-casearia di incrementare la produttività e allo stesso tempo soddisfare la richiesta dei consumatori di prodotti di elevata qualità. A tal fine, si possono proporre alle aziende lattiero-casearie nuovi metodi per migliorare la comprensione e il monitoraggio dei processi di produzione. La Process Analytical Technology (PAT) rappresenta uno strumento ideale per raggiungere questo scopo, grazie a sensori in grado di eseguire analisi rapide, green, non distruttive ed in tempo reale. Le tecniche più utilizzate in questo campo sono la spettroscopia del vicino e del medio infrarosso (NIR e MIR, rispettivamente), che forniscono informazioni chimico-fisiche sul prodotto grazie a sonde installate direttamente in punti critici del processo. Tuttavia, queste tecniche hanno lo svantaggio di fornire risultati (spettri) difficilmente interpretabili senza l’aiuto di un adeguato metodo statistico. In questo contesto, gli algoritmi Chemiometrici permettono l’estrazione di informazioni rilevanti dai dati spettroscopici, permettendo la comprensione del sistema studiato. La prima parte del presente lavoro è focalizzata sul monitoraggio del processo di coagulazione, uno dei momenti più critici della caseificazione. A tal fine, è stata utilizzata una sonda FT-NIR per acquisire spettri durante il processo di coagulazione. variando alcuni fattori tecnologici cruciali, come temperatura, contenuto di grasso e pH, secondo un disegno Box-Behnken. Attraverso l’algoritmo Multivariate Curve Resolution - Alternating Least Squares (MCR-ALS) è stato possibile ottenere sia una efficiente descrizione delle tre differenti fasi del processo di coagulazione, sia lo sviluppo di carte di controllo multivariate (Multivariate Statistical Process Control charts, MSPC), capaci di individuare possibili non-conformità fin dai primi momenti del processo. Inoltre, il metodo ANOVA-Simultaneous Component Analysis (ASCA) è stato applicato ai dati spettrali al fine di ottenere una migliore comprensione della coagulazione, evidenziando in che modo ogni fattore sperimentale influenzi il processo. Nella seconda parte del lavoro, la spettroscopia FT-NIR è stata studiata come possibile strumento per sostituire le tecniche standard, come il Formagraph, per valutare l’attitudine alla coagulazione. Le prove di coagulazione sono state effettuate usando differenti campioni di latte in polvere. L’utilizzo dell’algoritmo MCR-ALS ha permesso la valutazione della miglior polvere in termini di attitudine alla coagulazione e, inoltre, ha evidenziato la non significatività degli effetti della concentrazione di CaCl2 e del trattamento termico del latte ricostituito sul tempo di coagulazione. Infine, le prove sperimentali eseguite con miscele di latte scremato e percentuali più elevate di latte ricostituito hanno mostrato una coagulazione più lenta. L’ultima parte del lavoro ha riguardato l’utilizzo della spettroscopia MIR per monitorare la produzione di galattooligosaccaridi (GOS) dal siero di formaggio, allo scopo di valorizzare questo prodotto e di ottimizzare il processo. La regressione Partial Least Square (PLS) è stata utilizzata con l’obiettivo di predire le componenti specifiche derivanti dalle differenti reazioni enzimatiche studiate. In conclusione, l’applicazione dei metodi proposti permetterà un efficiente controllo del processo garantendo un modesto impatto ambientale e soddisfacendo allo stesso tempo requisiti di legge e esigenze dei consumatori. Infine, l’affidabilità degli approcci PAT può essere rafforzata da future applicazioni industriali.
This thesis work wants to answer the need of dairy industry to increase productivity while satisfying the consumers request for higher quality products. In order to do that, dairy companies need innovative methods to improve the understanding and the monitoring of production processes. Process Analytical Technology (PAT) approaches are the perfect tool for this purpose, as they use green, fast, non-invasive and non-destructive sensors that allow to perform measurements in real time. The most used techniques in this field are Near- and Mid-Infrared (NIR and MIR, respectively) spectroscopy, whose probes can be directly installed in critical points of the process providing both physical and chemical information of the product. However, these techniques have the drawback of providing results (spectra) difficult to be interpreted without proper statistical tools. In this context, Chemometric methods and algorithms allow the extraction of relevant information from spectroscopic data, providing a better understanding of the studied system. The first part of the present work focused on the monitoring of the coagulation process, one of the most critical moments of cheesemaking. To this aim, an FT-NIR spectroscopy system was used, acquiring spectra along the rennet coagulation process. According to a Box-Behnken experimental design, several coagulation trials were carried out, changing crucial technological factors, such as temperature, fat content and pH. Through Multivariate Curve Resolution optimized by Alternating Least Squares (MCR-ALS) algorithm it was possible to both have a reliable description of the three different coagulation phases and, most importantly, to build Multivariate Statistical Process Control (MSPC) charts, able to detect failures from the first moment of the process. Moreover, ANOVA-Simultaneous Component Analysis (ASCA) method was applied on spectral data to obtain a better understanding of the process, highlighting in which way each physicochemical parameter affects the process. In the second part of the work, FT-NIR spectroscopy was tested as a possible tool to replace the golden standards of coagulation ability, i.e. Formagraph. Coagulation trials were carried out using different milk powder samples. The use of MCR-ALS algorithm permitted the assessment of the best powder in terms of coagulation attitude and, in addition, it highlighted the non-significant effect on coagulation occurrence of CaCl2 concentration and of heat treatment on reconstituted milk. Finally, experimental trials carried out with mixtures of skimmed milk and reconstituted milk showed a slower coagulation time when a higher reconstituted milk percentage was used. The last part of the work regarded the use of MIR spectroscopy to monitor Galactooligosaccharides (GOS) production from cheese whey, in order to avoid the waste of this compound and to optimize the studied process. To do so, Partial Least Square (PLS) regression was used to predict the specific compounds resultant from the different enzymatic reaction studied. In conclusion, the application of the proposed methods will implicate, with a modest environmental impact, an efficient control of the process, satisfying at the same time law requirements and consumers’ needs. Furthermore, reliability of PAT approaches could be strengthened by future industrial applications.

Les entreprises pharmaceutiques ont progressivement adopté le concept de Process Analytical Technology (PAT) afin de contrôler et d'assurer en temps réel la qualité des produits pharmaceutiques au cours de leur production. Le PAT et un composant central du concept plus général de Quality-by-Design (QbD) promu par les agence régulatrices et visant à construire la qualité des produits via une approche scientifique et la gestion des risques.Une méthode basée sur la spectroscopie proche infrarouge (PIR) a été développée comme un outil du PAT pour contrôler en ligne la cristallisation d'un principe actif pharmaceutique. Au cours du procédé les teneurs en principe actif et en solvant résiduel doivent être déterminées avec précision afin d'atteindre un point d'ensemencement prédéfini. Une méthodologie basée sur les principes du QbD a guidé le développement et la validation de la méthode tout en assurant l'adéquation avec son utilisation prévue. Des modèles basés sur les moindres carrés partiels ont été construits à l'aide d'outils chimiométriques afin de quantifier les 2 analytes d'intérêt. La méthode a été totalement validée conformément aux requis officiels en utilisant les profils d'exactitude. Un suivi du procédé en temps réel a permis de prouver que la méthode correspond à son usage prévu.L'implémentation de cette méthode comme à l'échelle industrielle au lancement de ce nouveau procédé permettra le contrôle automatique de l'étape de cristallisation dans le but d'assurer un niveau de qualité prédéfini de l'API. D'autres avantages sont attendus incluant la réduction du temps du procédé, la suppression d'un échantillonnage difficile et d'analyses hors ligne fastidieuses
Pharmaceutical companies are progressively adopting and introducing the Process Analytical Technology (PAT) concept to control and ensure in real-time product quality in development and manufacturing. PAT is a key component of the Quality-by-Design (QbD) framework promoted by the regulatory authorities, aiming the building of product quality based on both a strong scientific background and a quality risk management approach.An analytical method based on near infrared (NIR) spectroscopy was developed as a PAT tool to control on-line an API (active pharmaceutical ingredient) crystallization. During this process the API and residual solvent contents need to be precisely determined to reach a predefined seeding point. An original methodology based on the QbD principles was applied to conduct the development and validation of the NIR method and to ensure that it is fitted for its intended use. Partial least squares (PLS) models were developed and optimized through chemometrics tools in order to quantify the 2 analytes of interest. The method was fully validated according to the official requirements using the accuracy profile approach. Besides, a real-time process monitoring was added to the validation phase to prove and document that the method is fitted for purpose.Implementation of this method as an in-process control at industrial plant from the launch of this new pharmaceutical process will enable automatic control of the crystallization step in order to ensure a predefined quality level of the API. Other valuable benefits are expected such as reduction of the process time, and suppression of a difficult sampling and tedious off-line analyzes

Silicon based sensors is a commonly used technology in digital cameras today. That has made such cameras relatively cheap and widely used. Unfortunately they are constructed to capture and represent image quality for humans. Several image applications work better without the restrictions of the visible spectrum. Human visual restrictions are often indirectly put on technology by using images showing only visible light. Thinking outside the box in this case is seeing beyond the visible spectrum.

