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51.
Influence of Equilibration Time in Solution on the Inclusion/Exclusion Topology Ratio of Host–Guest Complexes Probed by Ion Mobility and Collision‐Induced Dissociation 下载免费PDF全文
Glenn Carroy Charlotte Daxhelet Dr. Vincent Lemaur Dr. Julien De Winter Prof. Edwin De Pauw Prof. Jérôme Cornil Prof. Pascal Gerbaux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4528-4534
Host–guest complexes are formed by the creation of multiple noncovalent bonds between a large molecule (the host) and smaller molecule(s) or ion(s) (the guest(s)). Ion‐mobility separation coupled with mass spectrometry nowadays represents an ideal tool to assess whether the host–guest complexes, when transferred to the gas phase upon electrospray ionization, possess an exclusion or inclusion nature. Nevertheless, the influence of the solution conditions on the nature of the observed gas‐phase ions is often not considered. In the specific case of inclusion complexes, kinetic considerations must be taken into account beside thermodynamics; the guest ingression within the host cavity can be characterized by slow kinetics, which makes the complexation reaction kinetically driven on the timescale of the experiment. This is particularly the case for the cucurbituril family of macrocyclic host molecules. Herein, we selected para‐phenylenediamine and cucurbit[6]uril as a model system to demonstrate, by means of ion mobility and collision‐induced dissociation measurements, that the inclusion/exclusion topology ratio varies as a function of the equilibration time in solution prior to the electrospray process. 相似文献
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Katharina Zielke Ondřej Kováč Michael Winter Dr. Jiří Pospíšil Prof. Mario Waser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8163-8168
The first highly asymmetric catalytic synthesis of densely functionalized dihydrobenzofurans is reported, which starts from ortho-hydroxy-containing para-quinone methides. The reaction relies on an unprecedented formal [4+1]-annulation of these quinone methides with allenoates in the presence of a commercially available chiral phosphine catalyst. The chiral dihydrobenzofurans were obtained as single diastereomers in yields up to 90 % and with enantiomeric ratios up to 95:5. 相似文献
54.
Redox‐Active Tetraruthenium Macrocycles Built from 1,4‐Divinylphenylene‐Bridged Diruthenium Complexes 下载免费PDF全文
Stefan Scheerer Dr. Michael Linseis Dr. Evelyn Wuttke Sabrina Weickert Prof. Dr. Malte Drescher Dr. Oliver Tröppner Prof. Dr. Ivana Ivanović‐Burmazović Andreas Irmler Prof. Dr. Fabian Pauly Prof. Dr. Rainer F. Winter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9574-9590
Metallamacrocylic tetraruthenium complexes were generated by treatment of 1,4‐divinylphenylene‐bridged diruthenium complexes with functionalized 1,3‐benzene dicarboxylic acids and characterized by HR ESI‐MS and multinuclear NMR spectroscopy. Every divinylphenylene diruthenium subunit is oxidized in two consecutive one‐electron steps with half‐wave potential splittings in the range of 250 to 330 mV. Additional, smaller redox‐splittings between the +/2+ and 0/+ and the 3+/4+ and 2+/3+ redox processes, corresponding to the first and the second oxidations of every divinylphenylene diruthenium entity, are due to electrostatic effects. The lack of electronic coupling through bond or through space is explained by the nodal properties of the relevant molecular orbitals and the lateral side‐by‐side arrangement of the divinylphenylene linkers. The polyelectrochromic behavior of the divinylphenylene diruthenium precursors is retained and even amplified in these metallamacrocyclic structures. EPR studies down to T=4 K indicate that the dications 1‐H2+ and 1‐OBu2+ are paramagnetic. The dications and the tetracation of macrocycle 3‐H display intense (dications) or weak ( 3‐H4+ ) EPR signals. Quantum chemical calculations indicate that the four most stable conformers of the macrocycles are largely devoid of strain. Bond parameters, energies as well as charge and spin density distributions of model macrocycle 5‐HMe were calculated for the different charge and spin states. 相似文献
55.
Detrimental Ni(0) transfer in Kumada catalyst transfer polycondensation of benzo[2,1‐b:3,4‐b']dithiophene 下载免费PDF全文
Anjan Bedi Julien De Winter Pascal Gerbaux Guy Koeckelberghs 《Journal of polymer science. Part A, Polymer chemistry》2016,54(12):1706-1712
This article deals with the Kumada Catalyst Transfer Polycondensation (KCTP) of 4,7‐dioctylbenzo[2,1‐b:3,4‐b']dithiophene ( BDP‐Oct ) using Ni(II) catalyst or In/cat combination. A combination of MALDI MS, GPC, and 31P NMR spectroscopy is used to reveal the failure of the KCTP of this particular monomer. Intermolecular transfer reactions to monomer appeared to prevent the formation of polymer. This result is remarkable, since isomeric benzo[1,2‐b:4,5‐b']dithiophene polymerizes in a controlled way. The presence of a “non‐aromatic double bond” in annulated monomers is discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1706–1712 相似文献
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Rudolf Gompper Jan-Gerd Hansel Joachim Hock Kurt Polborn Elmar Dormann Hubert Winter 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):521-525
Abstract Novel dithiolene metal complexes, some of which absorb in the near infrared, and tetrathiafulvalenes, in particular tetraiodotetrathia- fulvalene, have been prepared, and their magnetic properties studied. 相似文献
57.
Sodium, potassium, rubidium, caesium, ammonium and tetramethylammonium tetraphenylborates were studied by both positive and negative ion electrospray mass spectrometry. An affinity order of Cs+ > Rb+ > K+ ~ Na+ was obtained. The results obtained were compared with both calculations and solid-state structures, where available. The previously reported high affinity of caesium for tetraphenylborate concluded from NMR experiments was confirmed for the gas phase. The affinity does not appear to result from steric effects and a cation–pi interaction seems likely. In the positive ion mode, a unique acetonitrile complex of NaBPh4 was observed. 相似文献
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FT‐IR spectroscopic and thermodynamic measurements were designed to explore the effect of a macromolecular crowder, dextran, on the temperature and pressure‐dependent phase diagram of the protein Ribonuclease A (RNase A), and we compare the experimental data with approximate theoretical predictions based on configuration entropy. Exploring the crowding effect on the pressure‐induced unfolding of proteins provides insight in protein stability and folding under cell‐like dense conditions, since pressure is a fundamental thermodynamic variable linked to molecular volume. Moreover, these studies are of relevance for understanding protein stability in deep‐sea organisms, which have to cope with pressures in the kbar range. We found that not only temperature‐induced equilibrium unfolding of RNase A, but also unfolding induced by pressure is markedly prohibited in the crowded dextran solutions, suggesting that crowded environments such as those found intracellularly, will also oppress high‐pressure protein unfolding. The FT‐IR spectroscopic measurements revealed a marked increase in unfolding pressure of 2 kbar in the presence of 30 wt % dextran. Whereas the structural changes upon thermal unfolding of the protein are not significantly influenced in the presence of the crowding agent, through stabilization by dextran the pressure‐unfolded state of the protein retains more ordered secondary structure elements, which seems to be a manifestation of the entropic destabilization of the unfolded state by crowding. 相似文献
60.
Methyl acetoacetate and 2,4-pentanedione dianions were condensed with aldehydes and ketones to afford a 1,3,5-trioxygenated carboskeleton. Intramolecular cyclization of the aldol adducts delivered the title compounds in good yield. 相似文献