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1.
Small ; : e2402823, 2024 May 07.
Article in English | MEDLINE | ID: mdl-38712472

ABSTRACT

Perovskite oxides are proven as a striking platform for developing high-performance electrocatalysts. Nonetheless, a significant portion of them show CO2 electroreduction (CO2RR) inertness. Here a simple but effective strategy is reported to activate inert perovskite oxides (e.g., SrTiO3) for CO2RR through slight Cu2+ doping in B-sites. For the proof-of-concept catalysts of SrTi1-xCuxO3 (x = 0.025, 0.05, and 0.1), Cu2+ doping (even in trace amount, e.g., x = 0.025) can not only create active, stable CuO6 octahedra, increase electrochemical active surface area, and accelerate charge transfer, but also significantly regulate the electronic structure (e.g., up-shifted band center) to promote activation/adsorption of reaction intermediates. Benefiting from these merits, the stable SrTi1-xCuxO3 catalysts feature great improvements (at least an order of magnitude) in CO2RR activity and selectivity for high-order products (i.e., CH4 and C2+), compared to the SrTiO3 parent. This work provides a new avenue for the conversion of inert perovskite oxides into high-performance electrocatalysts toward CO2RR.

2.
Int J Mol Sci ; 25(8)2024 Apr 17.
Article in English | MEDLINE | ID: mdl-38673993

ABSTRACT

Cucumber (Cucumis sativus L.) is a globally prevalent and extensively cultivated vegetable whose yield is significantly influenced by various abiotic stresses, including drought, heat, and salinity. Transcription factors, such as zinc finger-homeodomain proteins (ZHDs), a plant-specific subgroup of Homeobox, play a crucial regulatory role in stress resistance. In this study, we identified 13 CsZHDs distributed across all six cucumber chromosomes except chromosome 7. Phylogenetic analysis classified these genes into five clades (ZHDI-IV and MIF) with different gene structures but similar conserved motifs. Collinearity analysis revealed that members of clades ZHD III, IV, and MIF experienced amplification through segmental duplication events. Additionally, a closer evolutionary relationship was observed between the ZHDs in Cucumis sativus (C. sativus) and Arabidopsis thaliana (A. thaliana) compared to Oryza sativa (O. sativa). Quantitative real-time PCR (qRT-PCR) analysis demonstrated the general expression of CsZHD genes across all tissues, with notable expression in leaf and flower buds. Moreover, most of the CsZHDs, particularly CsZHD9-11, exhibited varying responses to drought, heat, and salt stresses. Virus-induced gene silencing (VIGS) experiments highlighted the potential functions of CsZHD9 and CsZHD10, suggesting their positive regulation of stomatal movement and responsiveness to drought stress. In summary, these findings provide a valuable resource for future analysis of potential mechanisms underlying CsZHD genes in response to stresses.


Subject(s)
Cucumis sativus , Evolution, Molecular , Gene Expression Regulation, Plant , Phylogeny , Plant Proteins , Stress, Physiological , Cucumis sativus/genetics , Cucumis sativus/metabolism , Stress, Physiological/genetics , Plant Proteins/genetics , Plant Proteins/metabolism , Transcription Factors/genetics , Transcription Factors/metabolism , Zinc Fingers/genetics , Droughts , Chromosomes, Plant/genetics , Gene Expression Profiling
3.
Environ Res ; 222: 115361, 2023 04 01.
Article in English | MEDLINE | ID: mdl-36716807

