Regioselective alkylation of guanine via diacyloxyglyoxal-N2-acetylguanine adduct to obtain 7-alkylguanine derivatives. Studies on alkylation of guanine I

The acylated guanine-glyoxal adduct (I) has been alkylated with 4-bromobutyl acetate and in the presence of sodium hydride the reaction was regioselective to give 7-alkylguanine.     

Boundary Value Problems with Local Generalized Nevanlinna Functions in the Boundary Condition

For a class of abstract λ-dependent boundary value problems where a local variant of generalized Nevanlinna functions appears in the boundary condition, linearizations are constructed and their local spectral properties are investigated.     

Condensed‐Phase,Halogen‐Bonded CF3I and C2F5I Adducts for Perfluoroalkylation Reactions

A family of practical, liquid trifluoromethylation and pentafluoroethylation reagents is described. We show how halogen bonding can be used to obtain easily handled liquid reagents from gaseous CF₃I and CF₃CF₂I. The synthetic utility of the new reagents is exemplified by a novel direct arene trifluoromethylation reaction as well as adaptations of other perfluoroalkylation reactions.     

Characterization of Glycan Structures of Chondroitin Sulfate-Glycopeptides Facilitated by Sodium Ion-Pairing and Positive Mode LC-MS/MS

Purification and liquid chromatography-tandem mass spectrometry (LC-MS/MS) characterization of glycopeptides, originating from protease digests of glycoproteins, enables site-specific analysis of protein N- and O-glycosylations. We have described a protocol to enrich, hydrolyze by chondroitinase ABC, and characterize chondroitin sulfate-containing glycopeptides (CS-glycopeptides) using positive mode LC-MS/MS. The CS-glycopeptides, originating from the Bikunin proteoglycan of human urine samples, had ΔHexAGalNAcGlcAGalGalXyl-O-Ser hexasaccharide structure and were further substituted with 0-3 sulfate and 0-1 phosphate groups. However, it was not possible to exactly pinpoint sulfate attachment residues, for protonated precursors, due to extensive fragmentation of sulfate groups using high-energy collision induced dissociation (HCD). To circumvent the well-recognized sulfate instability, we now introduced Na⁺ ions to form sodiated precursors, which protected sulfate groups from decomposition and facilitated the assignment of sulfate modifications. Sulfate groups were pinpointed to both Gal residues and to the GalNAc of the hexasaccharide structure. The intensities of protonated and sodiated saccharide oxonium ions were very prominent in the HCD-MS2 spectra, which provided complementary structural analysis of sulfate substituents of CS-glycopeptides. We have demonstrated a considerable heterogeneity of the bikunin CS linkage region. The realization of these structural variants should be beneficial in studies aimed at investigating the importance of the CS linkage region with regards to the biosynthesis of CS and potential interactions to CS binding proteins. Also, the combined use of protonated and sodiated precursors for positive mode HCD fragmentation analysis will likely become useful for additional classes of sulfated glycopeptides.

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Thickness difference induced pore structure variations in cellulosic separators for lithium-ion batteries

The pore structure of the separator is crucial to the performance of a lithium-battery as it affects the cell resistance. Herein, a straightforward approach to vary the pore structure of Cladophora cellulose (CC) separators is presented. It is demonstrated that the pore size and porosity of the CC separator can be increased merely by decreasing the thickness of the CC separator by using less CC in the manufacturing of the separator. As the pore size and porosity of the CC separator are increased, the mass transport through the separator is increased which decreases the electrolyte resistance in the pores of the separator. This enhances the battery performance, particularly at higher cycling rates, as is demonstrated for LiFePO₄/Li half-cells. A specific capacity of around 100 mAh g^?1 was hence obtained at a cycling rate of 2 C with a 10 µm thick CC separator while specific capacities of 40 and close to 0 mAh g^?1 were obtained for separators with thicknesses of 20 and 40 µm, respectively. As the results also showed that a higher ionic conductivity was obtained for the 10 µm thick CC separator than for the 20 and 40 µm thick CC separators, it is clear that the different pore structure of the separators was an important factor affecting the battery performance in addition to the separator thickness. The present straightforward, yet efficient, strategy for altering the pore structure hence holds significant promise for the manufacturing of separators with improved performance, as well as for fundamental studies of the influence of the properties of the separator on the performance of lithium-ion cells.     

Delay resistant line planning with a view towards passenger transfers

The line planning step, as part of the public transportation planning process, is an elementary problem. When generating public transportation systems in a conventional fashion, the line planning problem is one of the first to solve. Hence, subsequent problems rely on the solution of the line planning problem. Line planning has been studied from various perspectives and is understood very well. Still, the effect of this planning step on to the next ones has only received minor attention. In this paper, we study the effect of transfers on the delay resistance and propose a line planning model which provides a good basis for a delay resistant transportation system. To this end, the concept of preferable paths from the direct travelers line planning model is further extended. The model includes the routing of passengers in order to minimize passenger transfers. A column generation approach is shown to properly solve the proposed model. As such, this is the first line planning model which detailedly routes the passengers and is still tractable on realistically sized instances. Finally, it is shown that minimizing the passenger transfers at the line planning stage contributes to an increasing delay resistance in the public transportation system.     

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.