Die Gasphasenintercalation von Graphit durch SbCl4F

Gas Phase Intercalation of Graphite by SbCl₄F Gas Phase Intercalation of Graphite by SbCl₄F using a two-zone technique is a method to prepare intercalation compounds of different stage index n in temperature range between 120 and 140°C. The reaction is a process of successive decrease of stage index. Increasing the reaction time, i. e. concentration, regions of pure stages alternate with two-phase regions. Intercalation compounds were characterized by X-ray technique, EPMA, and chemical methods. The compounds are stable in ordinary air, with aqueous HCl as well as KOH only pentavalent but not any trivalent antimony can be removed. The identity periods along c-axis in pure stages are I_c = 9.33 Å (n = 1), 12.72 Å (n = 2), 16.06 Å (n = 3) and 19.40 Å (n = 4). A (√7 × √ 7) 19.1° in-plane structure of intercalants was found. The uptake curve of mass with time reveals a discontinuity connected with formation of stage 2. Concave shape of curve during starting period at 120 and 125°C will be interpreted as a consequence of an induction time. From X-ray and EPMA studies it may be concluded that nucleation at the prismatic crystal edges controls the kinetics of reaction. Assuming a first order kinetics of filling the vacant sites, the same activation energy in case of formation of stage 1 and stage 2 have been determined approximately (97 and 102 kJ/mol).     

Biologically Active 1-Aminodeoxy and 1-O-Alkyl Derivatives of The Powerful D-Glucosidase Inhibitor 2,5-Dideoxy-2,5-Imino-D-Mannitol

ABSTRACT

By an Amadori rearrangement of easily available 5-azido-5-deoxy-D-glucofuranose with dibenzylamine and subsequent catalytic hydrogenation of the resulting 5-azido-1-(N,N-dibenzyl)amino-1,5-dideoxy-D-fructopyranose, 1-amino-1,2,5-trideoxy-2,5-imino-D-mannitol was obtained in only two steps and in excellent overall yield. Likewise, other amines were employed to introduce extended side chains ultimately suitable for attachment of the inhibitor to solid supports. The reported rearrangement reaction is a high yielding, convenient and apparently general entry to 1-aminodeoxyketopyranoses modified at C-5, facilitated by the ring enlargement of the aldofuranose to the ketopyranose as an additional driving force. A range of selected chain extended analogues was prepared by acylation of N-1. Inhibitors obtained exhibit K _i-values with D-glucosidases in the micromolar range. Interestingly, 1-N-acylation resulted in superior inhibitory activities, as did the addition of a hexyl chain.     

High-resolution dissociative recombination of cold H3+and first evidence for nuclear spin effects

The energy-resolved rate coefficient for the dissociative recombination (DR) of H(3)(+) with slow electrons has been measured by the storage-ring method using an ion beam produced from a radiofrequency multipole ion trap, employing buffer-gas cooling at 13 K. The electron energy spread of the merged-beams measurement is reduced to 500 microeV by using a cryogenic GaAs photocathode. This and a previous cold- measurement jointly confirm the capability of ion storage rings, with suitable ion sources, to store and investigate H(3)(+) in the two lowest, (J,G) = (1,1) and (1,0) rotational states prevailing also in cold interstellar matter. The use of para-H(2) in the ion source, expected to enhance para-H(3)(+) in the stored ion beam, is found to increase the DR rate coefficient at meV electron energies.     

Determination of the binding sites for oxaliplatin on insulin using mass spectrometry-based approaches

Using insulin as a model protein for binding of oxaliplatin to proteins, various mass spectrometric approaches and techniques were compared. Several different platinum adducts were observed, e.g. addition of one or two diaminocyclohexane platinum(II) (Pt(dach)) molecules. By top-down analysis and fragmentation of the intact insulin–oxaliplatin adduct using nano-electrospray ionisation quadrupole time-of-flight mass spectrometry (nESI-Q-ToF-MS), the major binding site was assigned to histidine5 on the insulin B chain. In order to simplify the interpretation of the mass spectrum, the disulphide bridges were reduced. This led to the additional identification of cysteine6 on the A chain as a binding site along with histidine5 on the B chain. Digestion of insulin–oxaliplatin with endoproteinase Glu-C (GluC) followed by reduction led to the formation of five peptides with Pt(dach) attached. Identification of several of the binding sites was obtained using matrix-assisted laser desorption/ionization (MALDI)-ToF-ToF-MS and liquid chromatography-nESI-Q-ToF-MS. Upon comparing the top-down and bottom-up approaches, the suitability of the bottom-up approach for determining binding sites was questioned, as the release and possible re-association of Pt(dach) were demonstrated upon enzymatic digestion. The associated advantages and disadvantages of ESI and MALDI were also pointed out.     

Modulation theory solution for nonlinearly resonant,fifth‐order Korteweg–de Vries,nonclassical, traveling dispersive shock waves

A new class of resonant dispersive shock waves was recently identified as solutions of the Kawahara equation— a Korteweg–de Vries (KdV) type nonlinear wave equation with third‐ and fifth‐order spatial derivatives— in the regime of nonconvex, linear dispersion. Linear resonance resulting from the third‐ and fifth‐order terms in the Kawahara equation was identified as the key ingredient for nonclassical dispersive shock wave solutions. Here, nonlinear wave (Whitham) modulation theory is used to construct approximate nonclassical traveling dispersive shock wave (TDSW) solutions of the fifth‐ order KdV equation without the third derivative term, hence without any linear resonance. A self‐similar, simple wave modulation solution of the fifth order, weakly nonlinear KdV–Whitham equations is obtained that matches a constant to a heteroclinic traveling wave via a partial dispersive shock wave so that the TDSW is interpreted as a nonlinear resonance. The modulation solution is compared with full numerical solutions, exhibiting excellent agreement. The TDSW is shown to be modulationally stable in the presence of sufficiently small third‐order dispersion. The Kawahara–Whitham modulation equations transition from hyperbolic to elliptic type for sufficiently large third‐order dispersion, which provides a possible route for the TDSW to exhibit modulational instability.     

An improved preparation of substituted phosphoryl difluorides. Synthesis of trifluoromethylthiodifluorophosphine and trifluoromethylthiophosphoryl difluoride

Difluorobromophosphine reacts readily with bis(trifluoromethylthio)- mercury to yield the fluorophosphine CF₃SPF₂ in excellent yields. The resulting new phosphine is readily oxidized under very moderate conditions by ClF, Cl₂ and O₂ to give new chlorofluorophosphorane and fluorophosphoryl compounds which contain the CF₃S moiety. CF₃SPF₂Cl₂ and CF₃SPF₂Cl were not characterized because of their tendency to disproportionate. CF₃SP(O)F₂ has, however, been isolated and characterized. All the new compounds are relatively unstable and decompose with a fluoride shift from the methyl group to the phosphorus atom. A new synthetic route to the known difluorophosphoryl compounds OPF₂Cl, OPF₂Br, OPF₂NCS and OPF₂(CH₃)₂, by the direct oxidation of the respective difluorophosphine with oxygen, has been found.