Charge transport in anodic TiO2 nanotubes studied by terahertz spectroscopy

We report on the photoelectrochemical and terahertz measurements, of the charge transport properties of 1 μm thick self‐organized TiO₂ nanotube layers, prepared by the anodization of titanium. We provide evidence regarding the complexity of electron transport, and dynamics in the nanotubes. Shortly after photoexcitation, charge mobilites in amorphous and crystalline nanotubes are similar, but still lower compared to the bulk anatase. The mobility subsequently decreases due to trapping‐detrapping processes. The recombination rate in anatase nanotubes is much slower than in the amorphous ones, enabling the material to reach an internal photon to electron conversion efficiency exceeding 60%.     

Observation of two resonant structures in e+ e- -->pi+ pi- psi(2S) via initial-state radiation at Belle

The cross section for e+ e- --> pi+ pi- psi(2S) between threshold and sqrt[s]=5.5 GeV is measured using 673 fb(-1) of data on and off the Upsilon(4S) resonance collected with the Belle detector at KEKB. Two resonant structures are observed in the pi+ pi- psi(2S) invariant-mass distribution, one at 4361 +/- 9 +/- 9 MeV/c2 with a width of 74 +/- 15 +/- 10 MeV/c2, and another at 4664 +/- 11 +/- 5 MeV/c2 with a width of 48 +/- 15 +/- 3 MeV/c2, if the mass spectrum is parametrized with the coherent sum of two Breit-Wigner functions. These values do not match those of any of the known charmonium states.     

Thin-film-based sensitivity enhancement for total internal reflection fluorescence live-cell imaging

We investigated experimentally the evanescent field enhancement based on dielectric thin films in total internal reflection microscopy. The sample employed two layers of Al2O3 and SiO2 deposited on an SF10 glass substrate. Field intensity enhancement measured by fluorescent excitation of microbeads relative to that of a control sample without dielectric films was polarization dependent, determined as 4.2 and 2.4 for TE and TM polarizations, respectively, and was in good agreement with numerical results. The thin-film-based field enhancement was also applied to live-cell imaging of quantum dots, which confirmed the sensitivity enhancement qualitatively.     

Simultaneous In Situ Quantification of Two Cellular Lipid Pools Using Orthogonal Fluorescent Sensors

Lipids regulate a wide range of biological activities. Since their local concentrations are tightly controlled in a spatiotemporally specific manner, the simultaneous quantification of multiple lipids is essential for elucidation of the complex mechanisms of biological regulation. Here, we report a new method for the simultaneous in situ quantification of two lipid pools in mammalian cells using orthogonal fluorescent sensors. The sensors were prepared by incorporating two environmentally sensitive fluorophores with minimal spectral overlap separately into engineered lipid‐binding proteins. Dual ratiometric analysis of imaging data allowed accurate, spatiotemporally resolved quantification of two different lipids on the same leaflet of the plasma membrane or a single lipid on two opposite leaflets of the plasma membrane of live mammalian cells. This new imaging technology should serve as a powerful tool for systems‐level investigation of lipid‐mediated cell signaling and regulation.     

Third-order Nonlinear Optical Properties of Octa-substituted Metal-free Phthalocyanine Thin Films

Third-order nonlinear optical susceptibility, χ⁽³⁾ of symmetrically octa-substituted metal-free phthalocyanine thin films measured by the third-harmonic generation technique are reported. The metal-free phthalocyanine has been found to show a χ⁽³⁾ (−3ω; ω,ω, ω) value as large as 7.73×10⁻¹² esu at 1.80 μm. The figure of merit, χ⁽³⁾/α, was estimated to be 4.17×10¹⁷ esu cm at 1.05 μm and 6.97×10¹⁶ esu cm at 1.65 μm. Both linear and third-order optical properties of liquid-crystalline metal-free phthalocyanines are discussed     

Reaction of 4,5-dichloro-3-nitropyridazin-6-one with dimethylchloromethyleneammonium chloride

3,4,5-Trichloropyridazin-6-one, 3,4,5,6-tetrachloropyridzine and 4,5-dichloro-3-(N,N-dimethylamino)-pyridazin-6-one were synthesized from 4,5-dichloro-3-nitropyridazin-6-one and dimethylchloromethylene-ammonium chloride selectively.     

Effects of gamma and electron beam irradiation on polymer electrolytes

Polymer electrolytes based on poly(ethylene oxide) and lithium salts have been widely studied in recent years. In order to enhance the room temperature ionic conductivity of PEO-LiX complexes, various techniques, such as addition of plasticizers and crown ether, and also irradiation by γ and electron beams have been investigated. The enhancement of the conductivity by irradiation has been accounted for the decreasing of the crystallinity of PEO-LiX. We reviewed these results and have investigated the degradation processes of PEO using Tb³⁺ fluorescence probes. We have also studied on the effects of irradiation of polymers such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA) and PEO using Tb⁺³ fluorescence probe. Various monomers containing SO₃H and COOH have been grafted on poly(ethylene oxide) using irradiation technique. The structures and ionic conductivities of Li and Na salts of irradiated products were investigated in detail.     

