Polyol Synthesis: A Versatile Wet-Chemistry Route for the Design and Production of Functional Inorganic Nanoparticles.

The term "polyol process" was first used in the late eighties by Fiévet, Lagier, and Figlarz [...].

Intracellular biosynthesis of superparamagnetic 2-lines ferri-hydrite nanoparticles using Euglena gracilis microalgae.

The intracellular biosynthesis of superparamagnetic (blocking temperature 5.6K) 2-lines ferrihydrite (Fh2L) nanoparticles was observed within living Euglena gracilis microalgae.

Recycling and adaptation of Klebsormidium flaccidum microalgae for the sustained production of gold nanoparticles.

Targeting the development of cell-based bioreactors for the production of metal nanoparticles, the possibility to perform the sustained synthesis of colloidal gold using Klebsormidium flaccidum green algae was studied. A first strategy relying on successive growth/reduction/reseeding recycling steps demonstrated maintained biosynthesis capability of the microalgae but limitation in metal content due to toxic effects. An alternative approach consisting of progressive gold salt addition revealed to be suitable to favor cell adaptation to larger metal concentrations and supported particle release over month periods.

Size-dependent magnetic properties of CoFe2O4 nanoparticles prepared in polyol.

Highly crystalline CoFe(2)O(4) nanoparticles with different diameters ranging from 2.4 to 6.1 nm have been synthesized by forced hydrolysis in polyol. The size can be controlled through adjusting the nominal water/metal molar ratio. X-ray diffraction, transmission electron microscopy, x-ray absorption spectroscopy and (57)Fe Mössbauer spectrometry were employed to investigate the structure and the microstructure of the particles produced. Magnetic measurements performed on these particles show that they are superparamagnetic with a size-dependent blocking temperature. At 5 K, high saturation magnetization (~85 emu g(-1)) approaching that of the bulk was found for the larger particles, whereas a very large coercivity (14.5 kOe) is observed for the 3.5 nm sized particles.

Ecotoxicological studies of CdS nanoparticles on photosynthetic microorganisms.

The potential ecotoxicity of nanosized cadmium sulfide (CdS), synthesized by the polyol process, was investigated using common Anabaena flos-aquae cyanobacteria and Euglena gracilis euglenoid microalgae. The photosynthetic activities of these microorganisms, after addition of free Cd2+ ions and CdS nanoparticles, varied with the presence of tri-n-octylphosphine oxide (TOPO) used to protect surface particle to avoid toxicity and also to control particle size and shape during the synthesis. The nanoparticle concentration was varied from 10(-3) to 5 x 10(-4) M. It was observed that the cadmium concentration, the addition of TOPO protective agent and the particle dissolution process in the culture medium play an important role during the ecotoxicological tests. Viability tests were followed by PAM fluorimetry. Cd2+ ions were very toxic for Anabaena flos aquae. The same behavior was observed after contact with CdS and CdS-TOPO nanoparticles. However, for Euglena gracilis, the photosynthetic activity was stable for more than 1 month in the presence of Cd2+ ions. Moreover, it was observed that the toxicity varies with the concentration of CdS and CdS-TOPO nanoparticles, both kind of nanoparticles are toxic for this microorganism. Transmission electron microscopy (TEM) analyses of microorganisms ultrathin sections showed that polysaccharides produced by Anabaena flos-aquae, after contact with CdS and CdS-TOPO nanoparticles, protect the microalgae against particle internalization. Only some particles were observed inside the cells. Moreover, the nanoparticle internalization was observed after contact with all nanoparticles in the presence of Euglena gracilis by endocytosis. All nanoparticles are inside vesicles formed by the cells.

Surface-enhanced Raman scattering on silver nanostructured films prepared by spray-deposition.

Silver nanostructured films were directly prepared by spray deposition of preformed polyol-based Ag-PVP nanoparticles. These homogeneous films of high optical quality were tested as SERS-active substrates. Laser excitation at 514.5 nm within the red part of the plasmon band leads to intense and reproducible SERS spectra of acridine, used as the probe molecule. From SERS measurements at different pH values, it was possible to determine the apparent pK(a) of acridine and to obtain specific surface properties of the film. Finally, these SERS titrations along with enhancement factor estimates allowed us to further depict the nature of the films.

ZnO nanoparticles: synthesis, characterization, and ecotoxicological studies.

