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Dr. Anna Notaro Marta Jakubaszek Severin Koch Dr. Riccardo Rubbiani Dr. Orsolya Dömötör Dr. Éva A. Enyedy Mazzarine Dotou Dr. Fethi Bedioui Mickaël Tharaud Dr. Bruno Goud PD Dr. Stefano Ferrari Prof. Dr. Enzo Alessio Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4997-5009
Cancer is one of the main causes of death worldwide. Chemotherapy, despite its severe side effects, is to date one of the leading strategies against cancer. Metal-based drugs present several potential advantages when compared to organic compounds and they have gained trust from the scientific community after the approval on the market of the drug cisplatin. Recently, we reported the ruthenium complex ([Ru(DIP)2(sq)](PF6) (where DIP is 4,7-diphenyl-1,10-phenantroline and sq is semiquinonate) with a remarkable potential as chemotherapeutic agent against cancer, both in vitro and in vivo. In this work, we analyse a structurally similar compound, namely [Ru(DIP)2(mal)](PF6), carrying the flavour-enhancing agent approved by the FDA, maltol (mal). To possess an FDA approved ligand is crucial for a complex, whose mechanism of action might include ligand exchange. Herein, we describe the synthesis and characterisation of [Ru(DIP)2(mal)](PF6), its stability in solutions and under conditions that resemble the physiological ones, and its in-depth biological investigation. Cytotoxicity tests on different cell lines in 2D model and on HeLa MultiCellular Tumour Spheroids (MCTS) demonstrated that our compound has higher activity than cisplatin, inspiring further tests. [Ru(DIP)2(mal)](PF6) was efficiently internalised by HeLa cells through a passive transport mechanism and severely affected the mitochondrial metabolism. 相似文献
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Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
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Electrochemiluminescence Bioassays with a Water‐Soluble Luminol Derivative Can Outperform Fluorescence Assays 下载免费PDF全文
Michael Mayer Prof. Dr. Shigehiko Takegami Michael Neumeier Simone Rink Prof. Dr. Axel Jacobi von Wangelin Silja Schulte Moritz Vollmer Prof. Dr. Axel G. Griesbeck PD Dr. Axel Duerkop Prof. Dr. Antje J. Baeumner 《Angewandte Chemie (International ed. in English)》2018,57(2):408-411
The most efficient and commonly used electrochemiluminescence (ECL) emitters are luminol, [Ru(bpy)3]2+, and derivatives thereof. Luminol stands out due to its low excitation potential, but applications are limited by its insolubility under physiological conditions. The water‐soluble m‐carboxy luminol was synthesized in 15 % yield and exhibited high solubility under physiological conditions and afforded a four‐fold ECL signal increase (vs. luminol). Entrapment in DNA‐tagged liposomes enabled a DNA assay with a detection limit of 3.2 pmol L?1, which is 150 times lower than the corresponding fluorescence approach. This remarkable sensitivity gain and the low excitation potential establish m‐carboxy luminol as a superior ECL probe with direct relevance to chemiluminescence and enzymatic bioanalytical approaches. 相似文献
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Controlling the size and alignment of ZnO microrods using ZnO thin film templates deposited by pulsed laser ablation 总被引:2,自引:0,他引:2
S.J. Henley M.N.R. Ashfold D.P. Nicholls P. Wheatley D. Cherns 《Applied Physics A: Materials Science & Processing》2004,79(4-6):1169-1173
The production of dense arrays of well aligned ZnO nano- and microrods with a controllable distribution of diameters is demonstrated. The rods were grown using a hydrothermal method, on pre-deposited ZnO thin films exhibiting a range of different grain sizes. These template ZnO thin films were deposited by pulsed laser ablation, at 193 nm, in a low background pressure of O2; average grain sizes ranged from 10 nm (room temperature deposition) to 50 nm when deposited at a substrate temperature (Tsub) of 500 °C. The morphology of the ZnO microrod arrays grown onto these ZnO thin films was found to depend on the Tsub used during film deposition. Increasing Tsub resulted in a lower density of larger nanorods, with a more pronounced [0001] alignment. The diameters of the rods produced are typically an order of magnitude greater than the grain size of the template ZnO film. Thus the rods cannot be a direct continuation of the grain structure of the template films. Rather, we suggest that the rod diameter is controlled by the density of sites at which the initial nucleation occurs, which is expected to be higher on the smaller grain size films deposited at lower temperatures. The factor controlling the final size of the rods is thus the available free space into which they can grow, which is smaller at the higher nucleation densities. The increased extent of [0001] texturing of the thin film templates deposited at higher Tsub is proposed as the reason for the improved [0001] alignment of rods grown on these templates. PACS 81.07.De; 81.10.Dn; 52.38.Mf 相似文献
