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11.
Ronald Callahan Orlando Ramirez Kerstin Rosmarion Robert Rothchild Kevin C. Bynum 《Journal of heterocyclic chemistry》2005,42(5):889-898
A series of hindered Diels‐Alder adducts have been prepared from phencyclone, 1 , with various unusual symmetrical cyclic dienophiles, including cyclohexene, 2a ; vinylene carbonate, 2b ; vinylene trithiocarbonate, 2c ; and the N‐aryl maleimides: N‐(4‐dimethylamino‐3,5‐dinitrophenyl)maleimide (“Tuppy's maleimide”), 2d ; and N‐[3,5‐bis(trifluoromethyl)phenyl]maleimide, 2e . The highly hindered adducts, 3a‐e , respectively, were extensively characterized by one‐ and two‐dimensional NMR methods, observing proton, carbon‐13 and fluorine‐19. High resolution COSY45 spectra permitted rigorous proton NMR assignments. The 2D heteronuclear C‐H chemical shift correlation spectra (HETCOR, XHCORR) were obtained for adducts 3a‐d , allowing specific assignments for protonated carbons. Corrections to earlier proton NMR assignments for the vinylene carbonate adduct are given; results of the gated decoupling 13C NMR experiment for this adduct supported endo adduct stereochemistry. Relative proton chemical shifts for bridgehead phenyls of adduct 3c appeared anomalous relative to other adducts, suggesting possible special anisotropic interactions (with endocyclic sulfur or other anisotropic groups in the product) due to the unusual calculated orientation of the phenyls. The unsubstituted bridgehead phenyls in all adducts were shown to exhibit slow exchange limit (SEL) 1H and 13C spectra on the NMR timescales at ambient temperatures (7 tesla) showing slow rotations about the C(sp3)‐C(aryl sp2) bonds. The rapid rotation of the N‐aryl rings of the maleimide adducts was indicated by fast exchange limit spectra, suggesting that ortho substitution of the N‐aryl ring may be necessary to slow this rotation to the SEL regime. Ab initio geometry optimizations at the Hartree‐Fock level were carried out for each adduct, with the 6‐31G* basis sets. Appreciable geometry differences were seen in calculated structures, and significant NMR chemical shift differences were experimentally observed, depending on the nature of the groups attached to the (Z)‐HC=CH moiety of the dienophiles. 相似文献
12.
A miniaturised technique to analyse and detect heterocyclic aromatic amines (HAs) using micro solid-phase extraction (SPE) coupled on-line (in-capillary) to capillary electrophoresis (CE) separation with nanospray (nESI) mass spectrometry (MS) detection has been developed. HAs are mutagenic and carcinogenic compounds formed at low levels in protein-rich food during cooking. Due to the low concentrations of HAs and the high complexity of the matrix in which they exist, sensitive and selective analytical methods are required for quantification. SPE was performed on a packed bed of C18 particles inside the CE capillary, which minimised the dead volume. The on-line coupling of SPE, CE and nESI-MS reduced the time for extraction and identification to less than half an hour, which will allow for screening of several samples per day. The new technique provides short analysis time, low sample and solvent consumption, and HAs in standard solutions were easily detected at 12–17 fmol injections, and in spiked urine samples at 750–810 fmol injections. 相似文献
13.
14.
Dietmar Rahner Stefan Machill Heike Schlörb Kerstin Siury Matthias Kloss Waldfried Plieth 《Journal of Solid State Electrochemistry》1998,2(2):78-84
An overview is given of intercalation materials for both the negative and the positive electrodes of lithium batteries, including
the results of our own research. As well as lithium metal as a negative electrode, we consider insertion materials based on
aluminium alloys. In the case of the positive electrode metal-oxides based on manganese, nickel and cobalt are discussed.
Received: 27 May 1997 / Accepted: 30 July 1997 相似文献
15.
Herber U Pechmann T Weberndörfer B Ilg K Werner H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):309-319
A series of dinuclear chelate complexes of the general composition [Rh2(kappa2-L)2(mu-CR2)2(mu-SbiPr3)] (R = Ph, p-Tol; L = CF3CO2-, acac-, acac-f3-) and [Rh2Cl(kappa2-L)(mu-CR2)2(mu-SbiPr3)] (R = Ph, p-Tol; L = acac-, acac-f3-) has been prepared by replacement of the chloro ligands in the precursors [Rh2Cl2(mu-CR2)2(mu-SbiPr3)] by anionic chelates. The lability of the SbiPr3 bridge in the rhodium dimers is illustrated by the reactions of [Rh2(kappa2-acac)2(mu-CR2)2(mu-SbiPr3)] (7, 8) with Lewis bases such as CO, CNtBu, and SbEt3 which lead to the formation of the substitution products [Rh2(kappa2-acac)2(mu-CR2)2(mu-L')] (13-16) in excellent yields. Treatment of 7 and 8 with sterically demanding tertiary phosphanes PR3 (R3 = iPr3, iPr2Ph, iPrPh2, Ph3) affords the mixed-valence Rh0-RhII complexes [(kappa2-acac)2Rh(mu-CPh2)2Rh(PR3)] (21-24) and [(kappa2-acac)2Rh(mu-C(p-Tol)2]2Rh(PiPr3)] (25) for which there is no precedence. The terminal PiPr3 ligand of 21 is easily displaced by alkynes, CNtBu, and CO to give, by preserving the [(kappa2-acac)2Rh(mu-CPh2)2Rh] molecular core, the related dinuclear compounds 26-31 in which the coordination number of the Rh0 center is 3, 4, or 5. The molecular structures of [Rh2Cl(kappa2-acac)(mu-CPh2)2(mu-SbiPr3)] (5), [Rh2(kappa2-acac)2(mu-CPh2)2(mu-CO)] (13), [(kappa2-acac)2Rh(mu-CPh2)2Rh(PiPr3)] (21), and [(kappa2-acac)2Rh(mu-CPh2)2Rh(CNtBu)2] (30) have been determined crystallographically. 相似文献
16.