Thesis (M. Tech. (Clinical technology)) - Central University of technology, Free State, 2012
The objective of this study was to investigate whether intra-operative regional cerebral tissue oxygen saturation (NIRS) and hemodynamic monitoring in patients with Acute Coronary syndrome (ACS) during coronary bypass graft surgery (CABG on-pump vs. off-pump) can predict clinical outcomes and complications. Data from 60 CABG patients (30 on-pump and 30 off-pump) were analyzed. The regional cerebral tissue oxygen saturation was monitored by using near-infrared spectroscopy (NIRS). The sensors were positioned in the middle of the patient's forehead and the cables were connected to the sensors and to the INVOS 5100C® Oximeter. According to NIRS values obtained, patients were subdivided into two groups. Patients in Group 1 had absolute NIRS values more than 50 or less than a 20% drop from the baseline value. Patients in Group 2 had absolute NIRS values of less than 50 or a drop of more than 20% from the baseline value. The lowest value recorded during the procedure was recorded for this purpose, irrespective of the time this value was obtained. Intra-operative hemodynamic monitoring was captured by a computer software program (Supplier Datex Ohmeda, South Africa). In order to describe surgical outcomes several parameters were analysed and compared. This included a Pre- and Post-operative Mini-Mental state examination that was performed to identify neurological outcomes or impairment. The NIRS values and trends in relation to renal function (U&E and creatinine, urine output, and urine electrolytes), as well as clinical outcomes were analyzed post-operatively for the different groups. Clinical outcomes were described using the Society of Thoracic Surgeons Database (STS database) data fields, and specifically the recording of complications. The overall clinical outcomes were analysed between the on-pump and off-pump groups as well as the NIRS results between the two groups. In order to elucidate the predictive role of NIRS the patients were divided into groups with either impaired /reduced NIRS values or acceptable NIRS values according to published results where a reduction of more than 20% from baseline or absolute values of less than 50 were associated with inferior outcomes. Finally, the predictive value of NIRS was evaluated within the on- and then the off-pump groups. In this analysis the outcomes of patients with reduced NIRS values was compared to those of patients with acceptable NIRS values. The study demonstrated that by far the majority of patients with reduced cerebral flow/oxygen delivery as reflected in cerebral NIRS, had on-pump CABG procedures (84% fell in risk group 2). It also showed that a NIRS reduction of more than 20 % from baseline and values of less than 50, has an impact on post–operative renal function. Monitoring of cerebral oximetry intra-operatively by using near-infrared spectroscopy during cardiac surgery (especially in on-pump cardiac surgery patients) allows the perfusionist and anaesthesiologist to detect cerebral desaturation and to intervene as necessary. This study also showed a tendency towards less renal function impairment in patients with absolute NIRS values > 50 or where there was < 20% drop from baseline. It is probably important to consider studying the time spend below 50 or a drop of more than 20% from baseline NIRS values, or the “area under the curve” as a specific factor contributing to the increased risk for post-operative complications applied on an increased study population. The study supports the routine use of NIRS as a non-invasive trend monitor of cerebral saturation and certainly initiated interventions by both anaesthetic and perfusion staff which contributed to excellent clinical outcomes in this research study.

Abstract This thesis explores the use of assistive in-situ technologies for formal caregivers in nursing homes. More specifically, focus is placed on improving context awareness and medication management. Although these topics have previously been researched for elderly care in general, few solutions targeting nursing homes have been generated. As the aging population further increases the burden on this care environment, it is important that solutions are found to help maintain care quality. The main findings in this thesis emphasise how technology can assist formal caregivers and facilitate increased patient wellbeing. The articles presented in this thesis describe our creation of a context-aware sensor system (named CARE) and a non-expert miniaturised near-infrared spectroscopy (MNIRS) solution. Both systems were designed iteratively with the help of nurses and were evaluated in a nursing home. CARE quantifies elderly residents’ behaviour, analyses the resulting data and produces valuable and actionable insights for nurses. Results from a two-month-long user study demonstrate that the system can facilitate increased awareness of patients’ needs and enhance care service. The custom MNIRS solution allows nurses to scan pharmaceuticals and obtain accurate identifications. This method significantly outperforms currently available tools in nursing homes and represents a promising solution that can reduce medication mismanagement. In the discussion section of the thesis, we revisit the research questions defined in the introduction and examine how each were answered. In addition, we discuss the augmentation of nursing home technology and various stakeholders’ perspectives. We then highlight how the work covered in this thesis was conducted in collaboration with industry and offer some conclusions, limitations and reflections
Tiivistelmä Tämä väitöstyö tutkii paikkasidonnaisten teknologioiden käyttöä hoitajien työn helpottamiseksi vanhusten palvelukodeissa. Työn keskiössä on erityisesti kontekstitietoisuuden lisääminen ja lääkehoidon valvonta. Näitä aiheita on tutkittu laajalti aiemminkin, mutta aitoihin ympäristöihin keskittyviä ratkaisuja on vielä vain vähän. Väestön ikääntyminen aiheuttaa haasteita vanhustenhoidossa, ja siksi on tärkeää kehittää ratkaisuja hoidon laadun ylläpitoa varten. Väitöstyön löydökset painottavat teknologian roolia hoitajien avustajana sekä hoidettavien hyvinvoinnin ylläpitäjänä. Työn artikkelit kuvailevat kontekstitietoisen järjestelmän (CARE) koko kehitys- ja elinkaaren sekä lähi-infrapunaspektroskopiaan perustuvan ratkaisun lääkehoidon prosessien parantamiseksi. Molemmat järjestelmät kehitettiin iteratiivisesti hoitajien avulla ja koestettiin aidossa ympäristössä vanhainkodissa. CARE analysoi asiakkaiden liikkeitä ja toimintoja sekä visualisoi niistä korkeamman tason tietoa hoitajille. Kahden kuukauden kenttäkokeen tuloksena voidaan todeta, että järjestelmät yhdessä voivat auttaa hoitajia ymmärtämään asiakkaiden tarpeita sekä parantamaan hoidon laatua. Lähi-infrapunaspektroskopiaan perustuvalla kannettavalla ratkaisulla puolestaan hoitajat voivat varmistaa lääkehoidon oikeellisuuden. Tämä menetelmä on tarkempi ja parempi kuin tämänhetkiset käytössä olevat ratkaisut lääkkeiden oikeaksi toteamiseen. Väitöstyön keskusteluosuus palaa tutkimuskysymyksiin ja selventää, kuinka tehty työ ja saavutetut tulokset vastaavat niihin. Lisäksi keskustelu antaa yleiskuvan eri osapuolien näkemyksistä kehitetyn ratkaisun hyödyistä ja sen soveltuvuudesta käytännön työhön. Lopuksi väitöstyö luo katsauksen yhteistyön rooliin eri osa-alueiden toteuttamisessa ja esittää kriittisen näkökulman työn puutteisiin sekä yhteenvedon

Many areas of science now generate huge volumes of data that present visualization, modeling, and interpretation challenges. Methods for effectively representing the original data in a reduced coordinate space are therefore receiving much attention. The purpose of this research is to test the hypothesis that molecular computing of vectors for transformation matrices enables spectra to be represented in any arbitrary coordinate system. New coordinate systems are selected to reduce the dimensionality of the spectral hyperspace and simplify the mechanical/electrical/computational construction of a spectrometer. A novel integrated sensing and processing system, termed Molecular Factor Computing (MFC) based near infrared (NIR) spectrometer, is proposed in this dissertation. In an MFC -based NIR spectrometer, spectral features are encoded by the transmission spectrum of MFC filters which effectively compute the calibration function or the discriminant functions by weighing the signals received from a broad wavelength band. Compared with the conventional spectrometers, the novel NIR analyzer proposed in this work is orders of magnitude faster and more rugged than traditional spectroscopy instruments without sacrificing the accuracy that makes it an ideal analytical tool for process analysis. Two different MFC filter-generating algorithms are developed and tested for searching a near-infrared spectral library to select molecular filters for MFC-based spectroscopy. One using genetic algorithms coupled with predictive modeling methods to select MFC filters from a spectral library for quantitative prediction is firstly described. The second filter-generating algorithm designed to select MFC filters for qualitative classification purpose is then presented. The concept of molecular factor computing (MFC)-based predictive spectroscopy is demonstrated with quantitative analysis of ethanol-in-water mixtures in a MFC-based prototype instrument.

This master’s thesis studies the effect of weathering on thermally modified Norway spruce (Picea abies) and Scots pine (Pinus sylvestris) with different surface treatments. Most importantly colour changes were analysed, especially, the greying. However, other aspects of appearance changes, like cracks, mould and chemical changes on the surface were included. Special emphasis was on analysing the influence of tree species, type of thermal modification and surface treatment on these properties. Furthermore, it was tested if near infra-red (NIR) spectroscopy allows to estimate the colour, in addition, to measuring chemical changes. The whole study was set up as a decking of a gangway in Northern Sweden and evaluated after the first year of exposure. With the help of colorimetry, changes in colour based on the CIE L*C*hab colour space were measured. Test results showed that within one year all surfaces turned greyer significantly due to changes in content of lignin and cellulose measured with NIR spectroscopy. Differences could neither be observed between the uses of the two tree species nor between the uses of the thermal modifications, pressurised saturated steam at a temperature of 180 °C and superheated steam at a temperature of 212 °C. However, the surface treatment affects the colour change. Timber treated with a silicon based treatment had from the beginning a greyer colour and turned greyest after one year, while oil and pigmented oil stain slowed down the greying compared to untreated and iron vitriol treated timber. After one year of exposure for none of the treatments the colour had stabilised. Qualitative analysis of cracks and mould growth on the surface indicated some dependence on thermal modification and surface treatment. The PLS model for the prediction was not good, so no universally valid conclusions could be drawn of them. Timber with silicon based treatment showed a tendency for mould growth and timber thermally modified with pressurised saturated steam at a temperature of 180 °C tends to have cracks more often. It was possible to estimate the colour from NIR spectroscopy. Best estimations were achieved for the Chroma, followed by lightness and hue. Even better prediction of the Chroma could be achieved by fitting different models based on the surface treatments.  Hence, NIR spectroscopy allows a good estimation of the greying without needing a further measurement instrument, like a colorimeter.