ABSTRACT

The Fenton process is a widely used to remedy organic wastewaters, but it has problems of adding H2O2, low utilization efficiency of H2O2 and low mineralization efficiency. Here, a new photocatalysis-self-Fenton process was exploited for the removal of persistent 4-chlorophenol (4-CP) pollutant through coupling the photocatalysis of 4-carboxyphenylboronic acid edge covalently modified g-C3N4 (CPBA-CN) with Fenton. In this process, H2O2 was in situ generated via photocatalysis over CPBA-CN, the photogenerated electrons assisted the accelerated regeneration of Fe2+ to improve the utilization efficiency of H2O2, and the photogenerated holes facilitated the enhancement of 4-CP mineralization. Under the conjugation of CPBA, the electronic structure of CN was optimized and the molecular dipole was enhanced, resulting in the deepening valence band position, accelerated electron-hole pair separation, and improved O2 adsorption-activation. Therefore, the incremental 4-CP degradation rate in the CPBA-CN photocatalysis-self-Fenton process was approaching 0.099 min-1, by a factor of 3.1 times compared with photocatalysis. The parallel mineralization efficiency increased to 74.6% that was 2.1 and 2.6 times than photocatalysis and Fenton, respectively. In addition, this system maintained an excellent stability in the recycle experiment and can be potentially applied in a wide range of pHs and under the coexistence of various ions. This study would provide new insights for improving Fenton process and promote further development of Fenton in organic wastewater purification.


Subject(s)
Environmental Pollutants , Persistent Organic Pollutants , Hydrogen Peroxide/chemistry , Oxidation-Reduction , Wastewater , Catalysis
4.
Sensors (Basel) ; 23(5)2023 Mar 06.
Article in English | MEDLINE | ID: mdl-36905071

ABSTRACT

OBJECTIVE: To accurately achieve distal contact force, a novel temperature-compensated sensor is developed and integrated into an atrial fibrillation (AF) ablation catheter. METHODS: A dual elastomer-based dual FBGs structure is used to differentiate the strain on the two FBGs to achieve temperature compensation, and the design is optimized and validated by finite element simulation. RESULTS: The designed sensor has a sensitivity of 90.5 pm/N, resolution of 0.01 N, and root-mean-square error (RMSE) of 0.02 N and 0.04 N for dynamic force loading and temperature compensation, respectively, and can stably measure distal contact forces with temperature disturbances. CONCLUSION: Due to the advantages, i.e., simple structure, easy assembly, low cost, and good robustness, the proposed sensor is suitable for industrial mass production.

5.
Angew Chem Int Ed Engl ; 62(44): e202305530, 2023 Oct 26.
Article in English | MEDLINE | ID: mdl-37533227

ABSTRACT

Despite the intriguing potential shown by Sn-based perovskite oxides in CO2 electroreduction (CO2 RR), the rational optimization of their CO2 RR properties is still lacking. Here we report an effective strategy to promote CO2 -to-HCOOH conversion of Sn-based perovskite oxides by A-site-radius-controlled Sn-O bond lengths. For the proof-of-concept examples of Ba1-x Srx SnO3 , as the A-site cation average radii decrease from 1.61 to 1.44 Å, their Sn-O bonds are precisely shortened from 2.06 to 2.02 Å. Our CO2 RR measurements show that the activity and selectivity of these samples for HCOOH production exhibit volcano-type trends with the Sn-O bond lengths. Among these samples, the Ba0.5 Sr0.5 SnO3 features the optimal activity (753.6 mA ⋅ cm-2 ) and selectivity (90.9 %) for HCOOH, better than those of the reported Sn-based oxides. Such optimized CO2 RR properties could be attributed to favorable merits conferred by the precisely controlled Sn-O bond lengths, e.g., the regulated band center, modulated adsorption/activation of intermediates, and reduced energy barrier for *OCHO formation. This work brings a new avenue for rational design of advanced Sn-based perovskite oxides toward CO2 RR.

