MALDI‐MS profiling of serum O‐glycosylation and N‐glycosylation in COG5‐CDG

Congenital disorders of glycosylation (CDG) are due to defective glycosylation of glycoconjugates. Conserved oligomeric Golgi (COG)‐CDG are genetic diseases due to defects of the COG complex subunits 1–8 causing N‐glycan and O‐glycan processing abnormalities. In COG‐CDG, isoelectric focusing separation of undersialylated glycoforms of serum transferrin and apolipoprotein C‐III (apoC‐III) allows to detect N‐glycosylation and O‐glycosylation defects, respectively. COG5‐CDG (COG5 subunit deficiency) is a multisystem disease with dysmorphic features, intellectual disability of variable degree, seizures, acquired microcephaly, sensory defects and autistic behavior. We applied matrix‐assisted laser desorption/ionization‐MS for a high‐throughput screening of differential serum O‐glycoform and N‐ glycoform in five patients with COG5‐CDG. When compared with age‐matched controls, COG5‐CDG showed a significant increase of apoC‐III_0a (aglycosylated glycoform), whereas apoC‐III₁ (mono‐sialylated glycoform) decreased significantly. Serum N‐glycome of COG5‐CDG patients was characterized by the relative abundance of undersialylated and undergalactosylated biantennary and triantennary glycans as well as slight increase of high‐mannose structures and hybrid glycans. Using advanced and well‐established MS‐based approaches, the present findings reveal novel aspects on O‐glycan and N‐glycan profiling in COG5‐CDG patients, thus providing an increase of current knowledge on glycosylation defects caused by impairment of COG subunits, in support of clinical diagnosis. Copyright © 2017 John Wiley & Sons, Ltd.     

Singlet Oxygen during Cycling of the Aprotic Sodium–O2 Battery

Aprotic sodium–O₂ batteries require the reversible formation/dissolution of sodium superoxide (NaO₂) on cycling. Poor cycle life has been associated with parasitic chemistry caused by the reactivity of electrolyte and electrode with NaO₂, a strong nucleophile and base. Its reactivity can, however, not consistently explain the side reactions and irreversibility. Herein we show that singlet oxygen (¹O₂) forms at all stages of cycling and that it is a main driver for parasitic chemistry. It was detected in‐ and ex‐situ via a ¹O₂ trap that selectively and rapidly forms a stable adduct with ¹O₂. The ¹O₂ formation mechanism involves proton‐mediated superoxide disproportionation on discharge, rest, and charge below ca. 3.3 V, and direct electrochemical ¹O₂ evolution above ca. 3.3 V. Trace water, which is needed for high capacities also drives parasitic chemistry. Controlling the highly reactive singlet oxygen is thus crucial for achieving highly reversible cell operation.     

Aptamer‐functionalized Fe3O4 magnetic nanoparticles as a solid‐phase extraction adsorbent for the selective extraction of berberine from Cortex phellodendri

The extraction adsorbent was fabricated by immobilizing the highly specific recognition and binding of aptamer onto the surface of Fe₃O₄ magnetic nanoparticles, which not only acted as recognition elements to recognize and capture the target molecule berberine from the extract of Cortex phellodendri , but also could favor the rapid separation and purification of the bound berberine by using an external magnet. The developed solid‐phase extraction method in this work was useful for the selective extraction and determination of berberine in Cortex phellodendri extracts. Various conditions such as the amount of aptamer‐functionalized Fe₃O₄ magnetic nanoparticles, extraction time, temperature, pH value, Mg²⁺ concentration, elution time and solvent were optimized for the solid‐phase extraction of berberine. Under optimal conditions, the purity of berberine extracted from Cortex phellodendri was as high as 98.7% compared with that of 4.85% in the extract, indicating that aptamer‐functionalized Fe₃O₄ magnetic nanoparticles‐based solid‐phase extraction method was very effective for berberine enrichment and separation from a complex herb extract. The applicability and reliability of the developed solid‐phase extraction method were demonstrated by separating berberine from nine different concentrations of one Cortex phellodendri extract. The relative recoveries of the spiked solutions of all the samples were between 95.4 and 111.3%, with relative standard deviations ranging between 0.57 and 1.85%.     

