Porphyrin-based covalent organic framework as oxidase mimic for highly sensitive colorimetric detection of pesticides.

A covalent organic framework-based strategy was designed for label-free colorimetric detection of pesticides. Covalent organic framework-based nanoenzyme with excellent oxidase-like catalytic activity was synthesized. Unlike other artificial enzymes, porphyrin-based covalent organic framework (p-COF) as the oxidase mimic showed highly catalytic chromogenic activity and good affinity toward TMB without the presence of H2O2, which can be used as substitute for peroxidase mimics and H2O2 system in the colorimetric reaction. Based on the fact that the pesticide-aptamer complex can inhibit the oxidase activity of p-COF and reduced the absorbance at 650 nm in UV-Vis spectrum, a label-free and facile colorimetric detection of pesticides was designed and fabricated. Under the optimized conditions, the COF-based colorimetric probe for pesticide detection displayed high sensitivity and selectivity. Taking fipronil for example the limit of detection was 2.7 ng/mL and the linear range was 5 -500,000 ng/mL. The strategy was successfully applied to the detection of pesticides with good recovery , which was in accordance with that of HPLC-MS/MS. The COF-based colorimetric detection was free of complicated modification H2O2, which guaranteed the accuracy and reliability of measurements. The COF-based sensing strategy is a potential candidate for the sensitive detection of pesticides of interests.

Progressive Insights into Metal-Organic Frameworks and Metal-Organic Framework-Membrane Composite Systems for Wastewater Management.

The sustainable management of wastewater through recycling and utilization stands as a pressing concern in the trajectory of societal advancement. Prioritizing the elimination of diverse organic contaminants is paramount in wastewater treatment, garnering significant attention from researchers worldwide. Emerging metal-organic framework materials (MOFs), bridging organic and inorganic attributes, have surfaced as novel adsorbents, showcasing pivotal potential in wastewater remediation. Nevertheless, challenges like limited water stability, elevated dissolution rates, and inadequate hydrophobicity persist in the context of wastewater treatment. To enhance the performance of MOFs, they can be modified through chemical or physical methods, and combined with membrane materials as additives to create membrane composite materials. These membrane composites, derived from MOFs, exhibit remarkable characteristics including enhanced porosity, adjustable pore dimensions, superior permeability, optimal conductivity, and robust water stability. Their ability to effectively sequester organic compounds has spurred significant research in this field. This paper introduces methods for enhancing the performance of MOFs and explores their potential applications in water treatment. It delves into the detailed design, synthesis strategies, and fabrication of composite membranes using MOFs. Furthermore, it focuses on the application prospects, challenges, and opportunities associated with MOF composite membranes in water treatment.

Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis.

Sulfur-containing functional groups have garnered considerable attention owing to their frequent occurrence in ligands, pharmaceuticals and insecticides. However, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging and long-standing goal. Herein we report a highly enantio- and chemoselective cross-coupling of sulfenamides with aryl electrophiles to construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide groups were crucial for attaining high reactivity and selectivity. This strategy offers a general, modular and divergent platform for rapid synthesis of chiral sulfilimines and sulfoximines that are otherwise difficult to access. Furthermore, the origins of the high chemoselectivity and enantioselectivity were extensively investigated using density functional theory calculations.

Improving the therapeutic efficacy of oncolytic viruses for cancer: targeting macrophages.

Oncolytic viruses (OVs) for cancer treatment are in a rapid stage of development, and the direct tumor lysis and activation of a comprehensive host immune response are irreplaceable advantages of cancer immunotherapy. However, excessive antiviral immune responses also restrict the spread of OVs in vivo and the infection of tumor cells. Macrophages are functionally diverse innate immune cells that phagocytose tumor cells and present antigens to activate the immune response, while also limiting the delivery of OVs to tumors. Studies have shown that the functional propensity of macrophages between OVs and tumor cells affects the overall therapeutic effect of oncolytic virotherapy. How to effectively avoid the restrictive effect of macrophages on OVs and reshape the function of tumor-associated macrophages in oncolytic virotherapy is an important challenge we are now facing. Here, we review and summarize the complex dual role of macrophages in oncolytic virotherapy, highlighting how the functional characteristics of macrophage plasticity can be utilized to cooperate with OVs to enhance anti-tumor effects, as well as highlighting the importance of designing and optimizing delivery modalities for OVs in the future.

