Liposome encapsulated electron donor strategy for signal-on CYFRA 21-1 photoelectrochemical analysis.

A novel electron donor controlled-release system is proposed based on liposome encapsulated L-cysteine for the sensitive determination of cytokeratin 19 fragment 21-1 (CYFRA 21-1). On the one hand, a defective TiO2 modified with methylene blue was employed as a photoactive platform which exhibited a high photoelectrochemical (PEC) response owing to the introduction of oxygen vacancies and the high  photosensitivity of the dye. On the other hand, L-cysteine as the sacrificial electron donor was encapsulated in the vesicles of liposomes, and this composite was used as the signal amplification factor, which is labeled on the secondary antibody of CYFRA 21-1 to further improve the photocurrent sensitivity. The excellent electron transfer path in photoactive materials coupled with the skilful electron donor controlled-release system, contributed to the sensitive  PEC analysis of CYFRA 21-1 underoptimum conditions. The PEC immunoassay showed a linear current response in the range 0.0001-100 ng/mL with a detection limitof 37 fg/mL. Enhanced stability and satisfactory reproducibility were also achieved. The proposed concept  provides a novel signal-on strategy for the sensitive detection of other cancer markers in the electrochemical sensing field.

An ultrasensitive electrochemical immunosensor for the detection of prostate-specific antigen based on conductivity nanocomposite with halloysite nanotubes.

A sensitive label-free amperometric electrochemical immunosensor for detection of prostate-specific antigen (PSA) was proposed in this work. The nanocomposite of halloysite nanotubes with polypyrrole shell and palladium nanoparticles (HNTs@PPy-Pd) was used as a novel signal label. The HNTs with adequate hydroxyl groups are economically available raw materials. PPy, as an electrically conducting polymer material, can be absorbed to the surface of HNTs by in situ oxidative polymerization of the pyrrole monomer and form a shell on the HNTs. The shell of PPy could not only improve the conductivity of the nanocomposite but also absorb large amounts of Pd nanoparticles (NPs). The Pd NPs with high electrocatalytic activity toward the reduction of H2O2 and the HNTs@PPy-Pd nanocomposite as the analytical signal label could improve the sensitivity of the immunosensor. Under optimal conditions, the immunosensor showed a low detection limit (0.03 pg/mL) and a wide linear range (0.0001 to 25 ng/mL) of PSA. Moreover, its merits such as good selectivity, acceptable reproducibility, and stability indicate that the fabricated immunosensor has a promising application potential in clinical diagnosis. Graphical Abstract A new label-free amperometric electrochemical immunosensor based on HNTs@PPy-Pd nanocomposite for quantitative detection of PSA.

Polyacrylic acid/polyethylene glycol hybrid antifouling interface for photoelectrochemical immunosensing of NSE based on ZnO/CdSe.

In this paper, a novel photoelectrochemical (PEC) immunosensor based on ZnO/CdSe semiconductor composite material was constructed to detect neuron-specific enolase (NSE) in a super-sensitive and quantitative way. The antifouling interface composed of polyacrylic acid (PAA) and polyethylene glycol (PEG) can prevent non-specific proteins from adhering to the electrode surface. As an electron donor, ascorbic acid (AA) can increase the photocurrent's stability and intensity by clearing away photogenerated holes. Because of the specific recognition between antigen and antibody, the quantitative detection of NSE can be achieved. The PEC antifouling immunosensor based on ZnO/CdSe has a wide linear range (0.10 pg mL-1-100 ng mL-1) and a low detection limit (34 fg mL-1), which has potential application in the clinical diagnosis of small cell lung cancer.

Dual-Signaling Electrochemical Ratiometric Method for Competitive Immunoassay of CYFRA21-1 Based on Urchin-like Fe3O4@PDA-Ag and Ni3Si2O5(OH)4-Au Absorbed Methylene Blue Nanotubes.