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We present a combined Monte‐Carlo/molecular dynamics study of a Cu0.327Ni0.673 alloy system. On the basis of nearest‐neighbor coordination number analyses atomic clustering and phase segregation is explored. Along this line, free energy profiles are calculated and separated into entropic and energetic contributions. The competition of both terms was found in accordance to the experimental phase diagrams (phase separation of the solid solution below about 600 Kelvin). Two independent simulation runs were performed. At 1000 Kelvin the observed configurations correspond to solid solutions exhibiting a weak tendency to cluster atoms of identical species. At room temperature the energetic favoring of atomic separation is clearly dominant and leads to the formation of Ni‐rich and Cu‐rich domains. The latter are separated by interfacial regions whose width ranges from 0.5 to 1 nanometers. 相似文献
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Reaction of iron(II) thiocyanate with 4,4‐bipyridine (bipy) in methanol leads to the formation of three new solvates of different composition depending on the reaction conditions: At room temperature two new ligand‐rich 1:2 (1:2 = ratio between metal and N‐donor ligand) polymorphic forms [Fe(NCS)2(bipy)2 · 2MeOH]n ( 1I ) and [Fe(NCS)2(bipy)(MeOH)2 · (bipy)]n ( 1II ) are obtained, whereas solvothermal conditions leads to the formation of the new ligand‐deficient 1:1 compound [{Fe(NCS)2(bipy)(MeOH)}2]n ( 2 ). All crystal structures were determined by X‐ray single crystal structure analysis. In the crystal structure of modification 1I the metal atoms are coordinated by four bridging bipy ligands, which connect them into layers. The methanol molecules occupy voids in the structure. Compared to 1I in modification 1II the crystal structure contains of linear Fe–bipy–Fe chains, which are further connected by hydrogen bonds between coordinating MeOH and noncoordinated bipy ligands into layers. The ligand‐deficient 1:1 compound 2 shows a completely different coordination topology with linear Fe–bipy–Fe chains, which are connected by coordinating methanol molecules into double‐chains. In all compounds the thiocyanato anions are terminal N‐bonded to the metal atoms. Investigation of the thermal behavior of compound 1I shows a two‐step decomposition, in which ligand‐deficient intermediates are formed. Magnetic measurements on 1I reveal Curie–Weiss paramagnetism with increasing antiferromagnetic interactions on cooling. 相似文献
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Lithium and sodium intercalation in TiS2 have been studied by transmission electron microscopy using lattice imaging and diffraction contrast techniques. NaxTiS2 samples (0 ≤ x ≤ 0.6) from in propylene carbonate/TiS2 batteries were found to contain a complex variety of phases inhomogeneous on a fine scale. Observations showed variable staging and a 2H phase not previously reported for this system at ambient temperatures. Observations on both NaxTiS2 and chemically prepared LixTiS2 showed highly dislocated structures. A model is proposed whereby dislocations are introduced to accommodate misfit strains caused by nonuniform intercalation and, in the case of NaxTiS2, to initiate phase transformations, leading to potentially irreversible structural changes in cycled material. 相似文献
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Samuel Jorice Raccurt Olivier Poncelet Olivier Auger Aurélien Ling Wai-Li Cherns Peter Grunwald Didier Tillement Olivier 《Journal of nanoparticle research》2010,12(6):2255-2265
Journal of Nanoparticle Research - Fluorescent silica nanoparticles are widely used for various applications from mechanical reinforcement to biology. In many cases, their surface has to be... 相似文献