Green synthesis of azo-linked porous organic polymer for enrichment of nitroimidazoles from water, shrimp and Basa fish.

Reliable monitoring of nitroimidazoles (NDZs) is of great significance to public health. Herein, an azo-linked porous organic polymer (Res-POPs) was prepared by green synthesis method using natural resveratrol as monomer for the first time. Using Res-POPs as sorbent, a facile method coupling solid-phase extraction with high performance liquid chromatography-diode array detection was developed for effective detecting NDZs. The method achieved good linearities (0.06 âˆ¼ 100 ng mL-1 for water, 1.8 âˆ¼ 200 ng g-1 for shrimp, and 1.5 âˆ¼ 200 ng g-1 for Basa fish) with determination coefficients above 0.995, low detection limits (0.02 âˆ¼ 0.05 ng mL-1, 0.60 âˆ¼ 1.00 ng g-1 and 0.50 âˆ¼ 0.90 ng g-1 for water, shrimp and Basa fish), high method recovery (85 %∼114 %) and relative standard deviations below 8.2 %. The results demonstrated the superiority and the promising potential of the established method for detection of NDZs compared with the reported method.

Isolated Cutaneous Granuloma Caused by Candida Parapsilosis: Case Report and Literature Review.

Candidal granuloma is an uncommon type of deep chronic cutaneous candidiasis. Candida albican is the most common causative pathogen for candidal granuloma. We report herein the original case of a 69-year-old Chinese woman presented with a 3-year of painful cutaneous lesion on the back of left hand. Physical examination revealed a 4 × 5 cm large infiltrative reddish plaque with unclear boundaries. The yellow-white crusts were observed on the uneven surface of plaque. Histopathological examination of biopsy tissue revealed that yeast cells and the horizontal section of hyphae in the dermis by hematoxylin eosin staining and periodic acid-Schiff staining. Finally, the pathogen was identified as Candida parapsilosis by mycological examination and molecular identification. The patient was treated with itraconazole oral 200 mg twice daily combined with topical terbinafine hydrochloride cream for 2 months. The lesions were fully resolved and no recurrence was observed. Since the cutaneous infection caused by C. parasilosis were rarely reported, we also reviewed all 11 cases of cutaneous infection caused by C. parapsilosis in the PubMed. Our study highlighted that chronic unilateral infiltrated plaques or ulcers should be aware of the occurrence of fungal granuloma including candidal granuloma especially in immunocompromised patients.

A Phase-III Noninferiority, Randomized Controlled Trial of Letibotulinum Toxin A for the Improvement of Moderate-to-Severe Glabellar Wrinkles in China.

Background: Letibotulinum toxin A has an established efficacy and safety profile for aesthetic treatment of glabellar wrinkles. This study was conducted to demonstrate the noninferiority of letibotulinum toxin A versus onabotulinum toxin A in improving the appearance of moderate-to-severe glabellar wrinkles in Chinese patients. Methods: This phase-III multicenter, randomized, parallel positive control, double-blinded study compared the efficacy and safety of letibotulinum toxin A and onabotulinum toxin A. Eligible participants were randomized 3:1 to receive 20 U of letibotulinum toxin A or onabotulinum toxin A and were observed for 16 weeks postinjection. The primary endpoint was noninferiority in the proportion of study participants receiving a score of 0 or 1 for glabellar wrinkles on a four-point photographic evaluation scale, as assessed by an institution evaluator at maximum frown at week 4. Secondary endpoints included assessments at rest, photographic assessment of efficacy, and subjective self-assessment of the study participants. Results: The proportion of participants (N = 500) receiving a score of 0 or 1 at maximum frown by the institution evaluator at week 4 was 88.49% for letibotulinum toxin A and 87.39% for onabotulinum toxin A (difference, 1.10%; 95% confidence interval, -5.02 to 8.82; P = 0.7469). No significant differences were observed between the treatments for secondary efficacy or safety endpoints. Participants' self-assessment and satisfaction tended to be higher for letibotulinum toxin A than onabotulinum toxin A. Conclusion: Letibotulinum toxin A is noninferior to onabotulinum toxin A in improving the appearance of moderate-to-severe glabellar wrinkles in Chinese patients.

Post-synthetic modification of covalent organic framework for efficient adsorption of organochlorine pesticides from cattle's milk.

