Silver nanoparticles deposited carbon microspheres nanozyme with enhanced peroxidase-like catalysis for colorimetric detection of Hg2+ in seafood.

Novel methods for high-performance detection of Hg2+ in seafood are critical for ensuring food safety and human health. Herein, Ag nanoparticles (Ag NPs) were successfully deposited on carbon microspheres (CMs) to form Ag NPs-CMs nanocomplex. The proposed Ag NPs-CMs could oxidize colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidation state TMB (oxTMB) in the presence of hydrogen peroxide (H2O2) and had a significant UV-vis absorption peak at 652 nm. The excellent peroxidase-like activity was attributed to the increased electrostatic attraction of CMs and the catalytic synergistic effect. After adding Hg2+, the catalytic activity of Ag NPs-CMs was specifically enhanced and the Michaelis-Menten constant (Km) decreased from 0.067 to 0.052 mmol/L due to the formation of Ag-Hg amalgam which produced more superoxide anions (O2•-) and hydroxyl radicals (•OH). The linear response ranges for Hg2+ were 2~833 nmol/L and 2.5~40 µmol/L, with the low detection limit of 1.10 nmol/L. This method was applied to detect Hg2+ in seafood with satisfactory recoveries of 95.65~106.56%. A hydrogel kit was designed for portable detection of Hg2+, and the response range was 0.5~5 µmol/L. This work provides a reliable method for visual Hg2+ detection in seafood as well as a feasible strategy for the design of high-performance nanozymes.

Carbon dots based ratiometric fluorescent sensing platform for food safety.

Food safety has become a major global concern and the rapid detection of food nutritional ingredients and contaminants has aroused much more attention. Nanomaterials-based fluorescent sensing holds great potential in designing highly sensitive and selective detection strategies for food safety analysis. Carbon dots (CDs) possess tremendous prospects in fluorescent sensing food ingredients and contaminants due to their superior properties of chemical and photostability, highly fluorescence with tunability, and no/low-toxicity. Numerous endeavors are demanded to contribute to overcoming the challenge of lower sensitivity and selectivity of the sensors interfered by various components in intricate food matrices to ensure food safety and human health. Nanohybrid CDs based ratiometric fluorescent sensing with self-calibration is regarded as an efficient strategy for the CDs based sensors for the specific recognition of target analyte in the food matrices. This work is devoted to reviewing the development of nanohybrid CDs based ratiometric fluorescent sensing platform and the perspectives of the platform for food safety. The applications of nanohybrid CDs in sensing are summarized and the sensing mechanisms are briefly discussed.

Construction of ratiometric fluorescence sensor and test strip with smartphone based on dual-emission carbon dots for the specific detection of chlortetracycline.

Concerns about environmental and food contamination caused by chlortetracycline (CTC) residues have prompted people to explore efficient and convenient CTC monitoring platforms. However, the reported fluorescent probes generally fail to selectively detect CTC due to the structural similarity of tetracycline antibiotics. Herein, an intrinsic dual-emission carbon dots (D-CDs) ratiometric fluorescence sensor was prepared for highly sensitive and selective determination of CTC over other tetracyclines by one-step synthesis. The sensor exhibited a significant fluorescence enhancement at 425 nm after introducing CTC. The fluorescence "turn on" of the sensing system is due to aggregation-induced emission (AIE) phenomenon formed by hydrogen bonds and π conjugation promoting the specific recognition of CTC by D-CDs. The linear detection varied from 0.98 to 143.67 ng mL-1 with a low limit of detection (LOD) of 1.29 ng mL-1 (R2 = 0.998), which was lower than most reported in the literature. The D-CDs sensor was applied to detect CTC in spiked milk, blocked normal human serum, and fish samples with recoveries of 95.5-104.2% and relative standard deviations (RSDs) of 2.6%. Particularly, D-CDs based test papers with a smartphone were prepared for portable and visual detection of CTC by analyzing the various color changes of RGB of fluorescence color, with an LOD of 7.18 ng mL-1 (R2 = 0.9909). The fluorescence sensor designed in this work could be used as a rapid tool with high performance and selectivity for monitoring control in foods.

