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In this work, an ultra-sensitive signal quenched photoelectrochemical (PEC) aptasensor for dibutyl phthalate (DBP) detection was constructed by using a target induced cruciform DNA structure as signal amplifier and g-C 3 N 4 /SnO 2 composite as signal indicator. Impressively, the designed cruciform DNA structure shows high signal amplification efficiency due to the reduced reaction steric hindrance because of its mutually separated and repelled tails, multiple recognition domains, and a fixed direction for the sequential identification of the target. Therefore, the fabricated PEC biosensor demonstrated a low detection limit of 0.3 fM for DBP in a wide linear range of 1 fM to 1 nM. This work offered a novel nucleic acid signal amplification approach for enhancing the sensitivity of PEC sensing platforms for the detection of phthalates (PAEs)-based plasticizer, laying the foundation for its utilization in the determine of real environmental pollutants., 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.)

Herein, driven by the need of highly-efficient DNAzyme-amplified detection strategy, a novel 3D DNAzyme motor was designed as a biosensor platform for realizing sensitive detection of target DNA. The 3D DNAzyme motor was composed of target-activated DNAzyme nanowires and substrates H1-Fc that co-immobilized on Au@Fe 3 O 4 nanoparticles (Au@Fe 3 O 4 NP S ) surface, possessing high local concentration of DNA reactants and shortened distance between DNAzyme and substrates for enhancing electrochemical signal. Compared with traditional DNAzyme-powered machines, the target-activated DNAzyme nanowires of 3D DNAzyme motor had greater flexibility and more powerful cleavage capability without troublesome sequence optimization, which overcame the space limitation and simultaneously interacted with adjacent and distant substrates H1-Fc to output a large amount of cleavage products with high signal response. Therefore, on account of the above-mentioned merits of nanoparticles localization DNA design and DNAzyme nanowires, the reported 3D DNAzyme motor ingeniously overcame many defects existing in traditional DNAzyme-amplified detection strategies such as low reactants concentration, limited flexibility of DNAzyme and small DNAzyme swing range, realizing the sensitive detection of target DNA with a detection limit of 1.7 fM ranging from 5 fM to 50 nM. Impressively, the 3D DNAzyme motor here presented a new strategy to achieve effective DNAzyme signal amplification and provided a reference for the assembly of various and functional 3D DNA machines in the future., 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 © 2022 Elsevier B.V. All rights reserved.)

In this work, we found that polyethyleneimine (PEI), a widely applied organic high-molecular polymer, could act as a new co-reactant to obviously improve the electrochemiluminescence (ECL) of S 2 O 8 2- -O 2 system. And owing to its abundant amine groups in the polymeric structure, PEI was further used to covalently crosslink with massive L-cysteine (L-Cys), an effective co-reactant of S 2 O 8 2- -O 2 ECL system, to obtain a new co-reactive high-molecular polymer (PEI-L-Cys) with higher co-reaction efficiency. As loading platform, hierarchically branched Au/Pd dendrimers (Au/Pd DRs G 2 ) were prepared to immoblize the obtained PEI-L-Cys, detection antibody, and bolocking reagent glucose oxidase (GOD). With the existence of target carcinoembryonicantigen (CEA), an ECL immunosensor was constructed through the sandwiched immunoreaction between the capture antibody on the electrode and the bioconjugate based on Au/Pd DRs G 2 . Besides the high enhancement of PEI-L-Cys, the ECL signal was also greatly increased by the dual catalysis to generate O 2 in situ around the electrode induced by the synergistic effect of GOD and Au/Pd DRs G 2 in presence with D-glucose. Especially, due to the special hierarchically branched bimetallic structure, the Au/Pd DRs G 2 had more excellent catalytic effect to H 2 O 2 decomposition in this process. As a result, the proposed ECL immunosensor realized the ultrasensitive detection of CEA, which could provide meaningful reference to the prevention and treatment of related disease., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, a new label-free biosensor based on highly effective decomposition of a branched DNA polymer and target-transition recycling amplification was designed for ultrasensitive electrochemical determination of lead ion (Pb 2+ ). The branched DNA polymer formed by hybridization chain reaction (HCR) was first immobilized on electrode and served as the carrier for loading abundant silver nanoparticle (AgNPs) to generate an extremely high initial current signal output. Then, the molecular triggers T 1 and T 2 , which were produced through a target-transition recycling amplification, could respectively disassemble the backbone and side chain of the branched DNA polymer with remarkably decreased current for sensitive detection of Pb 2+ . Compared with traditional one-trigger induced disassembly strategy, the proposed approach exhibited higher decomposition efficiency. The experimental data showed that this developed biosensor had a superior performance for Pb 2+ detection with a low detection limit down to 0.24 pM. Furthermore, the established strategy set up a new way to achieve the ultrasensitive detection of other metal ions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Herein, a novel electrochemiluminescence resonance energy transfer (ERET) strategy between in situ electrogenerated silver nanoclusters (AgNCs) as the donor and Ru(bpy) 2 (5-NH 2 -1,10-phen)Cl 2 (Ru(II)) as the acceptor was reported, which was applied for the construction of a ultrasensitive immunosensor for the determination of apolipoprotein-A1 (Apo-A1). Notably, the Ag NCs were in suit electro-reducted on glassy carbon electrode (GCE) based on a simple, fast and controllable electrochemical technique, which acted as not only biocompatible ECL emitters, but also protein immobilization platform via Ag-N or Ag-S bond. Subsequently, the acceptor probe was constructed by modifying Ru(II) and secondary antibody on the nanocarriers of carboxyl-functionalized MWCNTs. Based on the sandwiched immunoassay method, the ECL signals declining at 449nm (Ag NCs) and the increasing at 650nm (Ru(II)) both reflect the amount of Apo-A1. By measuring the ratio of ECL 650nm /ECL 449nm , we could accurately quantify the concentration of Apo-A1 in range from 1.0pg/mL to 1.0ng/mL and limit of detection down to 0.33pg/mL, which opened up a new research direction for ultrasensitive ECL bioanalysis based metal NCs., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this work, the luminophor tris (4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium (II) dichloride (Ru(dcbpy) 3 2+ ) was linked to coreactant polyethylenimine (PEI) with effectively shorted distance, forming a novel self-enhanced PEI-Ru(II) complex to fabricate ultrasensitive electrochemiluminescence immunosensor for carcinoembryonic antigen (CEA) detection by using polyamino acid l-cysteine (pL-Cys) as booster for further signal amplification. The light-emitting species (PEI-Ru(II)*) based on intramolecular electron transfer between PEI • and Ru(III) could efficiently amplify the ECL signal of Ru(dcbpy) 3 2+ owing to its benefit for electron transmission. Secondly, the pL-Cys film was fabricated on the glassy carbon electrode by cyclic voltammogram. After that, the pL-Cys acted as a strongly reducing radical could react with PEI-Ru(III) to generate the excited state PEI-Ru(II)*, which further amplify the ECL signal. With the signal amplification factors, the prepared ECL immunosensor exhibited great advantages in simplification, rapidity, stability and selectivity. Furthermore, the linear range for the determination of CEA was from 0.10 pg/mL to 80 ng/mL with a correlation coefficient of 0.9942 and a detection limit of 0.045 pg/mL (S/N = 3)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this work, a Pt nanoparticles-functionalized Co-based metal organic frameworks (PtNPs@Co(II)MOFs@PtNPs) was synthesized and applied in electrochemical aptasensor for thrombin (TB) detection. First, the Co(II)MOFs@PtNPs were prepared via the mixed solvothermal method, which consists of inner Pt nanoparticles (PtNPs) encapsulated by aminofunctionalized Co(II)MOFs materials. Following that, additional PtNPs were adsorbed on the surface of Co(II)MOFs@PtNPs, resulting in the formation of PtNPs@Co(II)MOFs@PtNPs nanocomposite. The PtNPs@Co(II)MOFs@PtNPs nanocomposites with a large surface area were implimented as nanocarriers to immobilize a mass of TBA II for the formation of the TBA II bioconjugates that could be captured onto the electrode surface by sandwich-type format. Moreover, the PtNPs@Co(II)MOFs@PtNPs nanocomposites could directly use as redox tags for charge-generating and electron-transporting with the electron transfer from Co(II) to Co(III). Furthermore, in the presence of H 2 O 2 , the PtNPs@Co(II)MOF@PtNPs could effectively catalyze H 2 O 2 oxidation with improvement electron transfer of redox probe, resulting in electrochemical signal amplification. Based on the above superior advantages, TB was determined in the concentration range from 0.1pM to 50nM with a detection limit of 0.33fM. Furthermore, the excellent sensitivity and selectivity can be easily established for quantitative analysis of other analytes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A label-free electrochemical biosensor for sensitive detection of miRNA-155 was presented by coupling enzyme-catalyzed in situ generation of electronic mediator for signal introduction with catalytic hairpin assembly (CHA) induced target recycling amplification strategy. In this work, alkaline phosphatase (ALP) was adopted to hydrolyze inactive substrate 1-naphthyl phosphate (NPP) to produce phosphate ion (PO 4 3- ), which could further react with acidic molybdate to form abundant molybdophosphate anion (PMo 12 O 40 3- ) on the surface of electrode. The produced PMo 12 O 40 3- could directly generate a strong and stable electrochemical signal for quantitative detection of targets. In addition, CHA induced the cyclic reuse of the target was also employed as an effective strategy for improving the sensitivity of biosensor. This electrochemical method for miRNA-155 detection had achieved a good linear relationship ranging from 10fM to 1nM with a detection limit of 1.64fM. With this assay successfully applied in tumor cell lysates, it holds great potential for early cancer diagnosis by employing miRNA as the effective biomarker., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Herein, we report on the development of a simple and sensitive biosensor for electrochemiluminescent (ECL) detection of microRNAs (miRNA) based on the intercalation of doxorubicin-conjugated quantum dot nanoparticles (Dox-QDs) into the DNA/RNA hybrids as the new signal acquisition and amplification platform. The thiolated DNA capture probes are self-assembled onto gold electrodes via the formation of Au-S bonds. The sensing surface is then incubated in a target miRNA-containing buffer solution to form the double-stranded duplexes. In this case, massive Dox-QDs can intercalate into the base pairs of the hybrid duplexes, resulting in amplified ECL emissions due to their reactions with the coreactant [Formula: see text] and the dissolved oxygen in the detection buffer. The increase in ECL intensity proportional to the amount of target miRNA in the testing samples serves as the quantitative basis. Different from traditional QDs-based methods such as labeling and embedding, our sensor involves the employment of the intercalation of the Dox-QDs as the signal acquisition and amplification platform. The combination of the QDs intercalation amplification with the high sensitivity of the ECL technique enables us to detect miRNA down to the low femtomolar level. Moreover, our method is also coupled with acceptable selectivity in discriminating the target miRNA and against its family members as well as other interference sequence, and can monitor miRNAs from human prostate carcinoma (22Rv1) cell lysates., (Copyright © 2015 Elsevier B.V. All rights reserved.)

