Turning over silanes: The first nanotube‐based catalytic system for silane oxidation is reported (see scheme). The reusable gold–nanotube hybrid cleanly oxidizes both alkyl and aryl silanes in high ...yields, under mild reaction conditions, and compares most favorably to any other catalytic system in terms of overall efficacy and turnover values.
During past decade, special focus has been laid on ultrasmall nanoparticles for nanomedicine and eventual clinical translation. To achieve such translation, a lot of challenges have to be solved. ...Among them, size determination is a particularly tricky one. In this aim, we have developed a simple hyphenation between Taylor dispersion analysis and inductively coupled plasma-mass spectrometry (ICP-MS). This method was proven to allow the determination of the hydrodynamic radius of metal-containing nanoparticles, even for sizes under 5 nm, with a relative standard deviation below 10% (with a 95% confidence interval) and at low concentrations. Moreover, its specificity provides the opportunity to perform measurements in complex biological media. This was applied to the characterization of an ultrasmall gadolinium-containing nanoparticle used as a theranostic agent in cancer diseases. Hydrodynamic radii measured in urine, cerebrospinal fluid, and undiluted serum demonstrated the absence of interaction between the particle and biological compounds such as proteins.
Homogeneous coating of carbon nanotubes with metallic nanoparticles was achieved using supramolecular auto-organization of amphiphilic molecules as template. The resulting Pd nanoparticles/carbon ...nanotube nanohybrids were then evaluated in electrocatalysis experiments, showing superior activity in ethanol oxidation compared to analogous systems.
Nanostructured materials play a critical role in the catalysis of various relevant reactions in fuel cells, resulting in enhanced intrinsic electroactivity with high surface area, superior ...conductivity and better mass transport. The catalytic activity and stability of Pd nanoplates (Pd-NPLs) for the oxidation of ethanol were studied by using cyclic voltammetry and chronoamperometry. The poly(diphenylbutadyine) (PDPB) polymer nanofiber can be used as support to enhance the catalytic activity of Pd nanoplates for the oxidation of ethanol. The chronoamperometric response confirms the better activity and stability of the nanofiber-based support compared to commercial nafion (5 wt%). The nanofiber morphology of the poly(diphenylbutadyine) polymer helps in the effective dispersion of the Pd nanoplates, facilitating an easier access of ethanol molecules to the catalytic sites. The dispersion of the Pd nanoplates within the polymer nanofibers is connected with an enhancement of the catalytic activity. These results show that the polymer-supported Pd nanoplate based hybrid structure is a promising anode catalyst in direct alcohol fuel cells (DAFCs).
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•Conducting polymer supported Pd nanoplates show superior electrocatalytic activity.•The onset potentials Eonset tuned by varying the ethanol and KOH concentration.•The tafel plot explains mechanism controlled by the adsorption of hydroxyl.
Uranium is a natural actinide present as uranyl U(VI) species in aqueous environments. Its toxicity is considered to be chemical rather than radiotoxicological. Whatever the route of entry, uranyl ...reaches the blood, is partly eliminated via the kidneys, and accumulated in the bones. In serum, its speciation mainly involves carbonate and proteins. Direct identification of labile uranyl–protein complexes is extremely difficult because of the complexity of this matrix. Thus, until now the biodistribution of the metal in serum has not been described, and therefore, little is known about the metal transport mechanisms leading to bone accumulation. A rapid screening method based on a surface plasmon resonance (SPR) technique was used to determine the apparent affinities for U(VI) of the major serum proteins. A first biodistribution of uranyl was obtained by ranking the proteins according to the criteria of both their serum concentrations and affinities for this metal. Despite its moderate concentration in serum, fetuin-A (FETUA) was shown to exhibit an apparent affinity within the 30 nM range and to carry more than 80% of the metal. This protein involved in bone mineralization aroused interest in characterizing the U(VI) and FETUA interaction. Using complementary chromatographic and spectroscopic approaches, we demonstrated that the protein can bind 3 U(VI) at different binding sites exhibiting K d from ∼30 nM to 10 μM. Some structural modifications and functional properties of FETUA upon uranyl complexation were also controlled. To our knowledge, this article presents the first identification of a uranyl carrier involved in bone metabolism along with the characterization of its metal binding sites.
A series of Tb-doped LaF3 nanoparticles (NPs) was prepared by systematically varying the Tb doping rate from 0 to 100%. The elemental composition was confirmed by inductively coupled plasma atomic ...emission spectroscopy (ICP-AES) analysis, and the size, morphology, and crystal structure were determined in the solid state by transmission electron microscopy and X-ray diffractometry, while the size and ζ-potential of the NPs in solution were studied by dynamic light scattering, Taylor dispersion analysis, and laser Doppler electrophoresis. While the crystal structure appears to be hexagonal for a doping rate of up to 70%, an admixture of hexagonal and orthorhombic phases is observed for 80 and 90% Tb contents with a pure orthorhombic phase being obtained for TbF3. The spectroscopic properties of the NPs were studied for bare NPs and in the presence of dipicolinic acid as a surface-capping antenna ligand in solution. The coverage of the NPs by the ligand resulted in an increase in the luminescence lifetime of the emitting Tb centers, as a consequence of a better protection toward luminescence quenching from water molecules, as well as a large improvement in the brightness of the NPs. Taking into account the various parameters, a doping rate of 40% Tb was shown to be the best compromise for the development of such NPs for bioanalytical applications.