6.
Opt Express ; 30(4): 5618-5633, 2022 Feb 14.
Article in English | MEDLINE | ID: mdl-35209520

ABSTRACT

In this paper, the Karhunen-Loeve transform (KLT) and wavelength domain interferometric spectral singular value decomposition (SVD) are used for the first time to demodulate the pressure of an optical fiber Fabry-Perot (F-P) micro-pressure sensor, and the feasibility of the proposed method is demonstrated experimentally. The eigenvalue decomposition of the dominant frequency part of the beam-domain interferometric spectrum after the fast Fourier transform (FFT) is performed using KLT, and the singular value decomposition of the wavelength domain interferometric spectrum is additionally performed using SVD. Both methods use high-order eigenvalues as a new metric and then derive the relation between the new metric and the reference pressure. The two demodulation methods are experimentally compared, and we used an optical fiber F-P pressure sensor with unknown structure and material for pressure measurements. Even though the interferometric spectral signal is acquired using a coarse spectrometer (2.5 nm wavelength resolution), one can still achieve high demodulation accuracy with both algorithms. However, the SVD demodulation accuracy decreases significantly after reducing the spectral data points in the wavelength domain from 1566 to 783. KLT still has high demodulation accuracy and linearity after spectral data points are reduced from 1024 to 256 in the wavenumber domain. The satisfactory linearity of the measured pressure versus reference pressure and low reading errors validate the feasibility of the proposed demodulation algorithm.

7.
Electrophoresis ; 43(11): 1140-1147, 2022 06.
Article in English | MEDLINE | ID: mdl-35287245

ABSTRACT

A capillary electrophoresis-acid barrage stacking online enrichment method has been established to detect the four isoflavones which are Daidzein, Genistein, Formononetin, and Biochanin A. The proposed method was optimized using a single factor alternative method, and the optimal conditions obtained from the optimization were: the BGE was 25 mM borax and 2 mM ß-cyclodextrin, the applied separation voltage was 20 kV, and the detection wavelength was 260 nm. The time ratio of the injection of sample and the injection of acid was 150 s:20 s, and the acid used was 250 mM acetic acid. The sample solvent used was 60% v/v acetonitrile. The established method had the enrichment factor of these four isoflavones at 24.5, 32.0, 29.2, and 33.7, respectively, LOD and LOQ are as low as nanograms per milliliter. Finally, the CE-acid barrage stacking method was successfully applied to the determination of four isoflavones in rat plasma and red clover extract, verifying the applicability and feasibility of the method.


Subject(s)
Isoflavones , Acids , Animals , Electrophoresis, Capillary/methods , Rats
8.
Mikrochim Acta ; 189(11): 419, 2022 10 17.
Article in English | MEDLINE | ID: mdl-36251095

ABSTRACT

A novel strategy is reported to access high-performance nanozymes via the self-coordination of ferrocyanides ([Fe(CN)6]4-) onto the surface of the Cu3BiS3 (CBS) nanorods. Notably, the in situ formed nanozymes had high catalytic activity, good stability, low cost, and easy mass production. The formed nanozyme catalyzed the oxidation of the typical chromogenic substrate of 3,3',5,5'-tetramethylbenzidine (TMB) with a distinctive absorption peak at 652 nm, accompanied by a blue color development. Moreover, the attachment of deoxyribonucleoside 5'-monophosphates (dNMP) beforehand onto the surface of CBS prevented coordination of ferrocyanides and resulted in the tunable formation of the nanozyme, thereby enabling the construction of an exquisite biosensing platform. Taking the aptasensing of chloramphenicol (CAP) as an example, the engineered nanozyme allowed the construction of a homogenous, label-free, and high-performance bioassay in terms of its convenience and high sensitivity. Under the optimal conditions, changes in the absorption intensity at 652 nm for the oxidized TMB provides a good linear correlation with the logarithm of CAP concentrations in the range 0.1 pM to 100 nM, and the limit of detection was 0.033 pM (calculated from 3σ/s). Considering a vast number of bioreactions can be connected to dNMP production, we expect the engineerable nanozyme as a universal signal transduction scaffold for versatile applications in bioassays. Through the attachment of deoxyribonucleoside 5'-monophosphate (dNMP) on the surface of CBS to regulate the generation of self-coordinated nanozyme CBS/BiHCF, a homogeneous, label-free, and high-performance universal aptasensing platform was constructed.