By using the aptamer proximity binding assay strategy, the development of a label-free and homogeneous approach for fluorescent detection of human platelet-derived growth factor BB (PDGF-BB) is described. Two G-quadruplex forming sequence-linked aptamers bind to the PDGF-BB proteins, which leads to the increase in local concentration of the aptamers and promotes the formation of the G-quadruplex structures. Subsequently, the fluorescent dye, N-methylmesoporphyrin IX, binds to these G-quadruplex structures and generates enhanced fluorescence emission signal for sensitive detection of PDGF-BB. The association of the aptamers to the PDGF-BB proteins is characterized by using native polyacrylamide gel electrophoresis. The experimental conditions are optimized to reach an estimated detection limit of 3.2nM for PDGF-BB. The developed method is also selective and can be applied for monitoring PDGF-BB in human serum samples. With the advantages of label-free and homogeneous detection, the demonstrated approach can be potentially employed to detect other biomarkers in a relatively simple way., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this study, a novel solid-state Ru(bpy)3(2+) electrochemiluminescence (ECL) sandwiched immunosensor for sensitive detection of α-fetoprotein (AFP) was constructed based on poly(ethylenimine) (PEI) functionalized reduced graphene oxide (PEI-rGO) and Au nanoparticles (AuNPs) decorated polyamidoamine (PAMAM) dendrimers. Both PEI and PAMAM are polymers with a lot of amino groups, which are able to serve as good co-reactant to remarkably enhance the ECL signal of Ru(bpy)3(2+). For improving the poor conductivity of PAMAM, the AuNPs were decorated on the amino groups of PAMAM. Through Au-N bonds, the formed AuNPs-PAMAM was decorated on the PEI-rGO. The obtained AuNPs-PAMAM/PEI-rGO was introduced to immobilize the detection antibody (Ab2). Then, the Ab2 labeled AuNPs-PAMAM/PEI-rGO was modified onto the glass carbon electrode surface via sandwiched immunoreactions. The ECL substrate was prepared by mixing nafion and the complex (Ru-PtNPs) of Pt nanoparticles (PtNPs) and Ru(bpy)3(2+), which could reduce the consumption of Ru complex, simplify the operation and enhance the ECL efficiency. The experimental results demonstrated that the proposed immunosensor had good response to AFP. The linear range was from 0.01 pg mL(-1) to 10 ng mL(-1) with a low detection limit of 3.3 fg mL(-1). Meanwhile, with satisfying stability, selectivity and reproducibility, the proposed sandwiched immunosensor was presented to possess good potential in clinical detection., (Copyright © 2014. Published by Elsevier B.V.)

In the present study, with the aggregated advantages of graphene and molybdenum disulfide (MoS2), we prepared poly(diallyldimethylammonium chloride)-graphene/molybdenum disulfide (PDDA-G-MoS2) nanocomposites with flower-like structure, large surface area and excellent conductivity. Furthermore, an advanced sandwich-type electrochemical assay for sensitive detection of thrombin (TB) was fabricated using palladium nanoparticles decorated PDDA-G-MoS2 (PdNPs/PDDA-G-MoS2) as nanocarriers, which were functionalized by hemin/G-quadruplex, glucose oxidase (GOD), and toluidine blue (Tb) as redox probes. The signal amplification strategy was achieved as follows: Firstly, the immobilized GOD could effectively catalyze the oxidation of glucose to gluconolactone, coupling with the reduction of the dissolved oxygen to H2O2. Then, both PdNPs and hemin/G-quadruplex acting as hydrogen peroxide (HRP)-mimicking enzyme could further catalyze the reduction of H2O2, resulting in significant electrochemical signal amplification. So the proposed aptasensor showed high sensitivity with a wide dynamic linear range of 0.0001 to 40 nM and a relatively low detection limit of 0.062 pM for TB determination. The strategy showed huge potential of application in protein detection and disease diagnosis., (Copyright © 2014 Elsevier B.V. All rights reserved.)

