THE REACTION CENTER OF PHOTOSYNTHETIC BACTERIA

Abstract. Investigations on the bacterial photosynthetic reaction center have recently made several important steps forward. Progress has been made in measuring the time course of the light-driven reactions, and in understanding the thermodynamics of these processes, in determining the chemical-structural properties of the protein and its constituents, and in elucidating the functional relationship of the reaction center with the chromatophore membrane. Although the well-characterized Rhodopseudomonas sphaeroides reaction center has been the main exploratory vehicle in many of these studies, we now have an ever increasing body of information from bacteria of other species and genera. This work is providing information from which we can underline features that are common to bacterial reaction centers, but it also reveals differences which may reflect different selection pressures on the separate species.
In this report we shall describe the early photochemical events of the reaction center, summarize the comparative biology of the reaction center, and discuss some of the current physical-chemical problems pertaining to the redox components of the reaction center.     

Resolving conflicting crystallographic and NMR models for solution-state DNA with solution X-ray diffraction

We report on synchrotron-based high-angle X-ray solution scattering measured to 2 A resolution for two synthetic DNA sequences for which there are conflicting X-ray crystal and solution NMR models. Our results demonstrate that high-angle X-ray scattering discriminates between differing X-ray crystal and NMR models for solution-state DNA and provides a direct, independent method for testing structural models and measuring solution-state configurational dispersions.     

A magnetic resonance imaging-based articulatory and acoustic study of "retroflex" and "bunched" American English /r/

Speakers of rhotic dialects of North American English show a range of different tongue configurations for /r/. These variants produce acoustic profiles that are indistinguishable for the first three formants [Delattre, P., and Freeman, D. C., (1968). "A dialect study of American English r's by x-ray motion picture," Linguistics 44, 28-69; Westbury, J. R. et al. (1998), "Differences among speakers in lingual articulation for American English /r/," Speech Commun. 26, 203-206]. It is puzzling why this should be so, given the very different vocal tract configurations involved. In this paper, two subjects whose productions of "retroflex" /r/ and "bunched" /r/ show similar patterns of F1-F3 but very different spacing between F4 and F5 are contrasted. Using finite element analysis and area functions based on magnetic resonance images of the vocal tract for sustained productions, the results of computer vocal tract models are compared to actual speech recordings. In particular, formant-cavity affiliations are explored using formant sensitivity functions and vocal tract simple-tube models. The difference in F4/F5 patterns between the subjects is confirmed for several additional subjects with retroflex and bunched vocal tract configurations. The results suggest that the F4/F5 differences between the variants can be largely explained by differences in whether the long cavity behind the palatal constriction acts as a half- or a quarter-wavelength resonator.     

Das Atomgewicht von Stickstoff und Silber

Ohne Zusammenfassung     

Intramolecular energy transfer within butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms

The synthesis and photophysical properties of butadiyne-linked chlorophyll and porphyrin dimers in toluene solution and in several self-assembled prismatic structures are described. The butadiyne linkage between the 20-positions of the macrocycles results in new electronic transitions polarized along the long axes of the dimers. These transitions greatly increase the ability of these dimers to absorb the solar spectrum over a broad wavelength range. Femtosecond transient absorption spectroscopy reveals the relative rate of rotation of the macrocycles around the butadiyne bond joining them. Following addition of 3-fold symmetric, metal-coordinating ligands, both macrocyclic dimers self-assemble into prismatic structures in which the dimers comprise the faces of the prisms. These structures were confirmed by small-angle X-ray scattering experiments in solution using a synchrotron source. Photoexcitation of the prismatic assemblies reveals that efficient, through-space energy transfer occurs between the macrocyclic dimers within the prisms. The distance dependence of energy transfer between the faces of the prisms was observed by varying the size of the prismatic assemblies through the use of 3-fold symmetric ligands having arms with different lengths. These results show that self-assembly of discrete macrocyclic prisms provides a useful new strategy for controlling singlet exciton flow in antenna systems for artificial photosynthesis and solar cell applications.     

Solution-phase structural characterization of supramolecular assemblies by molecular diffraction

Structures of four molecular squares based on rhenium coordination chemistry have been characterized in the solution phase using pair distribution function (PDF) analyses of wide-angle X-ray scattering measured to better than 1 A spatial resolution. In this report we have focused, in particular, on a comparison of structures for pyrazine- and bipyridine-edged squares measured in solution with structures determined for these molecules in the solid state using X-ray crystallography and models derived from geometry optimization and molecular dynamics simulations using a classical force field. The wide-angle scattering for these assemblies is dominated by pair correlations involving one or more rhenium atoms, with both edge and diagonal Re-Re interactions appearing prominently in PDF plots. The pyrazine square is characterized by a relatively rigid structure in solution, with PDF peak positions and linewidths corresponding closely to those calculated from crystal structure data. For the bipyridine-edged square, the experimental PDF peaks measured along the molecular sides match the positions and linewidths of the PDF peaks calculated from static models. In contrast, PDF peaks measured across the diagonal distances of the molecular square deviate significantly from those calculated from the static crystallographic and energy minimized models. The experimental data are instead indicative of configurational broadening of the diagonal distances. In this respect, molecular dynamics simulations point to the importance of butterfly type motions that modulate the Re-Re diagonal distance. Indeed, the experimental data are reasonably well fit by assuming a bimodal distribution of butterfly conformers differing by approximately 25 degrees in the Re-Re-Re-Re torsion angle. Additionally, the measurements provide evidence for solvent ordering by the supramolecular assemblies detected as regions of solvent association and exclusion.     

Effects of masking noise on vowel and sibilant contrasts in normal-hearing speakers and postlingually deafened cochlear implant users

The role of auditory feedback in speech production was investigated by examining speakers' phonemic contrasts produced under increases in the noise to signal ratio (N/S). Seven cochlear implant users and seven normal-hearing controls pronounced utterances containing the vowels /i/, /u/, /e/ and /ae/ and the sibilants /s/ and /I/ while hearing their speech mixed with noise at seven equally spaced levels between their thresholds of detection and discomfort. Speakers' average vowel duration and SPL generally rose with increasing N/S. Average vowel contrast was initially flat or rising; at higher N/S levels, it fell. A contrast increase is interpreted as reflecting speakers' attempts to maintain clarity under degraded acoustic transmission conditions. As N/S increased, speakers could detect the extent of their phonemic contrasts less effectively, and the competing influence of economy of effort led to contrast decrements. The sibilant contrast was more vulnerable to noise; it decreased over the entire range of increasing N/S for controls and was variable for implant users. The results are interpreted as reflecting the combined influences of a clarity constraint, economy of effort and the effect of masking on achieving auditory phonemic goals-with implant users less able to increase contrasts in noise than controls.