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41.
Dr. Lin Xu Dr. Dawei Zhang Dr. Tanya K. Ronson Prof. Jonathan R. Nitschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(19):7505-7508
The use of di(2-pyridyl)ketone in subcomponent self-assembly is introduced. When combined with a flexible triamine and zinc bis(trifluoromethanesulfonyl)imide, this ketone formed a new Zn4L4 tetrahedron 1 bearing twelve uncoordinated pyridyl units around its metal-ion vertices. The acid stability of 1 was found to be greater than that of the analogous tetrahedron 2 built from 2-formylpyridine. Intriguingly, the peripheral presence of additional pyridine rings in 1 resulted in distinct guest binding behavior from that of 2 , affecting guest scope as well as binding affinities. The different stabilities and guest affinities of capsules 1 and 2 enabled the design of systems whereby different cargoes could be moved between cages using acid and base as chemical stimuli. 相似文献
42.
Jonas Strh Laura Ruiz Arana Philipp Polzin Irma Vania Eliani Patric Lindenberg Niclas Heidenreich Csar dos Santos Cunha Sebastian Leubner Huayna Terraschke 《无机化学与普通化学杂志》2019,645(5):537-543
Despite the strong technological importance of lanthanide complexes, their formation processes are rarely investigated. This work is dedicated to determining the influence of synthesis parameters on the formation of [Ce(bipy)2(NO3)3] as well as Ce3+‐ and Tb3+‐substituted [La(bipy)2(NO3)3] (bipy = 2,2′‐bipyridine) complexes. To this end, we performed in situ luminescence measurements, synchrotron‐based X‐ray diffraction (XRD) analysis, infrared spectroscopy (IR), and measured pH value and/or ion conductivity during their synthesis process under real reaction conditions. For the [Ce(bipy)2(NO3)3] complex, the in situ luminescence measurements initially presented a broad emission band at 490 nm, assigned to the 5d→4f Ce3+ ions within the ethanolic solvation shell. Upon the addition of bipy, a red shift to 700 nm was observed. This shift was attributed to the changes in the environment of the Ce3+ ions, indicating their desolvation and incorporation into the [Ce(bipy)2(NO3)3] complex. The induction time was reduced from 8 to 3.5 min, by increasing the reactant concentration by threefold. In contrast, [La(bipy)2(NO3)3] crystallized within days instead of minutes, unless influenced by high Ce3+ and Tb3+ concentrations. Monitoring and controlling the influence of the reaction parameters on the structure of emissive complexes is important for the development of rational synthesis approaches and optimization of their structure‐related properties like luminescence. 相似文献
43.
Dr. Philipp Le Dr. Matthew B. Nodwell Dr. Jürgen Eirich Prof. Stephan A. Sieber 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12644-12651
The illudin natural product family are fungal secondary metabolites with a characteristic spirocyclopropyl-substituted fused 6,5-bicyclic ring system. They have been extensively studied for their cytotoxicity in various tumor cell types, and semisynthetic derivatives with improved therapeutic characteristics have progressed to clinical trials. Although it is believed that this potent alkylating compound class acts mainly through DNA modification, little is known about its binding to protein sites in a cellular context. To reveal putative protein targets of the illudin family in live cancer cells, we employed a semisynthetic strategy to access a series of illudin-based probes for activity-based protein profiling (ABPP). While the probes largely retained potent cytotoxicity, proteomic profiling studies unraveled multiple protein hits, suggesting that illudins exert their mode of action not from addressing a specific protein target but rather from DNA modification and unselective protein binding. 相似文献
44.
Philipp Meysel Lothar Oellrich P. Raj Bishnoi Matthew A. Clarke 《The Journal of chemical thermodynamics》2011,43(10):1475-1479
The three-phase (vapour + liquid + solid) equilibrium conditions for semi-clathrates formed from three mixtures of (CO2 + N2), in aqueous solutions of tetra-butyl ammonium bromide (TBAB), were measured in an isochoric reactor. The experiments were conducted at temperatures between (281 and 290) K, at pressures between (1.9 and 5.9) MPa and in aqueous TBAB solutions of wTBAB = (0.05, 0.10, and 0.20). The experimental results obtained in this study were compared with previously obtained results for gas hydrates, formed from the same three mixtures of (CO2 + N2) and it was observed that semi-clathrates formed at a substantially lower pressure than did gas hydrates. 相似文献
45.
Two-dimensional condensation in camphor-10-sulphonic acid films at the mercury/electrolyte interface
The electrosorption properties of camphor-10-sulphonic acid (CS) in different electrolytes (Na2SO4, LiClO4, KNO3, KCl, KBr, KJ) were investigated experimentally by ac polarographic measurements at different temperatures. Depending on the type of electrolyte and on the temperature, film condensation was observed.The Frumkin interaction coefficient, determined from the critical degree of coverage, does not depend linearly on the reciprocal temperature as would be the case in correspondence to the temperature dependence of the pit width. This contradiction does not occur if the interaction coefficient is determined from the critical degree of coverage using the lattice gas model. The temperature dependence of the pit width of the differential capacity-potential curves, found in the experiment, can be theoretically described by both these models. The interaction coefficient in the models is inversely proportional to the temperature. Furthermore, the parameters of the standard free energy of adsorption, the interaction energy, the interaction coefficient of the Frumkin isotherm, the adsorption coefficient, and the maximal surface concentration of CS in the film were estimated and compared. 相似文献
46.
