Effect of Anomeric Linkage on the Sialylation of Glycosides by Cells

The synthesis of sialylated glycosides using saccharide primers and cells was investigated. α · and β · Saccharide primers were chemically synthesized and introduced into B16 melanoma cells to prime oligosaccharide synthesis. Incorporation of α‐ and β‐dodecyl lactosides into B16 cells resulted in the sialylation of the galactose residue to give GM3‐type oligosaccharides. The β‐dodecyl galactoside primer was sialylated but the α‐dodecyl galactoside primer was not. Both the α‐ and β‐dodecyl glucoside primers were not elongated. In the glycosylation of primers by cells, this research confirmed that sialyl transferases tolerate acceptor modifications and are permissive to primer elongation regardless of the α‐ or β‐linkage to the aglycon unit. However, the presence of the terminal galactose residue that is β‐linked to the adjacent saccharide or aglycon unit is essential for sialylation by cellular enzymes to occur.     

Design and synthesis of novel spirocyclopropyl cyclohexane-1,3-diones and -1,3,5-triones for their incorporation into potent HPPD inhibitors

We report the design and the efficient synthesis of novel spirocyclopropyl cyclohexane-1,3-dione and -1,3,5-trione units to be incorporated into potent HPPD inhibitors. New routes involving original combinations of synthetic equivalents of α-cyclopropyl ketone-α-anion and α-cyclopropyl ester-β-cation are described.     

Comparison on photo-initiators for the preparation of methacrylate monolithic columns for capillary electrochromatography

The synthesis of lauryl methacrylate monoliths for capillary electrochromatography by UV polymerization using several free-radical initiators (α,α′-azobisisobutyronitrile, 2,2-dimethoxy-2-phenylacetophenone, dibenzoyl peroxide (BPO) and lauroyl peroxide (LPO)) has been investigated. Using a 1,4-butanediol/1-propanol mixture as porogenic solvent, the influence of each initiator and its content on the morphological and electrochromatographical properties of beds was evaluated. Under their respective optimum content, satisfactory separations of a test mixture of PAHs with similar efficiencies (minimum plate heights of 8.0–12.7 μm obtained from Van Deemter plots) were achieved for the four investigated photo-initiators. The columns photo-polymerized with LPO provided the best compromise between chromatographic performance and analysis time. Moreover, this initiator showed a fine control in the column retention properties. The resulting monolithic columns exhibited a good run-to-run repeatability in the tested chromatographic parameters (RSD < 2.4%) for all initiators investigated; and satisfactory column-to-column repeatability (RSD < 6.0%), except for beds photo-polymerized with BPO (RSD < 10.8%).     

Interaction between α-actinin and negatively charged lipids membrane investigated by surface plasmon resonance and electrochemical methods

α-Actinin has been shown to be capable of interacting with some special membrane phospholipids directly, which is important for its function. In this study, hybrid bilayer membranes composed of negatively charged lipids are constructed on the surface plasmon resonance gold substrate and on the gold electrode, respectively, and the interaction between α-actinin and negatively charged lipids membrane is investigated by surface plasmon resonance, cyclic voltammetry and electrochemical impedance spectroscopy methods. α-Actinin is proved to be able to interact with the negatively charged lipids membrane directly. It can also insert at least partly into the membrane or lead to some defect or lesion in the membrane, which increase the permeability of the membrane. This study would bring some insight on the interaction between the α-actinin and the cell membranes in vivo.     

