Chlorophyll‐Derived Yellow Phyllobilins of Higher Plants as Medium‐Responsive Chiral Photoswitches

The fall colors are signs of chlorophyll breakdown, the biological process in plants that generates phyllobilins. Most of the abundant natural phyllobilins are colorless, but yellow phyllobilins (phylloxanthobilins) also occur in fall leaves. As shown here, phylloxanthobilins are unique four‐stage photoswitches. Which switching mode is turned on is controlled by the molecular environment. In polar media, phylloxanthobilins are monomeric and undergo photoreversible Z/E isomerization, similar to that observed for bilirubin. Unlike bilirubin, however, the phylloxanthobilin Z isomers photodimerize in apolar solvents by regio‐ and stereospecific thermoreversible [2+2] cycloadditions from self‐assembled hydrogen‐bonded dimers. X‐ray analysis revealed the first stereostructure of a phylloxanthobilin and its hydrogen‐bonded self‐templating architecture, helping to rationalize its exceptional photoswitch features. The chemical behavior of phylloxanthobilins will play a seminal role in identifying biological roles of phyllobilins.     

FT Raman investigation of sodium cellulose sulfate

FT Raman investigation of sodium cellulose sulfates (NaCS) was reported. Different NaCS were prepared by two diverse sulfation methods and their total degrees of substitution (DS) of sulfate groups were determined through either ¹³C-NMR spectroscopy or elemental analysis. Subsequently, these NaCS were characterized with FT Raman spectroscopy. The caused bands through the introduction of the sulfate groups in cellulose chain were explained and assigned. Additionally, a strong linear correlation between the areas under the bands ascribed to the stretching vibrations of C–O–S groups and the total DS of NaCS was presented. A rapid method of quantifying the total DS of NaCS was established. Finally, sodium sulfate (Na₂SO₄), a salt that is very often produced during the sulfation of cellulose, was found to be analyzable even with a weight content of 0.12% in NaCS. The method of quantifying the content of this salt in NaCS was investigated with Raman spectroscopy.     

Transitivity conditions in infinite graphs

We study transitivity properties of graphs with more than one end. We completely classify the distance-transitive such graphs and, for all k≥3, the k-CS-transitive such graphs.     

Continuity of the SLE trace in simply connected domains

We prove that the SLE _κ trace in any simply connected domain G is continuous (except possibly near its endpoints) if κ < 8. We also prove an SLE analog of Makarov’s Theorem about the support of harmonic measure.     

The Susceptibility of Non-UV Fluorescent Membrane Dyes to Dynamical Properties of Lipid Membranes

Fluorescence spectroscopy and microscopy are powerful techniques to detect dynamic properties in artificial and natural lipid membrane systems. Unfortunately, most fluorescent dyes that sense dynamically relevant membrane parameters are UV sensitive. Their major disadvantage is a high susceptibility to fluorescence bleaching. Additionally, the risk for hazardous damages in biological components generally increases with decreasing excitation wavelength. Therefore the use of non-UV–sensitive membrane dyes would provide significant advantage, particularly for applications in fluorescence microscopy, which usually implies high local excitation intensities. We applied steady-state fluorescence spectroscopy techniques to several UV and non-UV membrane dyes to detect and compare dynamically relevant excitation and emission characteristics. Small unilamellar liposomes (composed of egg yolk phosphatidylcholine) served as a model system for biological membranes. The dynamic properties of the membranes were varied by two independent parameters: the intrinsic cholesterol content (0–50 mol%) and temperature (10–50°C). We tested four non-UV–sensitive membrane dyes: 9-diethylamino-5H-benzophenoxazine-5-one (Nile Red), 4-(dicyanovinyl)julolidine (DCVJ), N-(3-triethylammoniumpropyl)-4-(4-(dibutylamino)styryl) pyridinium dibromide (FM 4-64), and 1,1-dioctadecyl-3,3,3,3-tetramethylindocarbocyanine perchlorate (DiIC₁₈). We also tested three derivatives of DiIC₁₈: DiIC₁₆ and DiIC₁₂ differ in acyl chain length and Fast-DiIC₁₈ provides double bonds between hydrocarbon atoms. The spectral results were compared to established fluorescence characteristics of four UV membrane dyes: the anisotropy of 1-6-phenyl-1,3,5,-hexatrien (DPH), two derivatives of DPH (TMA-DPH and COO^–-DHP), and the generalized polarization of 6-dodecanoyl-2-dimethyl-aminonaphthalene (Laurdan). Our results indicate that the tested non-UV dyes do not reveal dynamically relevant membrane parameters in a direct manner. However, spectral characteristics make DiIC₁₈, Nile Red, and DCVJ promising probes for the microscopic detection of lateral lipid organization, an indirect indicator of membrane dynamics. In particular, DiIC₁₈ showed very selective shifts in the emission spectra at defined temperatures and cholesterol contents that have not been reported elsewhere.     

Efficiency of homonuclear Hartmann-Hahn and COSY-type mixing sequences in the presence of scalar and residual dipolar couplings

In the presence of scalar (J) and residual dipolar (D) couplings, the transfer efficiency of homonuclear Hartmann-Hahn and COSY-type mixing depends on the ratio D/J and on the mixing sequence. This dependence is analyzed theoretically and the results are confirmed experimentally. At least two different mixing sequences are required to yield good transfer efficiencies for all ratios D/J. In contrast to COSY-type experiments, homonuclear Hartmann-Hahn sequences can provide efficient transfer even if the sum of D and J is zero, i.e., if the coupling vanishes in the weak coupling limit.