UHF and CI calculations, using the direct CI method, and double-zeta plus polarization functions basis sets, have been performed on the more important parts of the energy hypersurface for CH5. The abstraction H + CH4 → H2 + CH3 and the inversion substitution reaction H′ + CH4 → CH3H′ + H have been studied in detail. The predicted barriers for these two reactions are 13.5 and 36.6 kcal/mol, respectively. The abstraction reaction is, in agreement with experiment, found to be almost thermo-neutral with a heat of reaction of 1.5 kcal/mol. 相似文献
17.
Jacob M. Wurlitzer Aleksa Stanii Sebastian Ziethe Paul M. Jordan Kerstin Günther Oliver Werz Hajo Kries Markus Gressler 《Chemical science》2022,13(31):9091
The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages. 相似文献
18.
Oliver Neudert Miriam Reh Hans W. Spiess Kerstin Münnemann 《Macromolecular rapid communications》2015,36(10):885-889
NMR studies of synthetic polymers and biomacromolecules, which provide insight into the conformation and dynamics of these materials, can benefit strongly from the increased sensitivity offered by dynamic nuclear polarization (DNP) and other hyperpolarizing methods. In this study 1H DNP nuclear spin hyperpolarization of two polybutadiene samples, representing a supercooled liquid and an entangled polymer melt, is demonstrated at 0.35 T magnetic field strength and at temperatures between −80 and +50 °C. Electron spin polarization transfer from the α,γ‐bisdiphenylene‐β‐phenylallyl radical to the sample nuclei is achieved by the Overhauser and solid effect. DNP signal enhancements are studied, varying the electron spin resonance offset, microwave power, and sample temperature. The influence of spin relaxation times, line widths, and molecular dynamics are discussed. The results show promising, up to 15‐fold NMR signal enhancements using noncryogenic temperatures and an inexpensive setup that is less technically demanding than current high‐field DNP setups.
19.
We demonstrate a technique to reduce first-order Doppler shifts in crossed atomic/molecular and laser beam setups by aligning two counterpropagating laser beams as part of a Sagnac interferometer. Interference fringes on the exit port of the interferometer reveal minute deviations from perfect antiparallelism. Residual Doppler shifts of this method scale with the ratio v/(4d) of the typical atomic/molecular velocity v and the laser beam diameter d. The method is implemented for precision frequency calibration studies at deep-UV wavelengths, both in one- and two-photon excitation schemes: the 6s(2) --> 6s30p(3/2)J=1 line in Yb at 199 nm and the 4p(6) --> 4p(5)p[1/2](0) transition in Kr at lambda=212 nm. The achieved precision of 6 x 10(-10) is limited by the characteristics of the laser system. 相似文献
20.
Christian Gentzsch Kerstin Seier Antonios Drakopoulos Dr. Marie-Lise Jobin Dr. Yann Lanoiselée Dr. Zsombor Koszegi Dr. Damien Maurel Dr. Rémy Sounier Dr. Harald Hübner Prof. Dr. Peter Gmeiner Dr. Sébastien Granier Prof. Dr. Davide Calebiro Prof. Dr. Michael Decker 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6014-6020
μ-Opioid receptors (μ-ORs) play a critical role in the modulation of pain and mediate the effects of the most powerful analgesic drugs. Despite extensive efforts, it remains insufficiently understood how μ-ORs produce specific effects in living cells. We developed new fluorescent ligands based on the μ-OR antagonist E-p-nitrocinnamoylamino-dihydrocodeinone (CACO), that display high affinity, long residence time and pronounced selectivity. Using these ligands, we achieved single-molecule imaging of μ-ORs on the surface of living cells at physiological expression levels. Our results reveal a high heterogeneity in the diffusion of μ-ORs, with a relevant immobile fraction. Using a pair of fluorescent ligands of different color, we provide evidence that μ-ORs interact with each other to form short-lived homodimers on the plasma membrane. This approach provides a new strategy to investigate μ-OR pharmacology at single-molecule level. 相似文献