2D Conjugated Metal-Organic Frameworks Bearing Large Pore Apertures and Multiple Active Sites for High-Performance Aqueous Dual-Ion Batteries.

2D conjugated metal-organic frameworks (2D c-MOFs) with large pore sizes and high surface areas are advantageous for adsorbing iodine species to enhance the electrochemical performance of aqueous dual-ion batteries (ADIBs). However, most of the reported 2D c-MOFs feature microporous structures, with few examples exhibiting mesoporous characteristics. Herein, we developed two mesoporous 2D c-MOFs, namely PA-TAPA-Cu-MOF and PA-PyTTA-Cu-MOF, using newly designed arylimide based multitopic catechol ligands (6OH-PA-TAPA and 8OH-PA-PyTTA). Notably, PA-TAPA-Cu-MOF exhibits the largest pore sizes (3.9 nm) among all reported 2D c-MOFs. Furthermore, we demonstrated that these 2D c-MOFs can serve as promising cathode host materials for polyiodides in ADIBs for the first time. The incorporation of triphenylamine moieties in PA-TAPA-Cu-MOF resulted in a higher specific capacity (423.4 mAh g-1 after 100 cycles at 1.0 A g-1) and superior cycling performance, retaining 96 % capacity over 1000 cycles at 10 A g-1 compared to PA-PyTTA-Cu-MOF. Our comparative analysis revealed that the increased number of N anchoring sites and larger pore size in PA-TAPA-Cu-MOF facilitate efficient anchoring and conversion of I3 -, as supported by spectroscopic electrochemistry and density functional theory calculations.

A Redox-Active Covalent Organic Framework with Highly Accessible Aniline-Fused Quinonoid Units Affords Efficient Proton Charge Storage.

Owing to their intrinsic safety and sustainability, aqueous proton batteries have emerged as promising energy devices. Nevertheless, the corrosion or dissolution of electrode materials in acidic electrolytes must be addressed before practical applications. In this study, a cathode material based on a redox-active 2D covalent organic framework (TPAD-COF) with aniline-fused quinonoid units featuring inherently regular open porous channels and excellent stability is developed. The TPAD-COF cathode delivers a high capacity of 126 mAh g-1 at 0.2 A g-1 , paired with long-term cycling stability with capacity retention of 84% after 5000 cycles at 2 A g-1 . Comprehensive ex situ spectroscopy studies correlated with density functional theory (DFT) calculations reveal that both the -NH- and C=O groups of the aniline-fused quinonoid units exhibit prominent redox activity of six electrons during the charge/discharge processes. Furthermore, the assembled punch battery consisting of a TPAD-COF//anthraquinone (AQ) all-organic system delivers a discharge capacity of 115 mAh g-1 at 0.5 A g-1 after 130 cycles, implying the potential application of the TPAD-COF cathode in aqueous proton batteries. This study provides a new perspective on the design of electrode materials for aqueous proton batteries with long-term cycling performance and high capacity.

A Brick-Wall Topological 2D Covalent Organic Framework Constructed from an H-Shaped "Two-in-One" Monomer.

As an emerging class of porous crystalline material, covalent organic frameworks (COFs) have received considerable research interests in terms of exploring new architectures and functions. Herein, we developed an unprecedented "H-shaped" monomer, upon self-polycondensation, which facilely produced a benzoimidazole-based COF (H-BIm-COF) with a rarely reported brick-wall topology. H-BIm-COF displayed high crystallinity, nano-sized porosity, and high thermal and chemical stabilities. Interestingly, H-BIm-COF based membranes showed selective permeability towards different solvents, which related to the size and polarity of the guest molecule. Additionally, initial study suggested the COF displayed excellent rejection efficiency towards ionic dyes, for example chromium black T (99.7 %) and rhodamine B (97.3 %). This work provides insights into developing new topological COFs by designing monomers with new configurations.

Copper-Catalyzed Three-Component Reaction of Alkynes, TMSN3, and Ethers: Regiocontrollable Synthesis of N1- and N2-Oxyalkylated 1,2,3-Triazoles.

A new copper-catalyzed selective synthesis of N1- and N2-oxyalkylated 1,2,3-triazoles has been developed through a three-component reaction of alkynes, TMSN3, and ethers. Through this methodology, a series of N1- and N2-oxyalkylated 1,2,3-triazoles could be efficiently and regioselectively obtained from simple and readily available starting materials with favorable functional group tolerance.

