Synthesis of Substituted Phenyl Esters of Amino Acids and Polycondensation in Langmuirblodgett Films

Long-alkyl-chain phenyl esters of β-alanine, glycine, and L-valine were prepared, and their monolayer properties were correlated with their molecular structures. These compounds formed stable monolayers on acidic subphases. In particular, the p-hexadecylphenyl esters of β-alanine and glycine were remarkably stable, and their monolayers could be deposited on calcium fluoride plates as Y-type film by Blodgett's technique. The polycondensation of multilayers under an atmosphere saturated with triethylamine was investigated by changes in the IR spectra. It was determined that the polycondensation proceeded by a first-order reaction mechanism in the initial stage and that the rate in multilayers was faster than that in the bulk crystalline powder. These results suggest that the polycondensation is accelerated by a regular arrangement of the monomer in the multilayers, where the active sites are concentrated and located better for the polycondensation. In the case of the polycondensation in multilayers of the glycine ester, two kinds of condensation proceeded to afford poly(glycine) and 2,5-piperazinedione.     

Synthesis of L-Lysine and L-Glutamic Acid Derivatives with Long Alkyl Chains and Polycondensation of Langmuir-Blodgett Films

Two esters of L-lysine and L-glutamic acid containing long alkyl groups were synthesized and their polycondensation in monolayers and multilayers was investigated. The pressure-area isotherms of the ester of L-lysine depend markedly on the time of residence at the air-water interface. The change of FT-IR spectra of the deposited film, which can be lifted as a Z-type film, indicates that polycondensation can occur in the monolayer at 10°C without any treatment. The spectrum of the film cast from chloroform hardly changed with time. These results lead to the conclusion that a regular arrangement of monomer molecules in the monolayer, where the amino and ester carbonyl groups are concentrated, is more suitable for the polycondensation. The ester of L-glutamic acid can also form stable monolayers which can be easily deposited on a hydrophobic plate as a Y-type film by the Blodgett technique. The polycondensation of multilayers under an atmosphere of triethylamine was investigated by IR spectroscopy. It indicates that the condensation in multilayers proceeds via intermolecular and intramolecular reactions, by which poly(L-glutamate) derivatives and 2-pyrrolidone derivatives are formed, respectively. The condensation in the bulk crystalline powder gives exclusively the 2-pyrrolidone derivative by intramolecular reaction. These results suggest that the monomer molecules in the multilayers are favorably aligned for the intermolecular reaction, in contrast to the situation in the bulk crystalline powder.     

The Polymerization of 1,3-Dioxolane Catalyzed by Ion Exchange Resin (Polystyrene Sulfonic Acid)

Polystyrene sulfonic acid resin (Amberlyst 15) was found to initiate the cationic polymerization of 1,3-dioxolane easily in bulk at 0 to 50° C, and polymers with a reduced viscosity of 0.1 were obtained. However, this resin showed only low initiator activity for the polymerizations of 2-methyl-1, 3-dioxolane and trioxane.     

Non‐Heme Dioxygenase Catalyzes Atypical Oxidations of 6,7‐Bicyclic Systems To Form the 6,6‐Quinolone Core of Viridicatin‐Type Fungal Alkaloids

The 6,6‐quinolone scaffold of the viridicatin‐type of fungal alkaloids are found in various quinolone alkaloids which often exhibit useful biological activities. Thus, it is of interest to identify viridicatin‐forming enzymes and understand how such alkaloids are biosynthesized. Here an Aspergillal gene cluster responsible for the biosynthesis of 4′‐methoxyviridicatin was identified. Detailed in vitro studies led to the discovery of the dioxygenase AsqJ which performs two distinct oxidations: first desaturation to form a double bond and then monooxygenation of the double bond to install an epoxide. Interestingly, the epoxidation promotes non‐enzymatic rearrangement of the 6,7‐bicyclic core of 4′‐methoxycyclopenin into the 6,6‐quinolone viridicatin scaffold to yield 4′‐methoxyviridicatin. The finding provides new insight into the biosynthesis of the viridicatin scaffold and suggests dioxygenase as a potential tool for 6,6‐quinolone synthesis by epoxidation of benzodiazepinediones.     

