pH-controlled uphill transport of ammonium ions through polymer membranes with sulfonic acid groups

Uphill transport of ammonium ions through a membrane with sulfonic acid groups were investigated with pH-controllers which keep the solution at a constant pH. A membrane with sulfonic acid groups was prepared by casting an aqueous solution containing poly(styrenesulfonic acid) and poly(vinyl alcohol) on a glass plate. When a membrane with one side alkaline and the other acidic was fixed as a diaphragm in a cell, ammonium ions were transported from the alkaline side to the acidic side through the membrane against the concentration gradient of the adjacent solutions. Uphill transport of ammonium ions with pH-controllers was more efficient than without, thus keeping the pH difference between both sides of the membrane constant, which is a driving force for the uphill transport. Furthermore, the effect of pH of the acidic side on the uphill transport was investigated and the mechanism of the pH-controlled uphill transport is discussed.     

Synthesis of functional π-conjugated polymers from aromatic acetylenes

Because of their unique structures and properties, π-conjugated polymers have attracted the attention of scientists and engineers. The authors have studied the synthesis of two kinds of π-conjugated poly(aromatic acetylene)s, i.e. poly(arylacetylene)s and poly(aryleneethynylene)s with the aim of obtaining new polymers having novel functions or higher performances. This review mainly concerns the authors' results, as follows: first, we describe the synthesis and properties of achiral poly(arylacetylene)s, containing trimethylsilyl groups, oligodimethylsiloxanyl groups, dendritic groups, and glavinoxyl groups, for application as oxygen permselective membrane materials. Their self-membrane-forming abilities and high oxygen permeabilities are presented. Second, the synthesis by asymmetric-induced polymerization of chiral poly(arylacetylene)s having both a main-chain chirality and chiral pendant groups and their application as optical resolution membranes are described. Third, two new synthetic methods for preparing chiral helical poly(phenylacetylene)s without the coexistence of any other chiral moieties are presented. One is helix-sense-selective addition polymerization and the other is in situ removal of chiral pendant groups from membranes of poly(arylacetylene)s that also contain a main-chain chirality. The chiral helical poly(arylacetylene)s were tested as optical resolution membranes. The chiral and achiral poly(arylacetylene)s were synthesized by addition polymerization using metathesis catalysts or rhodium complexes. Finally, the synthesis of regiospecific poly(aryleneethynylene)s bearing stable radicals by the polycondensation of bromoethynylanthracene derivatives using a Pd(0) complex is described. The magnetization and the static magnetic susceptibility of the polyradicals are explained.     

Low-Temperature Synthesis of ZrC Powder by Cyclic Reaction of Mg in ZrO2–Mg–CH4

We investigated the conditions for low-temperature synthesis of ZrC fine powder from ZrO₂–Mg–CH₄. The synthesis utilizes a thermite-type reaction, with Mg as the reducing agent, and a reaction between Mg and CH₄ gas as a carbon source. The Mg/ZrO₂ molar ratio as well as the heating rate were varied. Because C can be continuously fed into the reaction group by the cyclic reaction of Mg through the formation and decomposition of Mg₂C₃ (2Mg + 3CH₄→ Mg₂C₃+ 6H₂→ 2Mg + 3C), a molar ratio of 2.2 for Mg/ZrO₂ was sufficient for the synthesis of single-phase ZrC. ZrC powders were synthesized under the following conditions: Mg/ZrO₂ molar ratio = 2.2, heating rate = 20°C/min, and temperature maintained at 750°C for 30 min. The amount of reaction heat produced in the reduction reaction of ZrO₂ by Mg depended on the Mg/ZrO₂ molar ratio, specifically, the amount of ZrO₂ contained. Moreover, the cyclic reaction of Mg-Mg₂C₃–Mg was influenced by the amount of reaction heat described above and by the heating rate. The ZrC fine powder showed little aggregation and high dispersibility.     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Double organic modification by 3‐chloropropyl and methyl groups on pure silica MCM‐41 and Ti‐MCM‐41: efficient catalyst for epoxidation of cyclododecene

Simultaneous surface modification by 3‐chloropropyl and methyl groups on the same Si atoms resulted in hydrophobic and highly ordered mesoporous silica with a very high surface area. ¹³C and ²⁹Si MAS NMR spectra indicate homogeneous grafting of chloropropyl and methyl groups in the silica matrix and this organically modified Ti‐MCM‐41 shows outstanding catalytic performance in the epoxidation of cyclododecene using tert‐butyl hydroperoxide as oxidant. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.     

Synthesis and Magneto-mechanical Properties of Ce-TZP/La M-Type Hexaferrite Composite

An in situ composite composed of ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP) and La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was synthesized from a powder mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO. The dense Ce-TZP dispersed with platelike La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ crystals as a second phase were formed after sintering from 1250° to 1350°C. The saturation magnetization of the in situ composite Ce-TZP/La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was proportional to the mass fraction of the hexaferrite second phase in Ce-TZP. The coercivity of the composite with a 20 mass% of second phase decreased from 9.14 to 2.52 kOe (from 728 to 201 kA/m) after the pulverization of the composite. The susceptibility (χ) increased by 15%–25% under uniaxial stress on the composite. The change of the susceptibility (Δχ/χ) value increased with decreasing the mass fraction of the second phase in the composite. The Δχ was found to increase linearly with applied stress and abruptly change on cracking, which is expected for the application in fracture sensing of the composite.     

Decomposition of Carbon Dioxide to Carbon with Active Wustite at 300°C

Active wustite (FeδO, with a δ value of 0.98) was prepared by keeping normal wustite (δ value of 0.94) in a N₂ atmosphere at 300°C for 10 min. This reaction is given by (4δ₂–3)Fe_δ1O→(4δ₁–3)Fe_δ2O + (δ₂–δ₁)Fe₃O₄ where δ₁= 0.94 and δ₂= 0.98. The equation indicates that the normal wustite undergoes eutectoid decomposition into active wustite and stoichiometric magnetite (Fe₃O₄). Carbon dioxide (1.013 × 10⁵ Pa) was almost completely (100%) decomposed into carbon (zero valence) by the active wustite at the low temperature of 300°C, which was associated with the transformation of the active wustite into the stoichiometric magnetite. The internal pressure of the reaction cell eventually became a vacuum.     

Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.