Sandra Hildebrandt Andreas Eva Philipp Komissinskiy Claudia Fasel Ingo Fritsch Lambert Alff 《Journal of Sol-Gel Science and Technology》2012,63(3):307-314
Sodium and lithium cobaltates are important materials for thermoelectric and battery applications due to their large thermoelectric power and ability to (de-) intercalate the alkali metal. For these applications, phase pure materials with controlled microstructure are required. We report on the sol?Cgel synthesis of sodium- and lithium-based materials by using acetate precursors. The produced Na2/3CoO2, Li(Ni1/3Mn1/3Co1/3)O2, and Li(Ni1/2Co1/2)O2 powders are phase pure with grain sizes below 1???m. X-ray diffraction and energy-dispersive spectral analyses show that the cation stoichiometry is preserved in the lithium-based compounds. Despite the low temperatures, the sodium content is reduced by 1/3 as compared to the initial value. Chemical phases of the investigated powders are formed in the sol?Cgel route at temperatures typically 100?C200?K lower than those used in the conventional solid-state synthesis of these materials. The suggested sol?Cgel synthesis is a low temperature process suited for production of phase pure and homogeneous materials with volatile cations. 相似文献
47.
Costa JS Balde C Carbonera C Denux D Wattiaux A Desplanches C Ader JP Gütlich P Létard JF 《Inorganic chemistry》2007,46(10):4114-4119
A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long-lived metastable HS state. This underlines the preponderant role of the inner coordination sphere for stabilizing the lifetime of the photoinduced HS state. 相似文献
48.
Systematic Comparison of Peptidic Proteasome Inhibitors Highlights the α‐Ketoamide Electrophile as an Auspicious Reversible Lead Motif 下载免费PDF全文
Martin L. Stein Haissi Cui Philipp Beck Christian Dubiella Constantin Voss Prof. Dr. Achim Krüger Prof. Dr. Boris Schmidt Prof. Dr. Michael Groll 《Angewandte Chemie (International ed. in English)》2014,53(6):1679-1683
The ubiquitin–proteasome system (UPS) has been successfully targeted by both academia and the pharmaceutical industry for oncological and immunological applications. Typical proteasome inhibitors are based on a peptidic backbone endowed with an electrophilic C‐terminus by which they react with the active proteolytic sites. Although the peptide moiety has attracted much attention in terms of subunit selectivity, the target specificity and biological stability of the compounds are largely determined by the reactive warheads. In this study, we have carried out a systematic investigation of described electrophiles by a combination of in vitro, in vivo, and structural methods in order to disclose the implications of altered functionality and chemical reactivity. Thereby, we were able to introduce and characterize the class of α‐ketoamides as the most potent reversible inhibitors with possible applications for the therapy of solid tumors as well as autoimmune disorders. 相似文献
49.
M. Sc. Shih‐Fan Hsu Dipl.‐Chem. Susanne Rommel M. Sc. Philipp Eversfield Dr. Keven Muller Prof. Dr. Elias Klemm Prof. Dr. Werner R. Thiel Prof. Dr. Bernd Plietker 《Angewandte Chemie (International ed. in English)》2014,53(27):7074-7078
Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H2 battery which is based on the principle of the Ru‐catalyzed hydrogenation of CO2 to formic acid (charging process) and the Ru‐catalyzed decomposition of formic acid to CO2 and H2 (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure‐free conditions (discharging process). Up to five charging–discharging cycles were performed without decrease of storage capacity. The resulting CO2/H2 mixture is free of CO and can be employed directly in fuel‐cell technology. 相似文献
50.
Mechanism of Host–Guest Complex Formation and Identification of Intermediates through NMR Titration and Diffusion NMR Spectroscopy 下载免费PDF全文
M. Sc. Jan‐Hendrik Lamm B. Sc. Philipp Niermeier Dr. Andreas Mix Dr. Jasmin Chmiel Beate Neumann Dr. Hans‐Georg Stammler Prof. Dr. Norbert W. Mitzel 《Angewandte Chemie (International ed. in English)》2014,53(30):7938-7942
The formation of host–guest (H‐G) complexes between 1,8‐bis[(diethylgallanyl)ethynyl]anthracene (H) and the N‐heterocycles pyridine and pyrimidine (G) was studied in solution using a combination of NMR titration and diffusion NMR experiments. For the latter, diffusion coefficients of potential host–guest structures in solution were compared with those of tailor‐made reference compounds of similar shape (synthesized and characterized by NMR, HRMS, and in part XRD). Highly dynamic behavior was observed in both cases, but with different host–guest species and equilibria. With increasing concentrations of the pyridine guest, the equilibrium H2?H2κ1‐G1?HG2 is observed (in the second step a host dimer coordinates one guest molecule); for pyrimidine the equilibrium H2→H1κ2‐G1?HG2 is observed (the formation of a 1:1 aggregate is the second step). 相似文献