Function analysis of choline binding domains (CBDs) of LytA, LytC and CbpD in biofilm formation of Streptococcus pneumoniae.

Biofilm formation is an important strategy for the colonization of Streptococcus pneumoniae, which can increase the capacity to evade antibiotic and host immune stress. Extracellular choline-binding proteins (CBPs) are required for successful biofilm formation, but the function of extracellular CBPs in the process of biofilm formation is not fully understood. In this study, we tend to analyze the functions of LytA, LytC and CbpD in biofilm formation by in vitro studies with their choline-binding domains (CBDs). Biofilm formation of S. pneumoniae was enhanced when cultured in medium supplemented with CBD-C and CBD-D. Parallel assays with ChBp-Is (choline binding repeats with different C-terminal tails) and character analysis of CBDs reveal a higher isoelectric point (pI) is related to promotion of biofilm formation. Phenotype characterization of biofilms revel CBD-C and CBD-D function differently, CBD-C promoting the formation of membrane-like structures and CBD-D promoting the formation of regular reticular structures. Gene expression analysis reveals membrane transport pathways are influenced with the binding of CBDs, among which the phosphate uptake and PTS of galactose pathways are both up-regulated under conditions with CBDs. Further, extracellular substances detection revealed that extracellular proteins increased with CBD-A and CBD-D, exhibiting as increase in extracellular high molecular weight proteins. Extracellular DNA increased under CBD-A but decreased under CBD-C and CBD-D; Extracellular phosphate increased under CBD-C. These support the alterations in membrane transport pathways, and reveal diverse reactions to extracellular protein, DNA and phosphate of these three CBDs. Overall, our results indicated extracellular CBP participate in biofilm formation by affecting surface charge and membrane transport pathways of pneumococcal cells, as well as promoting reactions to extracellular substances.

Parameter identification framework of nonlinear dynamical systems with Markovian switching.

Extensive research has been conducted on models of ordinary differential equations (ODEs), yet these deterministic models often fail to capture the intricate complexities of real-world systems adequately. Thus, many studies have proposed the integration of Markov chains into nonlinear dynamical systems to account for perturbations arising from environmental changes and random variations. Notably, the field of parameter estimation for ODEs incorporating Markov chains still needs to be explored, creating a significant research gap. Therefore, the objective of this study is to investigate a comprehensive model capable of encompassing real-life scenarios. This model combines a system of ODEs with a continuous-time Markov chain, enabling the representation of a continuous system with discrete parameter switching. We present a machine discovery framework for parameter estimation in nonlinear dynamical systems with Markovian switching, effectively addressing this research gap. By incorporating Markov chains into the model, we adeptly capture the time-varying dynamics of real-life systems influenced by environmental factors. This approach enhances the applicability and realism of the research, enabling more precise representations of dynamical systems with Markovian switching in complex scenarios.

Signal Amplification-Based Biosensors and Application in RNA Tumor Markers.

Tumor markers are important substances for assessing cancer development. In recent years, RNA tumor markers have attracted significant attention, and studies have shown that their abnormal expression of post-transcriptional regulatory genes is associated with tumor progression. Therefore, RNA tumor markers are considered as potential targets in clinical diagnosis and prognosis. Many studies show that biosensors have good application prospects in the field of medical diagnosis. The application of biosensors in RNA tumor markers is developing rapidly. These sensors have the advantages of high sensitivity, excellent selectivity, and convenience. However, the detection abundance of RNA tumor markers is low. In order to improve the detection sensitivity, researchers have developed a variety of signal amplification strategies to enhance the detection signal. In this review, after a brief introduction of the sensing principles and designs of different biosensing platforms, we will summarize the latest research progress of electrochemical, photoelectrochemical, and fluorescent biosensors based on signal amplification strategies for detecting RNA tumor markers. This review provides a high sensitivity and good selectivity sensing platform for early-stage cancer research. It provides a new idea for the development of accurate, sensitive, and convenient biological analysis in the future, which can be used for the early diagnosis and monitoring of cancer and contribute to the reduction in the mortality rate.

