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Zinc-air batteries employing non-Pt cathodes hold significant promise for advancing cathodic oxygen reduction reaction (ORR). However, poor intrinsic electrical conductivity and aggregation tendency hinder the application of metal-organic frameworks (MOFs) as active ORR cathodes. Conductive MOFs possess various atomically dispersed metal centers and well-aligned inherent topologies, eliminating the additional carbonization processes for achieving high conductivity. Here, a novel room-temperature electrochemical cathodic electrodeposition method is introduced for fabricating uniform and continuous layered 2D bimetallic conductive MOF films cathodes without polymeric binders, employing the organic ligand 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and varying the Ni/Cu ratio. The influence of metal centers on modulating the ORR performance is investigated by density functional theory (DFT), demonstrating the performance of bimetallic conductive MOFs can be effectively tuned by the unpaired 3d electrons and the Jahn-Teller effect in the doped Cu. The resulting bimetallic Ni2.1Cu0.9(HITP)2 exhibits superior ORR performance, boasting a high onset potential of 0.93 V. Moreover, the assembled aqueous zinc-air battery demonstrates high specific capacity of 706.2 mA h g-1, and exceptional long-term charge/discharge stability exceeding 1250 cycles.
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A general approach for the α-arylation of heteroarenes with nitroarenes via denitrative coupling is reported for the first time. Various heteroarenes, including derivatives of furan, benzofuran, pyrrole, indole, thiophene, and benzothiophene, can be arylated at the α-position in moderate to good yields. Mechanistic studies demonstrate that the reaction proceeds via a CMD pathway, with C-H bond activation as the rate-determining step. Furthermore, the scalability and applicability in the synthesis of a drug molecule exemplify the utility of this protocol.
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Laccase (EC 1.10.3.2), as eco-friendly biocatalysts, holds immense potential for sustainable applications across various environmental and industrial sectors. Despite the growing interest, the exploration of cold-adapted laccases, especially their unique properties and applicability, remains limited. In this study, we have isolated, cloned, expressed, and purified a novel laccase from Peribacillus simplex (GenBank: PP430751), which was derived from permafrost layer. The recombinant laccase (PsLac) exhibited optimal activity at 30 °C and a pH optimum of 3.5. Remarkably, PsLac exhibited remarkable stability in the presence of organic solvents, with its enzyme activity increasing by 20 % after being incubated in a 30 % trichloromethane solution for 12 h, compared to its initial activity. Furthermore, the enzyme preserved 100 % of its activity after undergoing eight freeze-thaw cycles. Notably, the catalytic center of PsLac contains Zn2+ instead of the typically observed Cu2+ found in other laccases, and metal-ion substitution experiments raised the catalytic efficiency to 3-fold when Zn2+ was replaced with Fe2+. Additionally, PsLac has demonstrated a proficient ability to degrade phenolic pollutants, such as hydroquinone, even at a low temperature of 16 °C, positioning it as a promising candidate for environmental bioremediation and contributing to cleaner production processes.
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Hydrogen peroxide (H2O2) emerges as a viable oxidant for fuel cells, necessitating the development of an efficient and cost-effective electrocatalyst for the hydrogen peroxide reduction reaction (HPRR). In this study, we synthesized a self-supporting, highly active HPRR electrocatalyst comprising two morphologically distinct components: CeO2-NiCo2O4 nanowires and CeO2-NiCo2O4 metal organic framework derivatives, via a two-step hydrothermal process followed by air calcination. X-ray diffraction and transmission electron microscopy analysis confirmed the presence of CeO2 and NiCo2O4, revealing the amalgamated interface between them. CeO2 exhibits multifunctionality in regulating the surface electronic configuration of NiCo2O4, fostering synergistic connections, and introducing oxygen deficiencies to enhance the catalytic efficacy in HPRR. Electrochemical measurements demonstrate a reduction current density of 789.9 mA·cm-2 at -0.8 V vs. Ag/AgCl. The assembly of direct borohydride-hydrogen peroxide fuel cell (DBHPFC) exhibits a peak power density of 45.2 mW·cm-2, demonstrating durable stability over a continuous operation period of 120 h. This investigation providing evidence that the fabrication of heterostructured catalysts based on CeO2 for HPRR is a viable approach for the development of high-efficiency electrocatalysts in fuel cell technology.
