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51.
Ranveer Singh Maxime Vallet Vijay Singh Sanjeev K. Srivastava Alain Claverie Tapobrata Som 《Surface and interface analysis : SIA》2023,55(2):151-161
Due to its outstanding physical properties, CdTe is used to fabricate high efficiency solar cells. However, its high work function poses a challenge, and hence, to fabricate an efficient CdTe-based solar cell, Cu-doping may be useful. Here, we present the role of temperature-dependent Cu-doping in radio frequency sputter-deposited CdTe films and the related changes occurring in their optical, electrical, structural and microstructural properties. For instance, Cu-doping at different temperatures leads to an increase in the grain size and a reduction in the optical reflectance with increasing temperature. In addition, Kelvin probe force microscopy measurements reveal that the work function is found to be smaller corresponding to the annealing temperature of 473 K, whereas resistivity measurements show that it decreases with increasing temperature (the lowest value of resistivity is found to be 1.8 × 10−2 Ω-cm). To understand the electronic structure of CdTe before and after Cu-doping, we have carried out first-principles density functional theory (DFT) simulation, which reveals a strong hybridization among Cu, Cd and Te atoms. This study paves the way to fabricate efficient Cu-doped CdTe-based solar cells. 相似文献
52.
Erik Pieter van Geest Sina Katharina Götzfried David M. Klein Nadiya Salitra Sorraya Popal Yurii Husiev Corjan J. Van der Griend Xuequan Zhou Maxime A. Siegler Gregory F. Schneider Sylvestre Bonnet 《Photochemistry and photobiology》2023,99(2):777-786
Photosubstitutionally active ruthenium complexes show high potential as prodrugs for the photoactivated chemotherapy (PACT) treatment of tumors. One of the problems in PACT is that the localization of the ruthenium compound is hard to trace. Here, a ruthenium PACT prodrug, [Ru(3)(biq)(STF-31)](PF6)2 (where 3 = 3-(([2,2′:6′,2″-ter- pyridin]-4′-yloxy)propyl-4-(pyren-1-yl)butanoate) and biq = 2,2′-biquinoline), has been prepared, in which a pyrene tracker is attached via an ester bond. The proximity between the fluorophore and the ruthenium center leads to fluorescence quenching. Upon intracellular hydrolysis of the ester linkage, however, the fluorescence of the pyrene moiety is recovered, thus demonstrating prodrug cellular uptake. Further light irradiation of this molecule liberates by photosubstitution STF-31, a known cytotoxic nicotinamide phosphoribosyltransferase (NAMPT) inhibitor, as well as singlet oxygen via excitation of the free pyrene chromophore. The dark and light cytotoxicity of the prodrug, embedded in liposomes, as well as the appearance of blue emission upon uptake, were evaluated in A375 human skin melanoma cells. The cytotoxicity of the liposome-embedded prodrug was indeed increased by light irradiation. This work realizes an in vitro proof-of-concept of the lock-and-kill principle, which may ultimately be used to design strategies aimed at knowing where and when light irradiation should be realized in vivo. 相似文献
53.
Dif A Henry E Artzner F Baudy-Floc'h M Schmutz M Dahan M Marchi-Artzner V 《Journal of the American Chemical Society》2008,130(26):8289-8296
Due to their tunable optical properties and their well-defined nanometric size, core/shell nanocrystals (quantum dots, QDs) are extensively used for the design of biomarkers as well as for the preparation of nanostructured hybrid materials. It is thus of great interest to understand their interaction with soft lipidic membranes. Here we present the synthesis of water-soluble peptide CdSe/ZnS QDs and their interaction with the fluid lipidic membrane of vesicles. The use of short peptides results in the formation of small QDs presenting both high fluorescence quantum yield and high colloidal stability as well as a mean hydrodynamical diameter of 10 nm. Their interaction with oppositely charged vesicles of various surface charge and size results in the formation of hybrid giant or large unilamellar vesicles covered with a densely packed layer of QDs without any vesicle rupture, as demonstrated by fluorescence resonance energy transfer experiments, zetametry, and optical microscopy. The adhesion of nanocrystals onto the vesicle membrane appears to be sterically limited and induces the reversion of the surface charge of the vesicles. Therefore, their interaction with small unilamellar vesicles induces the formation of a well-defined lamellar hybrid condensed phase in which the QDs are densely packed in the plane of the layers, as shown by freeze-fracture electron microscopy and small-angle X-ray scattering. In this structure, strong undulations of the bilayer maximize the electrostatic interaction between the QDs and the bilayers, as previously observed in the case of DNA polyelectrolytes interacting with small vesicles. 相似文献
54.
