A Macrophage Membrane-Coated Cu-WO3-x-Hydro820 Nanoreactor for Treatment and Photoacoustic/Fluorescence Dual-Mode Imaging of Inflamed Liver Tissue.

A disease-targeting nanoplatform that integrates imaging with therapeutic activity would facilitate early diagnosis, treatment, and therapeutic monitoring. To this end, a macrophage membrane-coated Cu-WO3-x-Hydro820 (CWHM) nanoreactor was prepared. This reactor was shown to target inflammatory tissues. The reactive oxygen species (ROS) such as H2O2 and ·OH in inflammatory tissues can react with Hydro820 in the reactor to form the NIR fluorophore IR820. This process allowed photoacoustic/fluorescence dual-mode imaging of H2O2 and ·OH, and it is expected to permit visual diagnosis of inflammatory diseases. The Cu-WO3-x nanoparticles within the nanoreactor shown catalase and superoxide enzyme mimetic activity, allowing the nanoreactor to catalyze the decomposition of H2O2 and ·O2- in inflammatory cells of hepatic tissues in a mouse model of liver injury, thus alleviating the oxidative stress of damaged liver tissue. This nanoreactor illustrates a new strategy for the diagnosis and treatment of hepatitis and inflammatory liver injury.

Flexible Self-Powered Sensing System Based on Novel DNA Circuit Strategy and Graphdiyne for Thalassemia Gene by Rapid Naked-Eye Tracking and Open-Circuit Voltage.

Based on the controllable instantaneous self-assembly ability of long-chain branched DNA nanostructures and the synergistic effect between nucleic acid amplification without enzymes, a highly sensitive and highly specific self-powered biosensing platform is developed. Two-dimensional graphdiyne is prepared, modified on flexible carbon cloth, and then functionalized with gold nanoparticles. When DNA mi-tubes are applied on it, target thalassemia gene CD122 triggers a dual-catalytic hairpin assembly reaction. The generated nanoscale DNA is precisely captured by the DNA mi-tube, exposing binding sites and activating the hybridization chain reaction to form long-chain branched DNA. Double-stranded DNA, along with dendritic DNA carrying a large number of guanine bases, precisely captures the signal molecule methylene blue (MB), generating a significant electrochemical signal. The redox reaction of MB also causes a proportional change in the system's color, achieving a colorimetric detection functionality. An efficient dual-mode self-powered sensing platform, therefore, is established for detecting the thalassemia gene CD122. The linear response range of target concentration to open-circuit voltage and RGB Blue value is 0.0001-10,000 pM. The detection limit under electrochemical mode is 36.3 aM (S/N = 3), and under colorimetric mode, it is as low as 12.1 aM (S/N = 3). The new method exhibits high sensitivity, excellent selectivity, and high accuracy, providing a universal strategy for designing novel biosensing platforms that can be extended to the detection of other biomolecules.

Smart Target-Initiated Catalytic DNA Junction Circuit Amplification Strategy for the Ultrasensitive Electrochemiluminescence Detection of MicroRNA.

One of the highly attractive research directions in the electrochemiluminescence (ECL) field is how to regulate and improve ECL efficiency. Quantum dots (QDs) are highly promising ECL materials due to their adjustable luminescence size and strong luminous efficiency. MoS2 NSs@QDs, an ECL emitter, is synthesized via hydrothermal methods, and its ECL mechanism is investigated using cyclic voltammetry and ECL-potential curves. Then, a stable and vertical attachment of a triplex DNA (tsDNA) probe to the MoS2 nanosheets (NSs) is applied to the electrode. Next, an innovative ECL sensor is courageously empoldered for precise and ultrasensitive detection of target miRNA-199a through the agency of ECL-resonance energy transfer (RET) strategy and a dextrous target-initiated catalytic three-arm DNA junction assembly (CTDJA) based on a toehold strand displacement reaction (TSDR) signal amplification approach. Impressively, the ingenious system not only precisely regulates the distance between energy donor-acceptor pairs leave energy less loss and more ECL-RET efficiency, but also simplifies the operational procedure and verifies the feasibility of this self-assembly process without human intervention. This study can expand MoS2 NSs@QDs utilization in ECL biosensing applications, and the proposed nucleic acid amplification strategy can become a miracle cure for ultrasensitive detecting diverse biomarkers, which helps researchers to better study the tumor mechanism, thereby unambiguously increasing cancer cure rates and reducing the risk of recurrence.

