Electrochemiluminescent immunoassay enhancement driven by carbon nanotubes.

Electrochemiluminescence (ECL) is a leading analytical technique for clinical monitoring and early disease diagnosis. Carbon nanotubes are used as efficient nanomaterials for ECL signal enhancement providing new insights into the mechanism for the ECL generation but also affording application in bead-based immunoassay and ECL microscopy-based bioimaging.

Lighting up the Electrochemiluminescence of Carbon Dots through Pre- and Post-Synthetic Design.

Carbon dots (CDs), defined by their size of less than 10 nm, are a class of photoluminescent (PL) and electrochemiluminescent (ECL) nanomaterials that include a variety of carbon-based nanoparticles. However, the control of their properties, especially ECL, remains elusive and afflicted by a series of problems. Here, the authors report CDs that display ECL in water via coreactant ECL, which is the dominant mechanism in biosensing applications. They take advantage of a multicomponent bottom-up approach for preparing and studying the luminescence properties of CDs doped with a dye acting as PL and ECL probe. The dependence of luminescence properties on the surface chemistry is further reported, by investigating the PL and ECL response of CDs with surfaces rich in primary, methylated, or propylated amino groups. While precursors that contribute to the core characterize the PL emission, the surface states influence the efficiency of the excitation-dependent PL emission. The ECL emission is influenced by surface states from the organic shell, but states of the core strongly interact with the surface, influencing the ECL efficiency. These findings offer a framework of pre- and post-synthetic design strategies to improve ECL emission properties, opening new opportunities for exploring biosensing applications of CDs.

Dye-Doped Silica Nanoparticles for Enhanced ECL-Based Immunoassay Analytical Performance.

The combination of highly sensitive techniques such as electrochemiluminescence (ECL) with nanotechnology sparked new analytical applications, in particular for immunoassay-based detection systems. In this context, nanomaterials, particularly dye-doped silica nanoparticles (DDSNPs) are of high interest, since they can offer several advantages in terms of sensitivity and performance. In this work we synthesized two sets of monodispersed and biotinylated [Ru(bpy)3 ]2+ -doped silica nanoparticles, named bio-Triton@RuNP and bio-Igepal@RuNP, obtained following the reverse microemulsion method using two different types of nonionic surfactants. Controlling the synthetic procedures, we were able to obtain nanoparticles (NPs) offering highly intense signal, using tri-n-propylamine (TPrA) as coreactant, with bio-Triton@RuNps being more efficient than bio-Igepal@RuNP.

Insights into the mechanism of coreactant electrochemiluminescence facilitating enhanced bioanalytical performance.

Electrochemiluminescence (ECL) is a powerful transduction technique with a leading role in the biosensing field due to its high sensitivity and low background signal. Although the intrinsic analytical strength of ECL depends critically on the overall efficiency of the mechanisms of its generation, studies aimed at enhancing the ECL signal have mostly focused on the investigation of materials, either luminophores or coreactants, while fundamental mechanistic studies are relatively scarce. Here, we discover an unexpected but highly efficient mechanistic path for ECL generation close to the electrode surface (signal enhancement, 128%) using an innovative combination of ECL imaging techniques and electrochemical mapping of radical generation. Our findings, which are also supported by quantum chemical calculations and spin trapping methods, led to the identification of a family of alternative branched amine coreactants, which raises the analytical strength of ECL well beyond that of present state-of-the-art immunoassays, thus creating potential ECL applications in ultrasensitive bioanalysis.

Electrochemiluminescence as emerging microscopy techniques.

The use of electrochemiluminescence (ECL), i.e., chemiluminescence triggered by electrochemical stimulus, as emitting light source for microscopy is an emerging approach with different applications ranging from the visualization of nanomaterials to cell mapping. In this trend article, we give an overview of the state of the art in this new field with the purpose to illustrate all the possible applications so far explored as well as describing the mechanism underlying this transduction technique. The results discussed here would highlight the great potential of the combination between ECL and microscopy and how this marriage can turn into an innovative approach with specific application in analytical sciences. Graphical abstract.

A Combined XRD, Solvatochromic, and Cyclic Voltammetric Study of Poly (3,4-Ethylenedioxythiophene) Doped with Sulfonated Polyarylethersulfones: Towards New Conducting Polymers.

Despite the poor solubility in organic solvents, poly (3,4-ethylenedioxythiophene) (PEDOT) is one of the most successful conducting polymers. To improve PEDOT conductivity, the dopants commonly used are molecules/polymers carrying sulfonic functionalities. In addition to these species, sulfonated polyarylethersulfone (SPAES), obtained via homogeneous synthesis with different degrees of sulfonation (DS), can be used thanks to both the tight control over the DS and the charge separation present in SPAES structure. Here, PEDOTs having enhanced solubility in the chosen reaction solvents (N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone) were synthesized via a high-concentration solvent-based emulsion polymerization with very low amounts of SPAES as dopant (1% w/w with respect to EDOT monomer), characterized by different DS. The influence of solvents and of the adopted doping agent was studied on PEDOT_SPAESs analyzing (i) the chemical structure, comparing via X-ray diffraction (XRD) the crystalline structures of undoped and commercial PEDOTs with PEDOT_SPAES' amorphous structure; (ii) solvatochromic behavior, observing UV absorption wavelength variation as solvents and SPAES' DS change; and (iii) electrochemical properties: voltammetric peak heights of PEDOT_SPAES cast onto glassy carbon electrodes differ for each solvent and in general are better than the ones obtained for neat SPAES, PEDOTs, and glassy carbon.