Excitation energy transfer in isolated chlorosomes from Chlorobaculum tepidum and Prosthecochloris aestuarii

Excitation energy transfer in chlorosomes from photosynthetic green sulfur bacteria, Chlorobaculum (Cba.) tepidum and Prosthecochloris (Pst.) aestuarii, have been studied at room temperature by time-resolved femtosecond transient absorption spectroscopy. Bleach rise times from 117 to 270 fs resolved for both chlorosomes reflect extremely efficient intrachlorosomal energy transfer. Bleach relaxation times, from 1 to 3 ps and 25 to 35 ps, probed at 758 nm were tentatively assigned to intrachlorosomal energy transfer based on amplitude changes of the global fits and model calculations. The anisotropy decay constant of about 1 ps resolved at 807 nm probe wavelength for the chlorosomes from Chloroflexus aurantiacus, Pst. aestuarii and Cba. tepidum was related to energy transfer between bacteriochlorophyll a molecules of the baseplate and partly to intrachlorosomal energy transfer. The longer anisotropy components 6.6, 8.8 and 12.1 ps resolved for the three chlorosomes, respectively, were assigned to chlorosome to baseplate energy transfer. Global fits of magic-angle data also revealed longer chlorosome to baseplate energy transfer components from 95 to 135 ps, in accord with results from simulations.     

INTERACTIONS BETWEEN CATIONIC STARCH AND ANIONIC SURFACTANTS III RHEOLOGY AND STRUCTURE OF THE COMPLEX PHASE

This paper reports on studies of the rheological properties of cationic starch (CS)/ surfactant systems. The degree of substitution of the CS was 0.1 - 0.8. Surfactants investigated were sodium dodecyl sulfate (SDS), potassium octanoate (KOct), sodium decanoate (NaDe)potassium dodecanoate (KDod), sodium oleate (NaOl) and sodium erucate (NaEr). Aggregation of surfactant micelles with the polymer produces a hydrophobic and pseudoplastic gel-like complex phase with low water content and high viscosity. The rheological behavior of the gels is described by the Herschel-Bulkley model. In dilute aqueous solution the CS/surfactant aggregate structure resembles a randomly coiled polymer network, in which polymer molecules are linked by micelles. The rheological data for the gel are compatible with the assumption that the surfactants form liquid crystalline structures with the polymer anchored to the surfactant aggregates, as recently suggested for analogous systems. However, this conjecture needs to be corroborated by more direct determinations of the structure.     

Density functional calculations of electronic g-tensors for semiquinone radical anions. The role of hydrogen bonding and substituent effects

A recently developed density functional approach has been used to carry out a systematic computational study of electronic g-tensors for a series of 1,4-semiquinone radical anions. Good agreement with high-field EPR data in frozen 2-propanol is achieved only after taking into account the significant reduction of g-tensor anisotropy caused by hydrogen bonding to solvent molecules. The comparison of various model systems for the first solvation shell suggests two hydrogen bonds from 2-propanol molecules to each of the carbonyl groups of the radical anions, and one additional hydrogen bond to each of the methoxy groups in ubiquinone systems. 2-Propanol makes stronger hydrogen bonds than water and thus influences g-tensor anisotropy more strongly. Substituent effects at the semiquinone are reproduced quantitatively by the calculations. The g-tensor anisotropy is influenced significantly by the conformations of methyl and methoxy substituents, with opposite contributions. Analyses and interpretations of the interrelations between structure, bonding, and spectroscopic data are provided. The relevance of the computational results for the EPR spectroscopy of semiquinone radical anions in photosynthetic reaction centers is discussed.     

Novel Porphyrin-Cholic Acid Conjugates as Receptors for Biologically Important Anions

A series of novel receptors showing high binding affinity in aqueous media for biologically important anions are reported. These naturally chromophoric porphyrin-based receptors contain cholic acids connected via quaternary alkyl ammonium amido linkages.     

