Micelle formation of a diblock copolymer having pyridine as pendant groups by carboxylic acids in nonselective solvents

The micelle formation of a poly(4-pyridinemethoxymethylstyrene)-block-polystyrene diblock copolymer (PPySt-b-PSt) was investigated in nonselective solvents using bifunctional and trifunctional carboxylic acids. The copolymer showed no self-assembly in 1,4-dioxane and tetrahydrofuran (THF) because the PPySt and PSt blocks were solvophilic to the solvents. Dynamic light scattering studies demonstrated that the copolymer formed micelles in the nonselective solvents in the presence of bifunctional carboxylic acids. Oxalic acid, maleic acid, citric acid, and phospholic acid promoted the micellization, while malonic acid, succinic acid, and glutalic acid had no effect on the micellization. The micellar size, aggregation number, and critical micelle concentration were dependent not only on the acid strength but also on the type of acid and the functionality. The micellization was also affected by the solvent quality. The micellization proceeded more effectively in 1,4-dioxane than in THF. It was found that the micellization occurred by hydrogen bonding between the pyridine moiety and the carboxylic acid and by the interaction among the carboxylic acids. This is because the copolymer needed over an equivalent of the acid to the PySt unit to complete the micellization. Furthermore, monofunctional carboxylic acid such as trichloroacetic acid and trifluoroacetic acid promoted the micellization, although dichloroacetic acid had no effect on the micellization.     

Fullerene adlayers on various single-crystal metal surfaces prepared by transfer from L films

Fullerene adlayers prepared by the simple Langmuir-Blodgett (LB) method onto various well-defined single-crystal metal surfaces were investigated by in situ scanning tunneling microscopy (STM). The surface morphologies of fullerene adsorbed onto metal surfaces depended largely on the adsorbate-substrate interactions, which are governed by the types of surfaces. Too weak adsorption of C60 molecules onto iodine-modified Au(111) (I/Au(111)) allows surface migration of the molecules, and then, STM cannot visualize the C60 molecules. Stronger and appropriate adsorption onto bare Au(111) leads to highly ordered arrays relatively easily due to the limited surface migration of C60. On iodine-modified Pt(111) (I/Pt(111)) and bare Pt(111) surfaces, which have stronger adsorption, randomly adsorbed molecular adlayers were observed. Although C60 molecules on Au(111) were visualized as a featureless ball due to the maintenance of the rapid rotational motion (perturbation) of C60 on the surface at room temperature, those on I/Pt(111) revealed the intramolecular structures, thus indicating that the perturbation motion of molecules on the surface was prohibited.     

Effect of the degree of crosslinking on the interfacial layer structure of poly(vinyl chloride) dispersed with crosslinked poly(n-butyl methacrylate) particles

The interfacial layer structure of a model incompatible polymer blend system was analyzed using ¹H pulse nuclear magnetic resonance (pulse NMR) spectroscopy. Non-crosslinked and crosslinked poly(n-butyl methacrylate) particles with a mean size of ca. 0.9 μm were prepared by seeded emulsion polymerization, and the degree of crosslinking was varied. The particles were powdered using a freeze-dry method and dispersed in poly(vinyl chloride) by melt blending. Dynamic mechanical analysis indicated that the non-crosslinked particles were completely compatible. In contrast, mutual diffusion of the polymer chains in the crosslinked particles was restricted within the particle/matrix interfacial layer. As a result, an incompatible phase structure in which the crosslinked particles were dispersed in the continuous phase was formed. Pulse NMR analysis indicated that the interfacial layer thickness was in the range of 17–98 nm. The thickness decreased with an increase in the degree of crosslinking in the particles. The interfacial layer thickness in the particles was approximately 10 times larger than that for the incompatible polymer pair. Tensile test results indicated that the elongation at break was dependent on the thickness of the interfacial layer. The yield stress was developed for the particles with high hardness that was independent of the interfacial thickness.     

Reversible 1,4-cycloaddition of singlet oxygen to N-substituted 2-pyridones: 1,4-endoperoxide as a versatile chemical source of singlet oxygen

N-substituted pyridones (1) easily undergo singlet oxygenation to give exclusively the corresponding endoperoxides (2), which decompose to give pyridones again while liberating 1O2 in high yield.     

The Effects of Varying Production Rates on Inventory Control

In production activities, the control of production quantity and inventory is very important. The locus of the fluctuations of inventory can be represented by the minimal lattice paths on the two-dimensional planes. In this paper the effects of varying production rates on inventory control are discussed based on the minimal lattice paths.     

