Print-Light-Synthesis (PLS) combines the inkjet printing of a ruthenium precursor ink with the simultaneous photo-induced generation of ruthenium oxide films. During PLS, inkjet-printing generates on conductive as well as insulating substrates micrometer-thin reaction volumes that contain with high precision defined precursor loadings. Upon direct UV light irradiation, the Ru precursor converts to RuO2 while all other ink components escape in the gas phase. No post PLS processes are required, and the as-obtained RuO2 films can be immediately used as electrochemical devices. Two-dimensional RuO2 patterns with micrometric resolution and highly-controlled ruthenium loadings (few µg/cm2) are realized. Thin RuO2 films are generated on insulating substrates, such as polyimide, as well as individual RuO2 particles on conductive substrates, such as graphene layers. The RuO2 films are characterized by electron microscopy and spectroscopic techniques. The sensoristic applicability of the PLS-RuO2 electrodes is demonstrated by potentiometric pH sensing in cell cultures and amperometric detection of L-cysteine. For pH sensing the RuO2 film electrodes show Nernstian sensitivity. L-cysteine detection of RuO2-modified graphene electrodes showed an electrocatalytical effect and resulted in the possibility of selectively detecting L-Cysteine also in presence of the interfering compound uric acid.
Layered double hydroxides (LDHs), also named hydrotalcite-like compounds, are anionic clays with a lamellar structure which have been extensively used in the last two decades as electrode modifiers for the design of electrochemical sensors. These materials can be classified into LDHs containing or not containing redox-active centers. In the former case, a transition metal cation undergoing a reversible redox reaction within a proper potential window is present in the layers, and, therefore, it can act as electron transfer mediator, and electrocatalyze the oxidation of an analyte for which the required overpotential is too high. In the latter case, a negatively charged species acting as a redox mediator can be introduced into the interlayer spaces after exchanging the anion coming from the synthesis, and, again, the material can display electrocatalytic properties. Alternatively, due to the large specific surface area of LDHs, molecules with electroactivity can be adsorbed on their surface. In this review, the most significant electroanalytical applications of LDHs as electrode modifiers for the development of voltammetric sensors are presented, grouping them based on the two types of materials.
The one‐step fabrication of gold films by inkjet printing of a gold precursor ink and its photochemical reduction by exposure to UV light is presented. Inkjet printing creates on a substrate with high control micrometer‐thin reaction volumes in which upon direct high‐intensity light irradiation, the gold precursor reduces to pure and well‐adhered Au particles, while all other ink components escape in the gas phase, without the need for any further post‐treatment. The Au precursor ink does neither contain stabilizing agents, such as polymers or surfactants, nor sacrificial compounds, such as photoinitiators, to initiate and accelerate the reduction. This economic and green process is known as Print‐Light‐Synthesis (PLS) and is herein used to create gold patterns of thin compact Au films and separated Au nanoparticles. Gold loadings are in the µg cm −2 range and precisely controlled, thanks to the inkjet printing parameters. The gold films are characterized by spectroscopic and electrochemical methods. Finally, the applicability of Au films as electrochemical sensors is demonstrated for the detection of 1,4‐butanediol in comparison to a commercial screen‐printed Au electrode. The PLS Au electrode shows a 20 times higher sensitivity and opens new possibilities for disposable electrode production.
Due to the growing presence of pesticides in the environment and in food, the concern of their impact on human health is increasing. Therefore, the development of fast and reliable detection methods is needed. Enzymatic inhibition-based biosensors represent a good alternative for replacing the more complicated and time-consuming traditional methods (chromatography, spectrophotometry, etc.). This paper describes the development of an electrochemical biosensor exploiting alkaline phosphatase as the biological recognition element and a chemically modified glassy carbon electrode as the transducer. The biosensor was prepared modifying the GCE surface by a mixture of Multi-Walled-Carbon-Nanotubes (MWCNTs) and Electrochemically-Reduced-Graphene-Oxide (ERGO) followed by the immobilization of the enzyme by cross-linking with bovine serum albumin and glutaraldehyde. The inhibition of the biosensor response caused by pesticides was established using 2-phospho-L-ascorbic acid as the enzymatic substrate, whose dephosphorylation reaction produces ascorbic acid (AA). The MWCNTs/ERGO mixture shows a synergic effect in terms of increased sensitivity and decreased overpotential for AA oxidation. The response of the biosensor to the herbicide 2,4-dichloro-phenoxy-acetic-acid was evaluated and resulted in the concentration range 0.04–24 nM, with a limit of the detection of 16 pM. The determination of other pesticides was also achieved. The re-usability of the electrode was demonstrated by performing a washing procedure.
The fabrication of thin-film electrodes, which contain metal nanoparticles and nanostructures for applications in electrochemical sensing as well as energy conversion and storage, is often based on multi-step procedures that include two main passages: (i) the synthesis and purification of nanomaterials and (ii) the fabrication of thin films by coating electrode supports with these nanomaterials. The patterning and miniaturization of thin film electrodes generally require masks or advanced patterning instrumentation. In recent years, various approaches have been presented to integrate the spatially resolved deposition of metal precursor solutions and the rapid conversion of the precursors into metal nanoparticles. To achieve the latter, high intensity light irradiation has, in particular, become suitable as it enables the photochemical, photocatalytical, and photothermal conversion of the precursors during or slightly after the precursor deposition. The conversion of the metal precursors directly on the target substrates can make the use of capping and stabilizing agents obsolete. This review focuses on hybrid platforms that comprise digital metal precursor ink printing and high intensity light irradiation for inducing metal precursor conversions into patterned metal and alloy nanoparticles. The combination of the two methods has recently been named Print-Light-Synthesis by a group of collaborators and is characterized by its sustainability in terms of low material consumption, low material waste, and reduced synthesis steps. It provides high control of precursor loading and light irradiation, both affecting and improving the fabrication of thin film electrodes.
The manuscript describes the stereodynamic features of amino bis-mesityl-boranes bearing carbazole and benzocarbazole as donor heterocycles, and how they influence the photophysical properties.