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Background and aim: The global burden of invasive fungal infections (IFIs) is emerging in immunologic deficiency status from various disease. Patients with acute-on-chronic hepatitis B liver failure (ACHBLF) are prone to IFI and their conditions are commonly exacerbated by IFI. However, little is known about the characteristics and risk factors for IFI in hospitalized ACHBLF patients. Methods: A total of 243 hospitalized ACHBLF patients were retrospectively enrolled from January 2010 to July 2023. We performed restricted cubic spline analysis to determine the non-linear associations between independent variables and IFI. The risk factors for IFI were identified using logistic regression and the extreme gradient boosting (XGBoost) algorithm. The effect values of the risk factors were determined by the SHapley Additive exPlanations (SHAP) method. Results: There were 24 ACHBLF patients (9.84%) who developed IFI on average 17.5 (13.50, 23.00) days after admission. The serum creatinine level showed a non-linear association with the possibility of IFI. Multiple logistic regression revealed that length of hospitalization (OR = 1.05, 95% CI: 1.02-1.08, P = 0.002) and neutrophilic granulocyte percentage (OR = 1.04, 95% CI: 1.00-1.09, P = 0.042) were independent risk factors for IFI. The XGBoost algorithm showed that the use of antibiotics (SHAP value = 0.446), length of hospitalization (SHAP value = 0.406) and log (qHBV DNA) (SHAP value = 0.206) were the top three independent risk factors for IFI. Furthermore, interaction analysis revealed no multiplicative effects between the use of antibiotics and the use of glucocorticoids (P = 0.990). Conclusion: IFI is a rare complication that leads to high mortality in hospitalized ACHBLF patients, and a high neutrophilic granulocyte percentage and length of hospitalization are independent risk factors for the occurrence of IFI.
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Introduction: Exploring the energy expenditure and substrate metabolism data during exercise, 10-minute recovery, and 20-minute recovery phases in Tabata, HIIT(High-Intensity Interval Training), and MICT(Moderate-Intensity Continuous Training). This study explores the scientific aspects of weight reduction strategies, examining energy expenditure and substrate metabolism from various training perspectives. The aim is to establish a theoretical foundation for tailoring targeted exercise plans for individuals within the population with overweight/obesity. Methods: This study used an experimental design with fifteen male university students with overweight/obesity. Participants underwent random testing with Tabata, HIIT, and MICT. Tabata involved eight sets of 20 seconds exercise and 10 seconds rest, totaling 4 minutes. HIIT included four sets of power cycling: 3 minutes at 80% VO2max intensity followed by 2 minutes at 20% VO2max. MICT comprised 30 minutes of exercise at 50% VO2max intensity. Gas metabolism indices were continuously measured. Subsequently, fat and glucose oxidation rates, along with energy expenditure, were calculated for each exercise type. Results: During both the exercise and recovery phases, the Tabata group exhibited a significantly higher fat oxidation rate of (0.27 ± 0.03 g/min) compared to the HIIT group (0.20 ± 0.04 g/min, p<0.05) and the MICT group (0.20 ± 0.03g/min, p<0.001). No significant difference was observed between the HIIT and MICT groups (p=0.854). In terms of energy expenditure rate, the Tabata group maintained a substantially elevated level at 5.76 ± 0.74kcal/min compared to the HIIT group (4.81 ± 0.25kcal/min, p<0.01) and the MICT group (3.45 ± 0.25kcal/min, p<0.001). Additionally, the energy expenditure rate of the HIIT group surpassed that of the MICT group significantly (p<0.001). Conclusion: The study finds that male college students with overweight/obesity in both exercise and recovery, Tabata group has lower fat and glucose oxidation rates, and energy expenditure compared to HIIT and MICT groups. However, over the entire process, Tabata still exhibits significantly higher rates in these aspects than HIIT and MICT. Despite a shorter exercise duration, Tabata shows a noticeable "time-efficiency" advantage. Tabata can be used as an efficient short-term weight loss exercise program for male college students with overweight/obesity.
