Pairings of function spaces

Pairings and copairings of topological spaces induce pairings of function spaces. These induced pairings of function spaces are studied. For this purpose, the C-open topology of function spaces is studied for subcategories C of Top. It is shown that the C-open topology enjoys good properties for homotopy theory. Making use of the C-open topology, theory of induced pairings is established and fundamental results on pairings which deduce various commutativity properties of elements in homotopy set are extended to function spaces.     

Aerobic photo-oxidation of alcohols in the presence of a catalytic inorganic bromo source

Alcohols were found to be oxidized to the corresponding carboxylic acid in the presence of a catalytic inorganic bromo source, for example, lithium bromide, bromine, and hydrobromic acid, under photo-irradiation.     

Electron- or hole-transporting nature selected by side-chain-directed π-stacking geometry: liquid crystalline fused metalloporphyrin dimers

Novel liquid crystalline (LC) semiconductors were prepared from the copper complex of a fused porphyrin dimer as the electroactive core by attaching to its periphery dodecyl and semifluoroalkyl side chains site-specifically (P≡P(hetero)) and semifluoroalkyl side chains alone (P≡P(homo)). The former and latter formed rectangular columnar and orthorhombic LC mesophases, respectively, where the stacking geometries of the π-conjugated core are quite different from one another. Although the π-electronic properties of the core units in P≡P(hetero) and P≡P(homo) in solution are substantially identical to one another, transient photocurrent profiles of their LC states under time-of-flight conditions clearly showed that P≡P(hetero) behaves as an n-type semiconductor, whereas P≡P(homo), in contrast, behaves as a p-type semiconductor.     

Improvements in transfection efficiency with chitosan modified poly(DL-lactide-co-glycolide) nanospheres prepared by the emulsion solvent diffusion method, for gene delivery

This study sought to evaluate the in vitro transfection efficiency of plasmid DNA (pDNA)-loaded chitosan-modified poly(DL-lactide-co-glycolide) nanospheres (CS-PLGA NS) in a gene-delivery system. Using the emulsion solvent diffusion (ESD) method, pDNA-loaded PLGA NS was prepared and the surface of the PLGA NS was modified by binding to CS. Gene transfection ability of CS-PLGA NS was examined in A549 cells. The luciferase gene was used as a reporter gene. The pattern of luciferase activity by pDNA-loaded CS-PLGA NS was initially weak, but gradually grew stronger before decreasing activity. These phenomena should be in accordance with the sustained-release profile of pDNA from PLGA NS in the cytosol and the pDNA protection against DNase. Positively charged CS-PLGA NS was found, by 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt (MTS) assay, not to exhibit cytotoxicity on A549 cells. These results suggest that CS-PLGA NS are potential contributors to efficient pDNA delivery due to their increased interactions with cells and lack of cytotoxic effects.     

Exponential homeomorphisms in the category of topological spaces with base point

Topologies on base point preserving function spaces are studied making use of the Brown-Booth-Tillotson C-smash product and the topologies on function spaces defined by the classes C of exponentiable spaces. Some conditions on the classes C are obtained for exponential bijections and exponential homeomorphisms in the category of topological spaces with base point. Conditions for exponential homeomorphisms are obtained for CW-complexes whose cellular structure implies precise results.     

Rational synthesis of supramolecular assemblies based on tetraplatinum units: synthesis, characterization, and selective substitution reactions of four different Pt4 clusters

