New europium-doped carbon nanoparticles showing long-lifetime photoluminescence: Synthesis, characterization and application to the determination of tetracycline in waters.

The growing appearance of antibiotic-resistant strains of microorganisms originated from the widespread use and ubiquitous presence of such drugs is a major concern in the world. The development of methodologies able to detect such substances at low concentration in real water samples is mandatory to overcome this problem. Europium(III) is known to form complexes with tetracycline (TC) with photoluminescent characteristics useful for TC determination. In the present work, we synthesized for the first time carbon nanoparticles (CN) showing delayed photoluminescence using a Europium(III) doping synthesis. The new material (PCNEu) was characterized both morphologically and spectroscopically, showing an analytical photoluminescent signal in presence of TC, arising from the 5D0→7F2 transition of europium, one hundred times higher than that of the europium salt alone in presence of the antibiotic. This enhancement is a consequence of the amplifying effect exerted by nanoparticle structure itself, leading to an efficient synergistic "antenna effect" in the system PCNEu - TC. The analytical signal is affected both by pH and the nature of the buffer used, and it allows the detection of tetracycline in waters with a limit of detection of 2.18 nM and recoveries between 90 and 110%. The analytical performance of the developed methodology enables having lower limits of detection than other luminescent and chemiluminescent reported methodologies.

Controlled release of nafcillin using biocompatible "dummy" molecularly imprinted sol-gel nanospheres.

Different silicon-based xero-gel molecularly imprinted spheres in the nano boundary range with recognition capabilities for nafcillin have been synthesised, using tetraethylorthosilicate (TEOS) and (3- aminopropyl) triethoxysilane (APTEOS) as precursors. Imprinting has been achieved using both nafcillin (NAF) or structural analogous 'dummies' such as (+)-6-aminopenicillenic acid (APA), or ampicillin ((+)-6- aminobenzylpenicillin)sodium salt (AMP). Materials were fully characterized using ATR-FTIR, (29)Si solidstate NMR, TGA, TEM and BET. Adsorption isotherms for all the materials fit with a continuous Freundlich model with correlation coefficients better than 0.988 and mean affinity constants between 10(5) and 10(6) L·mol(-1). The use of 'dummies' as well as the template itself in the imprinting process resulted in materials with different release speed. Combinations of these materials allow designing mixtures with a continuous, controlled and constant release longer than four days. Thus, the non-imprinted and the AMP-imprinted material have a rapid release during the first five hours, nafcillin and APA imprinted ones release antibiotic mainly after a latency-period of 24 hours.

Molecularly imprinted silica-silver nanowires for tryptophan recognition.

We report on silver nanowires (AgNWs) coated with molecularly imprinted silica (MIP SiO2) for recognition of tryptophan (Trp). The use of AgNWs as a template confers an imprinted material with adequate mechanical strength and with a capability of recognizing Trp due to its nanomorphology when compared to spherical microparticles with a similar surface-to-volume ratio. Studies on adsorption isotherms showed the MIP-SiO2-AgNWs to exhibit homogeneous affinity sites with narrow affinity distribution. This suggests that the synthesized material behaves as a 1D nanomaterial with a large area and small thickness with very similar affinity sites. Trp release from MIP-SiO2-AgNWs was demonstrated to be dominated by the diffusion rate of Trp as controlled by the specific interactions with the imprinted silica shell. Considering these results and the lack of toxicity of silica sol-gel materials, the material offers potential in the field of drug or pharmaceutical controlled delivery, but also in optoelectronic devices, electrodes and sensors.

Assessment of molecularly imprinted sol-gel materials for selective room temperature phosphorescence recognition of nafcillin.

Sol-gel imprinted materials were prepared against nafcillin, a semisynthetic beta-lactamic antibiotic employed in the treatment of serious infections caused by penicillinase-producing staphylococci. Two approaches were addressed for preparation of the imprinted materials and the controls: as conventional monoliths, which were ground and sieved to a desired particle size for rebinding analysis, and as films on supporting glass slides. The specific binding sites that are created during the imprinting process are analyzed via selective room temperature phosphorescence (RTP) (sol-gel films) measurements as well as via competitive room temperature phosphorescence ligand assay. Results demonstrated the importance of the physical configuration of the imprinted material for minimizing non-specific binding. The close similarities between the structures of different beta-lactamic antibiotics made it possible to interpret the roles of the template structure on specific molecular recognition. In this article, we introduce the use of room temperature phosphorescence as selective transduction method for the template. The imprinted sol-gel films displayed enhanced specific binding characteristics respect to the monolithic sol-gel and can be envisaged for the use as recognition matrices for the screening and rapid selection of antibiotics from a combinatorial library or for the rapid control of nafcillin in biological samples (e.g. milk, serum, urine).