Screen-printed carbon electrodes (SPCEs) bear great potential in the detection of biomarker in clinical samples with low sample consumption. However, modification of electrode surfaces to improve the anti-interference ability and sensitivity is highly desirable for direct electroanalysis of whole blood samples. Here, a reliable and miniaturized electrochemical sensor is demonstrated based on SPCE equipped with vertically-ordered mesoporous silica-nanochannel film (VMSF). To achieve stable binding of VMSF and improve the electrocatalytic performance, electrochemically reduced graphene oxide (ErGO) is applied as a conductive adhesion layer, that is in situ reduced from GO nanosheets during fast growth (less than 10 s) of amino groups modified VMSF (NH2-VMSF) using electrochemically assisted self-assembly (EASA). In comparison with bare SPCE, NH2-VMSF/ErGO/SPCE exhibits decreased oxidation potential of uric acid (UA) by 147 mV owing to significant electrocatalytic ability of ErGO. The dual signal amplification based on electrocatalysis of ErGO and enrichment of nanochannels leads to enhanced peak current by 3.9 times. Thus, the developed NH2-VMSF/ErGO/SPCE sensor enables sensitive detection of UA in the range from 0.5 μM to 180 μM with a low limit of detection (LOD, 129 nM, S/N = 3). Owing to good anti-fouling ability and high selectivity of the sensor, direct and rapid detection of UA in human whole blood is realized with very low sample consumption (50 μL).

Rapid and highly sensitive determination of clozapine (CLZ), a psychotropic drug for the treatment of refractory schizophrenia, in patients is of great significance to reduce the risk of disease recurrence. However, direct electroanalysis of CLZ in human whole blood remains a great challenge owing to the remarkable fouling that occurs in a complex matrix. In this work, a miniaturized, integrated, disposable electrochemical sensing platform based on the integration of nanochannel arrays on the surface of screen-printed carbon electrodes (SPCE) is demonstrated. The device achieves high determination sensitivity while also offering the electrode anti-fouling and anti-interference capabilities. To enhance the electrochemical performance of SPCE, simple electrochemical polarization including anodic oxidation and cathodic reduction is applied to pretreat SPCE. The electrochemically polarized SPCE (p-SPCE) exhibits an enhanced electrochemical peak signal toward CLZ compared with bare SPCE. An electrochemically assisted self-assembly method (EASA) is utilized to conveniently electrodeposit a vertically ordered mesoporous silica nanomembrane film (VMSF) on the p-SPCE, which could further enrich CLZ through electrostatic interactions. Owing to the dual signal amplification based on the p-SPCE and VMSF nanochannels, the developed VMSF/SPCE sensor enables determination of CLZ in the range from 50 nM to 20 μM with a low limit of detection (LOD) of 28 nM (S/N = 3). Combined with the excellent anti-fouling and anti-interference abilities of VMSF, direct and sensitive determination of CLZ in human blood is also achieved.

Vertically ordered mesoporous silica film (VMSF) with uniform mesoporous channels perpendicular to electrode substrate has a wide range of applications in direct electroanalysis of complex samples. However, the detection of nucleic acid bases is difficult to realize at the commonly used VMSF-modified indium tin oxide (VMSF/ITO) electrode due to the high overpotentials of underlying ITO for many small organic molecules. In this work, we demonstrated an electrochemical method for the sensitive detection of guanine (G) by integration of VMSF/ITO and tris(2,2′-bipyridine) ruthenium (II) [Ru(bpy)32+] redox mediator. Ru(bpy)32+ electrostatically accumulated by VMSF is able to act as an electron shuttle between G and underlying ITO surface, showing electrocatalytic oxidation of G and enabling the quantitative determination of G with a limit of detection (LOD) of 0.058 μM and a limit of quantitation (LOQ) of 0.2 μM. Electrochemical detection performance for G could be regulated by changing the pH of the supporting electrolyte and the content of Ru(bpy)32+, achieving a wide dynamic linear range from 0.2 to 10 μM (R2 = 0.999), 2 to 100 μM (R2 = 0.999), and 10 to 500 μM (R2 = 0.998). Furthermore, owing to the good anti-fouling and anti-interference ability of VMSF, this simply sensing strategy can be applied to the direct and rapid detection of G in beer samples, and the detection of ganciclovir (G analog) content in ganciclovir eye drops.

Convenient and sensitive detection of tumors marked in serum samples is of great significance for the early diagnosis of cancers. Facile fabrication of reagentless electrochemical immunosensor with efficient sensing interface and high sensitivity is still a challenge. Herein, an electrochemical immunosensor was easily fabricated based on the easy fabrication of immunoassay interface with electron transfer wires, confined redox probes, and conveniently immobilized antibodies, which can achieve sensitive and reagentless determination of the tumor marker, carcinoembryonic antigen (CEA). Carboxyl multi-walled carbon nanotubes (MWCNTs) were firstly modified with an electrochemical redox probe, methylene blue (MB), which has redox potentials distinguished from those of redox molecules commonly existing in biological samples (for example, ascorbic acid and uric acid). After the as-prepared MB-modified MWCNT (MWCNT-MB) was coated on the supporting glassy carbon electrode (GCE), the MWCNT-MB/GCE exhibited improved active area and electron transfer property. Polydopamine (PDA) was then in situ synthesized through simple self-polymerization of dopamine, which acts as the bio-linker to covalently immobilize the anti-CEA antibody (Ab). The developed immunosensor could be applied for electrochemical detection of CEA based on the decrease in the redox signal of MB after specific binding of CEA and immobilized Ab. The fabricated immunosensor can achieve sensitive determination of CEA ranging from 10 pg/ml to 100 ng/ml with a limit of detection (LOD) of 0.6 pg/ml. Determination of CEA in human serum samples was also realized with high accuracy.