Metal-Free Catalytic Synthesis of Thiocarbamates Using Sodium Sulfinates as the Sulfur Source.

A novel molecular iodine-catalyzed protocol for the construction of thiocarbamates from readily available sodium sulfinates, isocyanides, and water has been described. The present methodology offers a facile and practical route to a variety of thiocarbamates in moderate to good yields with favorable functional group tolerance by use odorless sodium sulfinates as the sulfur source. The mechanistic studies suggest the present transformation involves a radical process.

Metal-Free C(sp2)-H/N-H Cross-Dehydrogenative Coupling of Quinoxalinones with Aliphatic Amines under Visible-Light Photoredox Catalysis.

A novel and efficient visible-light-induced C(sp2)-H/N-H cross-dehydrogenative coupling (CDC)-amination with both primary and secondary aliphatic amines at room temperature in air is developed. This photocatalytic reaction allows the direct formation of 3-aminoquinoxalin-2(1 H)-ones via CDC-amination in the absence of any external oxidant added from outside. Preliminary mechanistic studies reveal that the present reaction proceeds through a radical process.

Visible-Light-Enabled Construction of Thiocarbamates from Isocyanides, Thiols, and Water at Room Temperature.

A convenient visible-light-induced method for the synthesis of thiocarbamates from isocyanides, thiols, and water has been developed under mild reaction conditions. The present protocol offers a cost-effective and operationally straightforward approach to the various thiocarbamates in moderate to good yields by simple use of cheap Rose Bengal as the photocatalyst and water as the reaction reagent as well as an environmentally benign cosolvent.

Low-dose testosterone alleviates vascular damage caused by castration in male rats in puberty via modulation of the PI3K/AKT signaling pathway.

The aim of the present study was to investigate the effect of testosterone on glucolipid metabolism and vascular injury in male rats, and examine the underlying molecular mechanisms. A total of 40 male Sprague-Dawley rats were divided into a control group (n=10), high-fat-diet + castration group (n=10), high­fat­diet + castration + low dose testosterone group (n=10), and high-fat-diet + castration + high dose testosterone group (n=10). Hematoxylin and eosin staining was performed to evaluate the morphology of the thoracic aortic tissues. Immunohistochemical staining was used to detect biomarkers of the phosphoinositide 3­kinase (PI3K) signaling pathway. The mRNA and protein expression levels of PI3K, AKT, insulin receptor substrate­1 (IRS­1), glucose transporter type 4 (GLUT­4), nuclear factor (NF)­κB and tumor necrosis factor (TNF)­α in the aortas were determined using quantitative polymerase chain reaction and Western blot analyses, respectively. Apoptosis in the aortic tissues was detected using a TUNEL assay. Castration induced apoptosis in the animals fed a high­fat­diet, whereas low dose testosterone replacement ameliorated the apoptosis in the aorta. However, the levels of apoptosis was more severe following high­dose testosterone treatment. Low­dose testosterone induced upregulation in the levels of IRS­1, AKT, GLUT­4 protein, NF­κB, TNF­α and PI3K, compared with those in the animals fed a high­fat diet following castration. A high dose of testosterone resulted in a significant decrease in the levels of IRS­1, AKT, GLUT­4, NF­κB, TNF­α and PI3K. Compared with the rats in the high­fat diet + castration group, a low dose of testosterone induced upregulation in the mRNA levels of IRS­1, AKT and GLUT­4, and downregulation of the mRNA levels of NF­κB, TNF­α and PI3K. A high dose of testosterone resulted in a significant decrease in the levels of IRS­1, AKT and GLUT­4, and marked increases in the mRNA levels of NF­κB, TNF­α and PI3K, compared with the low dose group. Castration induced marked disorders of glucolipid metabolism and vascular injuries in the pubescent male rats. Low­dose testosterone treatment was found to ameliorate the vascular damage caused by castration via the PI3K/AKT signaling pathway.

Association between IL-6 and related risk factors of metabolic syndrome and cardiovascular disease in young rats.

