Synechococcus sp. PCC 7002 CpcB lyase null mutations alter phycocyanin chromophore function and, consequently, affect the redistribution of excitation energy via the light state transition /

Phycobilisomes are the major light harvesting complexes for cyanobacteria and phycocyanin is the primary phycobiliprotein of the phycobilisome rod. The phycocyanobilin lyases responsible for chromophorylating the phycocyanin p subunit (CpcB) have been recently identified in the cyanobacterium Synechococcus sp. PCC 7002. Surprisingly, mutants missing the CpcB lyases were nevertheless capable of producing pigmented phycocyanin. 10K absorbance measurements revealed that the energy states of the p phycocyanin chromophores were only subtly shifted; however, 77K steady state fluorescence emission spectroscopy showed excitation energy transfer involving the targeted chromophores to be highly disrupted. Such evidence suggests that phycobilin orientation within the binding domain is specifically modified. We hypothesized that alternate, less specific lyases are able to act on the p binding sites. A phycocyanin linker-polypeptide deficient mutant was similarly characterized. The light state transition, a short term adaptation of the photosynthetic light harvesting apparatus resulting in the redistribution of excitation energy among the photo systems, was shown to be dominated by the reallocation of phycocyanin-absorbed excitation energy. Treatment with a high M phosphate buffer effectively prevented the redistribution of both chlorophyll a- and phycobilisome- absorbed excitation energy, suggesting that the two effects are not strictly independent. The mutant strains required a larger redistribution of excitation energy between light states, perhaps to compensate for their loss in phycobilisome antenna function.

Rotation-electronic interaction in the 3p-complex Rydberg state of water

An energy theory is formulated for the rotational energy levels in a p-complex Rydberg state of an asymmetric top molecule of symmetry C2v. The effective Hamiltonian used consists of the usual rigid rotor Hamiltonian augmented with terms representing electronic spin and orbital angular momentum effects. Criteria for assigning symmetry species to the rotational energy levels, following Houganfs scheme that uses the full molecular group,are established and given in the form of a table. This is particularly suitable when eigenvectors are calculated on a digital computer. Also, an intensity theory for transitions to the Rydberg p-complex singlet states is presented and selection rules in terms of symmetry species of energy states are established. Finally, applications to HpO and DpO are given.

The mechanism of the regulation of energy distribution between photosystems 1 and 2 in the cyanobacterium Synechococcus sp. strain PCC 7002 /

Cyanobacteria are able to regulate the distribution of absorbed light energy between photo systems 1 and 2 in response to light conditions. The mechanism of this regulation (the state transition) was investigated in the marine cyanobacterium Synechococcus sp. strain PCC 7002. Three cell types were used: the wild type, psaL mutant (deletion of a photo system 1 subunit thought to be involved in photo system 1 trimerization) and the apcD mutant (a deletion of a phycobilisome subunit thought to be responsible for energy transfer to photo system 1). Evidence from 77K fluorescence emission spectroscopy, room temperature fluorescence and absorption cross-section measurements were used to determine a model of energy distribution from the phycobilisome and chlorophyll antennas in state 1 and state 2. The data confirm that in state 1 the phycobilisome is primarily attached to PS2. In state 2, a portion of the phycobilisome absorbed light energy is redistributed to photo system 1. This energy is directly transferred to photo system 1 by one of the phycobilisome terminal emitters, the product of the apcD gene, rather than via the photo system 2 chlorophyll antenna by spillover (energy transfer between the photo system 2 and photo system 1 chlorophyll antenna). The data also show that energy absorbed by the photo system 2 chlorophyll antenna is redistributed to photo system 1 in state 2. This could occur in one of two ways; by spillover or in a way analogous to higher plants where a segment of the chlorophyll antenna is dissociated from photo system 2 and becomes part of the photo system 1 antenna. The presence of energy transfer between neighbouring photo system 2 antennae was determined at both the phycobilisome and chlorophyll level, in states 1 and 2. Increases in antenna absorption cross-section with increasing reaction center closure showed that there is energy transfer (connectivity) between photosystem 2 antennas. No significant difference was shown in the amount of connectivity under these four conditions.

