Selective adsorption of biladien-ab-one and zinc biladien-ab-one to mesoporous silica

The adsorption of linear tetrapyrroles and porphyrins to mesoporous silicas with pore diameters of 2.3, 2.7, 4.0, and 7.0 nm from a benzene solution was investigated. As linear tetrapyrroles, 1,15,21,22-tetrahydro-19-benzoyl-5,10,15-triphenyl-15-hydroxybilin-1-one (biladien-ab-one, 1a), its zinc complexes (2 and 3), 1,15,21,22-tetrahydro-19-(4-hexyloxybenzoyl)-5,10,15-tri(4-hexyloxy)phenyl-15-hydroxybilin-1-one (C6-biladienone, 1b), 1,15,21,22-tetrahydro-19-(4-nonyloxybenzoyl)-5,10,15-tri(4-nonyloxy)phenyl-15-hydroxybilin-1-one (C9-biladienone, 1c), 1,15, 21,22-tetrahydro-19-(4-dodecyloxybenzoyl)-5,10,15-tri(4-dodecyloxy)phenyl-15-hydroxybilin-1-one (C12-biladienone, 1d), and 1,15,21,22-tetrahydro-19-(3,5-didodecyloxybenzoyl)-5,10,15-tri(3, 5-di-dodecyloxy)phenyl-15-hydroxybilin-1-one (1e) were employed. As porphyrins, 5,10,15,20-tetraphenylporphyrin (4a) and 5,10,15,20-tetra(4-methoxyphenyl)porphyrin (4b) were used. The isothermal adsorption curves were determined, showing that the amount of adsorption decreases in the order, 1a > 1b > 1c > 1d > 2, while neither 1e, 4a, nor 4b were adsorbed to mesoporous silicas. Mesoporous silica with the diameter of 4.0 nm adsorbed the largest amounts of biladienones. The adsorption was not observed in THF, acetone or ethanol. Neither 1c nor 1d was adsorbed to mesoporous silica with the pore diameter of 2.3 nm. These results indicate that the absorption is driven by polar interactions such as hydrogen bonding, and size exclusion effects are observed even for a molecule with flexible alkyl chains. The amount of adsorbed biladienone increased as the temperature was raised from 25 to 35 °C. The adsorption of biladien-ab-ones at 80 °C caused dehydration of biladien-ab-one to bilatrien-abc-one due to the acidity of the mesoporous silica.     

Characterization of economic requirements for a "carbon-debt-free country"

In recent years, greenhouse gas emission controls that incorporate the supply chains of products and services, thereby emphasizing the role of consumers rather than producers, have been drawing increasing attention. A country's consumption-based emissions, including those due to global supply chains, reflect the total emissions on which the national economy relies. To design effective emissions control strategies there is therefore an urgent need for countries to elucidate the structural relationship between their domestic economy and emissions occurring through global supply chains. Here we consider the structural characteristics of consumption-based emissions in Japan, which in 2005 totaled 1675 Mt CO(2)eq. Outside the country the Japanese economy generated global emissions of 541 Mt CO(2)eq, 35.7% of which were UNFCCC Annex I emissions and 64.3% were non-Annex I and other emissions. This figure of 64.3% reveals that Japan is actually relying to a considerable degree on emissions that are subject to no international obligations. We identify key economic contributors to consumption-based emissions at the commodity level and specify items of household expenditure that are effective options for both financial savings and emissions reduction. We then discuss the importance of emissions control for evolving toward a "carbon-debt-free country".     

Nutrition analysis by nanoparticle-assisted laser desorption/ionisation mass spectrometry

We analysed the bioactive compounds in Panax ginseng C.A. Meyer by using nanoparticle-assisted laser desorption/ionisation (nano-PALDI) mass spectrometry (MS). To this end, we prepared manganese oxide nanoparticles (d = 5.4 nm) and developed a nano-PALDI MS method to analyse the standard ginsenosides and identify these ginsenosides in an extract of P. ginseng. The nanoparticles served as an ionisation-assisting reagent in MS. The mass spectra did not show any background interference in the low-m/z range. Our pilot study showed that the nanoparticles could ionise the standard ginsenosides and also respective lipid and ginsenosides in the extract without the aid of chemical and liquid matrices used in conventional MS methods. Analysis of the post-source decay spectra obtained using nano-PALDI MS will yield information regarding the chemical structure of the analyte.     

