Dimeric G-Quadruplex: An Efficient Probe for Ultrasensitive Fluorescence Detection of Mustard Compounds.

Some mustard compounds (mustards) are highly toxic chemical warfare agents. Some are explored as new anticancer drugs. Therefore, the fast, selective, and sensitive detection of mustards is extremely important for public security and cancer therapy. Mustards mostly target the N7 position on the guanine bases of DNA. The guanine-rich G-quadruplex DNA (G4) has been widely studied in the sensing area, and it was found that dimeric G4 (D-G4) could dramatically light up the fluorescence intensity of thioflavin T (ThT). Based on this, we used for the first time the D-G4 DNA as a selective probe for ultrasensitive fluorescence detection of nitrogen mustard (NM). When NM occupies the N7 on guanine, it can block the formation of the D-G4 structure due to the steric hindrance, and hence, it inhibits the combination of D-G4 with ThT, leading to a sharp decrease of fluorescence intensity. The proposed reaction mechanism is proved using ultraviolet-visible (UV-Vis) spectra, circular dichroism (CD) spectra, and polyacrylamide gel electrophoresis. Herein, the concentration of D-G4/ThT used is as low as 50 nM due to its highly fluorescent performance, enabling both high sensitivity and low cost. NM can be detected with a wide linear range from 10 to 2000 nM. The detection limit of NM reaches a surprisingly low concentration of 6 nM, which is 2 or 3 orders of magnitude lower than that of previously developed fluorescence methods for mustards and simulants.

Single-Electrode Electrochemical System for the Visual and High-Throughput Electrochemiluminescence Immunoassay.

The electrochemiluminescence (ECL) immunoassay with its visual and high-throughput detection has received considerable attention in the past decade. However, the development of a facile and cost-effective ECL device is still a great challenge. Herein, a single-electrode electrochemical system (SEES) for the visual and high-throughput ECL immunoassay was developed. The SEES was designed by attaching a plastic sticker with multiple holes onto a single carbon ink screen-printed electrode based on a resistance-induced potential difference. Due to its excellent properties of adsorption and bioaffinity, the carbon ink screen-printed electrode is applied to immobilize antibodies. When cardiac troponin I (cTnI), a specific biomarker of acute myocardial infarction, is present, it will be captured by the immobilized cTnI antibodies on the electrode surface, inhibiting electron transfer, resulting in a decrease of the ECL intensity of the luminol-H2O2 system. Using a smartphone as the detector, cTnI could be determined, ranging from 1 to 1000 ng mL-1, with a detection limit of 0.94 ng mL-1. The SEES based on the carbon ink screen-printed electrode is characterized by its high simplicity, cost effectiveness, and user-friendliness compared with conventional three-electrode systems and bipolar electrochemical systems using electrode arrays and shows superior advantages over other immunoassay strategies, with the elimination of multistep assembling and labeling processes. What is more, the fabricated SEES holds great potential in the point-of-care testing due to its tiny size and the combination of a smartphone detector.

Rational Design of Electrochemiluminescent Devices.

Electrochemiluminescence (ECL) is a light-emitting process which combines the intriguing merits of both electrochemical and chemiluminescent methods. It is an extensively used method especially in clinical analysis and biological research due to its high sensitivity, wide dynamic range, and good reliability. ECL devices are critical for the development and applications of ECL. Much effort has been expended to improve the sensitivity, portability, affordability, and throughput of new ECL devices, which allow ECL to adapt broad usage scenarios.In this Account, we summarize our efforts on the recent development of ECL devices including new electrodes, ECL devices based on a wireless power transfer (WPT) technique, and novel bipolar electrochemistry. As the essential components in the ECL devices, electrodes play an important role in ECL detection. We have significantly improved the sensitivity of luminol ECL detection of H2O2 by using a stainless steel electrode. By using semiconductor materials (e.g., silicon and BiVO4), we have exploited photoinduced ECL to generate intense emission at much lower potentials upon illumination. For convenience, portability, and disposability, ECL devices based on cheap WPT devices have been designed. A small diode has been employed to rectify alternating current into direct current to dramatically enhance ECL intensity, enabling sensitive ECL detection using a smart phone as a detector. Finally, we have developed several ECL devices based on bipolar electrochemistry in view of the convenience of multiplex ECL sensing using a bipolar electrode (BPE). On the basis of the wireless feature of BPE, we have employed movable BPEs (e.g., BPE swimmers and magnetic rotating BPE) for deep exploration of the motional and ECL properties of dynamic BPE systems. To make full use of the ECL solution, we have dispersed numerous micro-/nano-BPEs in solution to produce intense 3D ECL in the entire solution, instead of 2D ECL in conventional ECL devices. In addition, the interference of ECL noise from driving electrodes was minimized by introducing the stainless steel with a passivation layer as the driving electrode. To eliminate the need for the fabrication of electrode arrays and the interference from the driving electrode and to decrease the applied voltage, we develop a new-type BPE device consisting of a single-electrode electrochemical system (SEES) based on a resistance-induced potential difference. The SEES is fabricated easily by attaching a multiperforated plate to a single film electrode. It enables the simultaneous detection of many samples and analytes using only a single film electrode (e.g., screen-printed electrode) instead of electrode arrays. It is of great potential in clinical analysis especially for multiple-biomarker detection, drug screening, and biological studies. Looking forward, we believe that more ECL devices and related ECL materials and detection methods will be developed for a wide range of applications, such as in vitro diagnosis, point-of-care testing, high-throughput analysis, drug screening, biological study, and mechanism investigation.

