Sol–gel synthesis of macro–mesoporous titania monoliths and their applications to chromatographic separation media for organophosphate compounds

We have developed a method of independently tailoring the macro- and mesoporous structures in titania (TiO₂) monoliths in order to achieve liquid chromatographic separations of phosphorous-containing compounds. Anatase TiO₂ monolithic gels with well-defined bicontinuous macropores and microstructured skeletons are obtained via the sol–gel process in strongly acidic conditions using poly(ethylene oxide) as a phase separator and N-methylformamide as a proton scavenger. Aging treatment of the wet gels in the mother liquor at temperatures of 100–200 °C and subsequent heat treatment at 400 °C allow the formation and control of mesoporous structures with uniform pore size distributions in the gel skeletons, without disturbing the preformed macroporous morphology. The monolithic TiO₂ rod columns with bimodal macro–mesoporous structures possess the phospho-sensitivity and exhibit excellent chromatographic separations of phosphorus-containing compounds.     

Bis‐copper(II) Complex of Triply‐linked Corrole Dimer and Its Dication

Copper complexes of corroles have recently been a subject of keen interest due to their ligand non‐innocent character and unique redox properties. Here we investigated bis‐copper complex of a triply‐linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply‐linked corrole dimer 2 with Cu(acac)₂ (acac=acetylacetonate) gave bis‐copper(II) complex 2Cu as a highly planar molecule with a mean‐plane deviation value of 0.020 Å, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF₄ gave complex 3Cu , which was characterized as a bis‐copper(II) complex of a dicationic triply‐linked corrole dimer not as the corresponding bis‐copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu . Importantly, the magnetic spin–spin interaction differs depending on the redox‐state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu .     

Morphology and properties of globular polymeric materials in the solid state: A composite material of DNA with a cationic surfactant

The aim of the present study was to control entanglements in order to regulate the properties of polymeric solids. Initially, fabrication of polymeric solids with few entanglements was attempted. Films of the DNA–cationic surfactant, cetyltrimethylammonium bromide (CTAB) (DNA–CTA), were cast from ethanol solution at room temperature. Morphological examination of DNA–CTA complex films using atomic force microscopy (AFM) revealed that these films were constructed by particle‐like substances. Geometrical analysis of AFM images showed that the particle‐like substances were the aggregates of several DNA–CTA globules. Mechanical characterization suggested that there were fewer entanglements than with normal plastic films. Small angle X‐ray scattering experiments during annealing indicated that molecular motions were highly excited in the surface region of each particle. In conclusion, a globular polymeric film with fewer entanglements was fabricated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 730–738     

Theoretical Study on the Relationship between Diradical Character and Second Hyperpolarizabilities of Four‐Membered‐Ring Diradicals Involving Heavy Main‐Group Elements

By using spin‐unrestricted density functional theory methods, the relationship between the diradical character y and the second hyperpolarizability γ (the third‐order nonlinear optical (NLO) properties at the molecular scale) for four‐membered‐ring diradical compounds, that is, cyclobutane‐1,3‐diyl, Niecke‐type diradicals, and Bertrand‐type diradicals, were investigated by focusing on the substitution effects of heavy main‐group elements as well as of donor/acceptor groups on the y and γ values. It has been found that i) γ is enhanced in the intermediate y region for these four‐membered‐ring diradicals, ii) Niecke‐type diradicals with intermediate y values, which are realized by tuning the combination of the main‐group elements involved, exhibit larger γ values than Bertrand‐type diradicals, and iii) the y value and thus γ value can be controlled by modifying the both‐end donor/acceptor substituents attached to carbon atoms in Nicke‐type C₂P₂ diradicals. These results demonstrate that four‐membered‐ring diradicals involving heavy main‐group elements exhibit high controllability of the y and γ, which indicates the potential applications of four‐membered‐ring diradicals as a building block of highly efficient open‐shell NLO materials.     