An IR study of protonation changes associated with heme-heme electron transfer in bovine cytochrome c oxidase

IR changes caused by photolysis of CO from the mixed valence form of bovine cytochrome c oxidase have been investigated over the pH/pD range 6-9.8. Band assignments were based on effects of H2O/D2O exchange and by comparisons with published IR data and crystallographic data. Changes arise both from CO photolysis and from subsequent reversed electron transfer from heme a3 to heme a. This reversed electron transfer is known to have pH-independent and, above pH 8, pH-dependent components. The pH-independent component is associated with a trough around the 1742 cm(-1) band attributable to one or more protonated carboxylic acids. Its peak position, but not extent, is pH-dependent, indicative of a titratable group with a pK of 8.2 whose acid form causes increased hydrogen bonding to the IR-detectable carboxylic group. A different protonatable group with pK above 9 controls the extent of the pH-dependent component. This phase is associated with perturbation of an arginine guanidinium that is most clearly observed as a trough at 1592 cm(-1) after H/D exchange. It is suggested that this group, probably Arg-438 that is in close contact with propionate groups of both hemes and already proposed to be of functional significance, lowers the energy of the transient charge-uncompensated electron-transfer intermediate by changing the charge distribution in response to heme-heme electron transfer. No other IR signature of a titratable group that controls the extent of the pH-dependent phase is present, and it most likely arises from a nonphysiological deprotonation of the proximal water ligand of ferric heme a3 at high pH that has been reported to exhibit a similar pK.     

β-Galactosidase fluorescence probe with improved cellular accumulation based on a spirocyclized rhodol scaffold

We identified a rhodol bearing a hydroxymethyl group (HMDER) as a suitable scaffold for designing fluorescence probes for various hydrolases. HMDER shows strong fluorescence at physiological pH, but phenolic O-alkylation of HMDER results in a strong preference for the spirocyclic form, which has weak fluorescence. As a proof of concept, we utilized this finding to develop a new fluorescence probe for β-galactosidase. This probe has favorable characteristics for imaging in biological samples: it has good cellular permeability, and its hydrolysis product is well-retained intracellularly. It could rapidly and clearly visualize β-galactosidase activity in cultured cells and in Drosophila melanogaster tissue, which has rarely been achieved with previously reported fluorescence probes.     

Enzymatic Production of Ferulic Acid from Defatted Rice Bran by Using a Combination of Bacterial Enzymes

Ferulic acid (FA), which is present in the cell walls of some plants, is best known for its antioxidant property. By combining a commercial enzyme that shows FA esterase activity with several Streptomyces carbohydrate-hydrolyzing enzymes, we succeeded in enhancing the enzymatic production of FA from defatted rice bran. In particular, the combination of three xylanases, an α-l-arabinofuranosidase, and an acetyl xylan esterase from Streptomyces spp. produced the highest increase in the amount of released FAs among all the enzymes in the Streptomyces enzymes library. This enzyme combination also had an effect on FA production from other biomasses, such as raw rice bran, wheat bran, and corncob.     

Molecular recognition between protein and nicotinamide dinucleotide in intact, proton-translocating transhydrogenase studied by ATR-FTIR Spectroscopy

Nicotinamide dinucleotide binding to transhydrogenase purified from Escherichia coli was investigated by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Detergent-free transhydrogenase was deposited as a thin film on an ATR prism, and spectra were recorded during perfusion with buffers in the presence and absence of dinucleotide (NADP(+), NADPH, NAD(+), or NADH) in both H(2)O and D(2)O media. IR spectral changes were attributable to the bound dinucleotides and to changes in the protein itself. The dissociation constant of NADPH was estimated to be approximately 5 muM from a titration of the magnitude of the IR changes against the nucleotide concentration. IR spectra of related model compounds were used to assign principle bands of the dinucleotides. This information was combined with IR data on amino acids and with protein crystallographic data to identify interactions between specific parts of the dinucleotides and their binding sites in the protein. Several IR bands of bound nucleotide were sharpened and/or shifted relative to those in aqueous solution, reflecting a restriction to motion and a change in environment upon binding. Alterations in the protein secondary structure indicated by amide I/II changes were distinctly different for NADP(H) and for NAD(H) binding. The data suggest that NADP(H) binding leads to perturbation of a deeply buried part of the polypeptide backbone and to protonation of a carboxylic acid residue.