Repeat sprint ability has been investigated thoroughly, however optimal training methodology to improve RSA remains elusive. Both kinetic and physiological viewpoints have been used to scrutinize aspects of RSA including, initial sprint performance (anaerobic power), maximal cardiorespiratory fitness (VO2max), lactate threshold, anaerobic capacity (mean power), muscle activation (EMG), and local muscle oxygenation kinetics. To our knowledge no study has utilized maximal strength levels as a separate factor among a homogenous group of cardiorespiratory fitness individuals (as determined by peak VO2 during RSA). The purpose of this study was to better understand the relationship between maximal strength, muscular characteristics, and cycling RSA- respective to muscle oxygenation responses. Fifteen participants completed fifteen 10-second maximal effort sprints on a cycle ergometer interspersed with 30-seconds passive recovery. Respiratory, muscle oxygenation, and kinetic responses were monitored continuously and evaluated relationships with maximal strength and muscular architecture as determined by isometric mid-thigh pull and ultrasonography respectively. A series of 2 x 15 mixed design, group x time, ANOVA’s were used to evaluate the effects of group and or sprint on muscle oxygenation kinetics. Strong individuals were found to have significantly greater levels of muscle oxygenation usage, recovery and the respective rates; p = 0.01, p = 0.02, p

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas
A espectroscopia de infravermelho próximo (NIRS) é uma técnica de análise bastante conhecida e utilizada em diversas indústrias, tais como a alimentar, química, petroquímica, agroquímica. É também usada na indústria farmacêutica desde há alguns anos (EMEA, 2003). A Farmacopeia Americana - United States Pharmacopeia (USP) considera a NIRS um ramo da espectroscopia vibracional, partilhando aplicações e princípios com muitas medições espectroscópicas. As suas aplicações utilizam espectros medidos em comprimento de onda. A interacção entre a radiação NIR e a matéria pode fornecer informação qualitativa e quantitativa avaliada a partir da composição química e física de amostras. A técnica é rápida, simples, não destrutiva e analisa múltiplos componentes em praticamente qualquer matriz, com níveis de exactidão e precisão comparáveis aos métodos de referência primários. Não é necessária qualquer preparação ou manipulação da amostra, nem utilização de reagentes (Foss, 2002). Na indústria farmacêutica, o método de análise NIRS vem sendo aplicado há mais de 20 anos, estando inicialmente focalizado na análise de matérias-primas, mais recentemente tem sido também aplicado na análise de formulações sólidas e liquidas para controlo de qualidade do produto final, bem como para monitorização de operações de produção. As amostras de material recebido são inspeccionadas por este método, e a identidade e qualidade do mesmo é confirmada, a partir de algoritmos de padrões conhecidos. O método fornece informação quase em tempo real para controlo de processos de produção, como sejam identificação de matériasprimas, sistemas de recuperação de solventes ou secagem da mistura, por intermédio de técnicas de regressão estatística (Reich, 2005). Para que um processo de análise se possa implementar em processos industriais é necessário assegurar a sua robustez, pelo que um método NIRS deve ser desenvolvido tendo em conta requisitos considerados na produção e controlo, como características ópticas da amostra, sensibilidade e selectividade para o analito (Foss,2002). Os principais objectivos deste trabalho monográfico consistem:  Estudo da técnica em análise, espectroscopia de infravermelho próximo;  As suas aplicações nas diversas fases do processo de produção;  Caracterizar o potencial da tecnologia em estudo, na análise dos diversos processos de controlo e produção farmacêutica. A elaboração deste trabalho de revisão bibliográfica foi efectuada através duma pesquisa sobre a temática, em publicações científicas, livros da especialidade e monografias. Os artigos consultados foram pesquisados, na sua maioria, em motores de busca disponibilizados pela Universidade Fernando Pessoa. As palavraschave utilizadas na realização da pesquisa foram as seguintes: “Espectroscopia de Infravermelho Próximo”, “Indústria Farmacêutica ”, “Aplicações NIRS”, “Tecnologias de Análise de Processos PAT”, “Monitorização de Processos”. Near infrared spectroscopy (NIRS) is an analyses technique very well known and used in many industries, like the chemical, petrochemical, biochemical and food industry. It is also being used in pharmaceutical industries in the recent years (EMEA, 2003). The United States Pharmacopeia (USP) considers NIRS as a branch of vibrational spectroscopy, sharing applications and principles with many spectroscopic measurements. Its applications use spectra measured in wavelength. The interactions between NIR radiation and matter may provide qualitative and quantitative information evaluated from the chemical and physical composition of the samples. This technique is fast, simple, non destructive and also analyzes multiple components in virtually any matrix, providing levels of precision and accuracy comparable with the primary reference methods. It’s not necessary any preparation or manipulation of the sample, and the reagent application is also discarded (Foss, 2002). In the pharmaceutical industry, NIRS method has been used for more than twenty years, initially focused in the analysis of raw materials, and more recently applied also to solid and liquid drug analysis, in the purpose of final quality control, and as well in the production line processes monitoring. Samples of incoming materials are inspected with this method, and the process of identity and quality of those products is assured, being compared with tables from confirmed acceptable samples. The process produces information almost in real time, using regression analysis, in the processes monitoring applications, as in raw material identification, solvent recovery systems or drying processes (Reich, 2005). For the application of the processes in industrial environment it is necessary to assure its strength, for that the NIRS must be developed bearing in mind the requirements considered in the production and control, as in the optical features of the sample, sensibility and selectiveness of the analyte (Foss, 2002). The main objectives of this monograph consist of:  Study of the analysis technique, near infrared spectroscopy;  Its applications in various stages of production;  To characterize the potential of the technology under study, the analysis of the various control processes and pharmaceutical production. The development of this literature review was conducted through a survey on the topic in scientific publications, specialty books and monographs. The selected papers were searched, mostly in search engines provided by the University. The keywords used in the research were as follows: "Near Infrared Spectroscopy", "Pharmaceutical Industry", "NIR Application", "Process Analytical Technology PAT", "Process Monitoring".

As Boas Práticas de Fabricação de Medicamentos (BPFM) enfatizam que a indústria farmacêutica deve dirigir seus esforços no sentido de compreender a variação do processo, incluindo as fontes, o grau de variação e o impacto dessa variação nas características de qualidade do produto. O processo de fabricação de medicamentos tem apresentado significativas mudanças, em especial no que se refere à introdução de tecnologias analíticas que permitem o controle do processo em tempo real. A abordagem baseada na análise de risco e no novo Sistema de Qualidade Farmacêutica constitui ponto central das BPFM para o século XXI. Os órgãos regulatórios têm exigido da indústria farmacêutica sua adesão na melhoria contínua relativa ao desempenho de seus processos e, por consequência, na qualidade do produto. O objetivo do presente trabalho foi o desenvolvimento e validação de método analítico empregando espectroscopia no infravermelho próximo, assim como a avaliação do processo de fabricação de comprimidos de Captopril 25 mg, empregando abordagem racional-científica. Com referência à avaliação do processo, foram adotadas as seguintes ferramentas: análise de modos e efeitos de falhas (FMEA); gráficos de controle; índices de capacidade e análise de variância (ANOVA). A espectroscopia por infravermelho próximo (NIR) foi selecionada por apresentar maior rapidez na obtenção dos resultados, maior simplicidade na preparação das amostras, multiplicidade das análises a partir de uma única leitura e por apresentar característica não invasiva. Os resultados comprovaram a adequação dessa tecnologia na avaliação quantitativa do Captopril nas etapas de mistura de pós e de compressão. Os desvios padrão relativos na determinação da uniformidade de Captopril na mistura de pós e nos comprimidos empregando método no NIR foram, respectivamente 3,15 e 0,18%. No que se refere à avaliação da estabilidade e da capacidade do processo, as ferramentas adotadas permitiram a compreensão das fontes de variabilidade, assim como a determinação de seu grau, nas diferentes etapas do processo. Os índices de capacidade (CpK) relativos à uniformidade de Captopril (% p/v) na mistura de pós, ao peso médio do comprimido, à uniformidade de conteúdo e à % (p/v) dissolvida de Captopril, no ensaio de dissolução, foram 0,70, 1,94, 1,80 e 2,19, respectivamente.
The Good Manufacturing Practices (GMP) for Medicinal Products point out that the pharmaceutical industry must direct efforts to understand the variation of the processes, including the sources, the level of variation and the variation impact on the process in characteristics of the product. The manufacturing process has shown meaningful changes, especially in the introduction of new analytical technologies that allow the process control in real time. The approach based on risk analyses and on the new Pharmaceutical Quality System is a central key for the GMP for the XXI century. The Regulatory Agencies have demanded the pharmaceutical industry to adhere the continuous improvement related to the performance of its processes and, consequently, the product quality. Thus, the present paper aimed the development and validation of the analytical method employing NIR spectroscopy as the assessment of manufacturing process of Captopril 25 mg tablets, using rational scientific approach. Regarding the process assessment, the following tools were adopted: analysis of failure modes and effects analysis (FMEA), control charts, capability indexes, as well as analysis of variance (ANOVA). The near-infrared spectroscopy was selected due to its greater speed in getting the results, simplicity in sample preparation, and multiplicity of analysis from a single reading and provide non-invasive feature. The results confirmed the suitability of this technology in quantitative assessment of Captopril on the steps of mixing powders and compression. The relative standard deviations for the determination of Captopril uniformity in the post mixtures and in the tablets employing NIR were 3,15 e 0,18%, respectively. In reference to the stability assessment and process capacity, the tools adopted permitted the understanding of the sources of variability, as well as the determination of their level in different phases of the process. The capacity indexes relating to Captopril uniformity (% p/v) in the powder mixture, the average weight of the tablet, the content uniformity and the % (p/v) dissolved Captopril, in the dissolution assay were 0,70, 1,94, 1,80 and 2,19, respectively.

