Direct Resinification of Two (1→3)-β-D-Glucans,Curdlan and Paramylon,via Hot-Press Compression Molding

Abstract

Hot-press compression molding was attempted to resinify two renewable source-derived linear (1→3)-β-D-glucan polymers, i.e., paramylon or curdlan via the generation of reactive aldehyde groups that tend to crosslink with hydroxyl groups of the glucans. As for the paramylon, the optimal molding temperature was found to be around 220?°C, keeping the pressure at 20?MPa for 3?min, due to its highly crystalline structure. On the other hand, the curdlan resin was producible in the temperature range of 180–240?°C at the same pressure and pressing time. Dynamic mechanical analysis revealed a large temperature dependence of the loss modulus, E’’, for the paramylon-based polymer resin whereas the semi-crystalline curdlan resin was stable in terms of both the storage and loss moduli, E’ and E’’, up to 160?°C. The vaporization of the water formed during the molding, due to the thermal decomposition, and the adsorption of moisture due to the hydrophilic property of the paramylon affected the thermal stability. The curdlan resin exhibited flexural strength and modulus extremely superior to those of regenerated and esterified curdlan films, and even a little superior to those of polyamide-12. The strain at break was comparable to the yield strain of an epoxy resin. On the other hand, the paramylon-based polymer resin was producible, but the resinification property and thermal stability of the paramylon resin was inferior to the curdlan resin due to the former’s highly crystalline structure.     

Triplet Diradical-Cation Salts Consisting of the Phenothiazine Radical Cation and a Nitronyl Nitroxide

The spin–spin and magnetic properties of two (nitronyl nitroxide)-(di-p-anisylamine-phenothiazine) diradical cation salts, ( DAA-PTZ ) ⁺ -NN⋅ MBr₄⁻ (M=Ga, Fe), have been investigated. These diradical-cation species were prepared by the cross-coupling of iodophenothiazine DAA-PTZ-I with NN-AuPPh₃ followed by oxidation with the thianthrenium radical cation ( TA⁺⋅ MBr₄⁻). These salts were found to be highly stable under aerobic conditions. For the GaBr₄ salt, large ferromagnetic intramolecular and small antiferromagnetic intermolecular interactions (J₁/k_B=+320 K and J₂/k_B=−2 K, respectively) were observed. The magnetic property of the Fe³⁺ salt was analyzed by using a six-spin model assuming identical intramolecular exchange interaction (J₃/k_B=+320 K) and the other exchange interactions (J₄/k_B=−7 K and J₅/k_B=−4 K). A significant color change was observed in the UV/Vis/NIR absorption spectra upon electrochemical oxidation of the doublet DAA-PTZ-NN to the triplet ( DAA-PTZ ) ⁺ -NN .     

Determination of trace levels of iron in a seawater sample using isotope dilution/inductively coupled plasma mass spectrometry.

An analytical method for trace levels of iron in a seawater sample using isotope dilution ICP-MS was developed. Preconcentration of iron and the removal of major elements in seawater such as alkali and alkaline-earth elements can be carried out quickly using a chelating resin disk by adjusting the sample pH to 3. The collision cell option of the ICP-MS instrument method was used to improve the performance of the instrument for iron measurements since ArO and ArN interferences could be reduced using this analytical method. About 4 ml min(-1) helium, as the collision gas, were introduced into the cell. 40Ar14N and 40Ar16O which interfere with 54Fe and 56Fe in water had their amounts decreased by 5 orders of magnitude. Then, the isotope dilution method was used for iron determination below ng g(-1) level of trace iron in four environmental reference materials (river water standard sample JAC-0031 (Japan Soc. for Analytical Chemistry), estuarine standard sample SLEW-2 (NRC Canada) and seawater standard samples CASS-3 and NASS-5 (NRC Canada)) were measured. Good agreement between analytical results and certified values of reference materials was obtained, which confirmed the effectiveness of this method.     

Statistical mechanics of thermal diffusion

Expressions of the flows of atoms A and B of a binary system in a crystal are derived as the response to the imposed gradients of temperature and chemical potentials. The formulation is done using the pair approximation of the Path Probability Method of irreversible statistical mechanics and atomic migration is assumed to be via the vacancy mechanism. The energy carried by photons (and electrons) under the temperature gradient is assumed to be independent of the atomic flux. For the case near equilibrium, linear relations are derived among the atomic fluxes, the energy flux (associated with atomic flux) and the gradients. The Onsager reciprocal relations are proved to hold among the coefficients, including those related to energy flows. The heat of transport (energy carried by a diffusing atom) and the heat conduction due to atomic flux are thus unambigously derived.     

Fluorination of carbinols with 2,2-difluoro-1,3-dimethylimidazolidine in ionic liquid

The utility of ionic liquids for fluorination using 2,2-difluoro-1,3-dimethylimidazolidine (DFI) is described. Further, the fluorination of chiral epoxyalcohols gave the chiral monofluoromethylated epoxides.