Analysis of organochlorine pesticides (OCPs) residues in milk faces a significant challenge. Herein, a sea urchin structured covalent organic framework bearing boric acid groups named COF-B(OH)2 was synthesized and applied as a coating material for solid-phase microextraction (SPME) of the OCPs in cattle's milk. Its performance was superior to that of three commonly used commercial SPME fibers, which could be due to the coexistence of hydrogen bonding, halogen bonding, π-stacking and electrostatic interactions. Besides, the fiber coating displayed good stability and reusability. After optimization, a COF-B(OH)2 based SPME coupled with gas chromatography-electron capture detection was established for the sensitive detection of the OCPs from milk samples. The limits of detection (S/N = 3) were between 0.04 and 1.00 µg kg-1. Satisfactory accuracy was achieved with the method recoveries in the range of 87.5 % to 112.5 %. These results manifest the feasibility of the COF-B(OH)2 coated fiber for the enrichment of the trace OCPs from milk samples.

Unveiling the synergistic mechanism of autochthonous fungal bioaugmentation and ammonium nitrogen biostimulation for enhanced phenanthrene degradation in oil-contaminated soils.

Autochthonous bioaugmentation and nutrient biostimulation are promising bioremediation methods for polycyclic aromatic hydrocarbons (PAHs) in contaminated agricultural soils, but little is known about their combined working mechanism. In this study, a microcosm trial was conducted to explore the combined mechanism of autochthonous fungal bioaugmentation and ammonium nitrogen biostimulation, using DNA stable-isotope-probing (DNA-SIP) and microbial network analysis. Both treatments significantly improved phenanthrene (PHE) removal, with their combined application producing the best results. The microbial community composition was notably altered by all bioremediation treatments, particularly the PHE-degrading bacterial and fungal taxa. Fungal bioaugmentation removed PAHs through extracellular enzyme secretion but reduced soil microbial diversity and ecological stability, while nitrogen biostimulation promoted PAH dissipation by stimulating indigenous soil degrading microbes, including fungi and key bacteria in the soil co-occurrence networks, ensuring the ecological diversity of soil microorganisms. The combination of both approaches proved to be the most effective strategy, maintaining a high degradation efficiency and relatively stable soil biodiversity through the secretion of lignin hydrolytic enzymes by fungi, and stimulating the reproduction of soil native degrading microbes, especially the key degraders in the co-occurrence networks. Our findings provide a fresh perspective of the synergy between fungal bioaugmentation and nitrogen biostimulation, highlighting the potential of this combined bioremediation approach for in situ PAH-contaminated soils.

Crosstalk between gut microbiota and gut resident macrophages in inflammatory bowel disease.

Macrophages residing in the gut maintain gut homeostasis by orchestrating patho-gens and innocuous antigens. A disturbance in macrophages leads to gut inflamma-tion, causing conditions such as inflammatory bowel disease (IBD). Macrophages ex-hibit remarkable plasticity, as they are sensitive to various signals in the tissue micro-environment. During the recent decades, gut microbiota has been highlighted refer-ring to their critical roles in immunity response. Microbiome-derived metabolites and products can interact with macrophages to participate in the progression of IBD. In this review, we describe recent findings in this field and provide an overview of the current understanding of microbiota-macrophages interactions in IBD, which may lead to the development of new targets and treatment options for patients with IBD.

Single-Fe-Atom Catalyst for Sensitive Electrochemical Detection of Caffeic Acid.

A single-atom catalyst (Fe SAs/-N-C) with excellent stability and conductivity was strategically fabricated via high-temperature calcination using the NiFe layered double hydroxide (LDH)/ZIF-8 composite as precursors. With the help of Ni as a catalyst, a great number of carbon nanotubes were produced whereby the isolated carbon bulks were interconnected to form an "island-bridge"-like 3D network structure, which greatly enhanced the exposure of active sites and the electron transfer. Accordingly, caffeic acid (CA) with versatile biological and pharmacological activities was chosen as the model analyte. The Fe SAs/-N-C with Fe-N4 as the catalytic active site was employed to establish the electrochemical sensing of CA with satisfactory sensitivity, selectivity, and long-term stability. This work expands the application range of single-atom catalysts and contributes a significant reference for the synthesis of hybrid double-atom catalysts.

