Solution properties of celluloses from different biological origins in LiCl · DMAc

Differences in the solution properties of cellulose in 8%LiCl·DMAc (dimethyl acetamide) were investigated usingcelluloses from different origins. The latter included plants (dissolving pulp(DP), cotton linters (CC), and kraft pulp), bacteria (Acetobacterxylinum, BC), and marine animals (tunicin fromHalocynthia). The celluloses from plants and bacteriaformed LiCl·DMAc solutions that were isotropic andanisotropic, respectively; and the animal cellulose was insoluble. The weightaverage molecular weights, M_w, of DP, CC and BC were found to be98.2×10⁴,170×10⁴ and192×10⁴, respectively. The solutionviscositieswere proportional to c (c; polymer concentration) in thedilute and semi-dilute regions, where the exponent was 1 for allsamplesin the dilute region; in the semi-dilute region, it was 4 for the DP and CCsolutions and 3 for the BC solution. Molecular weight differences werecompensated by plotting the viscosity against cM_w orc[] (where [] is the limiting viscosity number).The difference in viscosity behavior at elevated solutionconcentration indicates that the cellulose molecules from DP and CC behave asflexible polymer chains and those of BC as rod-like ones.These results suggest that differences in molecular structure andproperties exist between celluloses from different sources, and that thesedifferences relate to the mechanism or the type of the intermolecularinteraction between the celluloses of plants (DP and CC) and those of bacteria(BC).     

A new pentanorlanostane derivative, cladosporide A, as a characteristic antifungal agent against Aspergillus fumigatus, isolated from Cladosporium sp

In the course of searching for new antifungal agents, a new pentanorlanostane derivative, cladosporide A (1), was isolated along with ergosterol, ergosterol peroxide and 23,24,25,26,27-pentanorlanost-8-ene-3beta,22-diol (2) from Cladosporium sp. as a characteristic antifungal agent against the human pathogenic filamentous fungus Aspergillus fumigatus. The structure of 1 was established as 3beta,22-dihydroxy-23,24,25,26,27-pentanorlanostane-29-al by spectroscopic and chemical investigation and X-ray crystallographic analysis. Inhibitory activity against A. fumigatus (IC80 0.5-4.0 microg/ml) was observed for cladosporide A (1), but no activity was observed against pathogenic yeasts, Candida albicans and Cryptococcus neoformans, and other pathogenic filamentous fungi, Aspergillus niger and A. flavus. The 4beta-aldehyde residue in 1 might be essential for the antifungal activity, since 23,24,25,26,27-pentanorlanost-8-ene-3beta,22-diol (2) showed no inhibition against the above four fungi.     

TPR studies on steam reforming of 2-propanol on Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3

Reaction pathways for steam reforming of 2-propanol (isopropyl alcohol, IPA) on Rh/Al₂O₃, Ru/Al₂O₃ and Pd/Al₂O₃ have been studied by temperature-programmed reactions (TPRs) of IPA and acetone in the presence of steam. The results of TPRs suggest that that of IPA on Rh/Al₂O₃ and Ru/Al₂O₃ proceeds via acetone, while the steam reforming of IPA on Pd/Al₂O₃ takes place via propene from acetone. This revised version was published online in August 2006 with corrections to the Cover Date.     

Aerobic oxidative dehydrogenation of coordinated imidazoline units of pincer ruthenium complex

A new pincer ruthenium complex (1; [RuL¹(tpy)](PF₆); L¹ = 1,3-di(2-imidazoline-2-yl)benzene, tpy = 2,2′:6′,2″-terpyridine) having a κ³NCN pincer ligand with two imidazoline units and related ruthenium complexes were synthesized and characterized. The imidazoline units of 1 were oxidized in air to give an imidazole-ligated pincer complex (2; [RuL²(tpy)](PF₆); L² = 1,3-di(2-imidazolyl)benzene). Results of the ¹H NMR spectroscopic and cyclic voltammetric studies of the complexes indicate that the σ-donor character of the pincer ligand of 1 induces the Ru-promoted oxidative dehydrogenation of coordinated imidazoline moieties to imidazole units with oxygen in air.     

