Multifunctional Fe/Cu Dual-Single Atom Nanozymes with Enhanced Peroxidase Activity for Isoniazid Detection and Levofloxacin Degradation.

The design of single-atom nanozymes with dual active sites to increase their activity and for the detection and degradation of contaminants is rare and challenging. In this work, a single-atom nanozyme (FeCu-NC) based on a three-dimensional porous Fe/Cu dual active site was developed as a colorimetric sensor for both the quantitative analysis of isoniazid (INH) and the efficient degradation of levofloxacin (LEV). FeCu-NC was synthesized using a salt template and freeze-drying method with a three-dimensional hollow porous structure and dual active sites (Fe-Nx and Cu-Nx). In terms of morphology and structure, FeCu-NC exhibits excellent peroxidase-like activity and catalytic properties. Therefore, a colorimetric sensor was constructed around FeCu-NC for sensitive and rapid quantitative analysis of INH with a linear range of 0.9-10 µM and a detection limit as low as 0.3 µM, and the sensor was successfully applied to the analysis of INH in human urine. In addition, FeCu-NC promoted the efficient degradation of LEV by peroxymonosulfate activation, with a degradation rate of 90.4% for LEV at 30 min. This work sheds new light on the application of single-atom nanozymes to antibiotics for colorimetric sensing and degradation.

A highly sensitive and selective fluorescent "on-off-on" peptide-based probe for sequential detection of Hg2+ and S2- ions: Applications in living cells and zebrafish imaging.

Mercury ions (Hg2+) and sulfur ions (S2-), have caused serious harm to the ecological environment and human health as two kinds of highly toxic pollutants widely used. Therefore, the visual quantitative determination of Hg2+ and S2- is of great significance in the field of environmental monitoring and medical therapy. In this study, a novel fluorescent "on-off-on" peptide-based probe DNC was designed and synthesized using dipeptide (Asn-Cys-NH2) as the raw material via solid phase peptide synthesis (SPPS) technology with Fmoc chemistry. DNC displayed high selectivity in the recognition of Hg2+, and formed non-fluorescence complex (DNC-Hg2+) through 2:1 binding mode. Notably, DNC-Hg2+ complex generated in situ was used as relay response probe for highly selective sequential detection of S2- through reversible formation-separation. DNC achieved highly sensitive detection of Hg2+ and S2- with the detection limits (LODs) of 8.4 nM and 5.5 nM, respectively. Meanwhile, DNC demonstrated feasibility for Hg2+ and S2- detections in two water samples, and the considerable recovery rate was obtained. More importantly, DNC showed excellent water solubility and low toxicity, and was successfully used for consecutive discerning Hg2+ and S2- in test strips, living cells and zebrafish larvae. As an effective visual analysis method in the field, smartphone RGB Color Picker APP realized semi-quantitative detections of Hg2+ and S2- without the need for complicated device.

Determination of sulfonamide antibiotics by magnetic porous carbon solid-phase extraction coupled with capillary electrophoresis.

Sulfonamide antibiotics (SAs) have been widely used as antibacterial drugs for the prevention and treatment of livestock and poultry diseases, but they seriously threaten human health because they can accumulate in humans. Therefore, it is highly important to develop methods for monitoring sulfonamide residues in aquaculture and food. In this research, based on the generation of porous carbon (PC) by the pyrolysis of sodium citrate, magnetic porous carbon (PC@Fe3O4) was synthesized by a solvothermal method and used as an adsorbent for the magnetic solid-phase extraction of SAs. The effects of the proportion of PC in PC@Fe3O4, adsorbent dosage, adsorption time, eluent type, extraction pH, salt concentration and eluent dosage on the extraction efficiency were systematically studied. The adsorption performance and behavior of PC@Fe3O4 on SAs were evaluated using adsorption kinetics and adsorption isotherms, and the adsorption mechanism was preliminarily discussed. Under optimal conditions, combined with capillary electrophoresis diode array detection, a sensitive detection method for SAs was developed. The proposed method can be used for the determination of six SAs in fishpond water and milk samples, with a linear range of 0.5-200 ng mL-1, detection limits of 0.24-0.34 ng mL-1, and spiked recoveries of 85.9-109.0 %.

