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1.
Johannes C. B. Dietschreit Annika Wagner T. Anh Le Philipp Klein Prof. Dr. Hermann Schindelin Prof. Dr. Till Opatz Prof. Dr. Bernd Engels Prof. Dr. Ute A. Hellmich Prof. Dr. Christian Ochsenfeld 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):12769-12773
The absence of fluorine from most biomolecules renders it an excellent probe for NMR spectroscopy to monitor inhibitor–protein interactions. However, predicting the binding mode of a fluorinated ligand from a chemical shift (or vice versa) has been challenging due to the high electron density of the fluorine atom. Nonetheless, reliable 19F chemical-shift predictions to deduce ligand-binding modes hold great potential for in silico drug design. Herein, we present a systematic QM/MM study to predict the 19F NMR chemical shifts of a covalently bound fluorinated inhibitor to the essential oxidoreductase tryparedoxin (Tpx) from African trypanosomes, the causative agent of African sleeping sickness. We include many protein–inhibitor conformations as well as monomeric and dimeric inhibitor–protein complexes, thus rendering it the largest computational study on chemical shifts of 19F nuclei in a biological context to date. Our predicted shifts agree well with those obtained experimentally and pave the way for future work in this area. 相似文献
2.
Guojiao Wu Jennifer Brger Axel Jacobi von Wangelin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(48):17401-17405
Atom‐transfer radical addition (ATRA) reactions have gained a strong foothold in organic synthesis by virtue of their operational simplicity, synthetic versatility, and perfect atom economy. A rich chemical space can be accessed through clever combinations of the simple starting materials. Many variations of this general motif have been reported. However, the vast majority involve the addition of an organic halide across a C=C double bond, resulting in the formation of 1,2‐bifunctional products. This report introduces a significant expansion of this general reactivity concept to give 1,3‐bifunctional adducts through the combination of 1,1‐ATRA to a carbenoid and 1,2‐ATRA to an alkyne. Both processes operate under mild conditions (RT, 5 h) with the same commercial catalyst (CoBr2, dppbz). 相似文献
3.
Dr. Dinar Abdullin Nico Fleck Christoph Klein Philipp Brehm Sebastian Spicher Prof. Dr. Arne Lützen Prof. Dr. Stefan Grimme Prof. Dr. Olav Schiemann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2586-2596
Iron(III) porphyrins have the propensity to form μ2-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor. 相似文献
4.
Jared P. Klein Richard A. Register 《Journal of Polymer Science.Polymer Physics》2019,57(18):1188-1195
Hydrogenated polynorbornene (hPN) synthesized by ring‐opening metathesis polymerization (ROMP) exhibits a thermoreversible change in crystal polymorph at a temperature T cc below its melting point, T m. The polymorphic transition corresponds to a sharp increase in rotational disorder around the chain axis as the temperature is increased above T cc. Saturation of ROMP polynorbornene (PN) to hPN can be achieved through both catalytic and noncatalytic approaches. Here, three different hydrogenation routes were employed on the same precursor polymer: catalytic routes over either supported Pd0 or a Ni/Al complex, and noncatalytic saturation with diimide. The different hydrogenation routes result in hPNs with varying degrees of epimerization of the cyclopentylene ring (from cis to trans); these epimerized units are included in the hPN crystals. The crystal structure of the rotationally ordered hPN polymorph, observed below T cc, changes sharply at low levels of epimerization and then is weakly influenced by further increases in trans content. The stability of the rotationally ordered hPN polymorph decreases with increasing epimerization, as reflected in a reduction of T cc from 134 °C to 92 °C at 22% epimerization. T cc is less affected by epimerization than by the inclusion of a similar content of 5‐methylnorbornene units, reflecting the smaller size of the trans defect. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1188–1195 相似文献
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Prof. Dr. Axel Schulz Dr. Alexander Villinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2032-2038
Pure, solvent‐free Zn(N3)2 was prepared by reaction of diethyl zinc and hydrazoic acid in aprotic solvents. The single‐crystal structure determination, along with the comprehensive characterization of α‐Zn(N3)2 and two metastable polymorphs, could be achieved for the first time. Since these data disagree in large parts with the known, previously reported values, all previous syntheses of Zn(N3)2, and for comparison Zn(N3)2?2.5 H2O and Zn(OH)N3 were reinvestigated, indicating that some of the earlier work has to be revised. 相似文献
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Dr. Christian Hering‐Junghans Max Thomas Dr. Alexander Villinger Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6713-6717
This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [RAr*N(SiMe)ECl][A] (RAr*=2,6‐(CHPh2)‐4‐R‐C6H2, R=Me, tBu; E=Sb, Bi; A?=GaCl4, Al(OCH(CF3)2)4). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the RAr* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4‐dimethylaminopyridine (dmap) was investigated. 相似文献