Aerobic Oxidation of 5-Hydroxymethylfurfural via Hydrogen Bonds Reconstruction with Ternary Deep Eutectic Solvents.

Hydrogen bonding effect exists widely in various chemical and biochemical systems, primarily stabilizing the molecular structure as a positive factor. However, the presence of intermolecular hydrogen bonds among biomass molecules results in a formidable challenge for the efficient utilization of biomass resources. Here in, a novel strategy of "hydrogen bonds reconstruction" was developed by a series of ternary deep eutectic solvent (DESs) as molecular scissors, which disrupting the initial intermolecular hydrogen bonds and reconstructing the new ones to increase the reactivity of the biomass-based compound. The DESs played a crucial role in enhancing the reactivity of 5-hydroxymethylfurfural (HMF) and promoting its oxidation through reconstructing the hydrogen bonds interactions. Furthermore, DESs was also found to activate the Anderson-type catalyst Na5IMo6O24 (IMo6) through an electron-transfer mechanism, which facilitated the generation of oxygen vacancies and significantly enhances its ability to activate molecular oxygen. With this novel catalytic system, oxidation of HMF exhibited remarkable efficiency as HMF was almost entirely converted into FFCA with an impressive yield of 98 % under the optimized conditions. This finding offers novel insights into the utilization of biomass resources and endows the solvent with new functions in the chemical reaction.

Insertion of a totally implantable vascular access device in a patient with dextrocardia and colon cancer: a case report.

Colon cancer in patients with situs inversus totalis is rarely associated with dextrocardia, and chemotherapy is commonly used for treatment. Central venous access devices are used to administer intravenous fluids and chemotherapy in patients with colon cancer. Compared with peripherally inserted central catheters and Hickman-type tunneled catheters, totally implantable vascular access devices (TIVADs) are safer and more effective. However, positioning the catheter tip may be challenging in patients with dextrocardia and situs inversus. We herein describe a novel case involving a patient with dextrocardia and colon cancer who was treated by TIVAD insertion with intracavitary electrocardiography-aided tip localization.

Application of Microscopic Highly Hydrophilic Silica-Based Nanocomposites with High Surface Exposure in the Efficient Identification of Intact N-Glycopeptides.

Glycosylation of proteins regulates the life activities of organisms, while abnormalities of glycosylation sites and glycan structures occur in various serious diseases such as cancer. A separation and enrichment procedure is necessary to realize the analysis of the glycoproteins/peptides by mass spectrometry, for which the surface hydrophilicity of the material is an important factor for the separation and enrichment performance. In the present work, under the premise of an obvious increase of the surface silicon exposure (79.6%), the amount of surface polar silanol is remarkably generated accompanying the introduction of the active amino groups on the surface of silica. The microscopic hydrophilicity, which is determined with water physical-adsorption measurements and can directly reflect the interaction of water molecules and the intrinsic surface of the material, maximally increases by 44%. This microscopically highly hydrophilic material shows excellent enrichment ability for glycopeptides, such as extremely low detection limits (0.01 fmol µL-1), remarkable selectivity (1:8000), and size exclusion effects (1:8000). A total of 677 quantifiable intact N-glycopeptides were identified from the serum of patients with cervical cancer, and the glycosylation site and glycan structure were analyzed in depth, indicating that this novel material can show a broad practical application in cervical cancer diagnosis.

Zeolitic imidazolate framework-L loaded on melamine foam for removal tetracycline hydrochloride from water.

Zeolitic imidazolate framework-L/melamine foam (ZIF-L/MF) is fabricated by an in situ growth method to treat the tetracycline hydrochloride in wastewater. The results show that a large amount of leaf-like ZIF-L is vertically grown on the MF surface. ZIF-L/MF exhibits well adsorption performance with a maximum adsorption ability of 1346 mg/g. The pseudo-second-order kinetic model and the Langmuir isotherm model are used to describe the adsorption process well. In addition, the influences of pH and coexisting ions are studied. According to the experimental data and analysis, the adsorption mechanisms may involve H-bonding, π-π interaction, and weak electrostatic interaction. A dynamic adsorption experiment is also performed, and the results show that the time required to achieve the same removal efficiency as static adsorption is reduced by half. This work shows that the obtained ZIF-L/MF has practical applications in antibiotic adsorption.