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Treinamento Intervalado de Alta Intensidade , Sobrepeso , Humanos , Masculino , Sobrepeso/metabolismo , Universidades , Obesidade , Metabolismo Energético , GlucoseRESUMO
By introducing enantiomerically pure mono-bidentate N-donor ligands (LR/LS) into Yb(btfa)3(H2O)2 and Yb(dbm)3(H2O), respectively, two pairs of chiral YbIII enantiomers, namely Yb(btfa)3LR/Yb(btfa)3LS (D-1/L-1) and [Yb(dbm)3LR]·[Yb(dbm)3(C2H5OH)]/[Yb(dbm)3LS]·[Yb(dbm)3(C2H5OH)] (D-2/L-2) were isolated, where btfa- = 3-benzoyl-1,1,1-trifluoroacetonate, dbm- = dibenzoylmethanate, and LR/LS = (-)/(+)-4,5-pinenepyridyl-2-pyrazine. D-1/L-1 possess mononuclear structures in which the YbIII ions are eight-coordinated, while D-2/L-2 show cocrystal structures containing Yb(dbm)3(LR/LS) and Yb(dbm)3(C2H5OH) moieties in which the two YbIII ions are eight and seven-coordinated, respectively. They not only feature different molecular structures but also present distinct linear and nonlinear optical performances. Chiral mononuclear D-1 has better near infrared photo-luminescence (NIR-PL) and circularly polarized luminescence (CPL) performances than chiral cocrystal D-2. More remarkably, D-1/L-1 show large second-harmonic generation (SHG) responses (up to 1.25/1.28 × KDP) 18/16 times those of D-2/L-2 (0.07/0.08 × KDP). In addition, D-2/L-2 represent the first examples of lanthanide cocrystal complexes with NIR-PL, NIR-CPL and SHG properties.
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This study aimed to investigate the performance of 18F-DCFPyL positron emission tomography/computerized tomography (PET/CT) models for predicting benign-vs-malignancy, high pathological grade (Gleason score > 7), and clinical D'Amico classification with machine learning. The study included 138 patients with treatment-naïve prostate cancer presenting positive 18F-DCFPyL scans. The primary lesions were delineated on PET images, followed by the extraction of tumor-to-background-based general and higher-order textural features by applying five different binning approaches. Three layer-machine learning approaches were used to identify relevant in vivo features and patient characteristics and their relative weights for predicting high-risk malignant disease. The weighted features were integrated and implemented to establish individual predictive models for malignancy (Mm), high path-risk lesions (by Gleason score) (Mgs), and high clinical risk disease (by amico) (Mamico). The established models were validated in a Monte Carlo cross-validation scheme. In patients with all primary prostate cancer, the highest areas under the curve for our models were calculated. The performance of established models as revealed by the Monte Carlo cross-validation presenting as the area under the receiver operator characteristic curve (AUC): 0.97 for Mm, AUC: 0.73 for Mgs, AUC: 0.82 for Mamico. Our study demonstrated the clinical potential of 18F-DCFPyL PET/CT radiomics in distinguishing malignant from benign prostate tumors, and high-risk tumors, without biopsy sampling. And in vivo 18F-DCFPyL PET/CT can be considered a noninvasive tool for virtual biopsy for personalized treatment management. Supplementary Information: The online version contains supplementary material available at 10.1007/s43657-023-00108-y.
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With the advent of the information age and advancement of digital technology, film and television tourism is developing rapidly under the joint action of the film industry and tourism industry, and has become a crucial form of cultural and entertainment consumption for individuals to pursue a better life in the new age. This study designs three experiments from the perspectives of identity conversion, motivation transfer, and demand change to conduct an empirical study on the mediating role of empathy for further exploring the internal mechanism of film-induced tourism in film and television tourism. The findings suggest that the three mediation hypotheses are all valid, indicating that film-induced tourism involves identity conversion from audiences to visitors, motivation transfer from watching to traveling, and demand change from interest to expectation through emotional media.
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By utilizing Dy(hfac)3(H2O)2 to react with enantiomerically pure tridentate N,N,N-pincer ligands, namely (-)/(+)-2,6-bis(4',5'-pinene-2'-pyridyl)pyridine (LR and LS), respectively, homochiral DyIII enantiomeric pairs formulated as Dy(hfac)3LR/Dy(hfac)3LS (R-1/S-1) (hfac- = hexafluoroacetylacetonate) were achieved and structurally characterized. Meanwhile, their magnetic, photoluminescent (PL), and chiroptical properties were probed. The PL test results indicate that the precursor Dy(hfac)3(H2O)2 only shows very weak emission, while R-1 exhibits characteristic DyIII f-f transition emission bands at room temperature. Furthermore, the nonlinear optical responses of Dy(hfac)3(H2O)2, LR/LS, and R-1/S-1 were investigated in detail based on crystalline samples. The results reveal that LR and LS present the coexistence of second- and third-harmonic generation (SHG and THG) responses with more intense signals for SHG responses; and Dy(hfac)3(H2O)2 merely displays weak THG responses, while R-1 and S-1 also only exhibit THG responses. However, the THG intensities of R-1 and S-1 are more than six times larger than that of Dy(hfac)3(H2O)2 under the identical measurement conditions. These results demonstrate that introducing homochiral N,N,N-pincer ligands to replace two H2O molecules of Dy(hfac)3(H2O)2 results in significant improvements of both PL performances and THG responses of resultant R-1/S-1 enantiomers. R-1 and S-1 integrate PL, THG, and chiral optical activity in one molecule, suggesting their multifunctional merits. In particular, a convenient method is introduced to simultaneously test THG and SHG responses of molecular materials based on crystalline samples in this work.