Chameleon-like Response Mechanism of Gold-Silver Bimetallic Nanoclusters Stimulated by Sulfur Ions and Their Application in Visual Fluorescence Sensing.

Herein, 2-mercapto-5-benzimidazolesulfonate acid sodium salt dihydrate (MBZS)-protected gold-silver bimetallic nanoclusters, named MBZS-AuAg NCs, were synthesized. Interestingly, we found that MBZS-AuAg NCs solutions can exhibit different fluorescence color changes under sulfide stimulation. A series of modern analytical testing techniques were used to explore the interaction mechanism between MBZS-AuAg NCs and sulfide. Sulfide ions can not only cause MBZS-AuAg NCs to exhibit rich fluorescence color changes similar to those of a chameleon but also have four linear relationships between the response intensity and sulfide concentration. A wide-range sulfide fluorescence sensing platform was constructed based on four linear segments with different fluorescence color responses. This sensing platform can be directly used for the determination of S2- with a detection limit as low as 11 nM. The portable test paper based on MBZS-AuAg NCs can realize the visual and rapid detection of gaseous hydrogen sulfide with a detection limit of 100 ppb (v/v). The wide detection range of the proposed method not only allows it to be used as an alternative method for sulfide detection in environmental samples but also has potential applications in the rapid detection and early warning of hydrogen sulfide gas in industrial and mining scenarios.

Ratiometric fluorescence sensor based on europium-organic frameworks for selective and quantitative detection of cerium ions.

BACKGROUND: Due to the unavoidable use of cerium in daily life, the accumulation of cerium in the environment increases health risks for humans. Therefore, it is crucial to develop a chemical sensing technology for the rapid, sensitive, and selective detection of cerium ions. RESULTS: In this research work, a novel two-dimensional chain structure of a europium-based metal organic framework (Eu-MOF) [Eu2(tcpa)(Htcpa)2] was synthesized by using 3,4,5,6-tetrachloro-1,2-benzenedicarboxylic acid (H2TCPA) as the ligand and europium nitrate as the metal source. The results of powder X-ray diffraction and thermogravimetric analysis show that the synthesized Eu-MOF has excellent chemical and thermal stability. When the Eu-MOF suspension was excited by ultraviolet light at 292 nm, four fluorescence emissions were observed at 420, 595, 620 and 705 nm. It was particularly interesting that when cerium ions (Ce3+/Ce4+) were added to the Eu-MOF suspension, the fluorescence intensity at 420 nm was enhanced, while the fluorescence at 620 nm was quenched. On this basis, a ratiometric fluorescent sensor for detecting cerium ions was constructed, which has a good linear relationship in the range of 0.05-15 µM and a detection limit of 16 nM. The plausible mechanism of the change in the fluorescence characteristics of Eu-MOF caused by cerium ions was discussed in detail. Through the study of fluorescence lifetime and ultraviolet absorption, it was proven that the mechanism of Ce3+-quenching Eu-MOF fluorescence is the inner filter effect. Photoinduced electron transfer and internal filtering effects lead to fluorescence quenching at 620 nm, while redox reactions lead to fluorescence enhancement of the ligand at 420 nm. SIGNIFICANCE: The proposed ratiometric fluorescence sensor was successfully employed for the detection of cerium ions in real water samples, confirming that it can be used as an alternative method for the detection of Ce3+ and Ce4+ in environmental samples.

Recent Advancement on the Indirect or Combined Alternative Thiocyanate Sources for the Construction of S-CN Bonds.

The process of thiocyanation is a notable chemical conversion owing to the extensive range of applications associated with thiocyanate compounds in the field of organic chemistry. In past centuries, the thiocyanation reaction incorporated metal thiocyanates or thiocyanate salts as sources of thiocyanate, which are environmentally detrimental and undesirable. In recent literature, there have been numerous instances where combined or indirect alternative sources of thiocyanate have been employed as agents for thiocyanation, showcasing their noteworthy applications. The present literature review focuses on elucidating the ramifications associated with the utilization of indirect or combined alternative sources of thiocyanate in various thiocyanation reactions.

