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181.
Christina Heroven Victoria Georgi Gaurav K. Ganotra Prof. Paul Brennan Finn Wolfreys Prof. Dr. Rebecca C. Wade Amaury E. Fernández‐Montalván Apirat Chaikuad Prof. Dr. Stefan Knapp 《Angewandte Chemie (International ed. in English)》2018,57(24):7220-7224
Prolonged drug residence times may result in longer‐lasting drug efficacy, improved pharmacodynamic properties, and “kinetic selectivity” over off‐targets with high drug dissociation rates. However, few strategies have been elaborated to rationally modulate drug residence time and thereby to integrate this key property into the drug development process. Herein, we show that the interaction between a halogen moiety on an inhibitor and an aromatic residue in the target protein can significantly increase inhibitor residence time. By using the interaction of the serine/threonine kinase haspin with 5‐iodotubercidin (5‐iTU) derivatives as a model for an archetypal active‐state (type I) kinase–inhibitor binding mode, we demonstrate that inhibitor residence times markedly increase with the size and polarizability of the halogen atom. The halogen–aromatic π interactions in the haspin–inhibitor complexes were characterized by means of kinetic, thermodynamic, and structural measurements along with binding‐energy calculations. 相似文献
182.
Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials 下载免费PDF全文
Allison M. Rice Ekaterina A. Dolgopolova Brandon J. Yarbrough Gabrielle A. Leith Corey R. Martin Kenneth S. Stephenson Rebecca A. Heugh Amy J. Brandt Prof. Dr. Donna A. Chen Dr. Stavros G. Karakalos Dr. Mark D. Smith Prof. Dr. Kelsey B. Hatzell Dr. Perry J. Pellechia Prof. Dr. Sophya Garashchuk Prof. Dr. Natalia B. Shustova 《Angewandte Chemie (International ed. in English)》2018,57(35):11310-11315
We report the first examples of purely organic donor–acceptor materials with integrated π‐bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four‐orders‐of‐magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes. 相似文献
183.
Andrew N. Cammidge Rebecca J. Turner Rhoda D. Beskeni Tahani Almutairi 《Liquid crystals》2017,44(12-13):2018-2028
ABSTRACTWe report the unexpected observation of columnar mesophase formation in a simple 2,7-dibromotetramethoxytriphenylene – by far the most lightly substituted discotic mesogen in this class. This derivative was prepared alongside the 3,6-dibromotriphenylene isomer to demonstrate an alternative, modified synthetic strategy that permits late-stage interchange of alkyl chain substituents. The new method is employed alongside the original route to deliver several new materials, including a conjugated ferrocene–triphenylene–ferrocene triad, a BODIPY–triphenylene–BODIPY triad and a new nematic twin linked through imine bridges. 相似文献
184.
Volker Seibert Corinna Prohl Ida Schoultz Edward Rhee Rebecca Lopez Kareem Abderazzaq Chunshui Zhou Dieter A Wolf 《BMC biochemistry》2002,3(1):22-15
Background
SCF ubiquitin ligases share the core subunits cullin 1, SKP1, and HRT1/RBX1/ROC1, which associate with different F-box proteins. F-box proteins bind substrates following their phosphorylation upon stimulation of various signaling pathways. Ubiquitin-mediated destruction of the fission yeast cyclin-dependent kinase inhibitor Rum1p depends on two heterooligomerizing F-box proteins, Pop1p and Pop2p. Both proteins interact with the cullin Pcu1p when overexpressed, but it is unknown whether this reflects their co-assembly into bona fide SCF complexes. 相似文献185.
186.
Equalizer technology followed by DIGE‐based proteomics for detection of cellular proteins in artificial peritoneal dialysis effluents 下载免费PDF全文
Anton Michael Lichtenauer Rebecca Herzog Silvia Tarantino Christoph Aufricht Klaus Kratochwill 《Electrophoresis》2014,35(10):1387-1394
Peritoneal dialysis effluent (PDE) represents a rich pool of potential biomarkers for monitoring disease and therapy. Until now, proteomic studies have been hindered by the plasma‐like composition of the PDE. Beads covered with a peptide library are a promising approach to remove high abundant proteins and concentrate the sample in one step. In this study, a novel approach for proteomic biomarker identification in PDEs consisting of a depletion and concentration step followed by 2D gel based protein quantification was established. To prove this experimental concept a model system of artificial PDEs was established by spiking unused peritoneal dialysis (PD) fluids with cellular proteins reflecting control conditions or cell stress. Using this procedure, we were able to reduce the amount of high abundant plasma proteins and concentrate low abundant proteins while preserving changes in abundance of proteins with cellular origin. The alterations in abundance of the investigated marker for cell stress, the heat shock proteins, showed similar abundance profiles in the artificial PDE as in pure cell culture samples. Our results demonstrate the efficacy of this system in detecting subtle changes in cellular protein expression triggered by unphysiological stress stimuli typical in PD, which could serve as biomarkers. Further studies using patients’ PDE will be necessary to prove the concept in clinical PD and to assess whether this technique is also informative regarding enriching low abundant plasma derived protein biomarker in the PDE. 相似文献
187.