Biomimetic oxidation of thiol and application to odor-removing fiber

The oxidation of HO-CH₂-CH₂-SH (RSH) by molecular oxygen and Fe(III)- as well as Co(II)-multicarboxyphthalocyanine and the mechanism in homogeneous aqueous system were investigated. As application to enzyme-like heterogeneous catalysts, Fe(III)-as well as Co(II)-octacarboxyphthalocyanine were supported on amorphous enriched rayon staple fiber and their enzyme-like activities were estimated. These fibers were applicated to new odor-removers acting as artificial enzyme systems.     

Preparation of palladium clusters protected by silica-supported,crosslinking, partially phosphorylated poly(vinyl alcohol) and their catalytic activity

The palladium cluster protected by silica-supported, crosslinking, partially phosphorylated poly(vinyl alcohol) (P-PVA) was prepared from a crosslinking P-PVA–Pd(II) complex by reduction in alcohol. The P-PVA–Pd complex and the palladium cluster protected by P-PVA were analyzed by electron spectroscopy, X-ray photoelectron spectrometry and transmission electron microscopy. The complex formation between the Pd(II) ion and phosphoric acid groups in P-PVA was important in the formation of a fine palladium cluster. Palladium clusters protected by silica-supported crosslinking P-PVA were used as catalysts for the hydrogenation of nitrobenzene or acrylic acid at 30°C under atmospheric pressure. The palladium cluster protected by crosslinking P-PVA supported on silica was the most active catalyst, was stable and had no by-products, compared with the palladium cluster protected by silica-supported noncrosslinking P-PVA or PVA.     

Raman and infrared spectra of the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers of β-carotene: Key bands distinguishing stretched or terminal-bent configurations form central-bent configurations

Raman and infrared spectra in the region of 1800-150 cm⁻¹ were recorded for a set of cis-trans isomers of d̃-carotene, i.e. the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers. Spectral comparison revealed Raman and infrared key bands which (1) distinguish stretched or terminal-bent configurations (all-trans, 7-cis and 9-cis) from central-bent configurations (13-cis and 15-cis), and (2) distinguish unmethylated 7-cis and 15-cis configuratios. Keybands (1) include Raman bands at 1160 and 1140 cm⁻¹ and infrared bands at 825 and 775 cm⁻¹ (the intensity varies with the position of the cis-bend) Key bands (2) include Raman bands at 1274 and 962 cm⁻¹ and an infrared band at 741 cm⁻¹ (characteristic of the 7-cis configuration), and also a Raman band at 1247 cm⁻¹ and an infrared band at 775 cm⁻¹ (characteristic of the 15-cis configuration). The normal modes for the key bands were determined by a set of normal coordinate calculations for the isomeric configurations of a simplified model of d̃-carotene. The key bands were mainly related to the C H in-plane bendings, coupled with the CC or C C stretching, or to the C H out-of-plane wagging vibrations, some of which coupled with the CC torsion.     

An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni₆(NDI-Hpz)₆(dma)₁₂(NO₃)₆]·5DMA·nH₂O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H₂O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2–2.1) × 10⁻⁴ S cm⁻¹ (pressed pellet), which is superior to that of most NDI-based conductors including metal–organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.

Intrinsically electron-conductive metallocycle was synthesized. π-Radicals play a key role in constructing π-stacked columns among molecular hexagons and achieving high electrical conductivity over 10⁻⁴ S cm⁻¹ in polycrystalline pellet.     

Chaotic mixing generated by acoustic streaming

The acoustic mixer presented in this paper is a closed cylinder containing chemical solutions. The ultrasound was generated in a water bath outside of the cylinder. The mixing efficiency was measured by using a laser-photodiode system and by mixing iodine and sodium thiosulfate. Iodine solution has a light brown color which becomes transparent if the solution is mixed with sodium thiosulfate. The unmixed regions of the solution in the container remain dark. Starch was used to make the solution darker. Considering the relative position between the cylinder and the transducer, it was shown that displacements parallel to the axes of the streaming have little effect on the mixing speed. Indeed, the distance of the cylinder from the center of the streaming is more important to obtain ideal mixing performances. The frequency and size of the transducers has been investigated too and little effect was found. In contrast, the wave amplitude seems to be the biggest factor in obtaining rapid mixing.