An important class of substances in clinical chemistry are metabolites in b
ody fluids, which are accessible by near-infrared spectroscopy without samp
le treatment using reagentless, fast and readily automated in vitro assays.
Furthermore, noninvasive sensing systems are under development for the det
ermination of blood glucose, especially for diabetic patients or for monito
ring in intensive care and surgery. Near-infrared diffuse reflectance spect
rometry of skin was employed allowing a certain tissue volume to be integra
lly probed. For calibration, the partial least-squares (PLS) algorithm was
used either based on wide spectral intervals or using special spectral vari
able selection. Capillary blood glucose reference concentrations were obtai
ned by finger pricking and an automated laboratory method (hexokinase/G6P-D
H). Clear evidence is provided for the physical effect, as manifested by th
e spectral glucose absorptivities, underlying the individual single-person
calibration models, which still require improvements in the methodology in
the normo- and hypoglycemic concentration range. In extending the potential
of noninvasive blood assays by infrared spectroscopy, a novel technique is
presented for probing the intravascular fluid space by using fast spectral
near-infrared measurements of skin tissue. The pulsatile blood spectrum ca
n be derived from reflectance spectra of oral mucosa by Fourier analysis (n
ear-infrared plethysmography). Future applications and prospects for noninv
asive blood assays are discussed.