E-2-Benzylidenebenzocycloalkanones. IV. Studies on transmission of substituent effects on C NMR chemical shifts of E-2-(X-benzylidene)-1-tetralones, and -benzosuberones. Comparison with the C NMR data of chalcones and E-2-(X-benzylidene)-1-indanones

Single substituent parameter (SSP) and dual substituent parameter (DSP) analyses were applied to study the transmission of substituent effects on selected ¹³C NMR chemical shifts of the cyclic chalcone analogues, E-2-(4′-X-benzylidene)-1-tetralones (2) and E-2-(4′-X-benzylidene)-1-benzosuberones (3). In order to study how the geometry of the cyclic chalcone analogues affects the transmission of substituent effects similar investigations with the respective chalcones (4) were also performed. The results obtained earlier with the five-membered analogue E-2-(4′-X-benzylidene)-1-indanones (1) were also involved in the comparisons. Geometry optimization of the unsubstituted 1a, 2a, 3a and 4a as well as the substituted 2 and 3 was performed by ab initio quantum chemical calculations. Both SSP and DSP analyses reflected that resonance effects contribute more to the chemical shift of C- (C2), while inductive effects primarily affect that of C-β (C10) of the enone moiety of all the four series. This latter effect, however, is far not as pronounced as that of the former one. It was found that DSP analysis data (ρ_F and ρ_R values) of transmission of substituent effects on the δC2 data can serve as a measure of choice to study the conformation (planarity) of the investigated enones in the four series.     

Amphiphilic nanotubes in the crystal structure of a biosurfactant protein hydrophobin HFBII

Atomic scale experimental data by X-ray crystallography have been collected on an amphiphilic protein nanotube, consisting of a biosurfactant protein Trichoderma reesei hydrophobin HFBII.     

Nonlinear parabolic capacity and polar sets of superparabolic functions

We extend the theory of the thermal capacity for the heat equation to nonlinear parabolic equations of the $p$ -Laplacian type. We study definitions and properties of the nonlinear parabolic capacity and show that the capacity of a compact set can be represented via a capacitary potential. As an application, we show that polar sets of superparabolic functions are of zero capacity. The main technical tools used include estimates for equations with measure data and obstacle problems.     

On n-algebraic power series having polynomial growths 11

We study polynomial growth of algebraic series. It is proved that if an N-algebraic series r with arbitrarily many commuting variables has polynomial growth, then r is in fact N-rational. Also, polynomial growth is decidable. Similar results are proved for N-algebraic series with noncommuting variables having bounded supports. It is also shown that polynomial growth is not decidable for N-algebraic series having noncommuting variables without the additional condition on the supports.     

Polarised bidirectional reflectance factor measurements from soil, stones, and snow

The bidirectional reflectance factor and degree of linear polarisation of selected snow, soil, and gravel types have been measured using Finnish geodetic institute field goniospectropolariphotometer (FIGIFIGO). It was observed that with all measured samples the degree of linear polarisation is weakest 0–30 backwards from nadir, turning 1–5% negative in the backward direction, and growing larger (5–50%) in the forward and Brewster directions. Polarisation was found to be inversely but non-linearly proportional to reflectance. In addition, a wavelength-dependent trend was found to exist in some data, but in general, the wavelength dependence was smooth. Dry old snow polarises clearly more than melting snow or new snow. White gravel polarises somewhat similarly to snow in visible region, and black gravel resembles snow in infrared.The authors conclude that polarisation observations may be useful in land surface remote sensing, but that only far-forward angles (60–70) contain a strong enough signal for easy interpretation. The polarisation spectrum brings little additional information to reflection spectrum, but in conditions where the reflectance spectrum cannot be accurately normalised or incident irradiation is not known, polarisation spectrum could still be usable. The directional signal is strong and may yield refractive index or microstructure, and must be understood in any application. Polarisation near nadir is low for all known samples, and can thus be safely ignored with most non-polarised imaging applications. However, for accurate atmospheric polarimetry, e.g. by polarisation and directionality of the earth's reflectances (POLDER) or aerosol polarimetry sensor (APS) sensors, it is recommended to take into account land surface polarisation.