O uso de ferramentas estatísticas no ciclo de vida de um produto farmacêutico permite verificar e controlar o processo tendo como objetivo a sua melhoria contínua. No presente estudo foi avaliada a estabilidade e a capacidade estatística do processo de fabricação dos comprimidos revestidos de lamivudina 3TC e zidovudina AZT (150 + 300 mg) fabricados pela Fundação para o Remédio Popular \"Chopin Tavares de Lima\" (FURP). Esse medicamento, distribuido gratuitamente pelo programa DST/AIDS do Ministério da Saúde, e fabricado por compressão direta, processo rápido que permite a implementação futura da tecnologia analítica de processo (Process Analytical Technology - PAT). No Capítulo I foi realizada avaliação retrospectiva da variabilidade de atributos criticos da qualidade de 529 lotes dos comprimidos fabricados de acordo com a RDC ANVISA 17/2010 e as monografias oficiais, sendo tais atributos: peso médio, uniformidade de dose unitária e % m/v de fármaco dissolvido, antes e após o revestimento. O objetivo foi identificar eventuais causas especiais de variabilidade dos processos que permitam melhorias contínuas. No Capitulo II foi desenvolvida metodologia analítica empregando a espectroscopia no infravermelho próximo com transformada de Fourier para a avaliação da homogeneidade da mistura dos pós. Nesse estudo foram analisadas amostras de misturas dos fármacos lamivudina 3TC e zidovudina AZT e mistura excipiente, empregando como método de referência a CLAE, para a quantificação desses dois fármacos. No Capitulo I, a avaliação do processo para o peso médio revelou a necessidade de investigação das causa especiais de variabilidade, evidenciada por meio das cartas de controle. Os resultados do ano de 2015 indicaram necessidade de centralização e de consistência do processo, com redução de probabilidade de falha. As cartas de controle para uniformidade de dose unitária, no ano de 2013, revelaram menor variabilidade do processo. Porem, nesse ano, a análise estatística para a dissolução revelou processo descentralizado e sem consistência, com maior evidência para o fármaco 3TC que demonstrou menor desempenho, Cpk<1,0. A avaliação da estabilidade e da capacidade do processo de fabricação de comprimidos de lamivudina + zidovudina (150+300 mg), no período de 2012 a 2015, permitiu o maior entendimento de suas fontes de variação. Foi possível detectar e determinar o grau dessa variação e seu impacto no processo e nos atributos críticos de qualidade do produto com evidentes oportunidades de melhoria do processo, reduzindo os riscos para o paciente. No capítulo II, no desenvolvimento do método, as estatísticas de validação revelaram que os menores valores de BIAS foram observados para a 3TC, 0,000116 e 0,0021, respectivamente para validação cruzada e validação. Os valores de BIAS próximos a zero indicaram reduzida porcentagem de variabilidade do método. O presente estudo demonstrou a viabilidade do uso do modelo desenvolvido para a quantificação da 3TC e AZT por FT-NIR apos ajustes que contribuam para a elevação de R, R2 e RPD para valores aceitáveis. Valores de RPD acima de 5,0 que permitem o uso do modelo para uso em controle de qualidade.
The use of statistical tools in the life cycle of a pharmaceutical product allows verifying and controlling the process aiming at its continuous improvement. In the present study, the stability and statistical capacity of the lamivudine coated tablets 3TC and zidovudine AZT (150 + 300 mg) manufactured by the Chopin Tavares de Lima Foundation (FURP) were evaluated. This drug, distributed free of charge by the Ministry of Health\'s DST/AIDS program, is manufactured by direct compression, a rapid process that allows the future implementation of Process Analytical Technology (PAT). In Chapter I, a retrospective evaluation of the variability of critical quality attributes of 529 batches of tablets manufactured was carried out, such attributes being: mean weight, unit dose uniformity and % m/v of dissolved drug substances, before and after coating. The objective was to identify possible special causes of variability of the processes that allow continuous improvements. In Chapter II an analytical methodology was developed employing the near infrared spectroscopy with Fourier transform for the evaluation of the homogeneity of the powder mixture. In this study, samples of mixtures of the drugs lamivudine 3TC and zidovudine AZT and excipient mixture were analyzed, using as reference method the HPLC, for the quantification of these two drugs. In Chapter I, the evaluation of the process for the mean weight revealed the need to investigate the special cause of variability, as evidenced by the charts. The results of the year 2015 indicated the need for centralization and process consistency, with a reduction in the probability of failure. The control charts for unit dose uniformity, in the year 2013, revealed less process variability. However, in that year, the statistical analysis for dissolution revealed a decentralized process with no consistency, with greater evidence for the 3TC drug that showed lower performance, Cpk<1.0. The evaluation of the stability and capacity of the lamivudine + zidovudine tablet manufacturing process (150 + 300 mg) in the period from 2012 to 2015 allowed a better understanding of its sources of variation. It was possible to detect and determine the degree of this variation and its impact on the process and the critical quality attributes of the product with evident opportunities to improve the process, reducing risks for the patient. In Chapter II, in the development of the method, the validation revealed that the lowest values of BIAS were observed for 3TC, 0.000116 and 0.0021, respectively for cross validation and validation. BIAS values close to zero indicated a reduced percentage of variability of the method. The present study demonstrated the feasibility of using the model developed for the quantification of 3TC and AZT by FT-NIR after adjustments that contribute to the elevation of R, R2 and RPD to acceptable values. RPD values above 5.0 that allow the use of the model for use in quality control.

Résumé : À partir de 2002, grâce à l’introduction du concept de la Qualité par la Conception (en anglais Quality by Design : QbD) par l’agence américaine des produits alimentaires et médicamenteux, l’industrie pharmaceutique a intensifié les efforts et les investissements pour permettre une libération en temps réel des lots commerciaux. Le QbD propose que la qualité soit construite dès la conception initiale du médicament plutôt que d'être évaluée à la fin de sa fabrication. Ainsi, avec l’initiative QbD, les tests de contrôle de la qualité des médicaments, réalisés après la fabrication des comprimés, peuvent être éliminés si les paramètres qui les influencent sont contrôlés. En effet, ces tests de contrôle qualité dits traditionnels requièrent en général plusieurs heures pour leurs préparations et leurs réalisations. Tel est le cas du test de dissolution. Ce test est très consommateur de ressources matérielles et humaines. La réalisation de stratégies de contrôle pour les tests de dissolution basée sur une approche QbD pourrait être bénéfique pour l'industrie pharmaceutique. À travers ce travail, nous avons pu : • proposer différentes stratégies novatrices de contrôle du test de dissolution de comprimés pharmaceutiques sur la base des principes du QbD, • apporter un nouvel éclairage sur la compréhension des phénomènes impliqués dans la dissolution de comprimés pharmaceutiques. Les résultats de ce projet de recherche ont permis 1) la mise en évidence des paramètres critiques influençant le test de dissolution, 2) l’élaboration et l’évaluation de modèles statistiques pour les combinaisons de variation de paramètres selon un plan d’expérience préalablement conçu, 3) la corrélation du test de dissolution à des paramètres critiques de procédés de fabrication et d’attributs de matériaux grâce aux technologies d’analyse de procédés. // Abstract : With the introduction in 2002 of the concept of Quality by Design (QbD) by the Food and Drug Administration, the pharmaceutical industry intensified efforts and investments to reach real time release of commercial batches, reducing time between manufacturing and availability to the patient. QbD proposes that quality should be built in the initial design of a product rather than being assessed at the end of the tablet manufacturing. Thus, with the QbD initiative, quality control tests of tablets like dissolution testing performed after manufacturing could be removed if the parameters impacting them are controlled. Indeed, quality control tests such as traditional dissolution tests generally require several hours for their preparation and their realizations. Dissolution tests are time consuming, require large amounts of material and human resources. The elimination of these tests through a QbD approach could be beneficial for the pharmaceutical industry. Thanks to this work, it was possible to :  propose different innovative strategies to control the dissolution test of pharmaceutical tablets based on the principles of Quality by Design,  have a better understanding of this quality control test. The main results relies on 1) the identification of critical parameters influencing the dissolution test, 2) the development and evaluation of statistical models for the combination of variation of parameters according to an experimental design, 3) the correlation of dissolution test to critical manufacturing process parameters and attributes of materials through process analysis technology.