Sonochemiluminescence Using Apertureless USB Piezoelectric Ultrasonic Transducer and Its Applications for the Detection of Hydrogen Peroxide, Glucose, and Glucose Oxidase Activity.

The mesh-type USB piezoelectric ultrasonic transducer (USB-PUT) used in household humidifiers and inhalation therapy devices is very cheap, small, and energy saving. It holds great promise for sonochemistry. However, the microtapered apertures in the center of the stainless steel substrate of mesh-type USB-PUT can lead to rapid atomization of solution, leakage of solutions containing surfactants and organic solvent through the apertures, and high background emission. Herein, we design a new type of USB-PUT by replacing the meshed stainless steel substrate with an apertureless stainless steel substrate. We have found that this apertureless USB-PUT can not only induce intense sonochemiluminescence (SCL) but can also enable sensitive luminol SCL detection of hydrogen peroxide which is practically impossible using mesh-type PUT because of the strong background SCL emission. By using this apertureless device to induce SCL and using smart phone as a detector, a visual hydrogen peroxide SCL detection method with a linear range of 0.5-50 µM and a detection limit of 0.32 µM is established. Moreover, the device can achieve the detection of glucose oxidase (GOD) activity and glucose by enzymatic conversion of glucose to hydrogen peroxide. The linear range of GOD detection is 1-200U/L with a detection limit of 0.86 U/L. The linear range of glucose detection is 0.5-70 µM with a detection limit of 0.43 µM. The cheap (a few dollars) and user-friendly apertureless USB-PUT is promising for sonochemistry applications and chemical education.

Sonochemiluminescence Based on a Small, Cheap, and Low-Power USB Mesh-Type Piezoelectric Ultrasonic Transducer.

A small, cheap, and low-power mesh-type piezoelectric ultrasonic transducer (MPUT) from a household USB humidifier has been developed as a sonochemiluminescence generator for the first time. The ultrasonication of an MPUT facilitates the generation of reactive oxygen species to trigger sonochemiluminescence. There is no light emission of luminol without sonication. In contrast, the luminescence becomes very intense by ultrasonication using the MPUT and can be readily observed by a smart phone, enabling the visual detection of luminol without adding any coreactants. Interestingly, ascorbic acid, a common chemiluminescence quencher in the literature, increases the sonochemiluminescence in this system. As a result, a sensitive sonochemiluminescence method has been developed for the visual detection of ascorbic acid with a linear range of 1-40 µM and a limit of detection (LOD) of 0.35 µM. Moreover, the visual detection of superoxide dismutase has been achieved on the basis of its quenching effect, which has a linear range of 0.05-2.0 µg/mL and a LOD of 0.018 µg/mL. Because of its advantages of low cost, small size, and low-power consumption, the USB MPUT holds great potential in sonochemiluminescence (SCL) for the development of portable and disposable analysis devices in point-of-care testing and field analysis as well as chemical education.

Heptacyclic aromatic hydrocarbon isomers with two azulene units fused.

Azulene, known for its unique electronic properties and structural asymmetry, serves as a promising building block for the design of novel non-benzenoid polycyclic aromatic hydrocarbons (PAHs). Herein, we present the synthesis, characterization, and physical properties of three diazulene-fused heptacyclic aromatic hydrocarbons, 8,17-dioctyldiazuleno[2,1-a:2',1'-h]anthracene (trans configuration), 16,18-dioctyldiazuleno[2,1-a:1',2'-j]anthracene (cis configuration) and 3,18-dioctyldiazuleno[2,1-a:1',2'-i]phenanthrene (zigzag configuration). Three compounds are configurational isomers with different fusing patterns of aromatic rings. All three isomers exhibit pronounced aromaticity, as revealed by nuclear magnetic resonance spectroscopy and theoretical calculations. They exhibit characteristics of both azulene and benzenoid PAHs and are much more stable than their all-benzene analogues. The optical and electrochemical properties of these three isomers were investigated through UV-vis absorption spectra and cyclic voltammetry, revealing distinct behaviors influenced by their molecular configurations. Furthermore, the isomer in trans configuration exhibits promising semiconducting properties with a hole mobility of up to 0.22 cm2 V-1 s-1, indicating its potential in organic electronics applications.

Development of luminol-fluorescamine-PVP chemiluminescence system and its application to sensitive tyrosinase determination.

Fluorescamine is a popular fluorescent probe. We report for the first time that luminol chemiluminescence (CL) can be enhanced by fluorescamine in the presence of PVP. The CL intensity of luminol-fluorescamine-PVP is about 26 times stronger than that of luminol. Both the removal of oxygen and the addition of superoxide dismutase (SOD) decrease CL intensity, thiourea and NaN3 have little effect on CL intensities, indicating that O2•- is critical for CL. Interestingly, o-quinone generated from phenol by tyrosinase obviously inhibited the CL intensity. Inspired by such quenching effect on the luminol-fluorescamine-PVP CL system, a sensitive CL sensing for the determination of tyrosinase activity was developed. The method can detect tyrosinase in the range of 0.07-1.5 µg mL-1 (0.19-4.02 U mL-1) with the detection limit of 0.035 µg mL-1 (0.094 U mL-1). Moreover, this method exhibits satisfied recoveries for the spiked human serum samples.