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1.
Claudia Poloni Marc C. A. Stuart Pieter van der Meulen Wiktor Szymanski Ben L. Feringa 《Chemical science》2015,6(12):7311-7318
The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils. 相似文献
2.
A new asymmetric synthesis of 2-substituted chiral chromanes has been achieved. The key step is the intramolecular conjugate addition of a phenolic nucleophile on a α,β-unsaturated ester catalyzed by Cinchona alkaloids. The high ee’s obtained with cinchonine and its derivatives have been rationalized by ab initio quantum chemistry calculations of transition state structures. 相似文献
3.
Valuations of dense near polygons were introduced in 16 . In the present paper, we classify all valuations of the near hexagons ??1 and ??2, which are related to the respective Witt designs S(5,6,12) and S(5,8,24). Using these classifications, we prove that if a dense near polygon S contains a hex H isomorphic to ??1 or ??2, then H is classical in S. We will use this result to determine all dense near octagons that contain a hex isomorphic to ??1 or ??2. As a by‐product, we obtain a purely geometrical proof for the nonexistence of regular near 2d‐gons, d ≥ 4, whose parameters s, t, ti (0 ≤ i ≤ d) satisfy (s, t2, t3) = (2, 1, 11) or (2, 2, 14). The nonexistence of these regular near polygons can also be shown with the aid of eigenvalue techniques. © 2005 Wiley Periodicals, Inc. J Combin Designs 14: 214–228, 2006 相似文献
4.
5.
Pieter Vonk Reinoud Noordman Doeke Schippers Bouke Tilstra Hans Wesselingh 《Journal of membrane science》1997,130(1-2):249-263
We present a mathematical model to describe the ultrafiltration behaviour of polymer-electrolyte mixtures. The model combines the proper thermodynamic forces (pressure, chemical potential and electrical potential differences) with multicomponent diffusion theory. The model is verified with experimental data on the ultrafiltration of aqueous solutions of PEG-4000 and potassium phosphate. The single solute rejection of PEG-4000 goes through a maximum as also found by others. The single solute rejection of potassium phosphate depends on the ionic strength of the solution. At low ionic strength rejections are found of 50%. Solutions containing a high concentration of PEG-4000 and potassium phosphate show a negative rejection for potassium phosphate. This is caused by the strongly non-ideal behaviour of these aqueous solutions. The model predicts the behaviour of single solute experiments quite well, but some deviations are found with the mixed solute experiments. However, negative rejections found in the mixed solute experiments are predicted by the model. 相似文献
6.
Appleby I Boulton LT Cobley CJ Hill C Hughes ML de Koning PD Lennon IC Praquin C Ramsden JA Samuel HJ Willis N 《Organic letters》2005,7(10):1931-1934
Two methods to produce (2S)-5-amino-2-(1-n-propyl-1H-imidazol-4-ylmethyl)-pentanoic acid were investigated. Diastereoisomeric salt resolution, using the quinidine salt, gave the desired intermediate in 98% ee and 33% yield. Asymmetric hydrogenation of various substrates gave high conversions, with up to 83% ee. Integration of these two approaches via asymmetric hydrogenation of a quinidine salt substrate followed by crystallization provided the desired intermediate in 94% ee and 76% yield. 相似文献
7.
When a two-phase column consisting of paraffin oil and silicon oil is placed in an otherwise air-filled, horizontal glass capillary, the column starts moving spontaneously. Silicon oil displaces paraffin oil, which in its turn displaces air at atmospheric conditions; a stable film of silicon oil is left at the receding silicon oil/air meniscus. The driving force for the motion is the difference in capillary pressure at the free interfaces. However, the column moves considerably more slowly than predicted by the driving forces; it appears that the forces resisting the motion at the moving liquid/liquid/solid line are much larger than one would expect on the basis of the interfacial tension and the viscosities of the two phase system. Some considerations are made on the relationship of the theory of Fowkes to our system. Also, a method for measuring low interfacial tensions between immiscible liquids is proposed. 相似文献
8.
Pieter Van der VekenIstván Kertèsz Kristel SentenAchiel Haemers Koen Augustyns 《Tetrahedron letters》2003,44(33):6231-6234
(E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors were synthesized. A Wadsworth-Horner-Emmons reaction, followed by amide formation and reduction of the amide were used for the construction of the α-fluoro-α,β-unsaturated amine functionality. 相似文献
9.
Groothaert MH Smeets PJ Sels BF Jacobs PA Schoonheydt RA 《Journal of the American Chemical Society》2005,127(5):1394-1395
This work reports on the capability of the O2-activated Cu-ZSM-5 and Cu-MOR zeolites to selectively convert methane into methanol at a temperature of 398 K. A strong correlation between (i) the activity and (ii) the intensity of the 22 700 cm-1 UV-vis band, assigned to the bis(mu-oxo)dicopper core, is found (i) as a function of the reaction temperature, (ii) as a function of the Cu loading of the zeolite, and (iii) in comparison to other Cu materials. These three lines of evidence firmly support the key role of the bis(mu-oxo)dicopper core in this selective, low-temperature hydroxylation of methane. 相似文献
10.
Artyukhin AB Bakajin O Stroeve P Noy A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(4):1442-1448
Carbon nanotubes have been featured prominently in the nanotechnology research for some time, yet robust strategies for noncovalent chemical modification of the nanotube surface are still missing. Such strategies are essential for the creation of functional device architectures. Here, we present a new general procedure for carbon nanotube modification based on polyelectrolyte layer-by-layer assembly. We have built multilayer structures around individual carbon nanotube bridges by first modifying the nanotube surface with a pyrene derivative followed by layer-by-layer deposition of polyelectrolyte macroions on the nanotube. Transmission electron microscopy and scanning confocal fluorescence microscopy images confirm the formation of nanometer-thick amorphous polymer nanoshells around the nanotubes. These multilayer polyelectrolyte shells on individual carbon nanotubes introduce nearly unlimited opportunities for the incorporation of various functionalities into nanotube devices, which, in turn, opens up the possibility of building more complex multicomponent structures. 相似文献