Mechanism insight into the high-efficiency catalytic killing of E. coli by metal-phenolic network as a nanozyme.

Glutathione (GSH) as an antioxidant greatly attenuates the reactive oxygen species (ROS) treatment strategy based on peroxidase-activity nanozymes. Therefore, nanozymes with multiple properties that generate ROS and further GSH-depletion functions would be of great benefit to improve antimicrobial efficacy. Herein, focusing on the green, safe and abundant functional prospects of metal-phenolic networks (MPNs) and the strong prospect of biomedical applications, we have synthesized copper tannic acid (CuTA) nanozymes with dual functional properties similar to peroxidase-like activity and GSH depletion. CuTA can catalyze the decomposition of H2O2 to hydroxyl radicals (˙OH). In addition, CuTA nanozymes can efficiently deplete available GSH, thus enhancing ROS-mediated antimicrobial therapy. The antibacterial results show that CuTA has an excellent antibacterial effect against E. coli.

Rapid Trace Detection of Sulfite Residue in White Wine Using a Multichannel Colorimetric Nanozyme Sensor.

As a commonly used food additive, sulfite (SO32-) is popular with food manufacturers due to the functions of bleaching, sterilizing, and oxidation resistance. However, excess sulfites can pose a threat to human health. Therefore, it is particularly important to achieve rapid and sensitive detection of SO32-. Herein, a colorimetric sensor was invented for visual, meticulous, and rapid detection of SO32- based on MIL-53(Fe/Mn). Bimetallic nanozyme MIL-53(Fe/Mn) was prepared by a one-pot hydrothermal reaction. The prepared MIL-53(Fe/Mn) can effectively catalyze the oxidation of colorless TMB to a blue oxidation product (oxTMB). The introduction of SO32- causes significant discoloration of the reaction system, gradually transitioning from a visible blue color to colorless. Hence, a sensitive colorimetric sensor for SO32- detection was developed based on the decolorization degree of the detection system. Further, the discoloration was ascribed to the inactivation of nanozyme and the strong reducing ability of SO32-. Under the optimal experimental conditions, there was a good linear relationship between the absorbance at 652 nm and SO32- concentration in the linear range of 0.5-6 µg mL-1 with a limit of detection (LOD) of 0.05 µg mL-1. The developed method was successfully applied to the detection of actual samples of white wine with good accuracy and recovery. Compared to traditional methods, this colorimetric sensor produces similar detection results but significantly reduces the detection time. Compared to traditional methods, this colorimetric sensor can not only reduce the detection costs effectively but also help the food industry maintain quality standards. Strong anti-interference capability, simple operation, and low detection limits ensure the excellent performance of the colorimetric sensor in detecting SO32- in white wine. The combination of a smartphone and a colorimetric analysis application has also greatly facilitated the semi-quantitative, visual on-site detection of SO32-, which has opened up an application prospect of an MIL-53(Fe/Mn)-based detection platform. Our work has indicated a new direction for the detection of SO32- and provided important assurance for food safety.

Lanthanide bimetallic MOF-based fluorescent sensor for sensitive and visual detection of sulfamerazine and malachite.

A lanthanide terbium/europium metal-organic framework (Tb0.6Eu0.4-MOF) was prepared by one-step solvothermal method at room temperature. A series of characterizations including scanning electron microscopy, powder X-ray diffraction spectra, Fourier transform infrared spectra and X-ray photoelectron spectroscopy were carried out to clarify the physical characteristics of the synthesized material. The data clarified that the prepared Tb0.6Eu0.4-MOF possessed rod-like morphology with a width of 1-2 µm, and had good crystal structure, good stability, response speed and excitation-independent emission feature. The bunchy Tb0.6Eu0.4-MOF was then used to construct fluorescent sensors for rapid identification of malachite green and sulfamerazine. It was revealed that the detection mechanism was inner filter effect. The effects of different parameters such as excitation wavelength and incubation times were investigated on the fluorescence analysis performance. The data clarified that the optimal excitation wavelength and incubation time was 240 nm and 3 min, respectively. The detection platform exhibited the high sensitivity and selectivity toward malachite green in the linear range of 2-180 µM and determined limit of detection was 1.12 µM. Besides, the proposed sensor allowed sensitive detection of sulfamerazine in the linear range of 2-140 µM with a low detection limit of 0.1 µM. Meaningfully, a smartphone application was designed to assist the proposed sensor to realize visual, intelligent and rapid detection of malachite green and sulfamerazine. Furthermore, the practical application of the proposed sensor has been also verified by high performance liquid chromatography, showing good accuracy, sensitivity and satisfactory recoveries. The results suggested that the Tb0.6Eu0.4-MOF-based ratiometric fluorescent sensor had the potential to become a promising technique for rapid detection of malachite green or sulfamerazine with smartphone application. Therefore, the prepared Tb0.6Eu0.4-MOF is one kind of efficient and cost-effective potential materials for developing fluorescent sensor for rapid, sensitive and selective detection of sulfamerazine and malachite.

