Morphologies and enzymatic degradability of melt-crystallized poly(3-hydroxybutyric acid-Co-6-hydroxyhexanoic acid)

The films of poly[(R)-3-hydroxybutyric acid-co-10mol% 6-hydroxy-hexanoic acid] (P[(R)-3HB-co-6HH]) were prepared by melt-crystallized method at various crystallization temperatures. The morphologies and properties of melt-crystallized films were characterized by means of x-ray diffraction, differential scanning calorimetry, optical microscopy, and scanning electron microscopy. All of the melt-crystallized films showed the banded spherulite morphology. The enzymatic degradation of melt-crystallized films was carried out at 37 °C in an aqueous solution (pH 7.4) of PHB depolymerase from Alcaligenes faecalis. The rate of enzymatic erosion was strongly dependent on the crystallinity of films, and the highest rate was as large as 2.15 mg·h⁻¹·cm⁻². After enzymatic degradation, the banded morphology of P[(R)-3HB-co-6HH] spherulites was visible, suggesting that PHB depolymerase predominantly hydrolyzes polymer chains on the edges of crystalline lamellar stacks.     

Infrared spectroscopic study of thermal annealing effects of hydrocarbon species on a Si surface exposed to methane plasma

We have investigated the thermal annealing effects of hydrocarbon species on the methane-plasma exposed silicon surface, investigated by in situ infrared absorption spectroscopy (IRAS) in multiple internal reflection (MIR) geometry. The proportion of types of hydrocarbon species is not remarkably changed in the hydrocarbon network that consists of sp-, sp²- and sp³-CH_X species by annealing at moderate temperatures. On the other hands, the proportion is drastically changed in the network that is mainly composed of sp³-CH_X species by annealing at moderate temperatures. It suggests that excess CH₃ species in the film is not stable against thermal annealing and would be converted to sp³-CH_1-2 species by annealing at moderate temperatures. And the data also show that sp²-CH species is more stable against the thermal annealing than sp³-hydrocarbon species.     

Lewis acid-promoted rearrangement of 2,3-epoxy alcohol derivatives: stereochemical control and selective formation of two types of chiral quaternary carbon centers from the single carbon skeleton

The Lewis acid-promoted rearrangement of 2,2,3,3-tetrasubstituted 2,3-epoxy alcohols with several kinds of protecting groups was investigated. When SnCl4 is used as a Lewis acid, the reaction proceeds in a regio- and stereo-controlled manner to afford two types of carbonyl compounds selectively from a single 2,3-epoxy alcohol only by changing the protecting group of the alcohol. The method was then applied to the formation of two types of acyclic and cyclic quaternary carbon centers from the single compound in optically active forms.     

Effect of Nonmagnetic Substitution on the Magnetic Properties and Charge-Transfer Phase Transition of an Iron Mixed-Valence Complex, (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)] (dto = C(2)O(2)S(2))

The iron mixed-valence complex (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe(II) and Fe(III) occurs reversibly at ～120 K, in addition to the ferromagnetic phase transition at T(C) = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C(3)H(7))(4)N[Fe(II)(1-x)Zn(II)(x)Fe(III)(dto)(3)] (dto = C(2)O(2)S(2); x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and (57)Fe M?ssbauer spectroscopy. With increasing Zn(II) concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T(C)) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn(II) ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn(II) concentration. This anomalous dependence of T(C) on Zn(II) concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT.     

Infrared diode laser spectroscopy of the ν = 2 band of AlF

A vibrational–rotational spectrum of the ν = 2 transitions of a high-temperature molecule AlF was observed between 1490 and 1586 cm⁻¹ with a diode laser spectrometer. Measurements were made on the ν = 3–1, 4–2, 5–3 and 8–6 bands at a temperature of 900 °C. Measured spectral lines were fitted to effective band constants ν₀, B_ν and D_ν for each band. Present measurements were made with only one Pb-salt laser diode. Physical significance of the effective band constants is discussed.     

Reaction of Acetals with Various Carbon Nucleophiles under Non‐Acidic Conditions: C?C Bond Formation via a Pyridinium‐Type Salt

Mild substitution reactions of acetals with carbon nucleophiles via the pyridinium‐type salts generated by the treatment of acetals with TESOTf‐2,4,6‐collidine or 2,2′‐bipyridyl have been developed. Various carbon nucleophiles, such as organocuprates, silyl enol ethers, enamines, etc., reacted with the pyridinium‐type salts to give the corresponding substituted products in good yields. The reactions proceeded under very mild conditions (non‐acidic conditions) and thus acid‐sensitive functional groups can be tolerated during the reaction. In addition, only an acetal can form the pyridinium‐type salt and react with nucleophiles in the presence of a ketal. This unusual selectivity is in contrast to general methods conducted under acidic conditions.     

Thermal and chemical methods for producing zinc silicate (willemite): A review

Thermal and chemical methods for producing zinc silicate, Zn₂SiO₄ phosphor on industrial and laboratory scales are reviewed. Zinc silicate has a promising future in advanced materials as a highly versatile luminescent material due to the wide range of multi-colors that can be obtained from various guest ions. Candidates for future industrial methods of producing zinc silicate are critically reviewed from the point of view of phase formation and compared with the conventional solid-state reaction. Conventional methods require calcination at temperatures higher than 1000 °C and long reaction times to form Zn₂SiO₄ phase and these processes limit particle shape and size. Sol–gel methods are performed in a solvent at ambient pressure, while hydrothermal and solvothermal methods tend use high temperatures and high pressures, and especially supercritical water methods tend use conditions higher than 400 °C and 25 MPa. Hydrothermal and sol–gel literature shows that crystallization of Zn₂SiO₄ requires at least temperatures of around 100 °C. Of all the growth methods, supercritical water is able to bring about phase formation in the shortest reaction time. Vapor methods are performed with a gas phase as the reaction medium. Vapor and sol–gel methods require post-calcination for crystallization and have the advantage of providing characteristic particles such as uniform shapes, spherical particles, or nano-sized particles by varying the experimental conditions; they may be combined with the other crystallization routes in the future.     

Reaction of β-aminocrotonamide with dibasic acid derivatives

Reaction of β-aminocrotonamide ( 1 ) with succinic anhydride gave β-succinaminocrotonamide ( 3a ), which was treated with base to cyclize to 3,4-dihydro-6-methyl-4-oxo-2-pyrimidinepropanoic acid ( 4a ). Similarly, pyrimidinepentanoic acid derivative 4b was prepared from compound 1 and glutaric anhydride. Reaction of compound 1 with glutarate, adipate, and phthalate gave the corresponding pyrimidines 4b, 4c and 4d , while reaction of compound 1 with malonate gave 2-hydroxypyridine derivative 11 and dimethylpyrimidinone 4e . Reaction of dimethyl fumarate with compound 1 in the presence of methoxide gave a poor yield of pyrrolo[3,4-c]pyridine derivative 13 .