Ultrasensitive Photoelectrochemical Biosensing of Multiple Biomarkers on a Single Electrode by a Light Addressing Strategy

Ultrasensitive multiplexed detection of biomarkers on a single electrode is usually a great challenge for electrochemical sensors. Here, a light addressable photoelectrochemical sensor (LAPECS) for the sensitive detection of multiple DNA biomarkers on a single electrode was reported. The sensor was constructed through four steps: (1) immobilization of capture DNA (C-DNA) of different targets on different areas of a single large-sized gold film electrode, (2) recognition of each target DNA (T-DNA) and the corresponding biotin-labeled probe DNA (P-DNA) through hybridization, (3) reaction of the biotin-labeled probe DNA with a streptavidin-labeled all-carbon PEC bioprobe, and (4) PEC detection of multiple DNA targets one by one via a light addressing strategy. Through this principle, the LAPECS can achieve ultrasensitive detection of three DNA sequences related to hepatitis B (HBV), hepatitis C (HCV) and human immunodeficiency (HIV) viruses with a similar wide calibration range of 1.0 pM ∼ 0.01 μM and a low detection limit of 0.7 pM by using one kind of PEC bioprobe. Moreover, the detection throughput of LAPECS may be conveniently expanded by simply enlarging the size of the substrate electrode or reducing the size of the sensing arrays and the light beam. The present work thus demonstrates the promising applications of LAPECS in developing portable, sensitive, high-throughput, and cost-effective biosensing systems

Portable, Self-Powered, and Light-Addressable Photoelectrochemical Sensing Platforms Using pH Meter Readouts for High-Throughput Screening of Thrombin Inhibitor Drugs

In this work, a self-powered, portable, and light-addressable photoelectrochemical sensor (P-LAPECS) is developed for efficient drug screening using a handheld pH meter readout. The sensor, which employs thrombin inhibitors as the drug model, is constructed by evenly immobilizing biotin-labeled and thrombin-cleavable peptides on eight separated sensing zones of a single gold film electrode. The incubation of each peptide sensing zone with thrombin leads to the reduction of binding sites for streptavidin-labeled fullerene (C₆₀) PEC bioprobes, which directly reflects the activity of thrombin by the variation of both photocurrent and photovoltage, and therefore allows the screening of thrombin inhibitors using either a single-channel electrochemical analyzer or a portable pH meter. Consequenty, the inhibition efficiency evaluation of multiple thrombin inhibitors can be achieved by just one electrode, and the screening result obtained by the pH meter is very close to that acquired by the electrochemical analyzer. Moreover, P-LAPECS can realize the light-addressable detection of thrombin with a detection limit as low as 0.05 pM. The present work thus demonstrates the possibility of constructing portable, inexpensive, sensitive, and high-throughput biosensing platforms using ubiquitous pH meters for laboratories all over the world

Inkjet Printing of Nanoporous Gold Electrode Arrays on Cellulose Membranes for High-Sensitive Paper-Like Electrochemical Oxygen Sensors Using Ionic Liquid Electrolytes

A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O₂) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆). The sensor looked like a piece of paper but possessed high sensitivity for O₂ in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors

Ultrasensitive All-Carbon Photoelectrochemical Bioprobes for Zeptomole Immunosensing of Tumor Markers by an Inexpensive Visible Laser Light

A novel enzyme-free and all-carbon photoelectrochemical (PEC) bioprobe, based on carboxylated multiwalled carbon nanotube–Congo red–fullerene nanohybrids (MWNTCOOH–CR–C₆₀), for the ultrasensitive immunosensing of carcinoembryonic antigen (CEA) was reported. The MWNTCOOH–CR–C₆₀ nanohybrids, prepared by mechanically grinding a mixture of MWNTCOOH, C₆₀, and CR at a certain mass ratio, had good water dispersibility and high PEC conversion efficiency in visible light ranges. Covalent binding of the detection antibody of CEA on the MWNTCOOH–CR–C₆₀ nanohybrids produced a sensitive PEC bioprobe for detection of CEA by sandwich immunosensing. The corresponding immunosensor, employing an inexpensive and portable green laser light, possessed a wide calibration range of 1.0 pg/mL∼100.0 ng/mL and a low detection limit of 0.1 pg/mL (calculated 5 zmol for a 10.0 μL sample solution) (S/N = 3), which was successfully applied to the detection of CEA in serum samples from both healthy people and cancer patients. The present work thus demonstrated the promising application of fullerene-based nanocomposites in developing highly sensitive, environmentally friendly, and cost-effective PEC biosensors

Fully Converting Graphite into Graphene Oxide Hydrogels by Preoxidation with Impure Manganese Dioxide

Potassium permanganate (KMnO₄) has been proved to be an efficient oxidant for converting graphite into graphite oxide, but its slow diffusion in the interlayer of graphite seriously restricts the production of graphene oxide (GO). Here, we demonstrate that the preoxidation of graphite by impure manganese dioxide (MnO₂) in a mixture of concentrated sulfuric acid (H₂SO₄) and phosphorus pentoxide (P₂O₅) can efficiently improve the synthesis of GO when KMnO₄ is employed as the oxidant. The prepared honey-like GO hydrogels possess a high yield of single-layer sheets, large sizes (average lateral size up to 20 μm), wide ranges of stable dispersion concentrations (from dilute solutions, viscous hydrogels, to dry films), and good conductivity after reduction (∼2.9 × 10⁴ S/m). The mechanism for the improved synthesis of GO by impure MnO₂ was explored. The enhanced exfoliation and oxidation of graphite by oxidative Mn ions (mainly Mn³⁺), which are synergistically produced by the reaction of impure MnO₂ with H₂SO₄ and P₂O₅, are found to be responsible for the improved synthesis of such GO hydrogels. Particularly, preoxidized graphite (POG) can be partially dispersed in water with sonication, which allows the facile construction of flexible and highly conductive graphene nanosheet film electrodes with excellent electrochemical sensing properties