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91.
Adrian Pîrnău Mihaela Mic Mircea Bogdan Ioan Turcu 《Journal of inclusion phenomena and macrocyclic chemistry》2014,79(3-4):283-289
The inclusion of local anesthetic drug procaine hydrochloride by β-cyclodextrin was investigated by 1D and 2D proton NMR spectroscopy and isothermal titration calorimetry (ITC) at 298 K. The stoichiometry of the complex was determinate by the method of continuous variation, using the chemical induced shift of both host and guest protons. The association constant K, of the obtained complex was calculated and found to be 293.17 M?1. Rotating frame NOE spectroscopy, was used to ascertain the solution geometry of the host–guest complex. The result reveals that the procaine molecule penetrates into the β-cyclodextrin cavity with the aromatic ring. The energetics of complexation process is investigated by ITC technique. The analysis indicates that the complexation of procaine by β-CD is an exothermic process and show that both enthalpy and entropy contribute to the binding process. The obtained value for the association constant is in good agreement with that obtained from NMR. 相似文献
92.
Henry W. Orton Dr. Jan Stanek Dr. Tobias Schubeis Dylan Foucaudeau Claire Ollier Dr. Adrian W. Draney Dr. Tanguy Le Marchand Dr. Diane Cala-De Paepe Prof. Dr. Isabella C. Felli Prof. Dr. Roberta Pierattelli Prof. Dr. Sebastian Hiller Dr. Wolfgang Bermel Dr. Guido Pintacuda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(6):2400-2405
93.
Birgit Fuchs Prof. Dr. Gunter Heymann Xuefei Wang Abudukadi Tudi Dr. Lkhamsuren Bayarjargal Dr. Renée Siegel Adrian Schmutzler Prof. Dr. Jürgen Senker Dr. Bastian Joachim-Mrosko Dr. Andreas Saxer Prof. Dr. Zhihua Yang Prof. Dr. Shilie Pan Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(30):6851-6861
La3B6O13(OH) was obtained by a high-pressure/high-temperature experiment at 6 GPa and 1673 K. The compound crystallizes in the space group P21 (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3) Å, and β=90.36(10)°, and is built up of corner- as well as edge-sharing BO4 tetrahedra. It represents the first acentric high-pressure borate containing these B2O6 entities. The compound develops borate layers of „sechser“-rings with the La3+ cations positioned between the layers. Single-crystal and powder X-ray diffraction, vibrational and MAS NMR spectroscopy, second-harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B2O6 entities. 相似文献
94.
Chongqing Wang Christopher Lambert Maurice Hauser Adrian Deuschmann Dr. Carsten Zeilinger Prof. Dr. Klemens Rottner Prof. Dr. Theresia E. B. Stradal Prof. Dr. Marc Stadler Dr. Elizabeth J. Skellam Prof. Dr. Russell J. Cox 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13578-13583
Mutasynthesis of pyrichalasin H from Magnaporthe grisea NI980 yielded a series of unprecedented 4′-substituted cytochalasin analogues in titres as high as the wild-type system (≈60 mg L−1). Halogenated, O-alkyl, O-allyl and O-propargyl examples were formed, as well as a 4′-azido analogue. 4′-O-Propargyl and 4′-azido analogues reacted smoothly in Huisgen cycloaddition reactions, whereas p-Br and p-I compounds reacted in Pd-catalysed cross-coupling reactions. A series of examples of biotin-linked, dye-linked and dimeric cytochalasins was rapidly created. In vitro and in vivo bioassays of these compounds showed that the 4′-halogenated and azido derivatives retained their cytotoxicity and antifungal activities; but a unique 4′-amino analogue was inactive. Attachment of larger substituents attenuated the bioactivities. In vivo actin-binding studies with adherent mammalian cells showed that actin remains the likely intracellular target. Dye-linked compounds revealed visualisation of intracellular actin structures even in the absence of phalloidin, thus constituting a potential new class of actin-visualisation tools with filament-barbed end-binding specificity. 相似文献
95.
Dr. Caroline M. Storey Dr. Matthew R. Gyton Dr. Rhiann E. Andrew Dr. Adrian B. Chaplin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14715-14723
Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C2H4)][BArF4] (n=12, 14, 16; ArF=3,5-(CF3)2C6H3)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu2C6H3) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH2)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C2H4)][BArF4] and solvent effects. 相似文献
96.
