Occurrence, distribution, and ecological risks of polyhalogenated carbazoles in sediments from Daya Bay and Pearl River Estuary, China.

Polyhalogenated carbazoles (PHCZs) are a group of emerging organic pollutants attracting increasing concern. In this study, 32 sediment samples were collected from the Pearl River Estuary (PRE) and adjacent Daya Bay (DYB) in China and were investigated for the occurrence and distribution of PHCZs. Total concentration of sedimentary PHCZs (∑PHCZs) ranged from 0.79 to 3.08 ng/g in PRE and 0.89 to 1.95 ng/g in DYB, both containing 3,6-dichlorocarbazole as the main component. Higher concentrations of ∑PHCZs were found in the rivers-mouth and inner part of the PRE indicating their main origins from anthropogenic activities. Notably, concentrations of brominated carbazoles (BCZs) gradually increased offshore, which suggests the potential bio-transformation of BCZs under a saline environment. The toxic equivalent of PHCZs was estimated at 0.13-0.34 pg TEQ/g suggesting limited dioxin-like effects on local organisms.

Posterior fixation, anterior debridement and bone grafting in the treatment of thoracic and lumbar tuberculosis in children younger than 3 years of age.

PURPOSE: This study aimed to investigate the clinical outcomes of posterior fixation, combined with one- or two-stage anterior debridement and bone grafting in treating children younger than 3 years of age with thoracic and lumbar tuberculosis. METHODS: This was a retrospective study involving 16 young children with thoracic or lumbar tuberculosis. Surgical data were recorded. Frankel Grade was used to assess neurological function. The regional kyphosis angle was measured to evaluate the deformity correction. Erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP) levels were detected to assess the activity of tuberculosis. Bony fusion and complications were also recorded. RESULTS: The mean operation time was 204.4 ± 41.8 min. The mean estimated blood loss was 126.3 ± 94.4 ml. Preoperative Frankel Grade results indicated five patients with Grade C, six with Grade D, and five with Grade E. At the final follow-up, all patients were in Grade E. Twelve patients were brought back to normal spinal alignment and the rest four patients remained kyphotic. There was an improvement of 29.3° ± 18.3° in regional kyphotic angle postoperatively. And the deformity correction was 27.4° ± 19.1° at the final follow-up. ESR and CRP decreased to a normal range at three months follow-up. Bony fusion was achieved in all patients. None of the cases developed fixation failure, pseudoarthrosis, or tuberculosis recurrence. CONCLUSION: Posterior fixation, combined with one- or two-stage anterior debridement and bone grafting, is a safe and effective surgical strategy for treating young children with thoracic and lumbar tuberculosis.

Modulating the Coordination Environment of Carbon-Dot-Supported Fe Single-Atom Nanozymes for Enhanced Tumor Therapy.

Herein, carbon dot (CD)-supported Fe single-atom nanozymes with high content of pyrrolic N and ultrasmall size (ph-CDs-Fe SAzyme) are fabricated by a phenanthroline-mediated ligand-assisted strategy. Compared with phenanthroline-free nanozymes (CDs-Fe SAzyme), ph-CDs-Fe SAzyme exhibit higher peroxidase (POD)-like activity due to their structure similar to that of ferriporphyrin in natural POD. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analyses show that metal Fe is dispersed in ph-CDs-Fe SAzyme as single atoms. Steady-state kinetic studies show that the maximum velocity (Vmax ) and turnover number (kcat ) of H2 O2  homolytic cleavage catalyzed by ph-CDs-Fe SAzyme are 3.0 and 6.2 more than those of the reaction catalyzed by CDs-Fe SAzyme. Density functional theory (DFT) calculations show that the energy barrier of the reaction catalyzed by ph-CDs-Fe SAzyme is lower than that catalyzed by CDs-Fe SAzyme. Antitumor efficacy experiments show that ph-CDs-Fe SAzyme can efficiently inhibit the growth of tumor cells both in vitro and in vivo by synergistic chemodynamic and photothermal effects. Here a new paradigm is provided for the development of efficient antitumor therapeutic approaches based on SAzyme with POD-like activity.

