Site-selective surface enhanced Raman scattering study of ligand exchange reactions on aggregated Ag nanocubes.

Surface modification of ligand protected nanoparticles (NPs) can be driven by ligand exchange reactions (LER). Little is known about the mechanism of this reaction, especially when the particles are not spherical. Here, we use the intrinsic hot spots generated on the corners/edges of 40 nm silver nanocubes (AgNCs) and the extrinsic hot spots generated by the aggregation of AgNCs to obtain strong enhancements in surface enhanced Raman scattering (SERS) to monitor the displacement of poly(vinylpyrrolidone) with either a hydrophilic (sodium 11-mercapto-1-undecanesulfonate, MUS) or a hydrophobic ligand (1-octanethiol, OT). By focusing on the ratio (R) between the trans and gauche bands of the alkyl backbones of the ligands as an indicator of local order, we find that the LER proceeds in two different ways, particularly regarding the arrangement of the incoming ligands. In the case of OT, R becomes large almost immediately and stays high throughout the reaction, while in the case of MUS, R starts low and increases only towards the end of the reaction. We interpret the first behaviour as a LER that proceeds via the formation of densely packed and ordered OT islands, practically from the beginning of the reaction, that gradually grow over time. In the case of MUS, our interpretation is that molecules randomly deposit on the surface and form denser monolayer regions as the LER proceeds. Both monolayers evolved towards a homogeneous topography that corresponds to an ordered state (near all-trans) in the later stages (R≫1). Such mechanisms may be extended to the cube faces (as planar scaffolds) since clear differences in the topographic profile were found by Atomic Force Microscopy (AFM).

Synthesis of a thermoresponsive crosslinked MEO2MA polymer coating on microclusters of iron oxide nanoparticles.

Encapsulation of magnetic nanoparticles (MNPs) of iron (II, III) oxide (Fe3O4) with a thermopolymeric shell of a crosslinked poly(2-(2-methoxyethoxy)ethyl methacrylate) P(MEO2MA) is successfully developed. Magnetic aggregates of large size, around 150-200 nm are obtained during the functionalization of the iron oxide NPs with vinyl groups by using 3-butenoic acid in the presence of a water soluble azo-initiator and a surfactant, at 70 °C. These polymerizable groups provide a covalent attachment of the P(MEO2MA) shell on the surface of the MNPs while a crosslinked network is achieved by including tetraethylene glycol dimethacrylate in the precipitation polymerization synthesis. Temperature control is used to modulate the swelling-to-collapse transition volume until a maximum of around 21:1 ratio between the expanded: shrunk states (from 364 to 144 nm in diameter) between 9 and 49 °C. The hybrid Fe3O4@P(MEO2MA) microgel exhibits a lower critical solution temperature of 21.9 °C below the corresponding value for P(MEO2MA) (bulk, 26 °C). The MEO2MA coating performance in the hybrid microgel is characterized by dynamic light scattering and transmission electron microscopy. The content of preformed MNPs [up to 30.2 (wt%) vs. microgel] was established by thermogravimetric analysis while magnetic properties by vibrating sample magnetometry.

Optimization of Cost-Effective and Reproducible Flexible Humidity Sensors Based on Metal-Organic Frameworks.

In this letter, we present the extension of a previous work on a cost-effective method for fabricating highly sensitive humidity sensors on flexible substrates with a reversible response, allowing precise monitoring of the humidity threshold. In that work we demonstrated the use of three-dimensional metal-organic framework (MOF) film deposition based on the perylene-3,4,9,10-tetracarboxylate linker, potassium as metallic center and the interspacing of silver interdigitated electrodes (IDEs) as humidity sensors. In this work, we study one of the most important issues in efficient and reproducible mass production, which is to optimize the most important processes' parameters in their fabrication, such as controlling the thickness of the sensor's layers. We demonstrate this method not only allows for the creation of humidity sensors, but it also is possible to change the humidity value that changes the actuator state.

Carbon Dots as Sensing Layer for Printed Humidity and Temperature Sensors.