Characteristics and postoperative dynamic changes in circulating CD4+ helper T lymphocytes in patients with breast cancer.

Introduction: Circulating CD4+ helper T cell (Th) subsets provide potentially important information on disease progression in several cancers. In this study, we explored the characteristics and postoperative dynamic changes in circulating CD4+Th subsets in patients with breast cancer. Methods: Circulating CD4+Th subsets, including CD4+ naive T cells (Tn), CD4+ central memory T cells (Tcm), CD4+ effector memory T cells (Tem), CD4+CD57+T, and CD4+PD-1+T, were detected with multiparameter flow cytometry. T-test and Wilcoxon rank-sum test were used to compare differences between groups for normally and non-normally distributed continuous variables, respectively. Postoperative dynamic changes in CD4+Th subsets were assessed using the paired-sample rank-sum test. Results: Seventy-five patients with invasive breast cancer and fifty-three patients with benign breast tumors were enrolled. Compared with that in patients with benign tumors, the proportion of CD4+Tn in patients with breast cancer patients decreased, whereas the proportion and absolute number of CD4+CD57+T and CD4+PD-1+T increased. Moreover, the proportion of CD4+PD-1+T was correlated with the clinicopathology of breast cancer. After tumor resection, the proportion and absolute number of CD4+Tcm significantly decreased, while those of CD4+Tem significantly increased, compared with preoperative values. Tumor resection caused significant changes in the proportion and absolute number of CD4+CD57+T and CD4+PD-1+ T, both of which showed significant decreases. Discussion: We found significant changes in circulating CD4+Th subsets in patients with breast cancer. Additionally, complete tumor resection can benefit the patient as it balances the patient's immunosuppression and immune stress and improves the immune exhaustion and immunosenescence states.

Development and validation of a prediction model for in-hospital mortality of patients with severe thrombocytopenia.

Risk stratification and prognosis evaluation of severe thrombocytopenia are essential for clinical treatment and management. Currently, there is currently no reliable predictive model to identify patients at high risk of severe thrombocytopenia. This study aimed to develop and validate a prognostic nomogram model to predict in-hospital mortality in patients with severe thrombocytopenia in the intensive care unit. Patients diagnosed with severe thrombocytopenia (N = 1561) in the Medical Information Mart for Intensive Care IV database were randomly divided into training (70%) and validation (30%) cohorts. In the training cohort, univariate and multivariate logistic regression analyses with positive stepwise selection were performed to screen the candidate variables, and variables with p < 0.05 were included in the nomogram model. The nomogram model was compared with traditional severity assessment tools and included the following 13 variables: age, cerebrovascular disease, malignant cancer, oxygen saturation, heart rate, mean arterial pressure, respiration rate, mechanical ventilation, vasopressor, continuous renal replacement therapy, prothrombin time, partial thromboplastin time, and blood urea nitrogen. The nomogram was well-calibrated. According to the area under the receiver operating characteristics, reclassification improvement, and integrated discrimination improvement, the nomogram model performed better than the traditional sequential organ failure assessment (SOFA) score and simplified acute physiology score II (SAPS II). Additionally, according to decision curve analysis, a threshold probability between 0.1 and 0.75 indicated that our constructed nomogram model showed more net benefits than the SOFA score and SAPS II. The nomogram model we established showed superior predictive performance and can assist in the quantitative assessment of the prognostic risk in patients with severe thrombocytopenia.

Graphene functionalized with structurally complementary amino acids for sensitive recognition of N-linked glycopeptides.