Negli ultimi tre decenni la domanda globale di cibo, in particolare di proteine animali (carne, latte, uova), è aumentata in base alla crescita della popolazione che dovrebbe arrivare a 9 miliardi di persone entro il 2050. Questi alimenti rappresentano infatti un'importante fonte di energia, proteine di alta qualità, micronutrienti e vitamine. Pertanto, questo miglioramento potrebbe contribuire all'aumento della durata della vita e della domanda di cibo. Ciò ha costretto il settore agricolo ad un'ulteriore intensificazione che ha interessato anche la coltivazione di colture per l'alimentazione animale. Le produzioni agricole e zootecniche hanno un impatto ambientale rilevante, e questo argomento è oggetto di critiche e di indagini scientifiche anche per definire più accuratamente il loro contributo e le relative potenziali strategie di mitigazione, considerando anche che la fase agricola è il principale contributore dell'impatto ambientale della catena di produzione alimentare. Si riconosce infatti che il settore agricolo contribuisce direttamente al 21% delle emissioni totali di gas serra di origine antropica a livello mondiale e consiste per lo più di metano seguito da protossido di azoto e anidride carbonica. Queste emissioni sono per lo più associate alla produzione zootecnica, in particolare all'allevamento di ruminanti che contribuisce con le emissioni dirette di metano dovute alla fermentazione dei ruminanti e alla fermentazione del letame; la restante parte è composta da emissioni indirette dovute alla deforestazione, all'uso di energia e alla produzione di mangimi. Lo scopo di questa tesi è stato la valutazione dell'impronta ambientale nel settore zootecnico a diversi livelli di scala tematica. La filiera italiana della carne, gli allevamenti lattiero-caseari, un caseificio per la produzione di Grana Padano DOP e i singoli animali sono stati studiati per quantificare l'impronta ambientale. Nel primo lavoro è stata valutata la filiera italiana della carne con un approccio di analisi dei flussi di massa e di valutazione del ciclo di vita. In primo luogo, la quantificazione della carne è stata effettuata dalla macellazione al consumo domestico, partendo dal peso della carcassa fino alla carne realmente consumata. A questo livello si è tenuto conto della carne di bovini, suini, ovini e caprini, equidi e conigli. Durante la catena sono state quantificate anche le perdite di carne e i rifiuti. In particolare, i sottoprodotti di origine animale (SOA) sono stati quantificati per singole specie e classificati in base al rischio a livello sanitario secondo il regolamento (CE) 1069/2009. Secondo la categoria (Cat 1, Cat 2 o Cat 3), supponendo che tutti i SOA fossero destinati al processo di rendering, l'uso e lo smaltimento dei prodotti dopo rendering è stato identificato. L'analisi dei flussi di massa ha confermato come l'Italia sia un importatore netto di carne bovina e suina, mentre è autosufficiente per quanto la carne avicola. L'analisi dei flussi di massa rivela che nel 2013 sono stati consumati in Italia 2,86 Mt di carne. Questo valore equivale a 131 g/giorno/pro-capite e a 47,91 kg/anno/pro-capite di carne consumata. In percentuale la quantità totale di carne consumata è rappresentata dal 46% da carne suina, dal 28% di carne avicola, dal 23% di carne bovina e dal 3% di altre carni (coniglio, equini, ovini e caprini). Questo approccio ha permesso di quantificare anche sottoprodotti di origine animale (SOA) prodotti durante la fase di macellazione e gli scarti alimentari a livello di vendita al dettaglio e fase di consumo. La fase di macellazione è risultata essere la principale fonte di rifiuti, producendo il 48% di rifiuti originati nella filiera della carne. I risultati hanno evidenziato come i SOA siano già quasi completamente riutilizzati, compatibilmente con il loro rischio a livello sanitario, dimostrando la circolarità del sistema e permettendo di quantificare anche i prodotti evitati grazie al loro riutilizzo e le relative emissioni di gas serra evitate. Per quanto riguarda gli altri rifiuti alimentari, i risultati della presente valutazione possono essere considerati solo una stima per la mancanza di specifici coefficienti nazionali. Dopo la fase di quantificazione, è stato applicato l'approccio del Life Cycle Assessment (LCA) per valutare l'impronta ambientale, considerando anche il prodotto evitato grazie al riutilizzo dei sottoprodotti del rendering. I risultati dell'LCA rivelano che il consumo giornaliero di carne pro-capite emette 4,0 kg di CO2eq, con un contributo della care bovina pari al 30%, della carne suina pari al 9.6% e della carne avicola pari all’8%. Le emissioni relative ai SOA sono risultate essere pari al 60% di quelle totali e il loro riutilizzo ha permesso una riduzione di queste del 10%. Il secondo ed il terzo lavoro sono stati invece relativi al potenziale di riscaldamento globale (GWP) di latte bovino e Grana Padano DOP. Complessivamente sono stati valutate ventisette aziende zootecniche con bovine da latte, con latte destinato al formaggio Grana Padano DOP, e un caseificio, situato nella provincia di Piacenza. I dati primari sono stati raccolti utilizzando un questionario appositamente redatto. Questo ha incluso per le aziende agricole la richiesta di dati relativi alla composizione della mandria, la gestione dell'alimentazione, la produzione di latte e performance riproduttive, piani colturali e l'utilizzo delle risorse energetiche e dei materiali di lettime, mentre per il caseificio sono stati richiesti dati relativi all'utilizzo delle risorse energetiche e gli input richiesti dal processo di caseificazione. Nel secondo lavoro sono state valutate 10 aziende lattiere per valutare l'impronta di carbonio del latte (CF) e individuare le principali fonti di emissioni. Lo studio ha utilizzato un approccio dalla culla alla tomba considerando come unità funzionale un 1 kg di latte corretto per contenuto di grasso e proteine (FPCM). Il valore medio di CF di 1 kg di FPCM è risultato essere pari a 1,33 kg di CO2eq/kg FPCM con però un ampio range di variazione, da 1,02 a 1,62 kg di CO2eq/kg FPCM. Le emissioni dovute alle fermentazioni enteriche e alle fermentazioni da reflui rappresentano il 52% del totale, mentre le emissioni relative agli alimenti acquistati il 36%. L'autoproduzione e il consumo energetico rappresentano invece rispettivamente il 6% e il 6%. Nel terzo lavoro invece è stata presa in considerazione la produzione di Grana Padano DOP. In questo caso è stato utilizzato un approccio dalla culla al cancello del caseificio considerando come unità funzionali 1 kg di FPCM e 1 kg di Grana Padano DOP stagionato 9 mesi. Il latte destinato alla produzione del formaggio ha mostrato un valore medio di CF pari a 1,38 kg CO2eq/kg FPCM, con un valore minimo di 1,02 e uno massimo di 1,94 kg CO2eq/kg FPCM. Il valore medio di CF di 1 kg di formaggio Grana Padano DOP è stato invece pari a 9,99 kg di CO2eq, con un contributo della fase agricola pari al 94%. I risultati di questi lavori si sono mostrati in accordo con studi simili riportati in bibliografia e hanno inoltre permesso di evidenziare come gli allevamenti da latte mostrassero un maggior livello di sostenibilità ambientale ma con possibilità di miglioramento principalmente attraverso il miglioramento della gestione delle mandrie (prestazioni produttive e riproduttive). Il quarto lavoro ha riguardato invece lo sviluppo di proxy in grado di prevedere le emissioni di metano da singole bovine da latte. Questo focus è un punto caldo di ricerca, soprattutto perché di fondamentale importanza per individuare strategie di mitigazione efficaci per la riduzione delle emissioni di metano dovute a fermentazioni ruminali, gas ad effetto serra riconosciuto avere il maggior contributo sul totale delle emissioni. Le emissioni di metano dipendono principalmente dal quantitativo di concentrato assunto e dalla composizione generale della dieta, ma tuttavia nelle aziende agricole commerciali risulta difficile quantificare con precisione l’ingestione di alimenti. Lo studio ha quindi mirato a verificare la possibilità di utilizzare la tecnologia del vicino infrarosso (NIRS) utilizzando lo spettro di campioni di feci (NIRSf) e/o in combinazione con altri parametri fenotipici disponibili a livello aziendale per prevedere la produzione di metano (MP, g/giorno) dalle singole vacche da latte in lattazione. Il NIRSf da solo ha permesso una stima abbastanza buona della produzione di metano e le stime sono state migliorate in misura simile quando sono stati considerati il peso vivo o la produzione di latte tal quale o la produzione di latte corretta per il contenuto energetico, mentre la combinazione del NIRSf con più di un altro parametro ha migliorato le stime solo in misura molto limitata. Il metano può essere previsto utilizzando modelli che considerano l’ingestione di sostanza sezza, il peso vivo o la produzione di latte ma il limite principale è rappresentato dalla disponibilità dei dati a livello aziendale. La tecnica del vicino infrarosso applicata ai campioni fecali, in particolare se combinata con altri parametri fenotipici, può rappresentare una valida alternativa per misurazioni su larga scala in allevamenti da latte commerciali, quando l’ingestione di sostanza secca di solito non è disponibile, per la selezione genetica di vacche da latte a bassa emissione.
In the last three decades global demand of food, in particular animal proteins (meat, milk, and eggs), has increased according to the population growth, that is expected to go up to 9 billion by the 2050. These, in fact, represent an important source of energy, high-quality protein, micronutrients and vitamins. Therefore, this improvement could contribute to the lifespan increase and food demand. The latter forced the agricultural sector to a further intensification that affected also the cultivation of crops for animal feeding. Agricultural and livestock productions have a relevant environmental impact, and this topic is object of criticism and scientific investigation also to more accurately define its contribution and potential mitigation strategies, considering also that agricultural stage is the main contributor to the environmental impact of the food production chain. It is recognized, in fact, that agricultural sector directly contribute to the 21% of total global anthropogenic greenhouse gas emissions, mostly consisting of methane followed by nitrous oxide and carbon dioxide. These emissions are mainly associated with the livestock production, in particular with ruminants breeding that contributes directly to methane emissions due to ruminal and manure fermentation; the remaining part is composed by indirect emissions from deforestation, energy use and animal feed production. The scope of this thesis was the evaluation of environmental footprint in the livestock sector at different subject scale level. Italian meat supply chain, dairy farms, Grana Padano PDO cheese factory and single animals was investigated in order to quantify environmental footprint. In the first work, the Italian meat supply chain has been evaluated whit a mass flow analysis (MFA) approach and life cycle assessment (LCA) approach. Firstly, the quantification of meat had been made from slaughter to household consumption, starting form carcass weight to real meat consumed. At these levels, meat form cattle, pig, sheep and goat, equidae, and rabbit was taken in account. During the chain also meat losses and waste were quantified. In particular animal by-products (ABPs) were quantified for single species and categorized into heath level risk according to the Regulation (EC) 1069/2009. According to the category (Cat 1, Cat 2 or Cat3), assuming that all ABPs were destinated to rendering process, use and disposal of rendered products was identified. The MFA confirmed how Italy is a net importer of cattle and pork meat while it is self-sustaining for poultry meat. Mass flow analysis revealed that in 2013, 2.86 Mt of meat were consumed in Italy. It is equivalent to 131 g/day/pro-capita and to 47.91 kg/year/pro-capita of meat consumed. In percentage the total amount of consumed meat is represented by 46% of pig, 28% of poultry and 23% of cattle and 3% of other meat (rabbit, equidae, and sheep and goat). This approach quantified the ABPs produced at slaughtering level and food wastes at retail and consumer levels. Slaughter phase was the main source of waste, producing 0.80 Mt of ABPs, 48% of the total amount of waste originated in the meat supply chain. Results highlighted how the ABPs are already almost completely reused, compatibly with their health level risk, demonstrating the circularity of the system through the quantification of the avoided products and relative GHGs emissions. Concerning other food wastes, the results of the present evaluation could be considered only an estimate due to the lack of specific national coefficients. After quantification LCA was applied in order to evaluate environmental footprint, considering also avoided product due to the re-use of rendered ABPs. LCA results reveal that daily meat consumption pro-capita emits 4.0 kg CO2eq represented by 30% of cattle meat, 9.6% of pig meat and 8% of poultry meat. Emissions allocated to ABPs are the 60% and their re-use decrease the emissions about 10%. Second and third works focused the milk and PDO Grana Padano global warming potential (GWP). Overall, twenty-seven dairy farms, producing milk destinated to Grana Padano PDO cheese and one cheese factory, situated in the Piacenza province were evaluated. Primary data were collected by using a specific survey. This included for the farms the request of data regarding herd composition, feeding management, milk production, herd management and performace, crops cultivation and resource use, whereas for the cheese factory, the survey included energy resource use and input requested by cheese making process. In the second work, 10 dairy farms were evaluated in order to assess the milk Carbon Footprint (CF) and the main source of emissions. The system boundary was a cradle-to-farm-gate and functional unit is 1 kg of FPCM (Fat and Protein corrected milk). The CF of 1 kg of FPCM resulted equal to 1.33 kg CO2eq/kg FPCM with a wide range of variation from 1.02 to 1.62 kg CO2eq/kg FPCM. Emissions due to enteric fermentation and manure fermentation represented the 52% of the total, while acquired feed the 36%. Self-production and energetic consumption represented 6% and 6% respectively. In the third, Grana Padano PDO production was considered. The milk destinated to cheese processing showed an average value of CF equal to 1.38 kg CO2eq/kg FPCM, with a minimum value of 1.02 and a maximum one of 1.94 kg CO2eq/kg FPCM. Instead, the CF average value of 1 kg of PDO Grana Padano cheese was equal to 9.99 kg CO2eq, showing an agricultural stage contribution of 94%. Results of these works were in accord with similar studies reported in literature and had pointed out how dairy farms showed a greater level of environmental sustainability but with possibilities for improvement, mainly through herd management enhancement (productive and reproductive performances). Fourth work was about the development of proxies able to predict the methane emissions from individual cows. This focus is a hot research point in order to improve the mitigation strategies to reduce methane emissions because of the main GHG contributor. Methane emission is mainly driven by feed intake and diet composition, but it is difficult to measure intake in commercial farms. The study aimed to verify the possibility of using NIRS of faeces (NIRSf) alone and in combination with other phenotypic parameters available at a farm level to predict methane production (MP, g/d) from individual lactating dairy cows. NIRSf alone allowed a fairly good estimation of methane yield and the estimations were improved to a similar degree when BW, MY or ECM were considered, whereas combining NIRSf with more than one other parameters improved the estimations with a very little extent only. Methane can be predicted using models that consider the DMI, BW or MY but the main limitation is represented by the data availability. Near Infrared technique applied to faecal samples, in particular when combined with other phenotypic parameters, can represent a valid alternative for large-scale measurements in commercial dairy farms for genetic selection of low emitters dairy cows, when DMI measurement is usually not available.