This work presents an innovative application of carbon dots (Cdots) nanoparticles as sensing layer for relative humidity detection. The developed sensor is based on interdigitated capacitive electrodes screen printed on a flexible transparent polyethylene terephthalate (PET) film. Cdots are deposited on top of these electrodes. An exhaustive characterization of the nanoparticles has been conducted along with the fabrication of the sensor structure. The accompanied experiments give all the sensibility to the Cdots, showing its dependence with temperature and exciting frequency. To the best of our knowledge, this work paves the path to the use of these kind of nanoparticles in printed flexible capacitive sensors aimed to be employed in the continuously expanding Internet of Things ecosystem.

Evaluation of a reconfigurable portable instrument for copper determination based on luminescent carbon dots.

A portable reconfigurable platform for copper (Cu(II)) determination based on luminescent carbon dot (Cdots) quenching is described. The electronic setup consists of a light-emitting diode (LED) as the carbon dot optical exciter and a photodiode as a light-to-current converter integrated in the same instrument. Moreover, the overall analog conditioning is simply performed with one integrated solution, a field-programmable analog array (FPAA), which makes it possible to reconfigure the filter and gain stages in real time. This feature provides adaptability to use the platform as an analytical probe for carbon dots coming from different batches with some variations in luminescence characteristics. The calibration functions obtained that fit a modified Stern-Volmer equation were obtained using luminescence signals from Cdots quenching by Cu(II). The analytical applicability of the reconfigurable portable instrument for Cu(II) using Cdots has been successfully demonstrated in tap water analysis.

Carbon dots for copper detection with down and upconversion fluorescent properties as excitation sources.

Carbon dots were synthesized by a simple and green strategy for selective and sensitive Cu(2+) ion detection using both down and upconversion fluorescence. These fluorescent nanosensors show low cytotoxicity and are applied for intracellular sensing and imaging of Cu(2+) in biological systems.

Photographing the synergy between magnetic and colour properties in spin crossover material [Fe(NH2trz)3](BF4)2: a temperature sensor perspective.

We introduce the first method for imaging colour changes related to a spin crossover phenomenon induced by thermal variation which can be determined with the naked eye or with a photographic digital camera in a solid phase sensor.

Magnetic and fluorescent core-shell nanoparticles for ratiometric pH sensing.

This paper describes the preparation of nanoparticles composed of a magnetic core surrounded by two successive silica shells embedding two fluorophores, showing uniform nanoparticle size (50-60 nm in diameter) and shape, which allow ratiometric pH measurements in the pH range 5-8. Uncoated iron oxide magnetic nanoparticles (∼10 nm in diameter) were formed by the coprecipitation reaction of ferrous and ferric salts. Then, they were added to a water-in-oil microemulsion where the hydrophilic silica shells were obtained through hydrolysis and condensation of tetraethoxyorthosilicate together with the corresponding silylated dye derivatives-a sulforhodamine was embedded in the inner silica shell and used as the reference dye while a pH-sensitive fluorescein was incorporated in the outer shell as the pH indicator. The magnetic nanoparticles were characterized using vibrating sample magnetometry, dynamic light scattering, transmission electron microscopy, x-ray diffraction and Fourier transform infrared spectroscopy. The relationship between the analytical parameter, that is, the ratio of fluorescence between the sensing and reference dyes versus the pH was adjusted to a sigmoidal fit using a Boltzmann type equation giving an apparent pK(a) value of 6.8. The fluorescence intensity of the reference dye did not change significantly (∼3.0%) on modifying the pH of the nanoparticle dispersion. Finally, the proposed method was statistically validated against a reference procedure using samples of water and physiological buffer with 2% of horse serum, indicating that there are no significant statistical differences at a 95% confidence level.

Multi-ion detection by one-shot optical sensors using a colour digital photographic camera.