Four different types of square‐planar Pt₄ clusters, trans‐[Pt₄(μ‐OCOCH₃)₆(μ‐ArNCHNAr)₂] ( 2 : ArNCHNAr=N,N′‐diarylformamidinate), [Pt₄(μ‐OCOCH₃)₇(μ‐ArNCHNAr)] ( 8 ), cis‐[Pt₄(μ‐OCOCH₃)₆(κ⁴‐N₄‐DArBp)] ( 9 : DArBp=1,3‐bis(arylbenzamidinate)propane), and [Pt₄Cl₂(μ‐OCOCH₃)₅(κ⁴‐N₂,P₂‐dpfam)] ( 13 : dpfam=N,N′‐bis[(2‐diphenylphosphino)phenyl]formamidinate), were successfully prepared by using selective substitution reactions of in‐plane acetate ligands of [Pt₄(μ‐OCOCH₃)₈] ( 1 ), which has four in‐plane and four out‐plane acetate ligands, with appropriate capping ligands. Fundamental substitution reactions of the remaining in‐plane acetates with benzoic acid derivatives were also investigated. All newly prepared complexes were characterized from spectral and physical data and combustion analysis. X‐ray crystallographic studies of some of the clusters were also performed. Electrochemical measurements of amidinate‐modified Pt₄ clusters revealed stepwise oxidation processes of the Pt₄ core due to Pt₄⁹⁺/Pt₄⁸⁺ and Pt₄¹⁰⁺/Pt₄⁹⁺. Based on the lability of the in‐plane acetate ligands of the modified Pt₄ clusters, reactions of cis‐[Pt₄(μ‐OCOCH₃)₆(κ⁴‐N₄‐DArBp)] ( 9 c : Ar=C₆H₄tBu‐4) with ferrocenedicarboxylic acid and p‐phenylenedipropionic acid resulted in the selective formation of cyclic dimers 17 and 18 and the reaction of 13 with 4,4′‐biphenyldicarboxylic acid afforded a linear dimer 20 . The dimers were characterized by spectral data, as well as X‐ray analyses for 17 and 18 . The finding of two Fe³⁺/Fe²⁺ redox couples in the electrochemical measurement of dimer 17 indicated that two ferrocenyl units in dimer 17 communicated electronically.     

Highly efficient asymmetric conjugate addition of 5-benzylfurfurals to nitroalkenes using a thiourea organocatalyst

The asymmetric direct bisvinylogous conjugate addition of 5-benzylfurfural derivatives to nitroalkenes using a thiourea organocatalyst resulted in a corresponding ε-regioselective addition products in high yields and up to 95% enantiomeric excess.     

New Size-Expanded Fluorescent Thymine Analogue: Synthesis,Characterization, and Application

Here, the synthesis, photophysical characterization, and application of a new size-expanded thymine nucleoside, ^diox T , is described. ^diox T has desirable qualities as a T surrogate, including excellent quantum yield (0.36) and high environmental sensitivity. When incorporated into single- and double-stranded DNA, ^diox T showed excellent photophysical characteristics including a high quantum yield (average 0.20), and unlike BgQ, demonstrated dependence on neighboring bases without significant destabilization of the duplex. Interestingly, the matched base pair of adenine (A) and ^diox T has the unique property that it exhibits higher fluorescence than mismatched base pairs, and ^diox T has self-quenching effects. As one example of the possible applications of these promising features, single nucleoside polymorphism typing is demonstrated for discrimination of A by using ^diox T . The results suggest that ^diox T can be used for a broad range of applications in chemical biology.     

Fast and accurate radiance calculations using truncation approximation for anisotropic scattering phase functions

The phase function for solar light scattering by large particles such as cloud droplets is strongly anisotropic due to very strong peaking in the forward direction. This creates numerical difficulties when attempting to calculate accurate reflected and transmitted radiances, which are important for remote sensing of atmospheric and surface properties. A popular approach uses the delta function to approximate the forward-scattering peak in a fraction of energy and a limited number of polynomial terms or a geometrically truncated function for the remaining fraction (so-called truncation approximations). This article compares and discusses several methods for fast and accurate calculations using truncation approximations. When using a single truncation approximation for all scattering orders, large biases appear in directions near the solar and anti-solar points. As shown here, high accuracy can be obtained using different truncation approximations depending on the order of scattering. Of particular importance is the use of phase functions close to the exact phase functions for the first few orders of scattering. Applying the method in combination with the Monte Carlo (MC) method, in which the truncation fraction for a scattering order depends on the scattering angle at the previous scattering event, obtains accurate radiance calculations under almost all geometrical and optical conditions, including in directions near the solar point. Because the method also reduces computational noise due to the MC sampling of radiance, it is useful for fast and accurate radiance calculations for cloudy atmospheres.