7-endo selective aryl radical cyclization onto enamides leading to 3-benzazepines: concise construction of a cephalotaxine skeleton

Bu3SnH-mediated radical cyclizations of 2-(2-bromophenyl)-N-ethenylacetamide gave 6-exo cyclization product 15 as the major product, whereas N-[2-(2-bromophenyl)ethyl]-N-ethenylamides gave almost exclusively 7-endo cyclization products. These results indicated that the position of the carbonyl group on enamide played an important role in deciding the course of the cyclization. The 7-endo selective cyclization was applied to concise construction of a cephalotaxine skeleton.     

Opening mechanism of internal nanoporosity of single-wall carbon nanohorn

Single-wall carbon nanohorn (SWNH), which is a tubular particle with a cone cap, was oxidized in an oxygen flow at various temperatures. N(2) adsorption at 77 K, thermogravimetry (TG), differential thermal analysis (DTA), transmission electron microscopy, and Raman spectroscopy measurements were carried out on the oxidized SWNHs. The specific surface area of the oxidized SWNHs can be controlled by oxidation temperature, giving the maximum value of 1420 m(2)/g. The pore size distribution by the BJH method and the comparison plot of the N(2) adsorption isotherms of SWNH oxidized at different temperatures against that of as-grown SWNH revealed the minimum oxidation temperature for opening internal nanopores. TG-DTA analyses determined the components of as-grown SWNH: amorphous carbon 2.5 wt %, defective carbon at the cone part 15 wt %, tubular carbon 70 wt %, and graphitic carbon 12 wt %. These systematic analyses provided the exact internal nanopore volume of 0.49 mL/g for pure SWNH particles.     

Quasi one-dimensional nanopores in single-wall carbon nanohorn colloids using grand canonical Monte Carlo simulation aided adsorption technique

The average interstitial nanopore structure of single-wall carbon nanohorn (SWNH) assemblies was determined using X-ray diffraction and grand canonical Monte Carlo (GCMC) simulation aided N(2) adsorption at 77 K. The interstitial nanopores of SWNH assemblies can be regarded as quasi one-dimensional pores due to the partial orientation of the SWNH particles; the average pore width of the interstitial pores is 0.6 nm. Good agreement between the GCMC simulation of a structural model with one-dimensional interstitial nanopores and an experimental adsorption isotherm below P/P(0) = 10(-4) is evidence of the quasi one-dimensionality of the interstitial nanopores. A snapshot from the GCMC simulation showed one-dimensional growth of adsorbed N(2) molecules.     

Asymmetric synthesis,structures, and chiroptical properties of helical cycloparaphenylenes

Planar chiral carbon nanorings and nanobelts (CNRs and CNBs), the sidewall segment molecules of chiral-type carbon nanotubes (CNTs), have attracted attention owing to their characteristic chiroptical properties. From the appropriate CNTs, axially or planar chiral CNRs and CNBs have been designed and synthesized, but multiply helical sidewall segments were almost unexplored due to the difficulty in simultaneous control of multiple chiralities. In this article, we have succeeded in the perfectly diastereo- and enantiocontrolled catalytic synthesis of a cycloparaphenylene with four helical and two planar chiralities showing good chiroptical responses as chiral organic molecules. The perfectly stereocontrolled multiply helical structure was confirmed by a single-crystal X-ray diffraction analysis. The experimental and theoretical studies established the importance of the highly symmetric multiply helical structure in the cylindrical axis in obtaining good chiroptical responses.

The perfectly diastereo- and enantiocontrolled catalytic synthesis of a cycloparaphenylene with four helical and two planar chiralities showing good chiroptical responses was achieved by the rhodium-catalyzed alkyne cyclotrimerization.     

Improvement of the Derjaguin-Broekhoff-de Boer theory for capillary condensation/evaporation of nitrogen in mesoporous systems and its implications for pore size analysis of MCM-41 silicas and related materials

In this work, we propose an improvement of the classical Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in mesoporous systems. The primary idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the surface tension changes in mesopores. In addition, the statistical film thickness (so-called t-curve) evaluated accurately on the basis of the adsorption isotherms measured for the MCM-41 materials is used instead of the originally proposed t-curve (to take into account the excess of the chemical potential due to the surface forces). It is shown that the aforementioned modifications of the original DBdB theory have significant implications for the pore size analysis of mesoporous solids. To verify our improvement of the DBdB pore size analysis method (IDBdB), a series of the calcined MCM-41 samples, which are well-defined materials with hexagonally ordered cylindrical mesopores, were used for the evaluation of the pore size distributions. The correlation of the IDBdB method with the empirically calibrated Kruk-Jaroniec-Sayari (KJS) relationship is very good in the range of small mesopores. So, a major advantage of the IDBdB method is its applicability for small mesopores as well as for the mesopore range beyond that established by the KJS calibration, i.e., for mesopore radii greater than approximately 4.5 nm. The comparison of the IDBdB results with experimental data reported by Kruk and Jaroniec for capillary condensation/evaporation as well as with the results from nonlocal density functional theory developed by Neimark et al. clearly justifies our approach. Note that the proposed improvement of the classical DBdB method preserves its original simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the mean pore size by the powder X-ray diffraction method.     

