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DNA hydrogel represents a noteworthy biomaterial. The preparation of biosensors by combining DNA hydrogel with electrochemiluminescence can simplify the modification process and raise the experimental efficiency. In this study, an electrochemiluminescence (ECL) biosensor based on DNA hydrogel was fabricated to detect adenosine triphosphate (ATP) simply and quickly. CdTe-Ru@SiO 2 nanospheres capable of ECL resonance energy transfer (RET) were synthesized and encapsulated CdTe-Ru@SiO 2 in the DNA hydrogel to provide strong and stable ECL signals. DNA hydrogel avoided the labeling of ECL signal molecules. The aptamer of ATP as the linker of the hydrogel for the specificity of ATP detection. The cross-linked structure of the aptamer and the polymer chains was opened by ATP, and then the decomposition of the DNA hydrogel initiated the escape of CdTe-Ru@SiO 2 to generate an ECL signal. The designed biosensor detected ATP without too much modification and complex experimental steps on the electrode surface, with good specificity and stability, and a wide linear range. The detection range was 10-5000 nM, and the detection limit was 6.68 nM (S/N = 3). The combination of DNA hydrogel and ECL biosensor provided a new way for clinical detection of ATP and other biomolecule., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The occurrence of Alzheimer's disease (AD) is strongly associated with the progressive aggregation of a 42-amino-acid fragment derived from the amyloid-β precursor protein (Aβ 1-42 ). Therefore, it is crucial to establish a versatile platform that can effectively detect Aβ 1-42 to aid in the early-stage preclinical diagnosis of AD. Herein, we introduce a specialized split-type analytical platform that enables sensitive and accurate monitoring of Aβ 1-42 based on a self-corrected photoelectrochemical (PEC) sensing system. To realize this design, gelatinized Ti 3 C 2 @Bi 2 WO 6 Schottky heterojunctions were prepared and served as photoelectrodes for tackling the photoinduced charge carriers. Functionalized CaCO 3 @CuO 2 nanocomposites were used as signal converters to detect Aβ 1-42 and amplify the signal further. Benefiting from the glucose oxidation induced acid microenvironment and H 2 O 2 output, the nanocomposites are able to rapidly decompose, producing Ca 2+ and Fenton-like catalyst Cu 2+ . The Cu 2+ -driven Fenton-like reaction generated ·OH, which accelerated the 3,3',5,5'-tetramethylbenzidine (TMB) oxidation. Additionally, Ca 2+ was cross-linked with alginate inducing gelation on the surface of Ti 3 C 2 @Bi 2 WO 6 Schottky heterojunctions, influencing mass transfer and light absorption. Eventually results in the shift of photocurrent, allowing for precise quantification with a detection limit of 0.06 pg mL -1 . The combination of colorimetric variation and the photoelectric effect provide a more accurate and reliable result. This research opens up new possibilities for constructing PEC platforms and beyond., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

As a unique class of dynamic nanostructures, biomimetic DNA walking machines that exhibit geometrical complexity and nanometre precision have gained great success in photoelectrochemical (PEC) bioanalysis. Despite certain achievements, the slow reaction kinetics and low processivity severely restrict the amplification efficiency of the DNA walker-mediated biosensors. Herein, by taking advantage of efficient DNA rolling machines, a three-dimensional (3D) DNA nanomachine-mediated paper-based PEC device for speedy ultrasensitive detection of miR-486-5p was successfully constructed. To achieve it, a novel In 2 S 3 /SnS 2 sensitized heterojunction was firstly in-situ grown on the Au-modified paper fibers and implemented as the photoanode with effective separation of photogenerated carriers to achieve an enhanced initial photocurrent. Subsequently, the copper hexacyanoferrate(II)-modified CuO nanosphere was introduced as a multifunctional signal regulator via the competitive capture of electron donors and photon energy with the photoelectric layer for efficiently quenching the PEC signal. With the introduction of targets, the DNAzyme-driven DNA nanomachine with editable motion modes was gradually activated and it could continuously cleave the tracks DNA labeled quenching probes, finally achieving the recovery of PEC signal. As a proof of concept, the elaborated paper-based PEC device presented a wide linear range from 0.1 fM to 100 pM and a detection limit of 35 aM for miR-486-5p bioassay. This work provides an innovative insight to the exploitation of DNA nanobiotechnology and nucleic acid signal amplification strategy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Ready-to-use in vitro diagnosis of multiple genotypes is vital for the prevention and treatment of cervical cancer. Herein, a paper-film-based interactive dual readout differential lateral flow biosensor is proposed to simultaneously assay two high-risk types of human papillomavirus (HPV) within the body-fluid. The CuCo 2 S 4 /ZnIn 2 S 4 heterostructure is fabricated on the paper-film compound chip with high thermostability, and surface sulfur vacancy is introduced by mild annealing treatment to endow unexceptionable photoexcitation activity, such structure can be served as an initial energy harvester and converter. With the assistance of differential channels, the dual-target-propelled self-assembly of annular DNA and the cleavage activity of CRISPR-Cas12a are stepwise activated by sequential solution transfer. Accordingly, the input and release of polydopamine-coated gold nanoparticles with photothermal/photoelectric characteristic were implemented. The fabricated biosensor not only realized intelligent thermal-response without large instruments, but also actuated dynamic interfacial charge separation and transfer kinetics to further transmit photoelectric-signal, resulting in desirable interactive dual-signal with low limit-of-detection (0.21 pM for HPV-18 and 42.92 pM for HPV-16). Thanks to the sophisticated design of differential lateral flow paper-film compound chip and interactive dual-signal amplification strategy, sensitive detection of two HPV genotypes is realized, which provides a promising candidate for home medical intelligent diagnosis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Circulating tumour DNAs (ctDNAs) have been reported to be associated with real-time information of progression; however, an accurate and sensitive method has not been established. Herein, a novel dual-signal amplification strategy based on a pump-free surface-enhanced Raman scattering (SERS) microfluidic chip and a catalytic hairpin assembly (CHA) technique was developed for the dynamic monitoring of BRAF V600E and KRAS G12V, which are two non-small cell lung cancer (NSCLC)-related ctDNAs. In the presence of targets, CHA reactions can be triggered between two hairpin DNAs, fixing Pd-Au core-shell nanorods (Pd-AuNRs) onto the magnetic beads (MBs) surface. Thereafter, the composite structures can assemble under the action of magnet, enabling dual-amplification of SERS signal. Using this strategy, the limit of detection (LOD) was low (i.e. at the aM level) in serum. Furthermore, the entire chip-based analysis process could be completed within 5 min, eliminating manual incubation and heavy-duty injection pumps. The selectivity, reproducibility and uniformity of the proposed pump-free SERS microfluidic chip were satisfactory. This superior analysis strategy was finally applied to quantify BRAF V600E and KRAS G12V in tumour-bearing nude mice serum, the results of which corresponded with those of real-time polymerase chain reaction. Overall, this study provides a promising alternative tool for the dynamic monitoring of ctDNA expression level which can benefit the clinical diagnosis of NSCLC., (Copyright © 2022 Elsevier B.V. All rights reserved.)

