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91.
A Deadly Organometallic Luminescent Probe: Anticancer Activity of a ReI Bisquinoline Complex 下载免费PDF全文
Dr. Igor Kitanovic Suzan Can Dr. Hamed Alborzinia Dr. Ana Kitanovic Vanessa Pierroz Anna Leonidova Dr. Antonio Pinto Priv. Doz. Dr. Bernhard Spingler Priv. Doz. Dr. Stefano Ferrari Roberto Molteni Dr. Andreas Steffen Prof. Dr. Nils Metzler‐Nolte Prof. Dr. Stefan Wölfl Prof. Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2496-2507
The photophysical properties of [Re(CO)3(L ‐N3)]Br (L ‐N3=2‐azido‐N,N‐bis[(quinolin‐2‐yl)methyl]ethanamine), which could not be localized in cancer cells by fluorescence microscopy, have been revisited in order to evaluate its use as a luminescent probe in a biological environment. The ReI complex displays concentration‐dependent residual fluorescence besides the expected phosphorescence, and the nature of the emitting excited states have been evaluated by DFT and time‐dependent (TD) DFT methods. The results show that fluorescence occurs from a 1LC/MLCT state, whereas phosphorescence mainly stems from a 3LC state, in contrast to previous assignments. We found that our luminescent probe, [Re(CO)3(L ‐N3)]Br, exhibits an interesting cytotoxic activity in the low micromolar range in various cancer cell lines. Several biochemical assays were performed to unveil the cytotoxic mechanism of the organometallic ReI bisquinoline complex. [Re(CO)3(L ‐N3)]Br was found to be stable in human plasma indicating that [Re(CO)3(L ‐N3)]Br itself and not a decomposition product is responsible for the observed cytotoxicity. Addition of [Re(CO)3(L ‐N3)]Br to MCF‐7 breast cancer cells grown on a biosensor chip micro‐bioreactor immediately led to reduced cellular respiration and increased glycolysis, indicating a large shift in cellular metabolism and inhibition of mitochondrial activity. Further analysis of respiration of isolated mitochondria clearly showed that mitochondrial respiratory activity was a direct target of [Re(CO)3(L ‐N3)]Br and involved two modes of action, namely increased respiration at lower concentrations, potentially through increased proton transport through the inner mitochondrial membrane, and efficient blocking of respiration at higher concentrations. Thus, we believe that the direct targeting of mitochondria in cells by [Re(CO)3(L ‐N3)]Br is responsible for the anticancer activity. 相似文献
92.
Dr. Gilles Ulrich Dr. Alberto Barsella Dr. Alex Boeglin Dr. Songlin Niu Dr. Raymond Ziessel 《Chemphyschem》2014,15(13):2693-2700
A set of linear and dissymmetric BODIPY‐bridged push–pull dyes are synthesized. The electron‐donating substituents are anisole and dialkylanilino groups. The strongly electron‐accepting moiety, a 1,1,4,4‐tetracyanobuta‐1,3‐diene (TCBD) group, is obtained by insertion of an electron‐rich ethyne into tetracyanoethylene. A nonlinear push–pull system is developed with a donor at the 5‐position of the BODIPY core and the acceptor at the 2‐position. All dyes are fully characterized and their electrochemical, linear and nonlinear optical properties are discussed. The linear optical properties of dialkylamino compounds show strong solvatochromic behavior and undergo drastic changes upon protonation. The strong push–pull systems are non‐fluorescent and the TCBD‐BODIPY dyes show diverse photochemistry and electrochemistry, with several reversible reduction waves for the tetracyanobutadiene moiety. The hyperpolarizability μβ of selected compounds is evaluated using the electric‐field‐induced second‐harmonic generation technique. Two of the TCBD‐BODIPY dyes show particularly high μβ (1.907 μm) values of 2050×10?48 and 5900×10?48 esu. In addition, one of these dyes shows a high NLO contrast upon protonation–deprotonation of the donor residue. 相似文献
93.
Gilles Aubert Laure Blanc-Féraud Daniele Graziani 《Applied Mathematics and Optimization》2013,67(1):73-96
The paper is concerned with the analysis of a new variational model to restore point-like and curve-like singularities in biological images. To this aim we investigate the variational properties of a suitable energy which governs these pathologies. Finally in order to realize numerical experiments we minimize, in the discrete setting, a regularized version of this functional by fast descent gradient scheme. 相似文献
94.
95.
