A General Strategy for Food Traceability and Authentication Based on Assembly-Tunable Fluorescence Sensor Arrays.

Food traceability and authentication systems play an important role in ensuring food quality and safety. Current techniques mainly rely on direct measurement by instrumental analysis, which is usually designed for one or a group of specific foods, not available for various food categories. To develop a general strategy for food identification and discrimination, a novel method based on fluorescence sensor arrays is proposed, composed of supramolecular assemblies regulated by non-covalent interactions as an information conversion system. The stimuli-responsiveness and tunability of supramolecular assemblies provided an excellent platform for interacting with various molecules in different foods. In this work, five sensor arrays constructed by supramolecular assemblies composed of pyrene derivatives and perylene derivatives are designed and prepared. Assembly behavior and sensing mechanisms are investigated systematically by spectroscopy techniques. The traceability and authentication effects on several kinds of food from different origins or grades are evaluated and verified by linear discriminant analysis (LDA). It is confirmed that the cross-reactive signals from different sensor units encompassing all molecular interactions can generate a unique fingerprint pattern for each food and can be used for traceability and authentication toward universal food categories with 100% accuracy.

IRF4 induces M1 macrophage polarization and aggravates ulcerative colitis progression by the Bcl6-dependent STAT3 pathway.

Ulcerative colitis (UC) is an idiopathic chronic intestinal inflammation. An increasing body of evidence shows that macrophages play an important role in the pathogenesis of UC. Interferon regulatory factor 4 (IRF4) is crucial for the development of autoimmune diseases via regulating immune cells. This research was designed to explore the function of IRF4 in UC and its association with macrophage polarization. The in vitro model of UC was established by stimulating colonic epithelial cells with tumor necrosis factor α (TNF-α). A mouse model of UC was constructed by injecting C57BL/6 mice with dextran sulfate sodium salt. Flow cytometry was used to assess percentage of CD11b+ CD86+ and CD11b+ CD206+ cells in bone marrow macrophages. Occult blood tests were used to detect hematochezia. Hematoxylin and eosin staining assay was used to assess colon pathological changes. Enzyme-linked immunosorbent assay (ELISA) was used to detect concentrations of inflammatory cytokines. The interaction of IRF4 and B-cell lymphoma 6 (Bcl6) was confirmed using GST pull-down and coimmunoprecipitation assays. Our findings revealed that IRF4 promoted cell apoptosis and stimulated M1 macrophage polarization in vitro. Furthermore, IRF4 aggravated symptoms of the mouse model of UC and aggravated M1 macrophage polarization in vivo. IRF4 negatively regulated Bcl6 expression. Downregulation of Bcl6 promoted apoptosis and M1 macrophage polarization in the presence of IRF4 in vitro and in vivo. Moreover, Bcl6 positively mediated the Janus kinase 2 (JAK2)/signal transducer and activator of transcription 3 (STAT3) signaling pathway. In conclusion, IRF4 aggravated UC progression through promoting M1 macrophage polarization via Bcl6/JAK2/STAT3 pathway. These findings suggested that IRF4 might be a good target to competitively inhibit or to treat with UC.

A colorimetric probe for rapid and simultaneous detection of alkylresorcinols and ferulic acid based on in-situ coupling reaction in aqueous media.

Rapid and simultaneous detection of Alkylresorcinols (ARs) and ferulic acid (FA) could evaluate qualities of commercial wheat products comprehensively and improving product quality. In this work, we have developed a colorimetric strategy for rapid and simultaneous detection of ARs and FA by using in-situ coupling reaction between analytes and diazotized small molecule probe in aqueous media. This strategy featured a rapid response, obvious color change, simple preprocessing, high sensitivity and selectivity. The limit of detection (LOD) can be as low as 0.244 µM and 0.5 µM for ARs and FA, respectively. The sensing mechanism was investigated by spectroscopy technique. Excellent practical application of this method was further confirmed to simultaneously monitor ARs and FA in real samples. The accuracy of the method could be reached to 95.0 % and 99.6 % for ARs and FA respectively. To our knowledge, this work firstly reported a sensor for ARs and FA simultaneous determination.