A novel ratiometric electrochemical (EC) sensing platform was established for sensitive immunoassay of target cytokeratin 19 fragment 21-1 (CYFRA21-1) biomarker by combining competitive immunoreaction and multisignal output. This immunosensor utilized Ag nanoparticles (NPs)-functionalized urchin-like Fe3O4@polydopamine (u-Fe3O4@PDA-Ag) as a matrix to immobilize CYFRA21-1 antigens and methylene blue (MB)-absorbed Ni3Si2O5(OH)4-Au nanotubes (NTs) to label the anti-CYFRA21-1 (Ab). During the competitive immunoreaction, square wave voltammetric (SWV) current changes of Ag NPs from u-Fe3O4@PDA-Ag indicator and MB from Ni3Si2O5(OH)4-Au/MB indicator are relevant to the dosage of CYFRA21-1-acquired Ni3Si2O5(OH)4-Au/MB/Ab. More importantly, numerous CYFRA21-1 loaded stably on u-Fe3O4@PDA-Ag exhibited strong competitive capacity toward the target-CYFRA21-1 to combine Ni3Si2O5(OH)4-Au/MB/Ab, causing sensitive changes in the ratio of two measured SWV currents. Prominently, "ΔI = ΔIMB + |ΔIAg NPs|" (ΔIMB and |ΔIAg NPs| represents the change values of the oxidation peak currents of MB and Ag NPs, respectively) could be regarded as significantly amplifying the signal response and ultimately improving the sensitivity of CYFRA21-1 detection, from which we derived a wide dynamic range from 500 fg/mL to 50 ng/mL and a low detection limit of 0.39 pg/mL (S/N = 3). This work may exert a profound impact on monitoring other biomarkers in early diagnosis of diseases.

Quench-Type Electrochemiluminescence Immunosensor Based on Resonance Energy Transfer from Carbon Nanotubes and Au-Nanoparticles-Enhanced g-C3N4 to CuO@Polydopamine for Procalcitonin Detection.

A new type of sandwich electrochemiluminescence (ECL) immunosensor dependent on ECL resonance energy transfer (ECL-RET) to achieve sensitive detection of procalcitonin (PCT) has been designed. In brief, carbon nanotubes (CNT) and Au-nanoparticles-functionalized graphitic carbon nitride (g-C3N4-CNT@Au) and CuO nanospheres covered with polydopamine (PDA) layer (CuO@PDA) were synthesized and applied as ECL donor and receptor, respectively. g-C3N4-CNT nanomaterials were in situ prepared on the basis of π-π conjugation, and the CNT content in the composite were optimized to achieve a strong and stable ECL signal. At the same time, Au nanoparticles were used to functionalize g-C3N4-CNT to further increase the ECL intensity and the loading amount of primary antibody (Ab1). Moreover, CuO@PDA was first used to successfully quench the ECL signal of g-C3N4-CNT@Au. Under the optimum experimental conditions, the linear detection range for PCT concentration was within 0.0001-10 ng mL-1 and the detection limit was 25.7 fg mL-1 (S/N = 3). Considering prominent specificity, reproducibility, and stability, the prepared immunosensor was used to assess recovery rate of PCT in human serum according to the standard addition method and the result was satisfactory. In addition, it is worth mentioning that a novel ECL-RET pair of g-C3N4-CNT@Au (donor)/CuO@PDA (acceptor) was first developed, which offered an effective analytical tool for sensitive detection of biomarkers in early disease diagnostics.

A novel sandwich-type photoelectrochemical immunosensor based on Ru(bpy)32+ and Ce-CdS co-sensitized hierarchical ZnO matrix and dual-inhibited polystyrene@CuS-Ab2 composites.

A novel and sensitive sandwich-type photoelectrochemical (PEC) immunosensor was developed for the quantitative detection of ß-amyloid protein (Aß). A ITO electrode was sequentially coated with hierarchical porous zinc oxide (ZnO) microspheres with a large specific area, sensitized with tris(bipyridine)ruthenium(II) ion (Ru(bpy)32+) to achieve high visible light absorption, and modified with cerium-doped cadmium sulfide (Ce-CdS) nanoparticles to enhance the PEC response. Under the stimulation of visible light and ascorbic acid as an efficient electron donor, the photoelectric signal of ZnO/Ru(bpy)32+/Ce-CdS was 70 times that of pure ZnO. The amino-functionalized polystyrene (PS) microspheres coated with copper sulfide (CuS) was linked with a secondary antibody (Ab2) for the first time for the Aß detection by the immunosensor. The good insulation and steric resistance of the as-prepared polystyrene@CuS-Ab2 (PS@CuS-Ab2) composite significantly weakened the photocurrent response of the immunosensor in the specific immune recognition. Under the optimal conditions, the quantitative detection of Aß was achieved within the range of 0.001-100 ng/mL with the detection limit of 0.37 pg/mL. In addition, the PEC immunosensor is easy to make, stable and selective, which has provided a good experimental platform for the detection of disease biomarkers.