Redox‐Active‐Ligand‐Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands 下载免费PDF全文
Dr. Bidraha Bagh Daniël L. J. Broere Dr. Maxime A. Siegler Dr. Ir. Jarl Ivar van der Vlugt 《Angewandte Chemie (International ed. in English)》2016,55(29):8381-8385
Coordination of a redox‐active pyridine aminophenol ligand to RuII followed by aerobic oxidation generates two diamagnetic RuIII species [ 1 a (cis) and 1 b (trans)] with ligand‐centered radicals. The reaction of 1 a / 1 b with excess NaN3 under inert atmosphere resulted in the formation of a rare bis(nitrido)‐bridged trinuclear ruthenium complex with two nonlinear asymmetrical Ru‐N‐Ru fragments. The spontaneous reduction of the ligand centered radical in the parent 1 a / 1 b supports the oxidation of a nitride (N3?) to half an equivalent of N2. The trinuclear omplex is reactive toward TEMPO‐H, tin hydrides, thiols, and dihydrogen. 相似文献
55.
Christiane Auray-Blais Pamela Lavoie Shunji Tomatsu Vassili Valayannopoulos John J. Mitchell Julian Raiman Maxime Beaudoin Bruno Maranda Joe T.R. Clarke 《Analytica chimica acta》2016
Mucopolysaccharidoses (MPSs) are a group of disorders resulting from primary defects in lysosomal enzymes involved in the degradation of glycosaminoglycans (GAGs). Depending on the specific enzyme defect, the catabolism of one or more GAGs is blocked leading to accumulation in tissues and biological fluids. GAG measurements are important for high-risk screening, diagnosis, monitoring treatment efficacy, and patient follow up. The dimethylmethylene blue (DMB) spectrophotometric method commonly used in most biochemical genetics laboratories relies on a non-specific total GAG analysis which has led to false positive results, and even false negative results (mainly for MPS III and IV patients). The main objective of our project was to devise and validate a reliable tandem mass spectrometry multiplex analysis for the urine quantitation of four GAGs (dermatan sulfate (DS), heparan sulfate (HS), keratan sulfate (KS), and chondroitin sulfate (CS)) for an eventual technological transfer to the clinic. The developed methodology is rapid (7 min) and our results showed good intraday and interday precision (RSDs ≤ 8.7%) and accuracy (Biases range: −12.0%–18.4%). Linearity was good (r2 > 0.995) for DS, HS, CS, and KS calibration curves. In comparison with the DMB spectrophotometric method, this multiplex tandem mass spectrometry method allows GAG fractionation, thus a differentiation of MPS types, except for MPS I and II which are characterized by the same GAG profile. The devised method is a useful and reliable tool for diagnosis of MPS patients, as well as their monitoring and follow up, as shown by longitudinal studies. 相似文献
56.
Positioning a Carbon–Fluorine Bond over the π Cloud of an Aromatic Ring: A Different Type of Arene Activation 下载免费PDF全文
Maxwell Gargiulo Holl Mark D. Struble Prakhar Singal Dr. Maxime A. Siegler Prof. Thomas Lectka 《Angewandte Chemie (International ed. in English)》2016,55(29):8266-8269
It is known that the fluoro group has only a small effect on the rates of electrophilic aromatic substitutions. Imagine instead a carbon–fluorine (C?F) bond positioned tightly over the π cloud of an aryl ring—such an orthogonal, noncovalent arrangement could instead stabilize a positively charged arene intermediate or transition state, giving rise to novel electrophilic aromatic substitution chemistry. Herein, we report the synthesis and study of molecule 1 , containing a rigid C?F???Ar interaction that plays a prominent role in both its reaction chemistry and spectroscopy. For example, we established that the C?F???Ar interaction can bring about a >1500 fold increase in the relative rate of an aromatic nitration reaction, affording functionalization on the activated ring exclusively. Overall, these results establish fluoro as a through‐space directing/activating group that complements the traditional role of fluorine as a slightly deactivating aryl substituent in nitrations. 相似文献
57.