UiO-67 decorated on porous carbon derived from Ce-MOF for the enrichment and fluorescence determination of glyphosate.

A nanocomposite was prepared by loading UiO-67 nanoparticles onto porous carbon materials derived from Ce-MOF (Ce-PC) for fluorescence detection of glyphosate. The probe (UiO-67/Ce-PC) exhibits fluorescence emission at 414 nm as the response signal under excitation at 310 nm. The fluorescence enhancement mode of UiO-67 reduces the background interference, and the introduction of Ce-PC provide hierarchical nanostructure and large specific surface area that can increase the contact availability and improve the pre-enrichment effect, ensuring UiO-67/Ce-PC with superior sensitivity. The abundant metal hydroxyl group (M-O-H) of UiO-67/Ce-PC could recognize phosphoryl groups (-PO3H2) of glyphosate through ligand exchange, which synergizes with H-bonding interaction and electrostatic attraction to exhibit specificity toward glyphosate. The competitive coordination effects weaken the ligand-to-metal charge transfer (LMCT) and consequently induce the fluorescence recovery. The calibration plot of the fluorescence enhancement response of UiO-67/Ce-PC towards glyphosate was recorded in the range 0.02-30 µg mL-1 with a low limit of detection (LOD) of 0.0062 µg mL-1, which is superior to the pure UiO-67. In addition, the sensor exhibited high selectivity and satisfactory accuracy and precision with recoveries of 92.1-105.6% and RSDs below 3.4%. This work not only presents a feasible sensor for sensitive and selective determination of glyphosate from cereal samples, but also provides a promising strategy for the design of MOF-based nanocomposites to achieve trace detection of various pollutants.

Carbon dots@Cu metal-organic frameworks hybrids for ratiometric fluorescent determination of pesticide thiophanate-methyl.

A dual-emission fluorescent (FL) probe was constructed by coordinating Cu2+ of copper metal-organic frameworks (Cu-MOFs) with - COO- group of carbon dots (CDs) for pesticide thiophanate-methyl (TM) determination. TM was recognized by organic ligands (H2BDC and H2BDC-NH2) of Cu-MOFs via π stacking. Due to the higher affinity of Cu2+ to TM than ligands and CDs, TM chelated with Cu2+ to form TM-Cu complex. Thus coordination of Cu-MOFs was damaged and the ligands were released resulting in the FL intensity increase of Cu-MOFs (F430). And also CDs were released from CDs@Cu-MOFs hybrids and electron transfer from CDs to CuMOFs was inhibited, leading to the FL intensity increase of CDs (F600). The FL intensity ratio (F430/F600) showed a good linear relationship with TM concentrations of 0.0307-0.769 µmol L-1 with a limit of detection (LOD) of ~ 3.67 nmol L-1. The probe was successfully applied to detect TM in spiked food samples with satisfactory recoveries of 93.1-113%. Additionally, visual detection of TM was achieved according to the fluorescence color variation from blue to carmine, indicating promising application of CDs@Cu-MOFs probe.

A versatile platform for colorimetric, fluorescence and photothermal multi-mode glyphosate sensing by carbon dots anchoring ferrocene metal-organic framework nanosheet.

Concerns regarding pesticide residues have driven attempts to exploit accurate, prompt and straightforward approaches for food safety pre-warning. Herein, a nanozyme-mediated versatile platform with multiplex signal response (colorimetric, fluorescence and temperature) was proposed for visual, sensitive and portable detection of glyphosate (GLP). The platform was constructed based on a N-CDs/FMOF-Zr nanosensor that prepared by in situ anchoring nitrogen-doped carbon dots onto zirconium-based ferrocene metal-organic framework nanosheets. The N-CDs/FMOF-Zr possessed excellent peroxidase (POD)-like activity and thus could oxide colorless 3, 3', 5, 5'-tetramethylbenzidine (TMB) into a blue oxidized TMB (oxTMB) in presence of H2O2. Intriguingly, owing to the blocking effect triggered by multiple interaction between GLP and N-CDs/FMOF-Zr, its POD-like activity of the latter was remarkably suppressed, which can modulate the transformation of TMB into oxTMB, generating tri-signal responses of fluorescence enhancement, absorbance and temperature decrease. More significantly, the temperature mode can be facilely realized by a portable home-made mini-photothermal device and handheld thermometers. The proposed multimodal sensing was capable of providing sensitive results by fluorescence mode and simultaneously realized visual/portable testing by colorimetric and photothermal channels. Consequently, it exhibited more adaptability for practical applications, which can satisfy different testing requirements according to sensitivity and available instruments/meters, presenting a new horizon for exploiting multifunctional sensors.