A Purkinje cell to parabrachial nucleus pathway enables broad cerebellar influence over the forebrain.

In addition to its motor functions, the cerebellum is involved in emotional regulation, anxiety and affect. We found that suppressing the firing of cerebellar Purkinje cells (PCs) rapidly excites forebrain areas that contribute to such functions (including the amygdala, basal forebrain and septum), but that the classic cerebellar outputs, the deep cerebellar nuclei, do not directly project there. We show that PCs directly inhibit parabrachial nuclei (PBN) neurons that project to numerous forebrain regions. Suppressing the PC-PBN pathway influences many regions in the forebrain and is aversive. Molecular profiling shows that PCs directly inhibit numerous types of PBN neurons that control diverse behaviors that are not involved in motor control. Therefore, the PC-PBN pathway allows the cerebellum to directly regulate activity in the forebrain, and may be an important substrate for cerebellar disorders arising from damage to the posterior vermis.

Fluorescent detection of tartrazine based on the supramolecular self-assembly of cationic perylene diimide.

A cationic perylene probe was designed and synthesized for sensitive determination of tartrazine. In the presence of tartrazine, the fluorescence of the perylene probe was quenched by efficient supramolecular self-assembly of the perylene derivate. The quenching is caused by the synergistic effect of noncovalent interactions including static electricity, π-π stacking, and hydrophobic interaction. Benefiting from these advantages, the probe exhibited excellent sensing performance to tartrazine within 2 min. The detection and quantification limit of tartrazine are as low as 2.42 and 8.07 nmol L-1, respectively, with a wide linear operation range from 15 to 500 nmol L-1. Most importantly, due to the high binding affinity (3.22 × 107 mol L-1) between the perylene probe and tartrazine, the sensing system shows great anti-interference capacity. Subsequently, the visualization application of the approach was evaluated by portable device, and the limits of detection for visual detection for test strip, membrane, and hydrogel were 0.5, 0.5, and 5 µmol L-1, respectively. The approach has been applied to monitor tartrazine in various food condiments with recoveries in the range 91.29-108.83%. As far as we know, this is the first report of using perylene-based probe for tartrazine determination, offering a promising strategy for the construction of perylene-based detection system in the field of food safety.

Smartphone-assisted ratiometric sensing platform for on-site tetracycline determination based on europium functionalized luminescent Zr-MOF.

Accurate on-site analysis of tetracycline (TC) is of great research value for ensuring food safety and estimating environmental pollution. Herein, a smartphone-based fluorescent platform for TC detectionhas been developed based on a europium functionalized metal-organic framework (Zr-MOF/Cit-Eu). Based on the inner filter and antenna effect between Zr-MOF/Cit-Eu and TC, the probe exhibited a ratiometric fluorescent response toward TC, resulting in an emission color change from blue to red. Excellent sensing performance was achieved with a detection limit of 3.9 nM, consistent with the linear operation spanning nearly four orders of magnitude. Subsequently, visual test strips based on Zr-MOF/Cit-Eu were prepared, possessing the potential for accurate testing of TC via RGB signals. Finally, the proposed platform was well applied in actual samples with satisfied recoveries (92.27 to 110.22%). This MOF-based on-site fluorescent platform holds great potential on constructing intelligent platform for visual and quantitative detection of organic contaminants.

Ultrasensitive Detection of Organophosphorus Pesticides Using Single-Molecule Conductance Measurement.