SARS-CoV-2 variants of concern (VOCs) contain several single-nucleotide variants (SNVs) at key sites in the receptor-binding region (RBD) that enhance infectivity and transmission, as well as cause immune escape, resulting in an aggravation of the coronavirus disease 2019 (COVID-19) pandemic. Emerging VOCs have sparked the need for a diagnostic method capable of simultaneously monitoring these SNVs. To date, no highly sensitive, efficient clinical tool exists to monitor SNVs simultaneously. Here, an encodable multiplex microsphere-phase amplification (MMPA) sensing platform that combines primer-coded microsphere technology with dual fluorescence decoding strategy to detect SARS-CoV-2 RNA and simultaneously identify 10 key SNVs in the RBD. MMPA limits the amplification refractory mutation system PCR (ARMS-PCR) reaction for specific target sequence to the surface of a microsphere with specific fluorescence coding. This effectively solves the problem of non-specific amplification among primers and probes in multiplex PCR. For signal detection, specific fluorescence codes inside microspheres are used to determine the corresponding relationship between the microspheres and the SNV sites, while the report probes hybridized with PCR products are used to detect the microsphere amplification intensity. The MMPA platform offers a lower SARS-CoV-2 RNA detection limit of 28 copies/reaction, the ability to detect a respiratory pathogen panel without cross-reactivity, and a SNV analysis accuracy level comparable to that of sequencing. Moreover, this super-multiple parallel SNVs detection method enables a timely updating of the panel of detected SNVs that accompanies changing VOCs, and presents a clinical availability that traditional sequencing methods do not., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Exploring novel photoactive materials with high photoelectric conversion efficiency plays a crucial role in enhancing the analytical performance of paper-based photoelectrochemical (PEC) biosensor. SnO 2 , which possesses higher photostability and electron mobility, can be regarded as a promising photoactive material. Herein, paper-based one dimensional (1D) domed SnO 2 nanotubes (NTs) have been developed with the template-consumption strategy. What's more, their growth mechanism has also been proposed based on the controllable experiments. At first, the paper-based 1D ZnO nanorods (NRs) as the typical amphoteric oxide are prepared and serve as the sacrifice templates which can be etched by the generated alkaline environment during the formation of SnO 2 . At a certain stage, all the ZnO NRs can be completely etched by controlling the experimental conditions, resulting in the forming of vertically distributed hollow SnO 2 NTs. Furthermore, the Sn self-doping strategy is also proposed to suppress the recombination of charge carriers and broaden the light response range by introducing the impurity energy levels. Profiting from such doping strategy, the prominent photocurrent signal is obtained compared with pure paper-based SnO 2 NTs. Ultimately, an innovative visible light responsive paper-based Sn-doping SnO 2-x NTs are developed and employed as the photoelectrode for the PEC biosensor using the alpha fetoprotein (AFP) as the model analyte. Under the optimal conditions, the ultrasensitive AFP sensing is realized with the linear range and detection limitation of 10 pg mL -1 to 200 ng mL -1 and 3.84 pg mL -1 , respectively. This work provides a judiciously strategy for developing novel photoactive materials for paper-based PEC bioanalysis., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This paper introduces a paper-based closed Au-bipolar electrode (BPE) biosensing system for the rapid and sensitive electrochemiluminescence (ECL) detection of miRNA-155. This microfluidic paper-based sensing platform is formed by wax-printing technology, screen printing method and in-situ Au nanoparticles (NPs) growth to form hydrophilic cells, hydrophobic boundaries, water proof electronic bridge, driving electrode regions and bipolar electrode regions. For rapid and sensitive detection, the cathode of bipolar electrode was modified with the prepared DNA (S1)-AuPd NPs by hybridization chain reaction, in which the target could initiate multiple cycles reaction to load more AuPd NPs which catalyzed H 2 O 2 reduction. In addition, a classical ECL system tris (2,2'-bipyridine) ruthenium (II)- tripropylamine (Ru(bpy) 3 2+ /TPrA) exists at the anode of the bipolar electrode. Due to the charge balance between the anode and the cathode of BPE, the ECL signal response of Ru(bpy) 3 2+ /TPrA system was enhanced in the reporting cell. The intensity of ECL was quantitatively correlated with the concentration of miRNA-155 in the range of 1 pM-10 μM with the detection limit 0.67 pM. Moreover, this method paves a novel way for highly sensitive detection of miRNA-155 in clinical application., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, a peptide-based photoelectrochemical (PEC) biosensor was constructed based on CdTe/TiO 2 sensitized structure as electrode and CuS nanocrystals as signal amplifier for the ultrasensitive detection of protein. After peptide was fixed to the CdTe/TiO 2 electrode surface, the double-helix DNA (dsDNA) was immobilized at the end of the peptide and used as a carrier to immobilize the doxorubicin-copper sulfide nanocrystals (Dox-CuS) conjugates. As a proof of concept, prostate specific antigen (PSA) has been chosen as the model. In absence of PSA, CuS nanocrystals could consume electron donors and exciting light energy. Additionally, the steric hindrance effect of biomacromolecules hindered the movement of electron donors to the photoelectrode. Eventually, the photoelectric response signal was reduced, and the biosensor was in a "signal off" state. When PSA existed, the PSA specifically cleaved the peptide, and DNA/Dox-CuS probes were released from the electrode surface, resulting in a "signal on" state. The PEC biosensor revealed good specificity, stability, and reproducibility, and it exhibited excellent application in PSA analysis with a linear range from 0.005 to 20 ng mL -1 and a low detection limit of 0.0015 ng mL -1 . This PEC biosensor may have potential applications in bioanalysis, disease diagnostics, and clinical biomedicine., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A self-powered origami paper-based analytical device (oPAD), being with a pop-up structure as mechanical valve to first realize dual-mode of differential pulse voltammery (DPV)/supercapacitor amplified signal read out systems, was designed for detecting adenosine 5'-triphosphate (ATP) assisted by glucose oxidase (GOx)-triggered reaction. In order to accommodate the alternative step for dual-mode detection, a pop-up structure inspired by pop-up greeting cards was developed, making it possible to change the fluidic path with good registration and repeatability. To realize supercapacitor detection mode, a sandwich structure of a DNA sequence (DNA1), aptamer and a DNA sequence modified with GOx (GOx-DNA2) was formed on detection zone by hybridization reaction. With the addition of ATP, the GOx-DNA2 could be released with the specific binding between ATP and aptamer, and flowed into the reaction zone to catalyze the oxidation of glucose. Due to the difference in concentrations of [Fe(CN) 6 ] 3- and [Fe(CN) 6 ] 4- caused by the GOx-triggered reaction, a voltage could be produced to charge a paper supercapacitor which could provide a high instantaneous current with a digital multimeter to transduce the result of the assay, and realize the self-generation of an amplified electrical signal. By simply varying the direction of pop-up structure, the electrochemical signal from DPV read out mode could be achieved through catalytic oxidation of glucose by the remaining GOx-DNA2 on the detection zone. The proposed self-powered oPAD enabled the sensitive diagnosis of ATP in a linear range of 10-5000 nM with a limit of detection of 3 nM and 1.4 nM, respectively., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, an ultrasensitive photoelectrochemical (PEC) biosensor was proposed to detect nucleic acids on the basis of cascaded photoactive materials and triple-helix molecular switch. DNA sequence of human immunodeficiency virus type 1 (HIV-1) was chosen as the target DNA (T-DNA). Cascaded photoactive structure was formed via different sizes of CdTe quantum dots (QDs) sensitized ZnO nanorods (ZnO NRs), which was employed as a cascaded photoactive interface to amplify the photocurrent signal. A hairpin structure DNA (H-DNA) as capture probe was conjugated onto the photoactive interface through amide bond, and then a single-stranded DNA modified with gold nanoparticles labeled alkaline phosphatase (ALP-Au NPs-DNA) at each end was introduced to hybridize with the H-DNA to form a triple-helix conformation. The T-DNA detection was based on the photocurrent response change resulted from conformation change of the triple-helix molecule after hybridization with T-DNA. In the absence of T-DNA, the triple-helix molecule was in a closed state and the ALP of ALP-Au NPs-DNA could specifically catalyze the ascorbic acid 2-phosphate (AAP) to generate ascorbic acid (AA) as electron donors, which resulted in a significant photocurrent response due to the rapid electron transfer process. However, in the presence of T-DNA, the T-DNA hybridized with the ALP-Au NPs-DNA molecule, which caused triple-helix molecule in an opened state and compelled ALP-Au NPs-DNA away from the electrode surface, resulting in the absence of ALP which could catalyze AAP to generate AA. Subsequently, the photocurrent response significantly decreased. The proposed PEC biosensor not only had a wide detection range of 1fM-1nM and low detection limit (0.65 fM), but also showed excellent reproducibility, specificity and stability, which had great application prospect and opened up a new research method in the early clinical diagnosis and cancer research., (Copyright © 2019. Published by Elsevier B.V.)

