Structural events in the photocycle of green fluorescent protein

Picosecond time-resolved mid-infrared absorption changes of the wild type green fluorescent protein from Aequorea victoria are reported on structural events during the photocycle. Concomitant with rapid H/D transfer following excitation of the neutral A state at 400 nm, a transient signal at 1721/1711 cm(-1) (H/D) developed belonging to protonated glutamate 222, which was definitively assigned using the E222D mutant from the altered proton-transfer kinetics to aspartate in addition to the altered band position and intensity in the spectra. A transient at 1697 cm(-1), assigned to a structural perturbation of glutamine 69, had a H/D kinetic isotope effect of >32, showing the conformational dynamics to be sensitive to the active site H/D vibrations. The kinetic data up to 2 ns after excitation in the 1250-1800 cm(-1) region in D2O provided 10 and 75 ps time constants for the excited-state deuteron transfer and the associated A1* - A1 and A2* - A2 difference spectra and showed the radiative intermediate I state vibrations and the transient accumulation of the long-lived ground-state intermediate I2. Assignments of chromophore modes for the A1, A2, and I2 ground states are proposed on the basis of published model compound studies (Esposito, A. P.; Schellenberg, P.; Parson, W. W.; Reid, P. J. J. Mol. Struct. 2001, 569, 25 and He, X.; Bell, A. F.; Tonge, P. J. J. Phys. Chem. B 2002, 106, 6056). Tentative assignments for the singlet-state intermediates A1*, A2*, and I* are discussed. An unexpected and unassigned band that may be a C=C chromophore vibration was observed in the ground state (1665 cm(-1)) as well as in all photocycle intermediates. Optical dumping of the transient I population was achieved using an additional 532 nm pulse and the directly obtained I2 - I* difference spectrum was highly similar to the I2 - I* photocycle spectrum. The pump-dump-probe spectrum differed from the pump-probe photocycle difference spectrum with respect to the intensity of the phenol 1 mode at 1578 cm(-1), suggesting stronger delocalization of the negative charge onto the phenolic ring of the anionic chromophore in the dumped I2 state. Indication for structural heterogeneity of the chromophore, Glu 222, and the chromophore environment was found in the two parallel proton-transfer reactions and their distinct associated ground- and intermediate-state vibrations. Vibrational spectral markers at 1695 cm(-1) assigned to Gln 69, at 1631 cm(-1) belonging to a C=C mode, and at 1354 cm(-1) belonging to a phenolate vibration further indicated the I2 and I* states to be unrelaxed.     

Study of clay nanocomposites of the biodegradable polyhexamethylene succinate. Application of isoconversional analysis to nonisothermal crystallization

Nanocomposites of organomodified montmorillonites and the biodegradable polyester derived from hexanediol and succinic acid were prepared by the solution‐casting method using chloroform as solvent. Samples were studied by means of X‐ray diffraction and transmission electron microscopy. Intercalated structures differentiated by the stacking mode between silicate layers were observed. The highest variability in interlayer spacing was found when C30B organoclay was added. In this case, hydroxyl groups of the modifier could interact with polar carbonyl groups of the polyester. Thermal stability and crystallization behavior under both isothermal and nonisothermal conditions were evaluated. The overall crystallization rate of the intercalated nanocomposites was higher than that of the neat polyester due to a significant increase in their nucleation density, which compensated for their lower crystal growth rate. Isoconversional analysis was used to determine effective activation energies and to estimate nucleation and transport energy parameters from nonisothermal hot crystallization experiments. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2234–2248, 2008     

Photoswitchable Dissipative Two‐Dimensional Colloidal Crystals

Control over particle interactions and organization at fluid interfaces is of great importance both for fundamental studies and practical applications. Rendering these systems stimulus‐responsive is thus a desired challenge both for investigating dynamic phenomena and realizing reconfigurable materials. Here, we describe the first reversible photocontrol of two‐dimensional colloidal crystallization at the air/water interface, where millimeter‐sized assemblies of microparticles can be actuated through the dynamic adsorption/desorption behavior of a photosensitive surfactant added to the suspension. This allows us to dynamically switch the particle organization between a highly crystalline (under light) and a disordered (in the dark) phase with a fast response time (crystallization in ≈10 s, disassembly in ≈1 min). These results evidence a new kind of dissipative system where the crystalline state can be maintained only upon energy supply.     