Aggregation-induced emission for the detection of peptide ligases with improving ligation efficiency.

BACKGROUND: Monitoring peptide ligase activity is of great significance for biological research, medical diagnosis, and drug discovery. The current methods for the detection of peptide ligases suffer from the limitations of high background signal, elaborate design of substrate, and high reversibility of ligation reaction. In this work, we proposed a simple and sensitive method for ligase detection with reducing ligation reversibility on the basis of aggregation-induced emission (AIE) mechanism. RESULTS: The peptide probes labeled with AIE luminogens (AIEgens) were water-soluble and emitted weak fluorescence. After ligation reaction, the enzymatic products with AIEgens showed high hydrophobicity and could readily assembly into aggregates, thus lighting up the fluorescence. More interestingly, the formation of aggregates pushed the equilibrium to the generation of the desired ligation products, thus improving the catalytic efficiency by driving the reaction towards completion. The ligation reaction conversion rate (>80 %) is significantly higher than that without blocking the reversibility with additional treatment. With sortase A (SrtA) as the analyte example, the detection limit of this method was found to be 0.01 nM with a linear range of 0-50 nM. The system was applied to evaluate the inhibition efficiency of berberine chloride and quercetin and determine the activity of SrtA in serum, lysate and Staphylococcus aureus with satisfactory results. SIGNIFICANCE: This study indicated that the ligation efficiency and detection sensitivity can be improved by reducing ligation reversibility through AIE phenomenon. The proposed strategy could be used for the detection of other peptide ligases by adopting sequence-specific peptide substrates.

Metal-organic framework composite Mn/Fe-MOF@Pd with peroxidase-like activities for sensitive colorimetric detection of hydroquinone.

The construction of highly sensitive detection methods for hydroquinone (HQ) in environment and cosmetics is of great significance for environmental protection and human health. In this work, a novel detection method for HQ was successfully developed by constructing a metal-organic framework mimic enzyme colorimetric sensor (Mn/Fe-MOF@Pd1.0) with excellent peroxidase-like activity, which was synthesized by doping manganese ions into Fe-MOF by introducing bimetallic active centers, thereby improving the peroxidase-like activity of Fe-MOF, and the acid resistance and stability of Mn/Fe-MOF were improved by supporting palladium (Pd NPs). It is proven that Mn/Fe-MOF@Pd1.0 promoted the decomposition of hydrogen peroxide (H2O2) to generate active species, therefore, oxidized chromogenic substrate discoloration. On this basis, the detection of HQ based on the Mn/Fe-MOF@Pd1.0 colorimetric sensor was constructed, in which the limit of detection (LOD) was 0.09 µM in the linear range of 0.3-30 µM. Furthermore, Mn/Fe-MOF@Pd1.0 was successfully used for detecting HQ in hydroquinone whitening cream and actual water samples. The successful synthesis of Mn/Fe-MOF@Pd1.0 may provide new insights for further study of the enzyme-like activity of metal-organic framework composites, and the constructed facile and sensitive sensor system could broaden the application prospects of HQ detection.

Sensitive determination of thiram in apple samples using a ZIF-67 modified Si/Au@Ag composite as a SERS substrate.

Substrate materials with high sensitivity and storage stability are crucial for the practical analytical application of surface-enhanced Raman scattering (SERS) techniques. In this work, a SERS-active substrate (Si/Au@Ag/ZIF-67) was fabricated with a metal-organic framework (ZIF-67) on a plasmonic surface (Si/Au@Ag) via self-assembly. The as-prepared material combined the properties of the abundant hotspots of the Au@Ag nanoparticles and the excellent adsorption performance of ZIF-67 for organic molecules. The synergy leads to high sensitivity of the composite substrate with a low detection limit for 4-aminothiophenol (a typical Raman reporter molecule) down to 2.0 × 10-9 M and the analytical enhancement factor (AEF) of the SERS substrate is 3.4 × 106. Moreover, the substrates exhibited good repeatability, high reproducibility, and reliable stability due to the MOF coating. The SERS signal was stable after 60 days of storage at room temperature. Ultimately, the optimal Si/Au@Ag/ZIF-67 was applied as a SERS sensor to analyze thiram, and the results showed a linear concentration range from 10-7 to 10-5 M with good linearity (R2 = 0.9934). The recoveries of thiram in spiked apple juice were in the range of 95.7-102.3%, with relative standard deviations less than 4.3%. These results predict that the proposed SERS substrates may hold great potential for the detection of environmental and food pollution in practical applications.