Detection of organophosphorus pesticides (OPs) with high sensitivity in environmental samples is of vital importance for environmental safety and human health. However, it remains a challenge to achieve fM (10-15 mol/L) sensitivity for detecting OPs. Herein, we developed an acetylcholinesterase sensor based on 3,3',5,5'-tetramethylbenzidine (TMB) combining an enzyme-mediated strategy and scanning tunneling microscopy break junction (STM-BJ). Benefiting from the enzyme inhibition kinetics of OPs and the customized spectral clustering analysis method, our new strategy achieved the detection of methamidophos (MTMP) with a limit of 10 aM (10-17 mol/L) and 3 times higher selectivity in mixed OPs. As applied to natural lake waters, it also exhibited high reproducibility, high stability, and good recovery. This work paves a new avenue toward the application of single-molecule conductance characterizations for biochemical analysis and environmental monitoring.

Prediction of distant metastasis and specific survival prediction of small intestine cancer patients with metastasis: A population-based study.

BACKGROUND: Small intestine cancer (SIC) is difficult to diagnose early and presents a poor prognosis due to distant metastasis. This study aimed to develop nomograms for diagnosing and assessing the prognosis of SIC with distant metastasis. METHODS: Patients diagnosed with SIC between 2010 and 2015 were included from the Surveillance, Epidemiology and End Results database. Univariate and multifactor analysis determined independent risk factors for distant metastasis and prognostic factors for overall and cancer-specific survival. We then constructed the corresponding three nomograms and assessed the diagnostic accuracy of the nomograms by net reclassification improvement, receiver operating characteristic curves and calibration curves, assessed the clinical utility by decision curve analysis. RESULTS: The cohort consisted of 6697 patients, of whom 1299 had distant metastasis at diagnosis. Tstage, Nstage, age, tumor size, grade, and histological type were independent risk factors for distant metastasis. Age, histological type, T stage, N stage, grade, tumor size, whether receiving surgery, number of lymph nodes removed, and the presence of bone or lung metastases were predictors of both overall survival and cancer-specific survival. The nomograms showed excellent accuracy in predicting distant metastasis and prognosis. CONCLUSION: Nomograms were developed and validated for SIC patients with distant metastasis, aiding physicians in making rational and personalized clinical decisions.

Nanoassemblies Based on a Cationic Perylene Diimide Derivative and Sodium Dodecyl Sulfate: A Simple Fluorescent Platform for Efficient Analysis of Aflatoxin B1.

Aflatoxin B1 (AFB1) is a kind of potently carcinogenic fungal metabolite in food threatening human health, and it is crucial and challenging to develop advanced nonimmune approaches for AFB1 determination. Addressing this challenge, we successfully constructed a nanoassembly (PdE-PDI/SDS) by noncovalently coupling a cationic perylene diimide derivative (PdE-PDI) and sodium dodecyl sulfate (SDS), exhibiting high-density charges and a specific surface area for rapid sensing of AFB1. The large electronic conjugate structure and rigid plane of PdE-PDI enable it to form more stable σ-π, π-π coordination, and hydrogen bonds with AFB1. Additionally, the introduction of SDS significantly amplifies noncovalent interactions and enhances the quenching efficiency of PdE-PDI toward AFB1. The proposed PdE-PDI/SDS exhibited excellent specificity to AFB1 and showed dosage-sensitive detection with detection limit as low as 0.74 ng mL-1. Finally, the PdE-PDI/SDS was successfully applied in cereal samples with good recoveries from 94.61 to 109.92%. To our knowledge, this is the first time a fluorescent strategy from the point of self-assembly for AFB1 determination is reported, which holds great promise for wide applications of perylene diimide derivative in food safety.

Cerebellar granule cell signaling is indispensable for normal motor performance.

Within the cerebellar cortex, mossy fibers (MFs) excite granule cells (GCs) that excite Purkinje cells (PCs), which provide outputs to the deep cerebellar nuclei (DCNs). It is well established that PC disruption produces motor deficits such as ataxia. This could arise from either decreases in ongoing PC-DCN inhibition, increases in the variability of PC firing, or disruption of the flow of MF-evoked signals. Remarkably, it is not known whether GCs are essential for normal motor function. Here we address this issue by selectively eliminating calcium channels that mediate transmission (CaV2.1, CaV2.2, and CaV2.3) in a combinatorial manner. We observe profound motor deficits but only when all CaV2 channels are eliminated. In these mice, the baseline rate and variability of PC firing are unaltered, and locomotion-dependent increases in PC firing are eliminated. We conclude that GCs are indispensable for normal motor performance and that disruption of MF-induced signals impairs motor performance.

