Protein separation with surfactant-coated polystyrene involving Cibacron Blue 3GA-conjugated triton X-100

Through mixing of porous polystyrene particles (Amberlite XAD-4), non-ionic surfactants, and surfactant-conjugated substrates (affinity ligand) in an aqueous solution led to the formation of a novel medium (affinity admicelle) for protein separation. The ligand (CB-Triton) was synthesized by mixing a triazine dye (Cibacron Blue 3GA (CB)) and a polyoxyethylene-type non-ionic surfactant (Triton X-100) in weakly alkaline solutions. Triton X-100 and CB-Triton were competitively sorbed onto XAD-4. Albumin (bovine serum), alcohol dehydrogenase (yeast), and lysozyme (chicken egg) having specific interaction to CB were collected onto the affinity admicelle. On the other hand, the collection of ovalubmin (chicken egg white), having no binding ability to CB, was negligibly small. Lysozyme in 100 microl of chicken egg white, diluted with 900 microl of 10 mM Tris-HCl (pH 7.4), was successfully collected on 18 mg of CB-Triton admicelles and, then, it was eluted with 1 ml of aqueous solution of 100 mM phosphate (pH 7.4). The recovery based on the activity for the lysis of micrococcus and the concentration factor were 60% and 40 (n = 3), respectively.     

Synthesis of Sequential Polypeptides Containing O‐Phospho‐L‐Serine

The chemistry of phosphoserine [Ser(P)] containing peptides and polypeptides was extensively investigated to explore a new biomineralization material science. The selective cleavage of the O,O′‐diphenyl phospho‐protecting groups of Ser(PO₃Ph₂) was examined using hydrogenolysis catalysts. Among the catalysts examined, only PtO₂ in 50% trifluoroacetic acid (TFA)/AcOH successfully cleaved the protecting group of Ser(PO₃Ph₂) to give Ser(P). Based on these characteristic new findings, Ser(P)‐containing dipeptides such as Gly‐Ser(P), Ala‐Ser(P), Ser‐Ser(P), Asp‐Ser(P), Glu‐Ser(P), and Lys‐Ser(P), and tetrapeptide [Asp‐Ser(P)]₂ were synthesized by a facile method. When we used the Ser(PO₃Ph₂) residues at the C terminals, the amino functional groups of amino acids and peptides can be coupled by the unsymmetric mixed anhydride using isobutyl chloroformate but cannot be by the symmetric anhydride method using dicyclohexylcarbodiimide. Neither unsymmetric mixed anhydride nor symmetric anhydride can be coupled with p‐nitrophenol at their C terminals. High‐molecular‐weight sequential polypeptides containing Ser(P) such as poly[Ser(P)‐Xaa] (Xaa: Gly, Ala, Ser, Lys, Asp, Glu) and poly[Gly‐Ser(P)‐Gly] were first synthesized by the polycondensation of the di‐ and tripeptide p‐nitrophenyl active esters, followed by the quantitative elimination of the diphenyl protecting groups by PtO₂ in TFA/AcOH. The new strategy to synthesize Ser(P)‐containing peptides and model proteins may help the development of hybrid formulations of marine and biomimetic protein minerals.

     

Utilization of agro-resources by radiation treatment -production of animal feed and mushroom from oil palm wastes

The production of animal feeds and mushrooms from oil palm cellulosic wasres by radiation and fermentation has been investigated in order to utilize the agro-resources and to reduce the smoke pollution. The process is as follows: decontamination of microorganisms in fermentation media of empty fruit bunch of oil palm (EFB) by irradiation, inoculation of useful fungi, and subsequently production of proteins and edible mushrooms. The dose of 25 kGy was required for the sterilization of contaminating bacteria whereas the dose of 10 kGy was enough to eliminate the fungi. Among many kinds of fungi tested, C. cinereus and P. sajor-caju were selected as the most suitable microorganism for the fermentation of EFB. The protein content of the product increased to 13 % and the crude fiber content decreased to 20% after 30 days of incubation with C. cinereus at 30°C in solid state fermentation. P. sajor-caju was suitable for the mushroom production on EFB with rice bran.     