Recent Advances in Tailored Fabrication and Properties of Biobased Self-Healing Polyurethane.

With the emergence of challenges in the environmental degradation and resource scarcity fields, the research of biobased self-healing polyurethane (BSPU) has become a prevailing trend in the technology of the polyurethane industry and a promising direction for developing biomass resources. Here, the production of BSPU from lignocellulose, vegetable oil, chitosan, collagen, and coumarin is classified, and the principles of designing polyurethane based on compelling examples using the latest methods and current research are summarized. Moreover, the impact of biomass materials on self-healing and mechanical properties, as well as the tailored performance method, are presented in detail. Finally, the applications of BSPU in biomedicine, sensors, coatings, etc. are also summarized, and the possible challenges and development prospects are explored to helpfully make progress in the development of BSPU. These findings demonstrate valuable references and practical significance for future BSPU research.

An all-graphdiyne electrochemiluminescence biosensor for the ultrasensitive detection of microRNA-21 based on target recycling with DNA cascade reaction for signal amplification.

Graphdiyne oxide quantum dots (GDYO QDs), as derivatives of graphdiyne (GDY), have excellent electroconductibility and luminous properties and can be applied as a new ECL emitter. Herein, an electrochemiluminescence (ECL) biosensor for miRNA-21 ultrasensitive determination is constructed based on AuNPs/GDY, GDYO QD and oligonucleotide signal amplification strategy that integrates DNA walker and hybridization chain reaction (HCR) amplification. As electrode substrate material, AuNPs/GDY can not only bond with the aptamer CP but can also enhance the conductivity of the interface. When miRNA-21 exists, the DNA walker process is initiated, and the signaling probes are introduced on the electrode surface, producing abundant double-stranded H1/H2; then, H3/H4 undergoes complementary base pairing with H1/H2 through HCR. With the increase in miRNA-21, the 3D DNA nanomachine is actively manipulated, resulting in a gradual increase in ECL signal. This ECL biosensor demonstrates outstanding performance in the determination of miRNA-21 in the linear range from 0.1 fM to 1 nM. This study offers a new sensitive idea for the clinical analysis of cancer biomarkers.

A carbon dot-based nanoscale covalent organic framework as a new emitter combined with a CRISPR/Cas12a-mediated electrochemiluminescence biosensor for ultrasensitive detection of bisphenol A.

Exploring new highly efficient electrochemiluminescence (ECL) luminophores is a necessary condition for developing ultrasensitive ECL biosensors. Therefore, a luminescent carbon dot-based covalent organic framework (CD-COF) was prepared using aldehyde-based carbon dots (CDs) and 1,3,5-tris (4-aminophenyl) benzene (TPB). Because the CD-COF made the regular arrangement of CDs conducive to improving the ECL response, CD-COF had a higher ECL intensity and efficiency than CDs. What's more, the ECL intensity of the CD-COF/S2O82-/Bu4N+ system was about 2.98, 7.50, and 28.08 times higher than those of the CD-COF/S2O82-, CDs/S2O82- and S2O82- systems, respectively. Considering the remarkable ECL performance, the CD-COF/S2O82-/Bu4N+ system was employed combined with the CRISPR/Cas12a trans-cutting strategy to construct an "off-on" ECL biosensor for BPA detection. The proposed ECL biosensor exhibited excellent performance with a wide linear range from 1.0 × 10-14 mol L-1 to 1.0 × 10-5 mol L-1 with a low detection limit of 2.21 fM (S/N = 3) under the optimized conditions. The biosensor demonstrated that CD-COF can be used as an efficient ECL emitter, thus expanding the application field of COFs. In addition, the good stability and specificity of the biosensor enabled the rapid detection of BPA, which will provide valuable insights into promising ultrasensitive ECL biosensors.

Fabrication of MIL-101(Cr)/silver nanocomposites as SERS substrate for sensitive determination of malachite green and crystal violet in tilapia.