Immune-Ageing Evaluation of Peripheral T and NK Lymphocyte Subsets in Chinese Healthy Adults.

Ageing is often accompanied with a decline in immune system function, resulting in immune ageing. Numerous studies have focussed on the changes in different lymphocyte subsets in diseases and immunosenescence. The change in immune phenotype is a key indication of the diseased or healthy status. However, the changes in lymphocyte number and phenotype brought about by ageing have not been comprehensively analysed. Here, we analysed T and natural killer (NK) cell subsets, the phenotype and cell differentiation states in 43,096 healthy individuals, aged 20-88 years, without known diseases. Thirty-six immune parameters were analysed and the reference ranges of these subsets were established in different age groups divided into 5-year intervals. The data were subjected to random forest machine learning for immune-ageing modelling and confirmed using the neural network analysis. Our initial analysis and machine modelling prediction showed that naïve T cells decreased with ageing, whereas central memory T cells (Tcm) and effector memory T cells (Tem) increased cluster of differentiation (CD) 28-associated T cells. This is the largest study to investigate the correlation between age and immune cell function in a Chinese population, and provides insightful differences, suggesting that healthy adults might be considerably influenced by age and sex. The age of a person's immune system might be different from their chronological age. Our immune-ageing modelling study is one of the largest studies to provide insights into 'immune-age' rather than 'biological-age'. Through machine learning, we identified immune factors influencing the most through ageing and built a model for immune-ageing prediction. Our research not only reveals the impact of age on immune parameter differences within the Chinese population, but also provides new insights for monitoring and preventing some diseases in clinical practice. Supplementary Information: The online version contains supplementary material available at 10.1007/s43657-023-00106-0.

A dual-function chitosan packaging film for simultaneously monitoring and maintaining pork freshness.

Exploring food packaging films simultaneously possess freshness monitoring and maintaining can effectively tackle food safety issues. Here, we constructed a chitosan/N-doped carbon dots (CS/N-CDs) film which can monitor the freshness of pork based on pH-mediated fluorescent sensing and extend the shelf life based on the antioxidant, antibacterial and UV shielding properties. The fluorescent intensity of CS/N-CDs films increased with the increase of pork pH from 5.77 to 6.84 which positively related to the change of TVB-N from 6.68 to 17.53 mg/100 g. CS/N-CDs films had a maintaining effect on pork freshness corroborated by the scavenging activity on DPPH and ABTS radicals and antibacterial efficiency and inhibition zones of S. aureus and E.coli, and the total viable count, a value, weight loss, hardness and springiness of pork. Cell viability and hemolytic activity assay proved that CS/N-CDs films was safe. A novel chitosan-based intelligent and active food packaging film was provided.

Ratiometric fluorescent sensing carbendazim in fruits and vegetables via its innate fluorescence coupling with UiO-67.

