Absorption spectra of the isolated D1/D2/cytochrome b-559 complex have been measured in the temperature range 80-300 K. All spectra were analyzed in terms of a linear combination of Gaussian bands and the thermal broadening data interpreted in terms of a model in which the spectrum of each pigment site is broadened by (a) a homogeneous component due to linear electron-phonon coupling to a low-frequency protein vibration and (b) an inhomogeneous component associated with stochastic fluctuations at each pigment site. In order to obtain a numerically adequate description of the absorption spectra, a minimum number of five sub-bands is required. Further refinement of this sub-band description was achieved by taking into account published data from hole burning and absorption difference spectroscopy. In this way, both a six sub-band description and a seven sub-band description were generated. In arriving at the seven sub-band description, the original five sub-band wavelength positions were essentially unchanged. Thermal broadening analysis of the seven sub-band description yielded data which displayed the closest correspondence with the literature observations. The wavelength positions of the sub-bands were near 661, 667, 670, and 675 nm, with two bands near 680 and 684 nm. The two almost isoenergetic sub-bands near 680 nm, identified as P680 and pheophytin, have optical reorganization energies around 40 and 16 cm-1, respectively. All other sub-bands, identified as accessory pigments, have optical reorganization energies close to 16 cm-1.(ABSTRACT TRUNCATED AT 250 WORDS)

The potential toxicological properties of platinum group elements, usually present in real matrices at sub-ng/g level, explain the increasing interest in developing specific and sensitive analytical methods. In this work, a validation study was performed in order to ensure the fitness-for-purposes of procedures developed for quantifying platinum in tap water, beer and lettuce using an extremely sensitive method based on catalytic adsorptive stripping voltammetry. The work involved the estimation of selectivity, detection and quantitation limits, range, accuracy (trueness plus precision), uncertainty of measurement (UOM), robustness and recovery. The results are discussed in the light of the most recent literature findings.

The limit of detection is one of the fundamental metrological characteristics of any chemical measurement systems but, even now, it is a highly controversial matter because of the existing differences in terminology, formulations and understanding. Even when limiting the analysis to those operational approaches that, because of their simplicity, are often suggested by the guidelines of some international bodies, the available approaches can return appreciably different estimates. In this paper, the matter is critically reconsidered, and the different approaches compared with the aid of some case studies.

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