Den tekniska utvecklingen har lett till att massiva mängder av information sänds, i högahastigheter. Detta flöde måste vi lära oss att hantera. För att maximera nyttan av de nyateknikerna och undkomma de problem som detta enorma informationsflöde bär med sig, börinteraktionskvalitet studeras. Vi måste anpassa gränssnitt efter användaren eftersom denneinte har möjlighet att anpassa sig till, och sortera i för stora informationsmängder. Vi måsteutveckla system som gör människan mer effektiv vid användande av gränssnitt.För att anpassa gränssnitten efter användarens behov och begränsningar krävs kunskaperom den mänskliga kognitionen. När kognitiv belastning studeras är det viktigt att en såflexibel, lättillgänglig och icke-påträngande teknik som möjligt används för att få objektivamätresultat, samtidigt som pålitligheten är av största vikt. För att kunna designa gränssnittmed hög interaktionskvalitet krävs en teknik att utvärdera dessa. Målet med uppsatsen är attfastställa en mätmetod väl lämpad för mätning av interaktionskvalitet.För mätning av interaktionskvalitet rekommenderas en kombinering av subjektiva ochfysiologiska mätmetoder, detta innefattar en kombination av Functional near-infraredspecroscopy; en fysiologisk mätmetod som mäter hjärnaktiviteten med hjälp av ljuskällor ochdetektorer som fästs på frontalloben, Electrodermal activity; en fysiologisk mätmetod sommäter hjärnaktiviteten med hjälp av elektroder som fästs över skalpen och NASA task loadindex; en subjektiv, multidimensionell mätmetod som bygger på kortsortering och mäteruppfattad kognitiv belastning i en sammanhängande skala. Mätning med hjälp av dessametoder kan resultera i en ökad interaktionskvalitet i interaktiva, fysiska och digitalagränssnitt. En uppskattning av interaktionskvalitet kan bidra till att fel vid interaktionminimeras, vilket innebär en förbättring av användares upplevelse vid interaktion.
Technical developments have led to the broadcasting of massive amounts of information, athigh velocities. We must learn to handle this flow. To maximize the benefits of newtechnologies and avoid the problems that this immense information flow brings, interactionquality should be studied. We must adjust interfaces to the user because the user does nothave the ability to adapt and sort overly large amounts of information. We must developsystems that make the human more efficient when using interfaces.To adjust the interfaces to the user needs and limitations, knowledge about humancognitive processes is required. When cognitive workload is studied it is important that aflexible, easily accessed and non assertive technique is used to get unbiased results. At thesame time reliability is of great importance. To design interfaces with high interaction quality,a technique to evaluate these is required. The aim of this paper is to establish a method that iswell suited for measurement of interaction quality.When measuring interaction quality, a combination of subjective and physiologicalmethods is recommended. This comprises a combination of Functional near-infraredspectroscopy; a physiological measurement which measures brain activity using light sourcesand detectors placed on the frontal lobe, Electrodermal activity; a physiological measurementwhich measures brain activity using electrodes placed over the scalp and NASA task loadindex; a subjective, multidimensional measurement based on card sorting and measures theindividual perceived cognitive workload on a continuum scale. Measuring with these methodscan result in an increase in interaction quality in interactive, physical and digital interfaces.An estimation of interaction quality can contribute to eliminate interaction errors, thusimproving the user’s interaction experience.

In this work the development and construction of a new near-infrared imaging spectrometer utilising inexpensive components is presented. The instrument is applied to measuring the distribution of constituents in fruit, in particular, soluble solids and dry matter in kiwifruit. The spectrometer, designed for collecting spectral-images of fruit, uses a diffraction grating for spectral dispersion, a scanning slit system for spatial resolution and a CCD detector to allow images of samples to be examined in different wavebands. The system described has a spectral range of 650 nm to 1100 nm at a resolution of better than 5 nm. Each spectral-image contains 150 x 242 pixels on the spatial plane and 755 pixels for the spectral ads. An interchangeable imaging lens enables investigation of samples at different scales. With a 58 mm camera lens objects up to 50 mm x 50 mm may be imaged at a spatial resolution of up to 2 line-pairs per millimetre (0.5 millimetre). One difficulty with calibration using spectral-images is that the independent measurements of concentration often come from areas much larger than a pixel. For spectral-imaging to be useful it is important that the calibration can estimate concentration at the pixel level. In effect this means estimates calculated using the model are more accurate than the independent measurements used in calibration. Using synthetic spectra and an investigation of the principal component regression algorithm, the ability of a calibration, from spectral-images, to estimate these pixel level concentrations has been demonstrated. To calibrate the instrument for measuring soluble solids concentration and dry matter content in kiwifruit, reflectance spectra from 650 nm to 1100 nm were collected from cut sections of 200 fruit. A near-infrared calibration was obtained by recording the soluble solids concentration and dry matter content of plugs extracted from thin slices of the fruit and relating these to the spectra collected. A prediction error of 1.2 °Brix over a range of 4.7 - 14.1 °Brix was achieved. It was not possible to obtain a useful model for estimating dry matter due to interference from specular reflections off free juice in the fruit. The models developed were used to show the spatial distribution of soluble solid concentrations over cut sections of fruit.