Inspired by the design of folding greeting cards and tissue drawing covers, a photoelectrochemical (PEC) lab-on-paper device with a controllable fluid separator, producing both reaction zone and detection zone, was explored for ultrasensitive detection of adenosine 5'-triphosphate (ATP) via mimic peroxidase-transfer enhancement of photocurrent response. To realize it, the DNA1, aptamer, and DNA2 as well as the mimic peroxidase of G-quadruplex/hemin modified Au nanocubes were linked on the graphene oxide-functionalized reaction zone via the DNA hybridization. Meanwhile, three-dimensional CuO nanoflowers (CuO NFs) as a photoactive material with outstanding electron transfer ability and absorption of light were grown in situ on the detection zone, providing a PEC active interface. Besides, an innovative fluid separator was elaborately designed by assembling a strip of paper with a hydrophilic channel, providing an effective way to bridge the gap between the two zones with a controllable drawing way, which could successfully avoid the signal interference caused by modifying biomolecules layer by layer on photosensitive materials. In the presence of ATP, the G-quadruplex/hemin modified in the reaction zone was dissociated due to the specific recognition of ATP with aptamer and released into the detection zone with the assistance of controllable fluid separator. The free G-quadruplex/hemin could catalyze hydrogen peroxide to generate oxygen for the consumption of photo-induced electrons from CuO NFs, which could further promote the electron-hole carriers separation efficiency, and eventually resulting in the enhancement of PEC signal. The proposed PEC lab-on-paper device could be employed for specific detection of ATP in the range from 5.0 to 3.0 × 10 3 nM with a detection limit of 2.1 nM., (Copyright © 2019 Elsevier B.V. All rights reserved.)

By controlling target-induced signal quencher release, a label-free and modification-free microfluidic paper based photoelectrochemical analytical device (μ-PAD) for cardiac troponin-I (cTnI) detection was designed for the first time. To achieve it, cellulose paper based single-crystalline three-dimensional aloe like TiO 2 arrays (PSATs) were firstly fabricated as the electron transporting material, providing direct pathways for the charge carriers transfer, and subsequently coupled with CdS to form PSATs/CdS heterojunction for extending the solar spectrum response. Meanwhile, positive charged mesoporous silica nanoparticles (PMSNs) were prepared as the nanocarrier to efficient entrap the Cu 2+ which could be regarded as signal quencher due to their reaction with CdS to form Cu x S. Single stranded DNAs (ssDNAs), which could bind specifically with the target of cTnI, were then introduced to couple with the PMSNs and used as the bio-gate to encapsulate the signal quencher of Cu 2+ , endowing the functional PMSNs with responsiveness to cTnI. When the cTnI existed, the ssDNAs were dissociated from PMSNs due to the formation of cTnI-ssDNAs complexes, triggering controllable release of the trapped Cu 2+ , and further decreasing the photocurrent signal caused by the formation of Cu x S. Accordingly, the concentration of cTnI could be accurately quantified via the photocurrent, realizing the target-induced modification-free μ-PAD assay. We believe this work could provide an ingenious idea to construct the easy-to-use novel modification-free μ-PAD., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Inspired by the pop-up greeting cards, a 3D collapsible auto-cleaning paper-based electrochemiluminescence (ECL) biosensor (CAPEB) with different functions of signal collection and residual multiple cleaning, is developed for sensitive detection of Ni 2+ and Hg 2+ by simply regulating its 3D configurations. The multiple fluidic paths and the hollow-channel structure were firstly integrated into the paper substrate, realizing simultaneously repetitive auto-cleaning of the two working electrodes. For achieving ultrasensitive Ni 2+ and Hg 2+ monitoring, binary catalysis consisting of the intermolecular co-reaction (H 2 O 2 and N-(4-Aminobutyl)-N-ethylisoluminol (ABEI)) and intramolecular catalysis (polyethyleneimine (PEI)-ABEI) was introduced. Specifically, silver nanospheres with a large specific surface area and excellent conductivity were grown on the paper working electrode and served as the sensor substrate for fixing PEI-ABEI and Ni 2+ -specific DNAzyme. With the assistance of DNAzyme, Cu 2 O-Au and ferrocene (Fc) labeled strand S2 were immobilized on electrode surface through the hybridization reaction, and catalyzed H 2 O 2 to generate reactive oxygen species, promoting the luminescence of ABEI. In the existence of Ni 2+ , DNAzyme was activated followed by cleavage of strand S2 to induce the release of Fc, which quenched the ECL signal of ABEI, eventually realizing the detection of Ni 2+ . Similarly, for sensitive quantification of Hg 2+ , full thymine (T) bases strand S3 was modified on surface of Cu 2 O-Au and anchored Hg 2+ by T-Hg 2+ -T pairing interaction. The ECL intensity was decreased along with increasing of Hg 2+ due to the quenching effect of Hg 2+ on ECL emission of ABEI. Based on this ingenious system, the detection of Ni 2+ and Hg 2+ had high sensitivity, wide linear ranges, and low detection limits. The results indicated that the integration of a multi-channel structure into a paper device chips opened new opportunities for designing promising paper-based devices for metal ions diagnosis., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The construction of a photoelectrochemical (PEC) strategy for multi-component detection represents a great challenge in the field of sensing. To address these challenges, herein we presented a hollow-channel paper-based PEC analytical platform based on chemiluminescence (CL) addressable strategies excited PEC strategy for multiplexed sensing application. Sandwich-structured CdS quantum dots (QDs)/reduced graphene oxide (RGO)/ZnO nanorods arrays (NRAs) heterostructure where CdS serves as visible light sensitizers, RGO acts as an electron relay between ZnO NRAs and CdS QDs, were simply assembled on the gold nanoparticles modified paper working photoelectrode (Au-PWE). The PEC performance of the CdS/RGO/ZnO can be greatly improved benefiting from the formation of type II band alignment between CdS QDs and ZnO NR as well as the super charge collection and shuttling property of RGO. Multiplexed CL emission could be achieved through controlling the CL co-reagents transport. By the virtue of CL addressable technique and the excellent PEC activity of CdS/RGO/ZnO, a highly sensitive, and selective multiple microRNAs (miRNAs) quantification method was achieved. Such a tailored strategy would break the bottleneck of the current PEC detection techniques in multiplex tracing, as well as serve as a novel concept for designing multi-channel PEC sensing method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The photoelectrochemical (PEC) technique has resulted in substantial progress in chemical sensing applications. However the complicated photoelectrode modification procedures would enable undesired background noise and decreasing sensitivity. Hence, it is important to explore a new approach alternative to inconvenient substrate modification. Herein, inspired by the stimuli-responsive drug delivery systems, an innovative PEC system is developed for efficiently microRNA-21 (miRNA-21) tracing. Hierarchical nanocomposites based on hematite (α-Fe 2 O 3 ) coated self-ordered titanium dioxide nanorod arrays (TiO 2 NRAs) exhibited enhanced response to solar light, promoted charge carrier separation and transfer efficiency was adopted as photoelectrode directly. Functional mesoporous silica nanomaterial (MSN) is prepared as nanocarriers for efficient loading of Cu 2+ , further capped with miRNA-21 responsive capture RNA probe. Thereafter, the capture RNA probe endows the functional MSN with responsiveness to miRNA-21. With the presence of miRNA-21, this system is thus triggered and a quickly release of capped Cu 2+ occurs due to the dissociation of capture RNA probe presented on the MSN surface via base-pair hybridization. The released Cu 2+ was then served as electron acceptor reduced to Cu° at the counter electrode to enhance electron-hole pair separation efficiency, leading to a promoted photocurrent response. Consequently, the miRNA-21 can be accurately quantified. Taking advantage of its sensitivity and specificity, this versatile strategy demonstrates a new route for the design PEC sensing approach without any photoelectrode modification