Different supramolecular architectures mediated by different weak interactions in the crystals of three N‐aryl‐2,5‐dimethoxybenzenesulfonamides

The synthesis and evaluation of the pharmacological activities of molecules containing the sulfonamide moiety have attracted interest as these compounds are important pharmacophores. The crystal structures of three closely related N‐aryl‐2,5‐dimethoxybenzenesulfonamides, namely N‐(2,3‐dichlorophenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₄H₁₃Cl₂NO₄S, (I), N‐(2,4‐dichlorophenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₄H₁₃Cl₂NO₄S, (II), and N‐(2,4‐dimethylphenyl)‐2,5‐dimethoxybenzenesulfonamide, C₁₆H₁₉NO₄S, (III), are described. The asymmetric unit of (I) consists of two symmetry‐independent molecules, while those of (II) and (III) contain one molecule each. The molecular conformations are stabilized by different intramolecular interactions, viz. C—H…O interactions in (I), N—H…Cl and C—H…O interactions in (II), and C—H…O interactions in (III). The crystals of the three compounds display different supramolecular architectures built by various weak intermolecular interactions of the types C—H…O, C—H…Cl, C—H…π(aryl), π(aryl)–π(aryl) and Cl…Cl. A detailed Hirshfeld surface analysis of these compounds has also been conducted in order to understand the relationship between the crystal structures. The d _norm and shape‐index surfaces of (I)–(III) support the presence of various intermolecular interactions in the three structures. Analysis of the fingerprint plots reveals that the greatest contribution to the Hirshfeld surfaces is from H…H contacts, followed by H…O/O…H contacts. In addition, comparisons are made with the structures of some related compounds. Putative N—H…O hydrogen bonds are observed in 29 of the 30 reported structures, wherein the N—H…O hydrogen bonds form either C (4) chain motifs or R ₂²(8) rings. Further comparison reveals that the characteristics of the N—H…O hydrogen‐bond motifs, the presence of other interactions and the resultant supramolecular architecture is largely decided by the position of the substituents on the benzenesulfonyl ring, with the nature and position of the substituents on the aniline ring exerting little effect. On the other hand, the crystal structures of (I)–(III) display several weak interactions other than the common N—H…O hydrogen bonds, resulting in supramolecular architectures varying from one‐ to three‐dimensional depending on the nature and position of the substituents on the aniline ring.     

Applications of ‐invariant distributions

In this sequel to the article 17 , a criterion for the regularity of fundamental solutions of differential operators with positive symbol is proved in analogy to Hörmander's criteria, see 9 , 12 . It implies that the temperate fundamental solution of the operator is not regular. Furthermore, a formula for the convolution of two ‐invariant distributions is presented, and, finally, L. Schwartz' question on the surjectivity of linear partial differential operators with constant coefficients on the space is completely answered in the case of ‐invariant differential operators.     

Micromechanics of cleavage fracture initiation in ferritic steels by carbide cracking

Cleavage fracture in ferritic steels is often initiated in brittle carbides randomly distributed in the material. The carbides break as a result of a fibre loading mechanism in which the stress levels in the carbides are raised, as the surrounding ferrite undergoes plastic deformation. The conditions in the vicinity of the nucleated micro-crack will then determine whether the crack will penetrate or be arrested by the ferrite. The ferrite is able to arrest nucleated cracks through the presence of mobile dislocations, which blunt and shield the microcrack and thus lowers the stresses at the crack tip. Hence, the macroscopic toughness of the material directly depends on the ability of the ferrite to arrest nucleated micro-cracks and in turn on the plastic rate sensitivity of the ferrite. The initiation of cleavage fracture is here modelled explicitly in the form of a micro-crack, which nucleates in a brittle carbide and propagates into the surrounding ferrite. The carbide is modelled as an elastic cylinder or in a few cases an elastic sphere and the ferrite as an elastic viscoplastic material. The crack growth is modelled using a cohesive surface, where the tractions are governed by a modified exponential cohesive law. It is shown that the critical stress, required to propagate a microcrack from a broken carbide, increases with decreasing plastic rate sensitivity of the ferrite. The results also show that a low stress triaxiality and a high aspect ratio of the carbide promote the initiation of cleavage fracture from a broken carbide.     