Graft copolymerization of methyl methacrylate to poly(vinyl alcohol) initiated by ferric ion-hydrogen peroxide system

The reaction occurring on treatment of samples of poly(vinyl alcohol) previously oxidized by sodium hypochlorite with ferric ion and hydrogen peroxide was studied. The graft copolymerization taking place on adding methyl methacrylate to the above system was also studied. Early in the reaction there was a period during which hydrogen peroxide was greatly reduced by the poly(vinyl alcohol), and this corresponded with a rapid cleavage reaction of the main chain of the polymer. Moreover, it was found that the reaction was quantitatively proportional to the formation of carbonyl groups in the sample. On the other hand, very few grafts were scarcely formed during this period; they formed by a mild reaction which took place immediately after this period. It seems that this behavior is quite different from that observed with the ceric ion initiating system. It is presumed that the formation of grafts is due to radicals formed by the cleavage of the main chain, and that the structure of the copolymer so formed is something like a block polymer.     

The surface of TiO2 gate of 2DEG-FET in contact with electrolytes for bio sensing use

In order to apply two-dimensional electron-gas-field-effect-transistors (2DEG-FETs) for cell-viability sensors, we investigated the chemical/electrical properties of TiO₂ thin films (13-17 nm) prepared with the sol-gel technique on the gate surface of AlGaAs/GaAs 2DEG-FETs. Photochemical/electrochemical reactions on GaAs surface in electrolytes, which induce the degradation of 2DEG-FET performance, are effectively suppressed by introducing a TiO₂ thin film on the gate area of 2DEG-FETs. Compared to conventional ion-selective FETs (ISFETs), the TiO₂/2DEG-FETs in this study exhibit a high sensitivity (410 mV/mM) for H₂O₂ detection. TiO₂ surfaces show better biocompatibility than GaAs surfaces as demonstrated by direct cell culture on these surfaces.     

Structural changes of silica particles in elongated rubber by two-dimensional small-angle X-ray scattering and extended reverse Monte Carlo analysis

Two-dimensional pattern reverse Monte Carlo method is applied to investigate structural changes of silica particle filler in uniaxially elongat ed rubber. We calculated three-dimensional confor mations of spherical silica particles using a series of two-dimensional patterns of structure factors during elongation. The structure factors we used are inter polated from experimentally observed structure factors for the elongation ratio ε?=?0.0, 0.5, 1.0, and 1.5. To make a continuous motion of particles, we set the elongation ratio with small interval Δε?=?0.001. It is found that the structural change of the particles seem to be reliable at least for small ε regions because spurious motions like the Brownian motions are not observed.     

Photo-responsive retention behavior of azobenzene-modified cyclodextrin stationary phase in micro-HPLC.

An azobenzene-modified gamma-cyclodextrin stationary phase (Az gamma-CDSP) was prepared and its photo- and temperature-responses for the retention of perylene and pentacene were investigated using a mixture of methanol and water as the mobile phase in micro-HPLC. The retention of perylene slightly increased, whereas that of pentacene significantly decreased by UV light irradiation to Az gamma-CDSP. These retentions recovered upon irradiation with visible light. Both retentions decreased upon an increase in the column temperature. It was presumed that the trans-azobenzene moiety acts as a preventive cap for perylene and a spacing for pentacene in filling the CD cavity. An azobenzene-modified stationary phase changed its retention behavior with the column temperature and the light irradiation. An improvement in the micro-HPLC system and the optimization of the molecular structure of the photo-responsive stationary phase would provide selective retention control by the irradiation of light in micro-separation systems.     

Chiral separation of NBD-amino acids by ligand-exchange micro-channel electrophoresis.

The chiral separation of amino acid derivatives by ligand-exchange electrophoresis in a microchannel chip was performed for the first time. A Cu(II) complex with L-prolinamide was used as a chiral selector. The migration behaviors of eleven NBD-DL-amino acids were investigated by ligand-exchange capillary electrophoresis (LE-CE). The enantiomer of five NBD-amino acids (Ser, Thr, Val, Phe and His) could be separated by LE-CE using a 20 mM ammonium acetate buffer (pH 9.0) containing 10 mM copper acetate, 20 mM L-prolinamide and 1 mM SDS. NBD-His was eluted in the order D-form and L-form, while the elution order of another enantiomers was L-form and D-form. Under this condition, the enantioseparation of these five NBD-amino acids by ligand-exchange microchip electrophoresis (LE-ME) was investigated using a glass microchip. The enantioseparation of NBD-Ser, -Thr and -His could be successfully accomplished by LE-ME. LE-ME was superior to LE-CE in terms of the short migration time and a good enantiomeric separation.