The potential ecotoxicity of nanosized zinc oxide (ZnO), synthesized by the polyol process, was investigated using common Anabaena flos-aquae cyanobacteria and Euglena gracilis euglenoid microalgae. The photosynthetic activities of these microorganisms, after addition of ZnO nanoparticles, varied with the presence of protective agents such as tri-n-octylphosphine oxide (TOPO) and polyoxyethylene stearyl ether (Brij-76) used to control particle size and shape during the synthesis. In the case of Anabaena flos-aquae , the photosynthetic activity, after addition of ZnO, ZnO-TOPO, and ZnO-Brij-76, decreased progressively due to stress induced by the presence of the nanoparticles in the culture medium. After contact with ZnO-TOPO nanoparticles, this decrease was followed by cell death. On the other hand, after 10 days, a progressive increase of the photosynthetic activity was observed after contact with ZnO and ZnO-Brij-76 nanoparticles. In the case of Euglena gracilis , cell death was observed after contact with all nanoparticles. Transmission electron microscopy (TEM) analyses of ultrathin sections of microorganisms showed that polysaccharides produced by Anabaena flos-aquae avoid particle internalization after contact with ZnO and ZnO-Brij-76 nanoparticles. On the other hand, nanoparticle internalization was observed after contact with all nanoparticles in the presence of Euglena gracilis and also with ZnO-TOPO nanoparticles after contact with Anabaena flos-aquae .

Photosynthetic microorganism-mediated synthesis of akaganeite (beta-FeOOH) nanorods.

Common Anabaena and Calothrix cyanobacteria and Klebsormidium green algae are shown to form intracellularly akaganeite beta-FeOOH nanorods of well-controlled size and unusual morphology at room temperature. X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy X-ray energy dispersive spectrometry (SEM-EDS) analyses are used to investigate particle structure, size, and morphology. A mechanism involving iron-siderophore complex formation is proposed and compared with iron biomineralization in magnetotactic bacteria.

Cyanobacteria as bioreactors for the synthesis of Au, Ag, Pd, and Pt nanoparticles via an enzyme-mediated route.

Common Anabaena, Calothrix, and Leptolyngbya cyanobacteria are shown to form Au, Ag, Pd, and Pt nanoparticles of well-controlled size. These nanoparticles are synthesized intra-cellularly, and naturally released in the culture medium, where they are stabilized by algal polysaccharides, allowing their easy recovery. The size of the recovered particles as well as the reaction yield is shown to depend on the cyanobacteria genus. Investigations of nanoparticle formation indicate that the intracellular nitrogenase enzyme is responsible for the metal reduction but that the cellular environment is involved in the colloid growth process.

Toxicological impact studies based on Escherichia coli bacteria in ultrafine ZnO nanoparticles colloidal medium.

We report here preliminary studies of biocidal effects and cellular internalization of ZnO nanoparticles on Escherichia coli bacteria. ZnO nanoparticles were synthesized in di(ethylene glycol) (DEG) medium by forced hydrolysis of ionic Zn2+ salts. Particle size and shape were controlled by addition of small molecules and macromolecules such as tri-n-octylphosphine oxide, sodium dodecyl sulfate, polyoxyethylene stearyl ether, and bovine serum albumin. Transmission electron microscopy (TEM) and X-ray diffraction analyses were used to characterize particle structure, size, and morphology. Bactericidal tests were performed in Luria-Bertani medium on solid agar plates and in liquid systems with different concentrations of small and macromolecules and also with ZnO nanoparticles. TEM analyses of bacteria thin sections were used to study biocidal action of ZnO materials. The results confirmed that E. coli cells after contact with DEG and ZnO were damaged showing a Gram-negative triple membrane disorganization. This behavior causes the increase of membrane permeability leading to accumulation of ZnO nanoparticles in the bacterial membrane and also cellular internalization of these nanoparticles.

Synthesis and characterization of nanoheterostructures based on oligothiophene functionalized Ru nanoparticles.

Monodisperse ruthenium nanoparticles functionalized by electroactive oligothiophenes have been prepared and characterized. Using TEM, UV-visible and FTIR we established that the organization of these nanoparticles into nanospheres can be directly controlled via modulation of the pi-pi interaction between the organic components adsorbed on the surface. This finding also shows that the self-assembled nanoheterostructures may be switched from monodisperse nanoparticles to ordered nanospheres by tuning the pH.

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Formation of assembled silver nanowires by reduction of silver thiolate in polyol/toluene medium.

Reduction of silver nitrate in polyol/toluene biphasic medium containing dodecanethiol led to organised silver nanowires, results of an interaction between silver nanoparticles and the layered phase AgSC12H25.