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BACKGROUND: Neoadjuvant chemoradiotherapy(nCRT) for rectal cancer can lead to structural changes in collagen in the tumor microenvironment and increase the risk of postoperative anastomotic stenosis (AS). However, the quantitative relationship between AS and collagen has not been defined. This study is to quantitatively analyze the collagen features in rectal cancer and explore the relationship between the changes of collagen and postoperative anastomotic stenosis after nCRT. STUDY DESIGN: This study is a retrospective study. A total of 371 patients with rectal cancer were included. Collagen features in the resection margin of rectal cancer anastomosis was extracted by multi-photon imaging. LASSO-logistic regression was performed to select features related to AS and the collagen score (CS) was constructed. Area under the receiver operating curve (AUROC) and decision curve analysis was performed to evaluate the discrimination and clinical benefit of the nomogram. RESULTS: The probability of AS was 23% in the training cohort and 15.9% in the validation cohort. In the training cohort, the distance between tumor and resection margin, anastomotic leakage and CS were independent risk factors for postoperative AS in univariate and multivariate analyses. A nomogram was constructed based on the above results. The prediction nomogram showed good discrimination (AUROC, 0.864;95% CI, 0.776 to 0.952) and was validated in the validation cohort (AUROC, 0.918;95% CI, 0.851 to 0.985). CONCLUSIONS: CS is an independent risk factor for AS in rectal cancer after nCRT. The predictive model based on CS can predict the occurrence of postoperative AS.
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Solar-light photosynthesis of ammonia form N2 reduction in ultrapure water over the artificial photocatalysts is attractive but still challenging compared with Haber-Bosch process. In this work, ultrathin Fe-Ta2O5-x nanobelts were fabricated via the controllable solvothermal process for ammonia photosynthesis. The formed oxygen vacancies and Fe doping narrowed their bandgap energies and promoted the carriers' separation and transfer for Fe-Ta2O5-x nanobelts. In addition, Fe doping also resulted in the reduced working functions of the samples, indicating a weaker electron binding restriction and stronger separation and transfer of photo-induced carriers. The experimental results showed that Fe-Ta2O5-x nanobelts showed remarkably enhanced photocatalytic ammonia production performance under simulated sunlight irradiation, and the relevant ammonia production rate reached approximately 3030.86 µM g-1 h-1, which was 9.63 times of pristine Ta2O5-x and 491.0 times of commercial Ta2O5, and a relatively stable photocatalytic ammonia production performance under simulated sunlight irradiation for Fe-Ta2O5-x nanobelts. Meanwhile, it was also found that Fe doping has great influences on the photocatalytic performance under visible light and simulated sunlight irradiation, mainly because of their suitable bandgap energies and enhanced solar-light harvesting capacity. Current work indicates the great potentials of ultrathin tantalum-based functional materials for high-efficiency ammonia photosynthesis.
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Nitroarenes are known for their stability, low toxicity, easy availability, and cost-effectiveness, making them one of the most fundamental chemical feedstocks. The direct utilization of nitroarenes as nitrogen sources in amidation reactions offers significant advantages over using arylamines. Herein, we disclose a streamlined method for constructing α-ketoamides through the direct coupling of nitroarenes with α-oxocarboxylic acids. This transformation obviates the need for preparing, isolating, and purifying arylamines, leading to improved efficiency, cost-effectiveness, and time savings.
