Near-Infrared Light-Initiated Photoelectrochemical Biosensor Based on Upconversion Nanorods for Immobilization-Free miRNA Detection with Double Signal Amplification.

Photoelectrochemical (PEC) sensors are relatively new sensing platforms with high detection sensitivity and low cost. However, the current PEC biosensors dependent on ultraviolet or visible light as the exciting resource cause injuries to biological samples and systems, which restrains the applications in complicated matrixes. Herein, a near-infrared light (NIR)-initiated PEC biosensor based on NaYF4:Yb,Tm@NaYF4@TiO2@CdS (csUCNRs@TiO2@CdS) was constructed for sensitive detection of acute myocardial infarction (AMI)-related miRNA-133a in an immobilization-free format coupled with a hybridization chain reaction and a redox circle signal amplification strategy. A low-energy 980 nm NIR incident laser was converted to 300-480 nm light to excite the adjacent TiO2@CdS photosensitive shell to generate photocurrent by NaYF4:Yb,Tm@NaYF4 upconversion nanorods. Also, magnetic beads were employed for the homogeneous determination of target miRNA-133a to reduce the recognition steric hindrance and improve the detection sensitivity. The photocurrent response was positively correlated with the level of ascorbic acid as the energy donor to consume photoacoustic holes produced on the surface of csUCNRs@TiO2@CdS, which was generated by alkaline phosphatase catalyzation and regenerated by tris(2-carboxyethyl) phosphine reduction upon the appearance of miRNA-133a. Exerting a NIR-light-driven and immobilization-free strategy, the as-constructed biosensor displayed linearly sensitive and selective determination of miRNA-133a with a detection limit of 36.12 aM. More significantly, the assay method provided a new concept of the PEC sensing strategy driven by NIR light to detect diverse biomarkers with pronounced sensitivity, light stability, and low photodamage.

Self-powered photoelectrochemical immunosensing platform for sensitive CEA detection using dual-photoelectrode synergistic signal amplification.

Self-powered photoelectrochemical (PEC) sensing, as an emerging sensing mode, can effectively solve the problems such as weak anti-interference ability and poor signal response of individual photoanode or photocathode sensing. In this work, an ITO/Co-CuInS2 photocathode and ITO/WO3@CdS photoanode based self-powered cathodic PEC immunosensor was developed, which integrated dual-photoelectrode to synergistic amplify the signal for highly sensitive and specific detection of carcinoembryonic antigen (CEA). The self-powered PEC sensor could drive electrons transfer through the difference in Fermi levels between the two photoelectrodes without an external bias voltage. The photoanode was introduced to amplify the photoelectric signal, and the photocathode was only designed for the construction of sensing interfaces. The proposed sensor quantitatively determined the target CEA with the detection limit of 0.23 pg/mL and a linear correlation confine of 0.1 pg/mL ∼100 ng/mL. The constructed immunosensing platform exhibited high sensitivity, satisfactory stability and great biological detection selectivity, providing a feasible and effective strategy for the manufacture of new self-powered sensors in high-performance PEC bioanalytical applications.

An enzyme-activated two-photon ratiometric fluorescent probe with lysosome targetability for imaging ß-glucuronidase in colon cancer cells and tissue.

Colon cancer is a malignant neoplasm with high mortality that has seriously threatened human life. Accumulating evidence reveals that the ß-glucuronidase (GLU), a lysosomal exoglycosidase enzyme, plays important roles in the pathological progression of colon cancer. Unfortunately, understanding the pathological roles of GLU remains a challenge due to the lack of effective detection methods for visualization the fluctuations of GLU in tissues. In this paper, based on hydrolysis function of GLU, an enzyme-activated ratiometric two-photon (TP) fluorescent probe (RN-GLU) was designed. RN-GLU was synthesized by introducing a glucopyranuronic acid methyl ester as the recognition group and 1, 8-naphthalimide as a TP fluorophore. In the presence of GLU, the trigger group was removed made an ICT process occurred induced enhancement of fluorescence ratio (I553 nm/I441 nm, 214-fold). Probe RN-GLU displayed low detection limit (1.2 × 10-2 µg/L) and rapid detection to GLU in vitro through a ratiometric response mode. Meanwhile, RN-GLU exhibited high selectivity for GLU and showed nearly no response to other relevant biological species. The imaging results demonstrated that RN-GLU could be applied for ratiometric monitoring of endogenous GLU levels in HCT116 cells with good lysosome targetable ability. Due to its two-photon excitation, RN-GLU could monitor GLU in colon cancer tumor tissue with good penetration ability (imaging depth of 200 µm). RN-GLU could be developed as a potential method for evaluating and confirming the functions of GLU in colon cancer diagnosis and complex biosystem.

Integrating Ti3C2/MgIn2S4 heterojunction with a controlled release strategy for split-type photoelectrochemical sensing of miRNA-21.

The harsh operating conditions and time-consuming fabrication process of the photoelectrode modification process have limited the potential applications of photoelectrochemical (PEC) sensors. To overcome these drawbacks, this study introduced a unique split-type PEC biosensor for microRNA-21 (miRNA-21) detection. Specifically, a Ti3C2/MgIn2S4 heterojunction was adopted as the photosensitive material, and a target-controlled glucose release system, comprising a multifunctional porphyrin-based metal-organic framework (PCN-224), was used for signal amplification. The Ti3C2/MgIn2S4 heterojunction effectively separated the photogenerated electrons and holes, and improved the photoelectric conversion efficiency, offering a strong initial photocurrent signal during PEC biosensing. Meanwhile, the porous PCN-224 acted as a nimble nanocontainer that encapsulated glucose using a capture probe (CP). In the presence of miRNA-21, the CP formed a CP-miRNA-21 complex and then detached from PCN-224, controllably releasing the trapped glucose. The oxidization of glucose by glucose oxidase resulted in hydrogen peroxide generation, which acted as a scavenger for the holes generated on the surface of Ti3C2/MgIn2S4, and significantly enhanced the photocurrent response under visible light irradiation. Finally, the sensor exhibited good performance for miRNA-21 detection with a low detection limit (0.17 fM) and wide linearity range (0.5 fM-1.0 nM). Thus, the proposed Ti3C2/MgIn2S4-based split-type PEC sensor is a promising tool for sensitive and accurate detection of miRNA-21 and provides an innovative basis for the preparation of other high-performance sensors.