Reductive dechlorination of trichloroethene by sulfided microscale zero-valent iron in fresh and saline groundwater: Reactivity, pathways, and selectivity.

S/mZVI is a promising material for groundwater remediation due to its excellent properties. However, the reactivity and electron selectivity toward target contaminant are critical. Thus, this study investigated the effect of complex groundwater chemistries (Milli-Q water, fresh groundwater and saline groundwater) on the reactivity of S/mZVI toward trichloroethylene (TCE), dechlorination pathway, hydrogen evolution kinetic, electron efficiency and aging behaviors. Results showed that sulfidation appreciably increased the reactivity and electron selectivity. The major degradation product of TCE dechlorination by S/mZVI was acetylene, which was consistent with TCE dechlorination by ß-elimination. Moreover, reductive ß-elimination was still the dominant dechlorination pathway for the application of S/mZVI in three groundwater conditions. However, the rates and the quantities of major products from TCE degradation varied significantly. S/mZVI in saline groundwater can maintain the reactivity towardTCE due to the protection of Fe0 by Fe3O4 deposited on the surface. Thus, the higher TCE removal efficiency and less hydrogen accumulation resulted in the greatest electron efficiency (4.3-79.2%). Overall, S/mZVI was more effective for the application in saline groundwater. This study proved insight into the comprehensive evaluation and implications for the application of S/mZVI based technologies in saline contaminated groundwater.

Sensitive determination of bisphenols in environmental samples by magnetic porous carbon solid-phase extraction combined with capillary electrophoresis.

Bisphenol compounds exist widely in the environment and pose potential hazards to the environment and human health, which has aroused widespread concern. Therefore, there is an urgent need for an efficient and sensitive analytical method to enrich and determine trace bisphenols in environmental samples. In this work, magnetic porous carbon (MPC) was synthesized by one-step pyrolysis combined with a solvothermal method for magnetic solid-phase extraction of bisphenols. The structural properties of MPC were characterized by field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and saturation magnetization analysis. Its adsorption properties were evaluated by adsorption kinetics and adsorption isotherm studies. By optimizing the magnetic solid-phase extraction and capillary electrophoresis separation conditions, a capillary electrophoresis separation and detection method for four bisphenols was successfully constructed. The results showed that the detection limits of the proposed method for the four bisphenols were 0.71-1.65 ng/mL, the intra-day and inter-day precisions were 2.27-4.03% and 2.93-4.42%, respectively, and the recoveries were 87.68%-108.0%. In addition, the MPC could be easily recycled and utilized, and even if the magnetic solid-phase extraction was repeated 5 times, the extraction efficiency could still be kept above 75%.

Atomically dispersed Fe-Zn dual-site nanozymes with synergistic catalytic effects for the simultaneous detection of Cr(VI) and 8-hydroxyquinoline.

Single-atom catalysts with atomically dispersed sites have been widely used as nanozymes for colorimetric sensing because their tunable M-Nx active centers are similar to those of natural enzymes. However, their low metal atom loading leads to insufficient catalytic activity and affects the sensitivity of colorimetric sensing, which limits their further applications. Herein, multi-walled carbon nanotubes (MWCNs) are selected as carriers to reduce the aggregation of ZIF-8 and improve the electron transfer efficiency of nanomaterials. Meanwhile, MWCN/FeZn-NC single-atom nanozymes with excellent peroxidase-like activity were prepared by pyrolysis on ZIF-8 doped with a second metal Fe. Based on the excellent peroxidase activity of MWCN/FeZn-NCs, a dual-functional colorimetric sensing platform for Cr(VI) and 8-hydroxyquinoline was established. The detection limits of the dual-function platform are 40 nM for Cr(VI) and 55 nM for 8-hydroxyquinoline. This work provides a highly sensitive and selective strategy for the detection of Cr(VI) and 8-hydroxyquinoline in hair care products, which has great application prospects in the field of pollutant detection and control.