Palladium nanowires (of length a few tens of nanometers) are synthesized in a hexagonal mesophase formed by a quaternary system (Pd-doped water, surfactant, cosurfactant, and oil) by electron beam ...irradiation. The mesophases can be doped by high concentrations of palladium (0.1 M) without any disturbance of the structure of the mesophases which allows the quantitative synthesis of 1D Pd nanostructures. We found an increase in the average length of the nanowires with the amount of cosurfactant (pentanol) that assists the reduction/growth processes. The electrocatalytic oxidation of ethanol was selected as a test reaction in alkaline medium where Pd is known to be among the best electrode materials. We found that the Pd nanowires exhibit both a very important electrocatalytic activity for ethanol oxidation and a very high stability.
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•Fast preparation of graphene nanosheets by one-pot radiolytic reduction of GO.•One-pot synthesis of graphene nanosheets supported Au-Pt-Pd nanoparticles.•Radiolysis enables to ...engineer highly active Metal/rGO nanocomposites.•Ternary Au50Pt25Pd25/rGO electrocatalyst is 5-fold higher effective than Pt/rGO.•Selective glucose oxidation reaction in a 2-electron process leads to gluconate.
We report a novel “one-pot”, convenient and efficient method based on radiolysis to synthesize gold-based nanoparticles finely dispersed on reduced graphene oxide (rGO) nanosheets obtained from reductive transformation of graphene oxide (GO). Extensive characterizations of the metal/rGO nanocomposites were performed and revealed that the optimized bimetallic Au90Pd10 and trimetallic Au50Pd25Pt25 materials were mostly nano-alloyed. Not only the multimetallic catalysts demonstrate high electrocatalytic performances towards glucose in alkaline medium, but they also surpass the majority of the reported noble metals based nanocatalysts. The spectroelectrochemical investigations have highlighted a 2-electron reaction process leading to gluconate, a high added-value chemical used in various industries. Definitely, the strategies developed herein pave new rational pathways for the design of effective anode catalysts for glucose-based electrochemical energy converters and the scalability in the catalyst composition opens up new avenues in the efficient application of graphene-based nanocomposites as promising electrode materials in the electrocatalysis of carbohydrates.
Silver has been used for its antimicrobial properties to fight infection for thousands of years. Unfortunately, some Gram-negative bacteria have developed silver resistance causing the death of ...patients in a burn unit. The genes responsible for silver resistance have been designated as the sil operon. Among the proteins of the sil operon, SilE has been shown to play a key role in bacterial silver resistance. Based on the limited information available, it has been depicted as an intrinsically disordered protein that folds into helices upon silver ion binding. Herein, this work demonstrates that SilE is composed of 4 clearly identified helical segments in the presence of several silver ions. The combination of analytical and biophysical techniques (NMR spectroscopy, CD, SAXS, HRMS, CE-ICP-MS, and IM-MS) reveals that SilE harbors four strong silver binding sites among the eight sites available. We have also further evidenced that SilE does not adopt a globular structure but rather samples a large conformational space from elongated to more compact structures. This particular structural organization facilitates silver binding through much higher accessibility of the involved His and Met residues. These valuable results will advance our current understanding of the role of SilE in the silver efflux pump complex mechanism and will help in the future rational design of inhibitors to fight bacterial silver resistance.
In the search of new robust and environmental-friendly analytical methods able to answer quantitative issues in pharmacology, we explore liquid chromatography (LC) associated with elemental mass ...spectrometry (ICP-MS) to monitor peptides in such complex biological matrices. The novelty is to use mass spectrometry to replace radiolabelling and radioactivity measurements, which represent up-to now the gold standard to measure organic compound concentrations in life science. As a proof of concept, we choose the vasopressin (AVP)/V1A receptor system for model pharmacological assays. The capacity of ICP-MS to provide highly sensitive quantitation of metallic and hetero elements, whatever the sample medium, prompted us to investigate this technique in combination with appropriate labelling of the peptide of interest. Selenium, that is scarcely present in biological media, was selected as a good compromise between ICP-MS response, covalent tagging ability using conventional sulfur chemistry and peptide detection specificity. Applying selenium monitoring by elemental mass spectrometry in pharmacology is challenging due to the very high salt content and organic material complexity of the samples that produces polyatomic aggregates and thus potentially mass interferences with selenium detection. Hyphenation with a chromatographic separation was found compulsory. Noteworthy, we aimed to develop a straightforward quantitative protocol that can be performed in any laboratory equipped with a standard macrobore LC-ICP-MS system, in order to avoid time-consuming sample treatment or special implementation of instrumental set-up, while allowing efficient suppression of all mass interferences to reach the targeted sensitivity. Significantly, a quantification limit of 57 ng Se L-1 (72 femtomoles of injected Se) was achieved, the samples issued from the pharmacological assays being directly introduced into the LC-ICP-MS system. The established method was successfully validated and applied to the measurement of the vasopressin ligand affinity for its V1A receptor through the determination of the dissociation constant (Kd) which was compared to the one recorded with conventional radioactivity assays.
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