The metabolic significance of octulose phosphates in the photosynthetic carbon reduction cycle in spinach

(14)C-Labelled octulose phosphates were formed during photosynthetic (14)CO(2) fixation and were measured in spinach leaves and chloroplasts. Because mono- and bisphosphates of d-glycero-d-ido-octulose are the active 8-carbon ketosugar intermediates of the L-type pentose pathway, it was proposed that they may also be reactants in a modified Calvin–Benson–Bassham pathway reaction scheme. This investigation therefore initially focussed only on the ido-epimer of the octulose phosphates even though (14)C-labelled d-glycero-d-altro-octulose mono- and bisphosphates were also identified in chloroplasts and leaves. (14)CO(2) predominantly labelled positions 5 and 6 of d-glycero-d-ido-octulose 1,8-P(2) consistent with labelling predictions of the modified scheme. The kinetics of (14)CO(2) incorporation into ido-octulose was similar to its incorporation into some traditional intermediates of the path of carbon, while subsequent exposure to (12)CO(2) rapidly displaced the (14)C isotope label from octulose with the same kinetics of label loss as some of the confirmed Calvin pathway intermediates. This is consistent with octulose phosphates having the role of cyclic intermediates rather than synthesized storage products. (Storage products don’t rapidly exchange isotopically labelled carbons with unlabelled CO(2).) A spinach chloroplast extract, designated stromal enzyme preparation (SEP), catalysed and was used to measure rates of CO(2) assimilation with Calvin cycle intermediates and octulose and arabinose phosphates. Only pentose (but not arabinose) phosphates and sedoheptulose 7-phosphate supported CO(2) fixation at rates in excess of 120 μmol h(−1) mg(−1) Chl. Rates for octulose, sedoheptulose and fructose bisphosphates, octulose, hexose and triose monophosphates were all notably less than the above rate and arabinose 5-phosphate was inactive. Altro-octulose phosphates were more active than phosphate esters of the ido-epimer. The modified scheme proposed a specific phosphotransferase and SEP unequivocally catalysed reversible phosphate transfer between sedoheptulose bisphosphate and d-glycero-d-ido-octulose 8-phosphate. It was also initially hypothesized that arabinose 5-phosphate, an L-Type pentose pathway reactant, may have a role in a modified Calvin pathway. Arabinose 5-phosphate is present in spinach chloroplasts and leaves. Radiochromatography showed that (14)C-arabinose 5-phosphate with SEP, but only in the presence of an excess of unlabelled ribose 5-phosphate, lightly labelled ribulose 5-phosphate and more heavily labelled hexose and sedoheptulose mono- and bisphosphates. However, failure to demonstrate any CO(2) fixation by arabinose 5-phosphate as sole substrate suggested that the above labelling may have no metabolic significance. Despite this arabinose and ribose 5-phosphates are shown to exhibit active roles as enzyme co-factors in transaldolase and aldolase exchange reactions that catalyse the epimeric interconversions of the phosphate esters of ido- and altro-octulose. Arabinose 5-phosphate is presented as playing this role in a New Reaction Scheme for the path of carbon, where it is concluded that slow reacting ido-octulose 1,8 bisphosphate has no role. The more reactive altro-octulose phosphates, which are independent of the need for phosphotransferase processing, are presented as intermediates in the new scheme. Moreover, using the estimates of phosphotransferase activity with altro-octulose monophosphate as substrate allowed calculation of the contributions of the new scheme, that ranged from 11% based on the intact chloroplast carboxylation rate to 80% using the carboxylation rate required for the support of octulose phosphate synthesis and its role in the phosphotransferase reaction

The Supply Side Determinants of Territory and Conflict

What determines the geographic extent of territory? We microfound and extend Boulding’s “Loss of Strength Gradient” to predict the extensive and intensive margins of conflict across space. We show how economies of scale in the production of violence and varying costs of projecting violence at a distance combine to affect the geographic distribution of conflict and territory. We test and probe the boundaries of this model in an experiment varying the fixed costs of conflict entry. As predicted, higher fixed costs increase the probability of exclusive territories; median behavior closely tracks equilibrium predictions in all treatments

Level 0 to 1 processing of the imaging Fourier transform spectrometer GLORIA: generation of radiometrically and spectrally calibrated spectra

The Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) is an imaging Fourier transform spectrometer that is capable of operating on various high-altitude research aircraft. It measures the atmospheric emission in the thermal infrared spectral region in limb and nadir geometry. GLORIA consists of a classical Michelson interferometer combined with an infrared camera. The infrared detector has a usable area of 128 × 128 pixels, measuring up to 16 384 interferograms simultaneously.Imaging Fourier transform spectrometers impose a number of challenges with respect to instrument calibration and algorithm development. The optical setup with extremely high optical throughput requires the development of new methods and algorithms for spectral and radiometric calibration. Due to the vast amount of data there is a high demand for scientifically intelligent optimisation of the data processing.This paper outlines the characterisation and processing steps required for the generation of radiometrically and spectrally calibrated spectra. Methods for performance optimisation of the processing algorithm are presented. The performance of the data processing and the quality of the calibrated spectra are demonstrated for measurements collected during the first deployments of GLORIA on aircraft

New calibration noise suppression techniques for the GLORIA limb imager

The Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) presents new opportunities for the retrieval of trace gases in the upper troposphere and lower stratosphere. The radiometric calibration of the measured signal is achieved using in-flight measurements of reference blackbody and upward-pointing "deep space" scenes. In this paper, we present techniques developed specifically to calibrate GLORIA data exploiting the instrument's imaging capability. The algorithms discussed here make use of the spatial correlation of parameters across GLORIA's detector pixels in order to mitigate the noise levels and artefacts in the calibration measurements. This is achieved by combining a priori and empirical knowledge about the instrument background radiation with noise-mitigating compression methods, specifically low-pass filtering and principal component analysis. In addition, a new software package for the processing of GLORIA data is introduced which allows us to generate calibrated spectra from raw measurements in a semi-automated data processing chain