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71.
Andreas Leng Cornelius Weiß Nina Straßner Prof. Dr. Andreas Hirsch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(53):e202201446
An unprecedented compound class of functional organic hybrids consisting of a photoswitchable norbornadiene building block and a redoxactive chromophore, namely naphthalene diimide, were designed and synthesized. Within these structures the capability of rylene chromophores to function as a redox active catalyst upon their photoexcitation was utilized to initiate the oxidative back-conversion of the in situ formed quadricyclane unit to its norbornadiene analogue. In this way successive photoexcitation at two different wavelengths enabled a controlled photoswitching between the two isomerical states of the hybrids. Beyond this prove of concept, the dependency of the reaction rate to the intramolecular distance of the two functional molecular building blocks as well as the concentration of the photoexcited sample was monitored. The experimental findings and interpretations were furthermore supported by quantum chemical investigations. 相似文献
72.
Christian Balischewski Hyung-Seok Choi Karsten Behrens Alkit Beqiraj Thomas Körzdörfer André Geßner Dr. Armin Wedel Prof. Dr. Andreas Taubert 《ChemistryOpen》2021,10(2):272-295
Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples. 相似文献
73.
Capillary sieving electrophoresis utilizing SDS (CE(SDS)) is one of the most applied methods for the analysis of antibody (mAb) size heterogeneity in the biopharmaceutical industry. Inadequate peak identification of observed protein fragments is still a major issue. In a recent publication, we introduced an electrophoretic 2D system, enabling online mass spectrometric detection of generic CE(SDS) separated peaks and identification of several mAb fragments. However, an improvement regarding system stability and handling of the approach was desired. Here, we introduce a novel 8-port valve in conjunction with an optimized decomplexation strategy. The valve contains four sample loops with increased distances between the separation dimensions. Thus, successively coinjection of solvent and cationic surfactant without any additional detector in the second dimension is enabled, simplifying the decomplexation strategy. Removal efficiency was optimized by testing different volumes of solvents as presample and cationic surfactant as postsample zone. 2D measurements of the light and heavy chain of the reduced NIST mAb with the 8-port valve and the optimized decomplexation strategy demonstrates the increased robustness of the system. The presented novel set-up is a step toward routine application of CE(SDS)-CZE-MS for impurity characterization of proteins in the biopharmaceutical field. 相似文献
74.
Natalia Tiessen Dr. Nico Schwarze Mira Keßler Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(43):11041-11044
While alkyl-substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C2F5)3]−, which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron-withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C2F5)3O]−. In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C2F5)3OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C2F5)3SiOSi(C2F5)3. Deprotonation of Si(C2F5)3OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C2F5)3O}2]2−, implies Lewis amphoteric character of the monomeric [Si(C2F5)3O]− anion. 相似文献
75.
Maria Haimerl Dr. Christian Graßl Dr. Michael Seidl Dr. Martin Piesch Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18129-18134
The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [(L1Ni)2tol] ( 1 , L1=[{N(C6H3iPr2-2,6)C(Me)}2CH]−) and [K2][(L1Ni)2(μ,η1 : 1-N2)] ( 6 ) were reacted with P4, As4 and the interpnictogen compound AsP3, respectively, yielding the homobimetallic complexes [(L1Ni)2(μ-η2,κ1:η2,κ1-E4)] (E=P ( 2 a ), As ( 2 b ), AsP3 ( 2 c )), [(L1Ni)2(μ,η3 : 3-E3)] (E=P ( 3 a ), As ( 3 b )) and [K@18-c-6(thf)2][L1Ni(η1 : 1-E4)] (E=P ( 7 a ), As ( 7 b )), respectively. Heating of 2 a , 2 b or 2 c also leads to the formation of 3 a or 3 b . Furthermore, the reactivity of these compounds towards reduction agents was investigated, leading to [K2][(L1Ni)2(μ,η2 : 2-P4)] ( 4 ) and [K@18-c-6(thf)3][(L1Ni)2(μ,η3 : 3-E3)] (E=P ( 5 a ), As ( 5 b )), respectively. Compound 4 shows an unusual planarization of the initial Ni2P4-prism. All products were comprehensively characterized by crystallographic and spectroscopic methods. 相似文献
76.
Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase
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Dipl.‐Biol. Mechthild Gall Dipl.‐Biochem. Maren Thomsen Dipl.‐Biochem. Christin Peters Dr. Ioannis V. Pavlidis M. Sc. Patrick Jonczyk M. Sc. Philipp P. Grünert Dr. Sascha Beutel Prof. Dr. Thomas Scheper Egon Gross Dr. Michael Backes Dr. Torsten Geißler Dr. Jakob P. Ley Dr. Jens‐Michael Hilmer Dr. Gerhard Krammer Dr. Gottfried J. Palm Prof. Dr. Winfried Hinrichs Prof. Dr. Uwe T. Bornscheuer 《Angewandte Chemie (International ed. in English)》2014,53(5):1439-1442
Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction. 相似文献
77.
Dr. Dmitry Katayev Kai F. Pfister Timo Wendling Prof. Dr. Lukas J. Gooßen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9902-9905
Various (hetero)arenecarboxylic acids were converted to the corresponding Daugulis amides and nitrated selectively in the ortho‐position in the presence of [CuNO3(PPh3)2] and AgNO2 at 50 °C. A microwave‐assisted saponification allows regenerating the carboxylate group within minutes, which may then be removed tracelessly by protodecarboxylation, or substituted by aryl‐ or alkoxy‐groups via decarboxylative cross‐coupling. 相似文献
78.
Dr. Damien Hudry Dr. Christos Apostolidis Dr. Olaf Walter Dr. Arne Janßen Dr. Dario Manara Dr. Jean‐Christophe Griveau Dr. Eric Colineau Dr. Tonya Vitova Tim Prüßmann Dr. Di Wang Dr. Christian Kübel Dr. Daniel Meyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10431-10438
Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2(NO3)2] ? 3 H2O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. 相似文献
79.
The linear density-density response function represents a formulation of the generalized density response of a molecular (or extended) system to arbitrary perturbing potentials. We have recently established an approach for reducing the dimension of the (in principle infinite) eigenspace representation (the moment expansion) and generalized it to arbitrary self-adjoint, positive-definite, and compact linear operators. Here, we present a modified representation—the reduced eigensystem representation—which allows to define a trivial criterion for the convergence of the approximation to the density response. By means of this novel eigensystem-like structure, the remarkable reduction of the dimensionality becomes apparent for the calculation of the density-density response function. 相似文献
80.
Jochen C. Lauer Ziwei Pang Paul Janßen Dr. Frank Rominger Tobias Kirschbaum Prof. Dr. Marcus Elstner Prof. Dr. Michael Mastalerz 《ChemistryOpen》2020,9(2):183-190
Three shape-persistent [4+4] imine cages with truncated tetrahedral geometry with different window sizes were studied as hosts for the encapsulation of tetra-n-alkylammonium salts of various bulkiness. In various solvents the cages behave differently. For instance, in dichloromethane the cage with smallest window size takes up NEt4+ but not NMe4 + , which is in contrast to the two cages with larger windows hosting both ions. To find out the reason for this, kinetic experiments were carried out to determine the velocity of uptake but also to deduce the activation barriers for these processes. To support the experimental results, calculations for the guest uptakes have been performed by molecular mechanics’ simulations. Finally, the complexation of pharmaceutical interested compounds, such as acetylcholine, muscarine or denatonium have been determined by NMR experiments. 相似文献