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Two homochiral EuIII and SmIII tris(ß-diketonate) enantiomeric pairs, based on fluorinated ß-diketone (Hbtfa) and enantiopure asymmetric N,N'-donor ligands (LR and LS), Λ-Eu(btfa)3LR (R-1-Eu)/Δ-Eu(btfa)3LS (S-1-Eu) and Λ-Sm(btfa)3LR (R-2-Sm)/Δ-Sm(btfa)3LS (S-2-Sm) (btfa- = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and LR/LS = (-)/(+)-4,5-pineno-2,2'-bipyridine) were synthesized. The electronic circular dichroism (ECD) spectra confirmed their enantiomeric nature. R-1-Eu/S-1-Eu and R-2-Sm/S-2-Sm exhibit intense characteristic emissions of EuIII (red) and SmIII (orange-red) ions both in the solid state and in DCM with long lifetimes and high luminescence quantum yields. For example, the overall quantum yields reach up to 61% and 53% along with very high sensitization efficiency values of 82 and 79 for R-1-Eu in the solid state and in DCM, respectively. Notably, the corresponding values are determined to be 6.5% (solid state) and 3.1% (DCM) for R-2-Sm, which are among the highest quantum yields for rare SmIII tris(ß-diketonate) luminescent complexes reported to date. Furthermore, R-1-Eu and R-2-Sm show a strong triboluminescence (TL) phenomenon visible with the naked eye in daylight. Moreover, R-1-Eu/S-1-Eu and R-2-Sm/S-2-Sm show circularly polarized luminescence (CPL) properties. Particularly, the luminescence dissymmetry factors (glum) for R-2-Sm/S-2-Sm are larger than those for R-1-Eu/S-1-Eu despite the fact that SmIII complexes usually show poorer emission than EuIII homologues, which is very rare in the reported EuIII and SmIII CPL-active complexes.
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PURPOSE: This retrospective study aimed to investigate the clinical value of -deoxy-2-(F)-fluorodeoxyglucose positron emission tomography/computed tomography (F-FDG PET/CT) in detecting primary lesions of hepatic metastases. METHODS: A total of 124 patients with hepatic metastatic carcinoma of unknown primary underwent whole body F-FDG PET/CT imaging. According to the final diagnoses for both primary sites and hepatic metastases that were confirmed either histopathologically or by clinical follow up, all patients were divided into 4 groups: a true positive group (TP, 95 cases), a false positive group (FP, 9), a true negative group (TN, 8) and a false negative group (FN, 12). RESULTS: The TP rate of primary lesions, detected by F-FDG PET/CT, was 76.61%, the FP rate 7.26%, the TN rate 6.45% and the FN rate 9.68%. The sensitivity, specificity, positive predictive value, negative predictive value and accuracy of F-FDG PET/CT in the detection of primary tumors were 88.78%, 52.94%, 91.35%, 40%, and 83.06%, respectively. Accurate diagnosis groups (TP, TN) showed a significantly higher SUVmax (standard uptake maximum value) level than that in error diagnosis groups (FP, FN). The SUVmax between hepatic metastases and primary lesions had a positive correlation. The primary tumor sites of hepatic metastases were mainly located in the gastrointestinal organs and the lungs. CONCLUSIONS: Whole body F-FDG PET/CT imaging was sensitive for detecting primary sites/lesions with hepatic metastatases of unknown primary, especially when the SUVmax of hepatic metastases were greater than 4.7.