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One of the most widely utilized methods for the construction of C(sp2)-N bonds is the transition-metal-catalyzed cross-coupling of aryl halides/boronic acids with amines, known as Ullmann condensation, Buchwald-Hartwig amination, and Chan-Lam coupling. However, aryl halides/boronic acids often require multi-step preparation while generating a large amount of corrosive and toxic waste, making the reaction less attractive. Herein, we present an unprecedented method for the C(sp2)-N formation via Buchwald-Hartwig-type reactions using synthetically upstream nitroarenes as the sole starting materials, thus eliminating the need for arylhalides and pre-formed arylamines. A diverse range of symmetrical di- and triarylamines were obtained in a single step from nitroarenes, and more importantly, various unsymmetrical di- and triarylamines were also highly selectively synthesized in a one-pot/two-step process. Furthermore, the success of the scale-up experiments, the late-stage functionalization of a drug intermediate, and the rapid preparation of hole-transporting material TCTA showcased the utility and practicality of this protocol in synthetic chemistry. Mechanistic studies indicate that this transformation may proceed via an arylamine intermediate generated in situ from the reduction of nitroarenes, which is followed by a denitrative Buchwald-Hartwig-type reaction with another nitroarene to form a C-N bond.
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OBJECTIVE: Acute necrotic collection (ANC), acute peripancreatic fluid collection (APFC), pleural effusion, and ascites are common early complications of acute pancreatitis. This study aimed to investigate the relationship between 12 serum cytokines and the early complications and severity of acute pancreatitis (AP). METHODS: We retrospectively analyzed the clinical data of 307 patients with AP, and divided them into severe group and mild-to-moderate group according to the revised Atlanta classification. Propensity score matching was used to control for confounding factors. Binary logistic regression analysis was used to explore the relationship between cytokine levels and early complications of AP. RESULTS: Serum levels of interleukin (IL)-1ß, IL-5, IL-6, IL-8, IL-10, IL-17, and tumor necrosis factor-α were significantly higher in the severe acute pancreatitis (SAP) group than in the non-SAP group (p < .05). After adjusting for confounding factors, the upper quartiles of IL-6, IL-8, and IL-10 were associated with an increased risk of ANC compared with those in the lowest quartile (IL-6: quartile 3, odds ratio [OR] = 3.99, 95% confidence interval [CI] = 1.95-8.16; IL-8: quartile 4, OR = 2.47, 95% CI = 1.27-4.84; IL-10: quartile 2, OR = 2.22, 95% CI = 1.09-4.56). APFC was associated with high serum levels of IL-6 (quartile 3, OR = 1.32, 95% CI = 1.02-1.72), pleural effusions were associated with high serum levels of IL-1ß, IL-6, IL-8, and IL-10 (IL-1ß: quartile 4, OR = 2.36, 95% CI = 1.21-4.58; IL-6: quartile 3, OR = 4.67, 95% CI = 2.27-9.61; IL-8: quartile 3, OR = 2.95, 95% CI = 1.51-5.79; IL-10: quartile 4, OR = 3.20, 95% CI = 1.61-6.36), and high serum levels of IL-6 and IL-10 were associated with an increased risk of ascites (IL-6: quartile 3, OR = 3.01, 95% CI = 1.42-6.37; IL-10: quartile 3, OR = 2.57, 95% CI = 1.23-5.37). CONCLUSION: Serum cytokine levels, including IL-1ß, IL-6, IL-8, and IL-10 may be associated with the occurrence of early complications of AP. In daily clinical practice, IL-6 may be the most worthwhile cytokine to be detected.
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Citocinas , Pancreatite , Humanos , Interleucina-10 , Doença Aguda , Ascite/etiologia , Interleucina-6 , Interleucina-8 , Estudos Retrospectivos , Pancreatite/complicações , Hospitais , Interleucina-1betaRESUMO
Postoperative adjuvant chemotherapy (AC) for poor responders to neoadjuvant chemoradiotherapy (nCRT) remains debatable among patients with locally advanced rectal cancer (LARC), necessitating biomarkers to accurately predict the benefits of AC. This study aimed to develop a patient-derived tumor organoid (PDTO) platform to predict the benefit of AC in LARC patients showing poor nCRT response. PDTOs were established using irradiated rectal cancer specimens with poor nCRT responses, and their sensitivity to chemotherapy regimens was tested. The half-maximal inhibitory concentration (IC50) value for the PDTO drug test was defined based on the clinical outcomes, and the accuracy of the PDTO prognostic predictions was calculated. Predictive models were developed and validated using the PDTO drug test results. Between October 2018 and December 2021, 86 PDTOs were successfully constructed from 138 specimens (success rate 62.3%). The optimal IC50 cut-off value for the organoid drug test was 39.31 µmol/L, with a sensitivity of 84.75%, a specificity of 85.19%, and an accuracy of 84.88%. Multivariate Cox regression analysis revealed that the PDTO drug test was an independent predictor of prognosis. A nomogram based on the PDTO drug test was developed, showing good prognostic ability in predicting the 2-year and 3-year disease-free survivals (AUC of 0.826 [95% CI, 0.721-0.931] and 0.902 [95% CI, 0.823-0.982], respectively) and overall survivals (AUC of 0.859 [95% CI, 0.745-0.973] and 0.885 [95% CI, 0.792-0.978], respectively). The PDTO drug test can predict the benefit of postoperative AC in poor responders with LARC to nCRT.
