Synthesis of Metallic Nanostructures Using Ionizing Radiation and Their Applications.

This paper reviews the radiation-induced synthesis of metallic nanostructures and their applications. Radiolysis is a powerful method for synthesizing metallic nanoparticles in solution and heterogeneous media, and it is a clean alternative to other existing physical, chemical, and physicochemical methods. By varying parameters such as the absorbed dose, dose rate, concentrations of metallic precursors, and nature of stabilizing agents, it is possible to control the size, shape, and morphology (alloy, core-shell, etc.) of the nanostructures and, consequently, their properties. Therefore, the as-synthesized nanoparticles have many potential applications in biology, medicine, (photo)catalysis, or energy conversion.

Colloidal Silver Nanoparticles Obtained via Radiolysis: Synthesis Optimization and Antibacterial Properties.

Silver nanoparticles (AgNPs) with broad-spectrum antimicrobial properties are gaining increasing interest in fighting multidrug-resistant bacteria. Herein, we describe the synthesis of AgNPs, stabilized by polyvinyl alcohol (PVA), with high purity and homogeneous sizes, using radiolysis. Solvated electrons and reducing radicals are induced from solvent radiolysis and no other chemical reducing agents are needed to reduce the metal ions. Another advantage of this method is that it leads to sterile colloidal suspensions, which can be directly used for medical applications. We systematically investigated the effect of the silver salt precursor on the optical properties, particle size, and morphology of the resulting colloidal AgNPs. With Ag2SO4 precursor, the AgNPs displayed a narrow size distribution (20 ± 2 nm). In contrast, AgNO3 and AgClO4 precursors lead to inhomogeneous AgNPs of various shapes. Moreover, the optimized AgNPs synthesized from Ag2SO4 were stable upon storage in water and phosphate-buffered saline (PBS) and were very effective in inhibiting the growth of Staphylococcus aureus (S. aureus) at a concentration of 0.6 µg·mL-1 while completely eradicating it at a concentration of 5.6 µg·mL-1. When compared with other AgNPs prepared by other strategies, the remarkable bactericidal ability against S. aureus of the AgNPs produced here opens up new perspectives for further applications in medicine, cosmetics, the food industry, or in elaborating antibacterial surfaces and other devices.

A mathematical approach to deal with nanoparticle polydispersity in surface enhanced Raman spectroscopy to quantify antineoplastic agents.

Antineoplastic agents are, for most of them, highly toxic drugs prepared at hospital following individualized prescription. To protect patients and healthcare workers, it is important to develop analytical tools able to identify and quantify such drugs on a wide concentration range. In this context, surface enhanced Raman spectroscopy (SERS) has been tested as a specific and sensitive technique. Despite the standardization of the nanoparticle synthesis, a polydispersity of nanoparticles in the suspension and a lack of reproducibility persist. This study focuses on the development of a new mathematical approach to deal with this nanoparticle polydispersity and its consequences on SERS signal variability through the feasibility of 5-fluorouracil (5FU) quantification using silver nanoparticles (AgNPs) and a handled Raman spectrophotometer. Variability has been maximized by synthetizing six different batches of AgNPs for an average size of 24.9 nm determined by transmission electron microscopy, with residual standard deviation of 17.0%. Regarding low performances of the standard multivariate data processing, an alternative approach based on the nearest neighbors were developed to quantify 5FU. By this approach, the predictive performance of the 5FU concentration was significantly improved. The mean absolute relative error (MARE) decreased from 16.8% with the traditional approach based on PLS regression to 6.30% with the nearest neighbors approach (p-value < 0.001). This study highlights the importance of developing mathematics adapted to SERS analysis which could be a step to overcome the spectral variability in SERS and thus participate in the development of this technique as an analytical tool in quality control to quantify molecules with good performances, particularly in the pharmaceutical field.

Gold(i)-silver(i)-calix[8]arene complexes, precursors of bimetallic alloyed Au-Ag nanoparticles.

In this paper, we report the first synthesis and characterisations of bimetallic gold(i)-silver(i) calix[8]arene complexes. We show that the radiolytic reduction of these complexes leads to the formation of small bimetallic nanoparticles with an alloyed structure, as evidenced by XPS, HR-TEM and STEM/HAADF-EDX measurements.

Hexacyano Ferrate (III) Reduction by Electron Transfer Induced by Plasmonic Catalysis on Gold Nanoparticles.