To promote the luminous efficiency of luminophore, traditional electrochemiluminescence (ECL) immunoassay usually adopts the adding of coreactant into testing solution. However, many adverse micro-environmental factors in the solution are a limiting factor in ECL analytical techniques and received extensive attention. In our work, a self-enhanced ECL luminophore was synthesized by combining the coreactant (l-cysteine) and the luminophor (tris (4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium(II) dichloride (Ru(dcbpy)3(2+))) to form one Ru(II) complex and was applied to fabricate a reagentless immunosensor for the detection of cardiac troponin I (cTnI) for the first time. Herein gold nanorods (AuNRs), due to their high specific surface area and good electrocatalytic ability, were used as carriers for the immobilization of Ru(II) complex and cTnI antibody to obtain the Ab2 bioconjugates as signal labels. The application of the self-enhanced Ru(II) complex not only avoided the addition of any coreactant into testing solution for simplifying the operation, but also achieved the intramolecular reaction for improving the ECL signal due to shorter electron transfer path and less energy loss. In view of these advantages, the proposed immunosensor achieved a wide linear range from 0.25 pg/mL to 0.1 ng/mL with an impressive detection limit of 0.083 pg/mL for cTnI (S/N=3)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this work, based on terminal protection of folate-linked ssDNA (FA-ssDNA) and the SYBR Gold fluorescent dye, we describe the development of a label-free fluorescent strategy for the detection of folate receptors (FRs). The binding between the target FR and the FA moiety of the FA-ssDNA protects the FR bound FA-ssDNA from digesting by Exo I. The binding of SYBR Gold to the terminal protected, un-digested FA-ssDNA leads to enhanced fluorescent emission for the monitoring of FR with a detection limit of 30 pM. Besides, the developed method also shows high selectivity toward FR against other control proteins. Moreover, our approach avoids the labeling of the probes with fluorescent tags and achieves label-free detection of FR. With these advantages, the proposed method thus holds promising potential for the development of simple and convenient strategies for the detection of other proteins by using different small molecule receptor/protein ligand pairs., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Based on the recovery of the quantum dot (QD) electrochemiluminescence (ECL) and exonuclease-catalyzed target recycling amplification, the development of a highly sensitive aptasensor for Ochratoxin A (OTA) detection is described. The duplex DNA probes containing the biotin-modified aptamer are immobilized on a CdTe QD composite film-coated electrode. The presence of the OTA target leads to effective removal of the biotin-aptamers from the electrode surface via exonuclease-catalyzed recycling and reuse of OTA, which prevents the attachment of streptavidin-alkaline phosphatase (STV-ALP) through biotin-STV interaction. The electron transfer (ET) from the excited state CdTe QD ([CdTe](⁎)) to the electro-oxidized species of the enzymatic product of ALP during the potential scan is thus inhibited and the QD ECL emission is restored for quantitative OTA detection. Due to the exonuclease-catalyzed target recycling amplification, the inhibition effect of ET is significantly enhanced to achieve sensitive detection of OTA down to 0.64 pg mL(-1). The proposed method is selective for OTA and can be used to monitor OTA in real red wine samples. Our developed ECL recovery-based aptasensor thus offers great potential for the development of new ECL sensing platforms for various target analytes., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Our present work aimed at developing a pseudo triple-enzyme cascade electrocatalytic electrochemical aptasensor for determination of thrombin with the amplification of alcohol dehydrogenase (ADH)-Pt-Pd nanowires bionanocomposite and hemin/G-quadruplex structure that simultaneously acted as NADH oxidase and HRP-mimicking DNAzyme. With the addition of ethanol to the electrolyte, the ADH immobilized on the Pt-Pd nanowires catalyzed ethanol to acetaldehyde accompanied by NAD(+) being converted to NADH. Then the hemin/G-quadruplex firstly served as NADH oxidase, converting the produced NADH to NAD(+) with the concomitant local formation of high concentration of H2O2. Subsequently, the hemin/G-quadruplex acted as HRP-mimicking DNAzyme, bioelectrocatalyzing the produced H2O2. At the same time, the Pt-Pd nanowires employed in our strategy not only provided a large surface area for immobilizing thrombin binding aptamer (TBA) and ADH, but also served as HRP-mimicking DNAzyme which rapidly bioelectrocatalyzed the reduction of the produced H2O2. Thus, such a pseudo triple-enzyme cascade electrochemical aptasensor could greatly promote the electron transfer of hemin and resulted in the dramatic enhancement of electrochemical signal. As a result, a wide dynamic concentration linear range from 0.2 pM to 20 nM with a low detection limit of 0.067 pM for thrombin (TB) determination was obtained. The excellent performance indicated that our strategy was a promising way for ultrasensitive assays in electrochemical aptasensors., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this work, a new signal amplified strategy was constructed based on isothermal exponential amplification reaction (EXPAR) and hybridization chain reaction (HCR) generating the hemin/G-quadruplex horseradish peroxidase-mimicking DNAzyme (HRP-mimicking DNAzyme) nanowires as signal output component for the sensitive detection of thrombin (TB). We employed EXPAR's ultra-high amplification efficiency to produce a large amount of two hairpin helper DNAs within a minutes. And then the resultant two hairpin helper DNAs could autonomously assemble the hemin/G-quadruplex HRP-mimicking DNAzymes nanowires as the redox-active reporter units on the electrode surface via hybridization chain reaction (HCR). The hemin/G-quadruplex structures simultaneously served as electron transfer medium and electrocatalyst to amplify the signal in the presence of H2O2. Specifically, only when the EXPAR reaction process has occurred, the HCR could be achieved and the hemin/G-quadruplex complexes could be formed on the surface of an electrode to give a detectable signal. The proposed strategy combines the amplification power of the EXPAR, HCR, and the inherent high sensitivity of the electrochemical detection. With such design, the proposed assay showed a good linear relationship within the range of 0.1 pM-50 nM with a detection limit of 33 fM (defined as S/N=3) for TB., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Based on target recycling amplification, the development of a new label-free, simple and sensitive colorimetric detection method for ATP by using un-modified aptamers and DNAzymes is described. The association of the model target molecules (ATP) with the corresponding aptamers of the dsDNA probes leads to the release of the G-quadruplex sequences. The ATP-bound aptamers can be further degraded by Exonuclease III to release ATP, which can again bind the aptamers of the dsDNA probes to initiate the target recycling amplification process. Due to this target recycling amplification, the amount of the released G-quadruplex sequences is significantly enhanced. Subsequently, these G-quadruplex sequences bind hemin to form numerous peroxidase mimicking DNAzymes, which cause substantially intensified color change of the probe solution for highly sensitive colorimetric detection of ATP down to the sub-nanomolar (0.33nM) level. Our method is highly selective toward ATP against other control molecules and can be performed in one single homogeneous solution, which makes our sensing approach hold great potential for sensitive colorimetric detection of other small molecules and proteins., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this work, an ultrasensitive peroxydisulfate electrochemiluminescence (ECL) immunosensor using in situ generation of L-homocysteine (L-Hcys) for signal amplification was successfully constructed for detection of carcinoembryonic antigen (CEA). In the reaction of biological methylation, S-adenosyl-L-homocysteine hydrolase (SAHH) catalyzed the reversible hydrolysis of S-adenosyl-L-homocysteine (SAH) to produce L-Hcys, which was inducted into ECL system to construct the immunosensor for signal amplification in this work. Simultaneously, Gold and palladium nanoparticles functionalized multi-walled carbon nanotubes (Au-PdNPs@MWCNTs) were prepared, which were introduced to immobilize the secondary antibody (Ab2) and SAHH with high loading amount and good biological activity due to their improved surface area and excellent biocompatibility. Then the proposed ECL immunosensor was developed by a sandwich-type format using Au-PdNPs@MWCNTs-SAHH-Ab2 as tracer and graphene together with AuNPs as substrate. Besides the enhancement of Au-PdNPs, the enzymatic catalysis reaction also amplified the ECL signal dramatically, which was achieved by efficient catalysis of the SAHH towards the hydrolysis of SAH to generate improved amount of L-Hcys in situ. Furthermore, due to the special interaction between Au-PdNPs and -SH or -NH2 in L-Hcys, L-Hcys would gradually accumulate on the surface of the immunosensor, which greatly enhanced the concentration of L-Hcys on the immunosensor surface and further improved the ECL intensity. With the amplification factors above, a wide linear ranged from 0.1 pg mL(-1) to 80 ng mL(-1) was acquired with a relatively low detection limit of 33 fg mL(-1) for CEA., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this study, we for the first time presented an efficient, accurate, rapid, simple and ultrasensitive detection system for small molecule ochratoxin A (OTA) by using the integration of loop-mediated isothermal amplification (LAMP) technique and subsequently direct readout of LAMP amplicons with a signal-on electrochemiluminescent (ECL) system. Firstly, the dsDNA composed by OTA aptamer and its capture DNA were immobilized on the electrode. After the target recognition, the OTA aptamer bond with target OTA and subsequently left off the electrode, which effectively decreased the immobilization amount of OTA aptamer on electrode. Then, the remaining OTA aptamers on the electrode served as inner primer to initiate the LAMP reaction. Interestingly, the LAMP amplification was detected by monitoring the intercalation of DNA-binding Ru(phen)3(2+) ECL indictors into newly formed amplicons with a set of integrated electrodes. The ECL indictor Ru(phen)3(2+) binding to amplicons caused the reduction of the ECL intensity due to the slow diffusion of Ru(phen)3(2+)-amplicons complex to the electrode surface. Therefore, the presence of more OTA was expected to lead to the release of more OTA aptamer, which meant less OTA aptamer remained on electrode for producing LAMP amplicons, resulting in less Ru(phen)3(2+) interlaced into the formed amplicons within a fixed Ru(phen)3(2+) amount with an obviously increased ECL signal input. As a result, a detection limit as low as 10 fM for OTA was achieved. The aptasensor also has good reproducibility and stability., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Herein, a novel sensitive pseudobienzyme electrocatalytic DNA biosensor was proposed for mercury ion (Hg(2+)) detection by using autonomously assembled hemin/G-quadruplex DNAzyme nanowires for signal amplification. Thiol functionalized capture DNA was firstly immobilized on a nano-Au modified glass carbon electrode (GCE). In presence of Hg(2+), the specific coordination between Hg(2+) and T could result in the assembly of primer DNA on the electrode, which successfully triggered the HCR to form the hemin/G-quadruplex DNAzyme nanowires with substantial redox probe thionine (Thi). In the electrolyte of PBS containing NADH, the hemin/G-quadruplex nanowires firstly acted as an NADH oxidase to assist the concomitant formation of H2O2 in the presence of dissolved O2. Then, with the redox probe Thi as electron mediator, the hemin/G-quadruplex nanowires acted as an HRP-mimicking DNAzyme that quickly bioelectrocatalyzed the reduction of produced H2O2, which finally led to a dramatically amplified electrochemical signal. This method has demonstrated a high sensitivity of Hg(2+) detection with the dynamic concentration range spanning from 1.0 ng L(-1) to 10 mg L(-1) Hg(2+) and a detection limit of 0.5 ng L(-1) (2.5 pM) at the 3Sblank level, and it also demonstrated excellent selectivity against other interferential metal ions., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this paper, a simple and sensitive amperometric immunosensor for simultaneous detection of four biomarkers by using distinguishable redox-probes as signal tags was proposed for the first time. In sandwich immunoassay format, four kinds of capture antibodies (C-Ab) were immobilized by gold nanoparticles (AuNPs) electro-deposited on the surface of glass carbon electrode (GCE); four kinds of detection antibodies (D-Ab) labeled with different redox probes (including anthraquinone 2-carboxylic acid (Aq), thionine (Thi), ferrocenecarboxylic acid (Fc) and tris(2,2'-bipyridine-4,4'-dicarboxylic acid) cobalt(III) (Co(bpy)3(3+))), were combined with 3,4,9,10-perylenetetracarboxylic acid (PTCA), poly(diallyldimethylammonium chloride) (PDDA) and AuNPs functionalized carbon nanotubes, and served as signal tracer. When four target antigens were present, differential pulse voltammetry (DPV) scan exhibited four well-resolved peaks, each peak indicated one antigen, and its intensity was quantitative correlational to the concentration of corresponding analyte. To verify the strategy, four biomarkers for diagnosis of colorectal carcinoma, including carcinoembryonic antigen (CEA), carbohydrate antigen (CA) 19-9 CA125, and CA242, were used as model analytes, the immunosensor exhibited high selectivity and sensitivity, and peak current displayed good linear relationship to logarithm concentration in the ranges from 0.016 to 15 ng mL(-1) for CEA; 0.008 to 10 ng mL(-1) for CA19-9; 0.012 to 12 ng mL(-1) for CA125; 0.010 to 10 ng mL(-1) for CA242, and low detection limits of 4.2, 2.8, 3.3 and 3.8 pg mL(-1), respectively., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this work, we described a simple and highly sensitive electrochemiluminescence (ECL) strategy for IgG detection. Firstly, L-cysteine functionalized reduced graphene oxide composite (L-cys-rGO) was decorated on the glassy carbon electrode (GCE) surface. Then anti-IgG was immobilized on the modified electrode surface through the interaction between the carboxylic groups of the L-cys-rGO and the amine groups in anti-IgG. And then biotinylated anti-IgG (bio-anti-IgG) was assembled onto the electrode surface based on the sandwich-type immunoreactions. By the conjunction of biotin and streptavidin (SA), SA was immobilized, which in turn, combined with the biotin labeled initiator strand (S1). In the presence of two single DNA strands of glucose oxidase labeled S2 (GOD-S2) and complementary strand (S3), S1 could trigger the hybridization chain reaction (HCR) among S1, GOD-S2 and S3. Herein, due to HCR, numerous GOD was efficiently immobilizated on the sensing surface and exhibited excellent catalysis towards glucose to in situ generate amounts of hydrogen peroxide (H2O2), which acted as luminol's co-reactant to significantly enhance the ECL signal. The proposed ECL immunosensor presented predominate stability and high sensibility for determination of IgG in the range from 0.1 pg mL(-1) to 100 ng mL(-1) with a detection limit of 33 fg mL(-1) (S/N=3). Additionally, the designed ECL immunosensor exhibited a promising application for other protein detection., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Single nucleotide polymorphisms are the most common type of genetic variations among human beings and can serve as biomarkers for various types of diseases. In this work, based on ligase chain reaction amplification for the production of massive hemin/G-quadruplex DNAzymes to quench the electrochemiluminescent (ECL) emission of quantum dots (QDs), a universal and sensitive single nucleotide polymorphism detection method is described. During the ligase chain reaction process, the mutant K-ras target gene is recycled and exponentially duplicated, leading to the attachment of numerous G-rich sequences on the QD-embedded sensing surface. Upon the addition of the assistant sequences and hemin, numerous hemin/G-quadruplex DNAzymes are formed, which consume the dissolved oxygen in the detection buffer and result in significant quenching of QD ECL emission for sensitive single nucleotide polymorphism determination. The developed method shows a linear range of 50 fM to 50 pM and an estimated detection limit of 45 fM for the mutant K-ras gene. The proposed strategy also exhibits high selectivity towards the mutant K-ras gene against the co-existence of 10(3)-fold excess of the wild-type K-ras gene, which makes our method a useful addition to the alternatives for single nucleotide polymorphism monitoring., (Copyright © 2013 Elsevier B.V. All rights reserved.)

