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41.
Dr. Alasdair I. McKay Dr. James Barwick-Silk Max Savage Prof. Michael C. Willis Prof. Andrew S. Weller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(13):2883-2889
The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3-F3C6H3, 1,2,3,4-F4C6H2 and 1,2,3,4,5-F5C6H are shown to bind with cationic [Rh(Cy2P(CH2)xPCy2)]+ fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF3)3}4]− anion. 相似文献
42.
Dr. Joohyun Lim Ghoncheh Kasiri Dr. Rajib Sahu Kevin Schweinar Dr. Katharina Hengge Prof. Dr. Dierk Raabe Prof. Dr. Fabio La Mantia Prof. Dr. Christina Scheu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4917-4922
The structural changes of copper hexacyanoferrate (CuHCF), a Prussian blue analogue, which occur when used as a cathode in an aqueous Zn-ion battery, are investigated using electron microscopy techniques. The evolution of ZnxCu1−xHCF phases possessing wire and cubic morphologies from initial CuHCF nanoparticles are monitored after hundreds of cycles. Irreversible introduction of Zn ions to CuHCF is revealed locally using scanning transmission electron microscopy. A substitution mechanism is proposed to explain the increasing Zn content within the cathode material while simultaneously the Cu content is lowered during Zn-ion battery cycling. The present study demonstrates that the irreversible introduction of Zn ions is responsible for the decreasing Zn ion capacity of the CuHCF cathode in high electrolyte concentration. 相似文献
43.
Dr. Gao Li Wu-Yue Yang Wen-Hao Li Yun-Yi Luo Yeh-Jun Lim Prof. Dr. Yang Li Dr. Ashim Paul Prof. Dr. Daniel Segal Liu Hong Prof. Dr. Yan-Mei Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3499-3503
It has been reported that many molecules could inhibit the aggregation of Aβ (amyloid-β) through suppressing either primary nucleation, secondary nucleation, or elongation processes. In order to suppress multiple pathways of Aβ aggregation, we screened 23 small molecules and found two types of inhibitors with different inhibiting mechanisms based on chemical kinetics analysis. Trp-glucose conjugates ( AS2 ) could bind with fibril ends while natural products ( D3 and D4 ) could associate with monomers. A cocktail of these two kinds of molecules achieved co-inhibition of various fibrillar species and avoid unwanted interference. 相似文献
44.
Dr. Rebecca L. Greenaway Dr. Valentina Santolini Dr. Filip T. Szczypiński Dr. Michael J. Bennison Dr. Marc A. Little Andrew Marsh Dr. Kim E. Jelfs Prof. Andrew I. Cooper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3718-3722
Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling. 相似文献
45.
Dr. Thais F. Abelha Dr. Graeme Morris Dr. Sandro M. Lima Dr. Luis H. C. Andrade Dr. Andrew J. McLean Prof. Cameron Alexander Dr. Jesus Calvo-Castro Dr. Callum J. McHugh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3173-3180
Development of novel bioimaging materials that exhibit organelle specific accumulation continues to be at the forefront of research interests and efforts. Among the various subcellular organelles, mitochondria, which are found in the cytoplasm of eukaryotic cells, are of particular interest in relation to their vital function. To date, most molecular probes that target mitochondria utilise delocalised lipophilic cations such as triphenylphosphonium and pyridinium. However, the use of such charged motifs is known to be detrimental to the working function of the mitochondrial transmembrane potential and there remains a strong case for development of neutral mitochondrial fluorescent probes. Herein, we demonstrate for the first time the exploitation of diketopyrrolopyrrole-based chemistries for the realisation of a neutral fluorescent probe that exhibits organelle specific accumulation within the mitochondria at the nanomolar level. The synthesised probe, which bears a neutral triphenylphosphine oxide moiety, exhibits a large Stokes shift and high fluorescence quantum yield in water, both highly sought-after properties in the development of bioimaging agents. In vitro studies reveal no interference with cell metabolism when tested for the human MCF7 breast cancer cell and nanomolar subcellular organelle colocalisation with commercially available mitochondrial staining agent Mitotracker Red. In light of its novelty, neutral structure and the preferential accumulation at nanomolar concentrations we anticipate this work to be of significant interest for the increasingly larger community devoted to the realisation of neutral mitochondrial selective systems and more widely to those engaged in the rational development of superior organic architectures in the biological field. 相似文献
46.
Julia Leitl Dr. Andrew R. Jupp Dr. Evi R. M. Habraken Verena Streitferdt Dr. Peter Coburger Dr. Daniel J. Scott Prof. Dr. Ruth M. Gschwind Prof. Dr. Christian Müller Dr. J. Chris Slootweg Prof. Dr. Robert Wolf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7788-7800
Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2 . The C≡N triple bonds of nitriles insert into the P−B bond of 2 with concomitant C−B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4-phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus–boron bond in 2 , which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P−B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition. 相似文献
47.
Nikolaos V. Tzouras Dr. Fady Nahra Dr. Laura Falivene Prof. Dr. Luigi Cavallo Marina Saab Prof. Dr. Kristof Van Hecke Dr. Alba Collado Dr. Christopher J. Collett Prof. Dr. Andrew D. Smith Prof. Dr. Catherine S. J. Cazin Prof. Dr. Steven P. Nolan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4515-4519
We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds. 相似文献
48.
Adam I. Green Dr. Fruzsina Hobor Dr. Christopher P. Tinworth Dr. Stuart Warriner Prof. Andrew J. Wilson Prof. Adam Nelson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(47):10682-10689
Protein–protein interactions (PPIs) provide a rich source of potential targets for drug discovery and biomedical science research. However, the identification of structural-diverse starting points for discovery of PPI inhibitors remains a significant challenge. Activity-directed synthesis (ADS), a function-driven discovery approach, was harnessed in the discovery of the p53/hDM2 PPI. Over two rounds of ADS, 346 microscale reactions were performed, with prioritisation on the basis of the activity of the resulting product mixtures. Four distinct and novel series of PPI inhibitors were discovered that, through biophysical characterisation, were shown to have promising ligand efficiencies. It was thus shown that ADS can facilitate ligand discovery for a target that does not have a defined small-molecule binding site, and can provide distinctive starting points for the discovery of PPI inhibitors. 相似文献
49.
Teresa Lauria Dr. Creina Slator Prof. Vickie McKee Dr. Markus Müller Samuele Stazzoni Antony L. Crisp Prof. Thomas Carell Prof. Andrew Kellett 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16782-16792
Nucleic acid click chemistry was used to prepare a family of chemically modified triplex forming oligonucleotides (TFOs) for application as a new gene-targeted technology. Azide-bearing phenanthrene ligands—designed to promote triplex stability and copper binding—were ‘clicked’ to alkyne-modified parallel TFOs. Using this approach, a library of TFO hybrids was prepared and shown to effectively target purine-rich genetic elements in vitro. Several of the hybrids provide significant stabilisation toward melting in parallel triplexes (>20 °C) and DNA damage can be triggered upon copper binding in the presence of added reductant. Therefore, the TFO and ‘clicked’ ligands work synergistically to provide sequence-selectivity to the copper cutting unit which, in turn, confers high stabilisation to the DNA triplex. To extend the boundaries of this hybrid system further, a click chemistry-based di-copper binding ligand was developed to accommodate designer ancillary ligands such as DPQ and DPPZ. When this ligand was inserted into a TFO, a dramatic improvement in targeted oxidative cleavage is afforded. 相似文献