Single atom nanozymes for bacterial infection therapy.

Bacterial infection-related diseases continue to pose a significant challenge to global human health. Antibiotic therapy, as a conventional therapeutic strategy, has been extensively employed in clinical settings to treat bacterial infections. However, the effectiveness of these conventional strategies is often impeded by the antimicrobial resistance of bacteria. Consequently, the development of alternative antibacterial agents has emerged as a promising approach to addressing this issue. In recent years, single-atom nanozymes (SAzymes), a novel class of nanocatalytic medicines, have garnered increasing attention due to their numerous advantages, including uniformly dispersed metal active sites, tunable coordination structures, and maximal metal atomic utilization efficiency. To date, a variety of SAzymes have been developed and widely applied in antibacterial therapy. In this minireview, we provide an overview of the latest advances in the synthesis and antibacterial application of different metal-based SAzymes. Furthermore, we discuss the future challenges and opportunities of utilizing SAzymes for bacterial infection treatment. It is our hope that this minireview will contribute to the development of the next generation of SAzyme-based antibacterial agents.

Highly dispersed Co anchored on Ce-doped hydroxyapatite as a dual-functional catalyst for selective hydrogenolysis of 5-hydroxymethylfurfural.

Hydrodeoxygenation (HDO) is an indispensable approach to produce renewable biofuels and value-added chemicals using natural biomass and its derivatives. 2,5-Dimethylfuran (DMF) is considered to be a very promising liquid biofuel, and it can be fabricated by HDO of the biomass derivative 5-hydroxymethylfurfural (HMF). Herein, a highly efficient bifunctional catalyst, Co/HAP(Ce), was fabricated by anchoring highly dispersed Co on Ce-doped hydroxyapatite (HAP(Ce)). Co/HAP(Ce) displayed excellent HDO catalytic activity to convert HMF to DMF, and 99% HMF conversion and 96% DMF selectivity can be obtained under 150 °C, 2 MPa H2 conditions for 5 h. Density functional theory calculations revealed that H2 can be more easily activated by Co/HAP(Ce). Systematic studies confirmed that the high activity of Co/HAP(Ce) can be ascribed to the desired acid-alkali properties, highly dispersed cobalt species and strong metal-support interactions. This research provides a cost effective approach for designing efficient catalysts for HDO of biomass and its derivatives.

Application of cement-augmented pedicle screws in elderly patients with spinal tuberculosis and severe osteoporosis: a preliminary study.

OBJECTIVE: Surgical management of elderly patients with spinal tuberculosis and severe osteoporosis is challenging. Cement-augmented pedicle screws (CAPS) have been specifically designed for elderly patients with osteoporotic spines. Herein, we investigated the feasibility of CAPS applied in elderly patients with spinal tuberculosis and severe osteoporosis. METHODS: We retrospectively analyzed data of patients with spinal tuberculosis and severe osteoporosis between January 2017 and January 2021. Surgical data, including surgical duration and intraoperative blood loss, were recorded. Radiological parameters, such as correction of regional kyphotic angle and screw loosening, were also evaluated. Additionally, visual analog scores (VAS) and Oswestry disability index (ODI) were used to evaluate back pain and functional recovery, respectively. Erythrocyte sedimentation (ESR) and C-reactive protein (CRP) concentrations were detected to assess tuberculosis activity. The presence of complications and fusion rate was also assessed. RESULTS: A total of 15 patients were included in this study. The surgical duration was 263.0 ± 56.2 min, with an average blood loss of 378.7 ± 237.0 ml. The correction of regional kyphotic angle was 12.4° ± 15.0°, and it was well maintained until the final follow-up. The mean VAS decreased from 6.0 ± 1.2 points to 0.5 ± 0.6 points, and ODI reduced from 37.8% ± 7.6% to 8.3% ± 2.8% (P < 0.01). At the final follow-up, ESR and CRP levels were within normal range. Bony fusion occurred in all patients, with an average fusion duration of 8.8 ± 1.5 months. No cases of pedicle screw pullout, screw loosening, or pseudoarthrosis occurred. Tuberculosis recurrence and dissemination were not observed during the follow-ups. CONCLUSIONS: CAPS fixation is an effective and safe technique to achieve solid fixation and favorable clinical outcomes in elderly patients with spinal tuberculosis and severe osteoporosis.