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Carcinoma/diagnóstico por imagem , Neoplasias Hepáticas/patologia , Neoplasias Hepáticas/secundário , Tomografia por Emissão de Pósitrons combinada à Tomografia Computadorizada/métodos , Adulto , Idoso , Idoso de 80 Anos ou mais , Estudos de Casos e Controles , Feminino , Fluordesoxiglucose F18/administração & dosagem , Fluordesoxiglucose F18/metabolismo , Humanos , Masculino , Pessoa de Meia-Idade , Metástase Neoplásica/diagnóstico por imagem , Metástase Neoplásica/patologia , Neoplasias Primárias Desconhecidas/patologia , Valor Preditivo dos Testes , Compostos Radiofarmacêuticos/administração & dosagem , Compostos Radiofarmacêuticos/metabolismo , Estudos Retrospectivos , Sensibilidade e EspecificidadeRESUMO
INTRODUCTION: Hepatitis B virus (HBV) infection is a major public health issue but there are no powerful drugs to eradicate the virus. HBV markers including HBsAg, HBcrAg, HBV RNA, HBcAb, and HBV DNA are becoming promising biomarkers to reflect the natural phases of chronic HBV infection and predict the outcome of anti-HBV treatment. AREAS COVERED: The authors summarized the biomarkers of HBV replication and presented the current advances of these biomarkers on predicting the outcome of anti-HBV treatment and identifying the progression of chronic HBV infection. EXPERT OPINION: HBsAg, HBcrAg, HBV RNA, HBcAb, and HBV DNA are noninvasive and feasible biomarkers for monitoring the process of anti-HBV therapy and predicting the progress of HBV infection. However, there are still no strong biomarkers with high sensitivity and specificity for clinical application. Combination of two or more HBV biomarkers, new technique for measuring HBV cccDNA, and searching novel HBV biomarkers are essential for anti-HBV treatment in the future.
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Biomarcadores/sangue , Vírus da Hepatite B , Hepatite B Crônica/sangue , Replicação Viral , DNA Viral/sangue , Progressão da Doença , Hepatite B Crônica/diagnóstico , Hepatite B Crônica/tratamento farmacológico , HumanosRESUMO
Two novel cocrystals were successfully constructed by 1(2H)-Phthalazinone (PHT) and Tetrafluoroterephthalic acid (TETA) based on O-Hâ¯O, N-Hâ¯O, C-Hâ¯O, C-Hâ¯F, N-Hâ¯N and C-Hâ¯N hydrogen bonding networks, and were well depicted by single crystal diffraction analysis. As predicted by electrostatic potential analysis, the stoichiometry of PHT to TETA is 2:1 and stabilized by O-Hâ¯O and N-Hâ¯O hydrogen bonds. The single crystal X-ray diffraction characterized that the two cocrystals were all made up by 2PHT-TETA motif in different ways. AIM analysis and Hirshfeld surfaces indicated the adjacent 2PHT-TETA units assemble through C-Hâ¯O, C-Hâ¯F and C-Hâ¯N hydrogen bonds, producing a 2D plane structure in cocrystal I. Meanwhile, the C-Hâ¯F, N-Hâ¯N and C-Hâ¯O hydrogen bonds between 2PHT-TETA units were the stabilizing factors in cocrystal II. Topological parameters such as ∇2ρ and H revealed the strength of hydrogen bonds were moderate in nature except O31â¯H32-O34 (1.704Å, -60.336kJmol-1) in compound I. The hydrogen bonding interactions, cocrystal stability and electron donor-acceptor interactions were investigated using natural bonding orbital analysis. It showed that electron transfer of n(O) σ*(O-H) and n(O) σ*(N-H) between PHT and TETA influence the packing characteristics significantly. Structural changes accompanying cocrystal process have been rationalized through the IR spectrum along with the quantum chemical calculations. The frequency downshifts of CO, N-H and O-H stretching after cocrystallization have been attributed to hydrogen bonding interactions.
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In this work, two new enantiopure bis-monodentate N-donor chiral ligands, namely (-)/(+)-2-(4'-pyridyl)-4,5-pinene-pyridine (L R /L S ), have been designed and synthesized. Using L R and L S as bridging ligands to react with AgClO4, a pair of novel 2D chiral Ag(i) enantiomers formulated as [Ag2(L R )2(ClO4)2] n (R-1) and [Ag2(L S )2(ClO4)2] n (S-1) were isolated and characterized. In R-1 and S-1, each Ag(i) ion is bonded by two N atoms from two different chiral L R or L S ligands, leading to the formation of 1D right- or left-handed -L-Ag(i)-L- helical chains. Moreover, two adjacent helical chains are further doubly linked by two monodentate ClO4 - anions through weak Ag-O contacts to form 2D network structures, in which dual chiral elements, i.e., center chirality and helical chirality coexist. Interestingly, each free ligand L R /L S and R-1/S-1 enantiomers show very different ECD spectra in the solid state and in solution, which are correlated to the intermolecular interactions and molecular structures in each state, respectively. Notably, as a representative, R-1 exhibits intense room temperature photoluminescence both in the solid state and in solution with different emission features and mechanisms, while it also shows more intense emission than that of free ligand L R . In particular, R-1 and S-1 represent the first examples of 2D Ag(i) chiral coordination polymers (CCPs) supported by ClO4 - anions, possessing dual chiral elements.