High-loading Cu single-atom nanozymes supported by carbon nitride with peroxidase-like activity for the colorimetric detection of tannic acid.

The design of nanozymes with high metal atom loading is of great significance to improve enzyme activity and is also the key to furthering the construction of highly sensitive colorimetric sensors. In this work, a colorimetric sensor for the quantitative analysis of tannic acid (TA) was developed based on two-dimensional carbon nanosheet carbon nitride (CN)-supported Cu single-atom nanozymes (Cu/CN). Cu/CN was synthesized by supramolecular preorganization and calcination, with an ultrathin nanosheet structure and a high density of Cu active sites, with a Cu loading of up to 14.3 wt%. Benefiting from the above characteristics, Cu/CN exhibits peroxidase-mimicking activity and excellent catalytic performance. Therefore, a colorimetric sensor was constructed for the fast and sensitive quantitative analysis of TA with good linearity in the range of 0.09-3.2 µM and a low detection limit of 30 nM. Furthermore, the sensor was successfully applied to the analysis of TA in tea samples of different varieties. This work sheds new light on the design of nanozymes with a high density of active sites and the analysis of TA in real environments.

High performance isolation of circulating tumor cells by acoustofluidic chip coupled with ultrasonic concentrated energy transducer.

The isolation of circulating tumor cells (CTCs) from whole blood is a challenging task. Although various studies on the separation of CTCs by acoustofluidic devices have been reported, difficulties still persist, such as the complicated equipment, high cost, and difficult operation. Those problems should be resolved urgently. Herein, we developed an acoustofluidic chip separation system coupled with an ultrasonic concentrated energy transducer (UCET) system for efficient separation of CTCs. In the separation system, the acoustically sensitive particles were pre-focused by inertial forces of the PDMS chip channel structure. Then, the particles with different sizes were separated by acoustic radiation forces (ARF). In this study, the circulating tumor cells was simulated (CTCs-like particles) by aminated mesoporous acoustically sensitive particles (MSN@AM) encapsulated carboxylate polystyrene microspheres (PS-COOH). Subsequently, efficient CTCs-like particles separation was achieved by the acoustofluidic chip coupling system. This study effectively separated polystyrene microspheres carrying acoustically sensitive particles (MSN@AM@PS-COOH). However, the MSNs agglomerates and PS microspheres without acoustically sensitive particles did not show phenomenon of separation. This method allows to efficiently separate 2 µm MSNs agglomerates，8.0-8.9 µm PS microspheres and 10-10.5 µm MSN@AM@PS-COOH particles. It is demonstrated that the CTCs-like particles show more sensitive response, longer moving distance, and more obvious separation effect at the condition of the low frequency traveling wave sound field (20 kHz from UCET). This system can maintain the same separation with reduced amount of reagents used for cancer detection. It may provide a reliable basis for sorting out CTCs efficiently from the whole blood of cancer patients.

Fabrication of Two Luminescent Imidazolyl Cadmium-Organic Frameworks and Their Sensing Mechanism for 2,6-Dichloro-4-nitroaniline.

