Comparative quantitative analysis of phylloquinone content and photochemically competent P-700 has been performed on photosystem I particles subjected to photolysis with ultraviolet irradiation. Nonirradiated control particles exhibit a phylloquinone/P-700 stoichiometry of 1.9 + 0.2. Photolysis of the photosystem I particles induces a progressive depletion of phylloquinone, however, photochemistry as assayed at room temperature by the photooxidation of P-700 is unaffected. These data are not consistent with the assignment of phylloquinone as a functional intermediate at room temperature between P-700 and the iron-sulfur clusters, center A and center B.Electron carrier A1; P-700; Photosystem I; Phylloquinone; Signal 1; (Spinach subchloroplast particle)
Near-infrared spectra (1300–2500 nm) collected from lysed blood solutions were shown to correlate with the pH of the solutions measured potentiometrically. Cross-validated partial least-squares (PLS) models were developed from these spectral data, which provided standard error of prediction (SEP) values below 0.05 pH units for a pH range of 1.0 (6.8–7.8). Experiments were designed to eliminate possible correlation between pH and other components in the blood in order to ensure that variations in the spectral data correlated to pH were due to hydrogen ion changes only. Further work was performed to discern the primary source of pH information in the lysed blood spectra by using spectra collected from plasma and histidine solutions. The blood, plasma, and histidine data sets were compared with the use of loading vectors from principal component analysis (PCA). These loading vectors show that variations in the spectra of the titrated amino acid histidine mimic those seen in lysed blood, but not those seen in plasma. These results suggest that histidine residues of hemoglobin are providing the spectral variation necessary for pH modeling in the lysed blood solutions. It is further shown that the observed pH-sensitive histidine bands do not arise from the exchangeable proton on the imidazole ring of histidine; rather they arise from the variation in the C–H bonds of the C2 and/or the C4 carbons of the imidazole ring as they are influenced by the titration of the nitrogen-bound proton of the imidazole ring.
We have completed an experimental study to investigate the use of infrared emission spectroscopy (IRES) for the quantitative analysis of borophosphosilicate glass (BPSG) thin films on silicon monitor wafers. Experimental parameters investigated included temperatures within the range used in the microelectronics industry to produce these films so that the potential for using the IRES technique for real-time monitoring of the film deposition process could be evaluated. The film properties that were investigated included boron content, phosphorus content, film thickness, and film temperature. The studies were conducted over two temperature ranges, 125 to 225 °C and 300 to 400 °C. The latter temperature range includes realistic processing temperatures for the chemical vapor deposition (CVD) of the BPSG films. Partial least-squares (PLS) multivariate calibration methods were applied to spectral and film property calibration data. The cross-validated standard errors of prediction (CVSEP) from the PLS analysis of the IRES spectra of 21 calibration samples each measured at six temperatures in the 300 to 400 °C range were found to be 0.09 wt % for B, 0.08 wt % for P, 3.6 nm for film thickness, and 1.9 °C for temperature. Upon lowering the spectral resolution from 4 to 32 cm−1 and decreasing the number of spectral scans from 128 to 1, we were able to determine that all the film properties could be measured in less than one second to the precision required for the manufacture and quality control of integrated circuits. Thus, real-time in situ monitoring of BPSG thin films formed by CVD deposition on Si monitor wafers is possible with the methods reported here.
Whole blood pH has been determined in vitro by using near-infrared spectroscopy over the wavelength range of 1500 to 1785 nm with multivariate calibration modeling of the spectral data obtained from two different sample sets. In the first sample set, the pH of whole blood was varied without controlling cell size and oxygen saturation (O2 Sat) variation. The result was that the red blood cell (RBC) size and O2 Sat correlated with pH. Although the partial least-squares (PLS) multivariate calibration of these data produced a good pH prediction cross-validation standard error of prediction (CVSEP) = 0.046, R2 = 0.982, the spectral data were dominated by scattering changes due to changing RBC size that correlated with the pH changes. A second experiment was carried out where the RBC size and O2 Sat were varied orthogonally to the pH variation. A PLS calibration of the spectral data obtained from these samples produced a pH prediction with an R2 of 0.954 and a cross-validated standard error of prediction of 0.064 pH units. The robustness of the PLS calibration models was tested by predicting the data obtained from the other sets. The predicted pH values obtained from both data sets yielded R2 values greater than 0.9 once the data were corrected for differences in hemoglobin concentration. For example, with the use of the calibration produced from the second sample set, the pH values from the first sample set were predicted with an R2 of 0.92 after the predictions were corrected for bias and slope. It is shown that spectral information specific to pH-induced chemical changes in the hemoglobin molecule is contained within the PLS loading vectors developed for both the first and second data sets. It is this pH specific information that allows the spectra dominated by pH-correlated scattering changes to provide robust pH predictive ability in the uncorrelated data, and visa versa.
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