Nanocomposites with multiple functions have attracted much attention in designing novel SERS substrates. In this report, the enrichment ability of MIL-101(Cr) and the local surface plasma resonance (LSPR) of silver nanoparticles are combined to fabricate a SERS substrate denoted as MIL-101-MA@Ag, which can simultaneously produce high-density and uniformly distributed hot spots. Moreover, the enrichment ability of MIL-101(Cr) can further improve the sensitivity by concentrating and transferring the analytes in the vicinity of hot spots. Under optimal conditions, MIL-101-MA@Ag showed good SERS activity for malachite green (MG) and crystal violet (CV), with detection limits as low as 9.5×10-11 M and 9.2×10-12 M at 1616 cm-1, respectively. The prepared substrate has been successfully applied to detect MG and CV in tilapia, the recovery rate of fish tissue extract was 86.4~102%, and the relative standard deviation (RSD) was 8.9~15%. The results demonstrate that MOF-based nanocomposites are expected to be useful SERS substrates and have a universal applicability for the detection of other hazardous molecules.

Superior performance of a graphdiyne self-powered biosensor with exonuclease III-assisted signal amplification for sensitive detection of microRNAs.

Graphdiyne (GDY) is an sp and sp2 co-hydrocarbon allotrope whose particular structure endows it with many fascinating properties, including abundant chemical bonds, high conjugation, natural pores, high carrier mobility, high conductivity and stability, etc. In this work, two-dimensional graphdiyne is prepared as an electrode substrate material coupling with an exonuclease III-assisted amplification strategy to construct a superior-performance self-powered biosensor based on enzymatic biofuel cells for highly sensitive detection of the tumour marker miRNA-21. Glucose oxidase (GOD) is first immobilized on the GDY/AuNP composite to prepare a bioconjugate. GDY/AuNP modified carbon cloth is used as an enzyme biofuel cell electrode, which is then modified with bilirubin oxidase as a biocathode. The bioconjugate binds to GOD through specific binding to the bioanode. When miRNA-21 is present, specific recognition by exonuclease III in the system results in cleavage of the capture probe, and miRNA-21 is recovered and involved in the cycle. The target miRNA-21 then causes corresponding changes in the open-circuit voltage of the self-powered system. Based on this, a sensitive detection method was constructed, within the scope from 0.1 fM to 0.1 nM with a shallow detection limit of 55.2 aM (S/N = 3). The new approach triumphantly has been used to detect miRNA-21 in serum, which provides a compelling new way for early diagnosis of related cancers.

Flexible photoelectrochemical sensor for highly sensitive chloramphenicol detection based on M-TiO2-CdTe QDs/CdS QDs composite.

Chloramphenicol (CAP) is widely used in the food industry and animal husbandry due to its effective antibiotic effect active against gram-positive and gram-negative microorganisms. However, research shows that it can cause serious adverse reactions and side effects in the human body. In order to effectively monitor the residues of CAP, a novel and simple photoelectrochemical (PEC) sensor for sensitive detection of CAP is fabricated based on M-TiO2-CdTe QDs/CdS QDs composite. The results show that the prepared M-TiO2 not only retains the original morphology and structure of MIL-125(Ti), but also exhibits more abundant pore structure and good photoelectrochemical properties. Compared with M-TiO2, the as-prepared M-TiO2-CdTe QDs/CdS QDs composite exhibits excellent PEC performances including about ninefold enhancement of photocurrent intensity, which is ascribed to the large surface of M-TiO2 and the introduction of CdTe QDs and CdS QDs. Based on the selective inhibitory effect of CAP in the photocurrent intensity of the M-TiO2-CdTe QDs/CdS QDs PEC system, a novel PEC sensor for CAP concentration determination is constructed. The designed PEC sensor demonstrates a linear range from 1 to 140 nmol L-1 with a detection limit of 0.14 nmol L-1 (S/N = 3). Moreover, the method is applied to real milk samples to quantify the CAP residues with spiked recoveries in the range of 96.3-106%, and the possible detection mechanism of the M-TiO2-CdTe QDs/CdS QDs PEC system is also discussed.

Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies.