Redox reactions are of great importance in environmental catalysis. Gold nanoparticles (Au-NPs) have attracted much attention because of their catalytic activity and their localized surface plasmon resonance (LSPR). In the present study, we investigated, in detail, the reduction of ferricyanide (III) ion into a ferrocyanide (II) ion catalyzed by spherical gold nanoparticles of two different sizes, 15 nm and 30 nm, and excited at their LSPR band. Experiments were conducted in the presence (or absence) of sodium thiosulfate. This catalysis is enhanced in the presence of Au- NPs under visible light excitation. This reduction also takes place even without sodium thiosulfate. Our results demonstrate the implication of hot electrons in this reduction.

Oxidation of bromide ions by hydroxyl radicals: spectral characterization of the intermediate BrOH•-.

The reaction of (•)OH with Br(-) has been reinvestigated by picosecond pulse radiolysis combined with streak camera absorption detection and the obtained spectro-kinetics data have been globally analyzed using Bayesian data analysis. For the first time, the absorption spectrum of the intermediate species BrOH(•-) has been determined. This species absorbs in the same spectral domain as Br(2)(•-): the band maximum is roughly at the same wavelength (λ(max) = 352 nm instead of 354 nm) but the extinction coefficient is smaller (ε(max) = 7800 ± 400 dm(3) mol(-1) cm(-1) compared with 9600 ± 300 dm(3) mol(-1) cm(-1)) and the band is broader (88 nm versus 76 nm). Quantum chemical calculations have also been performed and corroborate the experimental results. In contrast to Br(2)(•-), the existence of several water-BrOH(•-) configurations leading to different transition energies may account for the broadening of the absorption spectrum in addition to the higher number of degrees of freedom.

Synthesis, electrochemical and photophysical properties of covalently linked porphyrin-polyoxometalates.

Two covalently linked porphyrin-polyoxometalate hybrids have been prepared: an Anderson-type hexamolybdate [N(C(4)H(9))(4)](3)[MnMo(6)O(18){(OCH(2))(3)CNHCO(ZnTPP)}(2)] with two pendant zinc(II)-tetraphenylporphyrins, and a Dawson-type vanadotungstate [N(C(4)H(9))(4)](5)H[P(2)V(3)W(15)O(59){(OCH(2))(3)CNHCO(ZnTPP)}] with one porphyrin. Electrochemical studies show independent redox processes for the organic and inorganic parts at usual potentials. Photophysical studies reveal an electron transfer from the excited porphyrin to the Dawson polyoxometalate, but not to the Anderson polyoxometalate. Time resolved absorption spectroscopy allows the identification of the electron transfer pathways and the determination of the time constants.

Pulse radiolysis studies on the temperature-dependent spectrum and the time-dependent yield of solvated electron in propane-1,2,3-triol.

With a revisit of the absorption coefficient of the solvated electron in propane-1,2,3-triol, the temperature-dependent behavior of the absorption spectrum of solvated electron was studied from room temperature to 573 K by pulse radiolysis techniques. The change in the absorption spectrum of solvated electron in propane-1,2,3-triol observed by cooling down from a high temperature to 333 K is compared with that occurring during the electron solvation process at 333 K. The effect of the specific molecular structure of propane-1,2,3-triol compared to other alcohols is discussed.

Temperature effect on the absorption spectrum of the hydrated electron paired with a lithium cation in deuterated water.

The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiClO4 deuterated water solutions were measured by pulse radiolysis techniques from room temperature to 300 degrees C at a constant pressure of 25 MPa. The results show that when the temperature is increased and the density is decreased, the absorption spectrum of the electron in the presence of a lithium cation is shifted to lower energies. Quantum classical molecular dynamics (QCMD) simulations of an excess electron in bulk water and in the presence of a lithium cation have been performed to compare with the experimental results. According to the QCMD simulations, the change in the shape of the spectrum is due to one of the three p-like excited states of the solvated electron destabilized by core repulsion. The study of s --> p transition energies for the three p-excited states reveals that for temperatures higher than room temperature, there is a broadening of each individual s --> p absorption band due to a less structured water solvation shell.

Time-dependent radiolytic yields of the solvated electrons in 1,2-ethanediol, 1,2-propanediol, and 1,3-propanediol from picosecond to microsecond.

The absorption spectra of the solvated electron in 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD) have been determined by nanosecond pulse radiolysis techniques. The maximum of the absorption band located at 570, 565, and 575 nm for these three solvents, respectively. With 4,4'-bipyridine (44Bpy) as a scavenger, the molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol-1 m2 for 12ED, 12PD, and 13PD, respectively. These values are two-thirds or three-fourths of the value usually reported in the literature. With these extinction coefficients, picosecond pulse radiolysis studies have allowed us to depict the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of water solution.