Subject(s)
Ferrocyanides , Nanotubes , Benzidines , Chloramphenicol , Chromogenic Compounds , Deoxyribonucleosides
9.
Anal Chem ; 93(51): 17119-17126, 2021 12 28.
Article in English | MEDLINE | ID: mdl-34908413

ABSTRACT

Most of the cathodic photoelectrochemical (PEC) bioassays rely on electron accepting molecules for signal stimuli; unfortunately, the performances of which are still undesirable. New signal transduction strategies are still highly expected for the further development of cathodic photoelectrochemistry as a potentially competitive method. This work represents a new concept of invoked cathodic photoelectrochemistry by a spontaneously formed electron transporter for innovative operation of the sensing strategy. Specifically, the hexacyanoferrate(II) in solution easily self-coordinated with CuO nanomaterials and formed electron transporting copper hexacyanoferrate (CuHCF) on the surface, which endowed improved carrier separation for presenting augmented photocurrent readout. Exemplified by the T4 polynucleotide kinase (T4 PNK) and its inhibitors as targets, a homogenous cathodic PEC biosensing platform was achieved with the distinctive merits of label-free, immobilization-free, and split-mode readout. The mechanism revealed here provided a totally different perspective for signal transduction in cathodic photoelectrochemistry. Hopefully, it may stimulate more interests in the design and construction of semiconductor/transporter counterparts for exquisite operation of photocathodic bioanalysis.


Subject(s)
Biosensing Techniques , Electrochemical Techniques , Electrodes , Electrons , Signal Transduction
10.
Opt Express ; 29(10): 15664-15677, 2021 May 10.
Article in English | MEDLINE | ID: mdl-33985263

ABSTRACT

A broadband single-polarization single-mode (SPSM) hollow core anti-resonant photonic crystal fiber (HC-ARPCF) is proposed and analyzed by the finite element method in this paper. The HC-ARPCF design consisted of outer semicircular cladding tubes and inner circular cladding tubes. The SPSM behavior is achieved through controlling the effective material absorption loss (EML) by loading epsilon negative (ENG) material in the selected semicircular cladding tubes. Optimization of the configuration parameters is conducted to yield a large loss difference (LD) between one of the two orthogonally polarized fundamental modes and all the other unwanted modes. Therefore, only one desired mode will exist after a proper propagation distance, i.e., SPSM guidance. Specially, the optimal design provides a 288 nm (from 1408 nm to 1676 nm and from 1680 nm to 1700 nm) bandwidth in terms of 40 dB/m minimum LD (MLD) and 168 nm (from 1452 nm to 1620 nm) bandwidth in terms of 100 dB/m MLD. Furthermore, this fiber also exhibits a large effective mode area and near-zero dispersion properties over the entire operation bandwidth. The proposed HC-ARPCF may find its applications in polarization maintaining and high-power laser systems.

11.
J Sep Sci ; 44(17): 3188-3198, 2021 Sep.
Article in English | MEDLINE | ID: mdl-34212486

ABSTRACT

Isoflavone is one of the phytoestrogens that have estrogenic effects, so it is usually served as an active ingredient for quality control of traditional Chinese medicines rich in isoflavones. Nine isoflavones commonly found in traditional Chinese medicines were separated in 30 min using mixed micellar liquid chromatography. The mobile phase consisted of 0.08 M sodium dodecylsulfate and 6.05 mM ß-cyclodextrin:methanol (87:13, v/v) at pH 3 and eluted isocratically at 1 mL/min through a C18 column. In this study, we systematically optimized the chromatographic conditions including the pH, the composition and concentration of surfactants, the type and ratio of organic solvents, and column temperature. The method was validated according to the International Council for Harmonization of Technical Requirements for Pharmaceuticals for Human Use guidelines. There is no report using micellar liquid chromatography to detect isoflavones, and the optimized method has been successfully applied to quantify isoflavones in red clover and Radix Puerariae. This method is efficient, cheap, and convenient. Finally, we verified the existence of supramolecular amphiphilic vesicles in the mobile phase by transmission electron microscopy to explain the increased chromatographic efficiency.


