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11.
Improved quantification limits in chiral capillary electrochromatography by peak compression effects
The peak compression effect has been applied to improve quantification limits in chiral capillary electrochromatography (CEC). A stationary phase based on the chiral selector vancomycin (Chirobiotic V) was used for separations of the enantiomers of mianserin. By adding solvents with a low dielectric constant, e.g. 2-propanol or tetrahydrofuran, to the sample solution, peak compression could be induced. The plate numbers for the minor enantiomer increased from approximately 100,000 to 1.4-1.6 million plates/m, when the composition of the mobile phase was adjusted so that the analyte eluted within either one of two system zones originating from the sample solution. A 10-fold improvement in the quantification limit for the minor enantiomer was obtained compared to elution under non-focused conditions. 相似文献
12.
The thermoreversible gelation of semi-diluted atactic polyacrylnitrile (PAN)/dimethylformamide (DMF)-solutions has been studied. The structural features of PAN/DMF-gels, formed by supercooling have been investigated by DSC-, x-ray- and swelling measurements. A new structural model has been introduced to describe the morphology of the junction zones of PAN/DMF-gels and to also explain the gelation behavior of PAN/DMF-solutions as the structural features of PAN/DMF-gels. The junction zones of a PAN/DMF-gel have been defined as ordered junction zones.A gelation enthalpy of about H=–6 kJ/mol supports the idea that an ordered junction zone is formed by intermolecularly neighboring stereoregular parts of atactic PAN chains due to a nucleation process in the solution. It can be defined as a strongly distributed fringed micelle. 相似文献
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14.
B. Gillot F. Bouton J.F. Ferriot F. Chassagneux A. Rousset 《Journal of solid state chemistry》1977,21(4):375-385
When Fe3+ ions are substituted by aluminum or chromium on magnetite octahedral sites, the ir spectrum shows the conversion of an inverse spinel to a normal spinel. Both broad bands of magnetite are gradually replaced by the four characteristic bands of normal spinels II–III. They are also observed for solid solutions, FeCr2O4FeAl2O4, with, however, a further band at 780 cm?1 which may be assigned to Al3+ ions on tetrahedral sites. Low-temperature (<400°C) oxidation of these compounds whose sizes are less than 2000 Å results in lacunar spinels III–III. The ir spectrum of these solids is characterized by two absorption bands (as for inverse spinels II–III) except for compounds close to pure γFe2O3 in which an order of vacancies could be put in evidence. 相似文献
15.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(28):8191-8194
We designed and conducted a series of primordial‐soup Miller‐Urey style experiments with deuterated gases and reagents to compare the spark‐discharge products of a “deuterated world” with the standard reaction in the “hydrogenated world”. While the deuteration of the system has little effect on the distribution of amino acid products, significant differences are seen in other regions of the product‐space. Not only do we observe about 120 new species, we also see significant differences in their distribution if the two hydrogen isotope worlds are compared. Several isotopologue matches can be identified in both, but a large proportion of products have no equivalent in the corresponding isotope world with ca. 43 new species in the D world and ca. 39 new species in the H world. This shows that isotopic exchange (the addition of only one neutron) may lead to significant additional complexity in chemical space under otherwise identical reaction conditions. 相似文献
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17.
Hidenori Okamura Antony Crisp Sarah Hübner Sidney Becker Petra Rov Thomas Carell 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(51):18864-18869
The RNA world hypothesis assumes that life on Earth began with nucleotides that formed information‐carrying RNA oligomers able to self‐replicate. Prebiotic reactions leading to the contemporary nucleosides are now known, but their execution often requires specific starting materials and lengthy reaction sequences. It was therefore proposed that the RNA world was likely proceeded by a proto‐RNA world constructed from molecules that were likely present on the early Earth in greater abundance. Herein, we show that the prebiotic starting molecules bis‐urea (biuret) and tris‐urea (triuret) are able to directly react with ribose. The urea‐ribosides are remarkably stable because they are held together by a network of intramolecular, bifurcated hydrogen bonds. This even allowed the synthesis of phosphoramidite building blocks and incorporation of the units into RNA. Investigations of the nucleotides’ base‐pairing potential showed that triuret:G RNA base pairs closely resemble U:G wobble base pairs. Based on the probable abundance of urea on the early Earth, we postulate that urea‐containing RNA bases are good candidates for a proto‐RNA world. 相似文献
18.
Yves Pomeau 《Comptes Rendus Mecanique》2018,346(3):184-197
The equations for a self-similar solution to an inviscid incompressible fluid are mapped into an integral equation that hopefully can be solved by iteration. It is argued that the exponents of the similarity are ruled by Kelvin's theorem of conservation of circulation. The end result is an iteration with a nonlinear term entering a kernel given by a 3D integral for a swirling flow, likely within reach of present-day computational power. Because of the slow decay of the similarity solution at large distances, its kinetic energy diverges, and some mathematical results excluding non-trivial solutions of the Euler equations in the self-similar case do not apply. 相似文献
19.
《Comptes Rendus Physique》2015,16(1):73-85
Particles of differing sizes are notoriously prone to segregate, which is a chronic problem in the manufacture of a wide variety of products that are used by billions of people worldwide every day. Segregation is the single most important factor in product non-uniformity, which can lead to significant handling problems as well as complete batches being discarded at huge financial loss. It is generally regarded that the most important mechanism for segregation is the combination of kinetic sieving and squeeze expulsion in shallow granular avalanches. These free-surface flows are more common than one might expect, often forming part of more complicated flows in drums, heaps and silos, where there is mass exchange with underlying regions of static or slowly moving grains. The combination of segregation and solid–fluid granular phase transitions creates incredibly complicated and beautiful patterns in the resulting deposits, but a full understanding of such effects lies beyond our capabilities at present. This paper reviews recent advances in our ability to model the basic segregation processes in a single avalanche (without mass exchange) and the subtle feedback effects that they can have on the bulk flow. This is particularly important for geophysical applications, where segregation can spontaneously self-channelize and lubricate the flow, significantly enhancing the run-out of debris-flows, pyroclastic flows, rock-falls and snow-slab avalanches. 相似文献
20.
《Comptes Rendus Physique》2015,16(5):489-498
This article describes the recent progress of optical lattice clocks with neutral strontium (87Sr), ytterbium (171Yb) and mercury (199Hg) atoms. In particular, we present frequency comparison between the clocks locally via an optical frequency comb and between two Sr clocks at remote sites using a phase-stabilized fibre link. We first review cryogenic Sr optical lattice clocks that reduce the room-temperature blackbody radiation shift by two orders of magnitude and serve as a reference in the following clock comparisons. Similar physical properties of Sr and Yb atoms, such as transition wavelengths and vapour pressure, have allowed our development of a compatible clock for both species. A cryogenic Yb clock is evaluated by referencing a Sr clock. We also report on an Hg clock, which shows one order of magnitude less sensitivity to blackbody radiation, while its large nuclear charge makes the clock sensitive to the variation of fine-structure constant. Connecting all three types of clocks by an optical frequency comb, the ratios of the clock frequencies are determined with uncertainties smaller than possible through absolute frequency measurements. Finally, we describe a synchronous frequency comparison between two Sr-based remote clocks over a distance of 15 km between RIKEN and the University of Tokyo, as a step towards relativistic geodesy. 相似文献