Impacts of Climate Changes on Geographic Distribution of Primula filchnerae, an Endangered Herb in China.

Primula filchnerae, an endangered plant endemic to China, has drawn people's attention in recent years due to its ornamental value in flower. It was rarely recorded since being described in 1902, but it was rediscovered in 2009 and is now known from a limited number of sites located in Hubei and Shaanxi Provinces. Since the species is still poorly known, a number of unanswered questions arise related to it: How has P. filchnerae responded to past climate change and how might it respond in the future? Why was P. filchmerae so rarely collected during the past century? We assembled geographic coordinates for P. filchnerae through the field surveys and website searches, and then used a maximum entropy model (MaxEnt) to simulate its potential suitable distribution in six periods with varied carbon emission levels by combining bioclimatic and environmental factors. MaxEnt showed that Min Temperature of the Coldest Month (bio6) and Precipitation of the Coldest Quarter (bio19) affected P. filchnerae's distribution most, with an aggregate contribution >60% and suitable ranges above -5 °C and below 40 mm, respectively. We also analyzed potential habitat distribution in various periods with differing impacts of climate change compared to today's suitable habitats, and in most cases, Shaanxi and Sichuan remained the most stable areas and with possible expansion to the north under various carbon emission scenarios, but the 2050s SSP5-8.5 scenario may be an exception. Moreover, we used MaxEnt to evaluate population shifts, with various scenarios indicating that geometric center would be concentrated in Sichuan Province in China. Finally, conservation strategies are suggested, including the creation of protected areas, long-term monitoring, raising public awareness of plant conservation, situ conservation measures, assisted migration, and species introduction. This study demonstrates how P. filchnerae may have adapted to changes in different periods and provides a scientific basis for germplasm conservation and management.

A randomized, double-blind, placebo-controlled phase II study to evaluate the efficacy and safety of ivarmacitinib (SHR0302) in adult patients with moderate-to-severe alopecia areata.

BACKGROUND: Alopecia areata (AA) is a CD8+ T cell-mediated autoimmune disease characterized by nonscarring hair loss. Ivarmacitinib, which is a selective oral Janus kinase 1 inhibitor, may interrupt certain cytokine signaling implicated in the pathogenesis of AA. OBJECTIVE: To evaluate the efficacy and safety of ivarmacitinib in adult patients with AA who have ≥25% scalp hair loss. METHODS: Eligible patients were randomized 1:1:1:1 to receive ivarmacitinib 2, 4, or 8 mg once daily or placebo for 24 weeks. The primary end point was the percentage change from baseline in the Severity of Alopecia Tool score at week 24. RESULTS: A total of 94 patients were randomized. At week 24, the least squares mean difference in the percentage change from baseline in the Severity of Alopecia Tool score for ivarmacitinib 2, 4, and 8 mg and placebo groups were -30.51% (90% CI, -45.25, -15.76), -56.11% (90% CI, -70.28, -41.95), -51.01% (90% CI, -65.20, -36.82), and -19.87% (90% CI, -33.99, -5.75), respectively. Two serious adverse events-follicular lymphoma and COVID-19 pneumonia-were reported. LIMITATIONS: A small sample size limits the generalizability of the results. CONCLUSION: Treatment with ivarmacitinib 4 and 8 mg doses in patients with moderate and severe AA for 24 weeks was efficacious and generally tolerated.

Green construction of hydroxyl-functionalized magnetic porous organic framework for effective extraction of triazine herbicides from environmental water and watermelon juice samples.

Triazine herbicides have been widely detected in water resources and food, which poses a potential hazard to both ecosystem and human health. Due to their high polarity, conventional adsorbents have limitations for their extractions. Herein, for the effective magnetic extraction of triazine herbicides, a novel and effective magnetic adsorbent was prepared with a satisfactory extraction performance. In the experiments, five porous organic frameworks (POFs) with hydroxyl functional groups were synthesized by diazo-coupling reactions in aqueous solution with ß-cyclodextrin (ß-CD) as a green monomer. After evaluation of the five POFs, the DDM-CD-POF, which was synthesized with 4'4-diaminodiphenylmethane (DDM) and ß-CD, showed the largest specific surface area and the best adsorption capacity for the five triazine herbicides. Then, it was magnetized by introducing Fe3O4@SiO2 into it to prepare a magnetic adsorbent (M-DDM-CD-POF) to facilitate separation and recycling. Finally, the M-DDM-CD-POF-based magnetic solid-phase extraction in combination with high performance liquid chromatographic detection method was established for the quantitative determination of the triazine herbicides in environmental water and watermelon juice samples. The current strategy showed low limits of detection of 0.03-0.11 ng mL-1 for environmental water and 0.07-0.22 ng mL-1 for watermelon juice sample. The method recoveries for spiked samples ranged from 84.0% to 113.0% with the relative standard deviations ≤8.8%. This work provides a new approach for the detection of the triazine herbicides with good application prospect.

New insight into the mechanisms of autochthonous fungal bioaugmentation of phenanthrene in petroleum contaminated soil by stable isotope probing.

Autochthonous fungal bioaugmentation (AFB) is considered a reliable bioremediation approach for polycyclic aromatic hydrocarbon (PAH) contamination, but little is known about its mechanisms in contaminated soils. Here, a microcosm experiment was performed to explore the AFB mechanisms associated with two highly efficient phenanthrene degrading agents of fungi (with laccase-producing Scedosporium aurantiacum GIG-3 and non-laccase-producing Aspergillus fumigatus LJD-29), using stable-isotope-probing (SIP) and high-throughput sequencing. The results showed that each fungus markedly improved phenanthrene removal, and microcosms with both fungi exhibited the best phenanthrene removal performance among all microcosms. Additionally, AFB markedly shifted the composition of the microbial community, particularly the phenanthrene-degrading bacterial taxa. Interestingly, based on SIP results, strains GIG-3 and LJD-29 did not assimilate phenanthrene directly during AFB, but instead played key roles in the preliminary decomposition of phenanthrene though secretion of different extracellular enzymes to oxidize the benzene ring (GIG-3 bioaugmentation with laccase, and LJD-29 bioaugmentation with manganese and lignin peroxidases). In addition, all functional degraders directly involved in phenanthrene assimilation were indigenous bacteria, while native fungi rarely participated in the direct phenanthrene mineralization. Our findings provide a new mechanism of AFB with multiple fungi, and support AFB as a promising strategy for the in situ bioremediation of PAH-contaminated soil.

Sustainable and green synthesis of porous organic polymer for solid-phase extraction of four chlorophenols in water and honey.

A novel hypercrosslinked polymer (API-HCP) was synthesized using as monomer for the first time. API-HCP exhibited high adsorption affinity toward chlorophenols due to the hydrogen bond, halogen bond and π-stacking interactions. With API-HCP as adsorbent, an efficient solid phase extraction method coupled with high performance liquid chromatography (SPE-HPLC) was established for the sensitive detection of chlorophenols in water and honey samples. Under the optimum conditions, the method provided a good linear response in the range of 0.07-100 ng mL-1 for water and 1.7-500 ng g-1 for honey sample. High sensitivity was achieved, with detection limits (S/N = 3) of 0.02-0.07 ng mL-1 for water and 0.5-1.5 ng g-1 for honey samples. The method recoveries for spiked sample were between 84.0 % and 116.0 %, with relative standard deviations ≤6.1 %. The API-HCP based SPE-HPLC method provided a robust platform for sensitive determination of chlorophenols in water and honey samples.

A hydrophilic-lipophilic triazine based hyper-crosslinked polymer for efficient enrichment of nitrobenzene compounds.

Sensitive, accurate, and simultaneous determination of nitrobenzene compounds (NBs) in environmental water samples is of great significance due to their high risk to human health. In this work, a new triazine-based hyper-crosslinked polymer named CC-Py was constructed via the Friedel-Crafts reaction between cyanuric chloride (CC), pyridine (Py) and 1,2-dichloroethane. Due to its excellent stability, high surface area and hydrophilic-lipophilic (amphiphilic) structure, the CC-Py exhibited a high affinity toward the NBs (nitrobenzene, 2-nitrotoluene, 2,6-dimethylnitrobenzene, 3-nitrotoluene, 4-nitrotoluene, 3-nitrochlorobenzene, 4-nitrochlorobenzene, 2-nitrochlorobenzene, 2,4-dimethylnitrobenzene, 3-nitrobromobenzene, 4-nitrobromobenzene and 4-nitroiodobenzene). Then, a CC-Py based solid-phase microextraction coupled with gas chromatography-flame ionization detection was developed to detect the twelve NBs in real water samples. The results showed that the method had low limits of detection (0.20-0.50 µg L-1), good reproducibility (relative standard deviations (RSDs) < 8.6%) and high enrichment factors (967-1590). The recoveries for the NBs in six different types of water samples were between 90% and 111% with the RSDs less than 7.5%. This work provides a facile and sensitive method for the determination of trace level of NBs in real water samples.

A carbazole-based spherical microporous polymer for the solid-phase extraction of chlorophenols from water and honey samples.

A new carbazole-based spherical microporous polymer (Car-BDA-POP) was fabricated by employing 4,4'-biphenyldicarboxaldehyde (BDA) and carbazole as monomers via a one-step and non-metal catalyst synthetic approach. It was then explored as an adsorbent for solid-phase extraction (SPE) of some chlorophenols (CPs). Under the optimized extraction conditions, the established Car-BDA-POP-based SPE coupled with high-performance liquid chromatography ultraviolet detection showed good linearity in the concentration range of 0.1-200 ng mL-1 for water samples and 5.0-800 ng g-1 for honey samples with the determination coefficients (r2) ≥ 0.9995 for the analytes. The limits of detection (S/N = 3) for the analytes were in the range of 0.03-0.06 ng mL-1 for water samples and 1.50-2.50 ng g-1 for honey samples. The method recoveries varied from 80.0 % to 116 % in spiked real samples, with the relative standard deviations less than 9.6 %. In addition, the possible adsorption mechanism, adsorption kinetics, and adsorption isotherms were also investigated.

A core-shell structured magnetic sulfonated covalent organic framework for the extraction of benzoylureas insecticides from water, pear juice and honey samples.

Three magnetic covalent organic frameworks (named M-TpPa-SO3Na, M-TpPa-SO3H and M-TpPa) were prepared by the solvothermal synthesis method with 1,3,5-trimethylphenol (TP) and either 2-sulfo-1,4-phenylenediamine (Pa-SO3H) or p-phenylenediamine (Pa) as monomers. Among them, the M-TpPa-SO3Na possessed relatively high hydrophilicity, good magnetic responsiveness, and high affinity for the benzoylureas (BUs) insecticides. It was then explored as the magnetic solid-phase extraction adsorbent for the extraction of six BUs (diflubenzuron, triflumuron, hexaflumuron, teflubenzuron, flufenoxuron and chlorfluazuron) from water, pear juice and honey samples prior to high-performance liquid chromatography with ultraviolet detection. Under the optimized experimental conditions, a good linearity was achieved within the concentration range of 0.27-40.0 ng mL-1 for water sample, 0.47-30.0 ng mL-1 for pear juice sample, and 2.70-200.0 ng g-1 for honey sample. The limits of detection for the analytes were 0.08-0.11 ng mL-1 for water sample, 0.14-0.19 ng mL-1 for pear juice sample and 0.80-1.00 ng g-1 for honey sample. The method recoveries for spiked samples were in the range of 85.0%-111.0% with the relative standard deviations less than 8.8%. The developed method was successfully used for the determination of the BUs in water, pear juice and honey samples.

Sensitive determination of auxins in environmental water and peach beverage by hyper crosslinked polymer-based solid-phase extraction with high performance liquid chromatography-fluorescence detection.

As plant regulators, auxins can promote plant growth. However, they have toxicity and may cause harm to humans. Due to their low concentrations in food sample matrices, the enrichment and analysis of trace auxins in food samples is a challenging work. In this work, a series of hyper crosslinked polymers (HCPs) were synthesized by Friedel-Crafts acylation to extract four auxins (indole-3-acetic acid, indole-3-propionic acid, indole-3-butyric acid and 1-naphthylacetic acid). Among these HCPs, the QP-TC-HCP, synthesized from p-quaterphenyl (QP) and terephthaloyl chloride (TC), showed the best adsorption performance for the auxins. It was then applied as the adsorbent for the solid-phase extraction of the auxins from environmental water and peach beverage samples, followed by high performance liquid chromatography-fluorescence detection. Under the optimized conditions, the limits of detection were 3.0-12.0 pg mL-1 for environmental water and 18.0-36.0 pg mL-1 for peach beverage sample. The method recoveries of the auxins for the spiked samples were in the range of 85.0-110.0%. The established method provided an alternative approach for the determination of auxins in food samples. In addition, different types of organic compounds were tested for the extraction by the QP-TC-HCP to assess its application potential and adsorption mechanism. It was concluded that the QP-TC-HCP had better extraction performance for the compounds with certain hydrophilicity and more hydrogen bonding sites.

Facile synthesis of magnetic hypercrosslinked polymer for the magnetic solid-phase extraction of benzoylurea insecticides from honey and apple juice samples.

In this work, a novel knitting aromatic polymer (KAP) was fabricated for the first time by knitting ferrocene with 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene via Friedel-Crafts reaction, and then the KAP was magnetically functionalized with Fe3O4 nanoparticles to produce a magnetic KAP (M-KAP). Combining M-KAP based magnetic solid-phase extraction with high performance liquid chromatography-ultraviolet detection, a simple and sensitive method was developed for simultaneous determination of six benzoylurea insecticides (BUs) in honey and apple juice samples. In the optimized conditions, a good linearity for the BUs existed in the range of 1.67-1000 ng g-1 for honey sample and 0.500-100.0 ng mL-1 for apple juice sample. The limits of detection were 0.500-1.50 ng g-1 and 0.150-0.400 ng mL-1 for honey and apple juice sample, respectively. Satisfactory recoveries were in the range of 85.5-105.5% with RSDs ≤ 8.3%. The developed method demonstrated an excellent practicability for sensitive analysis of the BUs.

Identification of a Novel MLPH Missense Mutation in a Chinese Griscelli Syndrome 3 Patient.

Melanophilin (MLPH) functions as a linker between RAB27A and myosin Va (MYO5A) in regulating skin pigmentation during the melanosome transport process. The MYO5A-MLPH-RAB27A ternary protein complex is required for anchoring mature melanosomes in the peripheral actin filaments of melanocytes for subsequent transfer to adjacent keratinocytes. Griscelli syndrome type 3 (GS3) is caused by mutations in the MLPH gene. So far, only five variants of MLPH associated with GS3 have been reported. Here, we reported the first patient with GS3 in a Chinese population. The proband carried a novel homozygous missense mutation (c.73G>C; p.D25H), residing in the conserved Slp homology domain of MLPH, and presented with hypopigmentation of the hair, eyebrows, and eyelashes. Light microscopy revealed the presence of abnormal pigment clumping in his hair shaft. In silico tools predicted this MLPH variant to be likely pathogenic. Using immunoblotting and immunofluorescence analysis, we demonstrated that the MLPH (D25H) variant had an inhibitory effect on melanosome transport by exhibiting perinuclear melanosome aggregation in melanocytes, and greatly reduced its binding to RAB27A, although the protein level of MLPH in the patient was not changed. Our findings suggest that MLPH (D25H) is a pathogenic variant that expands the genetic spectrum of the MLPH gene.

Facile fabrication of tyrosine-functionalized hypercrosslinked polymer for sensitive determination of nitroimidazole antibiotics in honey and chicken muscle.

The preparation of tyrosine-functional novel hypercrosslinked polymer (HCP@Tyr) was achieved by knitting 1,3,5-triphenylbenzene with l-tyrosine via simple Friedel-Crafts reaction. The HCP@Tyr displayed large surface area (1220 m2 g-1) and high adsorption capacity (30 mg g-1) for nitroimidazoles (NDZs). With HCP@Tyr as potent sorbent, an efficient extraction method was developed to simultaneously extract five NDZs from honey and chicken muscle samples before high performance liquid chromatography-diode array detection. Under optimized conditions, the proposed method provided a good linearity in the range of 0.75-200.0 ng g-1 for honey and 1.5-100.0 ng g-1 for chicken muscle sample. Low detection limits (S/N = 3) were obtained to be 0.10-0.24 ng g-1 for honey and 0.15-0.30 ng g-1 for chicken muscle. The method recovery was 80.7-120% with relative standard deviations below 9.2%. The HCP@Tyr based method can serve as a reliable and sensitive tool for detection of NDZs in honey and chicken muscle samples.