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131.
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133.
The amorphous aluminum silicate (Al2O3)2(SiO2) [AS2] is investigated by means of large scale molecular dynamics computer simulations. We consider fully equilibrated melts in the temperature range 6100 K> or =T> or =2300 K as well as glass configurations that were obtained from cooling runs from T=2300 to 300 K with a cooling rate of about 10(12) K/s. Already at temperatures as high as 4000 K, most of the Al and Si atoms are fourfold coordinated by oxygen atoms. Thus, the structure of AS2 is that of a disordered tetrahedral network. The packing of AlO4 tetrahedra is very different from that of SiO4 tetrahedra in that Al is involved with a relatively high probability in small-membered rings and in triclusters in which an O atom is surrounded by four cations. We find as typical configurations two-membered rings with two Al atoms in which the shared O atoms form a tricluster. On larger length scales, the system shows a microphase separation in which the Al-rich network structure percolates through the SiO2 network. The latter structure gives rise to a prepeak in the static structure factor at a wave number q=0.5 A(-1). A comparison of experimental x-ray data with the results from the simulation shows good agreement for the structure function. The diffusion dynamics in AS2 is found to be much faster than in SiO2. We show that the self-diffusion constants for O and Al are very similar and that they are by a factor of 2-3 larger than the one for Si. 相似文献
134.
Gerhard Holxe Titus A. Jenny Petr Nesvadba Albert Gossauer Ludger Ernst Walter Keller Christoph Kratky 《Helvetica chimica acta》1991,74(6):1287-1295
On treatment with H2SO4/MeOH, epimerization of hexamethyl cis-5,6-dihydroxycobyrinate c,8-lactam ( 3 ) takes place quantitatively at C(6), yielding the corresponding trans-diol 4 . The corresponding lactone 7 , whose structure has been established by X-ray analysis, is obtained from xanthocorrinoids 5 and 6 under similar conditions. 相似文献
135.
Under O2, the Aspidosperma alkaloid tabersonine ( 1 ) was converted by a crude enzyme preparation from leaves of mature plants of Catharanthus roseus G DON into the trimeric 3-hydroxy-14′-(3α″-tabersonyl)voafrine B ( 4 ) which was easily reduced by NaBH4 to 14′-(3α″-tabersonyl)voafrine B ( = tertabersonine; 5 ). Compounds such as 4 and 5 are the first trimeric alkaloids in the series of monoterpenoid indole alkaloids. 相似文献
136.
Walter Fischer Cyril A. Grob Reinhard Hanreich Georg von Sprecher Adrian Waldner 《Helvetica chimica acta》1981,64(7):2298-2311
The solvolysis rates and products of the 6-exo-substituted 2-exo- 1a - 1u , and 2-endo-norbornyl p-toluenesulfonates 2a - 2u , have been determined. In general, the rate constants for 1 and 2 (log k) correlate well with the inductive constants σ of the substitutents at C(6); however, their sensitivity to σ is much larger in the 2-exo-series 1 than in the 2-endo-series 2 . This differential transmission of polar effects is the cause of decreasing 2-exo/2-endo rate ratios from 2388 for R = t-C4H9 to 0.37 for R = Br, i. e. with increasing electron attraction by the substituent. The high sensitivity of the rate constants for the 2-exo-p-toluenesulfonates 1 to σ indicates an unusually strong inductive interaction between C(6) and the incipient cationic center at C(2). This interaction is ascribed to the participation of the pentacoordinate C(6)-atom, i. e. to 1,3-bridging, a consequence of steric hindrance of nucleophilic solvent participation in norbornanes. Donor substituents enhance 1,3-bridging, lead to faster reactions and to the formation of 2-exo substitution products. Conversely, acceptor substituents reduce 1,3-bridging, decrease rates and facilitate the formation of 2-endo substitution products. Graded 1,3-bridging is discussed in the light of Winstein's nonclassical ion concept. 相似文献
137.
