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41.
Methodological aspects of Curie-point pyrolysis in combination with field ionization mass spectrometry for the characterization and identification of carbohydrates are reported. Some monomeric sugars and sugar derivatives have been investigated as a first step towards a basic understanding of the pyrolysis pathways of polysaccharides.Curie-point pyrolysis is performed inside the ion source of a double-focusing mass spectrometer close to the field ion emitter. The pyrolysis products are ionized in a high electric field and spectra of high mass resolution are recorded photographically. This procedure essentially avoids mass spectrometric fragmentation and yields almost exclusively molecular ions of the pyrolysates. The best experimental conditions for pyrolysis were determined by investigating the influences of pyrolysis temperature, temperature pulse length, exposure time and trace impurities on the pyrolysis products. At a temperature of 500°C and a pulse length of 4–6 s, the most significant pyrolysis fragments appear with high relative intensity. Although most of the pyrolysis products with higher volatility are pumped out of the ion source after an exposure time of 3 min, the more characteristic degradation products of lower volatility can still be registered after 10 min. The spectra of monosaccharides such as glucuronic acid, d-glucose and some of its methylated derivatives show significant differences which can be correlated structurally with the position of the substituent. 相似文献
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43.
Cyano-bridged Mn(III)-M(III) single-chain magnets with M(III)=Co(III), Fe(III), Mn(III), and Cr(III)
Miyasaka H Madanbashi T Saitoh A Motokawa N Ishikawa R Yamashita M Bahr S Wernsdorfer W Clérac R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(13):3942-3954
A series of isostructural cyano-bridged Mn(III)(h.s.)-M(III)(l.s.) alternating chains, [Mn(III)(5-TMAMsalen)M(III)(CN)(6)]?4H(2)O (5-TMAMsalen(2-)=N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate), Mn(III)(h.s.)=high-spin Mn(III), M(III)(l.s.)=low-spin Co(III), Mn-Co; Fe(III), Mn-Fe; Mn(III), Mn-Mn; Cr(III), Mn-Cr) was synthesized by assembling [Mn(III)(5-TMAMsalen)](3+) and [M(III)(CN)(6)](3-). The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [-Mn(III)-NC-M(III)-CN-] repeating motif, for which the -NC-M(III)-CN- motif is provided by the [M(III)(CN)(6)](3-) moiety adopting a trans bridging mode between [Mn(III)(5-TMAMsalen)](3+) cations. The Mn(III) and M(III) ions occupy special crystallographic positions: a C(2) axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn-Teller axis of the Mn(III)(h.s.) ion is perpendicular to the N(2)O(2) plane formed by the 5-TMAMsalen tetradentate ligand. These Jahn-Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn-N(axis) -C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter-chain M???M distance being relatively large at 9?? due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5-TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn-Fe and Mn-Mn display intra-chain ferromagnetic interactions, whereas Mn-Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single-chain magnet (SCM) behavior of these three systems, whereas Mn-Co is merely paramagnetic with S(Mn)=2 and D/k(B)=-5.3?K (D being a zero-field splitting parameter). At low temperatures, the Mn-M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite-chain and finite-chain regimes for the SCM behavior. These isostructural hetero-spin SCMs offer a unique series of alternating [-Mn-NC-M-CN-] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits. 相似文献
44.
H. Balke I. Hofinger C. Häusler H.-A. Bahr H.-J. Weiß G. Kirchhoff 《Archive of Applied Mechanics (Ingenieur Archiv)》2000,70(1-3):193-200
Summary The problem of how to avoid damage of TBCs has been approached by calculating the energy release rate of two crack configurations
under thermal loading. This has been done for the limiting cases of perfect and lacking heat transfer across the crack. Suitable
grading of TBCs is a means of suppressing the tendency to delamination and damage by both decreasing the energy release rate
G and increasing its critical value G
c
. TBCs can be graded such that delamination cracks would be deflected into depth where G
c
is sufficiently high to avoid crack propagation.
Received 31 March 1999; accepted for publication 10 June 1999 相似文献
45.
Höfft O Bahr S Himmerlich M Krischok S Schaefer JA Kempter V 《Langmuir : the ACS journal of surfaces and colloids》2006,22(17):7120-7123
The near-surface electronic structure of the room-temperature ionic liquid (RT-IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf(2)N]) has been investigated with the combination of the electron spectroscopies metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS (HeI and HeII)), and monochromatized X-ray photoelectron spectroscopy (XPS). We find that the top of the valence band states originates from states of the cation (see also ref 1). The ultimately surface-sensitive technique MIES proves that the surface layer consists of both cations and anions. The temperature dependence of the spectra has been measured between about 160 and 610 K. Information on the glass transition and the possibility for low-temperature distillation of [EMIM][Tf(2)N] at reduced pressures is derived from the present results. 相似文献
46.
U. Braun V. Wachtendorf A. Geburtig H. Bahr B. Schartel 《Polymer Degradation and Stability》2010,95(12):2421-2429
The influence of weathering on the fire retardancy of polymers is investigated by means of a cone calorimeter test, before and after artificial weathering. The surface degradation was monitored using different techniques (ATR-FTIR, microscopy, colour measurement). Different kinds of polymeric materials were chosen, all as they are used in practice: polycarbonate (PC) blends, polyamide (PA) and polypropylene (PP) flame-retarded with arylphosphate, melamine cyanurate (MC) and intumescent formulation based on ammonium polyphosphate (APP), respectively.All samples show material degradation at the surface due to weathering. No significant weathering influence occurs on the flame retardancy when it is a bulk property, as was observed for aryl phosphates in PC blends and MC in PA. When the fire retardancy is dominated by a surface mechanism, dependence on the duration of weathering is detected: for intumescent formulations based on ammonium APP in PP, a worsening in the formation of the intumescent network was observed. 相似文献
47.
The interaction of NaI with amorphous solid water (ASW) and methanol (MeOH) has been investigated with metastable impact electron spectroscopy (MIES), UPS(HeI), and temperature programmed desorption (TPD). We have studied the electron emission from the ionization of the highest-lying states of H(2)O, CH(3)OH, and of 5pI. We have prepared NaI layers on ASW (MeOH) films at about 105 K and annealed them up to about 200 K. Surface segregation of iodide is observed in ASW, as predicted for NaI aqueous solutions. On the other hand, surface segregation is not observed in MeOH, again as predicted for the interaction of NaI with liquid methanol. Electronic properties (ionization potentials, optical band gaps) and water binding energies are reported and are analyzed on the basis of available DFT results for hydrated NaI clusters. 相似文献
48.
Lifetime of levels up to 22+, have been measured in 78Kr and an oblate shape is assigned to the ground state using the CSM and the configuration dependent shell correction calculations.
Calculations further show that 78Kr is highly γ-soft nucleus. The experimental Q
t values coupled with theoretical calculations indicate an oblate shape for 78Kr at low spins and triaxial shape at higher spins 相似文献
49.
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