Cheung, Siu Ming.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2010.
Includes bibliographical references (leaves 81-86).
Abstracts in English and Chinese.
Chapter 1. --- INTRODUCTION --- p.1
Chapter 1.1. --- Introduction to Face Recognition --- p.2
Chapter 1.1.1. --- Modes of Face Recognition --- p.2
Chapter 1.1.2. --- Typical Face Recognition System --- p.3
Chapter 1.1.3. --- Face Recognition Algorithms --- p.4
Chapter 1.1.4. --- The State of the Art --- p.5
Chapter 1.2. --- Outdoor Face Recognition --- p.6
Chapter 1.2.1. --- The Outdoor Environment --- p.6
Chapter 1.2.2. --- The Illumination Variation Problem in the Outdoors --- p.8
Chapter 1.3. --- Related works --- p.10
Chapter 1.3.1. --- Face Appearance Modeling --- p.10
Chapter 1.3.2. --- Illumination Invariant Features and Representations --- p.13
Chapter 1.3.3. --- Active Near-Infrared Illumination --- p.14
Chapter 1.4. --- Proposed method --- p.17
Chapter 1.5. --- Design Requirements --- p.18
Chapter 2. --- COMPENSATION METHODOLOGY FOR OUTDOOR FACE RECOGNITION --- p.20
Chapter 2.1. --- Illumination from the Sun --- p.21
Chapter 2.2. --- Effect of Sunlight Illumination --- p.22
Chapter 2.3. --- A Compensation Model --- p.24
Chapter 2.4. --- A Face Lighting Simulator --- p.28
Chapter 2.4.1. --- Face 3D Models --- p.29
Chapter 2.4.2. --- Light Sources --- p.30
Chapter 2.4.3. --- Synthesis of Face Image --- p.31
Chapter 2.5. --- Simulation Results --- p.32
Chapter 2.5.1. --- Optimum Compensation Angles --- p.33
Chapter 2.5.2. --- Effect of Illuminator Intensity --- p.36
Chapter 2.5.3. --- Effect of Illuminator Elevation Angle --- p.38
Chapter 2.5.4. --- Effect of Sunlight Elevation Angle --- p.41
Chapter 2.5.5. --- Illumination from Both Sides --- p.42
Chapter 2.6. --- Summary --- p.43
Chapter 3. --- AN ADAPTIVE ILLUMINATOR --- p.45
Chapter 3.1. --- Hardware Design --- p.45
Chapter 3.1.1. --- Near-infrared Camera --- p.45
Chapter 3.1.2. --- Illumination Panels --- p.48
Chapter 3.1.3. --- Illuminator Controller --- p.56
Chapter 3.1.4. --- Illumination Characteristics --- p.59
Chapter 3.2. --- Algorithms --- p.62
Chapter 3.2.1. --- Light Balance Estimation --- p.63
Chapter 4. --- EXPERIMENTS AND RESULTS --- p.67
Chapter 4.1. --- Effect of compensation angle on face similarity --- p.68
Chapter 4.2. --- Effect of illumination compensation under different sunlight conditions --- p.71
Chapter 4.3. --- Impact on recognition performance --- p.72
Chapter 5. --- CONCLUSIONS --- p.76
Chapter 6. --- BIBLIOGRAPHY --- p.81

碩士
國立彰化師範大學
機電工程學系
98
Based on the Beer-Lambert's analysis model, the commercial Pulse Oximeter senses the optical reflection or refraction to provide simply point signal. In this research report, a novel algorithms of optical image correction of the blood oxygen saturation is proposed. However, reflection images technique can present arterial oxygen saturation by pulse oximeter (SpO2) of non-invasive and non-contact and region information. We use the charge-coupled device (CCD) camera to receive the images. The system adopts 630nm red and 940nm near-infrared wavelengths to derive the tissue blood oxygen saturation and investigate their correlation. According to the experimental results, it proves the feasibility of measuring blood oxygen saturation by iris and hand tissue low oxygen approach, while variations trends are the same. Moreover, after adjustment measurement value average deviation reaches around 0.02% could be developed to provide more tissue information for research and medical uses in the future.

碩士
國立臺灣大學
生物產業機電工程學研究所
89
This study focuses on using near infrared (NIR) technology to investigate the sugar content and acidity in grape and mango using pre- and post-dispersive spectrophotometers. The calibration models of sugar content and acidity are developed and applied to design an on-line NIR inspection system. The spectra of juices and intact fruits were scanned and analyzed, and then the results points out that all the best analyzed model were modify partial least square regression (MPLSR) instead of the best grape juice transmittance spectra absorption of sugar content is multiple linear regression (MLR) with five wavelengths combination (2272, 2280, 1874, 1732, and 1436 nm) in the second derivative, which is rc=0.991, SEC=0.195, rp=0.990, and SEP=0.210. The best result of in grape juice is given by MPLSR method (first derivative , wavelength range: 800~1000＋1300~1500＋1600~1900＋2350~2450nm), which is rc=0.982, SEC=0.023, rp=0.976, and SEP=0.026. The post-dispersive model gets better results than the pre-dispersive in the analysis of pulp reflection spectra, and the results about sugar content and acidity of graph is better than mango. The best results of sugar content of graph are rc=0.961, SEC=0.416, rp=0.950, and SEP=0.463 (second derivative, wavelength range: 800~1100 nm), and the best acidity result is rc=0.935, SEC=0.042, rp=0.894, and SEP=0.052 (first derivative, wavelength range: 400~2500 nm). The best result of sugar content of mango is rc=0.938, SEC=0.601, rp=0.915, and SEP=0.649 (first derivative, wavelength range: 700~1300 nm), and the acidity result is rc=0.782, SEC=0.031, rp=0.749, and SEP=0.030 (first derivative, wavelength range: 500~2100 nm). The developed on-line NIR inspection system for measuring sugar content and acidity in fruits, which using post-dispersive model and dynamic-data-exchange (DDE) programming, was successfully designed. This computer controlled integrates NIR scanning, conveying mechanism, program logical controller and computer infacing. The investigation of system performance gave satisfactory results.

碩士
國立臺灣大學
生物產業機電工程學研究所
90
The constituents of sugar content, acidity, ascorbic acid (Vitamin C) and cellulose were analyzed using Modified Partial Least Squares Regression (MPLSR), Principal Component Regression (PCR), Artificial Neural Network (ANN) and Multiple Leaner Regression (MLR) to establish near-infrared (NIR) calibration models for the internal quality of wax apple and papaya. The best models and results for each constituent of wax apple pulp are: sugar content: MLR, rc＝0.981, SEC＝0.252 oBrix, SEP＝0.342 oBrix；acidity: ANN(PLSR), rc＝0.899, SEC＝0.043 Wt%, SEP＝0.057 Wt%；Vitamin C: MPLSR, rc＝0.880, SEC＝16.67 ppm, SEP＝17.02 ppm；cellulose: MPLSR, rc＝0.980, SEC＝0.016 g/100g, SEP＝0.028 g/100g. For wax apple juice, sugar content: MPLSR, rc＝0.999, SEC＝0.044 oBrix, SEP＝0.055 oBrix；acidity : MPLSR, rc＝0.983, SEC＝0.020 Wt%, SEP＝0.028 Wt%；Vitamin C: ANN(PCR), rc＝0.858, SEC＝15.98 ppm, SEP＝19.19 ppm. Regarding papaya pulp, sugar content: MPLSR, rc＝0.803, SEC＝0.481 oBrix, SEP＝0.661 oBrix；acidity: MPLSR, rc＝0.859, SEC＝0.061 Wt%, SEP＝0.077 Wt%；Vitamin C: MPLSR, rc＝0.815, SEC＝72.53 ppm, SEP＝78.91 ppm；cellulose: MPLSR, rc＝0.969, SEC＝0.021 g/100g, SEP＝0.028 g/100g. As for papaya juice, sugar content: MPLSR, rc＝0.996, SEC＝0.069 oBrix, SEP＝0.072 oBrix；acidity: MPLSR, rc＝0.979, SEC＝0.028 Wt%, SEP＝0.035 Wt%；Vitamin C: MPLSR, rc＝0.833, SEC＝60.97 ppm, SEP＝67.81 ppm. Among the models being evaluated, MPLSR and ANN (PLSR) are superior to others. The absorption bands found in MLR models are well corresponding to the chemical bonds of constituents of interest. In this study, conducting the wet chemistry analyses in time and adopting the water as a reference in NIR measurements improved the models’ accuracy. The models were successfully developed for the evaluation of internal quality including sugar content, acidity, Vitamin C and cellulose in wax apples and papayas.

博士
國立成功大學
化學工程學系碩博士班
101
This dissertation concerns the preparation of nanoparticles with near infrared photothermal conversion property via nano-grinding/dispersion technology. The effects of preparation conditions on the particle size, structure, and optical and NIR photothermal conversion properties were investigated. Two systems were studied, including LaB6 and Cs0.33WO3 nanoparticles. LaB6 nanoparticles have been prepared successfully by a stirred bead milling process. The anionic surfactantdodecylbenzenesulfonic acid was found to be suitable for the grinding and dispersion of LaB6 powders, but cationic surfactant polyethyleneimine and nonionic surfactant polyethylene glycol couldnot yield a stable dispersion. Three kinds of grinding beads with the diameters of 50, 100, and 200 µm all could reduce the mean hydrodynamic diameter of LaB6 powders to about 100 nm. However, although the grinding rate was slower, using the smaller grinding beads with a diameter of 50 µm could yield a dispersion of LaB6 nanoparticles with more uniform size. The resulting LaB6nanoparticles were confirmed to remain a cubic structure and the contaminant from ZrO2 beads was below 5 wt%. Furthermore, the LaB6 nanoparticles exhibited a characteristic absorption around 1000 nm and possessed an excellent near infrared (NIR) photothermal conversion property better than Au nanoshells. Because they were relatively cheap and easy-to-preparation than Au nanorods or nanoshells, the LaB6 nanoparticles could be used as a novel and effective NIR photothermal conversion material and might find great potential in the biomedical application. Cs0.33WO3 nanoparticles have been prepared successfully by a stirred bead milling process. By grinding micro-sized coarse powder with grinding beads of 50 μm in diameter, the mean hydrodynamic diameter of Cs0.33WO3 powder could be reduced to about 50 nm in 3 h, and a stable aqueous dispersion could be obtained at pH 8 via electrostatic repulsion mechanism. After grinding, the resulting Cs0.33WO3 nanoparticles retained the hexagonal structure and had no significant contaminants from grinding beads. Furthermore, they exhibited a strong characteristic absorption and an excellent photothermal conversion property in the near-infrared (NIR) region, owing to the free electrons or polarons. Also, the NIR absorption and photothermal conversion property became more significant with decreasing particle size or increasing particle concentration. When the concentration of Cs0.33WO3 nanoparticles was 0.08 wt. %。the solution temperature had a significant increase of above 30°C in 10 min under NIR irradiation (808 nm, 2.47 W/cm2). In addition, they had a photothermal conversion efficiency of about 73% and possessed excellent photothermal stability. Such an effective NIR absorption and photothermal conversion nanomaterial not only was useful in the NIR shielding, but also might find great potential in biomedical application.