Branched DNA-Based Electrochemical Biosensor for Sensitive Nucleic Acids Analysis with Gold Nanoparticles as Amplifier.

A branched DNA-based electrochemical biosensor was designed to sensitively detect specific nucleic acids. On this platform, novel a branched DNA with three sticky ends could be used as a biosensor to sensitively and specifically detect nucleic acids. Meanwhile, we also employed branched DNA-modified AuNPs as a signal amplifier to further improve the sensitivity. Branched DNA sensors, target DNA, and DNA-modified AuNPs formed a sandwich structure to produce an electronic signal for target DNA detection. The reaction primarily involved DNA hybridization without bulky thermal cyclers and enzymes. We proved that the hybridization reaction easily occurred under different conditions, such as the NaCl concentration, reaction time, pH, and temperature, except for a pH lower than 4. The limit of detection could go as low as 0.09 pM (S/N = 3) with excellent specificity and selectivity. There was a correlation curve relationship between the peak current and the logarithm of the target DNA concentration (0.10 pM to 10 nM). The correlation coefficient reached 0.987. The electrochemical platform enables a branched DNA nanostructure to determine nucleic acids for disease diagnosis.

Application of Biomedical Microspheres in Wound Healing.

Tissue injury, one of the most common traumatic injuries in daily life, easily leads to secondary wound infections. To promote wound healing and reduce scarring, various kinds of wound dressings, such as gauze, bandages, sponges, patches, and microspheres, have been developed for wound healing. Among them, microsphere-based tissue dressings have attracted increasing attention due to the advantage of easy to fabricate, excellent physicochemical performance and superior drug release ability. In this review, we first introduced the common methods for microspheres preparation, such as emulsification-solvent method, electrospray method, microfluidic technology as well as phase separation methods. Next, we summarized the common biomaterials for the fabrication of the microspheres including natural polymers and synthetic polymers. Then, we presented the application of the various microspheres from different processing methods in wound healing and other applications. Finally, we analyzed the limitations and discussed the future development direction of microspheres in the future.

Streamlined Alkylation via Nickel-Hydride-Catalyzed Hydrocarbonation of Alkenes.

Compounds rich in sp3-hybridized carbons are desirable in drug discovery. Nickel-catalyzed hydrocarbonation of alkenes is a potentially efficient method to synthesize these compounds. By using abundant, readily available, and stable alkenes as pro-nucleophiles, these reactions can have broad scope and high functional group tolerance. However, this methodology is still in an early stage of development, as the first efficient examples were reported only in 2016. Herein, we summarize the progress of this emerging field, with an emphasis on enantioselective reactions. We highlight major developments, critically discuss a wide range of possible mechanisms, and offer our perspective of the state and challenges of the field. We hope this Perspective will stimulate future works in this area, making the methodology widely applicable in organic synthesis.

Aptamer-based biosensors and application in tumor theranostics.

An aptamer is a short oligonucleotide chain that can specifically recognize targeting analytes. Due to its high specificity, low cost, and good biocompatibility, aptamers as the targeting elements of biosensors have been applied widely in non-invasive tumor imaging and treatment in situ to replace traditional methods. In this review, we will summarize recent advances in using aptamer-based biosensors in tumor diagnosis. After a brief introduction of the advantage of aptamers compared with enzyme sensors and immune sensors, the different sensing designs and mechanisms based on 3 signal transduction modes will be reviewed to cover different kinds of analytical methods, including: electrochemistry analysis, colorimetry analysis, and fluorescence analysis. Finally, the prospective advantages of aptamer-based biosensors in tumor theranostics and post-treatment monitoring are also evaluated in this review.

Cell damage and neutrophils promote the infection of Mycoplasma pneumoniae and inflammatory response.