载荷对Al2O3增强Y-TZP陶瓷磨损特性的影响

采用往复式摩擦磨损试验机研究了10%(质量分数计)Al2O3增强四方氧化锆多晶Y-TZP陶瓷材料(简称10ADZ)在不同载荷下的磨损行为与机制.结果表明:随着载荷的增加和滑动时间的延长,10ADZ陶瓷的磨损率增大,但并非呈线性增加,磨损率增长幅度不同;在62 N低载荷条件下,10ADZ陶瓷的磨损机制以犁沟和塑性变形为主;在124 N载荷下其主要的磨损形式为塑性变形、微切削和微断裂;而在310 N的高载荷下其主要的磨损机制为断裂磨损.     

三氧化二铝短纤维对ZA22合金干摩擦磨损性能的影响

针对无油润滑场合的实际需要，采用挤压铸造法制取了Ａｌ２Ｏ３短纤维强化ＺＡ２２合金复合材料，并对其在干摩擦条件下的摩擦磨损性能进行了试验研究，同时还用扫描电子显微镜对试样磨损表面形貌进行了观察，进而对材料的磨损机理作了分析与讨论。结果表明，随着Ａｌ２Ｏ３短纤维含量的增大，ＺＡ２２／Ａｌ２Ｏ３复合材料的耐磨性能提高，但摩擦性能降低；当纤维取向垂直于摩擦而时，复合材料的摩擦磨损性能比纤维平行于摩擦面取向     

From crack deflection to lattice vibrations—macro to atomistic examination of dynamic cleavage fracture

A set of cleavage experiments with strip-shaped single-crystal silicon specimens subjected to three-point bending is reported. The experiments enabled examination of the relationships between the dynamic energy release rate, the velocity, the orientation-dependent cleavage energy, and the cleavage plane of propagation.Dynamic crack propagation experiments show that when a [0 0 1] silicon single crystal is fractured under three-point bending at ‘parallel’ velocity (directly measured at the bottom surface of the specimen) of up to , it prefers to cleave along the vertical (1 1 0) plane, while when the specimen is fractured under the same conditions but at a velocity higher than , it cleaves along the inclined (1 1 1) plane. At intermediate velocities, the crack will deflect from the (1 1 0) plane to the (1 1 1) plane. Crack velocity was determined by the initial notch length. The local (calculated) velocity of deflection between the cleavage planes ranges from , for a crack propagating on the (1 1 0) plane in the direction, to about , for a crack on the (1 1 0) plane, but in the [0 0 1] direction.It is suggested that the cause of the deflection phenomenon is the anisotropic, velocity-dependent cleavage energy, resulted phonon radiation caused by anisotropic, velocity-dependent lattice vibrations. We have studied the effect of material properties and propose selection criteria to explain the deflection phenomenon: the crack will deflect to the plane of least-energy, for which G−Γ_i(V)=max, or to the plane with maximum crack tip velocity, V_i(Γ)=max.     

Nanospherical Surface‐Supported Seeded Growth of Au Nanowires: Investigation on a New Growth Mechanism and High‐Performance Hydrogen Peroxide Sensors

In this paper, a novel strategy with a new growth mechanism for fast and large‐scale growth of Au long nanowires on high‐curvature SiO₂ nanospherical surfaces has been developed. The synthesis includes three steps, i.e., amino modification of SiO₂ nanospheres, Au seed loading on aminated SiO₂ nanospheres and subsequently, Au seed‐mediated nanowire growth on SiO₂ nanospheres. The prepared Au nanowires (Au NWs) (exhibit long length, high aspect ratio, and good flexibility, and can naturally form the dense nanowire film, which is promising as a stable conductive electrode. In addition, the effect of synthetic conditions such as reactant feeding order, Au seeds and SiO₂@Au seeds on the morphology of Au nanostructures (nanowires, nanoteeth, and nanoflowers) has been investigated. It is found that Au seeds and high‐curvature SiO₂ nanospherical surfaces are necessary conditions for the successful preparation of Au NWs and nanowire films. The different growth mechanisms for Au NWs and nanoteeth have been proposed and discussed. Moreover, the novel nonenzymatic H₂O₂ sensor based on Au NWs exhibits much enhanced performance such as higher sensitivity, stability, and selectivity, wider linear range and lower detection limit, compared with that of Au nanoparticles‐based H₂O₂ sensor.