An integrated approach for trace detection of pollutants in water using polyelectrolyte functionalized magneto-plasmonic nanosorbents.

Resistance of pathogenic micro-organisms to conventional antibiotics is an essential issue for public health. The presence of such pharmaceuticals in aquatic ecosystems has been of major concern for which remediation and ultra-sensitive monitoring methods have been proposed. A less explored strategy involves the application of multifunctional nanosorbents for the uptake and subsequent detection of vestigial contaminants. In this study, colloidal nanoparticles (NPs) of iron oxide and gold were encapsulated in multi-layers of a charged polyelectrolyte (PEI: polyethyleneimine), envisaging the effective capture of tetracycline (TC) and its subsequent detection by Surface Enhanced Raman Scattering (SERS). Adsorption studies were performed by varying operational parameters, such as the solution pH and contact time, in order to evaluate the performance of the nanosorbents for the uptake of TC from water. While the magnetic nanosorbents with an external PEI layer (Fe3O4@PEI and Fe3O4@PEI-Au@PEI particles) have shown better uptake efficiency for TC, these materials showed less SERS sensitivity than the Fe3O4@PEI- Au nanosorbents, whose SERS sensitivity for TC in water has reached the limit of detection of 10 nM. Thus, this study highlights the potential of such magneto-plasmonic nanosorbents as multi-functional platforms for targeting specific contaminants in water, by taking into consideration both functionalities investigated: the removal by adsorption and the SERS detection across the nanosorbents' surfaces.

Magnetite-Supported Gold Nanostars for the Uptake and SERS Detection of Tetracycline.

Magnetite nanoparticles (MNPs) decorated with gold nanostars (AuNSs) have been prepared by using a seed growth method without the addition of surfactants or colloidal stabilizers. The hybrid nanomaterials were investigated as adsorbents for the uptake of tetracycline (TC) from aqueous solutions and subsequent detection using surface-enhanced Raman scattering (SERS). Several parameters were investigated in order to optimize the performance of these hybrid platforms on the uptake and SERS detection of TC, including variable pH values and the effect of contact time on the removal of TC. The spatial distribution of TC and AuNS on the hybrid composites was accomplished by coupling SERS analysis with Raman imaging studies, allowing also for the determination of the detection limit for TC when dissolved in ultrapure water (10 nM) and in more complex aqueous matrices (1 µM). Attempts were also made to investigate the adsorption modes of the TC molecules at the surface of the metal NPs by taking into account the enhancement of the Raman bands in these different matrices.

Ferromagnetic sorbents based on nickel nanowires for efficient uptake of mercury from water.

This work reports the preparation of ferro-magnetic nickel nanowires (NiNW) coated with dithiocarbamate-functionalized siliceous shells and its application for the uptake of aqueous Hg(II) ions by magnetic separation. NiNW with an average diameter and length of 35 nm and 5 µm, respectively, were firstly prepared by Ni electrodeposition in an anodic aluminum oxide template. The NiNW surfaces were then coated with siliceous shells containing dithiocarbamate groups via a one-step procedure consisting in the alkaline hydrolytic co-condensation of tetraethoxysilane (TEOS) and a siloxydithiocarbamate precursor (SiDTC). A small amount of these new nanoadsorbents (2.5 mg·L(-1)) removed 99.8% of mercury ions from aqueous solutions with concentration 50 µg·L(-1) and in less than 24 h of contact time. This outstanding removal ability is attributed to the high affinity of the sulfur donor ligands to Hg(II) species combined with the high surface area-to-volume ratio of the NiNW.

Functionalization of nickel nanowires with a fluorophore aiming at new probes for multimodal bioanalysis.

This work reports research on the development of bimodal magnetic and fluorescent 1D nanoprobes. First, ferromagnetic nickel nanowires (NiNW) have been prepared by Ni electrodeposition in an anodic aluminum oxide (AAO) template. The highly ordered self-assembled AAO nanoporous templates were fabricated using a two-step anodization method of aluminum foil. The surface of the NiNW were then modified with polyethyleneimine (PEI) which was previously labeled with an organic dye (fluorescein isothiocyanate: FITC) via covalent bonding. The ensuing functionalized NiNW exhibited the characteristic green fluorescence of FITC and could be magnetically separated from aqueous solutions by using a NdFeB magnet. Finally, the interest of these bimodal NiNW as nanoprobes for in vitro cell separation and biolabeling was preliminary assessed in a proof of principle experiment that involved the attachment of biofunctionalized NiNW to blood cells.

Composite blends of gold nanorods and poly(t-butylacrylate) beads as new substrates for SERS.

Polymer based composites containing metal nanoparticles are shown to provide new substrates for SERS detection and simultaneously enable the development of new tools for molecular sensing. A very important aspect on the use of hybrid materials relates to the observation of synergistic effects that result from the use of distinct components such as a polymer and metal nanoparticles. We report here the preparation of new SERS substrates made from blends of colloidal Au (nanospheres and nanorods) and PtBA (poly(t-butylacrylate)). The observed SERS enhancement depends on the characteristics of the obtained hybrid material. When compared to the starting Au colloids, the Au/PtBA nanocomposites led to SERS spectra with more intense bands, using 2,2'-dithiodipyridine as molecular probe. The origin of the stronger Raman signal in this case, is possibly due to a combination of events related to the nanocomposite characteristics, including the formation of Au assemblies at the polymer surface due to particle clustering, and the absorption increase in a spectral region closer to the laser excitation wavelength. The strategy described here is a low-cost process with potential for the up-scale fabrication of SERS substrates, namely by using other types of nanocomposites.

SERS study on adenine using a Ag/poly(t-butylacrylate) nanocomposite.

Enhancement of Raman signals of the nucleobase adenine on an Ag based composite was studied using the 1064 nm laser line. The composite comprise emulsions of Ag nanoparticles encapsulated in poly(t-butylacrylate) (PtBA) beads that act as substrate for the Surface-Enhanced Raman Scattering (SERS) of adenine. For this system, Raman enhancement was observed for the ring-stretching vibrational mode of adenine after aggregation of the Ag/poly(t-butylacrylate) emulsion and isolation of the solid composite. This is a convenient and alternative analytical approach to SERS monitoring of solutions of adenine over the more common use of pure Ag colloids. As a consequence, this research contributes to develop innovative studies on DNA fragments using polymeric platforms that can act as highly sensitive SERS substrates.

Fluorescent Magnetic Bioprobes by Surface Modification of Magnetite Nanoparticles.

Bimodal nanoprobes comprising both magnetic and optical functionalities have been prepared via a sequential two-step process. Firstly, magnetite nanoparticles (MNPs) with well-defined cubic shape and an average dimension of 80 nm were produced by hydrolysis of iron sulfate and were then surface modified with silica shells by using the sol-gel method. The Fe3O4@SiO2 particles were then functionalized with the fluorophore, fluorescein isothiocyanate (FITC), mediated by assembled shells of the cationic polyelectrolyte, polyethyleneimine (PEI). The Fe3O4 functionalized particles were then preliminary evaluated as fluorescent and magnetic probes by performing studies in which neuroblast cells have been contacted with these nanomaterials.