OBJECTIVE: Metabolic syndrome (MS) is conceived as the pathogenic basis of an increased cardiovascular burden. We investigate the correlation between interleukin-6 (IL-6) and the risk factors of MS and cardiovascular disease (CVD) in diet-induced model of MS and determined whether IL-6 was associated with the prevalence of MS and cardiovascular disease. METHODS: A total of 40 Spague-Dawley (SD) rats were randomly divided into high-fat and high salt (FSC) group, high-fat (FC) group and normal control (NC) group. After feeding for 7 weeks, fasting blood glucose (FBG) and fasting insulin (FIN) were measured at the 60 min, 120 min and 180 min after the glucose administration. Blood pressure, body weight, height, waist circumference (WC), liver weight, visceral fat weight as well as blood lipid profile were determined at the end of 7-week. Furthermore, IL-6 levels from adipose tissues were analyzed using ELISA, and the correlation between IL-6 and the risk factors of MS and cardiovascular disease was investigated. RESULTS: After treatment with different diets, significant difference was noted in the WC, body mass index (BMI), visceral fat weight and liver weight of FSC group compared with those of NC group (P<0.05). The levels of systolic blood pressure (SBP), diastolic blood pressure (DBP), total cholesterol (TC), triacylglycerol (TG) and low density lipoprotein (LDL) were markedly elevated in FSC group compared with those in NC group, while the level of high density lipoprotein (HDL) was remarkable lower in FSC group (P<0.05). After glucose administration, the concentrations of blood glucose and insulin were significant higher in FSC group than those in NC group at different time points (P<0.05). Moreover, high-fat and high salt diet brought about significant elevation of IL-6 compared with that with normal or high-fat diet in SD rats. Furthermore, IL-6 was significantly associated with FIN, HOMA-IR, LDL, TC, TG, HDL, visceral fat mass and body weight in FSC group, while IL-6 was markedly correlated with TC, LDL, TG, visceral fat mass and body weight (P<0.05). CONCLUSION: A characteristic rat model of MS may be induced by the high-fat and high-salt diet. IL-6 may be considered as an early and representative marker in the pathogenesis of MS and related cardiovascular burden.

Correlation between exon 3 polymorphism of growth hormone receptor gene and the responses to rhGH therapy.

OBJECTIVE: To investigate the correlation between the exon 3 polymorphism of growth hormone receptor (GHR) gene and the responses to the recombinant human growth hormone (rhGH) therapy in children with short stature. METHODS: Forty-five growth hormone deficiency (GHD) children (male: 30, female: 15, aged 10.39 ± 2.73 yrs) and twenty-five idiopathic short stature (ISS) children (male: 15, female: 10, aged 10.58 ± 2.56 yrs) admitted to our hospital were included. The polymorphism of exon 3 of GHR gene was determined using multiple PCR amplification. Treatment duration for each subject was at least 12 months. On this basis, we evaluated the correlation between treatment efficiency of rhGH therapy and GHR exon 3 polymorphism, GHD, and treatment duration. RESULTS: Significant difference was noted in the growth velocity (GV) of GHD children with a genotype of GHRfl compared with those with a genotype of GHRd3 (9.44 ± 2.35 vs. 11.36 ± 2.49, P < 0.05). Meanwhile, the GV of ISS patients with a genotype of GHRfl were remarkably decreased compared with those with a genotype of GHRd3 (8.74 ± 2.36 vs. 11.18 ± 2.44, P < 0.05). For the children with peak GH response of less than 5 ng/ml, statistical difference was noted in the GV of children with a genotype of GHRfl compared with those with a genotype of GHRd3 (9.55 ± 2.76 vs. 10.84 ± 1.53, P < 0.05). For the patients with peak GH response to clonidine or pyridostigmine bromide of > 5 ng/ml, a satisfactory response to rhGH therapy was noted in children with a genotype of GHRd3 compared with those of GHRfl (P < 0.05). CONCLUSIONS: GHRd3 was correlated with the response to rhGH therapy in children with short stature. For the patients with the same genotype, GHD caused no obvious effects on the final height. However, for the patients with peak GH response of > 5 ng/ml, a satisfactory response to rhGH therapy was noted in children with a genotype of GHRd3 compared with those of GHRfl (P < 0.05). A higher treatment efficiency was obtained in those received rhGH at an early age.

Association of plasma glucose, insulin, and cardiovascular risk factors in overweight and obese children.

