Thiol-Ene Click Reaction Modified Triazinyl-Based Covalent Organic Framework for Pb(II) Ion Effective Removal.

As a common water pollutant, Pb2+ has harmful effects on the nervous, hematopoietic, digestive, renal, cardiovascular, and endocrine systems. Due to the drawbacks of traditional adsorbents such as structural disorder, poor stability, and difficulty in introducing adsorption active sites, the adsorption capacity is low, and it is difficult to accurately study the adsorption mechanism. Herein, vinyl-functionalized covalent organic frameworks (COFs) were synthesized at room temperature, and sulfur-containing active groups were introduced by the click reaction. By precisely tuning the chemical structure of the sulfur-containing reactive groups through the click reaction, we found that the adsorption activity of the sulfhydryl group was higher than that of the sulfur atom in the thioether. Moreover, the incorporation of flexible linking groups was observed to enhance the adsorption activity at the active site. The maximum adsorption capacity of the postmodified COF TAVA-S-Et-SH for Pb(II) reached 303.0 mg/g, which is 2.9 times higher than that of the unmodified COF. This work not only demonstrates the remarkable potential of the "thiol-ene" click reaction for the customization of active adsorption sites but also demonstrates the remarkable potential of the "thiol-alkene" click reaction to explore the structure-effect relationship between the active adsorption sites and the metal ion adsorption capacity.

Nitrogen-Rich Conjugated Microporous Polymers with Improved Cobalt(II) Density for Highly Efficient Electrocatalytic Oxygen Evolution.

Developing efficient oxygen evolution catalysts (OECs) made from earth-abundant elements is extremely important since the oxygen evolution reaction (OER) with sluggish kinetics hinders the development of many energy-related electrochemical devices. Herein, an efficient strategy is developed to prepare conjugated microporous polymers (CMPs) with abundant and uniform coordination sites by coupling the N-rich organic monomer 2,4,6-tris(5-bromopyrimidin-2-yl)-1,3,5-triazine (TBPT) with Co(II) porphyrin. The resulting CMP-Py(Co) is further metallized with Co2+ ions to obtain CMP-Py(Co)@Co. Structural characterization results reveal that CMP-Py(Co)@Co has higher Co2+ content (12.20 wt %) and affinity toward water compared with CMP-Py(Co). Moreover, CMP-Py(Co)@Co exhibits an excellent OER activity with a low overpotential of 285 mV vs RHE at 10 mA cm-2 and a Tafel slope of 80.1 mV dec-1, which are significantly lower than those of CMP-Py(Co) (335 mV vs RHE and 96.8 mV dec-1). More interestingly, CMP-Py(Co)@Co outperforms most reported porous organic polymer-based OECs and the benchmark RuO2 catalyst (320 mV vs RHE and 87.6 mV dec-1). Additionally, Co2+-free CMP-Py(2H) has negligible OER activity. Thereby, the enhanced OER activity of CMP-Py(Co)@Co is attributed to the incorporation of Co2+ ions leading to rich active sites and enlarged electrochemical surface areas. Density functional theory (DFT) calculations reveal that Co2+-TBPT sites have higher activity than Co2+-porphyrin sites for the OER. These results indicate that the introduction of rich active metal sites in stable and conductive CMPs could provide novel guidance for designing efficient OECs.

Mediation effect of antithrombin III between chronic renal insufficiency and chronic coronary artery disease in T2DM patients.

PURPOSE: The study aimed to investigate the potential effect of Antithrombin III (ATIII) between chronic renal insufficiency and chronic coronary artery disease (chronic CAD) in type 2 diabetes mellitus (T2DM) patients. METHODS: T2DM patients hospitalized in ZhongDa Hospital from 2013 to 2018 were enrolled. Relationships between renal function, ATIII, and chronic CAD risk were explored using multivariate regression models. Multiplicative and additive interactions were investigated between ATIII and renal function for CAD risk, and the role of ATIII was determined by bootstrap mediation analysis in patients with chronic renal dysfunction. RESULTS: A total of 4197 patients were included in the study, with a chronic CAD prevalence of 23.02%. Low ATIII level was statistically associated with chronic renal insufficiency and elevated CAD risk even after adjustments (P < 0.05). A positive correlation between renal function and ATIII was demonstrated, and each 1 SD increase in renal function, ATIII increased by 2.947% (2.406-3.488%, P < 0.001) and 0.969% (0.297-1.642%, P < 0.001) in crude and adjusted models respectively. Patients with decreased renal function and ATIII were at the highest chronic CAD risk (OR = 1.51, 95%CI:1.15-1.98, P < 0.05), while no multiplicative and additive interaction effects were significant. Bootstrap mediation analysis estimated that ATIII mediated approximately 4.27% of the effect of chronic renal insufficiency on chronic CAD risk. CONCLUSION: ATIII may serve as a mediator between chronic renal insufficiency and chronic CAD, providing mechanistic clues for renal-heart association and new insight into clinical therapies.

