FePO4 supported Rh subnano clusters with dual active sites for efficient hydrogenation of quinoline under mild conditions.

Chemoselective hydrogenation of quinoline and its derivatives under mild reaction conditions still remains a challenging topic, which requires a suitable interaction between reactants and a catalyst to achieve high performance and stability. Herein, FePO4-supported Rh single atoms, subnano clusters and nanoparticle catalysts were synthesized and evaluated in the chemoselective hydrogenation of quinoline. The results show that the Rh subnano cluster catalyst with a size of ∼1 nm gives a specific reaction rate of 353 molquinoline molRh-1 h-1 and a selectivity of >99% for 1,2,3,4-tetrahydroquinoline under mild conditions of 50 °C and 5 bar H2, presenting better performance compared with the Rh single atoms and nanoparticle counterparts. Moreover, the Rh subnano cluster catalyst exhibits good stability and substrate universality for the hydrogenation of various functionalized quinolines. A series of characterization studies demonstrate that the acidic properties of the FePO4 support favors the adsorption of quinoline while the Rh subnano clusters promote the dissociation of H2 molecules, and then contribute to the enhanced hydrogenation performance. This work provides an important implication to design efficient Rh-based catalysts for chemoselective hydrogenation under mild conditions.

In Situ Transformation of ZIF-8 into Porous Overlayer on Ru/ZnO for Enhanced Hydrogenation Catalysis.

Supported metal catalysts play a significant role in heterogeneous catalysis in liquid phase reaction systems, but they usually suffer from a stability problem. Encapsulation of active metal species without the compromise of catalytic performance has been considered as an effective strategy. Here, we report an ultrastable Ru-based catalyst with particle size of around 1.1 nm for selective hydrogenation reaction. The highly dispersed Ru species are covered by the in situ formed porous N-C-ZnO overlayer, which is induced through the transforming of ZIF-8 shell that derives from a ZnO substrate. The resulting Ru/ZnO@N-C-ZnO catalyst can exhibit good stability in the hydrogenation of p-chloronitrobenzene after 20 cyclic runs with 100% selectivity toward p-chloroaniline. Comparatively, the naked Ru/ZnO catalyst with larger Ru particles shows serious metal leaching issue with inferior stability and poor selectivity. It is revealed that the excellent performance of Ru/ZnO@N-C-ZnO is attributed to the porous overlayer, which strengthens the bonding of Ru nanoparticles on ZnO.

Correlation between tumor markers and type 2 diabetes mellitus complications and their related influencing factors.

BACKGROUND: This study aims to investigate the correlation between type 2 diabetes mellitus (T2DM) and the tumor markers/biochemical parameters of patients, as well as the related factors leading to complications. METHODS: A total of 150 T2DM patients in our hospital were included as the research group, and 80 healthy persons were matched in the normal control group. The levels of tumor markers (CA199, CEA, CA153, CA125, AFP) and body mass index (BMI), waist-to-hip ratio (WHR), blood pressure (BP), fasting plasma glucose (FPG), glycosylated hemoglobin (HbA1c), urine microalbumin (M-ALB), and triglyceride (TG) in the two groups were determined. Based on the complications status of T2DM patients, the patients were further divided into a complication-free group (patients with simple diabetes) and complication group. Univariate analysis was performed between patients with and without complications. RESULTS: The levels of serum CA199, CEA, and CA125 in the study group were significantly higher than those in the normal control group (all P<0.0001), and the levels of BMI, WHR, systolic BP (SBP), diastolic BP (DBP), FPG, HbA1c, M-ALB, and TG in the study group were significantly higher than those in the control group (all P<0.05). Tumor markers CA199, CEA, and CA125 were positively correlated with BMI, WHR, BP, FPG, HbA1c, M-ALB, and TG. Smoking, family history of diabetes, combined hypertension, hyperlipemia, course of disease, CA199, CEA, CA153, CA125, AFP, SBP, DBP, FPG, HbA1c, M-ALB, and TG were the influencing factors of complications in T2DM patients. CONCLUSIONS: Relevant indicators of T2DM patients with complications should be fully evaluated clinically, and long-term follow-up observation should be conducted, so as to reduce the occurrence of complications.

Scutellarin alleviates type 2 diabetes (HFD/low dose STZ)-induced cardiac injury through modulation of oxidative stress, inflammation, apoptosis and fibrosis in mice.