Mycoplasma pneumoniae (MP) is an important respiratory pathogen of human. The infection of MP can cause direct damage and immune damage in lung, resulting in Mycoplasma pneumoniae pneumonia (MPP). In this study, we aim to investigate the pathogenesis of MPP by detecting the proliferation of MP under conditions of cell damages and neutrophils in vitro. Firstly, we found the supplements of intracellular fluid, protein and RNA derived from intracellular fluid of A549 cells contribute to the survival of MP, thereby promoting the infection of MP. Cell damage can also significantly contribute to the survival of MP without supplements. At the same time, the additions of supplements contribute to apoptosis and the expression of IL-8 and IL-1ß. Further, we found live neutrophils show bactericidal activity to MP, and the phagocytosis of MP promotes apoptosis of neutrophils. When co-incubated with MP and A549 cells, the proliferation of MP in the high neutrophils proportion groups were accelerated with functional decline of neutrophils, and the level of extracellular IL-1ß showed a time and dose dependent manner to neutrophils. These results suggest that the release of intracellular nutrients by damaged cells and functional decline of neutrophils can promote the infection of MP and play roles in the activation of inflammatory response. Therefore, lung damage and infiltration of neutrophils would be important factors affecting the development of MPP.

Theoretical Study of NO Adsorption by Hydroxyl-Containing Char with the Participation of Na/K.

The study of the effects of Na and K on the heterogeneous adsorption of hydroxyl-containing char with NO is important for the clean utilization of high alkali coal. In this paper, the effects of Na/K atoms on the adsorption of NO on the char surface were investigated at the GGA-PBE level by choosing zigzag type, armchair type, and saturated hydroxyl-containing char structures based on DFT. It was found that the adsorption stability of NO on structures with active sites was greater for sites close to the hydroxyl group than that for sites far from the hydroxyl group. The stability of char doped by Na/K is related to the char structure and the position of functional groups. The most stable Na/K doped structures are Z-OH-2 (Eads= -350.50 kJ/mol) and A-OH-1-2 (Eads= -339.17 kJ/mol), respectively. The participation of Na/K can increase the adsorption energy of the three structures with NO, and especially the adsorption energy of saturated char with NO is increased by as much as 5 times. The reason for that is the promotion of the hybridization of the C and NO p orbitals. The comprehensive analysis of electrostatic potential, charge transfer, and front orbitals indicates that the effects of decorated sodium and potassium atoms on the char surface are very similar. This study lays a theoretical foundation for the study of the heterogeneous reduction process.

Neural network in food analytics.

Neural network (i.e. deep learning, NN)-based data analysis techniques have been listed as a pivotal opportunity to protect the integrity and safety of the global food supply chain and forecast $11.2 billion in agriculture markets. As a general-purpose data analytic tool, NN has been applied in several areas of food science, such as food recognition, food supply chain security and omics analysis, and so on. Therefore, given the rapid emergence of NN applications in food safety, this review aims to provide a comprehensive overview of the NN application in food analysis for the first time, focusing on domain-specific applications in food analysis by introducing fundamental methodology, reviewing recent and notable progress, and discussing challenges and potential pitfalls. NN demonstrated that it has a bright future through effective collaboration between food specialist and the broader community in the food field, for example, superiority in food recognition, sensory evaluation, pattern recognition of spectroscopy and chromatography. However, major challenges impeded NN extension including void in the food scientist-friendly interface software package, incomprehensible model behavior, multi-source heterogeneous data, and so on. The breakthrough from other fields proved NN has the potential to offer a revolution in the immediate future.

Pyrolysis characteristics of biodried products derived from municipal organic wastes: Synergistic effect of bulking agents and modification of biodegradation.

Derived from the biodrying of municipal organic wastes (MOWs), biodried products (BPs) are widely identified as renewable energy sources. In this study, for efficient energy recovery, the pyrolysis characteristics of BPs were investigated by comprehensive kinetic analysis, with special focus on the synergistic effect of bulking agents and the influence of biodegradation. Compared with theoretical raw materials (RMs), it was suggested that the synergistic effect of organics and lignocelluloses in RMs promoted decomposition in Stage 1 (400-570 K), especially for the pyrolysis of RM using sawdust, during which the positive effect achieved decomposition in advance with lower overlap ratio (0.9264) and ΔW (-9.50% at 619.0 K) values. Furthermore, compared with RMs, it was indicated that the kinetic indices (Ea and ln A values) of the BPs were upward in Stage 1 and decreased in Stage 2 due to biodegradation. The results of ΔH, ΔG and ΔS indicated that BP pyrolysis required more heat supply as the reaction progressed but formed a more organized activated complex. In addition, biodegradation observably decreased the generation of gas products and typical functional groups of volatiles during BP pyrolysis, such as CO2 and CO, which presented decreasing ratios of 32.18-42.47% and 30.25-46.47%, respectively. In general, the pyrolysis of BPs was intensified by bulking agents and modified by biodegradation.