A ratiometric fluorescent sensor was facilely fabricated using innate fluorescence of carbendazim (MBC) and fluorescent UiO-67 to sensitively and selectively detect MBC in food matrixes. The innate fluorescence of MBC provided a signal at 311 nm (F311), and the fluorescent UiO-67 at 408 nm (F408) could recognize MBC through π-π stacking inducing fluorescent quenching relied on photoelectron transfer (PET). The ratio (F311/F408) of the fluorescence enhancement of MBC and the quenching of UiO-67 linearly responded to the MBC concentrations of 0-47.6 µmol/L with a low limit of detection (LOD) of 3.0 × 10-3 µmol/L. The reverse response signals of the sensor enhanced the sensitivity toward MBC and presented remarkable anti-interference capability in complex matrices. The as-prepared sensor was applied to detect MBC residues in apple, cucumber and cabbage, obtaining satisfactory accuracy and precision with the recovery of 90.82-103.45% and RSDs of lower than 3.03%.

Heavy metal ions' poisoning behavior-inspired etched UiO-66/CTS aerogel for Pb(II) and Cd(II) removal from aqueous and apple juice.

Here, inspired by the poisoning process of heavy metal in human body that the accidental ingested heavy metal can anchor to the functional groups of DNA/protein/enzyme to exert their toxicities during the rapid blood circulation, we developed the adsorbent that enveloped Etched UiO-66 with abundant functional groups into chitosan (CTS) aerogel to capture Pb(II) and Cd(II) in aqueous and apple juice. SEM, XRD and FTIR spectra were used to characterize the Etched UiO-66/CTS aerogel. The results showed that Etched UiO-66/CTS aerogel has a three-dimensional porous structure, and -OH groups of CTS interact with Zr(IV) of Etched UiO-66 to form the stable UiO-66/CTS aerogel. Benefiting from the intrinsic properties of porous and abundant functional groups, Etched UiO-66/CTS aerogel exhibits satisfactory adsorption capacities of 654.9 mg g-1 for Pb(II) and 343.9 mg g-1 for Cd(II) at 45 °C. Moreover, the aerogel shows excellent removal efficiencies of 98.21% for Pb(II) and 98.70% for Cd(II) with initial concentration of 1.0 mg L-1 in apple juice with little effect on the quality of apple juice. This strategy of mimetic heavy metal ions' poisoning behavior opens up a new avenue for the removal of heavy metal ions in complex matrices.

Terbium (III)-referenced N-doped carbon dots for ratiometric fluorescent sensing of mercury (II) in seafood.

A ratiometric fluorescence (FL) sensor was fabricated by coordinating 2, 6-pyridinedicarboxylic acid (DPA) sensitized Tb3+ (Tb-DPA) with NH2 and COOH on the surface of the N-doped carbon dots (N-CDs) for detecting Hg2+ in seafood. The sensor exhibited two FL emissions at 436 nm (N-CDs) as the response signal and at 543 nm (Tb-DPA) as the reference signal when excited at 290 nm. After adding Hg2+, the FL emission at 436 nm was significantly quenched and the FL emission at 543 nm was negligibly changed. The electron transfer (ET) between COO- of N-CDs and Hg2+ led to the FL quenching of N-CDs. The FL ratio (F436/F543) exhibited a good linear relationship in the Hg2+ concentrations of 1161.51 µM with a low limit of detection (LOD) of ~37 nM. The sensor presented high selectivity, satisfactory accuracy and precision toward Hg2+ in seafood with recoveries of 86.45-114.47% and RSDs of 0.20-1.92%.

Cu2+-Triggered Carbon Dots with Synchronous Response of Dual Emission for Ultrasensitive Ratiometric Fluorescence Determination of Thiophanate-Methyl Residues.

Copper ion (Cu2+)-triggered carbon dots (CDs/Cu) with dual emissions were utilized to develop a ratiometric fluorescence sensor for ultrasensitive detection of inert thiophanate-methyl (TM). TM could be recognized by CDs/Cu through π-π stacking and could chelate Cu2+ of CDs/Cu through metal ion coordination, inducing synchronous fluoresent quenching of the dual emission of CDs/Cu based on the excited state intramolecular proton transfer and the ligand-to-metal charge transfer. The fluorescence ratio of CDs/Cu (F416/F481) linearly responded in a TM concentration of 0.10-20.00 µmol/L with an ultralow limit of detection of 2.90 × 10-6 µmol/L. A synchronous response of the ratiometric sensor enhanced the specificity toward TM and presented remarkable capability of anti-interference in complex matrices. The sensor exhibited satifactory accuracy and precision for practical applications with recoveries of 88.33-101.09% and relative standard deviations of 1.61-5.06%, demonstrating an ultrasensitive ratiometric fluorescent nanosensor for detecting pesticides residues in complex matrices.

