Radical copolymerization of N-alkylmaleimides with isobutene and the properties of the resulting alternating copolymers

Radical copolymerization of N-methylmaleimide (MeMI) as well as other N-alkylmaleimides (RMI) and isobutene (IB) was carried out with 2,2′-azobis(isobutyronitrile) as an initiator at 60°C. The initial rate of the copolymerization (R_p) was dependent on the monomer composition and was maximum at the 40 mol % of MeMI in the feed. A solvent effect on the R_p and the monomer reactivity ratio was observed in this copolymerization system, i.e., copolymerization in chloroform produced a higher R_p and an alternating tendency compared with those in dioxane (r_MeMI = 0.14, r_1B = 0 in chloroform and r_MeMI = 0.47, r_1B = 0 in dioxane). The alternating copolymer of RMI and IB shows a high glass transition temperature (T_g) and excellent thermal stability, e.g., the T_g and the thermal decomposition temperature (T_d) were 152 and 363°C, respectively, for the alternating copolymer of MeMI and IB. Both the T_g and T_d increased as the concentration of the MeMI unit in the copolymers increased. Colorless transparent sheets were obtained from press molding the alternating copolymers. They showed excellent mechanical and optical properties. © 1996 John Wiley & Sons, Inc.     

Syntheses and radical polymerizations of novel optically active vinyl and isopropenyl carbamates having L-leucine structures

Syntheses and radical polymerizations of vinyl and isopropenyl carbamates having L -leucine methyl ester structures, N-vinyloxycarbonyl-L -leucine methyl ester (VOC-L-M) and N-isopropenyloxycarbonyl-L -leucine methyl ester (IOC-L-M), were carried out. VOC-L-M and IOC-L-M were prepared by the reactions of L -leucine methyl ester with vinyl and isopropenyl chloroformates in the presence of sodium hydrogen carbonate. The radical polymerization of VOC-L-M with AIBN (1 mol %) in bulk, chlorobenzene, methanol, and N,N-dimethylformamide afforded the corresponding polymer (poly(VOC-L-M)) with M _n 7,400–19,000. Meanwhile, IOC-L-M afforded no polymer with AIBN at 60°C but afforded a polymer having low molecular weight with BPO at 80°C. The glass transition temperatures of poly(VOC-L-M) and poly(IOC-L-M) were 53 and 65°C, respectively. The 10% weight loss temperatures of poly(VOC-L-M) and poly(IOC-L-M) under nitrogen were 255 and 173, respectively. The copolymerization parameters of VOC-L-M (M₁) and vinyl acetate (M₂) were evaluated as r₁ = 0.92 and r₂ = 0.63. © 1996 John Wiley & Sons, Inc.     

The number of labeled graphs placeable by a given permutation

Let S be a finite set and σ a permutation on S. The permutation σ* on the set of 2-subsets of S is naturally induced by σ. Suppose G is a graph and V(G), E(G) are the vertex set, the edge set, respectively. Let V(G) = S. If E(G) and σ*(E(G)), the image of E(G) by σ*, have no common element, then G is said to be placeable by σ. This notion is generalized as follows. If any two sets of {E(G), (σ¹)*(E(G)),…,(σ^l−1)* (E(G))} have no common element, then G is said to be I-placeable by σ. In this paper, we count the number of labeled graphs which are I-placeable by a given permutation. At first, we introduce the interspaced Ith Fibonacci and Lucas numbers. When I = 2 these numbers are the ordinary Fibonacci and Lucas numbers. It is known that the Fibonacci and Lucas numbers are rounded powers. We show that the interspaced Ith Fibonacci and Lucas numbers are also rounded powers when I = 3. Next, we show the number of labeled graphs which are I-placeable by a given permutation is a product of the interspaced Ith Lucas numbers. Finally, using a property of the generalized binomial series, we count the number of labeled graphs of size k which are I-placeable by σ. © 1996 John Wiley & Sons, Inc.     

1H and 13C NMR assignments for two new angular furanocoumarin glycosides from Peucedanum praeruptorum

Two novel angular-type furanocoumarin glycosides, peucedanoside A (1) and peucedanoside B (2), along with a known compound apterin (3), were isolated from the roots of Peucedanum praeruptorum Dunn. Their chemical structures were determined by MS, NMR spectroscopy and chemical analysis. Complete assignments of the 1H and 13C NMR spectroscopic data were achieved by 1D and 2D NMR experiments including DEPT, HSQC, HMBC and ROESY.     

Does B3LYP correctly describe magnetism of manganese complexes with various oxidation numbers and various structural motifs?