An ultrasensitive electrochemiluminescence (ECL) immunosensor was constructed for ultrasensitive detection of carcinoembryonic antigen (CEA) based on an amplified cathodic ECL of luminol at low potential. Firstly, Au nanoparticles (AuNPs) were electrodeposited onto single walled carbon nanotube-graphene composites (CNTs-Gra) coated glass carbon electrode (GCE) with enhanced surface area and good biocompatibility to capture primary antibody (Ab1) and then bind the antigen analytes. Secondly, Pd and Pt nanoparticles (Pd&PtNPs) decorated reduced graphene oxide (Pd&PtNPs@rGO) and glucose oxidase (GOD) labeled secondary antibody (Pd&PtNPs@ rGO-GOD-Ab2) could be captured onto the electrode surface by a sandwich immunoassay protocol to generate amplified cathodic ECL signals of luminol in the presence of glucose. The Pd&PtNPs@rGO composites and loaded GOD promoted luminol cathodic ECL response by efficiently catalyzing glucose to in-situ produce amount of hydrogen peroxide (H2O2) working as a coreactant of luminol. Then in turn Pd&PtNPs catalyzed H2O2 to generate various reactive oxygen species (ROSs), which accelerated the cathodic ECL reaction of luminol, enhanced the cathodic ECL intensity of luminol and improved the sensitivity of the immunosensor. The as-proposed ECL immunosensor exhibited sensitive response on the detection of CEA ranging from 0.0001 ng mL(-1) to 160 ng mL(-1) with a detection limit of 0.03 pg mL(-1) (S/N=3). Moreover, the stability, specificity, lifetime and reproducibility tests demonstrated the feasibility of the developed immunoassay, which can be further extended to the detection of other disease biomarkers., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This paper constructed a reusable electrochemical immunosensor for the detection of thyroxine at an ultralow concentration using cascade catalysis of cytochrome c (Cyt c) and glucose oxidase (GOx) as signal amplified enhancer. It is worth pointing out that numerous Cyt c and GOx were firstly carried onto the double-stranded DNA polymers based on hybridization chain reaction (HCR), and then the amplified responses could be achieved by cascade catalysis of Cyt c and GOx recycling with the help of glucose. Moreover, multi-functionalized magnetic graphene sphere was synthesized and used as signal tag, which not only exhibited good mechanical properties, large surface area and an excellent electron transfer rate of graphene, but also possessed excellent redox activity and desirable magnetic property. With a sandwich-type immunoreaction, the proposed cascade catalysis amplification strategy could greatly enhance the sensitivity for the detection of thyroxine. Under the optimal conditions, the immunosensor showed a wide linear ranged from 0.05pg mL(-1) to 5ng mL(-1) and a low detection limit down to 15fg mL(-1). Importantly, the proposed method offers promise for reproducible and cost-effective analysis of biological samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In the present study, a novel and ultrasensitive electrochemiluminescence (ECL) immunosensor based on luminol cathodic ECL was fabricated by using Au nanoparticles and Pt nanoparticles (nano-AuPt) electrodeposited on graphene-carbon nanotubes nanocomposite as platform for the detection of carcinoembryonic antigen (CEA). For this introduced immunosensor, graphene (GR) and single wall carbon nanotubes (CNTs) dispersed in chitosan (Chi-GR-CNTs) were firstly decorated on the bare gold electrode (GE) surface. Then nano-AuPt were electrodeposited (DpAu-Pt) on the Chi-GR-CNTs modified electrode. Subsequently, glucose oxidase (GOD) was employed to block the non-specific sites of electrode surface. When glucose was present in the working buffer solution, GOD immediately catalyzed the oxidation of glucose to in situ generate hydrogen peroxide (H2O2), which could subsequently promote the oxidation of luminol with an amplified cathodic ECL signal. The proposed immunosensor was performed at low potential (-0.1 to 0.4V) and low concentration of luminol. The CEA was determined in the range of 0.1 pg mL(-1) to 40 ng mL(-1) with a limit of detection down to 0.03 pg mL(-1) (SN(-1)=3). Moreover, with excellent sensitivity, selectivity, stability and simplicity, the as-proposed luminol-based ECL immunosensor provided great potential in clinical applications., (Copyright © 2013 Elsevier B.V. All rights reserved.)

