Simultaneous photoelectrochemical detection of dual microRNAs by capturing CdS quantum dots and methylene blue based on target-initiated strand displaced amplification

Herein,we propose a novel photoelectrochemical(PEC) biosensor for dual microRNAs(miRNAs) highly sensitive and simultaneous biosensing based on strand displaced amplification(SDA) reaction.The recognition of H_(miR-21) and H_(let-7 a) by microRNA-21 and let-7 a leads to their change in hairpin structures,subsequently initiating the immobilization of abundant CdS quantum dots(CdS QD s) and methylene blue(MB) based on SDA reaction.The immobilized CdS QDs and MB produce both high PEC currents under430 nm light and 627 nm light illumination,respectively,and the generated PEC currents are closely relied on target miRNAs amounts.Thus,highly sensitive and simultaneous detection of microRNA-21 and let-7 a was readily achieved with detection limit at 6.6 fmol/L and 15.4 fmol/L based on 3σ,respectively.Further,this PEC biosensor was applied in simultaneous analysis of miRNA-21 and let-7 a in breast cancer patient's serum with acceptable results.We expect this biosensor will find more useful application in diagnosis of miRNA-related diseases.     

Long‐Lived Charge Carriers in Mn‐Doped CdS Quantum Dots for Photoelectrochemical Cytosensing

Photoelectrochemical (PEC) biosensing with semiconductor quantum dots (QDs) has received great attention because it integrates the advantages of both photo‐excitation and electrochemical detection. During the photon‐to‐electricity conversion in PEC processes, electron–hole (charge) separation competes with electron–hole recombination, and the net effect essentially determines the performance of PEC biosensors. Herein, we propose a new approach for slowing down electron–hole recombination to increase charge separation efficiency for PEC biosensor development. Through doping with Mn²⁺, a pair of d bands (⁴T₁ and ⁶A₁) is inserted between the conduction and valence bands of CdS QDs, which alters the electron–hole separation and recombination dynamics, allowing the generation of long‐lived charge carriers with ms‐scale lifetime that decay about 10⁴–10⁵‐fold more slowly than in the case of undoped QDs. Photocurrent tests indicated that Mn²⁺ doping resulted in an approximately 80 % increase in photocurrent generation compared with undoped CdS QDs. For application, the Mn‐doped CdS QDs were coated on the surface of a glassy carbon electrode and functionalized with a cell surface carbohydrate‐specific ligand (3‐aminophenylboronic acid). In this way, a sensitive cytosensor for K562 leukemia cells was constructed. Moreover, the sugar‐specific binding property of 3‐aminophenylboronic acid allowed the electrode to serve as a switch for the capture and release of cells. This has been further explored with a view to developing a reusable PEC cytosensing platform.     

Amperometric biosensor based on hemoglobin immobilized on Cu2S nanorods/nafion nanocomposite film for the determination of polyphenols

A novel biosensor was fabricated based on hemoglobin (Hb) immobilized onto cuprous sulfide (Cu₂S) nanorods/nafion nanocomposite film for the detection of polyphenols in the presence of hydrogen peroxide (H₂O₂). The nanostructured inorganic–organic hybrid material formed by Cu₂S nanorods and nafion provided a biocompatible microenvironment for Hb and increased the sensitivity for polyphenols detection. The modified electrodes were characterized by electrochemical impedance spectroscopy and linear sweep voltammetry. Parameters such as pH, H₂O₂ concentration, and the applied potential were optimized. Under optimum conditions, the biosensor gave linear response ranges of 7.0–110, 0.6–10, and 8–100 μM for catechol, hydroquinone, and resorcin, with the detection limits of 0.5, 0.03, and 0.6 μM (S/N?=?3), respectively. The developed biosensor exhibited a short response time within only 8 s with good stability and reproducibility. Such a novel biosensor showed great promise for rapid, simple analysis of polyphenols contents in real samples.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