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Whether athletes' self-compassion predicts their emotional resilience to failure has yet to be empirically tested. Moreover, as an important physiological process of stress regulation, vagal reactivity is a plausible physiological mechanism for this relationship. Through a laboratory-based observational study of 90 college athletes, this research explores the influence of athletes' trait self-compassion on their emotional resilience when recalling failure, and examines whether vagal reactivity plays a mediating role. The results show that self-compassion did not significantly predict athletes' positive emotions but did significantly predict better recovery from negative emotions after recalling failure events. Furthermore, vagal reactivity was a significant mediator between self-compassion and recovery from negative emotions.
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Bacterial infection is a common clinical disease. Antibiotics have saved countless lives since their discovery and are a powerful weapon in the fight against bacteria. However, with the widespread use of antibiotics, the problem of drug resistance now poses a great threat to human health. In recent years, studies have investigated approaches to combat bacterial resistance. Several antimicrobial materials and drug delivery systems have emerged as promising strategies. Nano-drug delivery systems for antibiotics can reduce the resistance to antibiotics and extend the lifespan of novel antibiotics, and they allow targeting drug delivery compared to conventional antibiotics. This review highlights the mechanistic insights of using different strategies to combat drug-resistant bacteria and summarizes the recent advancements in antimicrobial materials and drug delivery systems for different carriers. Furthermore, the fundamental properties of combating antimicrobial resistance are discussed, and the current challenges and future perspectives in this field are proposed.
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In order to alleviate the energy crisis and propel a low-carbon economy, hydrogen (H2) plays an important role as a renewable cleaning resource. To break the hydrogen evolution reaction (HER) bottleneck, we need high-efficiency electrocatalysts. Based on the synergistic effect between bimetallic oxides, hierarchical mesoporous CoNiO2 nanosheets can be fabricated. Combining physical representations with electrochemical measurements, the resultant CoNiO2 catalysts present the hierarchical microflowers morphology assembled by mesoporous nanosheets. The ultrathin two-dimensional nanosheets and porous surface characteristics provide the vast channels for electrolyte injection, thus endowing CoNiO2 the outstanding HER performance. The excellent performance with a fewer onset potential of 94 mV, a smaller overpotential at 10 mA cm-2, a lower Tafel slope of 109 mV dec-1 and better stability after 1000 cycles makes CoNiO2 better than that of metallic Co and metallic Ni.
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Transmembrane serine proteinase 2 (TMPRSS2), which is an essential serine protease for priming spike protein of SARS-CoV-2, was found in low expression in many cancer tissue including lung cancer. However, the mechanism of severely downregulated in lung adenocarcinoma (LUAD) and lung squamous cell carcinoma (LUSC) was not reported yet; the correlation between TMPRSS2 and prognosis in LUAD and LUSC is also not clear. In our present research, we found that TMPRSS2 was severely downregulated in LUAD and LUSC, and the expression of TMPRSS2 in LUAD is much lower than that of LUSC. Low TMPRSS2 expression was an independent prognostic factor for poor OS in LUAD, but not in LUSC patients. Promoter hypermethylation is one of the results of TMPRSS2 downregulated in LUAD and LUSC, whereas copy-number alteration is another reason for TMPRSS2 downregulated in LUAD but not LUSC. Then, low TMPRSS2 expression has higher prognostic value in LUAD and may be due to different immune environments and different enriched immune cells subgroups.