For the first time, the analytical application of integrate ionophore-transducer material based on magnetic graphene hybrids and 2,2-dithiodipyridine (DTDP) in solid-contact lanthanum (III) selective electrode is reported. The attachment of Fe3O4 nanoparticles (NPs) to graphene oxide (GO) for magnetic graphene hybrid is achieved by covalent bonding, and the universal problem, Fe3O4 NPs may easily leach out from the graphene during application, is successfully solved by the method above. The proposed electrode exhibits an excellent near-Nernstian response to lanthanum (III) ranging from 1.0×10(-9) to 1.0×10(-3)M with a slope of 17.81 mV/dec. Moreover, the excellent performance on fairly good selectivity, wide applicable pH range (3.0(_)8.0), fast response time (10s) and long life time (2 months) reveal the superiority of the electrode. Most importantly, we have made a great improvement in the detection limit (2.75×10(-10)M), which brings new dawn to the real-time detection of lanthanum (III) using ion selective electrode., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A simple and sensitive electrogenerated chemiluminescence (ECL) cholesterol biosensor was prepared based on cerium oxide-graphene (CeO(2)-graphene) composites as an efficient matrix. CeO(2)-graphene composites were prepared by depositing CeO(2) onto graphene and were characterized by scanning electron microscopy. The experimental results demonstrated that CeO(2)-graphene could catalyze the ECL of a luminol-H(2)O(2) (hydrogen peroxide) system to amplify the luminol ECL signal greatly. In addition, the use of CeO(2)-graphene provided a better biocompatible microenvironment for the immobilized enzyme, resulting in excellent stability and a long lifetime of the ECL biosensor. The surface assembly process, ECL behaviors, and electrochemistry of the biosensor were investigated in detail. The quantity of cholesterol was in the linear range from 12 μM to 7.2 mM with a detection limit of 4.0 μM (signal/noise = 3). In addition, the biosensor exhibited outstanding reproducibility, long-term stability, and selectivity. Moreover, this cholesterol biosensor offers an alternative analytical method with low cost and high speed., (Copyright © 2013 Elsevier Inc. All rights reserved.)