Solvothermal synthesis and luminescence properties of CdS:Mn nanorods

CdS:Mn nanorods have been produced via a solvothermal approach in the nonaqueous solvent of ethylenediamine. An absolutely dominant single Mn²⁺ emission originating from the d-d (⁴T₁-⁶A₁) transition was obtained in CdS:Mn nanocrystals at room temperature. The effects of varying reaction temperature, molar ratio of S/Cd, and reaction time on the crystallinity and luminescence of CdS:Mn nanocrystals were systematically investigated. 1% Mn²⁺-doped CdS nanorods without any other additives were synthesized at 130°C for 10 h with an S/Cd molar ratio of 2:1. They show a rod-like shape, and their luminescence intensity around 593 nm is almost the strongest of all the nanorod samples investigated. CdS:Mn nanorods promise potential applications in nanoscale electronic and photonic devices.     

Hydrothermal synthesis, characterization and its photoactivity of CdS/Rectorite nanocomposites

CdS/Rectorite nanocomposites were prepared through hydrothermal method by using Cd[NH₂CSNH₂]₂Ac₂ complex as precursor of CdS which was derived from cadmium acetate and thiourea. The obtained nanocomposites were characterized by X-ray diffraction (XRD), Fourier transfer infrared spectra (FTIR), diffusion reflection spectra (DRS), transmission electron microscopy (TEM) and the selected area electron diffraction (SAED) patterns. Experimental results indicate that CdS exist in at least three forms: CdS adsorbed at surface, CdS pillared in montmorillonite-like layers of Rectorite and CdS pillared in the new layered structure formed during the hydrothermal process. Those CdS crystals are hexagonal symmetry. The photoactivity and photostability of the obtained CdS/Rectorite nanocomposites are improved significantly compared to that of the reference Rectorite and pure CdS.     

CdS‐Encapsulated TiO2 Nanotube Arrays Lidded with ZnO Nanorod Layers and Their Photoelectrocatalytic Applications

A novel TiO₂ nanotube array/CdS nanoparticle/ZnO nanorod (TiO₂ NT/CdS/ZnO NR) photocatalyst was constructed which exhibited a wide‐absorption (200–535 nm) response in the UV/Vis region and was applied for the photoelectrocatalytic (PEC) degradation of dye wastewater. This was achieved by chemically assembling CdS into the TiO₂ NTs and then constructing a ZnO NR layer on the TiO₂ NT/CdS surface. Scanning electron microscopy (SEM) results showed that a new structure had been obtained. The TiO₂ NTs looked like many “empty bottles” and the ZnO NR layer served as a big lid. Meanwhile the CdS NPs were encapsulated between them with good protection. After being sensitized by the CdS NPs, the absorption‐band edge of the obtained photocatalyst was obviously red‐shifted to the visible region, and the band gap was reduced from its original 3.20 eV to 2.32 eV. Photoelectric‐property tests indicated that the TiO₂ NT/CdS/ZnO NR material maintained a very high PEC activity in both the ultraviolet (UV) and the visible region. The maximum photoelectric conversion efficiencies of TiO₂ NT/CdS/ZnO NR were 31.8 and 5.98 % under UV light (365 nm) and visible light (420–800 nm), respectively. In the PEC oxidation, TiO₂ NT/CdS/ZnO NR exhibited a higher removal ability for methyl orange (MO) and a high stability. The kinetic constants were 1.77×10^?4 s^?1 under UV light, which was almost 5.9 and 2.6 times of those on pure TiO₂ NTs and TiO₂ NT/ZnO NR, and 2.5×10^?4 s^?1 under visible light, 2.4 times those on TiO₂ NT/CdS.     