Anaerobic biotransformation of two novel brominated flame retardants: Kinetics, isotope fractionation and reaction mechanisms.

1,2,5,6-tetrabromocyclooctane (TBCO) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), as safer alternatives to traditional brominated flame retardants, have been extensively detected in various environmental media and pose emerging risks. However, much less is known about their fate in the environment. Anaerobic microbial transformation is a key pathway for the natural attenuation of contaminants. This study investigated, for the first time, the microbial transformation behaviors of ß-TBCO and DPTE by Dehalococcoides mccartyi strain CG1. The results indicated that both ß-TBCO and DPTE could be easily transformed by D. mccartyi CG1 with kobs values of 0.0218 ± 0.0015 h-1 and 0.0089 ± 0.0003 h-1, respectively. In particular, ß-TBCO seemed to undergo dibromo-elimination and then epoxidation to form 4,5-dibromo-9-oxabicyclo[6.1.0]nonane, while DPTE experienced debromination at the benzene ring (ortho-bromine being removed prior to para-bromine) rather than at the carbon chain. Additionally, pronounced carbon and bromine isotope fractionations were observed during biotransformation of ß-TBCO and DPTE, suggesting that C-Br bond breaking is the rate-limiting step of their biotransformation. Finally, coupled with identified products and isotope fractionation patterns, ß-elimination (E2) and Sn2-nucleophilic substitution were considered the most likely microbial transformation mechanisms for ß-TBCO and DPTE, respectively. This work provides important information for assessing the potential of natural attenuation and environmental risks of ß-TBCO and DPTE.

Levels and diverse composition profiles of chlorinated paraffins in indoor dust: possible sources and potential human health related concerns.

Chlorinated paraffins (CPs), a group of mixtures with different carbon chain lengths and chlorine contents, are widely used as plasticizers and flame retardants in various indoor materials. CPs could be released from CP-containing materials into the ambient environment and then enter the human body via inhalation, dust ingestion and dermal absorption, resulting in potential effects on human health. In this study, we collected residential indoor dust in Wuhan, the largest city in central China, and focused on the co-occurrence and composition profiles of CPs as well as the resultant human risk via dust ingestion and dermal absorption. The results indicated that CPs with C9-40 were ubiquity in indoor dust with medium-chain CPs (MCCPs, C14-17) as the main components (6.70-495 µg g-1), followed by short-chain CPs (SCCPs, C10-13) (4.23-304 µg g-1) and long-chain (LCCPs, C≥18) CPs (3.68-331 µg g-1). Low levels (not detected-0.469 µg g-1) of very short-chain CPs (vSCCPs, C9) were also found in partial indoor dust. The dominant homolog groups were C9 and Cl6-7 groups for vSCCPs, C13 and Cl6-8 groups for SCCPs, C14 and Cl6-8 groups for MCCPs, and C18 and Cl8-9 groups for LCCPs. Based on the measured concentrations, vSCCPs, SCCPs, MCCPs, and LCCPs posed limited human health risks to local residents via dust ingestion and dermal absorption.

Surgical Treatment for Displaced Odontoid Synchondrosis Fracture: A Retrospective Case Series Study.