Thompson RS Guler LP Nelson ED Yu YQ Kenttämaa HI 《The Journal of organic chemistry》2002,67(15):5076-5084
The 1,3-dioxolane-2-phosphenium ion, 1,3-benzodioxole-2-phosphenium ion, and o-biphenylenephosphenium ion are reported to react in a stereoselective manner with cis- and trans-1,2-diaminocyclohexanes in the gas phase in a Fourier transform ion cyclotron resonance mass spectrometer. Elimination of NH3 from an addition product was observed only for the trans isomer. Several reaction mechanisms were experimentally and computationally examined (B3LYP/6-31G(d)//HF/6-31G(d) + ZPVE level of theory). The most plausible mechanism is initiated by addition of one of the amino groups to the electrophilic phosphorus atom followed by proton transfer between the amino groups. A change to a diaxial conformation for the trans isomer facilitates anchimeric assistance by the now nucleophilic phosphorus atom as the C-N bond breaks to release NH3. Intramolecular proton transfer competes with the conformational change and ultimately leads to ethylene glycol elimination. The transition states for the critical steps of these two reactions are calculated to be nearly equal in magnitude, which rationalizes the observation of both reactions for the trans-diamine. In contrast, the adduct of the cis isomer can eliminate NH3 via a concerted 1,2-hydride shift without a need for a conformational change. However, the barrier associated with this reaction was found to be substantially greater than for proton transfer between the N- and O-atoms. The latter reaction dominates and ultimately leads to ethylene glycol elimination. 相似文献
188.
Leonard J. Schulman 《Positivity》2009,13(3):559-574
Muirhead’s majorization inequality was extended by Rado to the case of arbitrary permutation groups. We further generalize
this inequality to compact groups and their linear representations over the reals. We characterize saturation of the inequality,
and describe the saturation condition in detail for the case of actions on Hermitian operators.
Supported in part by the National Science Foundation and the Center for the Mathematics of Information. 相似文献
189.
Aarne Kasikov Alar Gerst Arvo Kikas Leonard Matisen Agu Saar Aivar Tarre Arnold Rosental 《Central European Journal of Physics》2009,7(2):356-362
The resistive response of atomic layer deposited thin epitaxial α-Cr2O3(0 0 1) films, to H2 and CO in air, was studied. The films were covered with Pt nanoislands formed by electron-beam evaporation of a sub-monolayer
amount of the material. The gas measurements were performed at 250°C and 450°C. These temperatures led to different proportion
of chemical states, Pt2+ and Pt4+, to which the Pt oxidized. The modification was ascertained by the X-ray photoelectron spectroscopy method. As a result of
the modification, the response was fast at 250°C, but slowed at 450°C. A disadvantageous abundance of Pt4+ arising at 450°C in air could be diminished by high-vacuum annealing thus restoring the response properties of the system
at 250°C.
相似文献
190.
Dmytro Neshchadin Dr. Rebecca Levinn Georg Gescheidt Prof. Dr. Stephen N. Batchelor Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):7008-7016
Polyphenols occur naturally in a vast variety of plants. One of their predominant properties is their antioxidant activity. To provide a deeper understanding of the antioxidant mechanism, 1H CIDNP spectroscopy (CIDNP=chemically induced dynamic nuclear polarization) is used to study model hydrogen abstraction reactions with four catechin‐based polyphenols: catechin (CA), gallocatechin (GC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG). The experiments involve photoinduced hydrogen‐atom transfer to a hydrogen abstractor (e.g., excited isopropylthioxanthone) followed under steady‐state conditions and in a time‐resolved fashion (resolution 500 ns–1 ms). It is found that hydrogen abstraction is an essentially stochastic process with a slight preference for the B rings in the catechin‐based polyphenols. Remarkably, analogous reactivity patterns could be followed in the “real systems”, green tea and red wine. We also show that CIDNP can be used as a semiquantitative tool to assess chemical reactivity. 相似文献