The unique physical and chemical properties of nanomaterials are closely related to their surface thermodynamic functions, which mainly depend on their sizes. In this study, the thermodynamic properties of nano-cadmium sulphide (nano-CdS) were investigated by solubility technology. The nano-CdS powders with different particle sizes were prepared via a traditional solvothermal method, and the electrical conductivities of nano-CdS aqueous solutions at different temperatures were measured. The standard dissolution equilibrium constants of nano-CdS at different temperatures were calculated using the theory of dissolution thermodynamics. The standard molar dissolution thermodynamic functions, the molar surface thermodynamic functions and the specific surface thermodynamic functions of nano-CdS with different particle sizes were calculated by combining the thermodynamic functions of bulk-CdS, the principle of the thermodynamic cycle and the principle of electrochemical equilibrium. The experimental results show that the critical size values for the molar surface heat capacity and the specific surface heat capacity for approximately spherical nanoparticles are 9.3 nm and 8.7 nm, respectively. Within an acceptable range of error, the thermodynamic functions have linear and curved relationships with particle sizes and temperatures. Based on these results, it is disclosed that the critical size effect on surface heat capacities of nano-CdS is valuable to understand the energy storage processes of nanomaterials.

Correction: Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies.

Correction for 'Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies' by Shengjiang Zhang et al., Phys. Chem. Chem. Phys., 2022, 24, 6193-6207, https://doi.org/10.1039/D1CP04619E.

Novel Porphyrin Zr Metal-Organic Framework (PCN-224)-Based Ultrastable Electrochemiluminescence System for PEDV Sensing.

The sensitive detection of coronavirus is of vital importance for the prevention of its rapid spread. Porcine epidemic diarrhea virus (PEDV) is a highly contagious coronavirus that causes severe diarrhea and death in neonatal piglets. In this work, a novel PCN-224-based electrochemiluminescence (ECL) system was constructed for PEDV detection with high sensitivity. We found that PCN-224 can be employed as an ECL reporter with a strong signal because of its zirconium-based organic porous frame nanomaterial with a large specific surface area and stable structure. TiO2 nanoparticles were used as an accelerator for the first time to promote the reduction of coreactant potassium peroxydisulfate on the cathode; thus, the initial ECL signal of PCN-224 was significantly amplified. In the presence of PEDV, the ECL signal decreased due to the block effect to electron transfer. As a result, the novel "signal off" biosensor achieved a sensitive detection of PEDV ranging from 1 pg/mL to 10 ng/mL, with a detection limit of 0.4 pg/mL (S/N = 3). Importantly, the PCN-224 nanomaterial enriched the ECL system in biological analysis, and the proposed strategy provided a new route for coronavirus detection.

Construction of an Integrated Device of a Self-Powered Biosensor and Matching Capacitor Based on Graphdiyne and Multiple Signal Amplification: Ultrasensitive Method for MicroRNA Detection.

The detection of microRNA (miRNA) in human serum has great significance for cancer prevention. Herein, a novel self-powered biosensing platform is developed, which effectively integrates an enzymatic biofuel cell (EBFC)-based self-powered biosensor with a matching capacitor for miRNA detection. A catalytic hairpin assembly and hybrid chain reaction are used to improve the analytical performance of EBFC. Furthermore, the matching capacitor is selected as an auxiliary signal amplifying device, and graphdiyne is applied as substrate material for EBFC. The results confirm that the developed method obviously increases the output current of EBFC, and the sensitivity can reach 2.75 µA/pM, which is 786% of pure EBFC. MiRNA can be detected in an expanded linear range of 0.1-100000 fM with a detection limit of 0.034 fM (S/N = 3). It can offer a selective and sensitive platform for nucleotide sequence detection with great potential in clinical diagnostics.

A novel signal amplified electrochemiluminescence biosensor based on MIL-53(Al)@CdS QDs and SiO2@AuNPs for trichlorfon detection.