Herein, a hydrophilic graphene composite functionalized with glutathione (GSH) and L(+)-Cysteine (Cys) was prepared via a simple and fast synthesis route, which was named G@S@Au@GC. The combination attack with two different zwitterionic polymers resulted in enhanced adsorption sites for glycopeptides. The obtained G@S@Au@GC exhibited excellent performance on a low limit of detection (0.2 fmol), a high selectivity (HRP: bovine serum albumin = 1:1500), a good load capacity (250 µg•mg-1) and recovery rate (93%), which was also evaluated with IgG. Subsequently, 60 glycopeptides from complex biological sample (human saliva) were identified by Nano-LC-MS/MS. The advantages of combination attack, low-cost, simple and fast synthesis, and superior enrichment performance make G@S@Au@GC composite a bright future on glycoproteomics analysis and related diseases.

Association between lactate/albumin ratio and all-cause mortality in patients with acute respiratory failure: A retrospective analysis.

Previous studies have shown that lactate/albumin ratio (LAR) can be used as a prognostic biomarker to independently predict the mortality of sepsis and severe heart failure. However, the role of LAR as an independent prognostic factor in all-cause mortality in patients with acute respiratory failure (ARF) remains to be clarified. Therefore, we retrospectively analyzed 2170 patients with ARF in Medical Information Mart for Intensive Care Database III from 2001 to 2012. By drawing the receiver operating characteristic curve, LAR shows a better predictive value in predicting the 30-day mortality of ARF patients (AUC: 0.646), which is higher than that of albumin (AUC: 0.631) or lactate (AUC: 0.616) alone, and even higher than SOFA score(AUC: 0.642). COX regression analysis and Kaplan-Meier curve objectively and intuitively show that high LAR is a risk factor for patients with ARF, which is positively correlated with all-cause mortality. As an easy-to-obtain and objective biomarker, LAR deserves further verification by multi-center prospective studies.

Blood glucose-related indicators are associated with in-hospital mortality in critically ill patients with acute pancreatitis.

Acute pancreatitis (AP) results in potentially harmful blood glucose fluctuations, affecting patient prognosis. This study aimed to explore the relationship between blood glucose-related indicators and in-hospital mortality in critically ill patients with AP. We extracted data on AP patients from the Multiparameter Intelligent Monitoring in Intensive Care III database. Initial glucose (Glucose_initial), maximum glucose (Glucose_max), minimum glucose (Glucose_min), mean glucose (Glucose_mean), and glucose variability (glucose standard deviation [Glucose_SD] and glucose coefficient of variation [Glucose_CV]) were selected as blood glucose-related indicators. Logistic regression models and the Lowess smoothing curves were used to display the association between significant blood glucose-related indicators and in-hospital mortality. Survivors and non-survivors showed significant differences in Glucose_max, Glucose_mean, Glucose_SD, and Glucose_CV (P < 0.05). Glucose_max, Glucose_mean, Glucose_SD, and Glucose_CV were risk factors for in-hospital mortality in AP patients (OR > 1; P < 0.05). According to the Lowess smoothing curve, the overall trends of blood glucose-related indicators showed a non-linear correlation with in-hospital mortality. Glucose_max, Glucose_mean, Glucose_SD, and Glucose_CV were associated with in-hospital mortality in critically ill patients with AP.

CD4+ Memory Stem T Cell in Peripheral Blood: A Promising Immune Index for Early Screening and Auxiliary Diagnosis of Colorectal Cancer.