Development of Quantum Dots Modified Acetylcholinesterase Biosensor for the Detection of Trichlorfon

Poly (N‐vinyl‐2‐pyrrolidone) (PVP)‐capped CdS quantum dots (QCdS‐PVP) was synthesized with CdCl₂ and Na₂S in the presence of PVP. QCdS‐PVP has been used for the immobilization and stabilization of the acetylcholinesterase (AChE). The electrocatalytic activity of QCdS‐PVP leads to a greatly improved electrochemical detection of the enzymatically generated thiocholine product, and higher sensitivity and stability. The GCE/QCdS‐PVP/AChE biosensor was used for the detection of organophosphate pesticides (OPs), such as trichlorfon. The sensor performance, including pH and inhibition time, was optimized with respect to operating conditions. Under the optimal conditions, the biosensor was used to measure as low as 12 ppb trichlorfon with a 5‐min inhibition time.     

Fabrication of Hemoglobin/Ionic Liquid Modified Carbon Paste Electrode Based on the Electrodeposition of Gold Nanoparticles/CdS Quantum Dots and Its Electrochemical Application

A novel H₂O₂ amperometric biosensor based on the electrodeposition of gold nanoparticles (AuNPs) and CdS quantum dots (CdS QDs) onto a carbon paste electrode (CPE) and immobilizing hemoglobin (Hb) with ionic liquid (IL), is presented in this article. The modification process of the electrode was monitored by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Due to synergistic effects of AuNPs, CdS QDs and IL, the biosensor exhibited high stability and good bioelectrocatalytic ability to H₂O₂ with a linear concentration range from 10 to 750 µM and a detection limit of 4.35 µM (S/N=3).     

Fabrication of CdS Nanorods in PVP Fiber Matrices by Electrospinning

Summary: A controlled fabrication of rod‐like nanostructures of cadmium sulfide (CdS) incorporated into polymer fiber matrices has been developed by an electrospinning method. Here, poly(vinyl pyrrolidone) (PVP) was used as a polymer capping reagent, utilizing the interactions of cadmium ions with the carbonyl groups in the PVP molecules. The formation of CdS nanorods inside the PVP was carried out via the reaction of Cd²⁺ with H₂S. SEM images showed that the electrospun films of PVP/CdS are composed of fibers with a diameter between 100 and 900 nm. TEM proved that most of the CdS nanorods are incorporated in the PVP fibrous film. The diameter of the rod is about 50 nm and the length is from 100 to 300 nm.

TEM image of the CdS nanorods formed in the PVP fibrous film.     

Electrochemical DNA Biosensor Based on Graphene and TiO2 Nanorods Composite Film for the Detection of Transgenic Soybean Gene Sequence of MON89788

Based on graphene (GR), TiO₂ nanorods, and chitosan (CTS) nanocomposite modified carbon ionic liquid electrode (CILE) as substrate electrode, a new electrochemical DNA biosensor was effectively fabricated for the detection of the transgenic soybean sequence of MON89788. By using methylene blue (MB) as hybridization indicator for monitoring the hybridization with different ssDNA sequences, the differential pulse voltammetric response of MB on DNA modified electrodes were recorded and compared. Due to the synergistic effects of TiO₂ nanorods and GR on the electrode surface, the electrochemical responses of MB were greatly increased. Under optimal conditions the differential pulse voltammetric response of the target ssDNA sequence could be detected in the range from 1.0×10^?12 to 1.0×10^?6 mol/L with a detection limit of 7.21×10^?13 mol/L (3σ). This electrochemical DNA biosensor was further applied to the polymerase chain reaction (PCR) product of transgenic soybeans with satisfactory results.     