A new electrochemical biosensor with enhanced sensitivity was developed for detection of cholesterol by using platinum-palladium-chitosan-graphene hybrid nanocomposites (PtPd-CS-GS) functionalized glassy carbon electrode (GCE). An electrodeposition method was applied to form PtPd nanoparticles-doped chitosan-graphene hybrid nanocomposites (PtPd-CS-GS), which were characterized by scanning electron microscopy (SEM) and electrochemical methods. The presence of the PtPd-CS-GS nanocomposites not only accelerated direct electron transfer from the redox enzyme to the electrode surface, but also enhanced the immobilized amount of cholesterol oxidase (ChOx). Under optimal conditions, the fabricated biosensor exhibited wide linear ranges of responses to cholesterol in the concentration ranges of 2.2×10(-6) to 5.2×10(-4)M, the limit of detection was 0.75 μM (S/N=3). The response time was less than 7s and the Michaelis-Menten constant (Km(app)) was found as 0.11 mM. In addition, the biosensor also exhibited excellent reproducibility and stability. Along with these attractive features, the biosensor also displayed very high specificity to cholesterol with complete elimination of interference from UA, AA, and glucose., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In the present work, a tube-like structure of graphene hybrid as modifier to fabricate electrode for simultaneous detection of ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp) was reported. The hybrid was synthesized by a simple method based on graphene sheets (GS) and 3,4,9,10-perylenetetracarboxylic acid (PTCA) via π-π stacking interaction under ultrasonic condition. The combination of GS and PTCA could effectively improve the dispersion of GS, owing to PTCA with the carboxylic-functionalized interface. Comparing with pure GS or PTCA modified electrode, GS-PTCA displayed high catalytic activity and selectivity toward the oxidation of AA, DA, UA, and Trp. Moreover, cyclic voltammetry, different pulse voltammetry and scanning electron microscopy were employed to characterize the sensors. The experiment results showed that the linear response range for simultaneous detection of AA, DA, UA, and Trp were 20-420 μM, 0.40-374 μM, 4-544 μM and 0.40-138 μM, respectively, and the detection limits were 5.60 μM, 0.13 μM, 0.92 μM and 0.06 μM (S/N=3). Importantly, the proposed method offers promise for simple, rapid, selective and cost-effective analysis of small biomolecules., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A novel material, sol-gel derived La(OH)(3) nanorods (La(OH)(3)NRs) with excellent film forming ability was prepared, and it was first designed to incorporate with carbon nanotubes (CNTs) to modify glassy carbon electrode (GCE) to simultaneously voltammetric determine ascorbic acid (AA), dopamine (DA), uric acid (UA), and nitrite (NO(2)(-)). Cyclic voltammetry (CV), transmission electron microscopy (TEM), and X-ray diffraction (XRD) were employed to characterize the sensor. Under optimal conditions, the linear response range for AA, DA, UA, and NO(2)(-) were 0.5 μmol L(-1) to 1.46 mmol L(-1), 50 nmol L(-1) to 35.36 μmol L(-1), 50 nmol L(-1) to 0.79 mmol L(-1), and 0.55 μmol L(-1) to 0.72 mmol L(-1), respectively and the detection limits were 1.67 μmol L(-1), 1.67 nmol L(-1), 1.67 nmol L(-1), and 0.18 μmol L(-1). The sensor demonstrated well stability, high selectivity and sensitivity. More importance, this material can be extended to construct other electrochemical sensors by the immobilization of enzymes and antibodies., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In this work, an advanced sandwich-type electrochemical aptasensor for thrombin was proposed by integrating hemin/G-quadruplex with functionalized graphene-Pd nanoparticles composites (PdNPs-RGs). The hemin/G-quadruplex formed by intercalating hemin into thrombin binding aptamer (TBA), firstly acted as a NADH oxidase, assisting the oxidation of NADH to NAD(+) accompanying with the generation of H(2)O(2) in the presence of dissolved O(2). Subsequently, the hemin/G-quadruplex acted as HRP-mimicking DNAzyme that rapidly bioelectrocatalyze the reduction of the produced H(2)O(2). At the same time, the Pd nanoparticles supported on p-iodoaniline functionalized graphene were also adopted to catalyze the reduction of H(2)O(2). Thus, with the dual catalysis, a dramatically amplified electrochemical signal could be obtained. Besides, the avidin-biotin system for binding aptamer sequences on electrodes not only improved the sensitivity of thrombin analysis but also obtained an acceptable repeatability of the aptasensor. With several factors mentioned above, a wide linear ranged from 0.1 pM to 50 nM was acquired with a relatively low detection limit of 0.03 pM (defined as S/N=3). These excellent performances provided our approach a promising way for ultrasensitive assay in electrochemical aptasensors., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In this work, a sandwich-type electrochemical immunosensor for simultaneous sensitive detection of prostate specific antigen (PSA) and free prostate specific antigen (fPSA) is fabricated. Gold nanoparticles (AuNPs) modified Prussian blue and nickel hexacyanoferrates nanoparticles were firstly prepared, respectively, and then decorated onion-like mesoporous graphene sheets (denoted as Au@PBNPs/O-GS and Au@NiNPs/O-GS) as distinguishable signal tags to label different detection antibodies. Subsequently, streptavidin and biotinylated alkaline phosphatase (bio-AP) were employed to block the possible remaining active sites. With the employment of the as prepared nanohybrids, the dual catalysis amplification can be achieved by catalysis of the ascorbic acid 2-phosphate to in situ produce AA in the presence of bio-AP, and then AA was further catalyzed by Au@PBNPs/O-GS and Au@NiNPs/O-GS nanohybrids, respectively, to obtain the higher signal responses. The experiment results show that the linear range of the proposed immunosensor for simultaneous determination of fPSA is from 0.02 to 10 ng mL(-1) with a detection limit of 6.7 pg mL(-1) and PSA is from 0.01 to 50 ng mL(-1) with a detection limit of 3.4 pg mL(-1) (S/N=3). Importantly, the proposed method offers promise for rapid, simple and cost-effective analysis of biological samples., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In this work, we reported a sandwiched luminol electrochemiluminescence (ECL) immunosensor using ZnO nanoparticles (ZnONPs) and glucose oxidase (GOD) decorated graphene as labels and in situ generated hydrogen peroxide as coreactant. In order to construct the base of the immunosensor, a hybrid architecture of Au nanoparticles and graphene by reduction of HAuCl(4) and graphene oxide (GO) with ascorbic acid was prepared. The resulted hybrid architecture modified electrode provided an excellent platform for immobilization of antibody with good bioactivity and stability. Then, ZnONPs and GOD functionalized graphene labeled secondary antibody was designed for fabricating a novel sandwiched ECL immunosensor. Enhanced sensitivity was obtained by in situ generating hydrogen peroxide with glucose oxidase and the catalysis of ZnONPs to the ECL reaction of luminol-H(2)O(2) system. The as-prepared ECL immunosensor exhibited excellent analytical property for the detection of carcinoembryonic antigen (CEA) in the range from 10 pg mL(-1) to 80 ng mL(-1) and with a detection limit of 3.3 pg mL(-1) (SN(-1)=3). The amplification strategy performed good promise for clinical application of screening of cancer biomarkers., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A novel electrode was developed through electrodepositing gold nanoparticles (GNPs) on overoxidized-polyimidazole (PImox) film modified glassy carbon electrode (GCE). The combination of GNPs and the PImox film endowed the GNPs/PImox/GCE with good biological compatibility, high selectivity and sensitivity and excellent electrochemical catalytic activities towards ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp). In the fourfold co-existence system, the peak separations between AA-DA, DA-UA and UA-Trp were large up to 186, 165 and 285 mV, respectively. The calibration curves for AA, DA and UA were obtained in the range of 210.0-1010.0 μM, 5.0-268.0 μM and 6.0-486.0 μM with detection limits (S/N=3) of 2.0 μM, 0.08 μM and 0.5 μM, respectively. Two linear calibrations for Trp were obtained over ranges of 3.0-34.0 μM and 84.0-464.0 μM with detection limit (S/N=3) of 0.7 μM. In addition, the modified electrode was applied to detect AA, DA, UA and Trp in samples using standard addition method with satisfactory results., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In the present study, toluidine blue-graphene (Tb-Gra) nanocomposites were prepared to design a Lable-free electrochemical aptasensor for highly sensitive detection of thrombin based on layer-by-layer (LBL) technology. The nanocomposites with excellent redox electrochemical activities were first immobilized on the gold nanoparticles (nano-Au) modified glassy carbon electrodes (GCE). Then, the LBL structure was performed by electrostatic adsorption between the positively charged Tb-Gra and negatively charged nano-Au, which formed {Tb-Gra/nano-Au}(n) multilayer films for electroactive species enrichment and biomolecule immobilization. Subsequently, the thiolated thrombin binding aptamer (TBA) was assembled on the nano-Au surface through Au-S bond. In the presence of target thrombin (TB), the TBA on the multilayer could catch the thrombin onto the electrode surface, which resulted in a barrier for electro-transfer, leading to the decrease of the electrochemical signal of Tb-Gra nanocomposites. Under the optimal conditions, a wide detection range from 0.001 nM to 80 nM and a low detection limit of 0.33 pM (defined as S/N=3) for thrombin were obtained. In addition, the sensor exhibited excellent selectivity against other proteins., (Copyright © 2012 Elsevier B.V. All rights reserved.)

