Photodissociation of molecular beams of halogenated hydrocarbons at 193 nm

Molecular beams of halogenated hydrocarbons containing chlorine and bromine atoms were photodissociated using an excimer laser at 193 nm. Molecules photodissociated were HCCBr, HCCCH₂Br, HCCCH₂Cl, CH₃Cl, C₂H₅Cl and i-C₃H₇Cl. The time-of-flight distributions of the photofragments were measured in order to study the primary processes and the dissociation dynamics. Generalizations consistent with the data are that atomic products (RX → R + X) result from direct dissociation of the CX repulsive singlet state, molecular elimination (RX → R′ + HX) is a result of a crossover to the ground state and triplet states are involved in the photodissociation of alkyne compounds.     

Enhanced photoluminescence from very thin double-wall carbon nanotubes synthesized by the zeolite-CCVD method

Photoluminescence (PL) from purified (>90%) double-wall carbon nanotubes (DWNTs), which have been synthesized by zeolite catalyst-supported chemical vapor deposition (zeolite-CCVD), of very small diameters (0.8-nm average inner tube) is reported. The PL contour mappings for various ratios (1-90%) of double- versus single-wall carbon nanotubes by thermal oxidation have enabled us to unambiguously identify the chirality of inner tubes for the DWNTs synthesized. After the extensive high-temperature oxidation at 700 degrees C, high-purity (>90%) DWNTs of approximately 0.8 nm inner diameter are obtained, and most of these correspond to the DWNTs having inner tubes with chiralities of (7,5), (7,6), and (9,4).     

First-principles calculations of migration energy of lithium ions in halides and chalcogenides

Migration of Li+ ions via the vacancy mechanism in LiX (X = F, Cl, Br, and I) with the rocksalt and hypothetical zinc blende structures and Li2X (X = O, S, Se, and Te) with the antifluorite structure has been investigated using first-principles projector augmented wave calculations with the generalized gradient approximation. The migration paths and energies, determined by the nudged-elastic-band method, are discussed on the basis of two idealized models: the rigid-sphere and charged-sphere models. The trajectories and energy profiles of the migration in these lithium compounds vary between these two models, depending on the anion species and crystal structure. The migration energies in LiX with both the rocksalt and hypothetical zinc blende structures show a tendency to decrease with increasing periodic number of the anion species in the periodic table. This is consistent with the widely accepted view that anion species with large ionic radii and high polarizabilities are favorable for good ionic conduction. In contrast, Li2O exhibits the lowest migration energy among Li2X compounds, although O is the smallest among the chalcogens, indicating that electrostatic attractive interactions play the dominant role in the inter-ion interactions in Li2O and, therefore, in the ion migration.     

Ultrafast Primary Process of Photo-induced N-I Transition and Macroscopic Oscillation of Domain Boundary in TTF-CA

Initial dynamics of photo-induced ionic (I) to neutral (N) phase transition in tetrathiafulvalene- p -chloranil (TTF-CA) was investigated by femtosecond reflection spectroscopy with various excitation intensities. A charge transfer excitation in the I phase produces N donor (D 0 )-acceptor (A 0 ) strings within 2 ps. For a weak excitation intensity, these initial N states decay with a life time of 300 ps at 4 K, but rather multiply leading to macroscopic I-N conversion within 20 ps at 77 K just below the N-I transition temperature T NI . Near T NI , we also found the coherent motion of the macroscopic N-I domain boundary with a period of 85 ps.     

Chemo- and stereoselective six-membered oxonium ylide formation–[2,3]-sigmatropic rearrangement of 2-diazo-3-ketoesters with dirhodium(II) catalyst and its application to the synthesis of (+)-tanikolide

Dirhodium(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement of 6-allyloxy-2-diazo-3-ketoesters possessing a C-6 substituent is described. The reaction of 6-alkyl- or 6-aryl-substituted 6-allyloxy-2-diazo-3-ketoesters with a catalytic amount of Rh₂(S-PTTL)₄ proceeded in a chemoselective and stereoselective manner to provide 6-substituted 2-allyl-3-oxotetrahydropyran-2-carboxylates in good yields and with high diastereoselectivities. To demonstrate the utility of this sequential reaction, we conducted the total synthesis of (+)-tanikolide, in which the construction of the δ-lactone skeleton was achieved by employing a 2-iodobenzamide-catalyzed oxidative cleavage of tetrahydropyran-2-methanol.     

Direct observation of dark excitons in micelle-wrapped single-wall carbon nanotubes

We have performed electroabsorption spectroscopy on micelle-wrapped single-wall carbon nanotubes. In semiconducting nanotubes, many oscillating structures composed of the increase and decrease of absorption are observed in the spectra in the region of the first and second absorption bands, E11 and E22. The spectral shape is reproduced mainly by the second-derivative curve of the absorption spectrum, which indicates the presence of nearly degenerate bright and dark excitonic states.     

Asymmetric Total Synthesis of (−)‐Englerin A through Catalytic Diastereo‐ and Enantioselective Carbonyl Ylide Cycloaddition

An asymmetric total synthesis of the guaiane sesquiterpene (?)‐englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo‐ and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N‐tetrachlorophthaloyl‐(S)‐tert‐leucinate], [Rh₂(S‐TCPTTL)₄], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo‐face. Another notable feature of the synthesis is ruthenium tetraoxide‐catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.     

Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands

A new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin ( ZnP ) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.     

Controlling coupling reaction of EDC and NHS for preparation of collagen gels using ethanol/water co-solvents

To control the crosslinking rate of the collagen gel, ethanol/water co-solvent was adopted for the reaction solvent for the collagen microfibril crosslinking. Collagen gel was prepared by using EDC and NHS as coupling agents. Ethanol did not denaturate the helical structure of the collagen and prevented the hydrolysis of EDC, but showed the protonation of carboxylate anions. In order to control the intra- and interhelical crosslink of the collagen triple helix, variations of the mole ratio of carboxyl group/EDC/NHS, and of the ethanol mole concentration were investigated. Increase in the EDC ratio against the carboxyl group increased the crosslinking rate. Furthermore, an increase in the ethanol mole concentration resulted in an increase of the crosslinking rate until ethanol mole concentration was 0.12, but showed gradual decrease as the ethanol mole concentration was further increased. This is because the adsorption of solvent by the collagen gel, protonation of carboxylate anion, and hydrolysis of EDC is at its most optimum condition for the coupling reaction when the ethanol mole concentration is 0.12. The re-crosslinking of the collagen gel showed an increase in the crosslinking rate, but did not show further increase when the coupling reaction was executed for the third time. This implied that the highest possible crosslinking rate for the intra- and interhelical is approximately 60% when EDC/NHS is used.