Subject(s)
Drugs, Chinese Herbal/analysis , Isoflavones/analysis , Sodium Dodecyl Sulfate/chemistry , beta-Cyclodextrins/chemistry , Chromatography, Liquid , Hydrogen-Ion Concentration , Macromolecular Substances/chemistry , Medicine, Chinese Traditional , Micelles
12.
Sensors (Basel) ; 21(5)2021 Mar 05.
Article in English | MEDLINE | ID: mdl-33807600

ABSTRACT

A photonic crystal fiber (PCF) with high relative sensitivity was designed and investigated for the detection of chemical analytes in the terahertz (THz) regime. To ease the complexity, an extremely simple cladding employing four struts is adopted, which forms a rectangular shaped core area for filling with analytes. Results of enormous simulations indicate that a minimum 87.8% relative chemical sensitivity with low confinement and effective material absorption losses can be obtained for any kind of analyte, e.g., HCN (1.26), water (1.33), ethanol (1.35), KCN (1.41), or cocaine (1.50), whose refractive index falls in the range of 1.2 to 1.5. Besides, the PCF can also achieve high birefringence (∼0.01), low and flat dispersion, a large effective modal area, and a large numerical aperture within the investigated frequency range from 0.5 to 1.5 THz. We believe that the proposed PCF can be applied to chemical sensing of liquid and THz systems requiring wide-band polarization-maintaining transmission and low attenuation.

13.
Electrophoresis ; 41(3-4): 168-174, 2020 02.
Article in English | MEDLINE | ID: mdl-31705760

ABSTRACT

A new method for the measurement of aprotinin potency by CZE-UV detector was established for the first time. The on-line mixing of substrate, trypsin and aprotinin using at-inlet technology was realized by the established method. Enzymatic reaction, separation, and detection of substrate and product can be performed simultaneously online. The aprotinin potency can be measured within 4 min. The response surface methodology was used to optimize the incubation conditions of trypsin and substrate, and the optimized conditions were obtained under 17.39 mM phosphate buffer at pH 7.6, 1.40 min of incubation time. The repeatability of proposed method was evaluated in three different systems of capillary zone electrophoresis: (i) only substrate; (ii) trypsin and substrate; (iii) aprotinin, trypsin and substrate, and the RSDs of migration times and peak areas of substrate were less than 2.7 and 3.1%, respectively. The RSDs of migration times and peak areas of product were less than 2.1 and 3.0%, respectively. A formula was also developed to calculate the aprotinin potency in this method. In a word, the established CZE-UV method was convenient, fast, and environmentally friendly for the measurement of aprotinin potency.


Subject(s)
Aprotinin/analysis , Electrophoresis, Capillary/methods , Spectrophotometry, Ultraviolet/methods , Aprotinin/standards , Reproducibility of Results
14.
Anal Biochem ; 605: 113832, 2020 09 15.
Article in English | MEDLINE | ID: mdl-32717184

ABSTRACT

Immobilized enzyme has been gradually applied to the screening of enzyme inhibitors owing to its retained catalytic activity and reusability. In this work, the cheap and available cellulose filter paper (CFP) was used as a carrier for the immobilization of α-glucosidase (α-Glu). In virtue of the self-polymerization-adhesion behavior of dopamine, CFP was coated with a polydopamine composite layer and then α-glucosidase is covalently bound to the modified CFP through Schiff base reaction and Michael addition reaction. Combined with capillary electrophoresis (CE) analysis, enzyme reaction kinetics, inhibition kinetics and other performance of the prepared immobilized enzyme (CFP/Dopa/α-Glu) were examined and verified. Its Michaelis constant (Km) was calculated to be 0.83 mM. And the inhibition constant (Ki) and half-maximal inhibitory concentration (IC50) for acarbose were determined to be 0.16 and 0.17 µM, respectively. CFP/Dopa/α-Glu had the same optimum working pH value (7.0) as free α-Glu and slightly higher working temperature (65 °C) than free α-Glu. In addition, it exhibited good batch-to-batch reproducibility with an RSD value of 4.4% (n = 10), and excellent reusability with 71% of the initial enzyme activity after being recycled 11 times. Finally, the CFP/Dopa/α-Glu was applied to screen α-glucosidase inhibitors from 11 traditional Chinese medicines, and Terminalia chebula possessed the strongest inhibition effect on α-glucosidase.