Green, non-toxic and efficient adsorbent from hazardous ash waste for the recovery of valuable metals and heavy metal removal from waste streams.

As compared to alkali-activated geopolymers with phosphoric acid which may be used in high concentrations resulting in disposal concerns, acid-based geopolymers may have superior properties. A novel green method of converting waste ash to a geopolymer for use in adsorption applications such as water treatment is presented here. We use methanesulfonic acid, a green chemical with high acid strength and biodegradability to form geopolymers from coal and wood fly ashes. The geopolymer is characterized for its physico-chemical properties and tested for heavy metal adsorption. The material specifically adsorbs iron and lead. The geopolymer is coupled to activated carbon forming a composite, which adsorbs silver (precious metal) and manganese (hazardous metal) significantly. The adsorption pattern complies with pseudo-second order kinetics and Langmuir isotherm. Toxicity studies show while activated carbon is highly toxic, the geopolymer and the carbon-geopolymer composite have relatively less toxicity concerns.

Electrochemical synthesis of Co/Ni bimetal-organic frameworks: A high-performance SERS platform for detection of tetracycline.

Surface-enhanced Raman scattering (SERS) enables food contaminants monitoring become facile and efficient. Herein, a facile strategy of integrating three-dimensional Ni form with Co/Ni bimetal-organic frameworks combining Ag nanoparticles via electrochemical synthesis method was proposed to develop a high-performance SERS substrate (CoNi-ZIFs@Ag@NF) for efficient detection of tetracycline. The flexible Ni foam (NF) acted as scaffold which can contribute to dramatically enhancing intrinsic electrical conductivity and endowing prepared substrate with high stability and uniform distribution of Ag nanoparticles. Furthermore, the pre-concentration effect of CoNi-ZIFs@Ag@NF for target molecules enhanced SERS performance dramatically. Besides, tetracycline was sensitively detected using CoNi-ZIFs@Ag@NF with low limit of detection (1.0 × 10-11 M) and wide linear detection range (10-10 - 10-5 M) in aqueous solution. Also, the satisfactory recovery (94.45 - 114.25 %) was realized with less than 6.78 % of RSD in real samples. This method would provide a potential and high-performance substrate for SERS monitoring of tetracycline in food and environment.

Ratiometric detection of polymyxin B based on the disaggregation of pyrenyl nanoassemblies in 100% aqueous media.

Polymyxin B (PMB) was an antibiotic with highly effective antibacterial effect but narrow safety interval, and its residues in food had attracted widespread attention. It was important to develop an accurate method for the rapid detection of PMB in animal foods. In this work, we had established a ratiometric sensing system based on the formation of supramolecular assemblies of pyrenyl probes, which were driven by the synergy of noncovalent forces such as multiple-electrostatic and π-π stacking interactions. Compared with the traditional fluorescence detection based on the single wavelength change, the present approach showing two-wavelength fluorescence response could reduce the interference of other factors making the experimental results more accurate. The sensor exhibited high sensitivity and selectivity with a low detection limit (28.3 nM). This method could be used to realize visual detection and had a visual detection limit of 1 µM. As we had learned yet, this was the first ratiometric sensor for PMB detection in aqueous solution. We believed all our preliminary would not only provide a complementary strategy for the detection of PMB, but also develop some new ideas for the construction of sensors for rapid antibiotic detection.

Comparing Day 5 versus Day 6 euploid blastocyst in frozen embryo transfer and developing a predictive model for optimizing outcomes: a retrospective cohort study.

