Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior

Anionic polymerizations of three 1,3‐butadiene derivatives containing different N,N‐dialkyl amide functions, N,N‐diisopropylamide (DiPA), piperidineamide (PiA), and cis‐2,6‐dimethylpiperidineamide (DMPA) were performed under various conditions, and their polymerization behavior was compared with that of N,N‐diethylamide analogue (DEA), which was previously reported. When polymerization of DiPA was performed at ?78 °C with potassium counter ion, only trace amounts of oligomers were formed, whereas polymers with a narrow molecular weight distribution were obtained in moderate yield when DiPA was polymerized at 0 °C in the presence of LiCl. Decrease in molecular weight and broadening of molecular weight distribution were observed when polymerization was performed at a higher temperature of 20 °C, presumably because of the effect of ceiling temperature. In the case of DMPA, no polymer was formed at 0 °C and polymers with relatively broad molecular weight distributions (M_w/M_n = 1.2) were obtained at 20 °C. The polymerization rate of PiA was much faster than that of the other monomers, and poly(PiA) was obtained in high yield even at ?78 °C in 24 h. The microstructure of the resulting polymers were exclusively 1,4‐ for poly(DMPA), whereas 20–30% of the 1,2‐structure was contained in poly(DiPA) and poly(PiA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3714–3721, 2010     

Transfer efficiency in ballistic electron emission microscopy taking diffraction of emitted hot electrons into account

We have analyzed the transfer efficiency of ballistic electron emission microscopy (BEEM), taking the finite spot size of the emitted electron beam from scanning probes into account. Three-dimensional diffraction from an aperture at a surface-metal/air interface is introduced to model an effect caused by the finiteness of spot size. As a general trend, the diffraction decreases BEEM transfer efficiency. The diffraction effect increases as the spot size decreases and the air-gap distance increases. In a Au/GaAs sample, BEEM transfer efficiency markedly deteriorates down to 6% of the value derived from a conventional planar tunneling theory when a spot size of 0.2 nm, an air-gap distance of 0.6 nm, and an electron energy of 0.2 eV, measured from the bottom of the GaAs conduction band, are assumed. BEEM transfer efficiency is markedly dependent on the spot size of the emitted hot electron. This result indicates that the BEEM current depends on the spatial resolution of the scanning probe, that is, the condition of the tip apex.     

Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+: Experimental and Computational Studies of their Hydricities,Interaction with CO2, and Photochemistry

We prepared two geometric isomers of [Ir(tpy)(ppy)H]⁺, previously proposed as a key intermediate in the photochemical reduction of CO₂ to CO, and characterized their notably different ground‐ and excited‐state interactions with CO₂ and their hydricities using experimental and computational methods. Only one isomer, C‐trans‐[Ir(tpy)(ppy)H]⁺, reacts with CO₂ to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH₃CN/TEOA, a common reactive C‐trans‐[Ir(tpy)(ppy)]⁰ species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO₂ and produces CO with the same catalytic efficiency.     

Palladium‐Catalyzed Direct C?H Arylation of Isoxazoles at the 5‐Position

A palladium‐catalyzed direct arylation of isoxazoles with aryl iodides has been achieved. The C H bond at the 5‐position is activated selectively to give coupling products in moderate to good yields. This direct arylation was applied to the synthesis of a spiro‐type chiral ligand, which proved to be most effective to the palladium‐catalyzed tandem cyclization of a dialkenyl alcohol.     

Intramolecular Diels-Alder reaction of N-allyl 2-furoyl amides: effect of steric strain and amide rotational isomerism

Intramolecular Diels-Alder reactions of various N-allyl 2-furoyl amides with different substituents on the nitrogen atom were investigated. The reaction of amides having bulky substituents proceeded at a faster rate than the analogs whose substituents were of less bulkiness. From the systematic experimental survey of the substituent effects and the energetic evaluation based on the DFT calculations at the B3LYP/6-31G(d) level, the enhanced reactivity was ascribed to the relief of steric strain upon cyclization rather than the amide rotational isomerism governed by the bulky substituents.     

Fluorescence detection of potassium ion using the G-quadruplex structure

Oligonucleotides with sequences of human telomere DNA or thrombin binding aptamer (TBA) are known to form tetraplex structures upon binding the K(+) ion. Structural changes associated with the formation of tetraplex assemblies led to the development of potassium-sensing oligonucleotide (PSO) probes, in which two fluorescent dyes were attached to both termini of particular oligonucleotide. The combination of dyes included fluorescence resonance energy transfer (FRET) and excimer emission approaches, and the structural changes upon binding K(+) ion could be monitored by a fluorescence technique. These systems showed a very high preference for K(+) over Na(+) ion, which was suitable for fluorescence imaging of the potassium concentration gradient in a living cell. In the case of human telomere DNA, it was also possible to follow the polymorphism of its tetraplex structures.     

Low-temperature structural phase transition in synthetic libethenite Cu2PO4OH

Low-temperature structural properties of the synthetic mineral libethenite Cu₂PO₄OH were investigated by single-crystal X-ray diffraction, synchrotron X-ray powder diffraction, specific heat measurements, and Raman spectroscopy. A second-order structural phase transition from the Pnnm symmetry (a=8.0553(8) Å, b=8.3750(9) Å, c=5.8818(6) Å at 180 K) to the P2₁/n symmetry (a=8.0545(8) Å, b=8.3622(9) Å, c=5.8755(6) Å, β=90.0012(15) at 120 K) was found at 160 K during cooling. At 120 K, the monoclinic angle is 90.0012(15) from single crystal X-ray data vs 90.083(1) from powder X-ray diffraction data. The P2₁/n–to–Pnnm transition may be a general feature of the adamite-type compounds, M₂XO₄OH.     

The porosity, acidity, and reactivity of dealuminated zeolite ZSM-5 at the single particle level: the influence of the zeolite architecture

A combination of atomic force microscopy (AFM), high‐resolution scanning electron microscopy (HR‐SEM), focused‐ion‐beam scanning electron microscopy (FIB‐SEM), X‐ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron‐based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM‐5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol‐to‐olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM‐5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM‐5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.     

Selective photocatalytic oxidation of alcohols to aldehydes in water by TiO2 partially coated with WO3

Semiconductor TiO₂ particles loaded with WO₃ (WO₃/TiO₂), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO₃/TiO₂ catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO₂. In particular, a catalyst loading 7.6 wt % WO₃ led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO₂ surface of the catalyst, which is active for oxidation, is partially coated by the WO₃ layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO₂ surface. This suppresses subsequent decomposition of the aldehyde on the TiO₂ surface and results in high aldehyde selectivity. The WO₃/TiO₂ catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity.