Aggregation Inducing Reversible Conformational Isomerization of Surface Staple in Au18SR14 Nanoclusters.

The conformation of molecules and materials is crucial in determining their properties and applications. Here, this work explores the reversible transformation between two distinct conformational isomers in metal nanoclusters. This work demonstrates the successful manipulation of a controllable and reversible isomerization of Au18SR14 within an aqueous solution through two distinct methods: ethanol addition and pH adjustment. The initial driver is the alteration of the solution environment, leading to the aggregation of Au18SR14 protected by ligands with smaller steric hindrance. At the atomic level, the folding mode of the unique Au4SR5 staple underpins the observed structural transformation. The reversal of staple conformation leads to color shifting between green and orange-red, and tailors a second emission peak at 725 nm originating from charge transfer from the thiolate to the Au9 core. This work not only deepens the understanding of the surface structure and dual-emission of metal nanoparticles, but also enhances the comprehension of their isomerization.

Self-assembly of a AuNPs/Ti3C2 MXene hydrogel for cascade amplification of microRNA-122 biosensing.

A three-dimensional (3D) self-assembled AuNPs/Ti3C2 MXene hydrogel (AuNPs/Ti3C2 MXH) nanocomposite was prepared for the fabrication of a novel microRNA-122 electrochemical biosensor. The 3D hydrogel structure was gelated from two-dimensional MXene nanosheets with the assistance of graphite oxide and ethylenediamine. MXene hydrogels supported the in situ formation of Au nanoparticles (AuNPs) that predominantly exploring the (111) facet, and these AuNPs are utilized as carriers for hairpin DNA (hpDNA) probes, facilitating DNA hybridization. MXene acted as both a reductant and stabilizer, significantly improving the electrochemical signal. In addition, the conjugation of PAMAM dendrimer-encapsulated AuNPs and H-DNA worked as an ideal bridge to connect targets and efficient electrochemical tags, providing a high amplification efficiency for the sensing of microRNA-122. A linear relationship between the peak currents and the logarithm of the concentrations of microRNA-122 from 1.0 × 10-2 to 1.0 × 102 fM (I = 1.642 + 0.312 lgc, R2 = 0.9891), is obtained. The detection limit is  0.8 × 10-2 fM (S/N = 3). The average recovery for human serum detection ranged from 97.32 to 101.4% (RSD < 5%).

Guest-Stimulated Nonplanar Porphyrins in Flexible Metal-Organic Frameworks.

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules. Here, a series of porphyrinic zirconium metal-organic frameworks (MOFs) is reported that exhibit guest-stimulated breathing behavior. X-Ray diffraction analysis and skeleton deviation plots confirm that the material suffers from porphyrin distortion to form a ruffled geometry under the desorption of guest molecules. Further investigation reveals that not only the degree of nonplanarity can be precisely manipulated but also the partial distortion of porphyrin in a single crystal grain can be readily achieved. As Lewis acidic catalyst, the MOF with nonplanar Co-porphyrin exhibits active properties in catalyzing CO2 /propylene oxide coupling reactions. This porphyrin distortion system provides a powerful tool for manipulating nonplanar porphyrins in MOFs with individual distortion profiles for various advanced applications.

Nano-hybrid luminophores of Ti3C2TX quantum dots-gold nanoparticles based on in situ generation for sensitive electrochemiluminescence biosensing.

Nanomaterial-derived quantum dots (QDs) are excellent electrochemiluminescence (ECL) luminophores and play an important role in optical sensing due to their excellent water solubility, good biocompatibility and tunable molecular size. In this work, a novel strategy was designed to form nano-hybrid Ti3C2 QDs-AuNPs in situ as a luminophore based on the unique reducibility of Ti3C2 QDs, which showed remarkable and stable ECL performance. Here, AuNPs were formed in situ without the addition of reducing agents and stabilizers, leading to threefold enhancement of the ECL signal of Ti3C2 QDs due to their excellent charge transfer capability. Meanwhile, Ti3C2 QDs-AuNPs with abundant Ti atoms also acted as recognition units. Through skillful combination with hybridization chain reaction (HCR) to expose more phosphate, an ECL platform was constructed to detect polynucleotide kinase (PNK) with good specificity and sensitivity. A lower limit of detection limit of 2.7×10-5 U mL-1 was achieved, with a wide linear relationship ranging from 0.0001 to 10 U mL-1. This novel strategy provides a guide for the application of nano-hybrid Ti3C2 QDs-AuNPs as a luminophore in the field of ECL bioanalysis. Novel in situ-formed nano-hybrid Ti3C2 QDs-AuNPs were prepared as a luminophore, with threefold enhancement of the ECL signal of Ti3C2 QDs.