Biodegradation of soluble redox polymers. Part 2: (0.017ferrocene)amylose at a rotating disk electrode

The behavior of (ferrocene)amylose (FA), in the presence of amylolytic depolymerases (α-amylase from Aspergillus oryzae and human saliva), has been investigated by cyclic voltammetry at a rotating disk electrode (CVA/RDE). Growth of the limiting current with time in the presence of the enzymes is proportional to the amount of enzyme introduced. The quantitative data treatment to assay the endoamylolytic activity of enzymes at CVA/RDE involves plotting (i_dt/i_d0)^4.5 against time; the slope of the linear plot being equal to (rate) M_n0C⁻¹, where i_dt and i_d0 are the limiting currents at time t and 0, respectively, (rate) is the enzymatic activity, M_n0 is the number averaged molecular weight of FA at t = 0, and c is its concentration. The comparison of CVA/RDE with the 3,5-dinitrosalicylic acid and the Somogyi–Nelson reducing saccharides procedures shows advantages of the former, especially in assaying small quantities of enzymes. Also the CVA/RDE approach is simpler and takes place under much milder conditions. The main disadvantage of CVA/RDE is the inhibiting effect of Triton X-100 in the reaction between FA and the amylases which is not observed in the case of native, ferrocene-free amylose. In general, CVA/RDE appears to be an attractive analytical method for monitoring diverse enzymatic depolymerization reactions.     

Photolytic decarboxylation of α-arylcarboxylic acids mediated by HgF2 under a dioxygen atmosphere

Mercuric fluoride (HgF₂), as a light-sensitive inorganic compound, in the presence of dioxygen is able to convert various α-aryl- and α,α-diarylcarboxylic acids into the corresponding aldehydes and ketones selectively under photoirradiation via trapping of the benzylic radical by O₂.     

Lim-inf convergence in partially ordered sets

The lim-inf convergence in a complete lattice was introduced by Scott to characterize continuous lattices. Here we introduce and study the lim-inf convergence in a partially ordered set. The main result is that for a poset P the lim-inf convergence is topological if and only if P is a continuous poset. A weaker form of lim-inf convergence in posets is also discussed.     

温度对ZnO/Al2O3(0001)界面的吸附、扩散及生长初期模式的影响

构建了一个ZnO沉积在α-Al₂O₃(0001)表面生长初期的模型，采用基于密度泛函理论的平面波超软赝势法进行了动力学模拟.发现在400，600和800℃的条件下界面原子有不同的扩散能力，因此温度对ZnO/α-Al₂O₃(0001)表面界面结构以及ZnO薄膜生长初期模式有决定性的影响.在整个ZnO吸附生长过程中，O原子的扩散系数大于Zn原子的扩散系数，O原子的层间扩散对薄膜的均匀生长起着重要作用.进一步从理论计算上证实了ZnO在蓝宝石(0001)上两种生长模式的存在，400℃左右生长模式主要是Zn螺旋扭曲生长，具有Zn六角平面对称特征，且有利于Zn原子位于最外表面.600℃左右呈现为比较规则的层状生长，且有利于O原子位于最外表面.模拟观察到在ZnO薄膜临近Al₂O₃基片表面处，Zn的空位缺陷明显多于O的空位缺陷. 关键词： 扩散 薄膜生长 2O₃(0001)')" href="#">α-Al₂O₃(0001) ZnO     

Structural changes in β-lactoglobulin by conjugation with three different kinds of carboxymethyl cyclodextrins

β-Lactoglobulin-carboxymethyl cyclodextrin (β-LG-CMCyD) conjugates were prepared by using water soluble carbodiimide. Three kinds of CMCyDs differing in molecular mass were used to investigate the effects of different CMCyD contents, net charge and hydrophobicity on the structural changes in β-lactoglobulin. The effect of CMCyDs on the structure of β-lactoglobulin was utilized to investigate the contribution of hydrophobic interactions to the stability of the protein. Spectroscopic studies suggested that the conformation around had not changed in either conjugate but the α-helix content of β-LG-CMCyD conjugates had markedly increased as compared with that of β-lactoglobulin. The differential scanning calorimetry technique confirmed that the addition of one glucose unit in β-LG-CMCyD conjugates, enthalpy change of calorimetry decreased and the denaturation temperature of each conjugate was higher than that of native β-lactoglobulin. The heat contents agreed well with the conformational transition measured by molar ellipticity at 222 nm ([θ]₂₂₂) and Stoke's radius (R_S) values. Therefore, hydrophobic forces play an important role in stabilizing and shielding of the β-LG-CMCyD conjugates.