Electrodialytic ion isolation for matrix removal

We report a fully automated online sample pretreatment system for ionic analytes that extracts the ionic analytes from the sample and largely removes the nonionic sample matrix and can preconcentrate the analyte. Sample pretreatment is a key analytical process; conventional pretreatment is conducted in a difficult to automate batchwise manner. The present system relies on the transport of ions induced by an electric field to a water acceptor. Cations and anions are simultaneously and separately collected into individual acceptor streams which can be directly introduced to a chemical analyzer. Common inorganic ions (≤10 meq/L) are quantitatively transferred from samples within a few seconds. Small nonionic molecules are transferred by 0.5-10%, and proteins are not transferred at all. The method has been successfully applied to drinking water, urine, and cow's milk with 3.7 ± 2.5, 3.8 ± 2.6, and 4.6 ± 2.6%, respectively, in variance (n = 10). Present results agreed well with those from conventional pretreatment methods. Interestingly, when calcium in milk is measured by the present method, the results correspond to the total calcium by conventional methods; i.e., it can extract calcium from its protein-bound form in milk.     

Alkylated dihydroxybenzoic acid as a MALDI matrix additive for hydrophobic peptide analysis

Hydrophobic peptides are generally difficult to detect using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) because the majority of MALDI matrixes are hydrophilic and therefore have a low affinity for hydrophobic peptides. Here, we report on a novel matrix additive, o-alkylated dihydroxybenzoic acid (ADHB), which is a 2,5-dihydroxybenzoic acid (DHB) derivative incorporating a hydrophobic alkyl chain on a hydroxyl group to improve its affinity for hydrophobic peptides, thereby improving MALDI-MS sensitivity. The addition of ADHB to the conventional matrix α-cyano-4-hydroxycinnamic acid (CHCA) improved the sensitivity of hydrophobic peptides 10- to 100-fold. The sequence coverage of phosphorylase b digest was increased using ADHB. MS imaging indicated that hydrophobic peptides were enriched in the rim of a matrix/analyte dried spot when ADHB was used. In conclusion, the addition of ADHB to the standard matrix led to improved sensitivity of hydrophobic peptides by MALDI-MS.     

Role of in situ generated silica for rubber science and technology

Filled rubbers have a long history in rubber technology. Filler morphology in the rubber matrix significantly influences the performance of filled rubber products. Therefore, we have to achieve a certain morphology of filler in the rubbery matrix in order to enjoy good reinforcement. However, it has not been sufficiently known what kind of morphology is necessary for the reinforcement, because preparations of adequate models for the characterization of filler morphology have been difficult. The in situ silica filling of the rubber matrix can be modeled for the preparations. In this paper, the characteristic features of in situ silica generated in diene rubbers are reviewed, citing recent reports. Two important models are presented. One is a homogeneous silica filling in situ, producing soft rubber nanocomposites. The other is the formation of an in situ silica filler network, creating stiff rubber nanocomposites. The controlled in situ silica filling is useful to evaluate the reinforcement effect of filler in a rubber matrix. © 2016 Society of Chemical Industry     

Myristic Acid Enhances Diacylglycerol Kinase δ-Dependent Glucose Uptake in Myotubes

Decreased expression of diacylglycerol kinase (DGK) δ in skeletal muscles attenuates glucose uptake and is closely related to the pathogenesis of type 2 diabetes. Therefore, up‐regulation of DGKδ expression is thought to protect and improve glucose homoeostasis in type 2 diabetes. We recently determined that myristic acid (14:0), but not palmitic (16:0) or stearic (18:0) acid, significantly increased DGKδ2 protein expression in mouse C2C12 myotubes. In the current study, we analyzed whether myristic acid indeed enhances glucose uptake in C2C12 myotubes. We observed that myristic acid caused ~1.4‐fold increase in insulin‐independent glucose uptake. However, palmitic and stearic acids failed to enhance glucose uptake. DGKδ‐specific siRNA decreased myristic acid‐dependent increase of glucose uptake. Moreover, overexpression of DGKδ2 enhanced glucose uptake in C2C12 cells in the absence of myristic acid treatment. Taken together, these results strongly suggest that myristic acid enhances basal glucose uptake in myotubes in a DGKδ2 expression‐dependent manner.     

Synthesis and anomalous magnetic properties of LaFeO3 nanoparticles by hot soap method

Nanocrystalline LaFeO₃ particles were synthesized at low temperatures by using hot soap technique. The synthesis was based on the thermal decomposition of organometallic compounds precipitated in a hot coordinating solvent. Moderate heat treatment at low temperature far below the combustion point of organic compounds produced spherical LaFeO₃ nanoparticles with average diameter of about 15 nm. The crystalline phase, structure and particle size of obtained products were characterized by X-ray diffraction, infrared spectroscopy and transmission electron microscopy observations. In spite of the antiferromagnetic nature of bulk LaFeO₃, the obtained nanoparticles exhibited anomalous large magnetization. Superparamagnetic behavior with a blocking temperature of about 30 K was observed in both magnetization and Mössbauer spectroscopic analyses.