A cellulose nanofibril-reinforced hydrogel with robust mechanical, self-healing, pH-responsive and antibacterial characteristics for wound dressing applications.

BACKGROUND: Bacterial infection in wounds has become a major threat to human life and health. With the growth use of synthetic antibiotics and the elevated evolution of drug resistant bacteria in human body cells requires the development of novel wound curing strategies. Herein, a novel pH-responsive hydrogel (RPC/PB) was fabricated using poly(vinyl alcohol)-borax (PB) and natural antibiotic resveratrol grafted cellulose nanofibrils (RPC) for bacterial-infected wound management. RESULTS: In this hydrogel matrix, RPC conjugate was interpenetrated in the PB network to form a semi-interpenetrating network that exhibited robust mechanical properties (fracture strength of 149.6 kPa), high self-healing efficiency (> 90%), and excellent adhesion performance (tissue shear stress of 54.2 kPa). Interestingly, the induced RPC/PB hydrogel showed pH-responsive drug release behavior, the cumulative release amount of resveratrol in pH 5.4 was 2.33 times than that of pH 7.4, which was adapted well to the acidic wound microenvironment. Additionally, this RPC/PB hydrogel exhibited excellent biocompatibility and antioxidant effect. Moreover, in vitro and in vivo results revealed that such RPC/PB hydrogel had excellent antibacterial, skin tissue regeneration and wound closure capabilities. CONCLUSION: Therefore, the generated RPC/PB hydrogel could be an excellent wound dressing for bacteria-infected wound healing.

Qualitative and quantitative study of fetal posterior fossa during the first trimester in a Chinese population.

BACKGROUND: To establish the normal reference ranges for parameters related to the fetal posterior fossa in the first trimester (11 ~ 13+6 weeks of gestation) and to analyze the relationship between them and crown-rump length (CRL) among the Chinese population. METHODS: Singleton pregnancies of 11 ~ 13+6 weeks (CRL:45 ~ 84 mm) with both parents from China were randomly selected from January 2021 to November 2021. The related parameters of the posterior fossa including cisterna magna (CM), intracranial translucency (IT), brain stem (BS), brain stem to the occipital bone (BSOB), and brain stem/brain stem to occipital bone (BS/BSOB) were evaluated and measured in nuchal translucency (NT) mid-sagittal section clearly by an experienced sonographer (operator 1). To assess the reproducibility of the measurements, we randomly selected 50 pregnant women. According to the blind method, operators 1 and 2 respectively screened and measured relevant parameters. In addition, operator 1 examined and measured relevant parameters again 2 h after the first. RESULTS: This study included 1663 fetuses. All fetuses can clearly show the three spaces of the fetal posterior fossa. The ICCs (95% CI) of intra-operator reproducibility of CM, IT, BS, BSOB, BS/BSOB were 0.981 (0.952 ~ 0.991, P < 0.001), 0.929 (0.866 ~ 0.961, P < 0.001), 0.970 (0.946 ~ 0.983, P < 0.001), 0.991 (0.974 ~ 0.996, P < 0.001), 0.939 (0.892 ~ 0.965, P < 0.001), respectively; The ICCs (95% CI) of inter-operator reproducibility 0.926 (0.860 ~ 0.960, P < 0.001), 0.810 (-0.083 ~ 0.940, P < 0.001), 0.820 (0.645 ~ 0.904, P < 0.001), 0.804 (0.656 ~ 0.888, P < 0.001), 0.772 (0.599 ~ 0.871, P < 0.001), respectively. There was a linear correlation between CRL and the parameters related to the posterior fossa (CM, IT, BS, BSOB, BS/BSOB). CM (mm) = -1.698 + 0.532 × CRL (cm) (r = 0.829, P < 0.001); IT (mm) = 0.701 + 0.179 × CRL (cm) (r = 0.548, P < 0.001); BS (mm) = 0.403 + 0.349 × CRL (cm) (r = 0.716, P < 0.001); BSOB (mm) = -0.277 + 0.719 × CRL (cm) (r = 0.829, P < 0.001); BS/BSOB = 0.747-0.021 × CRL (cm) (r = 0.196, P < 0.001). CONCLUSIONS: Qualitative and quantitative assessment of the fetal posterior fossa structure was feasible in the first trimester. We constructed the normal reference ranges of CM, IT, BS, BSOB, and BS/BSOB. Furthermore, CM, IT, BS, and BSOB were positively correlated with CRL, but BS/BSOB was negatively correlated with CRL.

