Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Glycans, a family of compounds often attached to proteins and ceramides, are diverse molecules involved in a wide range of biological functions. Their structural analysis is necessary and is often carried out at the microscale level. Methods based on mass spectrometry are therefore used, although they do not provide information regarding isomeric structures often found in glycan structures. If one finds "factors" characteristic of a certain isomer, this information can be used to elucidate an unknown oligosaccharide sequence. One potential technique is to use energy-resolved mass spectrometry (ERMS) that has been used to distinguish a pair of isomeric compounds. Thus, compounds in a combinatorial library might be effectively used for this purpose. We analyzed a set of 16 isomeric disaccharides, the structures of which consisted of all possible combinations of anomeric configurations and interglycosidic linkage positions. All of the compounds were distinguished based on ERMS where normal collision-induced dissociation could distinguish only seven compounds. Furthermore, it was shown that alpha-glycosidic linkages of fucose were more reactive than the beta-isomers and the secondary glycosides were more reactive than the primary glycosides.     

Anomeric information obtained from a series of synthetic trisaccharides using energy resolved mass spectra

The majority of structural investigations of oligosaccharides based on mass spectrometry use naturally occurring oligosaccharides, which do not allow extracting any common feature associated with anomeric structures and linkage positions. In order to address the issue to find such characteristics possibly contained in oligosaccharide structure, a synthetic combinatorial trisaccharide library was analyzed. The trisaccharides used in the analysis consisted of L-fucose, D-galactose and D-glucose, in which individual glycosidic linkages existed in either alpha- or beta-anomers. The analysis of energy-resolved mass spectra (ERMS) and the scattered plot analysis of some parameters obtained from ERMS for a series of trisaccharides revealed that lower activation energy was required for the dissociation of alpha-glycosides of these sugars compared to those of the corresponding beta-anomers. It is suggested that this finding may be useful in structural analysis of natural oligosaccharides.     

The conformation of alkyl cyclohexanones and terpenic ketones. Interpretation for the ‘alkylketone effect’ based on the CH/π(CO) hydrogen bond

Ab initio MO calculations were carried out, at the MP2/6-311++G(d,p)//MP2/6-311G(d,p) level, to investigate the Gibbs free energy of the conformational isomers of 2-alkyl, 3-alkyl, and 4-alkyl cyclohexanones. The calculation gave results consistent with the general trend experimentally found. The genesis of stabilization of the axial conformers in 2- and 3-alkyl cyclohexanones, as compared to the structurally corresponding cyclohexane derivatives, was sought in the context of the attractive CH/π(CO) hydrogen bond. In support of this hypothesis, short nonbonded distances have been noted between CHs in the alkyl group and the carbonyl carbon in the relevant axial conformers. Calculations were also carried out to study the conformational energies of several terpenic ketones. For isomenthone, more than a half molecular fraction (ca. 55%) has been suggested to be in the isopropyl-axial conformation, while for isocarvomenthone ca. 77% has been suggested to be in the axial-isopropyl conformation; this is consistent with bibliographic experimental data. A crystallographic database search has provided results compatible with this conclusion. We suggest that the relative stability of the axial alkyl substituent, often observed in terpenic and steroidal ketones is rationalized in terms of an attractive molecular force, the CH/π(CO) hydrogen bond.     

Non-isothermal crystallization, melting behavior and polymorphism of polypropylene in β-nucleated polypropylene/recycled poly(ethylene terephthalate) blends

β-Nucleated polypropylene (PP), non-compatibilized and compatibilized β-nucleated PP/recycled poly(ethylene terephthalate) (r-PET) blends were prepared on a twin-screw extruder. The compatibilizers were maleic anhydride grafted PP (PP-g-MA), glycidyl methacrylate grafted PP (PP-g-GMA), maleic anhydride grafted polyethylene-octene (POE-g-MA) and polyethylene-vinyl acetate (EVA-g-MA) elastomers. Effects of r-PET content, compatibilizer type and content, pre-melting temperature and time on the non-isothermal crystallization and melting behavior, and polymorphism of PP in the blends were investigated by differential scanning calorimeter (DSC). DSC results show that the crystallization temperature of PP crystallized predominantly in β-modification was higher than that of neat PP. In the non-compatibilized blend, PP matrix crystallized mainly in α-modification even if r-PET content was only 10 wt%. However, PP-g-MA compatibilization made PP matrix crystallize mainly in β-modification, but PP-g-GMA, POE-g-MA and EVA-g-MA did not improve the β-modification content distinctly. The α-crystal melting peak temperature of PP decreased with increasing pre-melting temperature, but r-PET content, compatibilizer type and content as well as pre-melting time had no obvious effect on the melting temperature of PP. The increase in PP-g-MA content, pre-melting temperature and time was benefit for the formation of β-modification. It is suggested that the β-nucleating agent is encapsulated or dissolved in polar r-PET in β-nucleated PP/r-PET blend, addition of PP-g-MA to the non-compatibilized blend resulted in transferring β-nucleating agent from r-PET phase into PP phase, the increase in PP-g-MA content, melting temperature and time was benefit for transferring β-nucleating agent from r-PET phase into PP phase. The non-isothermal crystallization kinetics of PP in the blends were evaluated by Mo’s method.     

