Synthesis and chiroptical properties of helical poly(phenylacetylene) bearing optically active chiral oxazoline Pendants

The novel optically active (S)-4-benzyl-2-(ethynylphenyl)-oxazoline (BnEPhOx) was successfully prepared and polymerized using rhodium catalyst ([Rh(nbd)Cl]₂) to obtain the moderate molecular weight poly(phenylacetylene)s bearing chiral oxazoline derivatives with high yields (≥90%). The ¹H NMR spectra demonstrated that the resulting polymers had high stereoregular structures. Moreover, the poly(phenylacetylene)s bearing chiral oxazoline exhibited better thermal stability than poly(phenylacetylene). The resulting polymers showed higher absolute values of optical specific rotation than the monomer. The polymers also exhibited intense CD signal in the region of the π-π1 band of the conjugated polyacetylene backbone in chloroform solution. The results of specific rotation and CD spectroscopy indicated that all the polymers adopted higher-order structure with predominantly one-handed screw sense.In addition, the resulting polymers emitted fluorescence under UV irradiation.     

Simultaneous purification and site-specific modification of pyrroline-carboxy-lysine proteins

Sticky residue: Pyrroline-carboxy-lysine (Pcl) can be readily incorporated into proteins expressed in E. coli and mammalian cells by using the pyrrolysyl tRNA/tRNA synthetase pair. Pcl can be used as a single amino acid purification tag and can be site-specifically modified with functional probes during the elution process.     

Asymmetric anionic polymerization of n-diphenyl-methylitaconimide with chiral ligand-organometal complex

Summary Asymmetric anionic polymerizations of achiral N-diphenylmethylitaconimide (DPII) were performed with chiral ligand — organometal complexes in toluene. The obtained poly(DPII)s exhibited molecular weights of 1.5 × 10³ to 6.3 × 10³ and specific rotation between +7.5 to −18.4° (THF). The chirality of polymer was significantly affected by the organometals and chiral ligands. The poly(DPII) obtained with (4S)-2,2′-(1-ethylpropylidene)bis(4-benzyl-4,5-dihydrooxazole) (Bnbox) / n-butyllithium (n-BuLi) exhibited the highest specific rotation (−18.4°). The optical activities of the poly(DPII)s were attributed to configurational chirality of the main chain more than conformational chirality, judged from NMR, circular dichroism (CD) and GPC analyses using UV and polarimetric detectors. Received: 10 January 2002/ Revised: 12 April 2002/ Accepted: 22 April 2002     

Selectivity and mechanism for skeletal isomerization of alkanes over typical solid acids and their Pt-promoted catalysts

Selectivities for skeletal isomerizations of n-butane and n-pentane catalyzed by typical solid acids such as Cs_2.5H_0.5PW₁₂O₄₀ (Cs2.5), SO₄²⁻/ZrO₂, WO₃/ZrO₂, and H-ZSM-5 and their Pt-promoted catalysts were compared. High selectivities for n-butane and low selectivity for n-pentane were observed over Cs2.5 and SO₄²⁻/ZrO₂, while H-ZSM-5 was much less selective, and WO₃/ZrO₂ was highly selective for both reactions. The Pt-promoted solid acids were usually selective for these reactions in the presence of H₂ except for Pt-H-ZSM-5 for n-butane isomerization. Both the acid strength and pore structure would be factors influencing the selectivity. Mechanism of skeletal isomerization of n-butane was investigated by using 1,4-¹³C₂-n-butane over Cs2.5 and Pt–Cs2.5. It was concluded that n-butane isomerization proceeded mainly via monomolecular pathway with intramolecular rearrangement on Pt–Cs2.5, while it occurred through bimolecular pathway with intermolecular rearrangement on Cs2.5. The higher selectivity on Pt–Cs2.5 would be brought about by the monomolecular mechanism. In the skeletal isomerization of cyclohexane, Pt–Cs2.5/SiO₂ was highly active and selective, while Pt–Cs2.5 was less selective. Control in the acid strength of Cs2.5 by the supporting would be responsible for the high selectivity.     