procedure, and holds great potential for biosensing and clinical diagnosis., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A novel dual-mode cytosensor based on polyhedral AuPd alloy nanoparticles (PH-AuPd NPs) and three-dimentional reduced graphene oxide (3D-rGO) was constructed for highly sensitive detection of MCF-7 cells. The 3D-rGO was in situ synthesized on the paper working electrode (PWE) by a pollution-free hydrothermal method, increasing the specific surface area and further facilitating the modification of Au nanoparticles (AuNPs). After modified with AuNPs, the Au@ 3D-rGO/PWE was then functionalized by aptamer H1 to trap MCF-7 cells. To construct the cytosensor, PH-AuPd NPs was prepared as a novel catalytic material, and further modified with aptamer H2 for recognizing MCF-7 cells. With the occurrence of efficient recognition of MCF-7 cells, PH-AuPd NPs were bound onto the surface of the cells, and could catalyze H 2 O 2 to generate •OH, leading to an amplified electrochemical signal. Meanwhile, as the electrolyte solution flowed, the •OH are transferred outward to the colorimetric detection zone, and catalyzed a chromogenic substrate TMB forms a colored product. The electrical signal measurement and colorimetric detection were carried out on a compatibly designed lab-on-paper device (LPD), realizing a dual-mode signal readout. This paper-based dual-mode cytosensor provided a relatively low detection limit of 20 cells mL -1 and a sensitive detection from 50 cells mL -1 to 10 7 cells mL -1 for MCF-7 cells, providing a reliable pathway of sensitively detecting cancer cells in clinical applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this work, an electrochemical biosensor based on Au nanorods (NRs) modified microfluidic paper-based analytical devices (μPADs) were constructed for sensitive detection of microRNA (miRNA) by using cerium dioxide - Au@glucose oxidase (CeO 2 -Au@GOx) as an electrochemical probe for signal amplification. Au NRs were synthesized by in-situ growth method in μPADs surface to enhance the conductivity and modified hairpin probe through Au-S bonds. The construction of "the signal transducer layer" was carried out by GOx catalyzing glucose to produce H 2 O 2 , which was further electrocatalyzed by CeO 2 . After the biosensor was constructed, an obvious electrochemical signal was observed from the reduction of H 2 O 2 . In order to make the detection more convincing, the visual detection was performed based on the oxidation of 3,3',5,5'-tetramethylbenzidine by H 2 O 2 with the help of Exonuclease I. The electrochemical biosensor provided a wide linear range of 1.0fM to 1000fM with a relatively low detection limit of 0.434fM by the electrochemical measurement. Linear range of 10fM to 1000fM with a relatively low detection limit of 7.382fM was obtained by visual detection. The results indicated the proposed platform has potential utility for detection of miRNA., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this manuscript, a disposable paper-based analytical device comprised of a closed bipolar electrode (BPE) was fabricated for the ultrasensitive electrochemiluminescence (ECL) detection of intracellular H 2 O 2 and the number of cancer cells. In this approach, wax printing was used to fabricated reaction zone, and carbon ink-based BPE and driving electrodes were screen-printed into the paper. AuPd nanoparticles (NPs), which served as a carrier of the capture aptamer and as the catalyst for the ECL reaction of luminol and H 2 O 2 , were used to modify the BPE. Luminol/Au NPs were attached to the surface of the captured cells via hybridation chain reaction with two hairpin structure DNA labelled luminol/Au NPs. In the stimulation of phorbol myristate acetate, The coreactant H 2 O 2 was released from the target cells. The ECL response of the luminol-H 2 O 2 system was related to the number of cancer cells in the testing buffer, which served as a quantitative signal for the determination of cancer cells and the concentration of H 2 O 2 . In order to decrease the external voltage, K 3 [Fe(CN) 6 ] was introduced in the cathode resevoir of BPE because it gained electrons at the cathode more easily than oxygen. The ECL intensity was quantitatively related to the concentration of MCF-7 in the range of 1.0 × 10 2 -1.0 × 10 7 cells/mL. The detection limit was 40 cells/mL and it showed good specificity for cells with high overexpression of mucin-1 receptor, it was concluded that the developed protocol could be effectively utilized for the detection of MCF-7 cells., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Convenient biosensor for simultaneous multi-analyte detection was increasingly required in biological analysis. A novel flower-like silver (FLS)-enhanced fluorescence/visual bimodal platform for the ultrasensitive detection of multiple miRNAs was successfully constructed for the first time based on the principle of multi-channel microfluidic paper-based analytical devices (µPADs). Fluorophore-functionalized DNA 1 (DNA 1 -N-CDs) was combined with FLS, which was hybridized with quencher-carrying strand (DNA 2 -CeO 2 ) to form FLS-enhanced fluorescence biosensor. Upon the addition of the target miRNA, the fluorescent intensity of DNA 1 -N-CDs within the proximity of the FLS was strengthened. The disengaged DNA/CeO 2 complex could result in color change after joining H 2 O 2 , leading to real-time visual detection of miRNA firstly. If necessary, then the fluorescence method was applied for a accurate determination. In this strategy, the growth of FLS in µPADs not only reduced the background fluorescence but also provided an enrichment of "hot spots" for surface enhanced fluorescence detection of miRNAs. Results also showed versatility of the FLS in the enhancement of sensitivity and selectivity of the miRNA biosensor. Remarkably, this biosensor could detect as low as 0.03fM miRNA210 and 0.06fM miRNA21. Interestingly, the proposed biosensor also possessed good capability of recycling in three cycles upon change of the supplementation of DNA 2 -CeO 2 and visual substitutive device. This method opened new opportunities for further studies of miRNA related bioprocesses and will provide a new instrument for simultaneous detection of multiple low-level biomarkers., (Copyright © 2017 Elsevier B.V. All rights reserved.)

By incorporating the Prussian Blue (PB) electrochromic display as cathode, a solar-driven photoelectrochemical (PEC) cell was constructed through combining sandwich-structured graphite-like carbon nitride (g-C 3 N 4 )-Au-branched-titanium dioxide (B-TiO 2 ) nanorods as photoanode for self-powered hydrogen peroxide (H 2 O 2 ) sensing, which exhibits both direct photoelectrochemical and electrochromic response. The gold nanoparticles (Au NPs) sandwiched between the B-TiO 2 nanorods and the g-C 3 N 4 layer served as electron relay as well as plasmonic photosensitizer to enhance the solar-to-chemical energy conversion efficiency. Owing to the effective disproportionation of H 2 O 2 and specific recognition of mannose on cell surface, concanavalin-A conjugated porous AuPd alloy nanoparticles were introduced as the catalytically active nanolabels promoting generation of hydroxyl radicals (·OH). Based on the cleavage of DNA with the participation of ·OH radicals generated by the decomposition of H 2 O 2 under the catalysis of AuPd alloy result in the disassembly of cancer cells to achieve further signal enhancement. The multiple-signal-output sensing response not only provides a promising strategy for different analytical purposes based on novel stimuli-responsive materials, but also enhances the reliability in the analyte detection., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, based on in situ generation of CdS quantum dots (QDs) on the surface of branched TiO 2 (B-TiO 2 ) nanorods, an solar innovative photoelectrochemical (PEC) sensing platform was constructed for real-time, and sensitive detection of cellular H 2 S. Specifically, B-TiO 2 nanorods arrays consisting of TiO 2 nanorods directly grown on fluorine-doped tin oxide (FTO) further using TiCl 3 mediated surface treatment of TiO 2 nanorods are designed and fabricated as a new type of photoelectrode. CdS quantum dots (QDs) was formed on the surface of B-TiO 2 nanorods arrays through the reaction between Cd 2+ and S 2- . And a significant enhancement in the photocurrent was obtained that ascribed to the formation of CdS-B-TiO 2 heterostructures, thus leading to sensitive PEC recording of the H 2 S level in buffer and cellular environments. By using Prussian blue (PB) a electrochromic material to