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.

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%).

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.

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.

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.

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.

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.

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.

Hexagonal Phase Formation and Crystalline Structural Transition in Long-Spaced Aliphatic Polyesters with Side Groups.

Side substitution is an effective method for the chemical modification and functionalization of linear polyesters. The presence of side groups can have a profound effect on the crystalline structure and phase transition of semicrystalline polyesters. Herein, we synthesized the long-spaced polyesters with -OH and -CH3 side groups and various methylene segment lengths and studied the effects of the side groups on the crystal polymorph and phase transition of substituted polyesters. The substituted polyesters grow in the thermally stable phase (form I) at a higher temperature. However, the polyesters crystallize in a metastable hexagonal phase (form II) with trans chain conformation at a lower temperature. The metastable form II transforms into the more stable form I during long-time annealing or upon heating; this phase transition is accompanied by chain tilting and crystal lamellar thickening. This study has elucidated the critical role of side groups in the polymorphic crystallization and phase transition of linear polyesters.

A flexible and wearable three-electrode electrochemical sensing system consisting of a two-in-one enzyme-mimic working electrode.

In this work, a wearable and flexible three-electrode electrochemical sensing system (TESS) by using a two-in-one enzyme-mimic working electrode (TIOWE) is reported. The integrated three-electrode, including working electrodes, reference electrodes, and counter electrodes are formed by transfer printing of Ni2P-based composite electrode ink (Ni2P/G ink), Ag/AgCl ink, and carbon ink onto PDMS substrate, respectively. The Ni2P/G ink-based working electrodes have both good conductivity and enzyme-mimic catalytic activity towards glucose. Under optimized conditions, the TIOWE-TESS has a low detection limit of 0.37 µM and wide linear ranges of 0.001 mM-0.1 mM and 0.1 mM-1.4 mM. Furthermore, the TIOWE-TESS has good applicability in serum samples and reveals remarkable electrochemical performance at fluctuant working temperatures. The proposed TIOWE-TESS can be integrated on a waterproof bandage to fabricate a skin-friendly patch device for sweet glucose monitoring, which highlights its potential applications in flexible and wearable commercial devices for health-monitoring.

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.

Ultrasound-pretreatment combined with Ti3C2-TiO2-AuNPs enhancing the electrogenerated chemiluminescence of the air-saturated luminol for exosomes detection.

It is still a great challenge to develop effective strategies to improve the low electrogenerated chemiluminescence (ECL) of air-saturated luminol. Herein, the synergistic effects of Ti3C2-TiO2-AuNPs nano hybrid and high-intensity focused ultrasound pretreatment (ultrasound-pretreatment) were used to significantly improve the ECL emission of the air-saturated luminol, and the mechanism was proposed. The ultrasound-pretreatment as a green method with the cavitation effect could form O2-• and H2O2 in situ as an initiator. TiO2 and Au nanoparticles (AuNPs) were in situ decorated on the Ti3C2 surface to form Ti3C2-TiO2-AuNPs, and it was proved as a highly efficient booster which could catalyze and aggregate H2O2 to the O2-•. The utilization rate of intermediates has been greatly improved. Exosomes as model targets can be sensitively detected by the ECL sensor. The detection limit was 195 particles µL-1. The detection results of exosomes in actual samples are satisfactory. We believe that the ultrasound-pretreatment strategy could be extended to the sensitive detection in the biological sample.

AWI-Assembled TPU-BNNS Composite Films with High In-Plane Thermal Conductivity for Thermal Management of Flexible Electronics.

Thermal management of flexible/stretchable electronics has been a crucial issue. Mass supernumerary thermal heat is created in the repetitive course of deformation because of the large nanocontact resistance between electric conductive fillers, as well as the interfacial resistance between fillers and the polymer matrix. Here, we report a stretchable thermoplastic polyurethane (TPU)-boron nitride nanosheet (BNNS) composite film with a high in-plane thermal conductivity based on an air/water interfacial (AWI) assembly method. In addition to rigid devices, it was capable for thermal management of flexible electronics. During more than 2000 cycles of the bending-releasing process, the average saturated surface temperature of the flexible conductor covered with composite film with 30 wt % BNNSs was approximately 40.8 ± 1 °C (10.5 °C lower than that with pure TPU). Moreover, the thermal dissipating property of the composite under stretching was measured. All the results prove that this TPU-BNNS composite film is a candidate for thermal management of next-generation flexible/stretchable electronics with high power density.

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.

A novel electrochemical biosensor based on MIL-101-NH2 (Cr) combining target-responsive releasing and self-catalysis strategy for p53 detection.

