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101.
Chlorophyll‐Derived Yellow Phyllobilins of Higher Plants as Medium‐Responsive Chiral Photoswitches 下载免费PDF全文
Dr. Chengjie Li Dr. Klaus Wurst Dr. Steffen Jockusch Prof. Karl Gruber Dr. Maren Podewitz Prof. Klaus R. Liedl Prof. Bernhard Kräutler 《Angewandte Chemie (International ed. in English)》2016,55(51):15760-15765
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. 相似文献
102.
103.
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. 相似文献
104.
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. 相似文献
105.
Samy Chammaa Dr. Bianca Sperl Anke G. Roth Aybike Yektaoglu Steffen Renner Dr. Thorsten Berg Prof. Dr. Christoph Arenz Prof. Dr. Athanassios Giannis Prof. Dr. Tudor I. Oprea Dr. Daniel Rauh Dr. Markus Kaiser Dr. Herbert Waldmann Prof. Dr. 《Angewandte Chemie (International ed. in English)》2010,49(21):3666-3670
106.
107.
Steffen Härtel Svitlana Tykhonova Marcus Haas Horst A. Diehl 《Journal of fluorescence》2002,12(3-4):465-479
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. 相似文献
108.
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. 相似文献
109.
Comez L Fioretto D Palmieri L Verdini L Rolla PA Gapinski J Pakula T Patkowski A Steffen W Fischer EW 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》1999,60(3):3086-3096
The dynamics of the fragile glass-forming liquid diglycidyl ether of bisphenol-A was studied by depolarized Rayleigh-Brillouin light-scattering and photon correlation spectroscopy above the glass transition, in the temperature range from 261 to 473 K and in the frequency range from 1 Hz to 300 GHz. The structural (alpha-) relaxation process was revealed and no signature of the secondary relaxation previously evidenced by dielectric spectroscopy at about 0.1 GHz was observed. The characteristic time of the alpha process differs from that determined by dielectric spectroscopy of an amount, which increases with increasing temperature. The relaxation times were compared with viscosity data to test the predictions of the classic Stokes-Einstein-Debye model. The tau proportional, variant eta behavior was verified for dielectric data, while a fractional power law of viscosity tau proportional, variant eta(0.89) was obtained for light-scattering relaxation times, extending over more than seven decades in viscosity and time. This deviation of light scattering from viscosity data could be interpreted in terms of cooperative motion in the supercooled liquid with a characteristic length xi(a) proportional, variant(T-T0)(-v) where T(0)=229 K is the Vogel temperature and v is close to 2 / 3 which is consistent with the prediction of the fluctuation theory of glass transition. 相似文献
110.
Engelbert Dockner Steffen Jørgensen 《The Journal of the Operational Research Society》1984,35(8):731-739
A monopoly possesses a finite stock of a resource and wishes to determine an optimal pricing policy. The competitive fringe invests in production capacity and wishes to select an optimal investment rate. Demand towards the monopoly depends on price as well as on the sales rate of the competition. Modelling the situation as a differential game, non-cooperative (Nash and Stackelberg) and cooperative (Pareto) equilibria are determined. Owing to the special structure of the game, these solutions can be found in closed form. 相似文献