capture the photoelectron generated from the photoelectrode, a new visual system was proposed due to the formation of Prussian white (PW), which could be used to visualize the quantum photoelectric effect. This novel PEC sensing platform not only achieved satisfied analysis results toward S 2- , but also showed excellent sensitivity, selectivity, low cost, and portable features. The strategy through the in situ generation of semiconductor nanoparticles on the surface of wide band-gap semiconductor paves the way for the improvements of PEC analytical performance. Meanwhile, the quantitative read-out electrochromic display paves a facile avenue and initiates new opportunities for creation of cheap, miniaturization sensors for other relevant analytes., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A highly sensitive electrochemical (EC) biosensor combined with a 3D origami device for detection of Pb 2+ was developed based on novel Au nanoparticles modified paper working electrode (Au-PWE) as sensor platform and DNA functionalized iron-porphyrinic metal-organic framework ((Fe-P)n-MOF-Au-GR) hybrids as signal probes. In the presence of Pb 2+ , GR could be specifically cleaved at the ribonucleotide (rA) site, which produced the short (Fe-P) n -MOF-linked oligonucleotide fragment to hybridize with hairpin DNA immobilized on the surface of Au-PWE. Because of the mimic peroxidase property of (Fe-P) n -MOF, enzymatically amplified electrochemical signal was obtained to offer the sensitive detection of Pb 2+ . In addition, benefiting from the Pb 2+ dependent GR, the proposed assay could selectively detect Pb 2+ in the presence of other metal ions. This method showed a good linear relationship between the current response and the Pb 2+ concentration ranging from 0.03 to 1000nmolL -1 with a detection limit of 0.02nmolL -1 . The Au-PWE based electrochemical sensor along with the (Fe-P) n -MOF-Au-GR probe exhibited the advantages of low-cost, simple fabrication, high sensitivity and selectivity, providing potential application of real-time Pb 2+ detection both in environmental and biological samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A highly sensitive enzyme inhibition analytical platform was established firstly based on paper-supported 3D interwoven AuPd-reduced graphene oxide (rGO) network (NW) for real-time and in situ analysis of H 2 S released from cancer cells. The novel paper working electrode (PWE) with large electric conductivity, effective surface area and unusual biocompatibility, was fabricated via controllably assembling rGO and AuPd alloy nanoparticles onto the surface of cellulose fibers and into the macropores of paper, which was employed as affinity matrix for horseradish peroxidase (HRP) loading and cells capture. It was the superior performances of AuPd-rGO-NW-PWE that made the loaded HRP exhibit excellent electrocatalytic behavior to H 2 O 2 , bring the rapid enhancement of current response. After releasing H 2 S, the current response would be obviously decreased due to the efficient inhibition effect of H 2 S on HRP activity. The inhibition degree of HRP was directly proportional to the amount of H 2 S, and so, the flux of H 2 S released from cells could be recorded availably. Thus, this proposed enzyme inhibition cyto-sensor could be applied for efficient recording of the release of H 2 S, which had potential utility to cellular biology and pathophysiology., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A novel colorimetric/fluorescence bimodal lab-on-paper cyto-device was fabricated based on concanavalin A (Con A)-integrating multibranched hybridization chain reaction (mHCR). The product of mHCR was modified PtCu nanochains (colorimetric signal label) and graphene quantum dot (fluorescence signal label) for in situ and dynamically evaluating cell surface N-glycan expression. In this strategy, preliminary detection was carried out through colorimetric method, if needed, then the fluorescence method was applied for a precise determination. Au-Ag-paper devices increased the surface areas and active sites for immobilizing larger amount of aptamers, and then specifically and efficiently captured more cancer cells. Moreover, it could effectively reduce the paper background fluorescence. Due to the specific recognition of Con A with mannose and the effective signal amplification of mHCR, the proposed strategy exhibited excellent high sensitivity for the cytosensing of MCF-7 cells ranging from 100 to 1.0×10(7) and 80-5.0×10(7) cellsmL(-1) with the detection limit of 33 and 26 cellsmL(-1) for colorimetric and fluorescence, respectively. More importantly, this strategy was successfully applied to dynamically monitor cell-surface multi-glycans expression on living cells under external stimuli of inhibitors as well as for N-glycan expression inhibitor screening. These results implied that this biosensor has potential in studying complex native glycan-related biological processes and elucidating the N-glycan-related diseases in biological and physiological processes., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In situ imaging of miRNA in living cells could help us to monitor the miRNA expression in real time and obtain accurate information for studying miRNA related bioprocesses and disease. Given the low-level expression of miRNA, amplification strategies for intracellular miRNA are imperative. Here, we propose an amplification strategy with a non-destructive enzyme-free manner in living cells using catalyzed hairpin assembly (CHA) based on graphene oxide (GO) for cellular miRNA imaging. The enzyme-free CHA exhibits stringent recognition and excellent signal amplification of miRNA in the living cells. GO is a good candidate as a fluorescence quencher and cellular carrier. Taking the advantages of the CHA and GO, we can monitor the miRNA at low level in living cells with a simple, sensitive and real-time manner. Finally, imaging of miRNAs in the different expression cells is realized. The novel method could supply an effective tool to visualize intracellular low-level miRNAs and help us to further understand the role of miRNAs in cellular processes., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A platelike tungsten trioxide (WO3) sensitized with CdS quantum dots (QDs) heterojunction is developed for solar-driven, real-time, and selective photoelectrochemical (PEC) sensing of H2O2 in the living cells. The structure is synthesized by hydrothermally growing platelike WO3 on fluorine doped tin oxide (FTO) and subsequently sensitized with CdS QDs. The as-prepared WO3-CdS QDs heterojunction achieve significant photocurrent enhancement, which is remarkably beneficial for light absorption and charge carrier separation. Based on the enzymatic etching of CdS QDs enables the activation of quenching the charge transfer efficiency, thus leading to sensitive PEC recording of H2O2 level in buffer and cellular environments. The results indicated that the proposed method will pave the way for the development of excellent PEC sensing platform with the quantum dot sensitization. This study could also provide a new train of thought on designing of self-operating photoanode in PEC sensing, promoting the application of semiconductor nanomaterials in photoelectrochemistry., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A 3D microfluidic paper-based fluorescence analytical device with hollow channels based on the turn-on switching of a resonance energy transfer triggered by the •OH induced cleavage of a DNA strand was successfully constructed. And this fluorescent nanoplatform was first designed to achieve in situ and real-time determination of H2O2 released from cancer cells to obtain an accurate determination. With optimal conditions, the proposed method displayed excellent analytical performance for the detection of H2O2 ranging from 0.3 to 1.0mM with a detection limit of 0.1nM. The favorable performances of this sensor were due to the peroxidase-like activity of nitrogen-doped graphene quantum dots (multilayer porous SiO2 act as stabilizer to load more nitrogen-doped graphene quantum dots for signal amplification) and folic acid-pPdAu/GO (which also could act as an efficient fluorescence quencher and a recognition element of cancer cells by folic acid). It was worth noting that it could be used for visually determined the flux of H2O2 from the cells. Therefore, the developed biosensor holds potential for ultrasensitive quantitative analysis of H2O2 and supplies valuable information for diabetes mellitus research and clinical diagnosis., (Copyright © 2016. Published by Elsevier B.V.)