A novel electrochemical biosensor was constructed to detect p53 gene based on MIL-101-NH2 (Cr) by combining target-responsive releasing and self-catalysis strategy. MIL-101-NH2 (Cr) with suitable pore structure was used to encapsulate methylene blue (MB) as signal probe. The hairpin DNA (HP) containing rich-G sequences was used as gatekeeper to seal up the pores and avoid MB leakage through covalent immobilization. The p53 gene could hybridize with the loop portion of HP for the formation of dsDNA, which had the specific nicking site of the nicking endonuclease (Nt.BstNBI). Then Nt.BstNBI recognized the specific recognition site and cleaved HP to open the pore for releasing of MB. Meanwhile, the cleavage of HP released the target DNA to trigger the target recycling for signal amplification. More importantly, the plentiful rich-G sequences were exposed to form Hemin/G-quadruplex DNAzymes, which could unite MIL-101-NH2 (Cr) to catalyze redox reaction of MB released by itself for signal amplification. The biosensor for p53 had wide linear range from 1 × 10-14 to 1 × 10-7 M and a low detection limit of 1.4 × 10-15 M. The combination of target-responsive releasing and self-catalysis strategy provided a promising way for constructing ultrasensitive and simple biosensor.

An efficient multi-enzyme cascade platform based on mesoporous metal-organic frameworks for the detection of organophosphorus and glucose.

An efficient colorimetric detection platform based on multi-enzyme cascade has been developed for detection of organophosphorus. Firstly, the dual-enzyme platform was prepared and applied for sensitive glucose detection (detection limit 0.32 µM). And then three enzymes, including acetylcholinesterase, horseradish peroxidase and choline oxidase were encapsulated in cruciate flower-like zeolitic imidazolate framework-8 (CF-ZIF-8) through one-step co-precipitation to construct detection platform with acetylcholine chloride as substrate. The acephate inhibited the activity of acetylcholinesterase, obstructed the cascade reaction and reduced the production of H2O2, resulting in the changes of color intensity for the colorimetric detection. With suitable size and porous structure, CF-ZIF-8 provided a good microenvironment for guaranteeing the activity and spatial proximity of enzymes. The multi-enzyme platform displayed great performances with the detection limit of 0.23 nM for acephate. It was applied to the detection of acephate in Chinese cabbage and romaine, verifying the practicability of this platform.

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.

Aptamer-functionalized metal-organic frameworks (MOFs) for biosensing.

As a class of crystalline porous materials, metal-organic frameworks (MOFs) have attracted increasing attention. Due to the nanoscale framework structure, adjustable pore size, large specific surface area, and good chemical stability, MOFs have been applied widely in many fields such as biosensors, biomedicine, electrocatalysis, energy storage and conversions. Especially when they are combined with aptamer functionalization, MOFs can be utilized to construct high-performance biosensors for numerous applications ranging from medical diagnostics and food safety inspection, to environmental surveillance. Herein, this article reviews recent innovations of aptamer-functionalized MOFs-based biosensors and their bio-applications. We first briefly introduce different functionalization methods of MOFs with aptamers, which provide a foundation for the construction of MOFs-based aptasensors. Then, we comprehensively summarize different types of MOFs-based aptasensors and their applications, in which MOFs serve as either signal probes or signal probe carriers for optical, electrochemical, and photoelectrochemical detection, with an emphasis on the former. Given recent substantial research interests in stimuli-responsive materials and the microfluidic lab-on-a-chip technology, we also present the stimuli-responsive aptamer-functionalized MOFs for sensing, followed by a brief overview on the integration of MOFs on microfluidic devices. Current limitations and prospective trends of MOFs-based biosensors are discussed at the end.

Sonochemical fabrication of inorganic nanoparticles for applications in catalysis.

Catalysis covers almost all the chemical reactions or processes aiming for many applications. Sonochemistry has emerged in designing and developing the synthesis of nano-structured materials, and the latest progress mainly focuses on the synthetic strategies, product properties as well as catalytic applications. This current review simply presents the sonochemical effects under ultrasound irradiation, roughly describes the ultrasound-synthesized inorganic nano-materials, and highlights the sonochemistry applications in the inorganics-based catalysis processes including reduction, oxidation, degradation, polymerization, etc. Or all in all, the review hopes to provide an integrated understanding of sonochemistry, emphasize the great significance of ultrasound-assisted synthesis in structured materials as a unique strategy, and broaden the updated applications of ultrasound irradiation in the catalysis fields.