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31.
32.
Engel M 《Physical review letters》2011,106(9):095504
The self-assembly of novel [corrected] ordered structures with nanoparticles has recently received much attention. Here we use computer simulations to study a two-dimensional model system characterized by a simple isotropic interaction that could be realized with building blocks on the nanoscale. We find that the particles arrange themselves into hexagonal superstructures of twin boundaries whose superlattice vector can be tuned reversibly by changing the temperature. Thermodynamic stability is confirmed by calculating the free energy with a combination of thermodynamic integration and the Frenkel-Ladd method. Different contributions to the free energy difference are discussed. 相似文献
33.
Jernigan FE Sieracki NA Taylor MT Jenkins AS Engel SE Rowe BW Jové FA Yap GP Papish ET Ferrence GM 《Inorganic chemistry》2007,46(2):360-362
The recently synthesized 3-tert-butyl-5-methyl-1,2,4-triazole reacted with KBH4 to give the new potassium tris(3-tert-butyl-5-methyl-1,2,4-triazolyl)borate K(Ttz(tBu,Me)) ligand. Ttz(tBu,Me) formed a four-coordinate (Ttz(tBu,Me))CoCl complex and five-coordinate (Ttz(tBu,Me))CoNO3 and (Ttz(tBu,Me))ZnOAc complexes. When these complexes were compared to their Tp(tBu,Me) analogues, it was found that Ttz(tBu,Me) resulted in negligible steric differences. K(Ttz(tBu,Me)) is more water-soluble than K(Tp(tBu,Me)), so bulky tris(triazolyl)borate ligands should lead to functional models for enzyme active sites in an aqueous environment and the creation of water-soluble analogues of Tp catalysts. 相似文献
34.
Engel PS Tsvaygboym KP Bachilo S Smith WB Jiang J Chignell CF Motten AG 《The Journal of organic chemistry》2005,70(7):2598-2605
[reaction: see text] Although some aspects of azoxy group radical chemistry have been investigated, unhindered alpha-azoxy radicals remain poorly understood. Here we report the generation of alpha-azoxy radicals under mild conditions by irradiation of alpha-azoxy ketones 4a,b. These compounds undergo alpha-cleavage to yield radicals 5a,b, whose oxygen atom then recombines with benzoyl radicals to produce presumed intermediate 15. Formal Claisen rearrangement gives alpha-benzoyloxyazo compounds 8a,b, which are themselves photolabile, leading to both radical and ionic decomposition. The ESR spectrum of 5a was simulated to extract the isotropic hyperfine splitting constants, which showed its resonance stabilization energy to be exceptionally large. Azoxy compounds have been found for the first time to be good quenchers of triplet excited acetophenone, the main sensitized photoreaction of 7Z in benzene being deoxygenation. While this reaction has been reported previously, it was always in hydrogen atom donating solvents, where chemical sensitization occurred. The principal direct irradiation product of 4bZ and model azoxyalkane 7Z is the E isomer, whose thermal reversion to Z is much faster than that of previously studied analogues. 相似文献
35.
David Gode Christian Schmitt Matthias Engel Dietrich A. Volmer 《Analytical and bioanalytical chemistry》2014,406(12):2841-2852
Enzyme-catalyzed reactions play key roles in disease pathology, thus making them relevant subjects of therapeutic inhibitor screening experiments. Matrix-assisted laser desorption/ionization (MALDI) assays have been demonstrated to be able to replace established screening approaches. They offer increased sample throughput, but care must be taken to avoid instrumental bias from differences in ionization efficiencies. We compared a MALDI-triple-quadrupole (QqQ) method for the Dyrk1A peptide substrate woodtide to LC–MS, liquid chromatography with ultraviolet detection (LC–UV), luminescence, and radiometric assays. MALDI measurements were performed on a MALDI-QqQ instrument in the multiple-reaction monitoring mode. Different MALDI conditions were investigated to address whether matrix type, sample support, and MRM- or SIM-based detection conditions can be used to accommodate the molar responses of substrate peptide and its phosphorylated form. UV detection served as a reference method. The impact of MALDI matrix on IC50 values was small, even considering that matrix preparations were used that are known to alleviate response differences. IC50 values determined by MALDI were ca. 2-fold lower than those determined by LC–UV. Although MALDI generated lower ion yields for the phosphorylated peptide than for the peptide substrate, we found that a correction of compound potencies was readily possible using correction factors based on unbiased LC–UV results. A thorough method development delivered a robust assay with excellent performance (Z′ > 0.91) that was close to that seen for LC–UV. Figure
? 相似文献
36.
The prominence of multiply charged molecular and fragment ions upon electron-impact in the mass spectrometer is proposed as an experimental, empirical indication of aromatic character. The effects of electron withdrawing and donating substituents on the production of multiply charged ions are considered and appearance potentials are noted for several species. 相似文献
37.
W. Engel N. Eisenreich M. Alonso V. Kolarik 《Journal of Thermal Analysis and Calorimetry》1993,40(3):1017-1024
The application of TRXRD for thermal analysis is demonstrated using examples of phase transitions, solid-state reactions and high-temperature corrosion. The measuring system produces a series of diffraction patterns, which are evaluated by a difference procedure that a reduces the data to curves comparable to DSC and TG curves and thus suited to kinetic evaluation. 相似文献
38.
Engel T. G. Veracka M. J. Neri J. M. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》2010,38(2):194-198
39.
Joshua P. Gray Md. Nasir Uddin Rajan Chaudhari Margie N. Sutton Hailing Yang Philip Rask Hannah Locke Brian J. Engel Nefeli Batistatou Jing Wang Brian J. Grindel Pratip Bhattacharya Seth T. Gammon Shuxing Zhang David Piwnica-Worms Joshua A. Kritzer Zhen Lu Robert C. Bast Jr. Steven W. Millward 《Chemical science》2021,12(10):3526
In recent decades it has become increasingly clear that induction of autophagy plays an important role in the development of treatment resistance and dormancy in many cancer types. Unfortunately, chloroquine (CQ) and hydroxychloroquine (HCQ), two autophagy inhibitors in clinical trials, suffer from poor pharmacokinetics and high toxicity at therapeutic dosages. This has prompted intense interest in the development of targeted autophagy inhibitors to re-sensitize disease to treatment with minimal impact on normal tissue. We utilized Scanning Unnatural Protease Resistant (SUPR) mRNA display to develop macrocyclic peptides targeting the autophagy protein LC3. The resulting peptides bound LC3A and LC3B—two essential components of the autophagosome maturation machinery—with mid-nanomolar affinities and disrupted protein–protein interactions (PPIs) between LC3 and its binding partners in vitro. The most promising LC3-binding SUPR peptide accessed the cytosol at low micromolar concentrations as measured by chloroalkane penetration assay (CAPA) and inhibited starvation-mediated GFP-LC3 puncta formation in a concentration-dependent manner. LC3-binding SUPR peptides re-sensitized platinum-resistant ovarian cancer cells to cisplatin treatment and triggered accumulation of the adapter protein p62 suggesting decreased autophagic flux through successful disruption of LC3 PPIs in cell culture. In mouse models of metastatic ovarian cancer, treatment with LC3-binding SUPR peptides and carboplatin resulted in almost complete inhibition of tumor growth after four weeks of treatment. These results indicate that SUPR peptide mRNA display can be used to develop cell-penetrating macrocyclic peptides that target and disrupt the autophagic machinery in vitro and in vivo.SUPR peptide mRNA display was used to evolve a cell-permeable, macrocyclic peptide for autophagy inhibition. 相似文献
40.
An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties. 相似文献