Synthesis of copolymers containing a spiro orthocarbonate moiety and evaluation of the volume change during their cationic crosslinking

Spiro orthocarbonate (SOC) monomers having either an exomethylene group {3,3‐dimethyl‐9‐methylene‐1,5,7,11‐tetraoxaspiro[5.5]undecane (ExoSOC)} or an allyl group {9‐allyl‐3,3‐dimethyl‐1,5,7,11‐tetraoxaspiro[5.5]undecane (AllylSOC)} were radically copolymerized with vinyl monomers at several feed ratios to obtain the corresponding copolymers having SOC moieties in the side chain. The obtained copolymers were crosslinked via the double ring‐opening polymerization of the SOC moieties by a treatment with boron trifluoride etherate. The volume changes during the crosslinking of the copolymers were evaluated by density measurements with a gas pycnometer. As the SOC moiety composition increased, the volume shrinkage during the crosslinking was suppressed, and that finally changed into volume expansion. The volume changes during the crosslinking of the copolymers from AllylSOC were slightly larger than those of the copolymers from ExoSOC. The higher volume expansions in the crosslinking of AllylSOC‐based copolymers were ascribable to the lower steric hindrance around the SOC moieties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7040–7053, 2006     

Preparation and certification of the new reference materials; plastics (disk form, JSAC 0621-0625) for determination of mercury using x-ray fluorescent analysis.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.     

A generalization of the weighted Strichartz estimates for wave equations and an application to self‐similar solutions

Weighted Strichartz estimates with homogeneous weights with critical exponents are proved for the wave equation without a support restriction on the forcing term. The method of proof is based on expansion by spherical harmonics and on the Sobolev space over the unit sphere, by which the required estimates are reduced to the radial case. As an application of the weighted Strichartz estimates, the existence and uniqueness of self‐similar solutions to nonlinear wave equations are proved on up to five space dimensions. © 2006 Wiley Periodicals, Inc.     

A generalization of the katona theorem for crosst-intersecting families

LetX be ann-element set and letA and? be families of subsets ofX. We say thatA and? are crosst-intersecting if |A ∩ B| ≥ t holds for all A ∈A and for allB ∈ ?. Suppose thatA and ? are crosst-intersecting. This paper first proves a crosst-intersecting version of Harper's Theorem:

1. There are two crosst-intersecting Hamming spheresA ₀,? ₀ with centerX such that |A| ≤ |A ₀| and|?| ≤ |? ₀| hold.
2. Suppose thatt ≥ 2 and that the pair of integers (|A) is maximal with respect to direct product ordering among pairs of crosst-intersecting families. Then,A and? are Hamming spheres with centerX.

Using these claims, the following conjecture of Frankl is proven:

1. Ifn + t = 2k ? 1 then |A| |?| ≤ max \(\left\{ {\left( {K_k^n + \left( {_{k - 1}^{n - 1} } \right)} \right)^2 ,K_k^n K_{k - 1}^n } \right\}\) holds, whereK _l ⁿ is defined as \(\left( {_n^n } \right)\left( {_{n - 1}^n } \right) + \cdots + \left( {_l^n } \right).\)
2. Ifn + t = 2k then |A| |? ≤ (K _k ⁿ )² holds.

The extremal configurations are also determined.     

Tetrakis-acridinyl peptide: a novel fluorometric reagent for nucleic acid analysis based on the fluorescence dequenching upon DNA binding

Tetrakis-acridinyl peptide 1 assuming a right-handed helical stacked conformation of the acridinyl units can bind to DNA duplex with a very high affinity of 10(8) (M-bp)(-1) even at a high salt concentration of 0.2 M NaCl, irrespective of the base composition. Peptide 1 gave rise to 1600-times enhancement of its fluorescence upon binding to an AT polymer due to the collapse of this stacked structure, but the fluorescence is not enhanced with a GC polymer, though the binding constants of 1 for both polymers were the same.     

HPLC determination of (+)-pseudoephedrine and (-)-ephedrine in Japanese herbal medicines containing Ephedra herb using solid-phase extraction

We developed a rapid and simple HPLC method combined with solid-phase extraction (SPE) for quantitative analysis of (+)-pseudoephedrine (PEP) and (-)-ephedrine (EP) in Japanese herbal (Kampo) medicines such as Kakkon-to, Sho-seiryu-to, Goshaku-san and Bofu-tsusho-san. SPE was performed on TOYOPAK IC-SP M containing propylsulfonic groups. Determination of PEP and EP was carried out using ion-pair reversed-phase HPLC with sodium dodecyl sulfate. N-Benzyldiethylamine was used as an internal standard. The analytical procedure was validated with regard to specificity, linearity, accuracy, and precision. These data suggest that the analytical method developed in this study is useful for quantitative analysis of PEP and EP in various formulations of Kampo medicine containing Ephedra herb.     

Analysis of dielectric relaxations of w/o emulsions in the light of theories of interfacial polarization

An attempt is made to apply dielectric theories of interfacial polarization to observations of dielectric relaxations for W/O emulsions. Approximate formulas for disperse systems in a W/O type were derived from the two theories: one proposed by Maxwell and Wagner for dilute disperse systems of spherical particles, and the other developed by Hanai for concentrated disperse systems. Dielectric measurements were carried out on concentrated W/O emulsions prepared from kerosene and distilled water or KCl aqueous solutions by minimal use of emulsifiers. Marked dielectric relaxations were observed with the emulsions, the dielectric parameters having been determined to characterize the relaxation data. Phase parameters such as relative permittivity, electric conductivity and volume fraction of the disperse phase were evaluated from the dielectric parameters by use of the approximate formulas of the respective theories. The phase parameters evaluated and the frequency dependence of complex permittivity of the W/O emulsions deduced from the theory for concentrated disperse systems are in excellent agreement with the observed data in comparison to that for dilute disperse systems. It is concluded that the dielectric relaxations due to the interfacial polarization of disperse systems of spheres are explained satisfactorily by the theory for concentrated disperse systems.