Background: Optimal protocols for frozen-thawed embryo transfer (FET) after preimplantation genetic testing (PGT) remain unclear. This study compared Day 5 (D5) and Day 6 (D6) blastocysts and evaluated predictors of FET success. Methods: A total of 870 patients with genetic diseases or chromosomal translocations who received PGT at the First Affiliated Hospital of Zhengzhou University from January 2015 to December 2019 were recruited. All patients underwent at least one year of follow-up. Patients were divided into groups according to the blastocyst development days and quality. Univariate and multivariate logistic regression were applied to identify risk factors that affect clinical outcomes and to construct a predictive nomogram model. Area under the curve (AUC) of the subject's operating characteristic curve and GiViTI calibration belt were conducted to determine the discrimination and fit of the model. Results: D5 blastocysts, especially high-quality D5, resulted in significantly higher clinical pregnancy (58.4% vs 49.2%) and live birth rates (52.5% vs 45%) compared to D6. Multivariate regression demonstrated the number of blastocysts, endometrial preparation protocol, days of embryonic development and the quality of blastocysts independently affected live birth rates (P<0.05). A nomogram integrating these factors indicated favorable predictive accuracy (AUC=0.598) and fit (GiViTI, P=0.192). Conclusions: Transferring high-quality D5 euploid blastocysts after PGT maximizes pregnancy outcomes. Blastocyst quality, blastocyst development days, endometrial preparation protocols, and number of blastocysts, independently predicted outcomes. An individualized predictive model integrating these factors displayed favorable accuracy for counseling patients and optimizing clinical management.

Rapid detection of rocuronium based on host/guest complex between a pyrene derivative and sugammadex.

Rocuronium is widely used in surgery as a neuromuscular relaxant, but it has been difficult to accurately control its specific dosage in clinical operation. Therefore, the development of fast and instant rocuronium detection methods has important application value for reducing risks and safeguarding health. In this study, N, N, N-trimethyl-4-(pyrene-1-butyl)-ammonium bromide (PyBTA) was designed as a probe to detect rocuronium rapidly. The method relied on replacing PyBTA in sugammadex with rocuronium to induce changes in fluorescence intensity of PyBTA, thereby realizing quantitative detection. Its sensing performance and detection mechanism were explored systematically by spectroscopy. The linear range of this method was 0.5-10 µM and the detection limit of it was 0.3 µM. In addition, we confirmed that the host-guest interaction among PyBTA, sugammadex, and rocuronium was mainly driven by electrostatic and hydrophobic interactions.

Single-Molecule Tunneling Sensors for Nitrobenzene Explosives.

The tunneling current through the single-molecule junctions principally offers the ultimate solution for chemical and biochemical sensing via the interactions between probes and target analytes at the single-molecule level. However, it remains unexplored to achieve the sensitive and selective detection of targeted analytes using single-molecule junction techniques due to the challenge in quantitative evaluation of sensing sensitivity and selectivity. Herein, we demonstrate a single-molecule tunneling sensor for the highly sensitive and selective detection of nitrobenzene explosives using scanning tunneling microscope break junction (STM-BJ). Taking advantage of π-π stacking interactions between the molecular probes and nitrobenzene explosives, we use a spectral clustering algorithm to assign the signal of probes and π-stacked probes for sensitively detecting the targeted analytes and the distinguishable conductance change of probes when interacting with different nitroaromatic explosive compounds for selective detection. We find that pronounced conductance changes up to 0.8 orders of magnitude when the probes interact with TNT. Also, we obtain a sensitivity of up to ∼10 pM for TNT and high sensitivity for eight TNT analogues. Combined with theoretical calculations, we discover that the harness of the destructive quantum interference of the probe M1OH after interacting with TNT leads to high selectivity in sensing with TNT. Our work demonstrates the great potential of the single-molecule tunneling current for environmental sensing molecules with high selectivity and sensitivity.

Towards understanding respiratory particle transport and deposition in the human respiratory system: Effects of physiological conditions and particle properties.