An ultrasensitive electrochemiluminescence (ECL) biosensor was developed based on MIL-53(Al)@CdS QDs and SiO2@AuNPs for trichlorfon detection. Metal-organic frameworks (MOFs) were used as a loading platform that provided a large surface area to load targets and modified materials onto the electrode. At the same time, SiO2@AuNPs loaded plenty of AuNPs which effectively increased the ECL resonance energy transfer between the CdS QDs, so that the ECL signal was strongly quenched and resulted in an amplified response. In the range of 10-11-10-4 M, the ECL response showed a linear relationship with the concentration (logarithm) of trichlorfon, and the detection limit was 5.1 × 10-12 M (S/N = 3). When the biosensor was applied to detect trichlorfon in lettuce, broccoli, cucumber, and chives, the recoveries obtained from the spiked samples were 97%-105%, 102%-104%, 100%-104%, and 98%-104%, respectively. Thus, this novel ECL biosensor has potential applications for the analysis of trichlorfon in food samples.

Mitochondria-targetable ratiometric fluorescence probe for carbon monoxide based on naphthalimide derivatives.

The design of ratiometric probes for imaging of carbon monoxide (CO) in subcellular organelles is critical to elucidate its biological and pathological functions. In this work, we establish a ratiometric fluorescent probe (Mito-NIB-CO) for imaging of CO in mitochondria. The mitochondria-targeting unit (triphenylphosphonium moiety) and CO-responsive unit (allyl ether moiety) are covalently linking into the single molecule (Mito-NIB-CO) to achieve the multifunctional effect. Upon being treated with CO, Mito-NIB-CO underwent the cleavage of allyl ether element in the presence of PdCl2, resulting in the structural and spectral conversion. This characteristic afforded Mito-NIB-CO to be a ratiometric probe for CO with two fluorescent emission bands. Additionally, the probe Mito-NIB-CO exhibited other distinct merits, including preeminent selectivity and sensitivity. What's more, profiting from triphenylphosphonium moiety, the probe Mito-NIB-CO can specifically target the mitochondria and realize quantitative detection of exogenous/endogenous CO in mitochondria. Graphical abstract.

Assembling PVP-Au NPs as portable chip for sensitive detection of cyanide with surface-enhanced Raman spectroscopy.

Cyanide (C≡N) can lead to blood, cardiovascular system, and nervous system disorders owing to the acute and chronic toxicity; thus, aiming at the group or individual poisoning incidents, it is necessary to develop the sensitive and credible method for rapid on-site detection of poisons cyanide. Surface-enhanced Raman spectroscopy (SERS) with the advantages of providing fingerprint information of target molecules and single-molecules sensitivity has been widely used in on-site analysis; however, the SERS measurements always suffer from the problem of the stability of substrates. Here, the polyvinylpyrrolidone (PVP)-stabilized Au NPs (PVP-Au NPs) have been assembled through the simple, convenient evaporation-induced strategy with the large-scale hotspots substrates. The presence of PVP can not only facilitate the assembly of Au NPs but also prevent the corrosion of CN- towards the Au NPs with the formation of [Au (CN)2]-1, providing high stable and reproducible SERS signals. Moreover, the PVP-Au NPs have been assembled on the Si wafer to fabricate the portable SERS chip for rapid on-site detection of CN- with an RSD of 5.8% and limitation of 100 ppb. Furthermore, by coupling a portable Raman spectrometer, the SERS spectra of CN- spiked into different specimens to simulate the poison samples have been collected and analyzed on SERS chips with the recovery of 89-103% and RSD not higher than 11.3%. Consequently, the fabricated SERS chip with assembled PVP-Au NPs can provide sensitive and credible detection for CN- in different specimens, and then would satisfy the rapid on-site evaluation of CN- in poisoning incidents with the portable Raman spectrometer. Graphical Abstract.

Cauliflower-Inspired 3D SERS Substrate for Multiple Mycotoxins Detection.