Synergetic PtNP@Co3O4 hollow nanopolyhedrals as peroxidase-like nanozymes for the dual-channel homogeneous biosensing of prostate-specific antigen.

In this paper, novel synergetic PtNP@Co3O4 hollow nanopolyhedrals with peroxidase-like activities are designed and prepared, which can be used as electrochemical and colorimetric signal labels for the enzyme-free dual-channel homogeneous sensing of prostate-specific antigen. When prostate-specific antigens are present, the aptamer-modified PtNP@Co3O4 hollow nanopolyhedrals and magnetic beads form sandwich structures, which have excellent peroxidase-like activities, because of the synergetic effect of PtNP@Co3O4 hollow nanopolyhedrals. The sandwich structures can be separated from the mixture by the magnetic effect of the magnetic beads and catalyze the redox reactions between H2O2 and TMB, generating quantitative electrochemical and colorimetric responses in homogeneous solution simultaneously. Under the optimized conditions, the linear range of both electrochemical (0.01 to 10 ng/ml) and colorimetric (0.01-15 ng/ml) channels can satisfy the demand of prostate-specific antigen detection in clinic (4 ng/ml), and the electrochemical and colorimetric channels have a low detection limit of 0.0079 ng/ml and 0.01 ng/ml respectively without using natural enzymes. The strategy by using synergetic PtNP@Co3O4 hollow nanopolyhedrals as signal probes provides a promising scheme for developing simple, rapid, reliable, and ultrasensitive dual-channel homogeneous biosensors, which has a great potential as a powerful tool in prostate cancer diagnosis.

Aptamer and bifunctional enzyme co-functionalized MOF-derived porous carbon for low-background electrochemical aptasensing.

To improve the efficiency of aptasensors, a signal amplification strategy by coupling tyrosinase (Tyr)-triggered redox cycling with nanoscale porous carbon (NCZIF) has been proposed. The NCZIF was obtained by calcining ZIF-8 crystals in an inert atmosphere. It had high surface areas, great biocompatibility, and ease of functionalization, which was beneficial for immobilizing sufficient Tyr and aptamer covalently. When the target prostate-specific antigen (PSA) was present, the NCZIF functionalized with Tyr and an aptamer bound to the aptamer-modified Au electrode specifically through the sandwich structure. Then, Tyr acted to oxidize the electroinactive phenol, which led to low-background signal, in the substrate to electroactive catechol, and triggered the redox cycling under the action of NADH. The low detection limit of the proposed electrochemical aptasensor for PSA was 0.01 ng mL-1, and the wide detection range was from 0.01 to 50 ng mL-1. The use of ZIF-8 derived porous carbon and Tyr-triggered redox cycling system provided a promising solution for the development of simple, rapid, reliable, and low-background aptasensing methods, which had great potential in the field of disease diagnosis and biomedicine.

Gold Nanoparticle Aggregation-Induced Quantitative Photothermal Biosensing Using a Thermometer: A Simple and Universal Biosensing Platform.

A simple, low-cost, and universal gold nanoparticle (AuNP) aggregation-induced photothermal biosensing platform has been developed for the first time and applied for the visual quantitative genetic detection using a common thermometer. By exploiting the photothermal effect of target-induced gold nanoparticle aggregation, visual quantitative biochemical analysis can be achieved by simply recording temperature signals using a common thermometer. Compared to conventional genetic testing methods, it is label- and amplification-free and can be completed in 40 min without the aid of any advanced analytical instruments. Mycobacterium tuberculosis (MTB) DNA was used as a model target to demonstrate the application of this photothermal biosensing platform. Although no costly instrument was used, high sensitivity and specificity were achieved with the limit of detection (LOD) of 0.28 nM, which was nearly 10-fold lower than that of the colorimetric method using a spectrometer. This AuNP aggregation-induced photothermal biosensing strategy provides a simple, low-cost, and universal platform for broad application of visual quantitative detection of nucleic acids and many other biomolecules, particularly in point-of-care (POC) biosensing applications.

Electrochemical thrombin aptasensor based on using magnetic nanoparticles and porous carbon prepared by carbonization of a zinc(II)-2-methylimidazole metal-organic framework.

A homogeneous electrochemical aptasensor was obtained by modifying a glassy carbon electrode (GCE) with a porous carbon nanomaterial (Z-1000, about 70 nm, deteced by transmission electron microscopic) that was obtained by carbonization of a zinc(II)-2-methylimidazole metal-organic framework. Z-1000 possesses a large specific surface and outstanding electrochemical properties. A thrombin-binding aptamer (CP) was immobilized on the magnetite nanoparticles MNPs by the condensation reaction and further combined with reporter probe (RP) that is functionalized with electroactive methylene blue (MB). In the presence of thrombin, the CP was specifically recognized with it to form the CP/MNP/Thb complex, and the RP was dissociated from MNPs. The released RP was captured by the modified GCE through π-stacking interaction between nucleobases and carbon nanostructure. The electrical signal generated by MB can be monitored by differential pulse voltammetry (DPV). Under the optimized conditions, the DPV peak current at around -0.28 V (vs. SCE) increases with thrombin concentration. The sensor has a detection limit of 0.8 fM of thrombin and a linear range that extends from 10 fM to 100 nM. It was successfully applied to the analysis of spiked serum. The recoveries are 98.1-99.4% and RSDs are 3.9%-4.0%. Conceivably, this aptasensor scheme can be easily extended to other proteins and gives inspiration to manufacture sensitive aptasensor. Graphical abstract A homogeneous electrochemical aptasensor is obtained by modifying a glassy carbon electrode with the MOF-derived porous carbon. The sensor has a detection limit of 0.8 fM and a wide linear range from 10 fM to 100 nM for thrombin detection.

A hybrid material composed of reduced graphene oxide and porous carbon prepared by carbonization of a zeolitic imidazolate framework (type ZIF-8) for voltammetric determination of chloramphenicol.

Porous carbon was prepared from a zeolitic imidazolate framework (type ZIF-8) by carbonization at 800 °C (Z-800). A hybrid material was then obtained by direct co-electrodeposition of Z-800 with graphene oxide (Z-800/rGO). Z-800 is N-doped with good electrical conductivity and displays electrocatalytic activity. Z-800 readily undergoes mass transfer and also prevents graphene to agglomerate during electroanalysis. The hybrid was placed on a glassy carbon electrode (GCE) to obtain an electrochemical sensor for chloramphenicol (CAP) detection. Under the optimized conditions, the response of the modified GCE (typically measured at a low potential of -0.07 V vs. Ag/AgCl) is linear in the 1 to 180 µM CAP concentration range with a 0.25 µM detection limit (S/N = 3). In our preception, the method has a wide scope in that it may be applied to the preparation of various kinds of other (doped) porous carbon/rGO composites for use in (bio)chemical sensors. Graphical abstract Schematic presentation of the preparation process of the materials and the electrochemical detection of chloramphenicol.

One-step synthesis of a Methylene Blue@ZIF-8-reduced graphene oxide nanocomposite and its application to electrochemical sensing of rutin.

The authors demonstrate the exploitation of reduced graphene oxide (RGO) as a template for immobilizing zeolitic imidazolate framework-8 (ZIF-8) crystals loaded with the electrochemical probe Methylene Blue (MB). The framework was deposited on the surface of RGO in a one-pot process. Transmission electron microscopy, scanning electron microscopy and X-ray diffraction were employed to characterize the nanocomposite. The electrochemical behavior of rutin at a glassy carbon electrode (GCE) modified with the nanocomposite was investigated by cyclic voltammetry and differential pulse voltammetry. The modified GCE displays high electrocatalytic activity toward rutin oxidation at a relatively low working potential (0.4 V vs. Ag/AgCl). Under the optimal conditions, the sensor has an amperometric response that is linear in the 0.1 to 100 µM rutin concentration range, with a 20 nM detection limit (at an S/N ratio of 3). The method was successfully applied to the determination of rutin in tablets and urine samples. Graphical abstract The zeolitic imidazolate framework ZIF-8 was loaded with Methylene Blue and deposited on the surface of reduced graphene oxide. A glassy carbon electrode was modified with the nanocomposite and then used for the determination of rutin with a 20 nM detection limit and a linear range from 0.1 to 100 µM.

In Situ Growth of Three-Dimensional Graphene Films for Signal-On Electrochemical Biosensing of Various Analytes.

In this work, an in situ growth protocol is introduced to fabricate three-dimensional graphene films (3D GFs) on gold substrates, which are successfully utilized as working electrode for electrochemical detection of nucleic acid (microRNA) and protein (lysozyme) based on a signal-on sensing mechanism. To realize the bridge between the gold substrate and graphene film, a monolayer of 4-aminothiophenol is self-assembled on the substrate, which is then served as connectors for the growth of 3D GFs on the gold substrate by the hydrothermal reduction (HR) technique. Moreover, given the excellent properties, such as enlarged surface area, strong binding strength between 3D GFs and gold substrate, and improved conductivity, the proposed 3D GF-fabricated gold substrate is readily employed to the construction of electrochemical biosensing platforms through introduction of magnetic nanoparticles (MNPs) as probe carriers. On the basis of the strand displacement reaction and specific binding between aptamer and its target, the developed biosensors achieve signal-on detection of microRNA-155 (miR-155) and lysozyme (Lyz) with high sensitivity and selectivity and further successfully applied to human serum assay. Overall, the proposed strategy for in situ growth of 3D GFs provides a powerful tool for a wide range of applications, which is not limited to electrochemical biosensors and can be extended to other areas, such as electrocatalysis and electronic energy-related systems.

Two-photon excited quantum dots with compact surface coatings of polymer ligands used as an upconversion luminescent probe for dopamine detection in biological fluids.

Water-soluble multidentate polymer coated CdTe quantum dots (QDs) were prepared via a stepwise addition of raw materials in a one-pot aqueous solution under ambient conditions. Just by adjusting the compositions of raw materials, different sized CdTe QDs were achieved within a short time. The as-prepared QDs showed compact surface coating (1.6-1.8 nm) of polymer ligands and photoluminescence (PL) emitted at 533-567 nm, as well as high colloidal/photo-stability and quantum yields (58-67%). Moreover, these QDs exhibited significant upconversion luminescence (UCL) upon excitation using an 800 nm femtosecond laser. Experimental results confirm that the UCL was ascribed to the two-photon assisted process via a virtual energy state. Then, the two-photon excited QDs were further developed as a novel UCL probe of dopamine (DA) due to self-assembled binding of DA molecules with QDs via non-covalent bonding. As a receptor, the DA attached onto the QD surface induced an electron transfer from QDs to DA, triggering UCL quenching of QDs. This UCL probe of DA presented a low limit of detection (ca. 5.4 nM), and high selectivity and sensitivity in the presence of potential interferences. In particular, it was favorably applied to the detection of DA in biological fluids, with quantitative recoveries (96.0-102.6%).

Application of graphene for the SPE clean-up of organophosphorus pesticides residues from apple juices.

In this paper, an effective graphene-based SPE clean-up procedure coupled with GC-MS was developed for the determination of organophosphorus pesticide residues in apple juices. The apple juice samples were diluted with water and could be loaded onto the cartridge directly. Several parameters affecting the extraction efficiency were investigated, including the type of elution, washing solution, and sample pH. Under the optimized conditions, excellent limits of quantitation for the target analytes were found to be 0.15-1.18 ng/mL, and the average recoveries of the analytes at two spiked levels for real-sample analysis ranged from 69.8 to 106.2% with RSDs less than 7.3%. Furthermore, the graphene-based cartridges exhibited superior reusability for juice sample analysis. The proposed method is sensitive, simple, and cost saving, and provides a detection platform for the monitoring of pesticide residues.

A novel self-enhanced ECL-RET aptasensor based on the bimetallic MOFs with homogeneous catalytic sites for kanamycin detection.

The inappropriate use of antibiotics undoubtedly poses a potential threat to public health, creating an increasing need to develop highly sensitive tests. In this study, we designed a new type of porphyrin metal-organic frameworks (Fe TCPP(Zn) MOFs) with homogeneous catalytic sites. The ferric-based metal ligands of Fe TCPP(Zn) MOFs acted as co-reaction accelerators, which effectively improved the conversion efficiency of H2O2 on the surface of MOFs, then increased the concentration of •OH surrounding porphyrin molecules to achieve self-enhanced electrochemiluminescence (ECL). Based on this, an aptasensor for the specific detection of kanamycin (KAN) in food and environmental water samples was constructed in combination with resonance energy transform (RET), in which Fe TCPP(Zn) MOFs were used as luminescence donor and AuNPs were used as acceptor. Under the best conditions, there was a good linear relationship between the ECL intensity and the logarithm of KAN concentration with a detection limit of 0.28 fM in the range of 1.0 × 10-7-1.0 × 10-13 M, demonstrating satisfactory selectivity and stability. At the same time, the complexity of the detection environment was reduced, which further realized the reliable analysis of KAN in milk, honey and pond water. Overall, this innovative self-enhanced ECL strategy provides a novel approach for constructing efficient ECL systems in MOFs, and also extends the application of MOFs to the analysis and detection of trace antibiotics in food and the environment.

Enhancing electrochemiluminescence for chloramphenicol detection based on the synergistic effect of doped Ti3C2 with ultrasound.

Chloramphenicol (CAP) is known to be harmful to the environment and food, posing a threat to human health. Developing an effective and convenient method for detecting CAP is crucial. An electrochemiluminescence (ECL) biosensor has been designed for sensitive detection of CAP. The improved ECL behavior was attributed to the synergistic effect of N and P co-doped Ti3C2-Apt1 (N, P-Ti3C2-Apt1) nanoprobes and high intensity focused ultrasound (HIFU) pretreatment. The doping of N and P could improve the electrochemical performance of Ti3C2. HIFU pretreatment generated more reactive oxygen species (ROS) in the luminol-O2 system. N, P-Ti3C2 could aggregate and catalyze ROS, causing an increase in ECL intensity. Furthermore, N, P-Ti3C2 as a carrier loaded more aptamer, which could recognize CAP with high specificity. The detection limit was 0.01 ng/mL. This biosensor has been successfully applied in milk and environmental water samples, highlighting its potential in the field of food and environmental analysis.

Electrochemical aptasensors based on porous carbon derived from graphene oxide/ZIF-8 composites for the detection of Erwinia cypripedii.

In this research, self-screening aptamer and MOFs-derived nanomaterial have been combined to construct electrochemical aptasensor for environmental detection. By utilizing the large specific surface area of reduced graphene oxide (rGO), ZIF-8 was grown in situ on surface of rGO, and the composites was pyrolyzed to obtain MOFs-derived porous carbon materials (rGO-NCZIF). Thanks to the synergistic effect between rGO and NCZIF, the complex exhibits remarkable characteristics, including a high electron transfer rate and electrocatalytic activity. In addition, the orderly arrangement of imidazole ligands within ZIF-8 facilitated the uniform doping of nitrogen elements into the porous carbon, thereby significantly enhancing its electrochemical performance. After carboxylation, rGO-NCZIF was functionalized with self-screening aptamer for fabricating electrochemical aptasensor, which can be used to detect Erwinia cypripedii, a kind of quarantine plant bacteria, with detection limit of 4.92 × 103 cfu/mL. Due to the simplicity and speed, the aptasensor is suitable for rapid customs inspection and quarantine. Additionally, the universality of this sensing strategy was verified through exosomes detection by changing the aptamer. The results indicated that the rGO-NCZIF-based electrochemical aptasensor had practical value in the environmental and medical fields.

Construction of self-enhanced luminescence probes based on Ti3C2 reducibility for ultrasensitive PNK analysis.