STUDY DESIGN: Retrospective cohort study. OBJECTIVES: Odontoid synchondrosis fracture is rare, and there is a paucity of literature on its surgical treatments. This case series study analyzed patients treated with C1 to C2 internal fixation with or without anterior atlantoaxial release and discussed the clinical effectiveness of the procedure. METHODS: Data were retrospectively collected from a single-center cohort of patients who had undergone surgical treatments for displaced odontoid synchondrosis fracture. The operation time and blood loss volume were recorded. Neurological function was assessed and classified using the Frankel grades. The odontoid process tilting angle (OPTA) was used to evaluate fracture reduction. Fusion duration and complications were also analyzed. RESULTS: Seven patients (1 boy and 6 girls) were included in the analysis. Three patients underwent anterior release and posterior fixation surgery, and the other 4 underwent posterior-only surgery. The fixation segment was C1 to C2. The average follow-up period was 34.7 ± 8.5 months. The average operation time was 145.7 ± 45.3 min, with an average blood loss volume of 95.7 ± 33.3 mL. The OPTA was corrected from 41.9° ± 11.1° preoperative to 2.4° ± 3.2° at the final follow-up (P < .05). The preoperative Frankel grade of 1 patient was grade C, of 2 patients was grade D, and of 4 patients was grade E. The neurological function of the patients in grade C and grade D recovered to grade E at the final follow-up. None of the patients developed a complication. All the patients achieved odontoid fracture healing. CONCLUSIONS: Posterior C1 to C2 internal fixation with or without anterior atlantoaxial release is a safe and effective method for treating young children with displaced odontoid synchondrosis fracture.

Two-dimensional gas chromatography coupled to isotope ratio mass spectrometry for determining high molecular weight polycyclic aromatic hydrocarbons in sediments.

The accuracy of compound-specific isotope analysis (CSIA) of trace-level pollutants in complex environmental samples has always been limited by two main challenges: poor chromatographic separation and insufficient amounts of analytes. In this study, a two-dimensional gas chromatography-isotope ratio mass spectrometry (2DGC-IRMS) system was constructed for compound-specific δ13C analysis of high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) in estuarine/marine sediments. This construction occurred through hyphenating an extra gas chromatography system (GC) to a conventional GC-IRMS using a commercially available multi-column switching-cryogenic trapping system (MCS-CTS). Compared with the previous 2DGC-IRMS strategy, which utilizes a Deans Switch device, the newly implemented 2DGC-IRMS scheme resulted in online purification of target analytes as well as enriched them online via duplicate injection and cryogenic trapping in CTS; this resultingly lowered the limits of detection (LOD) of CSIA. To improve the sample transfer efficiency to the IRMS, a broader-bore and longer fused-silica capillary was utilized to replace the original sample capillary running from the sample open split to the IRMS. A ẟ13C analysis of PAH standards showed accurate ẟ13C values, and high precisions (standard deviations 0.13-0.37%) were achieved, with the LOD of HMW-PAHs reduced to at least 1.0 mg/L (i.e., 0.07 to 0.09 nmol carbon per compound on-column). The successful application of this newly developed 2DGC-IRMS scheme provides a practical solution for the reliable CSIA of trace-level pollutants in complex environmental samples that cannot be measured using the conventional GC-IRMS system.

Extensive hydatid cysts involving the lumbosacral vertebrae and pelvis.

•A patient with typical hydatid cysts involving both lumbosacral vertebrae and pelvis is presented in this paper.•Conservative treatment with antiparasitic medication may improve symptoms.•Surgical treatment followed by antiparasitic chemotherapy may reduce the relapse rate of bone hydatid cysts.

Citric acid modified ultrasmall copper peroxide nanozyme for in situ remediation of environmental sulfonylurea herbicide contamination.

Herbicide residues in the environment threaten high-quality agriculture and human health. Consequently, in situ remediation of herbicide contamination is vital. We synthesized a novel self-catalyzed nanozyme, ultrasmall (2-3 nm) copper peroxide nanodots modified by citric acid (CP@CA) for this purpose, which can break down into H2O2 and Cu2+ in water or soil. Ubiquitous glutathione reduces Cu2+ into Cu+, which promotes the decomposition of H2O2 into •OH through a Fenton-like reaction under mild acid conditions created by the presence of citric acid. The generated •OH efficiently degrade nicosulfuron in water and soil, and the maximum degradation efficiency could be achieved at 97.58% in water at 56 min. The possible degradation mechanisms of nicosulfuron were proposed through the 25 intermediates detected. The overall ecotoxicity of the nicosulfuron system was significantly reduced after CP@CA treatment. Furthermore, CP@CA had little impact on active components of soil bacterial community. Moreover, CP@CA nanozyme could effectively remove seven other sulfonylurea herbicides from the water. In this paper, a high-efficiency method for herbicide degradation was proposed, which provides a new reference for the in situ remediation of herbicide pollution.