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The capsaicin in hot peppers is an important biological active substance that is widely used in food and medicine. In this work, six capsaicin derivatives such as N-(4-Hydroxy-3-acetophenone benzyl)acrylamide (A), 2-hydroxy-3-(octyloxy)phenyl-5-acrylamidemethylbenzene phenyl methanone (B), N-(2,5-dihydroxybenzene)acetamide (C), N-(5-acetamidemethyl benzene-2,4-dihydroxybenzene)acetamide (D), 4-acetamideme thylbenzene-2-benzylphenol (E), and N-(2-methyl-4-hydroxy-5-methylthiobenzene)acetamide (F) were synthesized via the Friedel-Crafts (F-C) alkylation reaction and were characterized using IR, 1 H NMR, and HRMS. The antioxidant activity of compounds was evaluated using the reducing power and DPPH radical (DPPH·) scavenging assays, and Vitamin C (Vc) was used as a control. The antibacterial activity was tested using minimum inhibition concentration (MIC) and antibacterial rate assays, and Escherichia coli and Staphylococcus aureus were used as the tested strain. The results showed that all six capsaicin derivatives had certain antioxidant and antibacterial activities, and the activities increased with increasing mass concentration. The best properties were obtained for compounds C and F; the antioxidant activity of compound C was similar to Vc and the MIC of compound F was 0.0313 mg/ml, its antibacterial rate was greater than 99% at 3 mg/ml. PRACTICAL APPLICATIONS: As a vegetable, peppers can be eaten fresh or processed to other forms such as pepper powder or pepper jam, and it is very popular because of its long history, unique flavor, and special functions. Our current study shows that capsaicin derivatives have good antioxidant and antibacterial activities, and therefore, the present study of capsaicin derivatives with good activity provides a good foundation for future applications in natural food additives and medicine.
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Amidas/análise , Amidas/síntese química , Antibacterianos/farmacologia , Antioxidantes/farmacologia , Capsaicina/química , Escherichia coli/efeitos dos fármacos , Staphylococcus aureus/efeitos dos fármacos , Testes de Sensibilidade MicrobianaRESUMO
BACKGROUND AND AIMS: Hepatitis B virus-related decompensated cirrhosis is difficult to cure but has a high readmission rate due to multiple complications. Our aim was to investigate the diagnostic potential value of plasma diamine oxidase (DAO) for 6-month readmission of patients with HBV-related decompensated cirrhosis. METHODS: A total of 135 patients with HBV-related decompensated cirrhosis were prospectively collected at the onset of discharge of hospital, and then were followed up for at least 6 months with the readmission as the primary outcome. The plasma DAO level was measured using enzyme linked immunosorbent assay. In addition, 120 age and sex matched patients with HBV-related compensated cirrhosis were included as controls. RESULTS: A total of 36 patients (36.7%) with decompensated cirrhosis admitted to hospital during the 6-month follow up. The plasma DAO level of readmission group [21.1 (14.5; 29.0) ng/ml] was significantly higher than that in the non-readmission group [12.7 (9.3; 18.0) ng/mL, P < 0.001]. Multivariate analysis showed that the plasma DAO level (HR = 1.102, P < 0.05) and hepatic encephalopathy (HE) (HR = 5.018, P < 0.05) were independent factors for 6-month readmission of decompensated cirrhosis. DAO level showed higher area under the curve of receiver operating characteristic (AUROC) than HE (0.769 vs. 0.598, P < 0.05) and Child-Pugh-Turcotte (CPT) score (0.769 vs. 0.652, P < 0.05) for predicting 6-month readmission rate, with the best cut-off value as 19.7 ng/mL. Furthermore, plasma DAO level (HR = 1.184, P < 0.05) was an independent factor and has the higher AUROC than CPT score for the onset of recurrent HE (0.905 vs. 0.738, P < 0.05) during the 6-month follow up. CONCLUSIONS: Plasma DAO level > 19.7 ng/mL predicts high rate of 6-month readmission in patients with HBV-related decompensated cirrhosis.