Fluorescent Sensing of Ciprofloxacin and Chloramphenicol in Milk Samples via Inner Filter Effect and Photoinduced Electron Transfer Based on Nanosized Rod-Shaped Eu-MOF.

Rapid, facile, and accurate detection of antibiotic residues is vital for practical applications. Herein, we designed a sensitive, visual, and rapid analytical method for sensitive detection of ciprofloxacin and chloramphenicol based on a nanosized rod-shaped Europium metal organic framework (Eu-MOF). The fluorescent Eu-MOF was firstly synthesized by a simple synthetic route at room temperature, which displays a red emission. The mechanisms of detecting ciprofloxacin and chloramphenicol were confirmed to be the inner filter effect (IFE) and photoinduced electron transfer (PET). Under the optimized experimental conditions, the detection limits of the developed method for ciprofloxacin and chloramphenicol detection were 0.0136 and 3.16 µM, respectively. Moreover, the sensor was effectively applied for quantitative determination of ciprofloxacin and chloramphenicol milk samples with satisfactory recoveries of 94.5-102% and 97-110%, respectively. This work developed a new method for rapid detection of ciprofloxacin and chloramphenicol residues. In addition, the established method has potential practical application value for on-site safety regulation on antibiotic residues in animal-derived food.

A facile fluorescent sensor based on nitrogen-doped carbon dots derived from Listeria monocytogenes for highly selective and visual detection of iodide and pH.

Sensitive and visual analysis of iodide (I-) and pH is significant in environmental and food applications. Herein, we present a facile fluorescent sensor for highly selective and visual detection of I- and pH based on nitrogen-doped carbon dots derived from Listeria monocytogenes (NCDs-LM). The NCDs-LM-based fluorescent sensor showed a good linear relationship to I- concentrations, and the detection limit was calculated as 20 nmol L-1. The developed sensor was successfully applied to the detection of I- in drinking water and milk samples. Meanwhile, the as-synthesized NCDs-LM sensor can be used to detect pH, achieving a wide linear pH range. Furthermore, fluorescent test papers based on NCDs-LM were designed for semi-quantitative detection of I- and pH via the naked-eye colorimetric assay. The present work indicates that the NCDs-LM-based fluorescent sensor has high potential for use in environmental monitoring and food analysis.

A portable smartphone-assisted ratiometric fluorescence sensor for intelligent and visual detection of malachite green.

Developing intelligent, sensitive, and visual methods for rapidly detecting veterinary drug residues is essential for ensuring food quality and safety. A portable smartphone-assisted ratiometric fluorescent sensor was successfully designed using fluorescent Al-MOF nanosheet and rhodamine B (RhB) as fluorescent probes to adjust to the requirement of malachite green (MG) detection. The developed ratiometric fluorescent sensor allowed sensitive and selective detection of MG with good linear relationships in a wide range of 0.5-200 µg/mL. The Quantitative linearrange is 5.3 µg/mL to 200 µg/mL. The limit of detection (LOD) and limit of quantification (LOQ) were calculated to be 1.6 µg/mL and 5.3 µg/mL respectively. The practicability of the proposed method was verified using high performance liquid chromatography (HPLC) in spiked fish tissues with satisfying recoveries and RSD. Moreover, portable smartphone-assisted fluorescent test papers were fabricated for the intelligent detection of MG. This integration of smartphones and fluorescent test papers was economical and saved time, providing an alternative strategy for the qualitative discernment and semi-quantitative analysis of MG on-site.

Inner-filter effect induced fluorescent sensor based on fusiform Al-MOF nanosheets for sensitive and visual detection of nitrofuran in milk.

Developing highly sensitive and visual methods for rapid detection of antibiotics is significant to ensure food quality and safety. To meet the requirement of nitrofuran antibiotics detection, luminescent fusiform Al(III)-containing metal-organic frameworks (Al-MOF) nanosheets were successfully synthesized by one-step hydrothermal method. And then, the nanosheet served as a fluorescent probe to detect nitrofuran via the inner-filter effect mechanism. The developed sensor allowed sensitive and selective detection of nitrofuran with good linear relationships. And, the detection limit (LOD) values were estimated to be 0.53, 0.838 and 0.583 µM for nitrofurazone, nitrofurantoin and furazolidone detection, respectively. The practical application of the proposed system was verified by HPLC in spiked milk samples with satisfying recoveries ranging from 88.14 to 126.21% and low relative standard deviations of 2.85 ~ 8.13%. Moreover, we designed fluorescent test papers for semi-quantitative detection of nitrofuran via naked-eye colorimetric assay. The established method provides an alternative strategy for semiquantitative detection of nitrofuran.