Enhanced Photocatalytic Activity of Hyper-Cross-Linked Polymers Toward Amines Oxidation Coupled with H2 O2 Generation through Extending Monomer's Conjugation Degree.

Visible-light-driven amines oxidation coupled with hydrogen peroxide (H2 O2 ) generation is a promising way to convert solar energy to chemical energy. Herein, a series of hyper-cross-linked polymers (HCPs) photocatalysts with different arenes monomers, including benzene (BE), diphenyl (DP), p-terphenyl (TP), or p-quaterphenyl (QP), were synthesized by simple Friedel-Crafts alkylation reaction. Owing to the maximum monomer's conjunction degree and excellent oxygen (O2 ) adsorption capacity, QP-HCPs exhibited highest photocatalytic activity for benzylamine oxidation coupled with H2 O2 generation under the irradiation of 455 nm Blue LED lamp. More than 99 % of benzylamine could be converted to N-benzylidenebenzylamine within 60 min. In addition, nearly stoichiometric H2 O2 was synchronously obtained with a high production rate of 9.3 mmol gcat -1 h-1 . Our work not only demonstrated that the photocatalytic activity of HCPs photocatalysts significantly depends on monomer's conjunction degree, but also provided a new strategy for converting solar energy to chemical energy.

QuEChERS-based extraction and two-dimensional liquid chromatography-high resolution mass spectrometry for the determination of long chain chlorinated paraffins in sediments.

In this study, a method was established for the analysis of long-chain chlorinated paraffins (LCCPs) in sediment based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and two-dimensional liquid chromatography-Orbitrap high resolution mass spectrometry (2DLCOrbitrap HRMS). Compared with other reported methods, this method greatly reduces sample preparation time (2 h) and solvent consumption. The QuEChERS extraction method presented satisfactory recoveries, 90.5-95.2, 84.7-86.6, and 81.4-83.4% of 5, 50, and 200 ng/g LCCPs with 49% Cl spiked into sediments. Meanwhile, no matrix effects were found in the LCCPs analysis after online purification by the 2DLC system. With the current commercial LCCP standards and a mixture of three chlorinated paraffins (CPs) industrial products, a suspect screening strategy was established and accurate identification of LCCPs (including vLCCPs, which carbon chain length greater than 20) under the plight that the reference standards for vLCCPs are currently unavailable. A total of 21 C18-20-LCCP and 22 vLCCP congeners were identified in sediment samples collected from Dongting Lake, China. The total concentrations of LCCPs in six sediment samples ranged from 1.69 to 18.0 ng/g (median 6.66 ng/g) and was dominated by C18 groups (mean, 28.8%), C19 groups (mean, 19.1%) and C21 groups (mean, 16.9%). Taken together, the successful application of this method to analyze sediment samples shows great potential for the analysis of LCCPs in environmental samples in future studies.

Ulinastatin attenuates spinal cord injury by targeting AMPK/NLRP3 signaling pathway.

The AMPK and NLRP3 inflammasome signaling pathways are reported to participant in the inflammatory responses following spinal cord injury (SCI). Ulinastatin (ULI) is a urinary trypsin inhibitor with excellent anti-inflammatory effects, but the functions of ULI on SCI are rarely reported. Hence, this study was designed to investigate whether ULI could modulate SCI through regulating the AMPK/NLRP3 signaling pathway. Cell Counting Kit-8 (CCK-8) assays were used to investigate whether ULI had cytotoxic effects on BV-2 cells. Basso-Beattie-Bresnahan (BBB) scale, spinal cord water content detection, hematoxylin-eosin (HE) and Nissl stainings were used to investigate the protective effects of ULI on rat SCI. The expressions of inflammatory cytokines were detected by ELISA and RT-qPCR. The expressions of key proteins of AMPK and NLRP3 inflammasome were analyzed by western blot. The CCK-8 assays indicated that ULI did not significantly influence the viability of BV-2 cells at various concentrations below 10,000 U/ml. It was witnessed that ULI could dramatically inhibit the activation of NLRP3 inflammasome via activating the AMPK signaling pathway, thus relieving inflammatory responses. Besides, the in vivo experiment suggested that treatment with ULI remarkably relieve spinal cord edema, ameliorated spinal cord tissue architecture, and improved neurological function following SCI. The findings indicate that ULI significantly ameliorates neurological function following SCI by regulating the AMPK/NLRP3 inflammasome signaling pathway.