Subject(s)
Drugs, Chinese Herbal/chemistry , Glycoside Hydrolase Inhibitors/analysis , alpha-Glucosidases/chemistry , Enzyme Inhibitors/analysis , Enzymes, Immobilized/chemistry , Indoles/chemistry , Kinetics , Polymers/chemistry , Terminalia/chemistry
15.
Mikrochim Acta ; 187(1): 16, 2019 12 05.
Article in English | MEDLINE | ID: mdl-31802232

ABSTRACT

A method is described for modulating the anodic photoelectrochemistry of netlike CdS quantum dots through the deposition and dissolution of the electron acceptor manganese dioxide (MnO2) on the surface of the photoelectrode. Specifically, the photocurrent of a CdS-modified indium tin oxide (ITO/CdS) electrode is inhibited by chemical deposition of MnO2. However, the photocurrent becomes recovered by oxidative removal of MnO2 with H2O2. This deposition-dissolution reaction modulates the photoelectrochemistry of CdS effectively. A bioassay for Escherichia coli (E. coli) O157:H7 is designed that uses the antimicrobial peptide magainin I as the recognition element. Glucose oxidase (GOx) acts as a catalytic label tracer to produce the signaling molecule H2O2 in the microwell plates. The enzymatically generated H2O2 etches the deposited MnO2 on the photoelectrode and thus enhances the photocurrent. This detection scheme does not cause any damage to biomolecules. It also avoids the adverse effects of immobilized biomolecules for retarding signal production and leads to improved detection when compared to conventional PEC configurations. E. coli can be detected in the 10 to 5.0 × 106 CFU·mL-1 concentration range, and the limit of detection is 3 CFU·mL-1. Graphical abstractSchematic representation of the photoelectrochemical assay of E. coli through the deposition and dissolution of electron accepting manganese dioxide (MnO2) on the surface of the photoelectrode.

16.
Anal Chem ; 90(3): 1492-1497, 2018 02 06.
Article in English | MEDLINE | ID: mdl-29345904

ABSTRACT

Herein we report a general and novel strategy for high-throughput photoelectrochemical (PEC) enzymatic bioanalysis on the basis of enzyme-initiated quinone-chitosan conjugation chemistry (QCCC). Specifically, the strategy was illustrated by using a model quinones-generating oxidase of tyrosinase (Tyr) to catalytically produce 1,2-bezoquinone or its derivative, which can easily and selectively be conjugated onto the surface of the chitosan deposited PbS/NiO/FTO photocathode via the QCCC. Upon illumination, the covalently attached quinones could act as electron acceptors of PbS quantum dots (QDs), improving the photocurrent generation and thus allowing the elegant probing of Tyr activity. Enzyme cascades, such as alkaline phosphatase (ALP)/Tyr and ß-galactosidase (Gal)/Tyr, were further introduced into the system for the successful probing of the corresponding targets. This work features not only the first use of QCCC in PEC bioanalysis but also the separation of enzymatic reaction from the photoelectrode as well as the direct signal recording in a split-type protocol, which enables quite convenient and high-throughput detection as compared to previous formats. More importantly, by using numerous other oxidoreductases that involve quinones as reactants/products, this protocol could serve as a common basis for the development of a new class of QCCC-based PEC enzymatic bioanalysis and further extended for general enzyme-labeled PEC bioanalysis of versatile targets.