2,6-Dichloro-4-nitroaniline, alias dicloran (DCN), is a broad-spectrum pesticide that can cause irreversible damage to the human body. Therefore, it is of great significance to develop a technology for the rapid and convenient detection of DCN. Luminescent metal organic frameworks have attracted extensive attention in the field of sensing and detection due to their excellent optical properties. In this study, two kinds of 2D Cd-MOFs (CdMOF-1 and CdMOF-2) were developed for the detection of residual DCN in the environment. Both CdMOFs exhibit excellent solvent and acid-base stability and can respond to DCN quickly and sensitively in a short time (30 s). CdMOFs not only have good selectivity and anti-interference toward DCN but also have good reusability. Under the conditions of DCN concentrations of 1-15 and 0.3-30 µM, the change in fluorescence intensity of CdMOF-1 and CdMOF-2 showed a good linear relationship with DCN concentration (R2 = 0.999/0.991), and the detection limits were 0.36 and 0.12 µM, respectively. Through ultraviolet-visible absorption spectroscopy (UV-Vis), X-ray photoelectron spectroscopy, fluorescence lifetime, and density functional theory calculations, it is revealed that the fluorescence quenching mechanisms of DCN for two kinds of Cd-MOFs are competitive absorption and photoinduced electron transfer, and there may be a weak π-π interaction. Finally, it is demonstrated that by using two types of fluorescent CdMOFs to make the fluorescent test paper and detect actual soil, these can be applied to the actual scene and achieve onsite real-time detection.

Determination of trace bisphenols in milk based on Fe3O4@NH2-MIL-88(Fe)@TpPa magnetic solid-phase extraction coupled with HPLC.

Herein, a covalent organic framework (COF) was grown on a magnetic metal-organic framework (MOF) by a solvothermal method for the efficient extraction of bisphenols (BPs). The magnetic solid-phase extraction (MSPE) of four bisphenols (bisphenol A, bisphenol B, bisphenol AF and bisphenol C) was carried out without adjusting the pH and salt concentration. When 30 mg Fe3O4@NH2-MIL-88(Fe)@TpPa was used to adsorb for 25 min, 6 mL methanol was used to elute for 20 min, and the extract was detected by high-performance liquid chromatography (HPLC). The proposed method has a low detection limit of 0.011-0.036 ng mL-1, a wide linear range of 0.05-100 ng mL-1, and a correlation coefficient (R2) of 0.9980-0.9998. The intra-day and inter-day precisions are 0.74-2.54% and 1.68-3.72%, respectively. Bisphenol A was determined by applying the proposed method to the determination of actual milk samples. The standard addition experiment showed that the relative recovery of the four bisphenols was 85.70-119.7%. Pseudosecond-order, first-order, Langmuir and Freundlich models were applied to explore the adsorption characteristics of Fe3O4@NH2-MIL-88(Fe)@TpPa. In general, the established Fe3O4@NH2-MIL-88(Fe)@TpPa-MSPE-HPLC-UV method exhibits attractive sensitivity, simple manipulation, and excellent reusability, and it has excellent prospects for the detection of trace BPs in complex milk matrices.

A novel peptide-based relay fluorescent probe with a large Stokes shift for detection of Hg2+ and S2- in 100 % aqueous medium and living cells: Visual detection via test strips and smartphone.

Herein, a novel relay peptide-based fluorescent probe DGRK was synthesized via solid phase peptide synthesis (SPPS) technology. DGRK exhibited excellent water-solubility, good stability, remarkably large Stokes shift (230 nm) and high selectivity response to Hg2+ with a non-fluorescence complex DGRK-Hg2+ formation via a 1:1 binding mode. Further studies indicated that the DGRK-Hg2+ complex could act as a secondary probe for rapidly and sequentially detecting S2- based on fluorescent "off-on" response, and without interference from a range of anions. The limit of detection (LOD) for Hg2+ and S2- were calculated to be 33.6 nM and 60.9 nM, respectively. In addition, The reversibility of interaction of confirmed that the continuous and reversible recognition behavior of Hg2+ and S2- by the probe DGRK, and could be cycled more than 5 times. In addition, DGRK could be successfully applied to the fluorescence imaging of Hg2+ and S2- in two living cells based on excellent cells permeability and low cytotoxicity. Meanwhile, DGRK was successfully used to create the low-cost and portable test strips for visual detection and rapid analysis under 365 nm UV lamp, and the test strips combined with a smartphone (RGB color) was successfully applied to the semi-quantitative analysis and monitoring of dynamic changes of Hg2+ levels.