Surface-enhanced Raman spectroscopy (SERS) is a promising analytical tool, but simultaneous detection of multiple targets using SERS remains a challenge. Herein, a cauliflower-inspired 3D SERS substrate with intense hot spots was prepared through sputtering Au nanoparticles (Au NPs) on the surface of polydimethylsiloxane coated anodic aluminum oxide (PDMS@AAO) complex substrate. As a result, the cauliflower-inspired 3D SERS substrate achieved the highest SERS activities at a sputtering time of 8 min. Under the optimal conditions, this SERS substrate possessed a low detection limit of 10-12 M, excellent enhancement uniformity (relative standard deviation, RSD = 4.57%) and high enhancement factor (2.2 × 106) for 4-mercaptobenzoic acid (4-MBA). Furthermore, the results of Raman showed that the 3D-Nanocauliflower SERS substrates could realize the simultaneous label-free detection for three mycotoxins (aflatoxin B1, deoxynivalenol, and zearalenone) in maize for the first time. It behaved good linear relationship between the concentrations and Raman intensities of aflatoxin B1, zearalenone, and deoxynivalenol. For the three mycotoxins, this method exhibited the limit of detection (LOD) of 1.8, 47.7, and 24.8 ng/mL (S/N = 3), respectively. The 3D-Nanocauliflower SERS substrates with dense hot spots presented remarkable SERS effect and activity, which could be act as a potential candidate for SERS substrate applied in the rapid and label-free detection.

A water-soluble fluorescent probe for detecting creatinine in totally aqueous media and imaging exogenous creatinine in living cells.

The design of vigorous tools for creatinine determination is extremely important in the diagnosis and treatment of kidney diseases. In the study, we examine a robust fluorescent turn-on probe (NCP-Pd) for creatinine detection in a completely aqueous solution based on the metal palladium-catalyzed reaction. In the presence of creatinine, the NCP-Pd dissociates and subsequently restores the fluorescence due to elimination of the heavy atom quenching effect and prevention of the photoinduced electron transfer effect. The probe NCP-Pd displays excellent detecting performance with respect to creatinine such as good water solubility, high selectivity, and a low detection limit (0.16 µM). Additionally, in order to ensure its clinical application, this probe is operated in blood serum samples for detecting creatinine and compared with a commercial clinical method. The results indicate an extremely high agreement with the commercial clinical method. Furthermore, the results confirm that the probe NCP-Pd exhibits satisfactory cell permeability and low cytotoxicity and can detect creatinine in L929 and HCT116 cells. The study provides a potential application for detecting creatinine and conducting pathological research on creatinine-involved diseases.

Exploring Cycloreversion Reaction of Cyclobutane Pyrimidine Dimers Quantum Mechanically.

The cyclobutane pyrimidine dimer (CPD) is a major photoproduct of deoxyribonucleic acid (DNA) that is damaged by ultraviolet light. This DNA lesion can be repaired by DNA photolyase with the aid of UV light and two cofactors. To understand the repair mechanism of CPD and whether protonation of CPD participates in the DNA repair process, the cycloreversion reactions of four CPD models and proton transfers between the adjacent residue Glu283 and CPD models were explored through the quantum mechanical method. Two-dimensional maps of potential energy surface in a vacuum and in implicit water solution were calculated at the ωB97XD/6-311++G(2df,2pd) level. One-dimensional potential energy profiles were computed for proton transfer reactions. Among the models that have been considered, both in a vacuum and in water solution, the results indicate that the most likely repair mechanism involves CPD•2- radical anion splitting in a stepwise manner. C5-C5' splits first, and C6-C6' splits later. The computed free energies of activation of the two splitting steps are 0.9 and 3.1 kcal/mol, respectively. The adjacent Glu283 may stabilize the CPD•2- radical anion through hydrogen bond and increase the quantum yield; however, protonating the CPD radical anion by Glu283 cannot accelerate the rate of ring opening.

[A new polyketide from marine-derived Streptomyces sp.MDW-06].

To isolate and identify secondary metabolites of marine-derived Streptomyces sp.MDW-06,the isolations and purifications of compounds were performed by means of column chromatography over silica gel. And their structures were elucidated through the spectroscopic analysis of MS,NMR and specific rotations. The bioactivities were assayed by paper diffusion and DPPH method. From the fermentation broth of marine-derived Streptomyces sp.MDW-06,five compounds( 1-5) were isolated and identified as streptopentanoic acid( 1),germicidin A( 2),germicidin B( 3),isogermicidin A( 4),isogermicidin B( 5) and oxohygrolidin( 6),respectively. Compound 1 is a new compound. Compound 1 shows DPPH radical scavenging activity with 36. 4% at 100 mg·L~(-1).