N,S co-doped carbon dots based fluorescent "on-off-on" sensor for determination of ascorbic acid in common fruits.

A switchable sensor based on N and S co-doped carbon dots (N,S-CDs) was developed to determine ascorbic acid (AA) content in common fruits via fluorescence quenching of N,S-CDs by Fe3+ (off) and recovery by AA (on). TEM showed that the particle size was 2.35-7.95 nm with an average diameter of 5.12 nm. XPS and FTIR confirmed the presence of -OH, -COOH and -NH2 on N,S-CDs surface. UV-vis and FTIR revealed that the coordination of -COOH and -NH2 on N,S-CDs surface with Fe3+ accounted for FL quenching, and the release of -NH2 from coordination complexes due to the reduction of Fe3+ by AA led to partly FL recovery. The sensor allowed detecting AA in the linear range of 10-200 µmol/L with a LOD of 4.69 µmol/L. AA contents in common fruits detected by the sensor were in good agreement with the reference method (P > 0.05), indicating a practical fluorescent sensor for AA detection in common fruits.

Efficient removal and environmentally benign detoxification of Cr(VI) in aqueous solutions by Zr(IV) cross-linking chitosan magnetic microspheres.

Zirconium(IV) cross-linking chitosan (CTS) magnetic microspheres (Fe3O4@Zr-CTS) as a recoverable adsorbent were synthesized through the coordination reaction between zirconium oxychloride and CTS biopolymeric matrix for efficient adsorption and simultaneous detoxification of hexavalent chromium, Cr(VI), in aqueous solutions. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed the formation of core@shell magnetite microspheres. X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR) verified the crosslinking of Zr(IV) to CTS on the microspheres. Batch Cr(VI) adsorption performances of the resultant Fe3O4@Zr-CTS microspheres revealed that the maximum adsorption capacity of 280.97 mg/g were achieved under pH 4.0 at 298 K. The XPS analyses indicated that 61.1% of the adsorbed Cr(VI) was reduced to Cr(III) due to the oxidization of alcoholic groups on C-6 in CTS which served as electron donors to carbonyl groups. The adsorbent showed preferential Cr(VI) adsorption with the existence of co-existing cations (K+, Na+, Cu2+, Zn2+, Ca2+, Mg2+) and anions (NO3-, Cl-, SO42-, CO32-). The adsorbent exhibited excellent reusability, lower the effluent Cr(VI) contents down to the ppb level, which satisfied the drinking water standard recommended by the World Health Organization and was a promising candidate for water purification.

Surface molecularly imprinted polymer capped Mn-doped ZnS quantum dots as a phosphorescent nanosensor for detecting patulin in apple juice.

A Mn-doped ZnS quantum dots (QDs) based nanosensor for selective phosphorescent determination of patulin (PAT) was synthesized with 6-hydroxynicotinic acid (6-HNA) as dummy template via a surface molecular imprinting sol-gel process. FTIR and XRD indicated the successful graft of molecularly imprinted polymer (MIP) onto crystal QDs. Binding tests revealed that the MIP-QDs presented higher selectivity, adsorption capacity and mass transfer rate than non-imprinted polymers, demonstrating a specific recognition for PAT among competitive mycotoxins and its analogues with the imprinting factor of 2.02. The MIP-QDs could recognize PAT in a linear range of 0.43-6.50µmolL-1 with a detection limit of 0.32µmolL-1 and a correlation coefficient (R2) of 0.9945. Recoveries of 102.9-127.2% with relative standard deviations <4.95% were achieved in apple juice samples which were in good agreement with high-performance liquid chromatography (HPLC) (P>0.05). The results indicated a simple phosphorescent nanosensor for PAT detection in complex matrix.