A multi-amplified paper-based electrochemical strategy using Pb(2+) dependent DNAzyme as the recognition unit for Pb(2+) detection was developed. In this work, flower-like reduced graphene (FrGO) was prepared utilizing flower-like ZnO as template, which was first one step grown on the gold nanoparticles modified paper working electrode (Au-PWE). After being treated with acid and then modified with Au, a novel sensor platform named Au/FrGO/Au-PWE with large specific surface area and good electrical conductivity was fabricated. The Mn2O3 nanoparticle-assembled hierarchical hollow spheres (H-Mn2O3) was served as nanocarrier to immobilize GOx, HRP and signal strand (S3), resulting to the formation of S3/H-Mn2O3/HRP/GOx bioconjugations. In the presence of Pb(2+), the DNAzyme (S1) was activated and the substrate strand (S2) was cleaved. After the incubation with S3/H-Mn2O3/HRP/GOx in 0.1M HAc-NaAc solution (pH 4.3) containing 30 mM aniline and 15 mM glucose, a readily measurable "turn-on" electrochemical signal could be measured. On the basis of the signal amplification strategy of Au/FrGO/Au-PWE sensing platform and S3/H-Mn2O3/HRP/GOx bioconjugations, the developed biosensor exhibited a good linear response toward over a wide range of concentration from 0.005 to 2000 nM., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A highly sensitive and selective turn on fluorescent probe P-acid-aldehyde (P-CHO) is developed for the determination of cysteine (Cys) and homocysteine (Hcy). The probe is designed and synthesized by incorporating the specific functional group aldehyde group for thiols into a stable π-conjugated material 4,4'-(2,5-dimethoxy-1,4-phenylene) bis(ethyne-2,1-diyl) dibenzoic acid (P-acid). The probe fluorescence is quenched through donor photoinduced electron transfer (d-PET) between the fluorophore (P-acid) and the recognition group (aldehyde group). In the presence of thiols, Cys and Hcy can selectively react with aldehyde group of the probe because the inhibition of d-PET between fluorophore and recognition group. Therefore, a turn-on fluorescent sensor was established for the fluorescence recovery. Under the optimized conditions, the fluorescence response of probe is directly proportional to the concentration of Cys in the range of 4-95 NM L(-1), with a detection limit 3.0 nM. In addition, the sensing system exhibits good selectively toward Cys and Hcy in the presence of other amino acids. It has been successfully applied for bioimaging of Cys and Hcy in living cells with low cell toxicity., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Combining multibranched hybridization chain reaction (mHCR), the photoelectrochemical (PEC) immunosensor was fabricated with a microfluidic paper-based analytical devices using different sizes of CdTe quantum dots (QDs) sensitized flower-like 3D ZnO superstructures as photoactive materials. Firstly, 4-aminothiophenol (PATP) functioned ZnO was anchored on gold-paper working electrode. With the aid of PATP, large-sized CdTe-COOH QDs (QDs1) were conjugated onto the ZnO surface because of the formation of a strong bond (Zn-S) between the thiol of PATP molecule and the ZnO, and the remaining amino group formed an amide bond with carboxylic acid group capping CdTe. Then the small-sized CdTe-NH2 QDs (QDs2) were modified on the QDs1 by forming amide bond, which leaded to a very strong photocurrent response because of the formation of cosensitized structure. The designed mHCR produced long products with multiple branched arms, which could attached multiple PdAu nanoparticles and catalyze the oxidation of hydroquinone (HQ) using H2O2 as anoxidant. Double strands DNA with multiple branched arms (mdsDNA) was formed by mHCR. In the presence of carcinoembryonic antigen (CEA), PdAu-mdsDNA conjugates-labeled CEA antibody was captured. The concentrations of CEA were measured through the decrease in photocurrent intensity resulting from the increase in steric hindrance of the immunocomplex and the polymeric oxidation product of HQ. In addition, the oxidation product of HQ deposited on the as-obtained electrode, which could efficiently inhibit the photoinduced electron transfer. Under optimal conditions, the PEC immunosensor exhibited excellent analytical performance: the detection range of CEA was from 0.001 to 90 ng mL(-1) with low detection limit of 0.33 pg mL(-1). The as-obtained immunosensor exhibited excellent precision, prominent specificity, acceptable stability and reproducibility, and could be used for the detection of CEA in real samples. The proposed assay opens a promising platform of clinical immunoassay for other biomolecules., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Branched zinc oxide nanorods (BZR) arrays, an array with high charge carries collection efficiency and specific surface area, are grown on the reduced graphene oxide-paper working electrode for the first time to construct a paper-based electrochemical (EC) immunosensor. Typically, the BZR are fabricated via a simple hydrothermal process, which can provide abundant sites for antibodies loading. By combining the large surface area of porous zinc oxide (PZS) and good biocompatibility of gold nanoparticles (AuNPs), PZS-AuNPs (PZS@Au) nanocomposites are designed to label horseradish peroxide (HRP) and antigens. After a competitive reaction between antigens and PZS@Au nanocomposites labeled antigens, the signal labels are introduced into the immunosensor, in which, HRP participate in biocatalytic precipitation process. The produced precipitate reduces the electrode surface area and hinders the electron transfer. With the increase of concentration of antigens, the signal labels introduced into the sensor decrease, thus, a signal-on immunoassay for α-fetoprotein detection is constructed. The proposed paper-based EC immunosensor combines enzymatic biocatalytic precipitation reaction and competitive immunoassay mode for the first time, and possesses a wide linear range from 0.2 pg mL(-1) to 500 ng mL(-1) with a detection limit of 0.08 pg mL(-1). In addition, the proposed method is simple, sensitive and specific and can be a promising platform for other protein detection., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A mediator-less and compartment-less glucose/O2 enzymatic biofuel cell (BFC) was introduced into microfluidic paper-based analytical devices (μ-PADs) that relies on flow in hollow channels with silver nanoparticles/graphene modified paper electrode as the anodic and cathodic substrate, to implement self-powered sensitive carcinoembryonic antigen (CEA) detection. Glucose dehydrogenase (GDH)-gold nanoparticles bioconjugate modified with CEA acted as a biocatalyst for enhancing glucose oxidation in the bioanode, as well as the transducing enzyme for signaling magnification. Similarly, nanoporous PtNi/bilirubin oxidase (BOD) acted as a biocatalyst for enhancing O2 reduction in the biocathode. With an increase in the concentration of CEA, the amount of CEA-Au-GDH bioconjugate on bioanode decreases, thus leading to the lower output of the as-prepared BFC. This proposed BFC-based self-powered immunosensor for CEA possessed largely increased linear detection range from 1 pg mL(-1) to 0.5 μg mL(-)(1) with a detection limit of 0.7 pg mL(-)(1). The proposed BFC-based self-powered immunosensor shows high sensitivity, stability, and reproducibility and can become a promising platform for other protein detection., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Graphene has shown great potential for use in biosensors because of its versatile surface modification, good water dispersibility, and extraordinary electrical conductivity. Here, a novel enzyme-free and all-graphene electrochemical immunosensor, based on two novel graphene nanocomposites, for the ultrasensitive immunosensing of α-fetoprotein (AFP) was reported. Noncovalent ultrathin gold nanowire functionalized graphene sheets (GNWs/GO) with the extraordinary biological and electrical properties, which exhibited high water solubility and further biological molecule functionalization, was prepared in situ solution phase to be used as an enhanced electrochemical sensing platform. In addition, a new electrocatalyst, CuS nanoparticle-decorated graphene (CuS/GO) composites was successfully prepared by a simple method for in situ growth of CuS on the surface of graphene sheets. Covalent binding of the detection antibody of AFP on the CuS/GO composites produced a sensitive electrochemical bioprobe for detection of AFP by sandwich immunosensing. The corresponding immunosensor, employing an inexpensive and portable 3D paper-based analytical device, possessed a wide calibration range of 0.001-10 ng mL(-1) and a low detection limit of 0.5 pg mL(-1) (S/N=3), which was successfully applied to the detection of AFP in serum samples from both healthy people and cancer patients. The present work thus demonstrated the promising application of graphene-based nanocomposites in developing highly sensitive, environmentally friendly, and cost-effective electrochemical biosensors., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In our work, low potential and sensitive electrochemiluminescence (ECL) detection for CA153 on MCF-7 cell surface was firstly achieved based on a microfluidic paper-based analytical device. Au nanoflowers were grown in paper working electrode (PWE) to construct the ECL platform for primary antibodies immobilizing. After MCF-7 cells were captured in the modified PWE, and subsequently recognized with ECL signal substance labeled secondary antibodies, the sandwich-type cell sensor was fabricated. Graphene quantum dots (GQDs) loaded surface villous Au nanocages were synthesized as the ECL signal substance, and characterized by scanning electron microscope. The specific villous surface structure for Au nanocage permitted more GQDs being carried and electrons transporting, which largely benefited for the ECL performance. As the un-negligible impendence for MCF-7 cell would definitely influence the ECL signal, CA153 labeled HMEpic cell was used as the control cell to obtain more accurate determination result. This low-cost and fast strategy showed acceptable biocompatibility and stability, and will be promising for cellular immunochemistry., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Herein, an origami multiplexed enzyme-free electrochemical (EC) immunodevice is developed for the first time. Typically, ZnO nanorods (ZNRs) modified reduced graphene oxide (rGO)-paper electrode is used as a sensor platform, in which rGO improves the electronic transmission rate and ZNRs provide abundant sites for capture probes binding. Furthermore, by combining the large surface area of rGO and high catalytic activity of bovine serum protein (BSA)-stabilized silver nanoparticles (Ag@BSA) toward H2O2 reduction, rGO/Ag@BSA composites can be used as an excellent signal labels. The current signal is generated from the reduction of H2O2 and further amplified by a subsequent signal labels-promoted deposition of silver. Under optimal conditions, the proposed immunoassays exhibit excellent precision, high sensitivity and a wide linear range of 0.002-120 mIU mL(-1) for human chorionic gonadotropin, 0.001-110 ng mL(-1) for prostate-specific antigen, and 0.001-100 ng mL(-1) for carcinoembryonic antigen. The results for real sample analysis demonstrate that the newly constructed immunosensor arrays provide a simple and cost-effective method for clinical applications., (Copyright © 2015 Elsevier B.V. All rights reserved.)