Using an optimized generative model to infer the progression of complications in type 2 diabetes patients.

BACKGROUND: People live a long time in pre-diabetes/early diabetes without a formal diagnosis or management. Heterogeneity of progression coupled with deficiencies in electronic health records related to incomplete data, discrete events, and irregular event intervals make identification of pre-diabetes and critical points of diabetes progression challenging. METHODS: We utilized longitudinal electronic health records of 9298 patients with type 2 diabetes or prediabetes from 2005 to 2016 from a large regional healthcare delivery network in China. We optimized a generative Markov-Bayesian-based model to generate 5000 synthetic illness trajectories. The synthetic data were manually reviewed by endocrinologists. RESULTS: We build an optimized generative progression model for type 2 diabetes using anchor information to reduce the number of parameters learning in the third layer of the model from [Formula: see text] to [Formula: see text], where [Formula: see text] is the number of clinical findings, [Formula: see text] is the number of complications, [Formula: see text] is the number of anchors. Based on this model, we infer the relationships between progression stages, the onset of complication categories, and the associated diagnoses during the whole progression of type 2 diabetes using electronic health records. DISCUSSION: Our findings indicate that 55.3% of single complications and 31.8% of complication patterns could be predicted early and managed appropriately to potentially delay (as it is a progressive disease) or prevented (by lifestyle modifications that keep patient from developing/triggering diabetes in the first place). CONCLUSIONS: The full type 2 diabetes patient trajectories generated by the chronic disease progression model can counter a lack of real-world evidence of desired longitudinal timeframe while facilitating population health management.

A luminescent probe based on terbium-based metal-organic frameworks for organophosphorus pesticides detection.

Terbium-based metal-organic frameworks (Tb-MOF) prepared under mild conditions was utilized to construct a fluorescence probe for determination of organophosphorus pesticides (OPs) coupled with acetylcholinesterase (AChE), acetylcholine chloride (Ach), and choline oxidase (CHO). Since OPs have obvious inhibition on the activity of AChE in the Tb-MOF/ACh/CHO/AChE system, the detection of OPs was accomplished by restoring the fluorescence of Tb-MOF resulting from reduced production of H2O2. By taking chlorpyrifos (CPF) as a pesticide model, the method exhibits high sensitivity in the linear range 0.1-4.0 µg·L-1 with the limit of detection (LOD) of 0.04 µg·L-1 under optimum conditions (λex = 280 nm, λem = 544 nm). The Tb-MOF/ACh/CHO/AChE fluorescence system has high selectivity for CPF. The method was successfully applied to the detection of CPF in tap water and strawberry samples (recovery of 87.36-115.60% for tap water and 95.04-103.20% for strawberry). Free from complicated fabrication operation, the Tb-MOF-based system is rapid, simple, and stable, which provides a reference and new way for the design of OPs fluorescent probes in the future.

Enantioselective para-C(sp2 )-H Functionalization of Alkyl Benzene Derivatives via Cooperative Catalysis of Gold/Chiral Brønsted Acid.

An asymmetric para-C(sp2 )-H bond functionalization of alkyl benzene derivatives was successfully developed via cooperative catalysis of gold and chiral phosphoric acid (CPA), leading to synthetically useful chiral 1,1-diaryl motifs. Chiral phosphoric acid, ligand, and molecular sieves were found to be crucial for enantioselectivity control of this transformation. The salient features of this protocol include mild conditions, high efficiency, commercially available starting materials, highly chemo- and site- as well as enantioselective aromatic C-H functionalization, broad substrate scope, and extensive applications of the chiral products. The mechanistic studies suggested that two CPAs might be involved in chiral induction.