Multivariate spectroscopic methods for the analysis of solutions

In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins. In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles.

Calibration and linearity verification of capacitance type cryo level indicators using cryogenically multiplexed diode array

In space application the precision level measurement of cryogenic liquids in the storage tanks is done using triple redundant capacitance level sensor, for control and safety point of view. The linearity of each sensor element depends upon the cylindricity and concentricity of the internal and external electrodes. The complexity of calibrating all sensors together has been addressed by two step calibration methodology which has been developed and used for the calibration of six capacitance sensors. All calibrations are done using Liquid Nitrogen (LN2) as a cryogenic fluid. In the first step of calibration, one of the elements of Liquid Hydrogen (LH2) level sensor is calibrated using 700mm eleven point discrete diode array. Four wire method has been used for the diode array. Thus a linearity curve for a single element of LH2 is obtained. In second step of calibration, using the equation thus obtained for the above sensor, it is considered as a reference for calibrating remaining elements of the same LH2 sensor and other level sensor (either Liquid Oxygen (LOX) or LH2). The elimination of stray capacitance for the capacitance level probes has been attempted. The automatic data logging of capacitance values through GPIB is done using LabVIEW 8.5.

Laser diode array side-pumped acousto-optic induced unidirectional operation Q-switched Nd : YAG slab ring laser

A laser-diode array (LDA) side-pumped Nd:YAG slab ring laser is described that incorporates a prism-shaped acousto-optic modulator to enforce unidirectional operation and Q-switching. When pumped by the maximum power of 50 W, Q-switched energies of 3.6 mJ and 50 ns duration, corresponding to a peak power of 72 kW, are obtained. (C) 1999 Society of Photo-Optical Instrumentation Engineers. [S0091-3286(99)01306-9].

Line-width reduction of a laser diode array using an external cavity with two feedback mirrors

A novel Littman-Metcalf external cavity laser diode array with two feedback mirrors is introduced. The line-width broadening effect caused by smile can be reduced by the novel external cavity. At the drive current of 16A, the line-width is narrowed to 0.1nm from free-running width of 1.6nm with output efficiency of 84%.

Beam quality improvement of laser diode array by using off-axis external cavity

A novel off-axis external cavity is designed for laser diode array to improve the beam quality. In this external cavity, a circle aperture with variable size is used as a spatial filter. The diameter of aperture is optimized to 1.2mm and the off-axis angle of external cavity is optimized at 2.6 deg. In the optimal case, the beam parameter product (BPP) of laser diode array is reduced to 121 mm. mrad from 1050 mm. mrad with external cavity optical efficiency of 81%. (C) 2007 Optical Society of America.

Beam collimation of high-power laser diode array with graded-index fiber lens array

Graded-index (GRIN) fiber lens arrays are fabricated from commercial GRIN fibers to collimate a high-power laser diode array. The beam divergence angles are reduced to 4.2 and 14.7 mrad in the fast and slow axes, respectively. The influences of smile and fluctuation in fiber length are discussed. Using an aspherical focal lens system, about 74% power can be launched into a fiber with a numerical aperture (NA) of 0.22 and a core diameter of 400 mu m. (c) 2008 Society of Photo-Optical Instrumentation Engineers.

4-W single transverse mode Yb3+-doped fiber laser pumped by 915-nm laser diode array

A cladding-pumped ytterbium-doped fiber laser is described in this letter. Using unusual pumping source with 915-nm wavelength, slope efficiency up to 75% with respect to absorbed input power and output power is obtained, a maximum output power of 4.006 W with fundamental mode is measured.

AIN Monolithic Microchannel Cooled Heatsink for High Power Laser Diode Array

A novel AIN monolithic microchannel cooled heatsink for high power laser diode array is introduced.The high power stack laser diode array with an AIN monolithic microchannel heatsink is fabricated and tested.The thermal impedance of a 10 stack laser diode array is 0.121℃/W.The pitch between two adjacent bars is 1.17mm.The power level of 611W is achieved under the 20% duty factor condition at an emission wavelength around 808nm.

Fiber Optic Coupling of CW Linear Laser Diode Array

Based on a set of microoptics the output radiation from a continuous wave (CW) linear laser diode array is coupled into a multi-mode optical fiber of 400 ptm diameter. The CW linear laser diode array is a 1 cm laser diode bar with 19 stripes with 100 fxm aperture spaced on 500 (xm centers. The coupling system contains packaged laser diode bar, fast axis collimator, slow axis collimation array, beam transformation system and focusing system. The high brightness, high power density and single fiber output of a laser diode bar is achieved. The coupling efficiency is 65% and the power density is up to 1.03 * 10~4 W/cm~2.

Tunable diode Laser Absorption Spectroscopy ,Nir Overtone and Life Studies of Some Organic Compound

The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Validation of a stability-indicating HPLC method with diode array detection for the determination of beclomethasone dipropionate in aqueous suspension for nebulizer

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)