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Optica Publishing Group
  • Applied Spectroscopy
  • Vol. 53,
  • Issue 3,
  • pp. 316-324
  • (1999)

Measurement of pH in Whole Blood by Near-Infrared Spectroscopy

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Abstract

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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