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Amina Oxidase (contendo Cobre)/sangue , Hepatite B/complicações , Cirrose Hepática/sangue , Readmissão do Paciente , Adulto , Idoso , Feminino , Hepatite B/sangue , Vírus da Hepatite B , Humanos , Cirrose Hepática/complicações , Cirrose Hepática/virologia , Masculino , Pessoa de Meia-Idade , Estudos ProspectivosRESUMO
Cisplatin has been widely used as a conventional treatment for patients with nonsmall cell lung cancer (NSCLC). However, primary and acquired cisplatin resistances are frequently developed during the treatment of patients with NSCLC, leading to an increased mortality rate. Accumulating evidence demonstrated that aberrantly expressed microRNAs (miRs) are involved in the development of chemoresistance. In the present study, sensitivity of NSCLC cells to cisplatin was identified to increase following overexpression of miR608. Conversely, sensitivity to cisplatin was reduced following miR608 knockdown. Reverse transcriptionquantitative PCR and western blotting analyses identified that TEA domain transcription factor 2 (TEAD2), a key regulator of cell stemness, was negatively regulated by miR608 in NSCLC cells. By repressing TEAD2, miR608 decreased the expression level of several target genes of the Hippoyesassociated protein signaling pathway. Furthermore, TEAD2 mRNA was confirmed to be targeted by miR608 in NSCLC cells via a dualluciferase reporter assay. Importantly, the increased cisplatin sensitivity induced by miR608 overexpression was reversed by transfection of TEAD2 in NSCLC cells. The present data suggested that miR608 may represent a novel candidate biomarker for the evaluation of cisplatin sensitivity in patients with NSCLC.
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Biomarcadores Tumorais , Carcinoma Pulmonar de Células não Pequenas , Cisplatino/farmacologia , Proteínas de Ligação a DNA , Resistencia a Medicamentos Antineoplásicos , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Neoplasias Pulmonares , MicroRNAs , Proteínas de Neoplasias , RNA Neoplásico , Fatores de Transcrição , Células A549 , Biomarcadores Tumorais/biossíntese , Biomarcadores Tumorais/genética , Carcinoma Pulmonar de Células não Pequenas/tratamento farmacológico , Carcinoma Pulmonar de Células não Pequenas/genética , Carcinoma Pulmonar de Células não Pequenas/metabolismo , Carcinoma Pulmonar de Células não Pequenas/patologia , Proteínas de Ligação a DNA/biossíntese , Proteínas de Ligação a DNA/genética , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Resistencia a Medicamentos Antineoplásicos/genética , Humanos , Neoplasias Pulmonares/tratamento farmacológico , Neoplasias Pulmonares/genética , Neoplasias Pulmonares/metabolismo , Neoplasias Pulmonares/patologia , MicroRNAs/biossíntese , Proteínas de Neoplasias/biossíntese , Proteínas de Neoplasias/genética , RNA Neoplásico/biossíntese , RNA Neoplásico/genética , Fatores de Transcrição de Domínio TEA , Fatores de Transcrição/biossíntese , Fatores de Transcrição/genéticaRESUMO
Herein, two novel Evans-Showell-type polyoxometalate (POM)-based metal-organic complexes, namely, {[Cu(L)(H2O)3][Cu(L)0.5(H2O)][Cu(L)0.5(H2O)4][Co2Mo10H4O38]}·5H2O (1) and [(H2L)0.5]2{[Zn(L)0.5(H2O)4]2[Co2Mo10H4O38]}·2H2O (2) (L = N,N'-bis(3-pyridinecarboxamide)-piperazine), were hydrothermally synthesized using a semi-rigid bis-pyridyl-bis-amide ligand and structurally characterized via single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). The single-crystal X-ray diffraction analysis shows that complex 1 is a 3D Evans-Showell-type POM-based metal-organic network. In complex 1, the 1D infinite double chain structure constructed from {{Cu[Co2Mo10H4O38]}4-L} units and the µ4-bridging L ligand are linked by quadrate Cu2L2 loops to form a 2D layer, which is further connected by µ2-bridging L ligands, forming a 3D (2,3,4)-connected metal-organic framework. Complex 2 displays 3D supramolecular networks based on 1D {[Co2Mo10H4O38]-Zn-L}n infinite chains, which are constructed from Evans-Showell-type polyoxoanions and µ2-bridging 3-bpfp ligands (via ligation of pyridyl nitrogen atoms). The different coordination modes of the POM polyanions, bis(pyridylformyl)piperazine ligands and ratios play key roles in the construction of the title complexes. Significantly, the ligand L shows a µ4-bridging coordination mode in complex 1, which is observed for the first time in a POM system. Compounds 1 and 2 represent the first examples of metal-organic complexes based on Evans-Showell-type polyoxoanion and transition metal-bis-pyrazine-bis-amide coordination complexes. The fluorescence properties of the title complexes are reported herein. In addition, the title complexes act as heterogeneous Lewis acid catalysts for the oxidation of benzyl alcohol, and can also be recovered and reused without any significant loss in activity. Significantly, compound 1 with a 3D metal-organic framework showed higher catalytic performance with 99.4% conversion and 98.8% selectivity for benzoic acid at 10 h than compound 2 with 3D supramolecular networks.