We reported on the synthesis and application of ionophore-gold nanoparticle conjugates in Ag(+) graphene paste electrode. Ionophore was a novel graphene oxide nanosheets (NGO) covalently grafted 2-thiophenecarboxylic (TPC) hybrid material. The hybrid material NGO-TPC decorated with gold nanoparticles was used as both a receptor and an ion-to-electron transducer to fabricate Ag(+) graphene paste electrode. The developed electrode was highly selective to Ag(+) over other tested cations and exhibited an excellent Nernstian slope of 59.3 mV dec(-1) ranging from 8.4×10(-7) to 1.0×10(-) M with a detection limit of 6.3×10(-7) M. Moreover, it also showed a fast response time and a long lifetime. Importantly, the new method of immobilizing ligands on NGO nanosheets to construct electrode successfully solved the universal problem of the electrode components loss from ion-selective electrode., (Copyright © 2012 Elsevier B.V. All rights reserved.)

For the first time a novel carbon paste electrode (CPE) for the detection of trace silver(I) was designed by using derivatized silica-coated multi-walled carbon nanotubes (MWCNTs@SiO2) nanocomposites as a neutral carrier. This proposed electrode, with optimum composition, exhibits a wide dynamic range of 8.6×10(-8) to 1.0×10(-1) M toward silver(I) with a detection limit of 8.0×10(-8) M and a Nernstian slope of 60.8±0.2 mV dec(-1). Meanwhile, it also shows a good selectivity and a relatively fast response time (~20 s), a long lifetime (1 month) and a wide pH range (4.0-9.0). Finally, the developed CPEs were successfully applied in the potentiometric titration of potassium bromide and determination of Cl(-) ions in different water samples., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A novel tracer, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) functionalized graphene sheet (GS) composite (GS-TCDA), is employed to label the secondary anti-thrombin aptamer (TBA) to construct an ultrasensitive electrochemiluminescent sandwich-type aptasensor. The GS provided large surface area for loading abundant PTCDA and TBA with good stability and biocompatibility. Because of the excellent electroconductivity of GS and the desirable optical properties of PTCDA, the as-formed Apt II bioconjugate considerably amplified the electrochmiluminescence (ECL) signal of peroxydisulfate (S(2)O(8)(2-)) and worked as the desirable label for Apt II. On the basis of the considerably amplified ECL signal and sandwich format, an extremely wide range from 1 fM to 1 nM with an ultralow detection limit of 0.33 fM for thrombin was obtained. Additionally, the selectivity and stability of the proposed aptasensor were also excellent. Thus, this procedure has great promise for detection of thrombin present at ultra-trace levels during early stage of diseases., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A novel tracer, platinum-gold alloy nanoparticles (Pt-AuNPs) and horseradish peroxidase (HRP) functionalized single-walled carbon nanotubes (SWCNTs) composite, is employed to label the secondary thrombin aptamer for constructing an ultrasensitive electrochemical aptasensor. Thionine, immobilized on functionalized SWCNTs, provides a pair of distinguished redox peak for electrochemical detection. Both the high-content Pt-AuNPs and HRP on SWCNTs amplify the electrochemical signal of thionine through electrocatalytic reduction of H(2)O(2). Differential pulse voltammetry (DPV) is employed to detect thrombin with different concentrations. The reduction peak current is logarithmically related to the concentration of thrombin in an extremely wide range from 10 fM to 5 nM with a detection limit of 3.6 fM. The dual signal amplification of Pt-AuNPs and HRP functionalized nanocomposite provides a promising way for ultrasensitive assay in electrochemical aptasensors., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A new glucose amperometric biosensor, based on electrodeposition of platinum nanoparticles onto the surface of multi-wall carbon nanotube (MWNT)-polyaniline (PANI) nanocomposites, and then immobilizing glucose oxidase (GOD) with covalent interaction and adsorption effect, was constructed in this paper. Firstly, the MWNT-PANI nanocomposites had been synthesized by in situ polymerization and were characterized through transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, and ultraviolet and visible (UV-vis) absorption spectra. The assembled process of the modified electrode was probed by scanning electron microscopy (SEM) and cyclic voltammetry (CV). Chronoamperometry was used to study the electrochemical performance of the resulting biosensor. The glucose biosensor exhibited a linear calibration curve over the range from 3.0 μM to 8.2mM, with a detection limit of 1.0 μM and a high sensitivity of 16.1 μA mM(-1). The biosensor also showed a short response time (within 5s). Furthermore, the reproducibility, stability and interferences of the biosensor were also investigated., (Copyright © 2011 Elsevier B.V. All rights reserved.)

In this paper, a simple one-step electrodeposition method is described to fabricate chitosan-Prussian blue-multiwall carbon nanotubes-hollow PtCo nanochains (CS-PB-MWNTs-H-PtCo) film onto the gold electrode surface, then glucose oxidase (GOD) and Nafion were modified onto the film subsequently to fabricate a glucose biosensor. The morphologies and electrochemistry of the composite were investigated by using Fourier transform infrared (FTIR) spectrometry, scanning electron microscopy (SEM) and electrochemical techniques including cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), respectively. The performances of the biosensor have been investigated by chronoamperometry method under the optimized conditions. This biosensor showed a linear response to glucose range from 1.5 μM to 1.12 mM with a detection limit of 0.47 μM (S/N=3), a high sensitivity of 23.4 μA mM(-1) cm(-2), and a fast response time. The apparent Michaelis-Menten constant (K(M)(app)) was 1.89 mM. In addition, the biosensor also exhibited strong anti-interference ability, excellent stability and good reproducibility., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A novel strategy for "signal on" and sensitive one-spot simultaneous detection of multiple small molecular analytes based on electrochemically encoded barcode quantum dot (QD) tags is described. The target analytes, adenosine triphosphate (ATP) and cocaine, respectively, are sandwiched between the corresponding set of surface-immobilized primary binding aptamers and the secondary binding aptamer/QD bioconjugates. The captured QDs yield distinct electrochemical signatures after acid dissolution, whose position and size reflect the identity and level, respectively, of the corresponding target analytes. Due to the inherent amplification feature of the QD labels and the "signal on" detection scheme, as well as the sensitive monitoring of the metal ions released upon acid dissolution of the QD labels, low detection limits of 30 nM and 50 nM were obtained for ATP and cocaine, respectively, in our assays. Our multi-analyte sensing system also shows high specificity to target analytes and promising applicability to complex sample matrix, which makes the proposed assay protocol an attractive route for screening of small molecules in clinical diagnosis., (Copyright © 2010 Elsevier B.V. All rights reserved.)

