Synthesis and characterization of bioplastic curdlan esters with an introduced flexible carboxylic acid side chain.

Curdlan, a linear ß-1,3-glucan, was reacted with glutaric anhydride and heptanoyl chloride to afford thermoplastic curdlan esters (CrdE(HepGlu)) with a carboxylic acid side chain. CrdE(HepGlu) with a degree of substitution of the glutaric acid monoester moiety (DSGlu) in the range of 0-0.58 and that of the heptanoate moiety (DSHep = 3 - DSGlu) was prepared. The esterification of the hydroxy groups in the glucan skeleton effectively caused the cleavage of the interchain hydrogen bonds of curdlan and enhanced the formability of CrdE(HepGlu). Moreover, the flexible carboxylic acid side chain moderately affected hydrogen bonding. Thus, the glass transition temperature of CrdE(HepGlu), estimated by differential scanning calorimetry, increased with increasing DSGlu. CrdE(HepGlu) with DSGlu between 0 and 0.58 displayed high solubility in organic solvents and thermoplasticity, enabling the formation of homogeneous and free-standing films by solution casting. The mechanical properties of CrdE(HepGlu) films were evaluated by a stress-strain test, which showed that Young's modulus and the maximum stress increased with increasing DSGlu. CrdE(HepGlu) exhibited higher mechanical strength than non-hydrogen-bonded curdlan triheptanoate and hydrogen-bonded curdlan alkylcarbamates, with thermal stability comparable to that of thermally stable curdlan esters. In addition, these properties can be regulated by controlling DSGlu.

Characteristic terahertz absorption spectra of paramylon and paramylon-ester compounds.

Paramylon is a long-chain polysaccharide, composed of glucose units connected via ß-(1,3) glycosidic bonds, that spontaneously forms a three-strand helical bundle. Paramylon-esters can be made by partially or fully replacing saccharide chain hydroxide groups with carboxylic functional groups, such as stearoyl (CH3(CH2)16CO) and palmitoyl (CH3(CH2)24CO). The paramylon-ester with carboxylic acids has superior characteristics, including high thermal resistance, stability and transparency under visible light, which are necessary for thermoplastic applications. In this study, the absorption coefficient α(ν) and absorbance spectra of paramylons and paramylon-esters were measured in the 0.3-8.0 THz range and compared with the corresponding spectra of glucose and cellulose. Paramylon and paramylon-ester molecules were found to exhibit unique, so-called fingerprint, α(ν)peaks at 4.0, 6.0 and 8.0 THz, and 2.5 and 5.0 THz, respectively. We speculate that the spectral features observed are owing to intermolecular interaction modes of the weakly coupled polysaccharide chains. The paramylons with different molecular weights show very similar absorption features in the low-frequency side, both in spectral shapes and intensities, indicating that absorption is independent of molecular size. The paramylon-esters with varying degrees of substitution (DS) are similar spectral shapes but different intensities. A linear correlation between α(ν) peak intensity and the DS of paramylon-esters was established with the R2 value above 0.99. This behavior can be used for the detection and identification of novel paramylon-ester molecules.

Molecular vibration and Boson peak analysis of glucose polymers and ester via terahertz spectroscopy.

Complex permittivity spectra were obtained herein by performing broadband terahertz (THz) spectroscopy on cellulose, paramylon, and paramylon ester. Absorption peaks observed for cellulose and paramylon at approximately 3 THz are attributed to hydrogen bonds. In addition, a broad absorption peak around 2 THz was observed for all the polymers, demonstrating a general feature of polymer glasses derived from weak interatomic van der Waals forces. The boson peak was observed for cellulose and paramylon ester. The boson peak frequency for cellulose nearly equaled that for glassy glucose-a unit structure of the cellulose polymer. Additionally, the insensitivity of cellulose to the polymerization degree was consistent with recent results obtained via molecular dynamics simulations. In contrast, the boson peak frequency of paramylon ester was markedly smaller than that of cellulose. These results demonstrate the importance of hydrogen bonds as determinants of the boson peak frequency.

Conjugated Polymer Blend Microspheres for Efficient, Long-Range Light Energy Transfer.

Highly luminescent π-conjugated polymeric microspheres were fabricated through self-assembly of energy-donating and energy-accepting polymers and their blends. To avoid macroscopic phase separation, the nucleation time and growth rate of each polymer in the solution were properly adjusted. Photoluminescence (PL) studies showed that efficient donor-to-acceptor energy transfer takes place inside the microspheres, revealing that two polymers are well-blended in the microspheres. Focused laser irradiation of a single microsphere excites whispering gallery modes (WGMs), where PL generated inside the sphere is confined and resonates. The wavelengths of the PL lines are finely tuned by changing the blending ratio, accompanying the systematic yellow-to-red color change. Furthermore, when several microspheres are coupled linearly, the confined PL propagates the microspheres through the contact point, and a cascade-like process converts the PL color while maintaining the WGM characteristics. The self-assembly strategy for the formation of polymeric nano- to microstructures with highly miscible polymer blends will be advantageous for optoelectronic and photonic device applications.

Thermal conversion of alkaline lignin and its structured derivatives to porous carbonized materials.

Alkaline lignin was thermally converted to microporous carbon in ca. 50% yield by heating up from room temperature to 900°C without activation process under flowing of an argon gas. The carbonized material prepared by heating up conditions of 1°C min(-1) showed 530 m(2)/g of the Brunauer-Emmett-Teller (BET) specific surface area, which increased to 740 m(2)/g after washing with water. Furthermore, alkaline lignin derivatives were structured as micron scale particles by micelle formation and polymer gelation techniques. Carbonization of the structured lignins could afford high porous materials having BET surface areas above 1000 m(2)/g without surface activation processes.

A new series of luminescent phosphine stabilised platinum ethynyl complexes.

A series of cis-platinum ethynyl complexes with the general formula cis-[Pt(dppe)(C[triple bond]CR)2](dppe = 1,2-bis(diphenylphosphino)ethane; R = C6H4-p-NO2 1, C6H4-p-CH3 2, C6H4-p-C[triple bond]CH 3 and C6H4-p-C6H4-p-C[triple bond]CH 4) have been prepared by the coupling reaction of cis-[Pt(dppe)Cl2] with two equivalents of the appropriate alkyne. The new complexes have been fully characterized by spectroscopic techniques, and the cis square planar arrangement at the platinum centre has been confirmed by single-crystal X-ray diffraction studies of complexes 1, 2 and 4. The absorption spectra of the complexes 1-4 are dominated by a pi-->pi* band that contains some platinum (n + 1) p orbital character. The position of the band is dependent on the electron donating or withdrawing properties of the ethynyl substituents, R. Complex 1 displays a triplet emission in the green, at room temperature, while complexes 2-4, display singlet emissions in the blue. Again, the difference can be attributed to the nature of the R substituents.

Reduction of Pt usage in fuel cell electrocatalysts with carbon nanotube electrodes.

The 12 wt% Pt-deposited carbon nanotube electrode gives 10% higher voltages than 29 wt% Pt-deposited carbon black and reduces the Pt usage by 60% in polymer electrolyte fuel cells with hydrogen and oxygen.