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Two new Evans-Showell-type polyoxometalate (POM)-based metal-organic complexes, namely {Cu3(L1)1.5(H2O)5[Co2Mo10H4O38]}·5H2O (1), {[Cu(L2)0.5(H2O)2]2[Co2Mo10H4O38]}·6H2O (2) (L1 = N,N'-bis(2-pyrazinecarboxamide)-1,4-butane, L2 = N,N'-bis(2-pyrazinecarboxamide)-1,6-hexane), were successfully synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). In complex 1, the adjacent [Co2Mo10H4O38]6- polyoxoanions are linked by CuII ions to form a 1D Cu-[Co2Mo10H4O38]6- inorganic chain, which is further linked by ligand L1 and [Co2Mo10H4O38]6- polyoxoanions, forming a 3D metal-organic framework. In complex 2, the adjacent [Co2Mo10H4O38]6- polyoxoanions link the CuII ions to generate a 2D Cu-[Co2Mo10H4O38]6- inorganic layer, which is further connected with bidentate ligands L2 to obtain a 3D metal-organic framework. The structural diversities of compounds 1 and 2 showed that the spacer lengths of the flexible bis-pyrazine-bis-amide ligands play important roles in tuning the structures of the title complexes. Compounds 1 and 2 represent the first examples of 3D frameworks based on the Evans-Showell-type polyoxoanions and Cu-bis-pyrazine-bis-amide coordination complexes. Moreover, the ligand L1 was first successfully introduced into the POM system. The electrochemical and fluorescence properties of compounds 1 and 2 were discussed. As heterogeneous catalysts, compounds 1 and 2 have good catalytic activity for the oxidation of benzyl alcohol. Moreover, compound 2 has higher catalytic performance with 100% conversion and 98.0% selectivity for benzoic acid at 10 h. The difference in their catalytic performance may be mainly due to the difference of their structures. The catalysts can be recovered and reused without displaying any significant loss of activity.
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BACKGROUND: Acute-on-chronic hepatitis B liver failure (ACHBLF) has high 1-month mortality but it is difficult to predict. This present study was aimed to determine the diagnostic value of plasma diamine oxidase (DAO) in predicting the 1-month mortality of ACHBLF. METHODS: A total of 106 consecutive newly diagnosed ACHBLF patients were retrospectively collected. The plasma expression of DAO was determined using enzyme-linked immunosorbent assay (ELISA). RESULTS: The plasma DAO level of survivals [14.0 (7.1; 26.5) ng/mL] was significantly lower than the nonsurvivals [58.6 (32.5; 121.3) ng/mL, Pâ¯<â¯.001]. The plasma DAO level, hepatic encephalopathy, spontaneous bacterial peritonitis and model for end-stage liver disease (MELD) score were independent factors associated with the 1-month mortality for ACHBLF. The cut-off point of 15.2â¯ng/mL for plasma DAO level with sensitivity of 95.45%, specificity of 62.5%, 22.6 for MELD score with sensitivity of 90.91%, specificity of 67.5%, 0.07 for DAO plus MELD with sensitivity of 87.88%, specificity of 80% were selected to discriminate 1-month morality of ACHBLF. Furthermore, DAO plus MELD score showed high AUROC than MELD score for predicting 1-month (0.916 vs. 0.843, Pâ¯<â¯.01). CONCLUSIONS: The plasma DAO level plus MELDâ¯>â¯0.07 predicts poor 1-month mortality of ACHBLF.