Subject(s)
Biosensing Techniques , Chitosan/chemistry , Electrochemical Techniques , High-Throughput Screening Assays , Quinones/chemistry , Alkaline Phosphatase/chemistry , Alkaline Phosphatase/metabolism , Chitosan/metabolism , Electrodes , Lead/chemistry , Oxidoreductases/chemistry , Oxidoreductases/metabolism , Photochemical Processes , Quantum Dots/chemistry , Quinones/metabolism , Sulfides/chemistry , beta-Galactosidase/chemistry , beta-Galactosidase/metabolism
17.
Electrophoresis ; 39(11): 1410-1416, 2018 06.
Article in English | MEDLINE | ID: mdl-29464729

ABSTRACT

In this study, the capillary electrophoresis method with ultraviolet detection was established to directly determine amino acids in vinegar, according to the coordination interaction between amino acids (AAs) and copper ions. The online sweeping technique was combined to improve the detection sensitivity. The quality of vinegar was evaluated with AAs as parameters by United Nations Food Agriculture Organization/Word Health Organization AAs model and principal component analysis. Optimum conditions were obtained under 50 mM CuSO4 and adjusted pH 4.40 with 8 mM acetate, 70 s injection time, 22.5 kV separation voltage, and 254 nm detected wavelength. Method validation, indicating good linearity (R2  > 0.9989), precision with an RSD less than 8.0% (n = 5), LOD (0.13-0.25 µg/mL), LOQ (0.43-0.83 µg/mL) and recovery (80.5-112.6%). Under the optimal conditions, AAs in vinegar can be directly separated which is propitious for the quality evaluation of vinegar.


Subject(s)
Acetic Acid/standards , Amino Acids/analysis , Electrophoresis, Capillary/methods , Amino Acids/chemistry , Copper/chemistry , Food Quality
18.
Molecules ; 21(7)2016 Jul 09.
Article in English | MEDLINE | ID: mdl-27409598

ABSTRACT

In this study, a simple and amplified colorimetric assay is developed for the detection of the enzymatic activity of glucose oxidase (GOx) based on in situ formation of a photoswitchable oxidase mimetic of PO4(3-)-capped CdS quantum dots (QDs). GOx catalyzes the oxidation of 1-thio-ß-d-glucose to give 1-thio-ß-d-gluconic acid which spontaneously hydrolyzes to ß-d-gluconic acid and H2S; the generated H2S instantly reacts with Cd(2+) in the presence of Na3PO4 to give PO4(3-)-stabilized CdS QDs in situ. Under visible-light (λ ≥ 400 nm) stimulation, the PO4(3-)-capped CdS QDs are a new style of oxidase mimic derived by producing some active species, such as h⁺, (•)OH, O2(•-) and a little H2O2, which can oxidize the typical substrate (3,3,5,5-tetramethylbenzydine (TMB)) with a color change. Based on the GOx-triggered growth of the oxidase mimetics of PO4(3-)-capped CdS QDs in situ, we developed a simple and amplified colorimetric assay to probe the enzymatic activity of GOx. The proposed method allowed the detection of the enzymatic activity of GOx over the range from 25 µg/L to 50 mg/L with a low detection limit of 6.6 µg/L. We believe the PO4(3-)-capped CdS QDs generated in situ with photo-stimulated enzyme-mimicking activity may find wide potential applications in biosensors.


Subject(s)
Biomimetics , Colorimetry/methods , Glucose Oxidase/chemistry , Oxidoreductases/chemistry , Photochemical Processes , Biosensing Techniques , Catalysis , Enzyme Activation , Light , Photoelectron Spectroscopy
19.
Anal Chem ; 87(20): 10429-36, 2015 Oct 20.
Article in English | MEDLINE | ID: mdl-26419907