Electrophoretic Deposition Behavior of Aqueous Nanosized Zinc Oxide Suspensions

The rheological behavior and electrophoretic deposition (EPD) of ZnO nanopowder (nano-ZnO) in aqueous media have been described. A cationic polyelectrolyte (polyethylenimine, PEI) was used to disperse and modify the surfaces of the ZnO nanoparticles. The rheological properties of the ZnO aqueous suspension were investigated by measuring the viscosity versus the pH and amount of dispersant. The EPD processing was conducted via cathodic electrodeposition, using stable suspensions with low viscosity, and the depositional behavior was investigated. Bubble-free nano-ZnO deposits with uniform microstructures were successfully obtained, which was an indication of good sintering behavior.     

Immobilization of glucose oxidase on nonwoven fabrics with bombyx mori silk fibroin gel

The enzyme glucose oxidase (GOD) was immobilized on the nonwoven fabrics, which have excellent properties in diffusivity of substrates, mechanical strength, and handling, with Bombyx mori silk fibroin gel. The nonwoven fabrics of silk fibroin, viscose rayon, poly-ethyleneterephthalate, 6-nylon, and polypropylene with activated surface by fluoline treatment were used. The stabilities of GOD to heat or pH changes were much improved by the immobilization as well as the case of the GOD immobilized in the silk fibroin membrane. Among nonwoven fabrics, silk fibroin was the most excellent support material for the immobilization of GOD although all nonwoven fabrics used here are able to be used as the support materials. The increase of the sensitivity was observed when the glucose sensor was made with the GOD immobilized on nonwoven silk fabrics as four times compared with the case of the GOD immobilized in the silk fibroin membrane.     

Preparation of a Translucent, Conductive, Porous Nanocomposite

A translucent, conductive, porous nanocomposite was designed and prepared by depositing SnO₂ on the inner surfaces of the pores of a porous glass plate and on its outer surface using a chemical vapor deposition method. The porous nanocomposite almost maintained its large surface area and pore volume because the pores remained open after they were deposited with SnO₂. Conductivity between the two outer surfaces of the nanocomposite plate was confirmed for the first time.     

Sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer using H and C NMR

The triad-level sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer was reported in a solvent system of o-chlorophenol/deuterated chloroform mixture (50/50 v/v) at 80 °C using 600 MHz ¹H NMR. The well-resolved alcoholic CH₂ proton peak of the glycol units was observed, which made the detailed sequence analysis possible. The peaks of the cis- and trans-forms of the 1,4-cyclohexanedimethylene glycol units were split into the triad sequence in the chain and could be assigned by a comparison of the spectra with those of homopolymers and by an additional two-dimensional heteronuclear multiple bond correlation observation. The triad sequence distributions centered on 1,4-cyclohexanedimethylene glycol units were determined, which was independent of the cis- and trans-forms of the units and controlled according to Bernoullian statistics.     

Decomposition of CCl2F2 over metal sulfate catalysts

Activity for hydrolysis of CCl₂F₂ (CFC12) on various metal sulfate was investigated. Zr(SO₄)₂ was found to be the most active while FeSO₄, Cr₂(SO₄)₃, Al₂(SO₄)₃, La₂(SO₄)₃ and Ce₂(SO₄)₃ had intermediate activity. MnSO₄, CoSO₄, and MgSO₄ showed low activity and SrSO₄, CaSO₄, and BaSO₄ had even less activity. The major carbon containing product was CO₂ and small amount of CClF₃ and CO were formed over several sulfates. The crystal structure of the sulfates was stable during decomposition of CCl₂F₂, and the conversion reached a steady state after initial decrease at 275 °C over Zr(SO₄)₂ catalyst. The concentration of surface hydroxyl was larger than that over AlPO₄-based catalysts and a reaction mechanism similar to that over AlPO₄-based catalysts was proposed.