A sandwich-type photoelectrochemical immunosensor for NT-pro BNP detection based on F-Bi2WO6/Ag2S and GO/PDA for signal amplification.

A sandwich-type photoelectrochemical (PEC) immunosensing platform was designed for detection of amino-terminal pro-B-type natriuretic peptide (NT-pro BNP). Thereinto, flower-like Bi2WO6/Ag2S nanoparticles (F-Bi2WO6/Ag2S) were employed as photoelectrochemical matrix, and graphene oxide and polydopamine composite (GO/PDA) were prepared as signal labels. In this proposal, Ag2S was in-situ growth on the surface of F-Bi2WO6 modified with thioglycolic acid (TGA). Specially, a cascade-like band-edge level between F-Bi2WO6 and Ag2S effectively improved the photocurrent conversion efficiency and enhanced the photocurrent response. Then, the conjugated GO/PDA aimed to further amplify signal because PDA as electron donor could sweep the holes and inhibit the recombination of photogenerated electron-hole pairs, while GO owned brilliant conductivity speeding up the electrons transfer. The photocurrent increased with the amount of GO/PDA conjugates which had positive correlation with the NT-pro BNP. Under optimal experimental conditions, the proposed sandwich-type PEC immunosensor presented a desirable linear relationship ranged from 0.1 pg/mL to 100 ng/mL for NT-pro BNP with the detection limit of 0.03 pg/mL (S/N = 3). The prepared PEC immunosensor exhibited high stability and selectivity, which offered an innovative idea for the detection of other biomolecules.

Ultrasensitive sandwich-type photoelectrochemical immunosensor based on CdSe sensitized La-TiO2 matrix and signal amplification of polystyrene@Ab2 composites.

A novel and sensitive sandwich-type photoelectrochemical (PEC) sensor was fabricated using signal amplification strategy for the quantitative detection of the prostate specific antigen (PSA). CdSe nanoparticles (NPs) sensitized lanthanum-doped titanium dioxide (La-TiO2) composites were used to bind the primary antibodies (Ab1). The doping of lanthanum promoted the visible light absorption of TiO2 and remarkably enhanced the photocurrent. Moreover, 0.3%La-TiO2 displayed the highest photocurrent in the La-TiO2 composites, which was twice as much as that of undoped TiO2. Carboxyl modified CdSe NPs were assembled onto La-TiO2 composites via the dentate binding between -COOH and Ti atom in TiO2 NPs, which dramatically promoted the photocurrent intensity by approximately 2.1 times. Carboxyl functionalized polystyrene (PS) microspheres were coated with the secondary antibodies (Ab2). Owing to the better insulation property and steric hindrance of the prepared polystyrene@Ab2 (PS@Ab2) composites, the significant reduction of the photocurrent signal was achieved after the specific immune recognition. Under the optimum experimental conditions, the fabricated PEC sensor realized ultrasensitive detection of PSA in the range of 0.05-100pgmL-1 with a detection limit of 17fgmL-1. Moreover, this well-designed PEC immunoassay exhibited ideal reproducibility, stability, and selectivity, which is a promising platform for the detection of other important tumor targets.

Zinc-doping enhanced cadmium sulfide electrochemiluminescence behavior based on Au-Cu alloy nanocrystals quenching for insulin detection.

