A new interpretation of the reaction pathway of deprotonative metalation with TMP-Zn-ate/TMEDA Complex [TMEDA.Na(micro-tBu)(micro-TMP)Zn(tBu)

Density functional theory (DFT) calculations of possible reaction pathways and mechanisms for the deprotonation of benzene with Mulvey's reagent, TMEDA.Na(micro-R)(micro-TMP)Zn(R) (TMEDA=N,N,N',N'-tetramethylethylenediamine, R = alkyl, TMP = 2,2,6,6-tetramethylpiperidide) indicate that the deprotonation of benzene with Mulvey's reagent proceeds through a stepwise mechanism, not a one-step mechanism. In the first step, deprotonation involving the TMP ligand on the reagent is kinetically more favorable than that involving the alkyl ligand.     

Towards the selective formation of specific isomers of fullerenes: T - and p-dependence in the yield of various isomers of fullerenes C60–C84

Systematic fractional change in the yield of various isomers of fullerenes was revealed to strongly depend on temperature of a buffer gas. A new kinetic consideration is proposed for understanding the observed temperature- and pressure-dependence of yield of fullerenes. The model consists of three competitive reactions in consideration of plausible behaviors of a precursor, (1) decomposition into smaller fragments, (2) isomerization leading to formation of a stable fullerene cage, and (3) growth into a larger carbon cluster. Arrhenius activation energy of formation of stable fullerenes was determined to be 0.8 eV for both C₆₀ and C₇₀, while a higher energy of 2.0?3.3 eV for seven different isomers of higher fullerenes ranging from C₇₆ to C₈₄. Correlation in the activation energy is noted for a series of higher fullerenes with different sizes, suggesting the existence of a specific precursor in their formation processes.     

Preparation of Co–Al and Ni–Al layered double hydroxide thin films by a sol–gel process with hot water treatment

Using hot water treatment of sol–gel derived precursor gel films, Co–Al and Ni–Al layered double hydroxide (LDH) thin films were prepared. The precursor gel films of Al₂O₃–CoO or Al₂O₃–NiO were prepared from cobalt or nickel nitrates and aluminum tri-sec-butoxide using the sol–gel method. Then, the precursor gel films were immersed in a NaOH aqueous solution of 100 °C. Nanocrystallites of Co–Al and Ni–Al LDH were precipitated with the hot water treatment with NaOH solution. The largest amounts of nanocrystals were obtained with a solution of pH = 10 for Co–Al LDH, and with that of pH = 9 for Ni–Al LDH. X-ray diffraction measurements confirmed that this process formed CO₃ ²⁻ intercalated LDHs. Both Co–Al and Ni–Al LDH thin films were confirmed to work as electrodes for electrochemical devices by cyclic voltammogram measurements.     

Colloidal crystallization of thermo-sensitive gel spheres of poly (<Emphasis Type="Italic">N</Emphasis>-isopropyl acrylamide). Influence of gel size

Influence of the gel size on the morphology, phase diagram, and reflection spectroscopy of the colloidal crystals of thermo-sensitive gel spheres, poly (N-isopropylacrylamide) (pNIPAm), was discussed by adding the data of two gel samples of pNIPAm(400–5) and pNIPAm(600–5) of 412 nm (at 25 °C) and 220 nm (at 45 °C) and of 517 nm (at 20 °C) and 294 nm (at 45 °C), respectively. Colloidal single crystals formed, but not so large compared with the giant crystals of small pNIPAm gels reported previously. The suspensions even with ion-exchange resins were turbid and hard to observe the single crystals clearly with the naked eyes as gel size increased. The critical concentration of melting decreased sharply as the suspensions were deionized with coexistence of the mixtures of cation- and anion-exchange resins. The critical concentration increased as the gel size increased and/or dispersion temperature increased. Density of the gel spheres increased as their size increased. These results demonstrated that the colloidal crystallization takes place by the extended electrical double layers formed around the gel spheres in addition of the excluded volume effect of the gels. Contribution of the electrical double layers on the crystallization increased sharply as temperature increased and gel concentration decreased, respectively. The contribution also increased slightly as sphere size increased, when comparison was made at the same gel concentration in wt.%. The present work clarified that the colloidal interfaces, which are inevitable for the formation of the electrical double layers, are formed between the water phase and gel spheres, though the gel spheres contain a lot of water molecules at the inner sphere region.     

Adsorption and micelle formation of alkylammonium chloride-alkyltrimethylammonium chloride mixtures

The surface tension of the aqueous solutions of binary cationic surfactant mixtures of (1) dodecylammnonium chloride (DAC)-tetradecyltrimethylammonium chloride (TTAC), (2) decylammonium chloride (DeAC)-dodecyltrimethylammonium chloride (DTAC), and (3) DAC-DTAC was measured as a function of the total molality and composition of surfactants at 298.15 K. The compositions of surfactants in the adsorbed film and micelle were evaluated and the phase diagram of adsorption and that of micelle formation were constructed. Furthermore the excess Gibbs energies of adsorption and micelle formation were calculated to estimate the deviation from the corresponding ideal mixing. It was found that the surface and micelle are enriched in trimethylammonium salts in (1) and (2), while in ammonium salt in (3) compared to the bulk solution. On the other hand, the micelle is enriched in trimethylammonium salts compared to the surface at the critical micelle concentration (CMC) in all the systems. The miscibility of the surfactants was clarified from the standpoints of the structure of the head group and of the matching between the size of polar head group of surfactants and the difference in hydrocarbon chain length.     

Surfactant-mixing effects on the interfacial tension and the microemulsion formation in water/supercritical CO2 system

The effects of surfactant mixing on interfacial tension and on microemulsion formation were examined for systems of air/water and water/supercritical CO2 (scCO2) interfaces and for water/scCO2 microemulsions. A fluorinated surfactant, sodium bis(1H,1H,2H,2H-heptadecafluorodecyl)-2-sulfosuccinate (8FS(EO)2), was mixed with the three hydrocarbon surfactants, Pluronic L31, Tergitol TMN-6, and decyltrimethylammonium chloride (DeTAC), at equimolar ratio. For all the cases, the interfacial tension was significantly lowered by the mixing. The positive synergistic effect suggests that the mixed surfactants tend to pack more closely on the interface than the pure constituents. It was found, however, that the microemulsion formation in scCO2 was never facilitated by the mixing, except for the case of TMN-6. This is probably due to the segregation of the surfactants into hydrocarbon-rich and fluorocarbon-rich phases on the microemulsion surface.     

Total synthesis of borrelidin

The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is macrocyclization at C11-C12 for the construction of an 18-membered ring after esterification between two segments. A detailed examination of the macrocyclization led us to the samarium(II) iodide-mediated intramolecular Reformatsky-type reaction as the most efficient synthetic approach. The two key segments were synthesized through regioselective methylation, directed hydrogenation, stereoselective Reformatsky-type reaction, and MgBr2.Et2O-mediated chelation-controlled allylation.     

Anthracene array-type porous coordination polymer with host-guest charge transfer interactions in excited states

Confinement of electron donor guests affords an efficient, photo-induced charge transfer (CT) with the anthracene moieties of a porous coordination polymer.     

New synthetic method for orsellic acid type macrolides by intramolecular alkylation of protected cyanohydrin. The synthesis of (±)-zearalenone.

Zearalenone was synthesized by a general cyclization method of orsellic acid type macrolides having ketone moiety using the intramolecular alkylation of the protected cyanohydrin. This alkylation tolerates the presence of ester group and requires short reaction time.