Thin-layer chromatography of inorganic lons phosphate on cellulose in acetic acid and in acetic acid-ammonium acetate media

Summary Systematic study for the chromatographic behaviour of 49 inorganic ions has been carried out on cellulose phosphate layer in acetic acid and acetic acid — ammonium acetate media. Feasibilities for the effective separations of analytical interest are demonstrated on the 0.25 mm layer in both media.     

Grafting of polymers onto a carbon‐fiber surface by ligand‐exchange reaction of poly(vinyl ferrocene‐co‐vinyl monomer) with polycondensed aromatic rings of the surface

To improve the surface of carbon fiber, the grafting reaction of copolymer containing vinyl ferrocene (VFE) onto a carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber was investigated. The copolymer containing VFE was prepared by the radical copolymerization of VFE with vinyl monomers, such as methyl methacrylate (MMA) and styrene, using 2,2′‐azobisisobutyronitrile as an initiator. By heating the carbon fiber with poly(VFE‐co‐MMA) (number‐average molecular weight: 2.1 × 10⁴) in the presence of aluminum chloride and aluminum powder, the copolymer was grafted onto the surface. The percentage of grafting reached 46.1%. On the contrary, in the absence of aluminum chloride, no grafting of the copolymer was observed. Therefore, it is considered that the copolymer was grafted onto the carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber. The molar number of grafted polymer chain on the carbon‐fiber surface decreased with increasing molecular weight of poly(VFE‐co‐MMA) because the steric hindrance of grafted copolymer on the carbon‐fiber surface increases with increasing molecular weight of poly(VFE‐co‐MMA). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1868–1875, 2002     

Simplified evaluation of214Bi/238U activity ratios in fossil bones using non-destructive activation analysis

A simple and reliable method has been developed for the evaluation of radioactive disequilibrium state in fossil bones. The fossil bone samples were irradiated with an extremely low neutron fluence, together with a standard pitchblende prevailing the secular equilibrium among the uranium series. The²³⁹Np activity induced from²³⁸U in both samples were adjusted to be gamma-ray spectrometrically nearly equivalent to the naturally occurring radioactivities by controlling the neutron flux and cooling time. Using single gamma-ray spectrometry of the irradiated samples, the determination of²¹⁴Bi/²³⁸U in a fossil bone was carried out by comparing the photopeak ratios of²¹⁴Bi /609 keV/ and²³⁹Np /278 keV/ instead of²³⁸U with the same ratios from the pitchblende standard sample.     

Penicillin-cephalosporin conversion IV. Direct synthesis of 3'-thiosubstituted cephalosporins from thiazoline-azetidinones

Direct transformation of thiazoline-azetidinones $\text{2}$, derived from penicillin G and V, into 3′-thio-substituted cephalosporins $\text{4}$ has been performed by ring opening of the thiazoline moiety with sulfenyl chlorides followed by ring closure with NH₃ in dimethylformamide and simultaneous displacement of the allylic chlorine atom with the leaving thiolates.     

Biphenylene-substituted ruthenocenylphosphine for Suzuki-Miyaura coupling of aryl chlorides

High activity in the palladium-catalyzed Suzuki-Miyaura reactions of aryl chlorides with arylboronic acids was furnished using biphenylene-substituted di- tert-butylruthenocenylphosphine (R-Phos) as a supporting ligand. Substrate combinations even for the construction of highly hindered tetra- ortho-substituted biaryls can be achieved in good to excellent yields with low catalyst loadings in short reaction times.     

Pressure-induced superconductivity in noncentrosymmetric heavy-fermion CeRhSi3

We report the pressure-induced superconductivity in the noncentrosymmetric heavy-fermion CeRhSi3. The superconductivity emerges above about 12 kbar even though the antiferromagnetic ordering persists. Furthermore, another anomaly is observed in the superconducting phase. The anomalous magnetic field-temperature phase diagram with a high upper critical field suggests that an unconventional superconductivity is realized in CeRhSi3.     

High group birefringence in air-core photonic bandgap fibers

A numerical investigation of group birefringence is carried out on a recently reported highly birefringent hollow-core photonic bandgap fiber by use of an efficient vector finite-element method. The hollow fiber core has an area as large as that of approximately four airholes in the cladding region and assumes a rhombic shape with round corners, and the airholes in the cladding region are hexagonal and provide a high air-filling fraction. Numerical results show very high group birefringence of the order of 10(-2) and phase birefringence of the order of 10(-3).