BACKGROUND: Diabetes is a serious global health concern which severely affected public health as well as socio-economic growth worldwide. Scutellarin (SCU), a bioactive flavonoid, is known for its efficacious action against a range of ailments including cardiovascular problems. The present study was conducted to find out possible protective effect and its associated mechanisms of SCU on experimental type 2 diabetes-induced cardiac injury. METHODS: Type 2 diabetes was induced by treating animals with high fat diet for 4 weeks and a single intraperitoneal dose (35 mg/kg body weight) of streptozotocin and diabetic animals received SCU (10 or 20 mg/kg/day) for 6 weeks. RESULTS: Scutellarin attenuated type 2 diabetes-induced hyperglycemia, bodyweight loss, hyperlipidaemia, cardiac functional damage with histopathological alterations and fibrosis. Scutellarin treatment to type 2 diabetic mice ameliorated oxidative stress, inflammatory status and apoptosis in heart. Furthermore, the underlying mechanisms for such mitigation of oxidative stress, inflammation and apoptosis in heart involved modulation of Nrf2/Keap1 pathway, TLR4/MyD88/NF-κB mediated inflammatory pathway and intrinsic (mitochondrial) apoptosis pathway, respectively. CONCLUSIONS: The current findings suggest that SCU is effective in protecting type 2 diabetes-induced cardiac injury by attenuating oxidative stress and inflammatory responses and apoptosis, and it is also worth considering the efficacious potential of SCU to treat diabetic cardiomyopathy patients.

Predictive and prognostic role of tumour-infiltrating lymphocytes in breast cancer patients with different molecular subtypes: a meta-analysis.

BACKGROUND: Whether tumour-infiltrating lymphocytes (TILs) play different roles in different molecular subtypes of breast cancer remains unknown. Additionally, their prognostic and predictive value in different molecular subtypes of breast cancer is still controversial. The aim of our meta-analysis was to assess the prognostic and predictive value of TILs in different molecular subtypes of breast cancer by summarizing all relevant studies performing multivariate analysis. METHODS: PubMed, Embase, EBSCO, ScienceDirect, the Cochrane Database and Web of Science were comprehensively searched (until March 2020). Hazard ratios (HRs), odds ratios (ORs) and their 95% confidence intervals (CIs) were used as effect measures to perform our meta-analysis. A random effect model was used. Stata software, version 15 (2017) (StataCorp, College Station, TX, USA) was used to perform the statistical analysis. RESULTS: Thirty-three studies including 18,170 eligible breast cancer patients were analysed. The meta-analysis showed that high TIL expression was significantly associated with increased pathological complete response (pCR) rates after neoadjuvant chemotherapy in patients with the HER2-enriched molecular subtype (OR = 1.137, 95% CI [1.061 ~ 1.218], p < 0.001) and triple-negative breast cancer (TNBC) subtype (OR = 1.120, 95% CI [1.061 ~ 1.182], p < 0.001). However, high TIL expression was not significantly associated with high pCR rates after neoadjuvant chemotherapy in patients with the luminal molecular subtype of breast cancer (OR = 1.154, 95% CI [0.789 ~ 1.690], p = 0.460). We carried out a meta-analysis on the HRs of overall survival (OS) and disease-free survival (DFS) to assess the prognostic value of TILs in breast cancer with different molecular subtypes more deeply. Our meta-analysis confirmed that high TILs were associated with significantly improved DFS in patients with the HER2-enriched molecular subtype [HR = 0.940, 95% CI (0.903 ~ 0.979), p = 0.003] and TNBC molecular subtype [HR = 0.907, 95% CI (0.862 ~ 0.954), p < 0.001]. However, high TILs were not associated with significantly better DFS in patients with the luminal molecular subtype of breast cancer [HR = 0.998, 95% CI (0.977 ~ 1.019), p = 0.840]. Furthermore, the results confirmed that high TILs were significantly related to better OS in patients with the HER2-enriched molecular subtype [HR = 0.910, 95% CI (0.866 ~ 0.957), p < 0.001] and TNBC molecular subtype [HR = 0.869, 95% CI (0.836 ~ 0.904), p < 0.001]. Conversely, the summarized results indicated that high TILs were significantly associated with poor OS in patients with the luminal molecular subtype of breast cancer [HR = 1.077, 95% CI (1.016 ~ 1.141), p = 0.012]. CONCLUSIONS: Our meta-analysis confirms that high TILs are associated with favourable survival and predicts pCR in breast cancer patients with the TNBC and HER2-enriched molecular subtypes.