High Ionic Conductivity of Transparent Film of Hydroxyapatite and Poly(vinyl alcohol) Nanocomposite

Summary: Hydroxyapatite (HAp)-polyvinyl alcohol (PVA) nanocomposite film containing Li⁺ was designed as a solid polymer electrolyte. A composite was prepared by reacting Ca(OH)₂ with H₃PO₄ in the presence of PVA which is denatured in order to have the carboxyl group, and a LiN(CF₃SO₂)₂ was added. HAp particles were commonly formed in the shape of spindles (long axis ca. 80 nm and short axis ca. 25 nm). The obtained nanocomposite film, in which HAp particles were dispersed uniformly, is transparent, flexible and drawable. Its ionic conductivity is about 10⁻³ S/m at room temperature. This value is very large. This high ionic conductivity is considerable on the basis of the dynamic percolation theory.     

Deformation of a tensile membrane adjacent to a moving wall caused by viscous flow

Theoretical analysis is done for deformation of a tensile membrane caused by viscous flow between the membrane and a solid boundary (wafer) placed adjacent to the membrane. The membrane and its support are assumed to have circular shapes. The boundary is assumed to move perpendicularly to the membrane by a small fraction of the gap width. The Hele–Shaw flow theory is applied to the flow. Variation of the central gap width is obtained, and it is shown that the maximum membrane deformation depends on the membrane tension and the final gap width. The dependence agrees with experimental results.     

Pulsed Power Applications for Protein Conformational Change and the Permeabilization of Agricultural Products

Pulsed electric fields (PEFs), which are generated by pulsed power technologies, are being tested for their applicability in food processing through protein conformational change and the poration of cell membranes. In this article, enzyme activity change and the permeabilization of agricultural products using pulsed power technologies are reviewed as novel, nonthermal food processes. Compact pulsed power systems have been developed with repetitive operation and moderate output power for application in food processing. Firstly, the compact pulsed power systems for the enzyme activity change and permeabilization are outlined. Exposure to electric fields affects hydrogen bonds in the secondary and tertiary structures of proteins; as a result, the protein conformation is induced to be changed. The conformational change induces an activity change in enzymes such as α-amylase and peroxidase. Secondly, the conformational change in proteins and the induced protein functional change are reviewed. The permeabilization of agricultural products is caused through the poration of cell membranes by applying PEFs produced by pulsed discharges. The permeabilization of cell membranes can be used for the extraction of nutrients and health-promoting agents such as polyphenols and vitamins. The electrical poration can also be used as a pre-treatment for food drying and blanching processes. Finally, the permeabilization of cell membranes and its applications in food processing are reviewed.     

Fabrication of Highly Spherical Millimeter‐Sized Poly(amic acid) Capsules by Removing Non‐Volatile Solvent

Millimeter‐sized highly spherical poly(amic acid) (PAA) capsules were prepared by curing an emulsion containing non‐volatile N,N‐dimethylacetamide (DMAc). Although the sphericity of the capsules (>99%) obtained by the emulsion method was slightly lower than that of corresponding polystyrene capsules, their surface was smooth. The curing conditions to achieve the highest degree of sphericity require stabilization and deformation, which were governed by parameters, such as PAA concentration, the viscosity of the emulsion matrix, stirring speed, and temperature.     

Effect of zinc salts on the spontaneous copolymerization of 4-vinylpyridine with various electron-rich vinyl monomers

The spontaneous copolymerization of 4-vinylpyridine (4-VP) complexed with three different zinc salts (chloride, acetate, and triflate) with various electron-rich vinyl monomers (p-methoxystyrene, MeOSt; p-methylstyrene, MeSt; α-methylstyrene, α-MeSt; p-tert-butylstyrene, BuSt; styrene, St) was investigated in methanol at 75°C. Increasing the zinc salt concentration or the nucleophilicity of the electron-rich monomer increased the copolymer yields. All obtained copolymers are characterized by high molecular weight (10⁵) and broad molecular weight distribution. Both ¹H-NMR and elemental analyses confirmed the almost 1 : 1 copolymer structure. Changing the anion of the zinc salt does not have a considerable effect either on the copolymerization rate or on the molecular weight. The proposed mechanism exhibits the formation of a σ-bond between the β-carbons of the two donor–acceptor monomers. This creates the 1,4-tetramethylene biradical intermediate which can initiate the copolymerization reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2787–2792, 1997