Polycyclic heteroaromatics via hydrazine-catalyzed ring-closing carbonyl–olefin metathesis

The use of hydrazine-catalyzed ring-closing carbonyl–olefin metathesis (RCCOM) to synthesize polycyclic heteroaromatic (PHA) compounds is described. In particular, substrates bearing Lewis basic functionalities such as pyridine rings and amines, which strongly inhibit acid catalyzed RCCOM reactions, are shown to be compatible with this reaction. Using 5 mol% catalyst loadings, a variety of PHA structures can be synthesized from biaryl alkenyl aldehydes, which themselves are readily prepared by cross-coupling.

Hydrazine catalysis enables the ring-closing carbonyl–olefin metathesis (RCCOM) to form polycyclic heteroaromatics, especially those with basic functionality.

Polycyclic heteroaromatic (PHA) structures comprise the core framework of many valuable compounds with a diverse range of applications (Fig. 1A).¹ For example, polycyclic azines (e.g. quinolines) are embedded in many alkaloid natural products, including diplamine² and eupolauramine³ to name just a few. These types of structures are also of interest for their biological activity, such as with the inhibitor of the Src-SH3 protein–protein interaction shown in Fig. 1A.⁴ Many nitrogenous PHAs are also useful as ligands for transition metal catalysis, as exemplified by the widely used ligand 1,10-phenanthroline.⁵ Meanwhile, chalcogenoarenes⁶ such as dinaphthofuran⁷ and benzodithiophene⁸ have attracted high interest for both their medicinal properties⁹ and especially for their potential use as organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs), and organic field-effect transistors (OFETs).¹⁰ These and numerous other examples have inspired the development of a wide variety of strategies to construct PHAs.^1,11–14 Although these approaches are as varied as the structures they target, the wide range of molecular configurations within PHA chemical space and the challenges inherent in exerting control over heteroatom position and global structure make novel syntheses of these structures a topic of continuing interest.Open in a separate windowFig. 1(A) Examples of PHAs. (B) RCCOM strategy for PHA synthesis. (C) Lewis base inhibition for Lewis acid vs. hydrazine catalyzed RCCOM. (D) Hydrazine-catalyzed RCCOM for PHA synthesis.One potentially advantageous strategy for PHA synthesis is the use of ring-closing carbonyl–olefin metathesis¹⁵ (RCCOM) to forge one of the PHA rings, starting from a suitably disposed alkenyl aldehyde precursor 2 that can be easily assembled by cross-coupling (Fig. 1B). In related work, the application of RCCOM to form polycyclic aromatic hydrocarbons (PAHs) was reported by Schindler in 2017.¹⁶ In this case, 5 mol% FeCl₃ catalyzed the metathesis of substrates to form phenanthrenes and related compounds in high yields at room temperature. This method was highly attractive for its efficiency, its use of an earth-abundant metal catalyst, and the production of benign acetone as the only by-product. Nevertheless, one obvious drawback to the use of Lewis acid activation is that the presence of any functionality that is significantly more Lewis basic than the carbonyl group can be expected to strongly inhibit these reactions (Fig. 1C). Such a limitation thus renders this method incompatible with a wide swath of complex molecules, especially PHAs comprised of azine rings. This logic argues for a mechanistically orthogonal RCCOM approach that allows for the synthesis of PHA products with a broader range of ring systems and functional groups.We have developed an alternative approach to catalytic carbonyl–olefin metathesis that makes use of the condensation of 1,2-dialkylhydrazines 5 with aldehydes to form hydrazonium ions 6 as the key catalyst–substrate association step.^17–19 This interaction has a much broader chemoorthogonality profile than Lewis acid–base interactions and should thus be much less prone to substrate inhibition than acid-catalyzed approaches. In this Communication, we demonstrate that hydrazine-catalyzed RCCOM enables the rapid assembly of PHAs bearing basic functionality (Fig. 1D).For our optimization studies, we chose biaryl pyridine aldehyde 7 as the substrate (20 salt 11 was also productive (entry 2), albeit somewhat less so. Notably, iron(iii) chloride generated no conversion at either ambient or elevated temperatures (entries 3 and 4). Trifluoroacetic acid (TFA) was similarly ineffective (entry 5). Meanwhile, a screen of various solvents revealed that, while the transformation could occur in a range of media (entries 6–9), THF was optimal. Finally, by raising the temperature to 90 °C (entry 10) or 100 °C (entry 11), up to 96% NMR yield (85% isolated yield) of adduct 8 could be obtained in the same time period.Optimization studies^a

Copolymer sequence control by ring-opening polymerization of prestructured cyclic monomers

In search for the new synthetic methods which may lead to the copolymers of controlled mer sequences, several new carbocyclic and heterocyclic monomer systems such as 1,1-disubstituted 2-vinylcyclopropanes, 1-(p-anisyl)-2-vinylcyclopropanes, substituted 3,4-dihydro-2H-pyrans, substituted 4-vinyl-2-oxetanones and α-vinyl cyclic sulfones were synthesized and their polymerization behaviors were investigated. And other promising monomer systems were also examined.     

On the Interfacial Flow Over Porous Media Composed of Packed Spheres: Part 1-Identification of the Effective Slip Length

Transport in Porous Media - The effective slip length at the interface between pure fluid flow and porous media composed of packed spheres has been accurately characterized. In this study, as the...