Tunable Fullerene Affinity of Cages,Bowls and Rings Assembled by PdII Coordination Sphere Engineering

For metal-mediated host compounds, the development of strategies to reduce symmetry and introduce multiple functionalities in a non-statistical way is a challenging task. We show that the introduction of steric stress around the coordination environment of square-planar Pd^II cations and bis-monodentate nitrogen donor ligands allows to control the size and shape of the assembled product, from [Pd₂L₄] cages over [Pd₂L₃] bowl-shaped structures to [Pd₂L₂] rings. Therefore, banana-shaped ligand backbones were equipped with pyridines, two different quinoline isomers and acridine, the latter three introducing steric congestion through hydrogen substituents on annelated benzene rings. Differing behavior of the four resulting hosts towards the binding of C₆₀ and C₇₀ fullerenes was studied and related to structural differences by NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. The three cages based on pyridine, 6-quinoline or 3-quinoline donors were found to either bind C₆₀, C₇₀ or no fullerene at all.     

On the quenching of steel and zircaloy spheres in water-based nanofluids with alumina,silica and diamond nanoparticles

The quenching curves (temperature vs time) for small (∼1 cm) metallic spheres exposed to pure water and water-based nanofluids with alumina, silica and diamond nanoparticles at low concentrations (?0.1 vol%) were acquired experimentally. Both saturated (ΔT_sub = 0 °C) and highly subcooled (ΔT_sub = 70 °C) conditions were explored. The spheres were made of stainless steel and zircaloy, and were quenched from an initial temperature of ∼1000 °C. The results show that the quenching behavior in nanofluids is nearly identical to that in pure water. However, it was found that some nanoparticles accumulate on the sphere surface, which results in destabilization of the vapor film in subsequent tests with the same sphere, thus greatly accelerating the quenching process. The entire boiling curves were obtained from the quenching curves using the inverse heat transfer method, and revealed that alumina and silica nanoparticle deposition on the surface increases the critical heat flux and minimum heat flux temperature, while diamond nanoparticle deposition has a minimal effect on the boiling curve. The possible mechanisms by which the nanoparticles affect the quenching process were analyzed. It appears that surface roughness increase and wettability enhancement due to nanoparticle deposition may be responsible for the premature disruption of film boiling and the acceleration of quenching. The basic results were also confirmed by quench tests with rodlets.     

Fast–Slow Partially Hyperbolic Systems Versus Freidlin–Wentzell Random Systems

We consider a simple class of fast-slow partially hyperbolic dynamical systems and show that the (properly rescaled) behaviour of the slow variable is very close to a Freidlin–Wentzell type random system for times that are rather long, but much shorter than the metastability scale. Also, we show the possibility of a “sink” with all the Lyapunov exponents positive, a phenomenon that turns out to be related to the lack of absolutely continuity of the central foliation.     

Multipole expansions of the electrostatic molecular potential

Multipole expansions of the electrostatic molecular potential up to the hexadecapole terms are examined for H₂O, NH₃ and C₂H₄NH. A reasonable approximation to get unexpensive first order representations of the electrostatic potential for regions outside the van der Waals volume is found.     

Quantum mechanical studies of environmental effects on biomolecules

Ab initia SCF calculations on the hydration of N-methylacetamide are reported and compared to the results previously obtained for formamide. The hydration energies are all slightly decreased. The angular positions of the two carbonyl sites are brought closer to the CO axis and the orientation of the water molecule on the NH site remains very flexible in spite of the a methyl group.     

Teilaromatische Polyamide: Eine calorimetrische und dynamisch-mechanische Untersuchung

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