Preparation and Optoelectronic Property of a SnO2/CdS Nanocomposite Based on the Flowerlike Clusters of SnO2 Nanorods

A SnO₂/CdS nanocomposite based on the flowerlike clusters of SnO₂ nanorods was prepared and characterized with x-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM) and EDX analysis. The SEM and TEM images show the nanocomposite is composed of CdS nanoparticles and flowerlike clusters of SnO₂ nanorods. The UV–vis spectrum of the nanocomposite displays a new absorption band in the region of 350 to 530 nm, compared with that of the flowerlike clusters of SnO₂ nanorods. The measurement of optoelectronic property indicates that the photoresponse of the composite is extended into the visible region and the incident photon-to-current conversion efficiency (IPCE) of the composite is up to 6.5 in the range of 400 to 440 nm. These phenomena ought to be ascribed to the special nanostructure of the SnO₂/CdS composite obtained.     

层状光催化材料H2La2Ti3O10/CdS的制备及其性质研究

通过改善酸交换过程,用分步柱撑法制备了一种新的层柱材料H2La2Ti3O10/CdS.用X射线粉末衍射（XRD）、红外光谱（IR）、比表面（BET）等方法对材料进行了表征;以光催化降解苯胺为探针对材料的活性进行了研究.结果表明： 通过柱撑CdS,H2La2Ti3O10的光催化性能得到明显提高;同时,对试验条件进行了优化,得到了最佳催化反应条件.     

One-pot hydrothermal synthesis of willow branch-shaped MoS2/CdS heterojunctions for photocatalytic H2 production under visible light irradiation

Willow branch-shaped MoS₂/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS₂/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS₂. In particular, the optimized MC-5 (5 at.% MoS₂/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h^-1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS₂/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS₂ nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H₂ evolution by MoS₂/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.     

TiO2@CdS core–shell nanorods films: Fabrication and dramatically enhanced photoelectrochemical properties

In this paper, we prepared TiO₂@CdS core–shell nanorods films electrodes using a simple and low-cost chemical bath deposition method. The core–shell nanorods films electrodes were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–vis spectrometry techniques. After applying these TiO₂@CdS core–shell nanorods electrodes in photovoltaic cells, we found that the photocurrent was dramatically enhanced, comparing with those of bare TiO₂ nanorods and CdS films electrodes. Moreover, TiO₂@CdS core–shell nanorods film electrode showed better cell performance than CdS nanoparticles deposited TiO₂ nanoparticles (P25) film electrode. A photocurrent of 1.31 mA/cm², a fill factor of 0.43, an open circuit photovoltage of 0.44 V, and a conversion efficiency of 0.8% were obtained under an illumination of 32 mW/cm², when the CdS nanoparticles deposited on TiO₂ nanorods film for about 20 min. The maximum quantum efficiency of 5.0% was obtained at an incident wavelength of 500 nm. We believe that TiO₂@CdS core–shell heterostructured nanorods are excellent candidates for studying some fundamental aspects on charge separation and transfer in the fields of photovoltaic cells and photocatalysis.     

Sb掺杂ZnSnO3透明导电薄膜：制备与性能

采用溶胶-凝胶法（Sol-Gel）和旋涂法制备了未掺杂的ZnSnO₃薄膜和掺入不同物质的量的Sb的ZnSnO₃薄膜。采用X射线衍射（XRD）、场发射扫描电镜（FE-SEM）、X射线光电子能谱（XPS）、霍尔效应仪（Hall）以及紫外-可见光（UV-Vis）等表征了热处理后薄膜的晶相、微观形貌、晶格缺陷、电学性能以及紫外-可见光透过率。结果表明：所有薄膜都是ZnSnO₃结构;与未掺Sb的ZnSnO₃薄膜相比,掺入Sb后的ZnSnO₃薄膜的电阻率都有不同程度的降低,其中掺入8mol%Sb的薄膜具有最低的电阻率0.96Ω·cm;缺陷研究表明：Sb的掺入使得晶格中的间隙锌离子含量增加,这有利于薄膜电阻率的降低;薄膜的紫外-可见光（UV-Vis）表明：在波长大于475nm的可见光范围内,掺入Sb的ZnSnO₃薄膜的可见光透过率都在80%以上。     

Sb掺杂ZnSnO_3透明导电薄膜:制备与性能(英文)