Enhancing the stability of the Rh/ZnO catalyst by the growth of ZIF-8 for the hydroformylation of higher olefins.

Hydroformylation of olefins is one of the most important industrial processes for aldehyde production. Therein, the leaching of active metals for heterogeneous catalysts is an important issue in the hydroformylation reaction, particularly for higher olefins to produce higher alcohols. Here, different Rh/ZnO catalysts with diverse ZnO as a support were investigated and a home-made ZnO50 support was selected to prepare the Rh/ZnO50@ZIF-8 core-shell structure catalyst, which was synthesized by the growth of ZIF-8 with ZnO50 as the sacrificed template to afford Zn source. Compared with the Rh/ZnO50 catalyst, the Rh/ZnO50@ZIF-8 catalyst demonstrated a better cyclic stability in the hydroformylation of 1-dodecene. Combining the experiment and characterization results, it was concluded that the ZIF-8 shell on the Rh/ZnO50 catalyst effectively prevented the leaching of metal Rh into the reaction solution. Moreover, the Rh/ZnO50@ZIF-8 catalyst exhibited good universality for other higher olefins. This work provides a useful guideline for immobilizing the active species in heterogeneous catalysts for the hydroformylation reaction.

Effects of a diet with or without physical activity on angiopoietin-like protein 8 concentrations in overweight/obese patients with newly diagnosed type 2 diabetes: a randomized controlled trial.

Angiopoietin-like protein 8 (ANGPTL8) is a newly discovered adipokine plays an important role in energy homoeostasis, obesity and type 2 diabetes (T2D). Although lifestyle modification in obesity and T2D is known to offer metabolic benefits, there is paucity of comprehensive data on change in ANGPTL8. We investigated the effect of lifestyle intervention on ANGPTL8 concentrations. 384 obese/overweight adults with newly diagnosed T2D were randomly assigned (1:1:1) to diet (n = 128), diet + activity (n = 128) or usual care (control, n = 128) groups. All patients received usual care. Besides, the diet group received a calorie-restricted diet aiming for a weight loss of 5-10%. The diet + activity group additionally received a pedometer-based walking program. Primary outcome was change in ANGPTL8 concentration at 6 months. Data were analyzed according to intention-to-treat. From baseline to 6 months, the median ANGPTL8 level changed from 804.38 pg/mL to 792.86 pg/mL in control group. Compared with control, ANGPTL8 decreased with diet (baseline-adjusted between-group difference was -121.00 pg/mL, 95% CI -177.47 to -64.53; p < 0.0001) and diet + activity (-126.16 pg/mL, -181.21 to -71.11; p < 0.0001). There was no greater effect of diet + activity compared with diet (-5.16 pg/mL, -53.63 to 43.31; p = 0.8348). Both effects disappeared after adjusting for change in body fat, but did not differ significantly when adjusting for physical activity. A 6-month intervention inducing weight loss by a calorie-restricted diet or diet + activity, resulted in significant decrease on ANGPTL8 concentration. These effects were established by change in total body fat, and not by change in physical activity.

Clinicopathological and prognostic significance of FOXP3+ tumor infiltrating lymphocytes in patients with breast cancer: a meta-analysis.