National energy policies of the Federal Republic of Germany and Canada in the 1970s and 1980s: are economic and/or environmental concerns responsible for change?

The thesis presents a comparison of the national energy policies of the Federal Republic of Germany and Canada from 1973 until the late 1980s. The purpose of this paper is to analyze whether economic and/or environmental concerns were responsible for changes in the· West-German and Canadian national energy policies. Furthermore, the feasibility of implementing a soft energy path in West-Germany and Canada is examined. For better comprehension of the policy-making process and implemented changes in the national energy policies of the two states, the West-German and Canadian parliamentary systems and the political cultures were compared. For the analysis, several events with international impact were taken as guidelines. Furthermore, based on statistical data, the West-German and Canadian energy production and consumption were analyzed. With reference to these results the degree of the de facto changes in the national energy policies were analyzed. In addition, the thesis discusses the possibilities which a soft energy path offers to both national governments to renounce themselves from the dependencies on a few energy resources. The thesis reveals that changes in the West-German and Canadian national energy policies, in their energy production and consumption are correlated to various world events. In particular, governmental reponses security of energy supply by the two international oil crises of 1973 and 1979/1980 demonstrate that changes in the West-German and Canadian national energy policies were implemented in reaction to economic concerns than environmental ones. With the policies "away from oil" and "off oil", the West-German and Canadian government implemented the i i substitution of oil through various diverse energy supply resources. However, energy savings concepts and policies were initiated through the first oil crisis in 1973. The world recessions in 1975 and 1982 had no 'profound impacts on the agenda of West-German and Canadian energy policies. As a consequence of the stagnation or the negative growth of the world economic market, changes in their energy production and consumption can be perceived. However, the West-German and Canadian energy production and consumption intensified with the augmentation of the world economy. During the period of study, environmental concerns were taken into account in the energy policy agendas of the Federal Republic of Germany and Canada but they were not of primary concern. wi thin the decade of. the 1980s notably more environmental considerations were taken into account in the energy policies of the two states. The two nuclear reactor accidents in 1979 and 1986 sharpened to various degrees West-German and Canadian public discourse of present energy supply mix and attitude towards energy production and consumption. The statistical data reflects yet no changes in the energy policies in regard to the position of nuclear power. However, in the next several years possible changes can be observed through statistical data, because the planning, the construction and possible phase out of nuclear power requires several years. Finally, the thesis reveals that the implementation of a soft energy path requires profound changes in the consumer behaviour. As several studies indicate, a soft energy path is technological and economically feasible for the Federal Republic of Germany and Canada, its implementation remains to be a political decision.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Distribution of excitation energy in photosynthesis: a study of heat loss, photo chemical activity and fluorescence emission in intact calls of cyanobacterium.

Photosynthetic state transitions were investigated in the cyanobacterium Synechococcus sp. PCC 6301 by studying fluorescence emission, heat loss, and PS I activity in intact cells brought to state 1 and state 2. 77K fluorescence emission spectra were modelled with a sum of 6 components corresponding to PBS, PS II, and PS I emissions. The modelled data showed a large decrease in PS II fluorescence accompanied with a small increase in the PS I fluorescence upon transition to state 2 for excitation wavelengths absorbed by both PBS and ChI ll.. The fluorescence changes seen with ChI .a. excitations do not support the predictions of the mobile PBS model of state transition in PBS-containing organisms. Measurements of heat loss from intact cells in the two states were similar for both ChI it. and PBS excitations over three orders of magnitude of laser flash intensity. This suggests that the PBS does not become decoupled from PS II in state 2 as proposed by the PBS detachment model of state transition in PBS-containing organisms. PS I activity measurements done on intact cells showed no difference in the two states, in contrast with the predictions of all of the existing models of state transitions. Based on these results a model for state transition In PBScontaining organisms is proposed, with a PS II photoprotectory function.