Au nano-clusters (Au NCs) were promising electrochemiluminescence (ECL) nano-materials. However, the small size of Au NCs presented a challenge in terms of their immobilization during the construction of an ECL biosensing platform. This limitation significantly hindered the wider application of Au NCs in the ECL field. In this work, we successfully used the reducibility of Ti3C2 to fabricate in situ a self-enhanced nano-probe Ti3C2-TiO2-Au NCs. The strategy of in situ generation not only improved the immobilization of Au NCs on the probe but also eliminated the requirement of adding reducing agents during preparation. In addition, in situ generated TiO2 could serve as a co-reaction accelerator, shortening the electron transfer distance between S2O82- and Au NCs, thereby improving the utilization of intermediates and enhancing the ECL response of Au NCs. The constructed ECL sensing platform could achieve sensitive detection of polynucleotide kinase (PNK). At the same time, the 5'-end phosphate group of DNA phosphorylation could chelate with a large amount of Ti on the surface of Ti3C2, thereby achieving the goal of specific detection of PNK. The sensor based on self-enhanced ECL probes had a broad dynamic range spanning for PNK detection from 10.0 to 1.0 × 107 µU mL-1, with a limit of detection of 1.6 µU mL-1. Moreover, the ECL sensor showed satisfactory detection performance in HeLa cell lysate and serum. This study not only provided insights for addressing the issue of ECL luminescence efficiency in Au NCs but also presented novel concepts for ECL self-enhancement strategies.

Linearly-Changed Thermal Behavior and Depressed Brill Transition in Long-Chain Polyamides Substituted by Methyl Side Groups.

Side substitution is an effective way of functionalizing and modifying the properties of polyamides. Meanwhile, side substitution would significantly influence the crystallization kinetics and polymorphic phase transition of polyamides, which, however, has not been well elucidated. Herein, we synthesized the side-substituted long-chain polyamides with various content of methyl pendent groups and investigated their crystallization and phase transition behaviors. We find that the thermal parameters of side-substituted polyamides vary linearly with the side group content, analogous to the isomorphic crystallization of random copolymers. All the solution-crystallized polyamides experience the α-γ Brill transition during heating, with the Brill transition temperature linearly decreasing as the side group content increases. Intriguingly, the γ-α transition of polyamides during cooling is suppressed with the presence of side methyl groups due to the difficulty in H-bond reorganization and gauche-trans conformational changes. This work has demonstrated the critical role of side substitution in the polymorphic crystallization and phase transition of long-chain polyamides.

An electrochemiluminescence aptasensor based on Ti3C2 QDs-1T/2H MoS2 nano-hybrid material for the highly sensitive detection of lincomycin.

Developing a highly selective and sensitive analysis strategy for lincomycin (LIN) is of great significance for environmental protection and food safety. Herein, we reported a novel electrochemiluminescence (ECL) aptasensor based on Ti3C2 QDs-1T/2H MoS2 nano-hybrid luminophore for detection of LIN. The hybridization of Ti3C2 QDs and 1T/2H MoS2 endowed nanocomposite with structural and compositional advantages for boosting the ECL performance of QDs by about three times. This enhancement could be attributed to the remarkable electrocatalytic activity and high conductivity exhibited by 1T/2H MoS2. Secondly, the great surface area of 1T/2H MoS2 is conducive to the high dispersion of Ti3C2 QDs, and its good conductivity could promote charge transfer. On the other hand, the excellent catalytic performance of 1T/2H MoS2 could facilitate the reduction of S2O82- to produce more radical, which significantly enhance the ECL signal of Ti3C2 QDs. Given these features, a sensor for detection of LIN was established based on specific recognition between target and aptamer. The sensor showed a good linear relationship (0.05 ng mL-1 ∼100 µg mL-1) with a detection limit as low as 0.02 ng mL-1. It is worth noting that this work has been validated in testing milk samples, exhibiting great potential application prospects in food analysis.

Graphene-based solid-phase extraction disk for fast separation and preconcentration of trace polycyclic aromatic hydrocarbons from environmental water samples.

Graphene has great potentials for the use in sample preparation due to its ultra high specific surface area, superior chemical stability, and excellent thermal stability. In our work, a novel graphene-based SPE disk was developed for separation and preconcentration of trace polycyclic aromatic hydrocarbons from environmental water samples. Based on the strong π-π stacking interaction between the analytes and graphene, the analytes extracted by graphene were eluted by cyclohexane and then determined by GC-MS. Under the optimized conditions, high flow rate (30 mL/min) and sensitivity (0.84-13 ng/L) were achieved. The proposed method was successfully applied to the analysis of real environmental water samples with recoveries ranging from 72.8 to 106.2%. Furthermore, the property of anticlogging and reusability was also improved. This work reveals great potentials of graphene-based SPE disk in environmental analytical.