yes
A transflectance near infra red (NIR) spectroscopy approach has been used to simultaneously measure drug and plasticiser content of polymer melts with varying opacity during hot melt extrusion. A high temperature reflectance NIR probe was mounted in the extruder die directly opposed to a highly reflective surface. Carbamazepine (CBZ) was used as a model drug, with polyvinyl pyrollidone-vinyl acetate co-polymer (PVP-VA) as a matrix and polyethylene glycol (PEG) as a plasticiser. The opacity of the molten extrudate varied from transparent at low CBZ loading to opaque at high CBZ loading. Particulate amorphous API and voids formed around these particles were found to cause the opacity. The extrusion process was monitored in real time using transflectance NIR; calibration and validation runs were performed using a wide range of drug and plasticiser loadings. Once calibrated, the technique was used to simultaneously track drug and plasticiser content during applied step changes in feedstock material. Rheological and thermal characterisations were used to help understand the morphology of extruded material. The study has shown that it is possible to use a single NIR spectroscopy technique to monitor opaque and transparent melts during HME, and to simultaneously monitor two distinct components within a formulation.

碩士
國立臺灣海洋大學
食品科學系
93
Abstract The purpose of this research is to describe the probability of using near infrared spectroscopy to analyze histamine spectrogram of the unit of the fish meal. 176 samples were collected and analyzed. The value through HPLC for the analysis of benzoylated amines is 10.6-109.6 ppm. There were 125 samles under 100 ppm, 44 samples between 100-500 ppm, and 7 samples beyond 500 ppm. WinISI Ⅱwas used to analyze the correlation between histamine contents and absorption spectrums of fish meal measured by near infrared spectroscopy. The 2nd derivative treatments of absorption spectrum have more information and the absolute value of correlation increased to more than 0.5. The Modified Partial Least Square Regression (MPLSR), Principal Component Regression (PCR) and Artificial Neural Network (ANN) were used in discussion in the whole bands of 400-1098 and 1100-2498, and the partial bands of 700-900, 1200-1300, 1600-1700, and 2000-2200 under different mathematic models (original, first derivative and second derivative) and factors to find out the best prediction model. The MPLSR shows the best result in linear regression partial bands (factor = 5, rc =0.95, SEC=22.67 ppm, rp =0.85, SEP=36.21, RPD=1.88). In non-linear model, ANN shows the best result in both bands of study. (In the whole bands: rc =0.99, SEC=9.24 ppm, rp =0.98, SEP=12.69 ppm, RPD=5.51; in the partial band: best factor is 3 , rc=0.97, SEC=16.57 ppm, rp =0.88, SEP=33.72 ppm, RPD=3.06). The best prediction model, ANN shows the relationship between the values of prediction and chemical analysis. There are 53 samples whose contents of histamines are under 100 ppm ( rc =0.56, SEC=20.48 ppm ). There are 16 samples in another group, whose contents of histamine are between 100 and 350 ppm. The relative coefficient between the values of prediction and chemical analysis are rc =0.95, SEC=13.87 ppm. The results show the groups with higher concentration have higher relationship.

碩士
逢甲大學
資訊電機工程碩士在職專班
95
This paper demonstrates a new optical technique in which we apply the moire pattern theory to adjust the focal length of cell-phone camera. To increase the production capacity and reduce the cost of production of cell-phone camera, we develop a new adjustable focus system with this new technique. This method can test the resolution of cell-phone camera reaching 1.3 million pixels.

碩士
國立中興大學
生物產業機電工程學系所
96
In this study, the near infrared spectroscopy (NIRS, Kubota K-BA100) was used to determinate the reflective spectra of the banana, in the wavelength range from 500nm to 1010nm, and to analyze and compare it with the actual sugar content of the cut banana. By applying multiple linear regression (MLR) analysis, the correlation of sugar content and second derivative spectra could be obtained. From the results of analysis, the total calibration equation is better acquired when it consists of 6 wavelengths (i.e. 924nm, 782nm, 874nm, 814nm, 882nm and864nm). The calibration group is with RC=0.854, SEC=0.758˚Brix, the first prediction set is with RP=0.777, SEP=1.045˚Brix and the random set is with RP=0.770, SEP =1.151˚Brix. The sugar calibration equation is established in order to probe into the relationships among sugar content, vibration influence, and the ethylene absorbability during the store and transport process. These results are to manage the problem in a long-term transport when bananas are too mature to be sold. From the data we knew that the sugar content curve of the banana post-maturity within 6 ˚Brix shows a linear graph. Therefore, the analysis basis of this experimental design is from 4 ˚Brix to 6 ˚Brix (The store term is about 13 days). The conclusion is that when the banana is stored under 13℃ and is taken 4g/per kg ethylene absorbent, the maturity speed of bananas is moderated because the two conditions help restrain the ethylene from the ripening bananas and from the vibration influence. The vibration influence caused by the rub of the fruit skin leads to the increase of ethylene, with the obvious difference of P-value=0.023. Between the analysis of the banana sugar content and the regression analysis of the fruit solidity, the correlation coefficient, R = -0.899, and they prove that fruit solidity and sugar content are relatively existed.

The purpose of this thesis was to explore the potential of near-infrared spectroscopy (NIRS) as an access channel by establishing reliable signal detection to verify the existence of signal differences associated with changes in activity. This thesis focused on using NIRS to measure brain activity from the prefrontal cortex during an auditory Go-No-Go task. A singular spectrum analysis change-point detection algorithm was applied to identify transition points where the NIRS signal properties varied from previous data points in the signal, indicating a change in brain activity. With this algorithm, latency values for change-points detected ranged from 6.44 s to 9.34 s. The averaged positive predictive values over all runs were modest (from 49.41% to 67.73%), with the corresponding negative predictive values being generally higher (48.66% to 78.80%). However, positive and negative predictive values up to 97.22% and 95.14%, respectively, were achieved for individual runs. No hemispheric differences were found.

Master of Science
Department of Animal Sciences and Industry
Micheal J. Brouk
Two studies were conducted that focused on either the accuracy of hand-held near infrared spectrophotometer (NIR) units and two on-farm testing methods compared to conventional 105°C oven drying of corn silage or the use of a starling resistant supplement in total mixed rations (TMR) for lactating dairy cattle. Study 1 evaluated the accuracy of three NIR units (Digi-Star Moisture Tracker, Topcon Agriculture, Fort Atkinson, WI), food dehydrator (FD) (Nesco®, Two Rivers, WI), and a Koster Tester (KT) (Koster Moisture Tester, Inc., Brunswick, OH) to conventional 105°C forced air oven drying. Samples were taken at four Kansas dairy farms and analyzed for DM daily for 20 d. Two calibrations were tested within each NIR unit: NIRu was the DM predicted from the factory-preset calibration, and NIRc was a bias-adjusted DM prediction based on the average difference of oven-dried corn silage and NIRu over the 20-d study. Average oven DM of corn silage was 38.38% ± 0.59 for the 20-d experiment. All three NIRu measurements were lower (P<0.05) than the oven value. While all 3 NIRc predictions were similar (P>0.05) to oven value. KT value was similar (P>0.05) to the oven, while FD value was over estimated DM. (P<0.05). The hand-held NIRS units accurately predicted DM content of the corn silages when the factory preset calibrations were corrected for bias. While the food dehydrator over-estimated the DM of the corn silage and the Koster Tester accurately predicted DM. Study 2 was designed to evaluate the lactation performance of post-peak dairy cattle when using a starling resistant grain supplement. Sixteen prim- and multiparous Holstein cows were housed individually in a tie-stall barn, milked 3x daily, and fed 2x daily. Cows were fed two nutritionally similar diets: 1. TMR with grain in mash form and 2. TMR with grain supplement in a pellet with a 0.953-cm diameter. This study was designed as a single reversal experiment with two 14 d periods with the first 7 d used for an adaptation period and the last 7 d used for data collection in each period. Dry matter intake (DMI), water intake, and milk production was recorded daily. Feed ingredients, TMRS, refusals, and milk samples were collected the last 3 d of each period for analysis. TMRs and refusals were analyzed for particle size distribution with a Penn State Particle Separator. The pelleted supplement had a higher (P<0.05) percentage of DM retained on the 8.0-19.0mm sieve than the mash supplement as the pellet diameter was >8.0mm and could not pass through that sieve. There was no effect of diet (P>0.05) for DMI, feed efficiency, milk component percentage, and protein yield. There was a diet effect (P<0.05) for milk production, fat-corrected milk, energy-corrected milk, solid-corrected milk, and fat yield with lower observed values when cows were fed the pelleted supplement. This leads to the conclusion while a 0.953-cm diameter pellet will reduce starling consumption, it may result in lower milk production of post-peak Holstein cows.