ABSTRACT

The alkaline phosphatase (ALP) biocatalysis followed by the in situ enzymatic generation of a visible light responsive nanozyme is coupled to elucidate a novel amplification strategy by enzymatic cascade reaction for versatile biosensing. The enzymatic hydrolysis of o-phosphonoxyphenol (OPP) to catechol (CA) by ALP is allowed to coordinate on the surface of TiO2 nanoparticles (NPs) due to the specificity and high affinity of enediol ligands to Ti(IV). Upon the stimuli by CA generated from ALP, the inert TiO2 NPs is activated, which demonstrates highly efficient oxidase mimicking activity for catalyzing the oxidation of the typical substrate of 3,3',5,5'-tetramethylbenzidine (TMB) under visible light (λ ≥ 400 nm) irradiation utilizing dissolved oxygen as an electron acceptor. On the basis of the cascade reaction of ALP and the nanozyme of CA coordinated TiO2 (TiO2-CA) NPs, we design exquisitely colorimetric biosensors for probing ALP activity and its inhibitor of 2, 4-dichlorophenoxyacetic acid (2,4-DA). Quantitative probing of ALP activity in a wide linear range from 0.01 to 150 U/L with the detection limit of 0.002 U/L is realized, which endows the methodology with sufficiently high sensitivity for potentially practical applications in real samples of human serum (ALP level of 40-190 U/L for adults). In addition, a novel immunoassay protocol by taking mouse IgG as an example is validated using the ALP/nanozyme cascade amplification reaction as the signal transducer. A low detection limit of 2.0 pg/mL is attained for mouse IgG, which is 4500-fold lower than that of the standard enzyme-linked immuno-sorbent assay (ELISA) kit. Although only mouse IgG is used as a proof-of-concept in our experiment, we believe that this approach is generalizable to be readily extended to other ELISA systems. This methodology opens a new horizon for amplified and versatile biosensing including probing ALP activity and following ALP-based ELISA immunoassays.


Subject(s)
Alkaline Phosphatase/metabolism , Biosensing Techniques , Nanoparticles/metabolism , Nanoparticles/radiation effects , Alkaline Phosphatase/blood , Animals , Biocatalysis , Catechols/chemistry , Catechols/metabolism , Humans , Hydrolysis , Immunoassay , Immunoglobulin G/analysis , Light , Mice , Nanoparticles/chemistry , Photochemical Processes , Titanium/chemistry , Titanium/metabolism
20.
Anal Chem ; 87(5): 2892-900, 2015 Mar 03.
Article in English | MEDLINE | ID: mdl-25649393

ABSTRACT

We present a novel photoelectrochemical (PEC) biosensing platform by taking advantage of the phenomenon that hemin intercalated in G-quadruplex "switched-on" the cathode photocurrent of p-type PbS quantum dots (QDs). Photoinduced electron transfer between PbS QDs and G-quadruplex/hemin(III) complexes with the subsequent catalytic oxygen reduction by the reduced G-quadruplex/hemin(II) led to an obvious enhancement in the cathodic photocurrent of the PbS QDs. For the detection process, in the presence of hemin, the specific recognition of the targets with the sensing sequence would trigger the formation of a stable G-quadruplex/hemin complex, which will result in reduced charge recombination and hence amplified photocurrent intensity of the PbS QDs. By using different target sequences, the developed system made possible a novel, label-free "switch-on" PEC aptasensor toward versatile biomolecular targets such as DNA and thrombin. Especially, with ambient oxygen to regenerate G-quadruplex/hemin(II) to G-quadruplex/hemin(III), this substrate-free strategy not only promoted the photoelectric effect and thus the enhanced sensitivity of the system, but also avoided the addition of supplementary substrates of G-quadruplex/hemin such as H2O2 and organic substances.


Subject(s)
Biosensing Techniques/methods , Electrochemical Techniques/methods , G-Quadruplexes , Hemin/chemistry , Lead/chemistry , Photochemistry , Quantum Dots , Sulfides/chemistry , Catalysis , DNA/analysis , Electrodes , Electron Transport , Thrombin/analysis , X-Ray Diffraction
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