A new label-free amperometric immunosensor was developed for detection of human chorionic gonadotrophin (hCG) based on multiwall carbon nanotubes-chitosan (MWNTs-CS) complex film and three-dimensional AuNPs-TiO(2) hybrid. Firstly, MWNTs-CS film was deposited on a glassy carbon electrode (GCE) by a simple and controllable electrodeposition method. Next, thionine (Thi), as a redox probe, was covalently bound onto the MWNTs-CS film with glutaraldehyde (GA) to obtain the Thi/MWNTs-CS film. The free amino groups of the composite membrane were used to adsorb AuNPs-TiO(2) for immobilizing human chorionic gonadotrophin antibody (anti-hCG) because of its large surface area and satisfactory biocompatibility. At last, BSA was employed to block possible remaining active sites. Under optimized conditions, the immunosensor displayed high sensitivity, good reproducibility, and a low detection limit of 0.08mIU/mL at 3 times the background noise. The ease of non-manual technique and the promising feature of biocomposite could serve as a versatile platform for constructing other biosensors., (Copyright © 2010 Elsevier B.V. All rights reserved.)

A signal amplificatory electrochemical immunoassay with biotin-streptavidin conjunction and multienzymatic-based substrate recycling was developed in this work. Biotinylated secondary antibody (bio-IgG) was preliminarily assembled onto the immunosensor interface based on the sandwich format. Streptavidin was then loaded based on biotin-streptavidin conjunction. Owing to four identical binding sites of streptavidin to biotin, amounts of biotinylated alkaline phosphatase (bio-AP) were attached, and this improved the catalytic performance of the proposed immunosensor. Under the enzyme catalysis of AP, the electroinactive p-aminophenylphosphate (PAPP) substrate was rapidly hydrolyzed into the electroactive p-aminophenol (PAP) product, which next oxidized at the electrode surface into p-quinoneimine (PQI). In the presence of diaphorase (DI), PQI was reduced back to PAP, leading to a reversible cycle of PAP. Then the oxidized state of DI was regenerated into its reduced native state by its natural substrate, nicotinamide adenine dinucleotide (NADH). With the several amplification factors mentioned above, a wider linear ranged from 10(-14) to 10(-5) gml(-1) was acquired with a relatively low detection limit of 3.5 x 10(-5) gml(-1) for human IgG. In addition, the nonspecific adsorption of proposed immunosensor was also investigated here., (Copyright 2010 Elsevier Inc. All rights reserved.)

A simple and sensitive sandwich-type electrochemiluminescence immunosensor for alpha-1-fetoprotein (AFP) on a gold nanoparticles (nano-Au) modified glassy carbon electrode (GCE) was developed by using Ru-silica (Ru(bpy)(3)(2+)-doped silica) doped Au (Ru-silica@Au) composite as labels. The primary antibody, anti-AFP was first immobilized on the gold nanoparticles modified electrode due to the covalent conjugation, then the antigen and the Ru-silica@Au composite nanoparticles labeled secondary antibody was conjugated successively to form a sandwich-type immunocomplex through the specific interaction. The surfaces of Ru-silica nanoparticles were modified via the assemble of Au nanoparticles. The prepared Ru-silica@Au composite nanoparticles own the large surface area, good biocompatibility and highly effective electrochemiluminescence properties. The morphologies of the Ru-silica@Au composite nanoparticles were investigated by using transmission electronic microscope (TEM). The Ru-silica@Au composite nanoparticles labeled anti-AFP/AFP/bovine serum albumin (BSA)/anti-AFP/nano-Au modified GCE electrode was evaluated by means of cyclic voltammetry (CV) and electrogenerated chemiluminescence (ECL). The immunosensor performed high sensitivity and wide liner for detection AFP in the range of 0.05-50 ng/mL and the limit detection was 0.03 ng/mL (defined as S/N=3)., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)

In this work, protonated L-cysteine was entrapped in Nafion (Nf) membrane by cation exchange function, forming Nf-Cys (cysteine) composite membrane, which was more stable, compact, biocompatible, and favorable for mass and electron transfer compared with Nf film solely. Then gold (Au) nanoparticles were adsorbed onto the electrode surface by thiol groups on the composite membrane. After that, nano-Au monolayer was formed, onto which carcinoembryonic antibody was loaded to prepare carcinoembryonic antigen (CEA) immunosensor. The results indicated that the immunosensor had good current response for CEA using potassium ferricyanide as the redox probe. A linear concentration range of 0.01 to 100 ng/ml with a detection limit of 3.3 pg/ml (signal/noise=3) was observed. Moreover, the morphology of the modified Au substrates was investigated with atomic force microscopy, and the electrochemical properties and performance of modified electrodes were investigated by cyclic voltammograms and electrochemical impedance spectroscopy. The results exhibited that the immunosensor has advantages of simple preparation, high sensitivity, good stability, and long life expectancy. Thus, the method can be used for CEA analysis., (2010 Elsevier Inc. All rights reserved.)

A new glucose biosensor had been developed by immobilizing positively charged gold nanoparticles (PGNs) on organosilica nanosphere functionalized Prussian blue (OSiFPB)-modified gold electrode. The OSiFPB compound could not only effectively prevent the leakage of the PB mediator during measurements, but also easily form stable film on the electrode surface with efficient redox-activity and excellent conductivity. Furthermore, with the negatively charged surface of OSiFPB, this film could be used as an interface to adsorb the PGNs, which provided a congenial microenvironment for adsorbing biomolecules and decreased the electron-transfer impedance. So, with glucose oxidase as a model biomolecular, the proposed sensor showed rapid and highly sensitive amperometric response to glucose and this immobilization approach effectively improved the stability of the electron-transfer mediator. This work would be promising for construction of biosensor and bioelectronic devices., (Copyright 2010 Elsevier B.V. All rights reserved.)

Herein, a novel label-free electrochemical aptasensor based on direct immobilization of the redox probes on an electrode surface was reported. Gold electrode coated Nafion was firstly modified with redox probe-thionine (Thi) through ion exchange adsorption. Then, with the help of chemisorption and electrostatic adsorption, negatively charged nano-Au and positively charged Thi were layer-by-layer (LBL) self-assembled onto the modified electrode surface, which formed {nano-Au/Thi(+)}(n) multilayer films for improving the amount of redox probes and immobilizing thiolated thrombin aptamers (TBA). In the presence of target thrombin (TB), the TBA on the multilayer film could catch the TB onto the electrode surface, which resulted in a barrier for electro-transfer, leading to decrease of the current. The proposed method avoided the cubsome redox probe labeling process, increased the amount of redox probe and reduced the distance between the redox probe and electrode surface. Thus, the approach showed a high sensitivity and a wider linearity to TB in the range from 0.12 nM to 46 nM with a detection limit of 40 pM., (Copyright 2010 Elsevier B.V. All rights reserved.)