Mechanism of the Direct Coordination of Acetylene to the Polymer-Bound Cyclopentadienyl Manganese Complex

On irradiation by visible light in acetylene, polymer-bound (methyl-cyclopentadienyl)tricarbonylmanganese membrane, P-MeCpMn(CO)₃, was found to react with acetylene to give its acetylene complex, P-MeCpMn(CO)₂ (C₂ H₂). The reaction mechanism of the coordination and elimination of acetylene was investigated by means of resolution of the electronic absorption bands and IR spectra, and gas chromatographic analysis. Reversible coordination of acetylene was also studied by using divinylbenzene crosslinked polymer-bound (methyl-cyclopentadienyl)tricarbonylmanganese resin particles.     

Adsorption of xanthene food additive dyes to cellulose granules

It was found that three kinds of the synthetic food additive dyes, red nr. 3 (erythrosine), nr. 104 (phloxine), and nr. 105 (rose bengal) were adsorbed to the surface of charred cellulose granules and the maximum amounts of adsorption of these dyes were 3.75, 3.42, and 4.74 mg/g cellulose, respectively. Scanning electron microscopy-electron probe micro analysis (SEM-EPMA) showed a coating of the dyes on the surface of charred cellulose granules. Electron spectroscopy for chemical analysis (ESCA) suggested the presence of NH₃ ⁺ in the surface of charred cellulose granules. Since all three dye compounds have both anionic carboxylate and hydrophobic groups and were released from the surface of charred cellulose granules by 0.1 N NaOH solution, it was surmised that these three food additive dyes were bound to the surface of cellulose granules by both ionic and physical interactions.     

Synthesis,characterization, and properties of polyurethanes containing 1,4:3,6‐dianhydro‐D‐sorbitol

Two‐ and three‐component polyurethanes containing 1,4:3,6‐dianhydro‐D ‐sorbitol (isosorbide) derived from glucose were synthesized using n‐BuSn(?O)OH·H₂O as a catalyst, and the thermal properties (T_g, T_d) of the polymers were investigated by differential scanning calorimetry and thermogravimetric analysis. We carried out molds for polyurethanes, the molds of polyurethanes were obtained. The dynamic mechanical analyzes showed that the storage modulus values of the three‐component polymers were constant to a higher temperature than those of the two‐component polymers. The storage moduli (E′), loss moduli (E″), and values of tan δ for the polymers were obtained. The rigidity of three‐component polymers was increased by the introduction of bisphenol A and diphenylmethane group to two‐component polymer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6025–6031, 2009     

Fragment distribution of thermal decomposition for lignin monomer by QMD calculations using the excited and charged model molecules

Simulations with a quantum molecular dynamics (QMD) method (MD with MO) were demonstrated on the thermal decomposition of lignin monomer at the ground state including excited and positive charged states. Geometry and energy optimized results of the lignin monomer at the singlet and triplet states in single excitation, and at (+2) positive charged state by semi-empirical AM1 MO calculations were used as the initial MD step of QMD calculations. In the QMD calculations, we controlled the total energy of the system using Nóse-Hoover thermostats in the total energy range of 0.69-0.95 eV, and the sampling position data with a time step of 0.5 fs were carried out up to 5000 steps at 50 different initial conditions. The calculated neutral, positive and negative charged fragment distributions of the monomer model with 0.82 eV energy control were obtained as 90.6, 3.5, and 5.9% to the total fragments, respectively. The ratios seem to correspond well with to the values observed experimentally in SIMS.     

Synthesis of one-dimensional microporous todorokite and its catalytic activity in CO oxidation

Synthesis of an octahedral molecular sieve composed of Mn, Mg and O, known as todorokite, was studied in detail. The synthesis procedure is composed of three steps; layered birnessite synthesis, ion-exchange to buserite and final hydrothermal treatment of buserite. To obtain todorokites of different morphological properties, the aging time in the birnessite synthesis was varied. The effects of the aging time on properties of todorokites were studied by XRD, FE-SEM, TG-DTA, N₂ adsorption-desorption, FT-IR and CO-TPD. In addition, catalytic activities of various todorokites for CO oxidation were investigated and the correlation between properties and activities was discussed.     

Small‐angle x‐ray scattering study of thermoreversible poly(vinyl chloride) gels

Poly(vinyl chloride) (PVC)/bis(2‐ethylhexyl)phthalate (DOP) gels were prepared at room temperature from tetrahydrofuran solutions of PVC and DOP. PVC/DOP gels of different molecular weights at various PVC concentrations (c) were investigated with small‐angle X‐ray scattering (SAXS). The mean distance between two neighboring inhomogeneities (D) and two characteristic lengths, the intrainhomogeneity distance (d₁) and interinhomogeneity distance (d₂), were evaluated from Bragg's law and the distance distribution function, respectively. Both D and d₂ can be expressed by a power‐law relation (e.g., D and d₂ ∝ c^?0.5). After a period of rapid cooling to 25 °C from the sol state, the structural evolution was examined with time‐resolved SAXS measurements. An Avrami analysis with the SAXS invariant data revealed that the growth kinetics of PVC/DOP gels was one‐dimensional growth from predetermined nuclei, regardless of c. These results suggest that the PVC/DOP gels are constructed from a fibrillar structure that forms gel structures at high concentrations or low temperatures. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2340–2350, 2001