Three-dimensional porous carbon derived from different organic acid salts for application in electrochemical sensing.

Three-dimensional porous carbon materials were synthesized by the one-step pyrolysis of organic salts with different numbers of hydroxyl groups on the side chain (sodium tartrate, sodium malate and sodium succinate). Further, the formation of these porous carbon materials was explored. And then, three kinds of carbon materials were used for constructing electrochemical sensors for nitrite detection, respectively. Porous carbon derived from sodium tartrate (PCST) showed the highest electrocatalytic ability for nitrite oxidation among all three materials. The PCST-based sensors allow for rapid detection of nitrite in a wide linear range of 0.1-100 µM with a low detection limit of 0.043 µM. The sensor was applied to detect nitrite in meat samples and the results tested by the developed sensor were consistent with the results obtained by HPLC. We envision that PCST-based electrochemical sensor is promising as an alternative choice for the development of electrochemical analysis.

Peptide-conjugated hemin/G-quadruplex as a versatile probe for "signal-on" electrochemical peptide biosensor.

In this work, a novel "signal-on" electrochemical peptide biosensor based on peptide-conjugated hemin/G-quadruplex (DNAzyme-peptide) hybrid and rosebud-like MoSe2@reduced graphene oxide (MoSe2@rGO) nanocomposite, was developed for detection of prostate-specific antigen (PSA). Interestingly, the peptide not only served as recognition probe to detect PSA, but also acted as the enhancer to improve the enzyme activity of hemin/G4, which promoted the detection sensitivity. Up addition of PSA, Fe3O4-labeled DNAzyme-peptide probe was cleaved, followed by the magnetic separation. The cleaved DNAzyme-peptide was then captured onto the cysteine-modified electrode via the interaction between carboxyl groups of peptide and amino group of cysteine. A strong electrochemical signal was obtained from hemin and further was amplified by the enhanced electrocatalysis of DNAzyme-peptide. Compared to the original DNAzyme, DNAzyme-peptide exhibited more than 3-fold enhancement in signal amplification. And MoSe2@rGO amplified the electrochemical signal due to its good conductivity and large surface area. So the proposed strategy detected PSA down to 0.3 fg/mL, and it showed the advantages of simplicity, low cost by avoiding the use of expensive protein enzyme and additional electroactive species. Therefore, the proposed biosensor potentially provided a very effective tool for early diagnosis of cancer by the detection of PSA.

Selective electrochemical determination of tertiary butylhydroquinone in edible oils based on an in-situ assembly molecularly imprinted polymer sensor.

Developing selective and sensitive methods for tertiary butylhydroquinone (TBHQ) detection is of great significance to ensure the quality and safety of food. Herein, an electrochemical sensor was designed for selective and sensitive detection of TBHQ by integrating molecularly imprinted polymer, noble metal nanoparticles and carbon materials. The electrochemical sensor exhibited excellent performance for sensitive determination of TBHQ. The linear range was 0.5-60 µg mL-1 with a low detection limit of 0.046 µg mL-1. In addition, the results obtained by electrochemical method were well agreement with the detection results obtained by HPLC with good recoveries ranging from 99.4 to 108.5% in spiked edible oil samples. The present study not only has theoretical value to establish new methods for rapid detection of food additives but also has potential application values for monitoring the overuse of TBHQ.

Highly specific and sensitive determination of propyl gallate in food by a novel fluorescence sensor.

Propyl gallate (PG), one of the most widely used synthetic phenolic antioxidants in edible oil, cookies and fried food, has received extensive concern due to its possible toxic effects on human health. Herein, a novel fluorescence analytical method is firstly proposed to sensitively and selectively determine propyl gallate (PG) by utilizing the unique fluorescence quenching property of organic molybdate complex (OMC) formed by the specific reaction between MoO42- and PG to g-C3N4 nanosheets. Under the optimum conditions, the developed fluorescence sensor allows highly sensitive detection of PG in a wide range from 0.5 to 200 µg mL-1 with a detection limit of 0.11 µg mL-1, and possesses excellent specificity and good recoveries. All the analytical results indicate the present method provides an effective approach for rapid detection of PG in common products, which is beneficial for monitoring and reducing the risk of overuse of PG.

