Large-scale separation of metallic and semiconducting single-walled carbon nanotubes

In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way.     

Wavelength effect on the photoinduced reaction of polymethylmethacrylate

Polymethylmethacrylate (PMMA) containing benzophenone (BP) was photo-irradiated with monochromatic radiation of wavelength 260–360 nm using the Okazaki Large Spec-trograph (OLS). On irradiation of PMMA films containing BP in air, the sensitized main-chain scission and photocrosslinking of PMMA took place simultaneously. These reactions are dependent on irradiation wavelength. The threshold wavelength for both reactions is found to be ca. 380 nm. The number of main-chain scission and amount of gel increased with the increase of BP concentration in PMMA. Photosensitized main-chain scission favors the irradiation of radiation at ca. 280 nm and photocrosslinking takes place efficiently with the exposure of 340 nm radiation. A possible mechanism for photosensitized reaction is proposed. © 1995 John Wiley & Sons, Inc.     

Chemo-enzymatic synthesis of 2′,3′-dideoxy-3′-fluoro-β-d-guanosine via 2,3-dideoxy-3-fluoro-α-d-ribose 1-phosphate

2,3-Dideoxy-3-fluoro-α-d-ribose 1-phosphate 2 was stereoselectively synthesized and converted to 2′,3′-dideoxy-3-fluoro-β-d-guanosine 1 by enzymatic reaction using purine nucleoside phosphorylase. This chemo-enzymatic strategy was first applied to the synthesis of 1.     

The synthesis of hexahydrooxoepithiopyridinedicarboximides by the reaction of thioamides with N-substituted maleimides

The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X₂ = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated.     

Characterization of molecular transport in poly(dimethylsiloxane) microchannels for electrophoresis fabricated with synchrotron radiation-lithography and UV-photolithography

In the present paper, a study was undertaken of molecular transport in ploy(dimethylsiloxane) microchannels that were fabricated by ultraviolet (UV)-photolithography and synchrotron radiation (SR)-lithography characterized and compared for microchip capillary electrophoresis by evaluating in-channel molecular dispersion. A fluorescent tag, sulforhodamine B was used as the probing molecule. It was found that microchannels made by SR-lithography fabrication were superior to those made by UV-photolithography fabrication in terms of molecular transport performance. A deep insight into surface conditions characterized by scanning electron microscopy suggested it was related to the difference in surface roughness. Chromatographic retention in electropherograms further supported such a conclusion, which depended on the phase ratio of the channel surface. The results revealed for PDMS microchannels in this work were in good agreement with the phenomenon found for glass microchannels in the literature.     

Total synthesis of cis-solamin

[structure: see text] A convergent total synthesis of cis-solamin and its diastereomer was accomplished using VO(acac)2-catalyzed diastereoselective epoxidation followed by cyclization of bis-homoallylic alcohol as the key step. By comparison of the optical rotation of two possible diastereomers, it is suggested that the absolute configuration of natural cis-solamin is 1a.     

Synthesis and characterization of polystyrene‐b‐poly (1,2‐isoprene‐ran‐3,4‐isoprene) block copolymers with azobenzene side groups

Polystyrene‐b‐poly(1,2‐isoprene‐ran‐3,4‐isoprene) block copolymers with azobenzene side groups were synthesized by the esterification of azobenzene acid chloride with polystyrene‐b‐hydroxylated poly(1,2‐isoprene‐ran‐3,4‐isopenre) block copolymers for creating new photochromic materials. The resulting block copolymers with azobenzene side groups were characterized for structural, thermal, and morphological properties. IR and NMR spectroscopies confirmed that the polymers obtained had the expected structures. Differential scanning calorimetric measurements by heating runs clearly showed the glass transitions of polystyrene and polyisoprene main chains and two distinct first‐order transitions at temperatures of azobenzene side groups around 48 and 83 °C. The microstructure of these block copolymer films was investigated using both transmission electron microscopy (TEM) and near‐field optical microscopy (NOM). TEM images revealed typical microphase‐separated morphologies such as sphere, cylinder, and lamellar structures. The domain spacing of microphase‐separated cylindrical morphology in the NOM image agreed with that of the TEM results. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2406–2414, 2002     

Role of the special pair in the charge-separating event in photosynthesis

We synthesized special-pair/electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer. These results indicate that the radical cation is delocalized over the whole pi system of the dimer. Time-resolved transient absorption measurements revealed that, relative to the corresponding monomer, the dimer accelerated the charge separation rate, but decelerated the charge recombination rate. The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis.     

Synthetic studies on (+)-aplasmomycin. 1. Stereoselective synthesis of the C-12˜C-17 segment

The C-12˜C-17 segment of (+)-aplasmomycin ( ) was synthesized stereoselectively starting from (−)-malic acid based on the stereoselective ketone reduction.     

Radiation-induced addition reaction of carbon tetrachloride onto 1,2-polybutadiene

The γ-ray-induced addition reaction of carbon tetrachloride onto syndiotactic 1,2-polybutadiene film and liquid 1,2-polybutadiene was carried out at room temperature. In the film gelation was pronounced and the rate of addition increased as the crystallinity of the polymer decreased. In the liquid gelation, which makes the polymer insoluble in carbon tetrachloride, did not take place, although a definite crosslinking reaction was noticed. In this case the appearance of the product changed from a viscous liquid to a white powder as the reaction proceeded. Its structure was compared with that of chlorinated 1,2-polybutadiene. The addition of carbon tetrachloride to the vinyl group in liquid 1,2-polybutadiene caused an anti-Markownikoff-type reaction and was accompanied by an unexpectedly large vinyl depletion in the polymer. The total decrease in the vinyl group was found to be much larger than that brought about by the addition of carbon tetrachloride. This discrepancy was attributed to a cyclization and crosslinking reaction ascribed to the vinyl group bound by the main chain. Cyclization and crosslinking were less noticeable in the chlorination than in the carbon tetrachloride.