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Adenocarcinoma de Pulmão , COVID-19 , Carcinoma Pulmonar de Células não Pequenas , Carcinoma de Células Escamosas , Neoplasias Pulmonares , Humanos , Prognóstico , Serina Proteases , Medicina de Precisão , SARS-CoV-2 , Adenocarcinoma de Pulmão/genética , Adenocarcinoma de Pulmão/patologia , Neoplasias Pulmonares/diagnóstico , Neoplasias Pulmonares/genética , Neoplasias Pulmonares/prevenção & controle , Carcinoma de Células Escamosas/diagnóstico , Carcinoma de Células Escamosas/genética , Carcinoma de Células Escamosas/prevenção & controleRESUMO
Kirsten rat sarcoma virus (KRAS) mutation is considered to be the event that leads to the initiation of pancreatic ductal adenocarcinoma (PDAC), the mutation frequency of the KRAS gene in PDAC is 9095%. Studies have shown that wildtype KRAS (KRASWT) has a survival advantage in PDAC and can antagonize the effect of mutated KRAS G12D (KRASG12D), leading to a low cell transformation efficiency. The present study focused on the differences in biological behavior between KRASWT and KRASG12D and explored the mechanism in pancreatic cancer. Overexpressed KRASWT and KRASG12D was transfected into cells through lentiviral transfection. The differences and mechanisms were explored using cell counting kit8 (CCK8), clone formation, wound healing and Transwell assays, as well as western blotting, immunohistochemistry and tumor formation in nude mice. In vitro, the proliferation of KRASWT group was reduced compared with PANC1 group, while the proliferation of KRASG12D group was not significantly changed. In vivo, the proliferation of KRASWT group was reduced and that of KRASG12D group was enhanced compared with that in the PANC1 group. The invasion and migration of KRASWT group were decreased, while the invasion and migration of KRASG12D group were increased. Western blotting showed that the expression of Ecadherin, αEcatenin, MMP3, MMP9, STAT3 and phosphorylated STAT3 in KRASWT group was increased, while no significant difference was observed in KRASG12D group. The results of immunohistochemistry were consistent with those of western blotting. KRASWT group can inhibit the proliferation of pancreatic cancer in vitro and in vivo, while KRASG12D group can significantly promote proliferation in vivo, but not significantly in vitro. Wildtype KRAS may inhibit the invasion and migration of pancreatic cancer through the Wnt/ßcatenin pathway.
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Carcinoma Ductal Pancreático , Neoplasias Pancreáticas , Animais , Camundongos , beta Catenina/genética , beta Catenina/metabolismo , Carcinoma Ductal Pancreático/patologia , Vírus do Sarcoma Murino de Kirsten/metabolismo , Camundongos Nus , Mutação , Neoplasias Pancreáticas/patologia , Proteínas Proto-Oncogênicas p21(ras)/genética , Proteínas Proto-Oncogênicas p21(ras)/metabolismo , Via de Sinalização Wnt , Neoplasias PancreáticasRESUMO
Rivaroxaban (RIV) is a direct Factor Xa inhibitor anticoagulant, but the oral bioavailability of RIV is estimated to be only 60% due to its poor solubility. The aim of the present study was to improve the solubility and bioavailability of RIV. Five cocrystals-p-hydroxybenzoic acid (HBA), 2,4-dihydroxybenzoic acid (DBA), nicotinamide (NA), isonicotinamide (IA), and succinic acid (SA)-were used as cofomers and were successfully obtained and characterized by powder X-ray diffraction, thermal analysis, and Fourier transform infrared spectra. RIV-DBA and RIV-HBA cocrystals showed obvious improvements in solubility, dissolution (under sink conditions), and intrinsic dissolution rates versus RIV. Moreover, the dissolution of RIV-HBA, RIV-DBA, and RIV-SA cocrystals under non-sink conditions showed obvious "spring and parachute" patterns. The in vitro permeability levels in a Caco-2 cell model of RIV-DBA and RIV-IA cocrystals were significantly improved versus RIV. Pharmacokinetic studies in beagle dogs showed that RIV-DBA and RIV-HBA cocrystals had higher bioavailability than RIV. The enhancements in solubility and bioavailability indicate the potential of RIV cocrystals as a better candidate for the treatment of thrombosis versus RIV.