High-throughput assay of nitric oxide metabolites in human plasma without deproteinization by lab-on-a-chip electrophoresis using a zwitterionic additive

In order to develop a high-throughput assay for nitric oxide metabolites, nitrite (NO2-) and nitrate (NO3-), in biological fluids, we have investigated the simultaneous determination of them using an electrophoretic lab-on-a-chip (microchip capillary electrophoresis, MCE) technique. In this study, in order to establish an MCE assay process without deproteinization, the addition of a zwitterionic additive into the running buffer to reduce the adsorption of protein onto the surface of channel was investigated. Initially, some zwitterionic additives were investigated by making a comparison of relative standard deviations (RSDs) of the migration times for NO2(-) and NO3(-) on capillary electrophoresis. From the results of our comparison of the RSD values, 2% (w/w) N-cyclohexyl-2-aminoethanesulfonic acid (CHES) was selected. As a result of the application of the running buffer with CHES to the MCE process, the complete separation of NO2(-) and NO3(-) in human plasma without deproteinization was achieved within 1 min. Since the RSD values of the positions of the peaks were less than 2.3%, beneficial reduction effects on MCE were suggested. When we used an internal standard method in order to correct the injection volume, the RSDs of the peak heights and areas were less than 10%, and the correlation coefficients of spiked calibration curves ranging from 0 to 350 microM were 0.999 and 0.997 for NO2(-) and NO3(-), respectively. The limits of detection (S/N=3) were 53 microM for NO2(-) and 41 microM for NO3(-). Moreover, the correlation coefficients in excess of 0.99 between the MCE method and a conventional Griess method were achieved for both NO2(-) and NO3(-). Consequently, the possibility of establishing a high-throughput assay process was obtained by utilizing 2% (w/w) CHES to reduce protein adsorption.     

Mechanism of a gas-phase dissociation reaction of 4-aminobutyl glycosides under CID MS/MS conditions

The assembly of monosaccharides during the synthetic process of glycan structures is responsible for the diversity of this family of molecules. Because of the complexity of the glycan structure, synthesis of oligosaccharides and structural analysis have been difficult tasks. During efforts to develop glycosides carrying an aglycon that can be used in both functional and structural investigations, we found that 4-aminobutyl glycosides fulfill these criteria. We also observed that the glycosidic linkage underwent an interesting dissociation reaction under collision-induced MS/MS, and that the reaction product is very useful in structural investigation based on mass spectrometry, especially since it provides information regarding anomeric configurations. Despite its importance, the reaction mechanism of the dissociation is not fully understood. For this reason, we studied the mechanism by synthesizing possible products and used them in detailed analyses based on energy-resolved mass spectrometry where the energy dependence of the dissociation reaction was analyzed under collision-induced dissociation conditions. As a result of spectral match with one of synthesized reference compounds, it was suggested that the dissociation reaction to generate a C-ion species and a pyrrolidine took place through a five-membered transition state in two-step reaction sequence.     

反蛋白石结构ZnO@PDA用于增强光催化产H2O2性能

利用太阳能驱动生产高能量密度的H₂O₂太阳能燃料引起了广泛关注,但目前光催化剂缓慢的动力学限制了其实际应用。本文制备一种聚多巴胺(PDA)改性的反蛋白石结构ZnO(ZnO@PDA)光催化剂,用于可持续性的光催化产H₂O₂。由于电子的转移,因此当PDA与ZnO接触后,会在界面处形成一个从PDA指向ZnO的内建电场。在内建电场和能带弯曲的驱动下,ZnO导带中的光生电子与PDA最高占据分子轨道(HOMO)中的空穴复合,符合梯型异质结的电荷转移和分离途径。这种独特的梯型异质结确保了有效的电子或空穴的分离并且留存下具有强氧化还原能力的光生载流子。此外,与纯ZnO相比,反蛋白石结构的ZnO@PDA具有更强的光吸收能力。实验表明,归因于光吸收能力的提高,光生载流子的有效分离和强氧化还原能力,负载0.03% (原子分数) PDA的ZnO样品具有最佳的产H₂O₂性能(1011.4 μmol·L^-1·h^-1),分别是纯ZnO和PDA的4.4和8.9倍。     

Enzyme separation and isozyme heterogeneity analysis using non-denaturing two-dimensional electrophoresis

Carboxylesterase and sorbitol dehydrogenase are separated by non-denaturing two-dimensional electrophoresis (2-DE) of isoelectric focusing separation using 5% carrier ampholyte (pH 6-8) and 1.25% carrier ampholyte (pH 3-10) and size separation. Furthermore, activities of sorbitol, malate and lactate dehydrogenases are sequentially examined when the enzymes are separated by 2-DE and are sequentially reacted to sorbitol, malic and lactic acid, respectively, in the presence of nicotinamide adenine dinucleotide, nitro blue tetrazolium and phenazine methosulphate. Several kinds of enzymes including lactate dehydrogenize isozymes can be simultaneously separated using 2-DE. Furthermore, the binding differences between lactate dehydrogenase isozymes and concanavalin A (con A) can be examined using a combination of 2-DE and non-denaturing stacking gel electrophoresis. The results of this study indicate that non-denaturing 2-DE can be applied to both enzyme separation and isozyme heterogeneity analysis.     

Vertex operators in the conformal field theory on P 1 and monodromy representations of the braid group

Vertex operators (primary fields) are constructed for the conformal field theory on P ¹ by means of A ₁ ⁽¹⁾ modules. The commutation relations of vertex operators induce monodromy representations of the braid group on the spaces of vacuum expectations of compositions of vertex operators.