Cationic Polymerization of N-Vinylcarbazole in the Presence of (+)-D-Camphor-10-sulfonic Acid

Optical rotation values of the polymers of N-vinylcarbazole (VCZ) obtained by a (+)-D-camphor-10-sulfonic acid (DCS) catalyst were found to increase linearly with an increase in the donor numbers of such solvents as 1,2-dichloroethane, dioxane, and tetrahydro-furan and such additives as N,N-dimethylformamide and tetra-methylurea. Asymmetric induction is considered to be caused by a stereoselective fixation of the growing VCZ cation with the optically active DCS anion, and fixation is assisted by nucleophilic solvation. No optically active VCZ polymer was obtained by using p-toluenesulfonic acid as the catalyst and (2s)-N,N′-carbonyl-N-cyclohexyl-aminomethyl pyrolizine as the additive.     

Hydrophobic and electrostatic interactions in the adsorption of fibronectin at maleic acid copolymer films

Adsorption and desorption of fibronectin (FN) were investigated at thin films of alternating maleic acid copolymers with octadecene (POMA) and with propene (PPMA). The hydrophobicity and charge density of the polymers were modulated by the choice of the comonomer. In consequence, the dominant forces between the substrate and the protein were specified as hydrophobic interaction for POMA and electrostatic interaction for PPMA. The adsorption kinetics were investigated in situ as variations of the optical thickness, adsorbed mass, and viscoelastic properties (detected by reflectometric interference spectroscopy and quartz crystal microbalance technique, respectively) while alterations of the electrosurface properties were derived from surface conductivity data and isoelectric points (by streaming potential/current measurements using a microslit electrokinetic setup). The results demonstrate that the interfacial mode of adsorbed FN depends on the predominant interactions: large amounts of FN were tightly bound to POMA by hydrophobic interactions. In contrast, FN adsorbed on PPMA was concluded to attain an unfolded structure allowing for the "electrostatic matching" of positively charged residues on FN with the maleic acid groups. This conclusion was supported by the acidic IEP of 3.2 found for FN on PPMA and a significant reduction of the surface conductivity of the FN-covered polymer film, whereas FN on POMA showed an IEP of 4.2 (close to the intrinsic IEP of FN), indicating a stochastic orientation of the adsorbed protein.     

Elemental mapping of frozen‐hydrated cells with cryo‐scanning X‐ray fluorescence microscopy

Visualizing the elemental distributions of cells and tissues is of growing importance in biology and medical science because such data deepen our understanding of the behavior of metal‐binding proteins and ions. Elemental mapping by X‐ray fluorescence analysis with a hard X‐ray nanobeam is very well suited for this purpose owing to its high sensitivity and high resolution. Using this technique, samples must be prepared without artifacts that are caused by treatments such as chemical fixation and staining procedures. In many studies of elemental mapping, sample preparation is not explicitly considered. To overcome this deficiency, we developed a cryo‐scanning X‐ray fluorescence microscope and installed it in the second experimental hutch of BL29XUL of SPring‐8. We used it to observe frozen‐hydrated cells that had been fixed by a quick‐freezing technique to preserve elemental data of the living state at an X‐ray energy of 11.5 keV. The distributions of K, Ca, Fe, Cu and Zn were successfully visualized. The distributions of these elements (especially those of K, Ca and Fe) differed from those in cells fixed with paraformaldehyde. Copyright © 2010 John Wiley & Sons, Ltd.     

Sojourn time distributions in the queue defined by a general QBD process

We consider a general QBD process as defining a FIFO queue and obtain the stationary distribution of the sojourn time of a customer in that queue as a matrix exponential distribution, which is identical to a phase-type distribution under a certain condition. Since QBD processes include many queueing models where the arrival and service process are dependent, these results form a substantial generalization of analogous results reported in the literature for queues such as the PH/PH/c queue. We also discuss asymptotic properties of the sojourn time distribution through its matrix exponential form.     

Y2Si2O7:Eu/SiO2 core shell phosphor particles prepared by flame spray pyrolysis

This paper reports the synthesis of core shell phosphor particles (Y₂Si₂O₇:Eu/SiO₂) produced by flame spray pyrolysis with yttrium and europium nitrates and colloidal silica dispersed precursor solutions. Particles of various structures were produced, including heterogeneous, core shell and non-spherical core shell particles, depending on the synthesis conditions; the ideal core shell structure was obtained under the highest flame temperature and high silicon concentration in the precursor solution. Based on the phase diagram, the formation of the core shell structure was caused by the separation of each component at the liquid phase in the synthesis route. In the energy-dispersive X-ray spectroscopy, yttrium could be detected only at the core part of the particle, while silicon and oxygen could be detected at both the shell and core parts. Under ultraviolet excitation, the ideal core shell particles of Y₂Si₂O₇:Eu showed photoluminescent characteristics. Consequently, it could be concluded that Y₂Si₂O₇:Eu/SiO₂ core shell phosphor particles were successfully synthesized by flame spray pyrolysis.     

Organic Ligand Binding by a Hydrophobic Cavity in a Designed Tetrameric Coiled‐Coil Protein

The design and characterization of a hydrophobic cavity in de novo designed proteins provides a wide range of information about the functions of de novo proteins. We designed a de novo tetrameric coiled‐coil protein with a hydrophobic pocketlike cavity. Tetrameric coiled coils with hydrophobic cavities have previously been reported. By replacing one Leu residue at the a position with Ala, hydrophobic cavities that did not flatten out due to loose peptide chains were reliably created. To perform a detailed examination of the ligand‐binding characteristics of the cavities, we originally designed two other coiled‐coil proteins: AM2, with eight Ala substitutions at the adjacent a and d positions at the center of a bundled structure, and AM2W, with one Trp and seven Ala substitutions at the same positions. To increase the association of the helical peptides, each helical peptide was connected with flexible linkers, which resulted in a single peptide chain. These proteins exhibited CD spectra corresponding to superhelical structures, despite weakened hydrophobic packing. AM2W exhibited binding affinity for size‐complementary organic compounds. The dissociation constants, K_d, of AM2W were 220 nM for adamantane, 81 μM for 1‐adamantanol, and 294 μM for 1‐adamantaneacetic acid, as measured by fluorescence titration analyses. Although it was contrary to expectations, AM2 did not exhibit any binding affinity, probably due to structural defects around the designed hydrophobic cavity. Interestingly, AM2W exhibited incremental structure stability through ligand binding. Plugging of structural defects with organic ligands would be expected to facilitate protein folding.     

Association of tannins and related polyphenols with the cyclic peptide gramicidin S

The association of 10 different tannins and related polyphenols with gramicidin S, a cyclic peptide having a rigid beta-turn structure, has been examined using 1H-NMR spectroscopy. In the presence of pentagalloylglucose and epigallocatechin-3-O-gallate, the proton signals due to proline and the adjacent phenylalanine moieties selectively shifted to up field, suggesting a regioselective association with the beta-turn structure. The association was also supported by the observation of intermolecular nuclear Overhauser effects between epigallocatechin-3-O-gallate and the peptide. In contrast, ellagitannins, biogenetically derived from pentagalloylglucose, showed small and non-selective chemical shift changes, suggesting that interaction with these tannins is relatively weak. The hydrophobicity of the tannin molecules and the steric hindrance of the interaction site are thought to be important in the association.