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In recent years, hydrogel-based research in biomedical engineering has attracted more attention. Cellulose-based hydrogels have become a research hotspot in the field of functional materials because of their outstanding characteristics such as excellent flexibility, stimulus-response, biocompatibility, and degradability. In addition, cellulose-based hydrogel materials exhibit excellent mechanical properties and designable functions through different preparation methods and structure designs, demonstrating huge development potential. In this review, we have systematically summarized sources and types of cellulose and the formation mechanism of the hydrogel. We have reviewed and discussed the recent progress in the development of cellulose-based hydrogels and introduced their applications such as ionic conduction, thermal insulation, and drug delivery. Also, we analyzed and highlighted the trends and opportunities for the further development of cellulose-based hydrogels as emerging materials in the future.
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Background: Inflammation is closely associated with prognosis in patients with aneurysmal subarachnoid hemorrhage (aSAH), which is orchestrated by inflammatory cytokines. Therefore, this study aimed to investigate the levels of inflammatory cytokines in the early stage of aSAH and their predictive value for prognosis. Methods: In this retrospective study, 206 patients with aSAH were recruited and assigned to a severe group (WFNS grade ≥ 4) and a mild group (WFNS grade < 4) according to the severity of patients on admission. Flow cytometry was performed to detect the levels of 12 inflammatory cytokines in the serum of patients. Then, patients were grouped into a poor prognosis group (mRS score ≥ 4) and a good prognosis group (mRS score < 4) based on their prognosis after 3 months of discharge to compare the relationship between cytokines and prognosis. Propensity score matching (PSM) was utilized to control confounding factors. The correlation between inflammatory factors and prognosis was determined using Spearman correlation, and the predictive efficacy of inflammatory factors was tested by a receiver operating characteristic curve. Results: Serum IL-1ß, IL-5, IL-6, IL-8, IL-10, IFN-γ, and TNF-α levels were significantly higher in the mild group than in the severe group and in the poor prognosis group than in the good prognosis group. After PSM, the differences in IL-1ß, IL-5, IFN-α, and IFN-γ levels disappeared between the two groups, whereas IL-2, IL-6, IL-8, IL-10, and TNF-α levels remained higher in the poor prognosis group than in the good prognosis group. Additionally, IL-2, IL-6, IL-8, and IL-10 levels were positively correlated with mRS scores. Moreover, the predictive value was found to be the highest for IL-6 and the lowest for TNF-α. Conclusion: Inflammation degree was related to the severity of aSAH. Inflammatory markers, including IL-6, IL-10, IL-8, IL-2, and TNF-α, might predict the poor prognosis of aSAH.
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Hemorragia Subaracnóidea , Citocinas , Humanos , Inflamação/complicações , Interleucina-10 , Interleucina-2 , Interleucina-5 , Interleucina-6 , Interleucina-8 , Estudos Retrospectivos , Hemorragia Subaracnóidea/complicações , Hemorragia Subaracnóidea/diagnóstico , Fator de Necrose Tumoral alfaRESUMO
F11R receptor (F11R/junctional adhesion molecule-A/F11R-A) is preferentially concentrated at tight junctions and influences epithelial cell morphology and migration. Numerous studies have shown that the aberrant expression of F11R contributes to tumor progression including pancreatic cancer. However, the significance of F11R in various tumors is controversial, and the role of F11R in regulating the malignant behaviors of human pancreatic cancer is unknown. To investigate the role of F11R in the carcinogenesis of pancreatic cancer and the potential targets of F11R as a therapeutic target for pancreatic cancer, we knocked down F11R in the pancreatic cancer cell line PANC-1 using lentiviral approaches. We found that F11R silencing led to decreased cell proliferation, a loss of cell invasiveness, cell cycle arrest in the G1 phase, and enhanced cell apoptosis. The present results suggest that F11R may be a promising therapeutic target for pancreatic cancer.