Fly ash is a common solid residue of incineration plants and poses a great environmental concern because of its toxicity upon inhalation exposure. The inhalation health impacts of fly ash is closely related to its transport and deposition in the human respiratory system which warrants significant research for health guideline setting and inhalation exposure protection. In this study, a series of fly ash transport and deposition experiments have been carried out in a bifurcation airway model by optical aerosol sampling analysis. Three types of fly ash samples of different morphologies were tested and their respiratory deposition and transport processes were compared. The deposition efficiencies were calculated and relevant transport dynamics mechanisms were discussed. The influences of physiological conditions such as breathing rate, duration, and fly ash physical properties (size, morphology, and specific surface area) were investigated. The deposition characteristics of respiratory particles containing SARS-CoV-2 has also been analyzed, which could further provide some guidance on COVID-19 prevention. The results could potentially serve as a basis for setting health guidelines and recommending personal respiratory protective equipment for fly ash handlers and people who are in the high exposure risk environment for COVID-19 transmission.

Comparative study of Pd@Pt nanozyme improved colorimetric N-ELISA for the paper-output portable detection of Staphylococcus aureus.

Staphylococcus aureus is a frequent pathogenic bacterium that has a significant detrimental influence on the health of the human body. Therefore, developing a practical and portable detection platform is critical to ensuring food safety. Nanozymes are a kind of engineered nanomaterials with superior enzyme-like activities, providing infinite possibilities for the development of highly sensitive analytical assays. In this study, mesoporous core-shell palladium@platinum (Pd@Pt) nanozymes were synthesized and then applied as a signal amplifier in Staphylococcus aureus colorimetric immunoassay. At the same time, a careful comparative study of the catalytic performance with natural horseradish peroxidase (HRP), Pd@Pt nanozymes and their complexes Pd@Pt-HRP (HRP coupling with Pd@Pt nanozymes) were firstly performed, as well as clever using a colorimeter to achieve portable signal output. Pd@Pt-HRP bioprobes enable remarkable peroxidase-like catalytic activity, resulting in the highest sensitivity with a limit of detection (LOD) improved from 1 × 105 to 1 × 103 CFU/mL. In all, this work conducted a valuable comparative study and presented an improved strategy for the portable detection of pathogenic bacteria, which was expected to be used in a wide range of applications in food safety regulation and biomedicals arenas.

Phosphatase-like activity of single-atom CeNC nanozyme for rapid detection of Al3.

Single-atom nanozymes are a class of nanozymes with attractive enzyme-like activities. They usually mimic oxidoreductases and lack other types of enzyme-like activities. Hence, we verified a single-atom CeNC (SACeNC) nanozyme with an excellent phosphatase-like (PPA-like) activity, which could catalyze the dephosphorylation of inorganic phosphates. Meanwhile, we found that Al3+ could specifically combine with the O atom in its structure to form an Al-O bond, which could inhibit its PPA-like activity. Based on this principle, we have constructed a fast, portable, and efficient fluorescent liquid phase sensor to detect Al3+. The detection time was only 4 min, and the limit of detection (LOD) was 22.89 ng/mL in the linear range of 5-25 µg/mL. This study not only verified that single-atom nanozymes mimic phosphatase activities, but also applied its unique enzyme-like to the field of food safety rapid detection.

Rapid detection of hydrogen sulfide in vegetables and monosodium glutamate based on perylene supramolecular aggregates using an indicator displacement assays strategy.

Hydrogen sulfide (H2S) has been clearly identified as a hazardous chemical pollutant that seriously affects food safety and human health. In order to develop a rapid, accurate and efficient H2S tracking method, this work propose a strategy based on indicator displacement assays (IDA). A water-soluble histidine-modified perylene diimide fluorescent probe was synthesized by a one-step method, and the probe can form supramolecular aggregates in the presence of Cd2+. There will be a fluorescence transformation of probe, caused by the change of the state of aggregation and adjusted by various concentration of S2-, which can achieve the fluorescence detection of S2-. The limit of detection is as low as 0.41 µmol/L. Particularly worth mentioning is that the probe in this work can be recycled for at least 5 times, which is environmentally friendly and economical. Finally, this method was applied in three kinds of vegetables and monosodium glutamate samples.