OBJECTIVE: To investigate the association between fasting plasma glucose (FPG), 2-hour post challenge plasma glucose (2hPG), fasting plasma insulin (FINS), 2-hour post challenge plasma insulin (2hINS), and cardiovascular risk factors in obese and overweight children. METHODS: This is a cross-sectional study of 452 obese and overweight children (male: 312, female: 140, aged 6-16 years). This study was conducted in the Department of Pediatrics, General Hospital of Tianjin Medical University, Tianjin, China between June 2008 and November 2012. Anthropometries and blood analysis were carried out. Pearson correlation analysis and multiple stepwise linear regression analysis were used to investigate the association among FPG, 2hPG, FINS, 2hINS and cardiovascular risk factors. RESULTS: Body mass index, waist circumference, waist to hip ratio, systolic blood pressure, diastolic blood pressure, and triglyceride were highly correlated with FINS. Fasting plasma insulin influenced greater variance in most cardiovascular risk factors than 2hPG and 2hINS. CONCLUSION: Fasting plasma insulin was closely associated with most cardiovascular risk factors compared with FPG, 2hPG and 2hINS.

The association between metabolic syndrome and vascular endothelial dysfunction in adolescents.

The aim of this study was to investigate the association between metabolic syndrome (MS) and vascular endothelial cell dysfunction (ECD) in adolescents. Sixty obese pediatric inpatients at the General Hospital of Tianjin Medical University from February 2011 to February 2012 were included. Among these, 30 patients were obese and 30 patients were diagnosed with MS. Thirty healthy subjects were randomly selected as the control group. A series of indices, including height, body weight, waist circumference, hip circumference, waist/hip circumference and body mass index (BMI), as well as total cholesterol (TC), triglyceride (TG), low-density lipoprotein (LDL) and high-density lipoprotein (HDL) levels were evaluated. von Willebrand factor (vWF) and plasminogen activator inhibitor-1 (PAI-1) levels were determined using an enzyme linked immunosorbent assay (ELISA). Correlation analysis between height, body weight, waist circumference, hip circumference, waist/hip circumference, BMI, TC, TG, LDL, HDL and PAI-1, as well as vWF was performed. Significant increases of vWF and PAI-1 levels were observed in the MS group compared with the control group (P<0.05). For the adolescents in the obese group, a significant increase of PAI-1 level was observed compared with the control group (P<0.05). No significant difference was observed between the vWF levels in the obese and control groups. PAI-1 was positively associated with BMI, waist circumference, waist/hip circumference, TC, TG, LDL, fasting plasma glucose (FPG), fasting insulin (FINS), systolic blood pressure (SBP) and diastolic blood pressure (DBP), respectively (P<0.05). In addition, PAI-1 was negatively associated with HDL levels (P<0.05). PAI-1 and vWF may be used as biomarkers for the diagnosis of ECD. ECD in individuals with MS may be associated with obesity, blood fat, blood sugar and blood pressure. FPG, TC and TG may be risk factors for ECD.

[Correlation between vaspin concentration and insulin sensitivity in the visceral adipose tissue of young obese rats].

OBJECTIVE: To investigate the correlation between visceral adipose tissue-derived serine protease inhibitor (vaspin) concentration and insulin sensitivity in the visceral adipose tissue of young obese Sprague-Dawley (SD) rats. METHODS: Twenty-four SD rats which had been weaned 3 weeks before were randomly divided into two groups (n=12 each) to receive a high-fat and normal diet. The weight and abdominal circumference (AC) of each rat were measured, the fasting plasma glucose (FPG) and fasting insulin (FINS) in blood from the angular vein were measured after 12 hours of fasting and blood glucose (BG) and insulin (INS) levels in blood from the angular vein were measured at 60 and 120 minutes after intraperitoneal injection of 50% glucose (2 g/kg). The rats were sacrificed, and their liver and visceral adipose tissue were weighed. The vaspin concentration of the visceral adipose tissue in each rat was measured using ELISA. Correlation analysis was performed on the vaspin concentration and other indices. RESULTS: Compared with the normal diet group, the high-fat diet group showed significantly higher weight, AC, weight of visceral adipose tissue, FPG, FINS, 120 minute INS level, vaspin concentration, homeostasis model assessment for insulin resistance (HOMA-IR) and homeostasis model assessment of ß cell function (HOMA-ß) (P<0.05) Insulin sensitivity index (ISI) was significantly lower (P<0.01). Vaspin concentration was positively correlated with visceral adipose tissue and liver weight, AC, 120 minute INS level, FPG, FINS, HOMA-IR and HOMA-ß (P<0.05), and negatively correlated with ISI (P<0.05). CONCLUSIONS: High expression of vaspin is associated with insulin resistance in young obese SD rats. Vaspin is presumably an adipocytokine that can increase insulin sensitivity, promote insulin secretion by islet ß-cells and improve glucose tolerance, and it may be involved in insulin resistance and the disturbance of carbohydrate metabolism.