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Insuficiência Hepática Crônica Agudizada/sangue , Insuficiência Hepática Crônica Agudizada/mortalidade , Amina Oxidase (contendo Cobre)/sangue , Biomarcadores/sangue , Insuficiência Hepática Crônica Agudizada/diagnóstico , Insuficiência Hepática Crônica Agudizada/metabolismo , Adulto , Amina Oxidase (contendo Cobre)/metabolismo , Biomarcadores/metabolismo , Feminino , Humanos , Testes de Função Hepática , Masculino , Pessoa de Meia-Idade , Valor Preditivo dos Testes , Análise de Sobrevida , Fatores de TempoRESUMO
We demonstrate herein the use of a one-dimensional metal-organic material as a new type of electrode material for lithium-ion batteries (LIBs) in place of the classic porous three-dimensional materials, which are subject to the size of the channel for lithium-ion diffusion and blocking of the windows of the framework by organic solvents during the charging and discharging processes. Introducing a one-dimensional coordination compound can keep organic active substances insoluble in the electrolyte during the charging and discharging processes, providing a facile and general new system for further studies. The results show that both the aromatic ligand and the metal center can participate in lithium storage simultaneously, illustrating a new energy storage mechanism that has been well-characterized by X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and cyclic voltammetry. In addition, the fact that the one-dimensional chains are linked by weak hydrogen bonds rather than strong π-π stacking interactions or covalent bonds is beneficial for the release of capacity entirely without the negative effect of burying the active sites.
RESUMO
OBJECTIVE: To investigate the effect of IL-10 and the methylation of its promoter in acute on chronic liver failure (ACLF). METHODS: Patients were divided into three groups: 25 with ACLF, 25 with CHB, 10 healthy controls. Respectively detect the serum level of IL-10 via ELISA, and the methylation of IL-10 promoter via MSP, to analyze the difference among the three groups. RESULTS: Both the ACLF group and the CHB group have significant increase in serum level of IL-10 compared with the control group (P < 0.05); the ACLF group's level is higher than the CHB group, however without statistical significance (P > 0.05). The serum level of IL-10 in ACLF group has no significant relativity with ALT and HBV-DNA( r = -0.022, r = 0.033, respectively; P > 0.05); has positive relativity with TBIL and MELD ( r = 0.566, r = 0.443, respectively; P < 0.05); and negative relativity with PTA (r = -0.581, P < 0.05). The distribution of the methylation of IL-10 promoter in ACLF group is significantly different from the other two. CONCLUSION: The serum level of IL-10 in hepatitis patients is significantly higher and increases with the degree of liver failure. The promoter methylation may be important in the gene inactivation.
Assuntos
Metilação de DNA , Interleucina-10/sangue , Interleucina-10/genética , Falência Hepática Aguda/metabolismo , Adolescente , Adulto , Doença Crônica , Feminino , Humanos , Interleucina-10/metabolismo , Falência Hepática Aguda/sangue , Falência Hepática Aguda/genética , Masculino , Metilação , Pessoa de Meia-Idade , Regiões Promotoras Genéticas , Adulto JovemRESUMO
Acute-on-chronic hepatitis B liver failure (ACHBLF) refers to liver failure occurring in patients with chronic hepatitis B (CHB) related liver diseases. Interferon-γ (IFN-γ) plays an important role in the exacerbation of liver function. However, the exact mechanism, by which IFN-γ mediates ACHBLF, is not fully understood. Forty patients with ACHBLF, fifteen patients with CHB and ten healthy controls were included in this present study. ELISA was performed to measure the level of serum IFN-γ. The methylation status of IFN-γ promoter in peripheral blood mononuclear cells (PBMCs) was determined using methylation-specific PCR. Model for End-stage Liver Disease (MELD) scoring was performed for evaluating the severity of liver failure. The serum level of IFN-γ in patients with ACHBLF or CHB was significantly lower than that in healthy controls, while the serum IFN-γ level in ACHBLF patients was significantly higher than that in CHB patients. In ACHBLF patients, the level of IFN-γ was positively correlated with total bilirubin and MELD score, but negatively correlated with prothrombin time activity. These results suggest the involvement of IFN-γ in the pathogenesis of ACHBLF. Importantly, the degree of methylation of the IFN-γ gene promoter in ACHBLF patients (60%, 24/40) was significantly lower than that in CHB patients (93%, 14/15), but was higher than that in the control group (20%, 2/10). Furthermore, in ACHBLF patients, the serum IFN-γ level was significantly higher in unmethylation group than that in methylation group. In conclusion, enhanced demethylation of IFN-γ gene promoter in PBMCs may be associated with the onset of ACHBLF.