Novel and sensitive sandwich-type electrochemiluminescence (ECL) immunosensor was fabricated for insulin detection. Au-ZnCd14S combined nitrogen doping mesoporous carbons (Au-ZnCd14S/NH2-NMCs) acted as sensing platform and Au-Cu alloy nanocrystals were employed as labels to quench the ECL of Au-ZnCd14S/NH2-NMCs. Zinc-doping promoted the ECL behavior of CdS nanocrystals, with the best ECL emission obtained when the molar ratio of Zn/Cd was 1:14. Simultaneously, the modification of gold nanoparticles (Au NPs) and combination with NH2-NMC further enhanced the ECL emission of ZnCd14S due to its excellent conductivity and large specific surface area, which is desirable for the immunosensor construction. Au-Cu alloy nanocrystals were employed in the ECL system of ZnCd14S/K2S2O8 triggering ECL quenching effects. The ECL spectra of ZnCd14S, acting as the energy donor, exhibited well overlaps with the absorption band of Au-Cu alloy nanocrystals which acted as the energy acceptor, leading to an effective ECL resonance energy transfer (ECL-RET). On the basis of the ECL quenching effects, a sensitive ECL immunosensor for insulin detection was successfully constructed with a linear response range of insulin concentration from 0.1pg/mL to 30ng/mL and the limit of detection was calculated to be 0.03pg/mL (S/N = 3).

Visible light photoelectrochemical aptasensor for adenosine detection based on CdS/PPy/g-C3N4 nanocomposites.

In this work, a label-free photoelectrochemical (PEC) aptasensor was developed for adenosine detection based on CdS/PPy/g-C3N4 nanocomposites. The CdS/g-C3N4 heterojunction effectively prevented the photogenerated charges recombination of g-C3N4 and self-photocorrosion processes of CdS, improving photo-to-current conversion efficiency. The introduced polypyrrole (PPy) nanoparticles could lead to a more effective separation of photogenerated charges, thus resulting in a further increasing of photocurrent. The CdS/PPy/g-C3N4 was firstly employed as the photoactive materials for fabrication of aptasensor, and SH-aptamer was then adsorbed on the CdS/PPy/g-C3N4 modified electrodes through S-Cd bond. With increasing of adenosine concentration, the photocurrent decreased as the formation of SH-aptamer-adenosine bioaffinity complexes. Under optimal conditions, the PEC aptasensor had a sensitive response to adenosine in a linear range of 0.3nmolL(-1) to 200nmolL(-1) with a detection limit of 0.1nmolL(-1). Besides, the as-proposed aptasensor has also been applied in human serum samples analysis. The aptasensor exhibits high sensitivity and good stability, thus opening up a new promising PEC platform for some other small molecules analysis.

Honeycomb-patterned fluorescent films fabricated by self-assembly of surfactant-assisted porphyrin/polymer composites.

A novel honeycomb-patterned fluorescent film was fabricated by self-assembly of polystyrene (PS)/poly(ethylene glycol) (PEG)/meso-tetra (N-methy-4-pyridyl) porphinetetratosylate (TMPyP) blend system, at the assistance of diisooctyl sodium sulfosuccinate (AOT). Ordered microporous PS/PEG/TMPyP/AOT blend films were prepared by the breath figure method. The condensed water droplets acted as the sacrificial templates, which were stabilized by strong hygroscopic PEG and amphiphilic surfactant AOT. Relative humidity and evaporation conditions considered as critical factors were investigated to control the morphologies of the films. The introduction of surfactant AOT greatly promoted the dissolution of the TMPyP in PS/PEG polymer solution according to the UV-vis spectra data, which led to the fluorescence enhancement of ordered porous blend films. The unique "internal ring" structures were formed during phase separation and confirmed by scanning electron microscopy images and fluorescence micrographs.

Fabrication and electrocatalytic activities of porphyrin and 12-molybdophosphoric acid hybrid films.

Hybrid films composed of oppositely charged Keggin-type 12-molybdophosphoric acid H(3)PMo(12)O(40).nH(2)O (PMo(12)) and water-soluble cationic meso-tetra (N-methyl-4-pyridyl) porphinetetratosylate (TMPyP) were fabricated onto silicon and ITO substrates by a layer-by-layer (LbL) self-assembly technique. The LbL films were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and cyclic voltammetry (CV). The electrochemical properties of the prepared multilayer films were controlled by adjusting the solution pH. Moreover, with increase in the layer number of TMPyP/PMo(12), the electrocatalytic current toward the reduction of IO(3)(-) was enhanced. The LbL films also displayed good electrocatalytic activities toward the reduction of BrO(3)(-), IO(3)(-) , and S(2)O(8)(2-).