BACKGROUND AND AIMS: Colorectal cancer (CRC) lacks obvious symptoms in the early stage of the disease, making it is easy to be misdiagnosed and remain undetected. Here, we explored the role of CD4+ memory stem T cells (TSCM) in peripheral blood in the early screening and auxiliary diagnosis of CRC. MATERIALS AND METHODS: Patients diagnosed with a "colorectal mass" by colonoscopy, at the Dongyang People's Hospital (Zhejiang, China), between November 2020 and June 2021, were included in this prospective study. Using histopathological results as the gold standard for diagnosis, patients were divided into "CRC group" and "benign tumor group". Healthy volunteers were recruited as "healthy controls." Ten-color flow cytometry was used to detect CD4+ T cell subsets, and the results were analyzed using the Kaluza software. Carcinoembryonic antigen (CEA) and carbohydrate antigen 199 (CA199) were detected by the Roche Cobas e 602 electrochemiluminescence immunoassay analyzer. RESULTS: This study involved 33 patients with CRC, 41 patients with colorectal benign tumors, and 49 healthy volunteers. The absolute value and frequency of CD4+ TSCM can clearly distinguish colorectal cancer, benign tumors, and healthy controls. According to the area under the receiver operating characteristic curve (AUC), the absolute value of CD4+ TSCM used to assist in the diagnosis of CRC was 0.758 (sensitivity: 0.612; specificity: 0.788), which is higher than the values for CEA (AUC: 0.707) and CA199 (AUC: 0.552). In early screening, the sensitivity of the absolute value of CD4+ TSCM (sensitivity: 0.612) was significantly higher than that of CEA (sensitivity: 0.333) and CA199 (sensitivity: 0.259). CONCLUSION: CD4+ TSCM in peripheral blood may be a promising immune index for the early screening and auxiliary diagnosis of CRC.

Value of preoperative staging of endometrial carcinoma with contrast-enhanced ultrasonography: A PRISMA compliant meta-analysis.

INTRODUCTION: Endometrial carcinoma (EC) is the most common gynecologic carcinoma in developed countries and accounts for nearly 5% of carcinoma cases and more than 2% of deaths due to female carcinomas worldwide. Because of this reported risk, it is very important to diagnose and stage it accurately. Therefore, we investigated the staging accuracy of EC with contrast-enhanced ultrasonography (CEUS). Due to a lack of studies on the use of CEUS in staging EC, we performed a systematic review and meta-analysis. METHOD: We searched PubMed, EMBASE, Cochrane Library, Scopus, Web of science, China National Knowledge Infrastructure (CNKI), and CBM for studies on CEUS in EC diagnosis. Our search keywords were "ultrasonic angiography," "endometrial neoplasms," and their synonyms. The studies were screened according to the inclusion and exclusion criteria, and 4 tabular data were extracted. Quality evaluation was performed with the Quality Assessment of Diagnostic Accuracy Studies (QUADAS) scale. Statistical analysis was done with Stata version 15.1. A random effect model was selected to calculate the pooled sensitivity and specificity. The summary receiver operating characteristic (SROC) curve was obtained, and the area under the curve was calculated. RESULT: Fifteen studies with 685 patients were included in this quantitative synthesis. The pooled sensitivity, specificity, positive likelihood ratio, negative likelihood ratio, and diagnostic odds ratio (OR) of CEUS in the diagnosis of EC was 0.81 (95% confidence interval, .76-.85), .90 (.87-.92), 8 (5.8-11.1), .21 (.16-.28), and 38 (22-67), respectively. The area under the curve was 0.93 (.90-.95). CONCLUSION: CEUS has a high sensitivity and specificity in the diagnosis of EC. It can be considered as an effective and feasible method for EC staging.

NCEH1 may be a prognostic biomarker for pancreatic cancer.

Neutral Cholesterol Ester Hydrolase 1 (NCEH1) is an enzyme involved in ether lipid metabolism, and the NCEH1 gene is overexpressed in a variety of tumors. However, its role in pancreatic cancer remains unknown. Therefore, we compared the gene transcription data of healthy and pancreatic cancer tissues using the Cancer Genome Atlas and Genotype-Tissue Expression databases. R software (v3.6.1) was used for the differential, clinicopathological correlation, and survival analyses. We found that NCEH1 was overexpressed in pancreatic cancer tissues compared with that in healthy tissues (P = 1.732 e-50), and that its expression level was related to lymph node metastasis. High NCEH1 expression was associated with poor overall survival (P = 0.002). Using univariate and multivariate Cox regression analyses, we determined that NCEH1 is an independent risk factor for pancreatic cancer. Gene set enrichment analysis identified that NCEH1 overexpression is prominent in cell-cell adhesion junctions, pancreatic cancer, cancer-associated pathways, prostate cancer, and chronic myeloid leukemia. In contrast, low NCEH1 expression correlated to high oxidative phosphorylation. Thus, we conclude that NCEH1 may be a prognostic biomarker for pancreatic cancer.