Walter Deckert 《Fresenius' Journal of Analytical Chemistry》1956,150(6):421-425
Zusammenfassung Mit Hilfe von Reagenspapierstreifen, die mit Eisen(III)-rhodanid imprÄgniert sind, lassen sich alle in der Luft gelegentlich vorkommenden, alkalisch reagierenden Gase oder DÄmpfe (Ammoniak, Amine, Äthylenoxyd) nachweisen. Das dunkelrotbraune Reagenspapier wird hierbei entfÄrbt. Das Ausma\ der EntfÄrbung folgt stöchiometrischen Gesetzen. Der Grad der EntfÄrbung lÄ\t sich daher quantitativ auswerten. Eine untere und obere Nachweisgrenze gibt es bei diesem Verfahren theoretisch überhaupt nicht. Bei der vorgeschlagenen Ausführungsmethode, die eine Absaugung von Luftmengen bis zu 1 Liter vorsieht, liegt die untere Nachweisgrenze — in AnhÄngigkeit von dem Molekulargewicht des gefundenen Stoffes — z. B. bei 0,07 g NH3 je Liter Luft (=0,07 mg/m3) oder bei 0,25 g Trimethylamin/1 Liter (=0,25 mg/m3). Die praktische Begrenzung nach oben liegt dort, wo sich andere bekannte Bestimmungsmethoden mit höherem Genauigkeitsgrad anbieten.Die Herstellung eines in reiner Luft auch bei Licht und Zimmertemperatur lÄngere Zeit haltbaren Reagenspapiers wird beschrieben. Die praktische Anwendbarkeit des ER-Papiers liegt vor allem bei Luftuntersuchungen im Zusammenhang mit den Exhalationen und Emanationen von Fischmehlfabriken. 相似文献
138.
Molecular chaperones--cellular machines for protein folding 总被引:10,自引:0,他引:10
Proteins are linear polymers synthesized by ribosomes from activated amino acids. The product of this biosynthetic process is a polypeptide chain, which has to adopt the unique three-dimensional structure required for its function in the cell. In 1972, Christian Anfinsen was awarded the Nobel Prize for Chemistry for showing that this folding process is autonomous in that it does not require any additional factors or input of energy. Based on in vitro experiments with purified proteins, it was suggested that the correct three-dimensional structure can form spontaneously in vivo once the newly synthesized protein leaves the ribosome. Furthermore, proteins were assumed to maintain their native conformation until they were degraded by specific enzymes. In the last decade this view of cellular protein folding has changed considerably. It has become clear that a complicated and sophisticated machinery of proteins exists which assists protein folding and allows the functional state of proteins to be maintained under conditions in which they would normally unfold and aggregate. These proteins are collectively called molecular chaperones, because, like their human counterparts, they prevent unwanted interactions between their immature clients. In this review, we discuss the principal features of this peculiar class of proteins, their structure-function relationships, and the underlying molecular mechanisms. 相似文献
139.
Leister W Strauss K Wisnoski D Zhao Z Lindsley C 《Journal of combinatorial chemistry》2003,5(3):322-329
Solution-phase parallel synthesis has had a profound impact on the speed of compound synthesis delivering relatively pure compounds (>80%) in short order. However, to develop structure activity relationships (SAR) for a compound series, each library member should preferably be >95% pure. Historically, achieving and quantifying such high-purity criteria for each library member proved to be the slow step for most lead discovery groups. To address this issue, significant modifications have been made to a commercial Agilent preparative LC/MS system to allow for the general mass-guided purification of diverse compound libraries. The custom modifications include (1) the "DMSO slug" approach for the purification of samples with poor solubility; (2) an active splitter to reduce system back-pressure, reduce the delay volume, and allow for a variable split ratio; (3) a sample loading pump for the quick purification of large, dilute samples; (4) a preparative column-selection valve to quickly change column selectivity or sample loading; and (5) an analytical injector with a separate flow path for crude reaction or fraction analyses. 相似文献
140.