Versatile Oxidation Methods for Organic and Inorganic Substrates Catalyzed by Platinum‐Group Metals on Carbons

Platinum‐group metals on activated carbon catalysts, represented by Pd/C, Ru/C, Rh/C, etc., are widely utilized to accomplish green and sustainable organic reactions due to their favorable features, such as easy handling, recoverability, and reusability. The efficient oxidation methods of various organic compounds using heterogeneous platinum‐group metals on carbons with or without added oxidants are summarized in this Personal Account. The oxidation of internal alkynes into diketones was effectively catalyzed by Pd/C in the presence of dimethyl sulfoxide and molecular oxygen or pyridine N‐oxide. The Pd/C‐catalyzed mild combustion of gaseous hydrogen with molecular oxygen provided hydrogen peroxide, which could be directly utilized for the oxidation of sulfide derivatives into sulfoxides. Furthermore, the Ru/C‐catalyzed aerobic oxidation of primary and secondary alcohols gave the corresponding aldehydes and ketones, respectively. On the other hand, the dehydrogenative oxidation of secondary alcohols into ketones was achieved using Rh/C in water, and primary alcohols were effectively dehydrogenated by Pd/C in water under mildly reduced pressure to produce carboxylic acids.

     

Conformational Transformations of (C12H25NH3+)(Pyridinesulfonate) in the Solid State

The phase‐transition behaviors, crystal structures, and dielectric properties of four kinds of simple 1:1 organic salts of (C₁₂H₂₅NH₃⁺)(benzenesulfonate) and (C₁₂H₂₅NH₃⁺)(pyridine sulfonates) were examined from the viewpoint of intermolecular hydrogen‐bonding interactions and dynamic conformational transformation in molecular assemblies. Crystals of (C₁₂H₂₅NH₃⁺)(benzenesulfonate) and (C₁₂H₂₅NH₃⁺)(3‐pyridinesulfonate) were isostructural and solid–solid and solid–liquid‐crystal smectic A (SmA) phase transitions were observed. These two crystals formed rodlike cation–anion assemblies. However, the two salts, (C₁₂H₂₅NH₃⁺)(2‐pyridinesulfonate) and (C₁₂H₂₅NH₃⁺)(4‐pyridinesulfonate), formed largely bent L ‐shaped cation–anion conformations. Interesting conformational transformations from rodlike to L ‐shaped assemblies were observed in (C₁₂H₂₅NH₃⁺)(2‐pyridinesulfonate) and (C₁₂H₂₅NH₃⁺)(3‐pyridinesulfonate).     

Triply Linked Corrole Dimers

The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl₃ afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic ¹H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH₄ to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes.     

Life span of solutions with large initial data for a superlinear heat equation

We investigate the initial-boundary problem

     

Multiplex detection and identification of proteins on a PVDF membrane blocked with a synthetic polymer-based reagent

2-DE is one of the most powerful methods for analyzing proteins expressed in cells and tissues. Immunodetection of proteins blotted on a polymer membrane is the method of choice for detecting specific proteins in 2-D gels. To precisely locate spots of immunoreactive proteins in 2-D gels, both dye staining and immunodetection were performed on the same PVDF membrane. Prior to immunodetection, nonspecific adsorption of the antibodies to the membrane was blocked with a synthetic polymer-based reagent (N-102) after protein transfer. The protein was then stained with colloidal gold or CBB followed by protein spot identification by LC-MS. Described herein is a method for multiplex analysis of proteins transferred to a PVDF membrane. Proteins that were phosphorylated at tyrosine in the phosphoproteome of rice callus or human ovarian cancer cells were detected by immunoblotting and subsequently identified with high precision.     

Amidine-bearing lipoplex targeting to hepatocyte cells

A lipoplex （i.e., pDNA#1/lipid complex and transfection reagent for pDNA delivery） containing galactosylceramide （GalCer） and an amidine-bearing lipid （TRX） was examined whether the bound pDNA was specifically ingested by hepatocyte via asialoglycoprotein receptor （ASGPR） and then expressed protein. Gel electrophoresis and small-angle X-ray scattering （SAXS） confirmed that the TRX-GalCer liposome#2 complexed with pDNA and the resultant lipoplex took a hexagonally packed inverted cylinder structure when the GalCer composition was less than 20 wt.% of the total lipid. When the lipoplex carrying pGL3 （luciferase-cording pDNA） was administrated to HepG2, the luciferase activity was increased with increasing the GalCer composition until it reached 3 wt.% and then decreased upon further addition of GalCer. When we added galactose itself as a competitor, the luciferase activity was decreased, while glucose did not show such decrease, suggesting that HepG2 ingested the lipoplex via ASGPR-mediated endocytosis. This paper indicated that the hexagonally packed inverted cylinder structures of lipoplex may not always provide excellent transfection and presented a possibility that the TRX lipoplex#3 can obtain a cellulartargeting ability through the receptors for oligosaccharide.