The association of D-dimer with clinicopathological features of breast cancer and its usefulness in differential diagnosis: A systematic review and meta-analysis.

BACKGROUND: Studies have shown that D-dimer levels are significantly correlated with the differential diagnosis and clinicopathological features of breast cancer. However, the results are currently limited and controversial. Therefore, we performed this meta-analysis to evaluate the relationship between D-dimer levels and breast cancer. MATERIALS AND METHODS: The PubMed, Embase, Cochrane Library, China National Knowledge Infrastructure, Chinese Biomedical Literature, and Wanfang databases were searched to find studies that assessed the association of D-dimer with clinicopathological features of breast cancer and its usefulness in aiding with differential diagnosis. The standardized mean difference (SMD) was applied as the correlation measure. RESULTS: A total of 1244 patients with breast cancer from 15 eligible studies were included in the meta-analysis. D-dimer levels were higher in the breast cancer group than in the benign (SMD = 1.02; 95% confidence interval [CI] = 0.53-1.52) and healthy (SMD = 1.27; 95% CI = 0.85-1.68) control groups. In addition, elevated D-dimer levels were associated with progesterone receptor-negative tumors (SMD = -0.25; 95% CI = -0.44--0.05). Similarly, there was a significant correlation between D-dimer levels and tumor node metastasis staging (n = 11, SMD = 0.82; 95% CI = 0.57-1.06) and lymph node involvement (n = 8, SMD = 0.79; 95% CI = 0.50-1.09). In contrast, other clinicopathological factors, including estrogen receptor expression and human epidermal growth factor receptor 2 expression, were not associated with D-dimer levels. CONCLUSION: The results of this meta-analysis indicate that plasma D-dimer levels can be used as an important reference for the early identification and staging of breast cancer.

Why Can Normal Palladium Catalysts Efficiently Mediate Aerobic C-H Hydroxylation of Arylpyridines by Intercepting Aldehyde Autoxidation? A Nascent Palladium(III)-Peracid Intermediate Makes a Difference.

The direct C(sp2)-H hydroxylation of 2-arylpyridines catalyzed by normal palladium catalysts via interception of aldehyde autoxidation possesses a number of advantages, including convenient operating conditions, nontoxic and inexpensive aldehydes, and being economical in terms of steps and atoms. In this paper, we report a computational study of the mechanism of this catalytic process using density functional theory, revealing a novel catalytic cycle. We find that the rate-limiting step is C-H bond activation that occurs via a concerted metalation deprotonation mechanism, which is consistent with Guin's experimental kinetic isotope effect observations. The byproduct of the C-H bond activation, Brønsted acid HCl, promotes formation of a hexacoordinated Pd(III)-peracid intermediate. It provides a reservoir for the robust high-valent Pd(IV)-OH species via an easy O-O homolysis. The pathway that does not involve HCl is also energetically feasible but albeit less probable. Furthermore, the involvement of another radical OOH•, besides the acylperoxo radical nPrOO•, is needed to recover the tetracoordinated Pd(II) catalyst during the catalytic cycle. Our computational work sheds lights on the elusive oxygenation involving a radical that is mediated by palladium catalysts and will play a positive role in the further design of a rational reaction strategy and new catalysts.

Efficient catalytic oxidation of methyl aromatic hydrocarbon with N-alkyl pyridinium salts.

A series of N-alkyl pyridinium salts were synthesized and employed as metal-free catalyst for the selective oxidation of methyl aromatic hydrocarbon with molecular oxygen. The electronic effect of the substitutes was found to be an important factor for the catalytic performance. With the introduction of electron-donating substitute -N(CH3)2, the conversion of p-xylene and selectivity of p-toluic acid could be simultaneously increased. 1-Benzyl-4-N,N-dimethylaminopyridinium salt showed the highest catalytic activity, and 95% conversion with 84% of selectivity to p-toluic acid could be obtained for the selective oxidation of p-xylene. Several methyl aromatic hydrocarbons could all be efficiently oxidized with the reported catalyst at the absence of any metal species.