Au Promoted Nickel-Iron Layered Double Hydroxide Nanoarrays: A Modular Catalyst Enabling High-Performance Oxygen Evolution.

Oxygen evolution reaction (OER) plays a key role in various energy conversion and storage technologies, such as water electrolysis, regenerative fuel cells, and rechargeable metal-air batteries. However, the slow kinetics of OER limit the performance and commercialization of such devices. Herein, we report on NiFe LDH@Au hybrid nanoarrays on Ni foam for much enhanced OER. By hybridization of electronegative Au and NiFe LDH with intrinsic remarkable OER catalytic activity, this modular electrode could drive an overall ultrahigh-performance and robust OER in base with the demand of overpotentials of only 221, 235, and 270 mV to afford 50, 100, and 500 mA cm-2, respectively. Also, it exhibits superior catalytic activity and durability toward OER in 30 wt % KOH.

Highly Sensitive and Selective Determination of Tertiary Butylhydroquinone in Edible Oils by Competitive Reaction Induced "On-Off-On" Fluorescent Switch.

As one of most common synthetic phenolic antioxidants, tertiary butylhydroquinone (TBHQ) has received increasing attention due to the potential risk for liver damage and carcinogenesis. Herein, a simple and rapid fluorescent switchable methodology was developed for highly selective and sensitive determination of TBHQ by utilizing the competitive interaction between the photoinduced electron transfer (PET) effect of carbon dots (CDs)/Fe(III) ions and the complexation reaction of TBHQ/Fe(III) ions. This novel fluorescent switchable sensing platform allows determining TBHQ in a wider range from 0.5 to 80 µg mL(-1) with a low detection limit of 0.01 µg mL(-1). Furthermore, high specificity and good accuracy with recoveries ranging from 94.29 to 105.82% in spiked edible oil samples are obtained with the present method, confirming its applicability for the trace detection of TBHQ in a complex food matrix. Thus, the present method provides a novel and effective fluorescent approach for rapid and specific screening of TBHQ in common products, which is beneficial for monitoring and reducing the risk of TBHQ overuse during food storage.

Nickel sulfide microsphere film on Ni foam as an efficient bifunctional electrocatalyst for overall water splitting.

Developing low-cost, efficient, and bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is an appealing yet challenging task. Herein, for the first time, a NiS microsphere film was grown in situ on Ni foam (NiS/Ni foam) via a sulfurization reaction as an efficient bifunctional electrocatalyst for overall water splitting with superior activity and good durability. This NiS/Ni foam electrode delivers 20 mA cm(-2) at an overpotential of 158 mV for the HER and 50 mA cm(-2) at an overpotential of 335 mV for the OER in 1.0 M KOH. This bifunctional electrode also enables a high-efficiency alkaline water electrolyzer with 10 mA cm(-2) at a cell voltage of only 1.64 V, which could be promising in water splitting devices for large-scale hydrogen production.

DNA-mediated gold nanoparticle signal transducers for combinatorial logic operations and heavy metal ions sensing.

Herein, the structure of two DNA strands which are complementary except fourteen T-T and C-C mismatches was programmed for the design of the combinatorial logic operation by utilizing the different protective capacities of single chain DNA, part-hybridized DNA and completed-hybridized DNA on unmodified gold nanoparticles. In the presence of either Hg(2+) or Ag(+), the T-Hg(2+)-T or C-Ag(+)-C coordination chemistry could lead to the formation of part-hybridized DNA which keeps gold nanoparticles from clumping after the addition of 40 µL 0.2M NaClO4 solution, but the protection would be screened by 120 µL 0.2M NaClO4 solution. While the coexistence of Hg(2+), Ag(+) caused the formation of completed-hybridized DNA and the protection for gold nanoparticles lost in either 40 µL or 120 µL NaClO4 solutions. Benefiting from sharing of the same inputs of Hg(2+) and Ag(+), OR and AND logic gates were easily integrated into a simple colorimetric combinatorial logic operation in one system, which make it possible to execute logic gates in parallel to mimic arithmetic calculations on a binary digit. Furthermore, two other logic gates including INHIBIT1 and INHIBIT2 were realized to integrated with OR logic gate both for simultaneous qualitative discrimination and quantitative determination of Hg(2+) and Ag(+). Results indicate that the developed logic system based on the different protective capacities of DNA structure on gold nanoparticles provides a new pathway for the design of the combinatorial logic operation in one system and presents a useful strategy for development of advanced sensors, which may have potential applications in multiplex chemical analysis and molecular-scale computer design.