Development of a simple capillary electrophoretic determination of glucosamine in nutritional supplements using in-capillary derivatisation with o-phthalaldehyde

A simple capillary electrophoretic method was developed for the determination of glucosamine using in-capillary derivatisation. Glucosamine in commercial products was extracted with purified water. The CE separation was achieved on an uncoated fused-silica capillary using a 20 mM borate buffer (pH 9.2) containing 5 mM o-phthalaldehyde (OPA) and 5 mM 3-mercaptopropionic acid (MPA) at 25 kV, followed by UV detection at 340 nm. The detector response was linear (r² > 0.999) in the concentration range 10–1000 μg/mL. The limit of detection (LOD) was 1.3 mg/g. Spiked glucosamine recoveries at 50 and 100 mg/g level were 95.1% and 104.3%, respectively. The method was applied to 16 commercial products. The concentrations of glucosamine were 109–705 mg/g, and the ratios of detected glucosamine content to the labelled value were 88.8–124%. No significant bias was observed (r² = 0.989, p < 0.01), between results obtained by the proposed CE method and an official colorimetric method (Japanese Health Food & Nutrition Food Association).     

Chemical Recognition of Partner Plant Species by Foundress Ant Queens in Macaranga–Crematogaster Myrmecophytism

The partnership in the Crematogaster–Macaranga ant–plant interaction is highly species-specific. Because a mutualistic relationship on a Macaranga plant starts with colonization by a foundress queen of a partner Crematogaster species, we hypothesized that the foundress queens select their partner plant species by chemical recognition. We tested this hypothesis with four sympatric Macaranga species and their Crematogaster plant-ant species. We demonstrated that foundress Crematogaster queens can recognize their partner Macaranga species by contact with the surface of the seedlings, that they can recognize compounds from the stem surface of seedlings of their partner plant species, and that the gas chromatographic profiles are characteristic of the plant species. These findings support the hypothesis that foundress queens of the Crematogaster plant-ant species select their partner Macaranga species by recognizing nonvolatile chemical characteristics of the stem surfaces of seedlings.     

Hydrothermal Synthesis and Formation Mechanisms of Lanthanum Tin Pyrochlore Oxide

Well-defined La₂Sn₂O₇ with a phase-pure pyrochlore structure was produced by hydrothermal synthesis at temperatures as low as 200°C. Production of phase-pure La₂Sn₂O₇ requires a pH above 10, and higher pH accelerates the crystallization process. The synthesis produced spherical particles of average particle size ∼0.59 μm (±0.12) and surface area ∼14.1 m²/g. SEM and TEM observation for morphologic evolution and kinetic analysis during crystallization indicated that La₂Sn₂O₇ formation probably proceeds via a two-step reaction. First a transient dissolution–precipitation occurs. Then the primary crystallites aggregate because of their colloidal instability, and heterocoagulation with the lanthanum hydrous oxide precursor particles also occurs. The sluggish reaction rate at the later stage of reaction is characterized by an in situ transformation, where the soluble tin species is diffused through the porous La₂Sn₂O₇ aggregates to react with entrapped lanthanum precursors.     

Separation of C6H6 and C6H12 from H2 using ionic liquid/PVDF composite membrane

Ionic liquid/polyvinylidene fluoride composite membrane was successfully prepared by impregnation method and used for the separation on organic chemical hydride process. The separation factors of C₆H₆/H₂ and C₆H₁₂/H₂ in the ternary mixture system were 7500 and 300, respectively. The ionic liquid membrane showed an excellent possibility as a technology of H₂ purification in the organic chemical hydride process by removing aromatic hydrocarbon and cycloalkane simultaneously from the ternary system. © 2015 American Institute of Chemical Engineers AIChE J, 62: 624–628, 2016     

Influence of macromolecular structure of novel 2- and 4-armed polylactides on their physicochemical properties and in vitro degradation process

The objective of this study was to analyse how macromolecular structure of polylactides influences their properties and degradation rate. To achieve this, novel 2- and 4-armed PDLLA and PLLA (noted as 2b and 4b) were synthesized by ring-opening method. 1,4-butanediol and pentaerythritol were used as initiators and stannous octoate was used as catalyst. The obtained polymers were investigated in terms of molecular weight by size exclusion chromatography, thermal properties by differential scanning calorimetry and thermogravimetry, and hydrophilicity by the contact angle measurements. The in vitro degradation test was carried out in PBS solution at 37 °C by means of the mass loss, water uptake, molecular weight and thermal properties changes. The branched polylactides including 2bPDLLA, 4bPDLLA, 2bPLLA and 4bPLLA were successfully synthesized and the average molecular weights were around 40-45 kDa. The numbers of arms in each polymer just slightly influenced the thermal properties and the contact angle. The crystallinity of 4bPLLA was 23 %, whereas for 2bPLLA it was 41 %. The degradation rates of both 2b and 4bPLLA were similar and the degradation process was similar only during first 7 weeks. After this period, the degradation rate of 4bPDLLA increased. Consequently, thermal properties and degradation profiles of the branched polymers would depend on plural factors, such as chain length and crystallinity in branched structure.     

Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent

A novel vinyl ether-type RAFT agent, benzyl 2-(vinyloxy)ethyl carbonotrithioate (BVCT) was synthesized for various block copolymers via the combination of living cationic polymerization of vinyl ethers and reversible addition−fragmentation chain transfer (RAFT) polymerization. The novel BVCT–trifluoroacetic acid adduct play an important role to produce well-defined block copolymers, which is both as a cationogen under EtAlCl₂ initiation system in the presence of ethyl acetate for living cationic polymerization and a RAFT agent for blocks by RAFT polymerization. The resulting polymer, poly(vinyl ether)s, by living cationic polymerization had a high number average α-end functionality (≥0.9) as determined by both ¹H NMR and MALDI-TOF-MS spectrometry. In addition, this poly(vinyl ether)s worked well as a macromolecular chain transfer agent for RAFT polymerization. The RAFT polymerization of radically polymerizable monomers was conducted in toluene using 2,2′-azobis(isobutyronitrile) at 70 °C. For example, a double thermoresponsive block copolymer (MOVE₆₁-b-NIPAM₁₅₀) consisting of 2-methoxyethyl vinyl ether (MOVE) and N-isopropylacrylamide (NIPAM) was prepared via the combination of living cationic polymerization and RAFT polymerization. The block copolymer reversibly formed and deformed micellar assemblies above the phase separation temperature (T_ps) of poly(NIPAM) block in water. This BVCT is not only functioned as an initiator, but also acted as a monomer. When BVCT was copolymerized with MOVE by living cationic polymerization, followed by graft copolymerization with NIPAM via RAFT polymerization, well-defined graft copolymers (MOVE_n-co-BVCT_m)-g-NIPAM_x (n = 62–73, m = 1–9, x = 19–214) were successfully obtained. However, no micelle formed in water above T_ps of poly(NIPAM) graft chain unlike the case of block copolymers.     

Lewis Acid‐Catalyzed or Base‐Promoted Regioselective Cycloisomerization of N‐Imidoyl‐o‐alkynylanilines for Synthesis of N‐Imidoyl‐(1 H)‐indoles and 4‐Alkylidene‐3,4‐dihydroquinazolines

Product selectivity control for the synthesis of imidoylindoles and 4‐alkylidenedihydroquinazolines from N‐imidoyl‐o‐alkynylanilines via silver triflate‐catalyzed cycloisomerization or tetrabutylammonium fluoride‐promoted cyclization is described. The product selectivity depends mainly on the catalyst/promoter used, and on the substituents on the alkyne and amidine functions of the substrates.

     

Pial Vessel-Associated Microglia/Macrophages Increase in Female Dahl-SS/Jr Rats Independent of Pregnancy History

As the resident immune cells of the central nervous system, microglia have a wide range of functions such as surveillance, phagocytosis, and signaling through production of chemokines and cytokines. Recent studies have identified and characterized macrophages residing at the meninges, a series of layers surrounding the brain and spinal cord. While perivascular microglia within the brain parenchyma increase following chronic hypertension, there are no reports of changes at the meninges, and specifically, associated with the pial vasculature. Thus, we used female Sprague Dawley and Dahl salt-sensitive (SS/Jr) rat brains, stained for ionized calcium-binding adapter molecule (Iba1), and characterized microglia/macrophages associated with pial vessels in the posterior brain. Results indicate that Iba1⁺ pial vessel-associated microglia (PVAM) completely surrounded the vessels in brains from the Dahl-SS/Jr rats. PVAM density was significantly higher and distance between PVAMs lower in Dahl-SS/Jr compared to the Sprague Dawley rat brains. Pregnancy history did not affect these findings. While the functional role of these cells are not known, we contextualize our novel findings with that of other studies assessing or characterizing myeloid cells at the borders of the CNS (meninges and choroid plexus) and perivascular macrophages and propose their possible origin in the Dahl-SS/Jr model of chronic hypertension.