One-dimensional PtPd porous nanorods (PtPd PNRs) were successfully synthesized through a bromide-induced galvanic replacement reaction between Pd nanowires and K2PtCl6. The PtPd PNRs were porous and alloy-structured with Pt/Pd atomic ratio up to 1:1 which were demonstrated by spectroscopic methods. We had also proved that the nanorods could function as peroxidase mimetic for the detection of H2O2, with the detection limit of 8.6 nM and the linear range from 20 nM to 50 mM. The result demonstrated that PtPd PNRs exhibited much higher affinity to H2O2 over other peroxidase mimetics due to synergistically integrating highly catalytic activity of two metals. On the basis of the peroxidase-like activity, the PtPd PNRs were used as a signal transducer to develop a novel and simple colorimetric method for the study of the flux of H2O2 released from living cell. By using 3,3,5,5-tetramethylbenzidine as substrate, the H2O2 concentration could be distinguished by naked-eye observation without any instrumentation or complicated design. The method developed a new platform for a reliable collection of information on cellular reactive oxygen species release. And the nanomaterial could be used as a power tool for a wide range of potential applications in biotechnology and medicine., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A signal-off electrochemiluminescence (ECL) DNA sensor based on gold nanodendrites (Au NDs) modified indium tin oxide (ITO) electrode for the detection of lead ion (Pb(2+)) was developed. Well-defined Au NDs were prepared on ITO electrode using low-potential synthesis, assisted by ethylenediamine. Based on Pb(2+)-specific deoxyribozyme, the silver/zinc oxide (Ag/ZnO) with coupled structure, prepared by one-pot method, was close to the surface of the electrode to catalyze the reduction of part of H2O2, the coreactant for cathodic ECL emission, leading to a decrease of ECL intensity. In addition, taking advantage of the larger surface area to capture a large amount of capture probe as well as excellent conductivity of Au NDs, the sensor could detect Pb(2+) quantitatively in a wider range, and performed excellent selectivity. Furthermore, such simple and sensitive DNA sensor was successfully applied for the detection of Pb(2+) in lake water and human serum samples, respectively., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The detection of cancer cells is important and fundamental for cancer diagnosis and therapy, which has attracted considerable interest recently. Although traditional cyto-sensors have been widely explored due to their high sensitivity and selectivity, it is still a challenge to develop a low-cost, portable, disposable, fast, and easy-to-use cancer cell detection method for applying in the field of cancer diagnosis and therapy. Herein, to address these challenges, we developed a microfluidic paper-based electrochemiluminescence origami cyto-device (μ-PECLOC), in which aptamers modified 3D macroporous Au-paper electrodes were employed as the working electrodes and efficient platforms for the specific cancer cells capture. Owing to the effective disproportionation of hydrogen peroxide and specific recognition of mannose on cell surface, concanavalin-A conjugated porous AuPd alloy nanoparticles were introduced into this μ-PECLOC as the catalytically promoted nanolabels for peroxydisulfate ECL system. Under the optimal conditions, the proposed μ-PECLOC exhibited excellent analytical performance with good stability, reproducibility, and accuracy, towards the cyto-sensing of four types of cancer cells indicating the potential applications to facilitate effective and multiple early cancer diagnosis and clinical treatment., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A novel electrochemical lab-on-paper cyto-device (ELPCD) was fabricated to demonstrate sensitive and specific cancer cell detection as well as in-situ monitoring of multi-glycans on living cancer cells. In this ELPCD, aptamers modified three-dimensional macroporous Au-paper electrode (Au-PE) was employed as the working electrode for specific and efficient cancer cell capture. Using a sandwich format, sensitive and reproducible cell detection was achieved in this ELPCD on the basis of the electrochemical signal amplification of the Au-PE and the horseradish peroxidase-lectin electrochemical probe. The ELPCD displayed excellent analytical performance for the detection of four K562 cells with a wide linear calibration range from 550 to 2.0×10(7) cells mL(-1). Then, this ELPCD was successfully applied to determine cell-surface multi-glycans in parallel and in-situ monitor multi-glycans expression on living cells in response to drug treatment through in-electrode 3D cell culture. The proposed method provides promising application in decipherment of the glycomic codes as well as clinical diagnosis and treatment in early process of cancer., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Flexible biosensors are of considerable current interest for the development of portable point-of-care medical products, minimally invasive implantable devices, and compact diagnostic platforms. Here, we reported an electrochemical paper based analytical device fabricated (EPADs) by sequentially growing gold nanoparticles (AuNPs) and manganese oxide (MnO2) nanowires networks on a freestanding three dimensional (3D) origami device. This fabricated through the growth of an AuNPs layer on the surfaces of cellulose fibers in the screen-printed paper working electrode (PWE), and thus developed a gold paper working electrode (Au-PWE). Subsequently, MnO2 nanowires were successfully electrodeposited on Au-PWE to form a 3D network with large surface areas. Based on this novel EPADs and the principle of origami, we presented herein a simple immunosensing scheme using glucose oxidase (GOx) as an enzyme label, 3,3',5,5'-tetramethylbenzidine (TMB) as a redox terminator, and glucose as an enzyme substrate. The electrochemical enzymatic redox cycling was applied to the detection of prostate protein antigen (PSA), a biomarker of prostatic cancer. The proposed method successfully fulfilled the highly sensitive detection of PSA with a linear range of 0.005 ng mL(-1)-100 ng mL(-1) with a detection limit of 0.0012 ng mL(-1). This EPADs exhibited high sensitivity, specificity and excellent performance in real human serum assay, and could be applied in point-of-care testing of other tumor markers for remote regions and developing countries., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We reported here the preparation of "dioscorea batatas bean"-like silver nanoparticles (AgNPs) and the unique structure provided the AgNPs good localized surface plasmon resonance (LSPR) property. In addition, zinc oxide quantum dots (ZnO QDs) were also synthesized and found with good fluorescent property. Furthermore, the ZnO QDs decorated exfoliated graphene oxide (EGO-ZnO) was prepared via electrostatic interaction. The named nanomaterials were applied in a LSPR-induced fluorescent DNA sensor. To fabricate the DNA sensor, the EGO-ZnO was modified on the silica glass as the supporter for the capture probe ssDNA, and the complementary ssDNA was labeled on the surface of the AgNPs. After the hybridization step by step, the AgNPs was fastened on the surface of the EGO-ZnO, and the fluorescent intensity of the EGO-ZnO increased as a result. The prepared DNA sensor enabled the target ssDNA to be detected in the concentration range of 10(-19)-10(-14)M, and the limit of detection was 4.3 × 10(-20)M., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this paper, a pen-on-paper electrochemiluminescence (PoP-ECL) device was entirely hand drawn and written in commercially available crayon and pencil in turn for the first time, and a constant potential-triggered sandwich-type immunosensor was introduced into the PoP-ECL device to form a low-cost ECL immunodevice proof. Each PoP-ECL device contained a hydrophilic paper channel and two PoP electrodes, and the PoP-ECL device was produced as follows: crayon was firstly used to draw hydrophobic regions on pure cellulose paper to create the hydrophilic paper channels followed with a baking treatment, and then a 6B-type black pencil with low resistivity was applied for precision writing, as the PoP electrodes, across the hydrophilic paper channel. For further point-of-care testing, a portable, low-cost rechargeable battery was employed as the power source to provide constant potential to the PoP electrodes to trigger the ECL. Using Carbohydrate antigen 199 as model analyte, this PoP-ECL immunodevice showed a good linear response range from 0.01-200 U mL(-1) with a detection limit of 0.0055 U mL(-1), a high sensitivity and stability. The proposed PoP-ECL immunodevice could be used in point-of-care testing of other tumor markers for remote regions and developing countries., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In the paper, a simple and sensitive electrochemiluminescence (ECL) DNA sensor based on graphene-modified porous Au-paper working electrode (GR/Au-PWE) and calcium carbonate/carboxymethyl chitosan (CaCO3/CMC) hybrid microspheres @ luminescent silver nanoparticles (AgNPs) composites was developed. The GR/Au-PWE with excellent conductivity was successfully prepared for the immobilization of capture probe. The CaCO3/CMC hybrid microspheres were prepared by the precipitation of calcium carbonate in an aqueous solution containing CMC. The AgNPs was synthesized by thermal reduction of silver ions in glycine matrix, taking advantage of the solid-state matrix to control the nucleation and migration of reduced silver atoms. The CaCO3/CMC@AgNPs composites exhibited 3.6 times higher ECL intensity than the pure AgNPs-labeled reporter DNA. Taking advantage of dual-amplification effects, the paper-based DNA sensor could detect the target DNA quantitatively, in the range of 4.0×10(-17)-5.0×10(-11) M, with a limit of detection as low as 8.5×10(-18) M, and perform excellent selectivity. The simple, low-cost, sensitive device could be easily applied for point-of-care testing, public health and environmental monitoring in remote regions, developing or developed countries., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Combining microfluidic paper-based analytical device (μ-PAD) and the molecular imprinting technique, a visible light photoelectrochemical (PEC) sensing platform for the detection of pentachlorophenol (PCP) was established on gold nanoparticles (AuNPs) decorated paper working electrode using polypyrrole-functionalized ZnO nanoparticles. Ascorbic acid (AA) was exploited as an efficient and nontoxic electron donor for scavenging photogenerated holes under mild solution medium and facilitating the generation of stable photocurrent. The microfluidic molecular imprinted polymer-based PEC analytical origami device is developed for the detection of PCP in the linear range from 0.01 ng mL(-1) to 100 ng mL(-1) with a low detection limit of 4 pg mL(-1). This disposable microfluidic PEC origami device would provide a new platform for sensitive, specific, and multiplex assay in public health, environmental monitoring, and the developing world., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A 3D microfluidic electrochemical origami immunodevice (denoted as µ-ECOI in this work) for sensitive detection of tumor markers was designed. High sensitivity was achieved by using novel cuboid silver modified paper working electrode (CS-PWE) as sensor platform and different metal ions-coated nanoporous silver-chitosan (NSC) as labels. The CS-PWE was fabricated through a seed-mediated growth approach and served as a promising platform for antibodies attachment. The metal ions could be detected directly through square wave voltammetry without metal preconcentration, and each biorecognition event produced a distinct voltammetric peak, whose position and size reflected the identity and amount of the corresponding antigen. The large number of metal ions loading on the NSC greatly amplified the detection signals, and the good biocompatibility of CS-PWE retained good stability for the sandwich-type immunoassay. Using cancer antigen 125 (CA125) and carcinoma antigen 199 (CA199) as model analytes, the simultaneous multiplex immunoassay showed linear ranges of over 4 orders of magnitude with the detection limits down to 0.02 and 0.04 mU mL(-1), respectively. Moreover, this strategy accurately detected the concentrations of CA125 and CA199 in human serum samples. The detection limits of CA125 and CA199 were 0.08 and 0.10 mU mL(-1), respectively. This facile biosensing µ-ECOI exhibited high sensitivity and specificity with excellent stability, reproducibility, and accuracy, indicating its wide range of potential applications in point-of-care testing., (Copyright © 2014 Elsevier B.V. All rights reserved.)

ZnO/graphene (ZnO/G) composite and S6 aptamer were employed to sensitive photoelectrochemical (PEC) strategy for the specific detection of SK-BR-3 cancer cells based on a portable indium tin oxide microdevice. ZnO/G composite was synthesized using a facile ultrasonic method, and then applied to improve the PEC performance due to the unique hollow structure of ZnO naospheres and the superior properties of graphene. Subsequently, S6 aptamer was applied to this specific detection of SK-BR-3 cancer cells. And the concentration of SK-BR-3 cells was measured with a low detection limit of 58 cells mL(-1) and a wide linear range of 1×10(2)-1×10(6) cells mL(-1), through the decrease in photocurrent intensity resulting from the increase in steric hindrances when specifically recognized with S6 aptamers. Excellent discrimination against target and analogous cells was demonstrated, indicating the high selectivity of the proposed cell sensor. Our work also demonstrated a sensitive, stable and low cytotoxicity approach for early and accurate detection of cancer cells., (© 2013 Elsevier B.V. All rights reserved.)

The detection of pesticides has attracted considerable attention in numerous fields, such as environmental monitoring and food safety. Although traditional sensors for pesticides have been widely explored due to their high sensitivity and specificity, it is still challenging to develop a low-cost, portable, fast, and easy-to-use detection method for the public use at home or in the field. To address these challenges, herein, we report a novel paper-based molecular imprinted polymer (MIP)-grafted multi-disk micro-disk plate (P-MIP-MMP) for sensitive and specific chemiluminescence (CL) detection of pesticides through an indirect competitive assay using 2,4-dichlorophenoxyacetic acid (2,4-D) as a proof-of-concept analyte. The MIP-grafted paper disks were prepared by a simple in situ polymerization of MIP layer on the surface of cellulose fibers in paper. The quantification mechanism of this P-MIP-MMP is based on a competition between free 2,4-D and tobacco peroxidase (TOP) labeled 2,4-D and the enzyme catalyzed CL emission from the luminol-TOP-H2O2 CL system. At optimal conditions, this P-MIP-MMP can detect 2,4-D at the concentration of femtomolar level. This approach provided a powerful protocol for simple, low-cost, rapid, and high-throughput detection of pesticides in real samples with satisfactory results for use in areas such as food inspection and environmental monitoring., (Copyright © 2013 Elsevier B.V. All rights reserved.)

We developed a new electrochemiluminescence (ECL) platform for ultrasensitive and selective detection of leukemia cells. In order to construct the platform, the nonporous gold with controllable three-dimensional porosity and good conductivity was used to modify the screen-printed carbon electrode. The carbon quantum dots (CQDs) coated ZnO nanosphere (ZnO@CQDs) were used as good ECL label with low cytotoxicity and good biocompatibility. Structure characterization was obtained by means of transmission electron microscopy and scanning electron microscopy images. The aptamer was used for cell capture and the concanavalin A conjugated ZnO@CQDs was used for selective recognition of the cell surface carbohydrate. The proposed method showed a good analytical performance for the detection of K562 cells ranging from 1.0 × 10(2) to 2.0 × 10(7) cells mL(-1) with a detection limit of 46 cells mL(-1). The as-proposed device has the advantages of high sensitivity, nice specificity and good stability and could offer great promise for sensitive detection of leukemia cells in response to therapy., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A simple, low-cost and sensitive origami electrochemical immunoassay-device was developed based on a novel gold nanoparticle modified porous paper working electrode (Au-PWE) for point-of-care testing. Azide-functionalized Au-PWE was prepared by the functionalization of Au-PWE with 1-azidoundecan-11-thiol. Alkyne end-terminated antibody was prepared with 4-pentynoic acid and antibody by the 1-ethyl-3-(3-(dimethylamino) propyl) carbodiimide hydrochloride and N-hydroxysuccinimide activation reaction. Alkyne-antibody was coupled to azido-Au-PWE by click reaction as a recognition element. Nearly monodispersed sphere-like silica-coated ferroferric oxide (Fe3O4@SiO2) nanoparticles were prepared via the reverse microemulsion method. Azide-functionalized Fe3O4@SiO2 was prepared by the functionalization of silica shell with 3-bromopropyltrichlorosilane followed by substitution with sodium azide. Alkyne-functionalized antibody and horse radish peroxidase were coupled to azide-functionalized Fe3O4@SiO2 by click reaction as signal label. Horse radish peroxidase and ferroferric oxide could catalyze the oxidation of thionine in the presence of hydrogen peroxide. After the sandwich immunoreaction, the current was proportional to the logarithm of the Microcystin-LR. The linear regression equation was i(μA)=119.89+46.27 log cMC-LR (μg/mL) in the range from 0.01 to 200 μg/mL. The limit of detection was 0.004 μg/mL. This immunoassay would provide a universal immunoassay method in environmental monitoring and public health., (Copyright © 2013 Elsevier B.V. All rights reserved.)