采用溶胶-凝胶法(Sol-Gel)和旋涂法制备了未掺杂的ZnSnO3薄膜和掺入不同物质的量的Sb的ZnSnO3薄膜。采用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、X射线光电子能谱(XPS)、霍尔效应仪(Hall)以及紫外-可见光(UV-Vis)等表征了热处理后薄膜的晶相、微观形貌、晶格缺陷、电学性能以及紫外-可见光透过率。结果表明:所有薄膜都是ZnSnO3结构;与未掺Sb的ZnSnO3薄膜相比,掺入Sb后的ZnSnO3薄膜的电阻率都有不同程度的降低,其中掺入8mol%Sb的薄膜具有最低的电阻率0.96Ω·cm;缺陷研究表明:Sb的掺入使得晶格中的间隙锌离子含量增加,这有利于薄膜电阻率的降低;薄膜的紫外-可见光(UV-Vis)表明:在波长大于475 nm的可见光范围内,掺入Sb的ZnSnO3薄膜的可见光透过率都在80%以上。     

Aptamer based photoelectrochemical determination of tetracycline using a spindle-like ZnO-CdS@Au nanocomposite

The authors have synthesized spindle-like ZnO nanorods closely anchored to CdS nanoparticles (NPs) placed on gold NPs (ZnO-CdS@Au). It is shown that the ZnO-CdS@Au nanocomposite can serve as a photoactive material for use in photoelectrochemical (PEC) detection by efficiently absorbing light and then promoting electron transfer. A visible light-driven PEC detection platform for tetracycline (TET) was fabricated by placing the nanocomposite on an ITO and immobilizing the TET-binding aptamer as biorecognition element. PEC can be quantified by applying a bias potential of +?0.4 V (vs. SCE) and visible light irradiation. The aptamer on the electrode specifically captures the TET present in the solution to produce a restored photocurrent signal through the reaction between the captured TET and the photogenerated holes. The electrode has a linear response in the 50 to 200 nM TET concentration range, with a 4.5 nM detection limit (at an S/N ratio of 3). In our perception, this novel PEC detection strategy based on ZnO-CdS@Au nanocomposite demonstrated an ultrasensitive method for TET detection with high selectivity and good stability.

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Graphical abstract Gold nanoparticles and CdS nanoparticles were deposited on the spindle-like ZnO nanorod surface (ZnO-CdS@Au). Photoelectrochemical detection of tetracycline (TET) was realized with high selectivity and good stability utilizing ZnO-CdS@Au as transducer and TET-binding aptamer as biorecognition element.

     

In situ localization of BiVO4 onto two-dimensional MXene promoting photoelectrochemical nitrogen reduction to ammonia

The existing industrial ammonia synthesis usually adopts the Haber-Bosch process, which requires harsh conditions of high temperature and high pressure, and consumes high energy. Under this circumstance, photoelectrochemical (PEC) catalysis is regarded as a promising method for N₂ reduction reaction (NRR), but bears problems of low efficiency and yield. Thus, exploring active catalysts remains highly desirable. In this work, BiVO₄@MXene hybrids have been facilely synthesized by a hydrothermal route. The heterojunctions by the in situ growth of BiVO₄ onto two-dimensional (2D) MXene greatly increase the NRR efficiency: under photoelectric conditions, the optimized NH₃ yield is 27.25 µg h ^{? 1} cm^?2, and the Faraday efficiency achieves 17.54% at ?0.8 V relative to the reversible hydrogen electrode (RHE), which are higher than most state-of-the-art NRR (photo) electrocatalysts. The mechanism speculation shows the enhanced light absorption range and the heterojunction formation largely promote the separation and the transfer efficiency of photogenerated carriers, thereby improving the PEC catalytic ability. Therefore, this work provides a hybrid route to combine the advantages of photo and electric catalysis for effective artificial nitrogen fixation.