Analysis of sialo-N-glycans in glycoproteins as 1-phenyl-3-methyl-5-pyrazolone derivatives by capillary electrophoresis

A method for the analysis of the sialo-N-glycans in glycoproteins was established by the electrokinetic chromatography mode of capillary electrophoresis (CE) in sodium dodecyl sulfate (SDS) micelles as 1-phenyl-3-methyl-5-pyrazolone (PMP) derivatives, using sialo-N-glycans in fetuin as a model. Six major and some minor peaks were observed for the N-glycans in fetuin, which were well separated from each other using 50 mM phosphate buffer, pH 6.0, containing SDS to a concentration of 30 mM in an uncoated fused-silica capillary, and these peaks were assigned to sialo-N-glycans having either of the biantennary or β1-3/β1-4 linked galactose-containing complex type triantennary N-glycans as the basic structures, by an indirect method based on the assignment of the peaks in high-performance liquid chromatography separated in parallel with CE and peak collation between these two separation methods. The attaching position of the sialic acid residue was determined using the linkage preference of neuraminidase isozymes. The established system is considered to be useful for routine analysis of microheterogeneity of the carbohydrate moiety of this model glycoprotein from the following reasons: (1) the derivatization with PMP proceeds quantitatively under mild conditions without causing release of the sialic acid residue, (2) the derivatives can be sensitively detected by UV absorption, (3) the procedure is simple, rapid and reproducible. Preliminary results of N-glycan analysis for several other glycoproteins under these conditions are also presented.     

Radical Polymerization of Vinyl Monomers in Porous Organic Cages

The radical polymerization of vinyl monomers was performed in a tetrahedral imine‐linked organic cage with extrinsic porosity (CC3). Because of its dynamic and responsive packing structure, CC3 endowed the polymerization with specific behaviors. The adsorption of styrene triggered a change in the CC3 assembly, resulting in a monomer arrangement that was suitable for polymerization within the host matrix. The polymerization reaction was strongly dependent on the crystallinity of CC3 and was promoted by amorphization of the host in a cooperative manner, which is not possible with conventional rigid porous materials. Furthermore, CC3 can recognize the polarity of substrates, and thus polar monomers, such as methyl methacrylate and acrylonitrile, could not induce the structural changes in CC3 that are required for polymerization. This monomer specificity governed by the flexibility of CC3 is useful to the prevent incorporation of unfavorable monomers into the polymeric products.     

Boron Difluoride Complexes of Expanded N‐Confused Calix[n]phyrins That Demonstrate Unique Luminescent and Lasing Properties

Complexation of novel multiply N‐confused expanded calix[n]phyrins with boron difluoride afforded a new class of cyclic BODIPY (boron‐dipyrromethene) arrays. The structures of circularly arranged BODIPY subunits linked in an N‐confused fashion give rise to such photophysical properties unique to the macrocycles as redshifted emission wavelengths along with apparent large Stokes shifts, long emission lifetimes, and solid‐state lasing. The DFT calculations support the size‐dependent excited‐state dynamics of the macrocycles.     

Recognition of 1,3‐Butadiene by a Porous Coordination Polymer

The separation of 1,3‐butadiene from C₄ hydrocarbon mixtures is imperative for the production of synthetic rubbers, and there is a need for a more economical separation method, such as a pressure swing adsorption process. With regard to adsorbents that enable C₄ gas separation, [Zn(NO₂ip)(dpe)]_n (SD‐65; NO₂ip=5‐nitroisophthalate, dpe=1,2‐di(4‐pyridyl)ethylene) is a promising porous material because of its structural flexibility and restricted voids, which provide unique guest‐responsive accommodation. The 1,3‐butadiene‐selective sorption profile of SD‐65 was elucidated by adsorption isotherms, in situ PXRD, and SSNMR studies and was further investigated by multigas separation and adsorption–desorption‐cycle experiments for its application to separation technology.     

Sequential Synthesis of Coordination Polymersomes

Novel organic–inorganic hybrid liposomes, so‐called coordination polymersomes (CPsomes), with artificial domains that exhibit strong lateral cohesion were prepared by a three‐step procedure that formed a coordinative interaction leading to a lipid bilayer. First, the lipophilic complex (dabco‐C₁₈)[Mn(N)(CN)₄(dabco‐C₁₈)] ( 1 ; dabco‐C₁₈⁺=1,4‐diazabicyclo[2,2,2]octane‐(CH₂)₁₇? CH₃ cation), was synthesized. 1 has a lipophilic alkyl tail part and a tetracyanometallate head group, which can be used for an expansion to two‐dimensional coordination networks. Second, 1 and 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine were mixed to prepare the liposomes. Finally, CPsomes were obtained by the addition of transition‐metal ions ( M ) to form unilamellar faceted liposomes with plain CP raft domains with Mn? CN? M linkages. The concentration of 1 influences the size of the CP raft domains and the shape of the CPsomes. The synthesis of coordination polymers in lipid bilayers is a novel approach for the construction of artificial architectures as raft domains, for example, in cell membranes.     

Nanoporous Carbon Tubes from Fullerene Crystals as the π‐Electron Carbon Source

Here we report the thermal conversion of one‐dimensional (1D) fullerene (C₆₀) single‐crystal nanorods and nanotubes to nanoporous carbon materials with retention of the initial 1D morphology. The 1D C₆₀ crystals are heated directly at very high temperature (up to 2000 °C) in vacuum, yielding a new family of nanoporous carbons having π‐electron conjugation within the sp²‐carbon robust frameworks. These new nanoporous carbon materials show excellent electrochemical capacitance and superior sensing properties for aromatic compounds compared to commercial activated carbons.     

Formation of Foam‐like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand‐Assisted Foaming Process

Porous carbon material with a foam‐like microstructure has been synthesized by direct carbonization of porous coordination polymer (PCP). In situ generation of foaming agents by chemical reactions of ligands in PCP during carbonization provides a simple way to create lightweight carbon material with a foam‐like microstructure. Among several substituents investigated, the nitro group has been shown to be the key to obtain the unique foam‐like microstructure, which is due to the fast kinetics of gas evolution during carbonization. Foam‐like microstructural carbon materials showed higher pore volume and specific capacitance compared to a microporous carbon.     

Determination of Gaseous Formic and Acetic Acids by a Needle-Type Extraction Device coupled to a Gas Chromatography-Barrier Discharge Ionization Detector

Gaseous formic acid (FA) and acetic acid (AA) were concentrated by a needle-type extraction device, and the extracted analytes were determined using a gas chromatography-barrier discharge ionization detector. An activated carbon particle showed good extraction/desorption performance for FA and AA. The limit of quantification for FA and AA was 900 and 180 ng L^?1 at sample volumes of 100 mL, and 150 and 30 ng L^?1 at a sample volume of 600 mL, respectively. The storage performance of the analytes in the extraction needle was quantitatively evaluated at different temperatures, and the applicability of the proposed method to determine FA and AA in air samples was demonstrated.