کاربرد انتقال کالیبراسیون در تحلیل بر پایه مدل داده های سینتیکی اسپکتروفتومتری حاصل از تغییرات شیمیایی - درسیستم های بیولوشیکی و محیطی و آنالیس چند راهی داده های اسپکتروفلوریمتری سینتیک هیبریداسیون dna

in this thesis a calibration transfer method is used to achieve bilinearity for augmented first order kinetic data. first, the proposed method is investigated using simulated data and next the concept is applied to experimental data. the experimental data consists of spectroscopic monitoring of the first order degradation reaction of carbaryl. this component is used for control of pests in fruits, vegetables, forages, cotton and other crops. the kinetic experiment is performed at different ph-values and emission wavelengths using an excitation wavelength equal to 275 nm. rate constants of different data matrices at different ph values were calculated based on a hard modeling method. analysis of simulated and experimental data shows that if there is a deviation from bilinearity, applying the model based methods to augmented datasets leads to inaccurate results. the application of a calibration transfer method as an additional step in the hard modeling procedure improves the results, and accurate estimation of reaction rate constants are obtained. the proposed method was compared to local spectra mode of analysis (lsma). a comparison of the results shows that the proposed method is more efficient than lsma and leads to less uncertainty in estimated rate constants and less percent error in the relative residuals. 1. in second part, uv–vis spectroscopic data from a second order consecutive reaction between ortho-amino benzoeic acid (o-aba) and diazoniom ions (diazo) with one intermediate was studied. since o-aba was not absorbing species in visible region of interest the closure rank deficiency problem did not exist. analysis of simulated and experimental data shows that in presence of variations between spectra of pure species in different data matrices, applying the model based methods to augmented datasets leads to inaccurate results. the application of a calibration transfer method as an additional step in the hard modeling procedure improves the precision of results, and accurate estimation of reaction rate constants are obtained. effect of different types of spectral variations including intensity, shift or broadening are tested in simulated data. the proposed method is compared to local spectra mode of analysis (lsma). a comparison of the results shows that the proposed method is more efficient than lsma and leads to less uncertainty in estimated rate constants and less percent error in the relative residuals. 2. in third part, calibration transfer was applied for analysis of a second order rank deficient kinetic system. in this system, calibration transfer was applied for two purposes: first, it was applied to correct the effect of spectral differences between different data sets and estimation of parameters. after estimation of correct parameters, a new method was proposed based on calibration transfer in order to estimate the pure spectral profiles. the proposed method was applied on simulated second order kinetic data, successfully. 3. three-way fluorescence spectral data arrays of the dna hybridization were evaluated by restricted tucker3 model. kinetic behavior of dna hybridization was monitored by observing the changes in fluorescence spectra during the reaction. in this study, a 10 base single-stranded oligonucleotide, containing a sequence complementary to a target, was used as hybridization probe. the oligonucleotide was labeled with a donor–acceptor pair at the 3?- and 5?-ends (fc), respectively. the donor was fluorescein and the acceptor was cy5. the target was a 10 base single-stranded oligonucleotide labeled with fluorescein in 3’ end (f). the hybridization process was second-ordered kinetics which was monitored in different initial concentrations of probe. fluorescence resonance energy transfer (fret) was observed in the probe and static quenching was observed by addition of the target. the three way eem data arrays were rank deficient in all three modes and restricted tucker3 was used and a proper constrained core was designed. three way data sets were analyzed by restricted tucker3 individually. then the effect of temperature on three-way fluorescence spectral data arrays of the dna hybridization was investigated using precise analysis of the core. the resolving method was restricted tucker3 and the core was same as explained in previous part. it was shown that precise analysis of core can predict the extent of fret and contact quenching by change in temperature. two temperatures were tested in this part, 10?c and 5?c. 4. finally, partial uniqueness was approved in obtained results from restricted tucker3. it was approved that emission profiles and excitation profiles can be estimated uniquely base on defined constrained on core. for concentration profiles, non-unique profiles were obtained based on chemical information from experimental data and however, uniqueness in concentration profiles was not approved.