Advances on the Determination of the Astatine Pourbaix Diagram: Predomination of AtO(OH)2− over At− in Basic Conditions 下载免费PDF全文
Dumitru‐Claudiu Sergentu Dr. David Teze Dr. Andréa Sabatié‐Gogova Dr. Cyrille Alliot Ning Guo Dr. Fadel Bassal Dr. Isidro Da Silva Prof. Dr. David Deniaud Dr. Rémi Maurice Dr. Julie Champion Dr. Nicolas Galland Dr. Gilles Montavon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):2964-2971
It is generally assumed that astatide (At?) is the predominant astatine species in basic aqueous media. This assumption is questioned in non‐complexing and non‐reductive aqueous solutions by means of high‐pressure anion‐exchange chromatography. Contrary to what is usually believed, astatide is found to be a minor species at pH=11. A different species, which also bears a single negative charge, becomes predominant when the pH is increased beyond 7. Using competition experiments, an equilibrium constant value of 10?6.9 has been determined for the formation of this species from AtO(OH) with the exchange of one proton. The identification of this species, AtO(OH)2?, is achieved through relativistic quantum mechanical calculations, which rule out the significant formation of the AtO2? species, while leading to a hydrolysis constant of AtO(OH) in excellent agreement with experiment when the AtO(OH)2? species is considered. Beyond the completion of the Pourbaix diagram of astatine, this new information is of interest for the development of 211At radiolabeling protocols. 相似文献
96.
97.
Yella-Reddy Nelli Céline Douat-Casassus Paul Claudon Brice Kauffmann Claude Didierjean Gilles Guichard 《Tetrahedron》2012,68(23):4492-4500
A new N-Boc-protected monomer for the synthesis of oligourea foldamers containing the (1H-imidazolyl-4yl)methyl side chain of histidine, has been prepared in seven steps from Trt-His(τ-Trt)-OMe. This protecting group combination on histidine was found to be critical to ensure efficient access to the requisite activated building block. This new derivative, suitable for solid phase synthesis, expands the current arsenal of building blocks with proteinogenic side chains useful for the design of peptidomimetic oligourea foldamers. 相似文献
98.
Irene Bravo-Osuna Christine Vauthier Alessandra Farabollini Gioconda Millotti Gilles Ponchel 《Journal of nanoparticle research》2008,10(8):1293-1301
Surface modified nanoparticles composed of poly(isobutylcyanoacrylate) (PIBCA) cores surrounded by a chitosan and thiolated
chitosan gel layer were prepared and characterized in previous works. The presence of such biopolymers on the nanoparticle
surface conferred those nanosystems interesting characteristics that might partially overcome the gastrointestinal enzymatic
barrier, improving the oral administration of pharmacologically active peptides. In the present work, the antiprotease behaviour
of this family of core–shell nanoparticles was in vitro tested against two model metallopeptidases present in the gastrointestinal
tract (GIT): Carboxypeptidase A -CP A- (luminal protease) and Leucine Aminopeptidase M -LAP M- (membrane protease). As previous
step, the zinc-binding capacity of these nanoparticles was evaluated. Interestingly, an improvement of both the zinc-binding
capacity and the antiprotease effect of chitosan was observed when the biopolymers (chitosan and thiolated chitosan) were
used as coating component of the core–shell nanoparticles, in comparison with their behaviour in solution, thanks to the different
biopolymer chains rearrangement. The presence of amino, hydroxyl and thiol groups on the nanoparticle surface promoted zinc
binding and hence the inhibition of the metallopeptidases analysed. On the contrary, the occurrence of a cross-linked structure
in the gel layer surrounding the PIBCA cores of thiolated formulations, due to the formation of interchain and intrachain
disulphide bonds, partially limited the inhibition of the proteases. The low accessibility of cations to the active groups
of the cross-linked polymeric shell was postulated as a possible explanation of this behaviour. Results obtained in this work
make this family of surface-modified nanocarriers promising candidates for the successfull administration of pharmacologically
active peptides and proteins by the oral route. 相似文献
99.
A Topological Criterion for the Existence of Half-Bound States 总被引:1,自引:0,他引:1
The following theorem is proved: if (M4n+1,g) is a completeRiemannian manifold and M is an oriented hypersurface partitioningM and with non-zero signature, then the spectrum of the HodgedeRhamLaplacian is [0,]. This result is obtained by a new Callias-typeindex. This new formula links half-bound harmonic forms (thatis, nearly L2 but not in L2) with the signature of . 相似文献
100.
We show that suitable upper estimates of the heat kernel are sufficient to imply the L
p
boundedness of several families of operators associated with the Schr?dinger group in various situations. This generalizes
results by Sj?strand and others in the Euclidean case, and by Alexopoulos in the case of Lie groups and Riemannian manifolds.
RID="*"
ID="*"Research partially supported by the European Commission (European TMR Network "Harmonic Analysis" 1998-2001, Contract
ERBFMRX-CT97-0159). 相似文献