The feasibility and performance of a procedure to evaluate previously developed one-shot optical sensors as single and selective analyte sensors for potassium, magnesium and hardness are presented. The procedure uses a conventional colour digital photographic camera as the detection system for simultaneous multianalyte detection. A 6.0 megapixel camera was used, and the procedure describes how it is possible to quantify potassium, magnesium and hardness simultaneously from the images captured, using multianalyte one-shot sensors based on ionophore-chromoionophore chemistry, employing the colour information computed from a defined region of interest on the sensing membrane. One of the colour channels in the red, green, blue (RGB) colour space is used to build the analytical parameter, the effective degree of protonation (1-α(eff)), in good agreement with the theoretical model. The linearization of the sigmoidal response function increases the limit of detection (LOD) and analytical range in all cases studied. The increases were from 5.4 × 10(-6) to 2.7 × 10(-7) M for potassium, from 1.4 × 10(-4) to 2.0 × 10(-6) M for magnesium and from 1.7 to 2.0 × 10(-2) mg L(-1) of CaCO(3) for hardness. The method's precision was determined in terms of the relative standard deviation (RSD%) which was from 2.4 to 7.6 for potassium, from 6.8 to 7.8 for magnesium and from 4.3 to 7.8 for hardness. The procedure was applied to the simultaneous determination of potassium, magnesium and hardness using multianalyte one-shot sensors in different types of waters and beverages in order to cover the entire application range, statistically validating the results against atomic absorption spectrometry as the reference procedure. Accordingly, this paper is an attempt to demonstrate the possibility of using a conventional digital camera as an analytical device to measure this type of one-shot sensor based on ionophore-chromoionophore chemistry instead of using conventional lab instrumentation.

Surface-functionalized fluorescent silica nanoparticles for the detection of ATP.

The design of two-dyed fluorescent silica nanoparticles for ATP detection is presented. The indicator dye possesses a dipicolyl-amine (DPA) unit complexed with Zn(II) as a receptor function for ATP while a rhodamine derivative is used as the reference dye. The nanoparticles were fully characterized regarding analytical performance, morphology and cytocompatibility.

On the design of fluorescent ratiometric nanosensors.

Advances in nanoparticle technology have recently offered new tools to the bioanalytical field of research. In particular, new nanoparticle-based sensors have appeared able to give quantitative information about different species (ions, metabolites, biomolecules) in biosamples through ratiometric measurements. This article describes the methodologies developed so far in the design of such nanosensors. In particular, the different approaches to immobilize fluorescent chemosensor dyes to nanoparticles are presented. Concept designs of ratiometric nanosensors in terms of composition and architecture are also described and illustrated with examples taken from the literature.

Fluorescent polyacrylamide nanoparticles for naproxen recognition.

We present the synthesis of fluorescent acrylamide nanoparticles (FANs) capable of recognizing non-steroidal anti-inflammatory drugs (NSAIDs) in buffered aqueous solutions. Within this important group, we selected naproxen, one of the 2-arylpropionic acids (profens), due to its use for the treatment of moderate pain, fever, and inflammation. The nanosensors were prepared under mild conditions of inverse microemulsion polymerization using aqueous acrylamide as the monomer and N,N'-methylenebisacrylamide as the cross-linker, employing the surfactants polyoxyethylene-4-lauryl ether (Brij 30) and sodium bis(2-ethylhexyl)sulfosuccinate in hexane. Furthermore, a fluorescent monomer, (E)-4-[4-(dimethylamino)styryl]-1-[4-(methacryloyloxymethyl)benzyl]pyridinium chloride (mDMASP) has been synthesized and incorporated into the nanoparticles. The nanosensors exhibit a broad absorbance at around 460 nm and a structureless fluorescence band with maximum at 590 nm in 0.5 M phosphate buffer (pH = 7.2). The recognition process is performed on the basis of ionic interactions which are monitored by the fluorescence increase at 590 nm upon addition of different concentrations of naproxen. The FANs show a size distribution in the range of 20-80 nm, with a hydrodynamic diameter of 34 nm. In order to assess the selectivity of the FANs, a systematic study was conducted on the effect produced by drugs and biomolecules that could interfere with the analysis of naproxen.