[Mutation analysis of a FGG gene causing hereditary abnormal fibrinogen].

OBJECTIVE: To study the clinical phenotype and gene mutation analysis of a hereditary abnormal fibrinogenemia family and explore its molecular pathogenesis. METHODS: The STA-R automatic hemagglutination analyzer to detect the proband and its family members (3 generations of 5 people) of prothrombin time(PT), activated partial thromboplastin time (APTT), thrombin time (TT), fibrinogen activity (Fg: C), D-dimer (D-D), fibrinogen and fibrin degradation products (FDPs), plasminogen activity (PLG: A); The plasma levels of Fg: C and fibrinogen (Fg: Ag) were measured by Clauss method and immunoturbidimetry respectively. All exons and flanking sequences of FGA, FGB and FGG genes of fibrinogen were amplified by PCR, and the PCR products were purified and sequenced for gene analysis. The model was analyzed by Swiss software. RESULTS: The PT and APTT of the proband, her mother and sister were slightly prolonged, TT was significantly extend, Fg: C decreased significantly, Fg: Ag, PLG: A, D-D and FDPs are within the normal range; Her brother and daughter of the results are normal. Genetic analysis showed that g.7476 G>A heterozygous missense mutation in exon 8 of FGG gene resulted in mutations in arginine at position 275 of fibrinogen gamma D domain to histidine (Arg275His). Her mother and sister have the same Arg275His heterozygous mutation, brother and daughter for the normal wild type. CONCLUSION: The heterozygous missense mutation of FGG gene Arg275His in patients with hereditary dysfibrinogenemia is associated with a decrease in plasma fibrinogen activity.

N-Bromosuccinimide as an oxidant for the transition-metal-free synthesis of 2-aminobenzoxazoles from benzoxazoles and secondary amines.

A facile and transition-metal-free method was developed through merging the ring opening of benzoxazoles with secondary amines and N-bromosuccinimide (NBS) mediated oxidative cyclization toward the synthesis of 2-aminobenzoxazoles. NBS was selected as a powerful oxidant in the oxidative cyclization of ring-opening amidines to provide the desirable 2-aminobenzoxazoles in excellent yields (up to 94%).

Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation.

Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions.

[Diagnostic value of serum angiopoietin-2 level in pancreatic cancer].

OBJECTIVE: To evaluate the diagnostic value of serum angiopoietin-2 (Ang-2) level in pancreatic cancer patients. METHODS: Serum Ang-2 level was measured by enzyme-linked immunosorbent assays (ELISA) in samples from 116 patients with pancreatic cancer, 50 patients with chronic pancreatitis, and 50 normal control subjects. RESULTS: The serum Ang-2 level in patients with pancreatic cancer [(1539.0 ± 449.3) ng/L] was significantly higher than those in patients with pancreatitis [(1044.6 ± 246.1) ng/L, P < 0.01] and normal control subjects [(1075.6 ± 228.2) ng/L, P < 0.01]. There was no significant difference of serum Ang-2 levels between patients with pancreatitis and normal controls. Pancreatic caner patients with lymph node metastasis had a significantly higher serum Ang-2 level [(1890.1 ± 354.9) ng/L] than those without metastasis [(1212.1 ± 224.2) ng/L, P < 0.01]. The area under ROC curve of serum Ang-2 level for diagnosis of pancreatic cancer was 0.819. CONCLUSION: The serum Ang-2 level can be a useful indicator for diagnosis of pancreatic cancer.

Superhydrophobic materials as efficient catalysts for hydrocarbon selective oxidation.

A new type of superhydrophobic material, FP-Co-SiO(2) was prepared with organic groups immobilized on the surface of the SiO(2)-based nanocomposite. This material showed much higher catalytic activity for selective oxidation of hydrocarbons than an equivalent hydrophilic catalyst.