BACKGROUND: The prognostic significance of FOXP3+ tumor-infiltrating lymphocytes (TILs) in patients with breast cancer remains controversial. The aims of our meta-analysis are to evaluate its association with clinicopathological characteristics and prognostic significance in patients with breast cancer. METHODS: PubMed, Embase, Cochrane Database and the Ovid Database were systematically searched (up to April 2015). The meta-analysis was performed using hazard ratio (HR), odds ratio (OR) and 95 % confidence intervals (CI) as effect measures. Using the random-effects model, statistical analysis was performed using Stata software, version 12.0. RESULTS: Seventeen studies including 8277 patients with breast cancer were analyzed. The meta-analysis indicated that the incidence difference of FOXP3+ TILs was significant when comparing the lymph node positive group to negative group (OR = 1.305, 95 % CI [1.071, 1.590]), the histological grade III group to the I-II group (OR = 3.067, 95 % CI [2.288, 4.111]), the ER positive group to the negative group (OR = 0.435, 95 % CI [0.287, 0.660]), the PR positive group to the negative group (OR = 0.493, 95 % CI [0.296, 0.822]), the HER2 positive group to the negative group (OR = 1.896, 95 % CI [1.335, 2.692]), the TNBC group to the non TNBC group (OR = 2.456, 95 % CI [1.801, 3.348]). The detection of FOXP3+ TILs was significantly correlated with the recurrence-free survival (RFS) of patients (HR = 1.752, 95 % CI [1.188-2.584]) and the overall survival (OS) of patients (HR =1.447, 95 % CI [1.037-2.019]). CONCLUSIONS: Our meta-analysis demonstrates that the presence of high levels of FOXP3+ TILs is associated with prognosis for breast cancer patients and predicts lymph node metastasis, hormone receptor and HER-2 status.

Differential ß-catenin expression levels are associated with morphological features and prognosis of colorectal cancer.

ß-catenin, an epithelial-mesenchymal transition (EMT)-associated marker, is key in the progression of colorectal cancer (CRC). However, the prognostic significance of ß-catenin expression in patients with CRC remains controversial. In the present study, the expression of ß-catenin at the tumor invasive front and the tumor center was investigated, and the correlations amongst ß-catenin differential expression patterns and the clinicopathological characteristics and prognosis of CRC patients were determined. In total, 181 patients that were diagnosed with CRC (as determined by histopathological evaluation) and subjected to surgical resection at the First Hospital of China Medical University between 2000 and 2001 were examined, and CRC specimens were obtained. Immunohistochemical (IHC) staining of ß-catenin was performed for each specimen. The nuclear ß-catenin expression levels were identified to be significantly lower in the tumor center than at the tumor invasive front (immunoreactivity score, 0.05±0.303 versus 2.18±3.917; P<0.001). The presence of nuclear ß-catenin overexpression at the tumor invasive front was found to be correlated with the tumor, node, metastasis stage (P=0.020), lymph node metastasis (P=0.016) and histological differentiation (P=0.006). Survival analysis revealed that reduced membranous expression levels and increased nuclear expression levels of ß-catenin were statistically significantly associated with poor survival times. Furthermore, differential ß-catenin expression levels were associated with aggressive morphological features, EMT and a poor prognosis in CRC. Therefore, IHC analysis of ß-catenin is considered to be a useful marker to predict the prognosis in patients with CRC.

Breath ketone testing: a new biomarker for diagnosis and therapeutic monitoring of diabetic ketosis.

BACKGROUND: Acetone, ß -hydroxybutyric acid, and acetoacetic acid are three types of ketone body that may be found in the breath, blood, and urine. Detecting altered concentrations of ketones in the breath, blood, and urine is crucial for the diagnosis and treatment of diabetic ketosis. The aim of this study was to evaluate the advantages of different detection methods for ketones, and to establish whether detection of the concentration of ketones in the breath is an effective and practical technique. METHODS: We measured the concentrations of acetone in the breath using gas chromatography-mass spectrometry and ß -hydroxybutyrate in fingertip blood collected from 99 patients with diabetes assigned to groups 1 (-), 2 (±), 3 (+), 4 (++), or 5 (+++) according to urinary ketone concentrations. RESULTS: There were strong relationships between fasting blood glucose, age, and diabetic ketosis. Exhaled acetone concentration significantly correlated with concentrations of fasting blood glucose, ketones in the blood and urine, LDL-C, creatinine, and blood urea nitrogen. CONCLUSIONS: Breath testing for ketones has a high sensitivity and specificity and appears to be a noninvasive, convenient, and repeatable method for the diagnosis and therapeutic monitoring of diabetic ketosis.

Clinical significance of promoter region hypermethylation of microRNA-148a in gastrointestinal cancers.