We assessed the applicability and basis set dependency of the B3LYP functional to investigate magnetic interactions of Mn complexes. For the purpose, we constructed a test set consisting of 16 Mn complexes with various oxidation states and structural motifs.The B3LYP results correctly reproduced magnetism and magneto–redox correlation of the standard μ-oxo motifs with superexchange paths, while it does not work for weak magnetic complexes. We also showed that a modest basis set yields results similar to those of triple-zeta plus diffuse-and-polarization functions. This basis set is expected to be a standard basis set for investigating magnetism of manganese complexes.     

A sensitive and selective determination method of histamine by HPLC with intramolecular excimer-forming derivatization and fluorescence detection

A highly sensitive, selective and simple method is described for the determination of histamine by high-performance liquid chromatography (HPLC) with fluorescence detection. The method is based on an intramolecular excimer-forming fluorescence derivatization of histamine with 4-(1-pyrene)butyric acid N-hydroxysuccinimide ester (PSE), followed by reversed-phase HPLC. Histamine, having two amino moieties in a molecule, was converted to the dipyrene-labeled derivative by reaction with PSE. The derivative afforded intramolecular excimer fluorescence (450-540 nm), which can clearly be discriminated from the monomer fluorescence (370-420 nm) emitted from PSE. Typically, a 10 micro L sample solution was mixed with 100 micro L of derivatization reagent solution, which was a mixture of 0.5 mm PSE in acetonitrile and 0.5 mm potassium carbonate in water (8:2, v/v). The derivatization was carried out at 100 degrees C for 90 min. The PSE derivative of histamine could be separated by reversed-phase ODS column with isocratic elution using acetonitrile:water (82:18, v/v) containing 0.03% triethylamine. The detection limit (singnal-to-noise ratio = 3) of histamine was 0.5 fmol for a 30 micro L injection. The method was successfully applied to the determination of histamine in human urine, and had enough selectivity and sensitivity for urinary histamine quantification.     

Removal of phosphate by aluminum oxide hydroxide

The development and manufacture of an adsorbent to remove phosphate ion for the prevention of eutrophication in lakes are very important. The characteristics of phosphate adsorption onto aluminum oxide hydroxide were investigated to estimate the adsorption isotherms, the rate of adsorption, and the selectivity of adsorption. Phosphate was easily adsorbed onto aluminum oxide hydroxide, because of the hydroxyl groups. The adsorption of phosphate onto aluminum oxide hydroxide was influenced by pH in solution: the amount adsorbed was greatest at pH 4, ranging with pH from 2 to 9. The optimum pH for phosphate removal by aluminum oxide hydroxide is 4. The selectivity of phosphate adsorption onto aluminum oxide hydroxide was evaluated based on the amount of phosphate ion adsorbed onto aluminum oxide hydroxide from several anion complex solutions. It is phosphate that aluminum oxide hydroxide can selectively adsorb. The selectivity of phosphate onto aluminum oxide hydroxide was about 7000 times that of chloride. This result indicated that the hydroxyl groups on aluminum oxide hydroxide have selective adsorptivity for phosphate and could be used for the removal of phosphate from seawater.     

Development of a multi‐scale ocean model by using particle Laplacian method for anisotropic mass transfer

The direct injection of CO₂ into the deep ocean is one of the feasible ways for the mitigation of the global warming, although there is a concern about its environmental impact near the injection point. To minimize its biological impact, it is necessary to make CO₂ disperse as quickly as possible, and it is said that injection with a pipe towed by a moving ship is effective for this purpose. Because the injection ship moves over a spatial scale of O(10²km), a mesoscale model is necessary to analyse the dispersion of CO₂. At the same time, since it is important to investigate high CO₂ concentration near the injection point, a small‐scale model is also required. Therefore, in this study, a numerical model was developed to analyse CO₂ dispersion in the deep ocean by using a fixed mesoscale and a moving small‐scale grid systems, the latter of which is nested and moves in the former along the trajectory of the moving ship. To overcome the artificial diffusion of mass concentration at the interface of the two different grid systems and to keep its spatial accuracy almost the same as that in the small‐scale, a particle Laplacian method was adopted and newly modified for anisotropic diffusion in the ocean. Copyright © 2010 John Wiley & Sons, Ltd.     

Ultrasonic irradiation effect in the quenched benzene

On slow cooling, a precursor phenomenon in supercooled benzene was probed by longitudinal absorption. On quenching, in-situ observation of ultrasonic measurements was carried out at the fixed temperature. Sequence of the transmitted waves was multiple scattered in quenched benzene. The dynamic ultrasound scattering is sensitive to the local strain and dynamic inhomogeneous fluctuations. The quenched benzene shows the maximum value of longitudinal absorption at incubation time, t_inc. Crystal domain growth/coarsening is promoted by the ultrasonic irradiation at t_inc < t. In addition, t_inc depends on the quenching temperature. Ultrasonic irradiation and quenching effects dominate the extraordinal nucleation and growth process of benzene in spite of simple and non-polar molecular liquid.