Determination of nitroimidazole antibiotics based on dispersive solid-phase extraction combined with capillary electrophoresis.

For a long time, the detection of nitroimidazole antibiotics (NIABs) has been a research focus in environmental analytical chemistry. In this work, a novel technique for the analysis of nitroimidazoles was established based on capillary electrophoresis (CE). UiO-66, synthesized using a solvothermal method, was utilized as an adsorbent in the dispersive solid-phase extraction (DSPE) of five different NIABs. The separation and detection of NIABs in environmental water samples were accomplished using the CE diode array detection method. The optimal extraction conditions were obtained after systematically studying the effects of adsorption time, the amount of extractant, and elution solvent on extraction efficiency. According to the results of the study, the limit of detections of the five NIABs were between 16 and 97 ng/mL, the relative standard deviations were between 0.32% and 0.55%, and the spike recoveries were between 87.43% and 104.8%. This study presents a novel technique for measuring NIABs in complex water samples.

Dual-Color 2D Lead-Organic Framework with Two-Fold Interlocking Structures for the Detection of Nitrofuran Antibiotics and 2,6-Dichloro-4-nitroaniline.

The misuse of organic pollutants such as nitrofuran antibiotics (NFAs) and 2,6-dichloro-4-nitroaniline (DCN) has become a hot topic of global concern, and developing rapid, efficient, and accurate techniques for detecting NFAs and pesticides in water is a major challenge. Here, we designed a novel lead-based anion 2D metal-organic framework (MOF){[(CH3)2NH2]2[Pb(TCBPE)(H2O)2]}n (F3) with interlocking structures, in which TCBPE stands for 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene. Powder X-ray diffraction and thermogravimetric analysis revealed that F3 has excellent chemical and solvent stability. It is worth noting that F3 has a grinding discoloration effect. The solvent-protected grinding approach achieved F3B with a high quantum yield (QY = 73.77%) and blue fluorescence, while the direct grinding method produced F3Y with a high quantum yield (QY = 37.27%) and yellow-green fluorescence. Importantly, F3B can detect NFAs in water rapidly and sensitively while remaining unaffected by other antibiotics. F3Y can identify DCN in water quickly and selectively while remaining unchanged by other pesticides. F3B demonstrated high selectivity and rapid response to NFAs at a limit of detection (LOD) as low as 0.26 µM, while F3Y indicated high selectivity and responded quickly to DCN in water at an LOD as low as 0.14 µM. The method was successfully applied to detect NFAs in actual water samples of the fish tanks and ponds as well as the pesticide DCN in soil samples. The recovery rates were 97.0-105.15% and 102.2-106.48%, and the relative standard deviations were 0.63-1.45% and 0.29-1.69%, respectively. In addition, F3B and F3Y can be made into fluorescent test papers for the visual detection of NFAs and DCN, respectively. Combined with experiments and density functional theory calculations, the mechanism of fluorescence quenching of MOFs by target analytes was also revealed.

Peptide nanotube/hemin composite with enhanced peroxidase activity for the detection of dopamine in food and drug samples.

Inspired by natural enzymes, artificial enzymes have been widely studied due to their ease of mass production, robustness to harsh environments and high stability. In this work, a peptide nanotube/hemin composite (KL@hemin) as an artificial enzyme was prepared by immobilizing hemin onto self-assembled peptide nanotubes (PNTs). The successful loading of hemin was determined by a series of characterizations. The multiple noncovalent interactions between the PNTs and hemin endow KL@hemin with strong stability. Subsequent enzyme activity tests showed that the prepared KL@hemin exhibited enhanced peroxidase activity. Further experiments indicate that PNTs as carriers can not only protect hemin from dimerization to maintainenzyme activity but also increase the affinity of hemin to the substrate for faster binding and accelerate mass transfer, thus promoting the whole catalytic process. Coupled with a peroxidase-catalyzed chromogenic system, a colorimetric method for dopamine detection was constructed based on KL@hemin. The strategy shows high sensitivity and selectivity and has been applied to the determination of dopamine in dopamine injection and meat samples.