BACKGROUND: MicroRNAs are associated with tumor genesis and progression in various carcinomas. MicroRNA-148a (miR-148a) was reported to have low expression in gastrointestinal cancers, and might be regulated by promoter region DNA methylation. METHODS: Bisulfite-modified sequencing was used to determine the promoter region DNA methylation status of human gastrointestinal cancer cell lines. Expression levels of miR-148a in cell lines treated with 5-aza-2'-deoxycytidine were determined by quantitative real-time polymerase chain reaction. Total DNA was extracted from the tissues of 64 patients with gastric cancer and 51 patients with colorectal cancer. Methylation status was determined by methylation-specific polymerase chain reaction. All statistical analyses were performed with SPSS 17.0 software. RESULTS: The promoter regions of genes in human gastrointestinal cancer cell lines were all hypermethylated, except for HT-29, and the expression of miR-148a tended to be higher than in controls after treatment with 5-aza-2'-deoxycytidine. The methylation-specific polymerase chain reaction results showed that 56.25% of gastric cancer tissues and 19.61% of colorectal cancer tissues were hypermethylated. A strong correlation was found between the expression of miR-148a and the methylation status of promoter regions (P<0.001, chi-square test and Pearson's correlation). Furthermore, promoter region CpG site hypermethylation of miR-148a was correlated with increased tumor size (P=0.01) in gastric cancer after analyzing the correlation between methylation status and clinicopathologic characteristics. CONCLUSION: The promoter region CpG sites were hypermethylated in gastrointestinal cancers. Promoter region hypermethylation status was associated with the expression of miR-148a and tumor invasiveness in gastric cancer, and may prove to be a new biomarker and method for treating gastric cancer.

ILEI: a novel marker for epithelial-mesenchymal transition and poor prognosis in colorectal cancer.

AIMS: Accumulating evidence over the past decade has shown that abnormal activation of epithelial to mesenchymal transition (EMT) contributes to tumour progression and metastasis in colorectal cancer (CRC). In this study, we investigated the expression of interleukin-like EMT inducer (ILEI) and EMT-associated markers (E-cadherin, vimentin) in CRC tissues and determined the correlations between ILEI expression and clinicopathological characteristics, prognosis and EMT in CRC. METHODS AND RESULTS: In total, 194 patients diagnosed with CRC based on histopathological evaluation and those subjected to surgical resection at the First Hospital of China Medical University between 2003 and 2005 were examined. Immunohistochemical staining for ILEI, vimentin and E-cadherin was performed for each specimen. Cytoplasmic overexpression of ILEI usually accompanied down-regulation of E-cadherin and positive expression of vimentin. Conversely, ILEI was simultaneously down-regulated with overexpression of E-cadherin and negative expression of vimentin. ILEI overexpression was associated significantly with T-stage, N-stage, TNM stage and EMT phenotype (P = 0.024, <0.001, <0.001 and <0.001, respectively). Multivariate analysis revealed that ILEI expression was an independent prognostic factor for patient survival. CONCLUSIONS: Our findings indicate that cytoplasmic ILEI expression is a potential marker of EMT and tumour progression in CRC. ILEI is an independent predictive factor associated with poor prognosis in CRC.

Distribution characteristics of rare earth elements in children's scalp hair from a rare earths mining area in southern China.

In order to demonstrate the validity of using scalp hair rare earth elements (REEs) content as a biomarker of human REEs exposure, data were collected on REEs exposure levels from children aged 11-15 years old and living in an ion-adsorptive type light REEs (LREEs) mining and surrounding areas in southern China. Sixty scalp hair samples were analyzed by ICP-MS for 16 REEs (La Lu, Y and Sc). Sixteen REEs contents in the samples from the mining area (e.g., range: La: 0.14-6.93 microg/g; Nd: 0.09-5.27 microg/g; Gd: 12.2-645.6ng/g; Lu: 0.2-13.3 ng/g; Y: 0.03-1.27 microg/g; Sc: 0.05-0.30 microg/g) were significantly higher than those from the reference area (range: La: 0.04-0.40 microg/g; Nd: 0.04-0.32 microg/g; Gd: 8.3-64.6 ng/g; Lu: 0.4-3.3ng/g; Y: 0.03-0.29 microg/g; Sc: 0.11-0.36 microg/g) and even much higher than those published in the literature. The distribution pattern of REEs in scalp hair from the mining area was very similar to that of REEs in the mine and the atmosphere shrouding that area. In conclusion, the scalp hair REEs contents may indicate not only quantitatively but also qualitatively (distribution pattern) the absorption of REEs from environmental exposure into human body. The children living in this mining area should be regarded as a high-risk group with REEs (especially LREEs) exposure, and their health status should be examined from a REEs health risk assessment perspective.