Chencheng Dai Yuanmiao Sun Gao Chen Adrian C. Fisher Zhichuan J. Xu 《Angewandte Chemie (International ed. in English)》2020,59(24):9418-9422
Nitrates are widely used as fertilizer and oxidizing agents. Commercial nitrate production from nitrogen involves high‐temperature‐high‐pressure multi‐step processes. Therefore, an alternative nitrate production method under ambient environment is of importance. Herein, an electrochemical nitrogen oxidation reaction (NOR) approach is developed to produce nitrate catalyzed by ZnFexCo2?xO4 spinel oxides. Theoretical and experimental results show Fe aids the formation of the first N?O bond on the *N site, while high oxidation state Co assists in stabilizing the absorbed OH? for the generation of the second and third N?O bonds. Owing to the concerted catalysis, the ZnFe0.4Co1.6O4 oxide demonstrates the highest nitrate production rate of 130±12 μmol h?1 gMO?1 at an applied potential of 1.6 V versus the reversible hydrogen electrode (RHE). 相似文献
97.
Charlotte Kielar Siqi Zhu Guido Grundmeier Adrian Keller 《Angewandte Chemie (International ed. in English)》2020,59(34):14336-14341
High‐speed atomic force microscopy (HS‐AFM) is widely employed in the investigation of dynamic biomolecular processes at a single‐molecule level. However, it remains an open and somewhat controversial question, how these processes are affected by the rapidly scanned AFM tip. While tip effects are commonly believed to be of minor importance in strongly binding systems, weaker interactions may significantly be disturbed. Herein, we quantitatively assess the role of tip effects in a strongly binding system using a DNA origami‐based single‐molecule assay. Despite its femtomolar dissociation constant, we find that HS‐AFM imaging can disrupt monodentate binding of streptavidin (SAv) to biotin (Bt) even under gentle scanning conditions. To a lesser extent, this is also observed for the much stronger bidentate SAv–Bt complex. The presented DNA origami‐based assay can be universally employed to quantify tip effects in strongly and weakly binding systems and to optimize the experimental settings for their reliable HS‐AFM imaging. 相似文献
98.
A study of the effect of step excrescences and free‐stream disturbances on boundary layer stability 下载免费PDF全文
In this work, a study of the mechanism by which free‐stream acoustic and vorticity disturbances interact with a boundary layer flow developing over a flat plate featuring a step excrescence located at a certain distance from a blunt leading edge is included. The numerical tool is a high‐fidelity implicit numerical algorithm solving for the unsteady, compressible form of the Navier–Stokes equations in a body‐fitted curvilinear coordinates and employing high‐accurate compact differencing schemes with Pade‐type filters. Acoustic and vorticity waves are generated using a source term in the momentum and energy equations, as opposed to using inflow boundary conditions, to avoid spurious waves that may propagate from boundaries. The results show that the receptivity to surface step excrescences is largely the result of an overall adverse pressure gradient posed by the step, and that the free‐stream disturbances accelerate the generation of instabilities in the downstream. As expected, it is found that the acoustic disturbance interacting with the surface imperfection is more efficient in exciting the Tollmien–Schlichting waves than the vorticity disturbance. The latter generates Tollmien–Schlichting waves that are grouped in wave packets consistent with the wavelength of the free‐stream disturbance. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
99.
100.
Sonic boom focusing phenomenon can be predicted using the solution to the nonlinear Tricomi equation which is a hybrid (hyperbolic‐elliptic) second‐order partial differential equation. In this paper, the hyperbolic conservation law form is derived, which is valid in the entire domain. In this manner, the presence of two regions where the equation behaves differently (hyperbolic in the upper and elliptic in the lower half‐plane) is avoided. On the upper boundary, a new mixed boundary condition for the acoustic pressure is employed. The discretization is carried out using a discontinuous Galerkin (DG) method combined with a Runge–Kutta total‐variation diminishing scheme. The results show the accuracy of DG methods to solve problems involving sharp gradients and discontinuities. Comparisons with analytical results for the linear case, and other numerical results using classical explicit and compact finite difference schemes and weighted essentially non‐oscillatory schemes are included. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献