3D-printed electrochemical glucose device with integrated Fe(II)-MOF nanozyme.

Estimation of glucose (GLU) levels in the human organism is very important in the diagnosis and monitoring of diabetes. Scientific advances in nanomaterials have led to the construction of new generations of enzymatic-free GLU sensors. In this work, an innovative 3D-printed device modified with a water-stable and non-toxic metal-organic framework of iron (Fe(II)-MOF), which serves as a nanozyme, has been developed for the voltammetric determination of GLU in artificial sweat. In contrast to existing MOF-based GLU sensors which exhibit electrocatalytic activity for the oxidation of GLU in alkaline media, the nanozyme Fe(II)-MOF/3D-printed device can operate in the acidic epidermal sweat environment. The enzymatic-free GLU sensor is composed of a 3-electrode 3D-printed device with the MOF nanozyme immobilized on the surface of the working electrode. GLU sensing is conducted by differential pulse voltammetry without interference from other co-existing metabolites in artificial sweat. The response is based on the oxidation of glucose to gluconolactone, induced by the redox activity of the Fe-centers of the MOF. GLU gives rise to an easily detectable and well-defined voltammetric peak at about - 1.2 V and the limit of detection is 17.6 µmol L-1. The synergy of a nanozyme with 3D printing technology results in an advanced, sensitive, and low-cost sensor, paving the way for on-skin applications.

Wooden Tongue Depressor Multiplex Saliva Biosensor Fabricated via Diode Laser Engraving.

Since wood is a renewable, biodegradable naturally occurring material, the development of conductive patterns on wood substrates is a new and innovative chapter in sustainable electronics and sensors. Herein, we describe the first wooden (bio)sensing device fabricated via diode laser-induced graphitization. For this purpose, a wooden tongue depressor (WTD) is laser-treated and converted to an electrochemical multiplex biosensing device for oral fluid analysis. A low-cost laser engraver, equipped with a low-power (0.5 W) diode laser, programmably irradiates the surface of the WTD, forming two mini electrochemical cells (e-cells). The two e-cells consist of four graphite electrodes: two working electrodes, a common counter, and a common reference electrode. The two e-cells are spatially separated via programmable pen-plotting, using a commercial hydrophobic marker pen. Proof-of-principle for biosensing is demonstrated for the simultaneous determination of glucose and nitrite in artificial saliva. This wooden electrochemical biodevice is an easy-to-fabricate disposable point-of-care chip with a wide scope of applicability to other bioassays, while it paves the way for the low-cost and straightforward production of wooden electrochemical platforms.

3D Printed Voltammetric Sensor Modified with an Fe(III)-Cluster for the Enzyme-Free Determination of Glucose in Sweat.

In this work, a 3D printed sensor modified with a water-stable complex of Fe(III) basic benzoate is presented for the voltammetric detection of glucose (GLU) in acidic epidermal skin conditions. The GLU sensor was produced by the drop-casting of Fe(III)-cluster ethanolic mixture on the surface of a 3D printed electrode fabricated by a carbon black loaded polylactic acid filament. The oxidation of GLU was electrocatalyzed by Fe(III), which was electrochemically generated in-situ by the Fe(III)-cluster precursor. The GLU determination was carried out by differential pulse voltammetry without the interference from common electroactive metabolites presented in sweat (such as urea, uric acid, and lactic acid), offering a limit of detection of 4.3 µmol L-1. The exceptional electrochemical performance of [Fe3O(PhCO2)6(H2O)3]∙PhCO2 combined with 3D printing technology forms an innovative and low-cost enzyme-free sensor suitable for noninvasive applications, opening the way for integrated 3D printed wearable biodevices.

3D printed enzymatic microchip for multiplexed electrochemical biosensing.

The low-cost e-fabrication of specialized multianalyte biosensors within the point-of-care (POC) settings in a few minutes remains a great challenge. Unlike prefabricated biosensors, 3D printing seems to be able to meet this challenge, empowering the end user with the freedom to create on-demand devices adapted to immediate bioanalytical need. Here, we describe a novel miniature all-3D-printed 4-electrode biochip, capable of the simultaneous determination of different biomarkers in a single assay. The chip is utterly fabricated via an one-step 3D printing process and it is connected to a mini portable bi-potentiostant, permitting simultaneous measurements. The bioanalytical capability of the microchip is demonstrated through the simultaneous amperometric determination of two cardiac biomarkers (cholesterol and choline) in the same blood droplet, via enzymatic assays developed on its two tiny integrated electrodes. The simultaneous determination of cholesterol and choline is free from cross-talk phenomena and interferences offering limits of detection much lower than the cut-off levels of these biomarkers in blood for coronary syndromes. The biodevice is an easy-constructed, low-cost, sensitive and e-transferable POC chip with wide scope of applicability to other enzymatic bioassays.