Occurrence and distribution of triclosan and its transformation products in Taihu Lake, China.

The transformation products of triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) may be more persistent and toxic than their parent compound, yet their occurrence in aquatic environments is poorly understood. In this study, we identified three transformation products in sediment samples from Taihu Lake and compared their concentrations with the parent compound triclosan. Triclosan in Taihu Lake was at low level, ranging from 0.086 to 1.1 ng/L in surface water and 0.0058-8.3 ng/g in sediments. The three detected transformation products included methyl triclosan, chlorinated triclosan derivatives, and methyl chlorinated triclosan derivatives. Those transformation products constituted 0.73-87.5% of the total triclosan (total triclosan is the sum of triclosan, methyl triclosan, chlorinated triclosan derivatives, and methyl chlorinated triclosan derivatives on a molar basis), indicating that the ecological risk of transformation products should be considered in addition to the parent compound. Different transformation products had distinct spatial distributions. Chlorinated triclosan derivatives had the highest concentration in samples from the northwest region (0.016-0.21 ng/g) of the lake and were positively correlated with triclosan, which may indicate the possible transformation from triclosan to chlorinated triclosan derivatives. Methyl triclosan and methyl chlorinated triclosan derivatives were generally higher in samples from the center of the lake (0.22-0.28 ng/g for methyl triclosan and 0.017-0.021 ng/g for methyl chlorinated triclosan derivatives, respectively), indicating the possible occurrence of in situ microbial methylation of triclosan and chlorinated triclosan derivatives and the accumulation of those methylated analogues in Taihu Lake.

Urolithin A as a Potential Drug for the Treatment of Spinal Cord Injuries: A Mechanistic Study Using Network Pharmacology Approaches.

Objective: This research was focused to examine the potential targets, action network, and mechanism of urolithin A (UA) in spinal cord injury (SCI) management exploiting the network pharmacology (NP). Methods: We used the SwissTargetPrediction, PharmMapper, and TargetNet databases to obtain UA action targets. We searched the OMIM, GeneCards, CTD, and DrugBank databases to screen selected target genes for SCI treatment. The intersection of target genes between the UA and SCI databases was obtained by constructing Venn diagrams, which led to the identification of common druggable targets for the disease. The relationship network of the targets was built with Cytoscape 3.7.2, and the protein interaction network was analyzed with the STRING platform. The protein-protein interaction (PPI) network can be built on the STRING database. Gene Ontology (GO) function and KEGG pathway analyses of target intersections were completed with the DAVID 6.8 database. We constructed preliminary network targets for actions underlying UA-SCI interactions. Using the AutoDock software, we examined the molecular docking interactions between UA and its target proteins and further verified the mechanism of the action of UA. Results: We obtained 318 UA drug targets and 1492 SCI disease targets. We identified a total of 118 common UA-SCI targets. Based on the PPI analysis, we identified MAPK1, SRC, AKT1, HRAS, MAPK8, HSP90AA1, MAPK14, JAK2, ESR1, and NF-κB1 as possible therapeutic targets. Enrichment analysis revealed that the PI3K-AKT, VEGF, and TNF signaling pathways could be critical for the NP analysis. Molecular docking indicated that UA had a strong affinity for docked proteins (binding energy range: -6.3 to -9.3 kcal mol-1). Conclusions: We employed an NP approach to validate and predict the underlying mechanisms associated with UA therapy for SCI. An additional purpose of this study was to provide a theoretical basis for further experimental studies on UA's potential in SCI treatment.