58.
Hirel C Li L Brough P Vostrikova K Pécaut J Mehdaoui B Bernard M Turek P Rey P 《Inorganic chemistry》2007,46(18):7545-7552
Novel copper(II)-nitroxide complexes exhibiting a spin-transition-like behavior have been prepared and characterized. They include meso, chiral, and racemic 2-(3-pyridyl)-nitronyl nitroxides differently substituted in positions 4 and/or 5 by ethyl groups and pyrimidyl nitroxides. Depending on the stoichiometry of the reaction, tetranuclear and binuclear complexes were obtained whose structures are cyclic. The tetranuclear species, which include two intracyclic and two exocyclic metal sites, are similar to the previously reported complex of the tetramethylated analogue, while the binuclear complexes involve only endocyclic metal ions and have uncoordinated N-oxyl groups. The tetranuclear complexes exist as two isomers depending on the temperature of crystallization: at room temperature, N-oxyl ligand coordination is axial-axial, while it is axial-equatorial at low temperature. Unexpectedly, this isomerism concerns N-oxyl bonding to the exocyclic metal centers for the derivatives of 4,5-diethyl-substituted ligands while it involves the endocyclic metal site in the complex of the monoethylated ligand, which converts reversibly from a high-spin state to a low-spin state, as observed for the complex of the tetramethylated ligand. Binuclear complexes are diamagnetic at room temperature but convert to a paramagnetic state on warming (90-110 degrees C); the transition is irreversible and sharp. 相似文献
59.
Jin-Shuang Zhao Yan-Fei Mu Li-Yuan Wu Zhi-Mei Luo Lucia Velasco Maxime Sauvan Dooshaye Moonshiram Jia-Wei Wang Min Zhang Tong-Bu Lu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(21):e202401344
The development of high-performance photocatalytic systems for CO2 reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs2AgBiBr6 nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g−1 h−1 for visible-light-driven CO2-to-CO conversion coupled with water oxidation to O2, over 8 times of the unmodified Cs2AgBiBr6 (36±8 μmol g−1 h−1), also far surpassing the documented systems (<150 μmol g−1 h−1). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs2AgBiBr6 can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis. 相似文献
60.
Dr. Perumal Venkatesan Dr. Margarita Cerón Dr. Enrique Pérez-Gutiérrez Armando E. Castillo Dr. Subbiah Thamotharan Fernando Robles Dr. Maxime A. Siegler Prof. M. Judith Percino 《ChemistryOpen》2019,8(4):483-496
Experimental and theoretical insights into the nature of intermolecular interactions and their effect on optical properties of 1-allyl-4-(1-cyano-2-(4-dialkylaminophenyl)vinyl)pyridin-1-ium bromide salts ( I and II ) are reported. A comparison of optical properties in solution and in the solid-state of the salts ( I and II ) with their precursors ( Ia and IIa ) is made. The experimental absorption maxima (λmax) in CHCl3 is at 528 nm for I and at 542 nm for II , and a strong bathochromic shift of ∼110 nm is observed for salts I and II compared with their precursors. The absorption bands in solid-state at ∼627 nm for I and at ∼615 nm for II that are assigned to charge transfer (CT) effect. The optical properties and single crystal structural features of I and II are explored by experimental and computational tools. The calculated λmax and the CT are in good agreement with the experimental results. The intermolecular interactions existing in the crystal structures and their energies are quantified for various dimers by PIXEL, QTAIM and DFT approaches. Three types of interactions, (i) the cation⋅⋅⋅cation interactions, (ii) cation⋅⋅⋅anion interactions and (iii) anion⋅⋅⋅anion interactions are observed. The cationic moiety is mainly destabilized by C−H⋅⋅⋅N/π and π⋅⋅⋅π interactions whereas the cation and anion moiety is predominantly stabilized by strong C−H⋅⋅⋅Br− interactions in both structures. The existence of charge transfer between cation and anion moieties in these structures is established through NBO analysis. 相似文献