A.M. Parra-Alfambra

Diamond nanoparticles based biosensors for efficient glucose and lactate determination

In this work, we report the modification of a gold electrode with undoped diamond nanoparticles (DNPs) and its applicability to the fabrication of electrochemical biosensing platforms. DNPs were immobilized onto a gold electrode by direct adsorption and the electrochemical behavior of the resulting DNPs/Au platform was studied. Four well-defined peaks were observed corresponding to the DNPs oxidation/reduction at the underlying gold electrode, which demonstrate that, although undoped DNPs have an insulating character, they show electrochemical activity as a consequence of the presence of different functionalities with unsaturated bonding on their surface. In order to develop a DNPs-based biosensing platform, we have selected glucose oxidase (GOx), as a model enzyme. We have performed an exhaustive study of the different steps involved in the biosensing platform preparation (DNPs/Au and GOx/DNPs/Au systems) by atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM) and cyclic voltammetry (CV). The glucose biosensor shows a good electrocatalytic response in the presence of (hydroxymethyl)ferrocene as redox mediator. Once the suitability of the prototype system to determine glucose was verified, in a second step, we prepared a similar biosensor, but employing the enzyme lactate oxidase (LOx/DNPs/Au). As far as we know, this is the first electrochemical biosensor for lactate determination that includes DNPs as nanomaterial. A linear concentration range from 0.05 mM to 0.7 mM, a sensitivity of 4.0 µA mM(-1) and a detection limit of 15 µM were obtained.

One-step covalent microcontact printing approach to produce patterns of lactate oxidase

A comparative study of three different strategies to pattern lactate oxidase (LOx) onto bare gold substrates by microcontact printing (muCP) is presented. The quality of the resulting patterns in terms of homogeneity, compactness and stability has been evaluated by atomic force microscopy in both air and aqueous conditions. The following approaches have been tested: (i) LOx was directly stamped to a bare gold surface; (ii) LOx was previously covalently bonded to a thiolated molecule, dithiodipropionic acid di(N-succinimidyl ester) (DTSP), and this conjugate (LOx/DTSP) was transferred from an elastomeric stamp to a bare gold substrate; (iii) formation of a LOx/DTSP micropattern on a bare gold surface (as described in approach ii) was followed by exposure to a solution containing hexadecylmercaptane (HDM). In all cases, the catalytic activity of the final LOx patterns has been assessed by electrochemical measurements. From comparison of the three strategies, it can be concluded that the third one gives rise to LOx patterns that present a high stability and compactness, also offering the advantage of reducing the number of microcontact printing steps to one.

Electrocatalytic processes promoted by diamond nanoparticles in enzymatic biosensing devices.

We have developed a biosensing platform for lactate determination based on gold electrodes modified with diamond nanoparticles of 4nm of nominal diameter, employing the enzyme lactate oxidase and (hydroxymethyl)ferrocene (HMF) as redox mediator in solution. This system displays a response towards lactate that is completely different to those typically observed for lactate biosensors based on other nanomaterials, such as graphene, carbon nanotubes, gold nanoparticles or even diamond nanoparticles of greater size. We have observed by cyclic voltammetry that, under certain experimental conditions, an irreversible wave (E(0)=+0.15V) appears concomitantly with the typical Fe(II)/Fe(III) peaks (E(0)=+0.30V) of HMF. In this case, the biosensor response to lactate shows simultaneous electrocatalytic peaks at +0.15V and +0.30V, indicating the concurrence of different feedback mechanisms. The achievement of a biosensor response to lactate at +0.15V is very convenient in order to avoid potential interferences. The developed biosensor presents a linear concentration range from 0.02mM to 1.2mM, a sensitivity of 6.1μAmM(-1), a detection limit of 5.3μM and excellent stability. These analytical properties compare well with those obtained for other lactate-based biosensors that also include nanomaterials and employ HMF as redox mediator.

Synergistic effect of MoS 2 and diamond nanoparticles in electrochemical sensors: determination of the anticonvulsant drug valproic acid

AbstractThe authors describe an electrochemical sensor based on the use of diamond nanoparticles (DNPs) and molybdenum disulfide (MoS2) platelets. The sensor was applied to the voltammetric determination of the anticonvulsant valproic acid which was previously derivatized with ferrocene. The MoS2 platelets were obtained by an exfoliation method, and the DNPs were directly dispersed in water and subsequently deposited on a glassy carbon electrode (GCE). The sensor response was optimized in terms of the solvent employed for dispersing the MoS2 nanomaterial and the method for modifying the GCE. Sensors consisting of a first layer of MoS2 dispersed in ethanol/water and a second layer of DNPs give better response. The single steps of sensor construction were characterized by atomic force microscopy and electrochemical impedance spectroscopy. The differential pulse voltammetric response of the GCE (measured at +0.18 V vs. Ag/AgCl) was compared to that of sensors incorporating only one of the nanomateriales (DNPs or MoS2). The formation of a hybrid MoS2-DNP structure clearly improves performance. The GCE containing both nanomaterials exhibits high sensitivity (740 µA ⋅ mM−1 ⋅ cm−2), a 0.27 μM detection limit, and an 8% reproducibility (RSD). The sensor retained 99% of its initial response after 45 days of storage. Graphical abstractElectrochemical sensor by co-immobilization of MoS2 and diamond nanoparticles (DNP). The formation of a hybrid MoS2-DNP structure enhances the performance of the sensor towards valproic acid derivatized with a ferrocene group, when compared with sensors incorporating only DNP or MoS2.