Towards high-performance nonlinear optical materials through embedding a D-A system into ß-ketoenamine-linked COFs.

Two covalent organic framework (COF) films supported by a glass substrate were obtained by solvothermal reaction of an electron donor with electron acceptor 1,3,5-triformylbenzene (TF) or 2,4,6-triformylphloroglucinol (TFP), respectively. The TFP-BD film exhibits a nonlinear absorption coefficient of -3.01 × 105 cm GW-1. The TFP-BD film can aggregate electrons around the connected monomer through the D-A effect due to its highly polar and electronegative carbonyl oxygen atoms, thereby modulating the electronic structure of the COFs. This work provides a novel approach for the structural modulation of optical materials with strong nonlinearity.

Stabilization mechanism of Pb with an amino- and mercapto-polymer to assist phytoremediation.

An important concern during phytoremediation of heavy metal contamination in soils is the risk of leaching of heavy metals before they can be taken up by plants. The most effective method is to use heavy metal stabilizers. However, the stabilization without selectivity will greatly inhibit the phytoremediation effect of all heavy metals. A novel polymer with amino and mercapto groups named as AMP has been prepared as a new exclusive soil stabilizer for Pb. The adsorption of AMP toward Pb belonged to a monolayer adsorption and chemical process. The adsorption capacity of Pb increased with the increase of pH and initial Pb concentration, and obeyed the Langmuir model and pseudo-second-order model, respectively. An amazing maximum adsorption capacity of 588 mg Pb g-1 was reached for AMP when initial concentration was 300 mg Pb L-1, while K2 of 0.594 g mg-1 min-1 was obtained when the initial Pb concentration was 2.0 mg L-1. The distribution coefficient of AMP to Pb in the mixture of five heavy metals was as high as 3110 mL g-1, which was at least 7-fold greater than those of other heavy metals, exhibiting high selective to Pb. AMP showed a fast, large adsorption capacity and good selectivity due to the abundance of sulfhydryl and amino functional groups in the polymer and their interaction with metal ions. The effects of AMP in soil remediation were further tested by a soil column leaching experiment and a pot experiment, and the good stabilization effect of AMP on Pb and the less effect on bioavailability of other heavy metals at recommended doses were verified. This study was expected to solve the problem of leaching risk of the target metal such as Pb in sludge during land use. It provided a new idea of exclusive stabilization to assist phytoremediation of non-target heavy metals by reducing the leaching risk of some special target metal.

Synthesis and Visualization of Entangled 3D Covalent Organic Frameworks with High-Valency Stereoscopic Molecular Nodes for Gas Separation.

The structural diversity of three-dimensional (3D) covalent organic frameworks (COFs) are limited as there are only a few choices of building units with multiple symmetrically distributed connection sites. To date, 4 and 6-connected stereoscopic nodes with Td , D3h , D3d and C3 symmetries have been mostly reported, delivering limited 3D topologies. We propose an efficient approach to expand the 3D COF repertoire by introducing a high-valency quadrangular prism (D4h ) stereoscopic node with a connectivity of eight, based on which two isoreticular 3D imine-linked COFs can be created. Low-dose electron microscopy allows the direct visualization of their 2-fold interpenetrated bcu networks. These 3D COFs are endowed with unique pore architectures and strong molecular binding sites, and exhibit excellent performance in separating C2 H2 /CO2 and C2 H2 /CH4 gas pairs. The introduction of high-valency stereoscopic nodes would lead to an outburst of new topologies for 3D COFs.

Increased Plasma Level of 24S-Hydroxycholesterol and Polymorphism of CYP46A1 SNP (rs754203) Are Associated With Mild Cognitive Impairment in Patients With Type 2 Diabetes.

BACKGROUND: Abnormal cholesterol metabolism is common in type 2 diabetes mellitus (T2DM) and causes dementia. Cholesterol 24S-hydroxylase (CYP46A1) converts cholesterol into 24S-hydroxycholesterol (24-OHC) and maintains cholesterol homeostasis in the brain. OBJECTIVE: This study aimed to investigate the roles of 24-OHC and the CYP46A1 (rs754203) polymorphism in patients with T2DM and mild cognitive impairment (MCI). METHODS: A total of 193 Chinese patients with T2DM were recruited into two groups according to the Montreal Cognitive Assessment (MoCA). Demographic and clinical data were collected, and neuropsychological tests were conducted. Enzyme-linked immunosorbent assay (ELISA) and Seqnome method were used to detect the concentration of plasma 24-OHC and the CYP46A1 rs754203 genotype, respectively. RESULTS: Compared with 118 healthy cognition participants, patients with MCI (n = 75) displayed a higher plasma level of 24-OHC and total cholesterol concentration (all p = 0.031), while no correlation was found between them. In the overall diabetes population, the plasma level of 24-OHC was negatively correlated with MoCA (r = -0.150, p = 0.039), and it was further proved to be an independent risk factor of diabetic MCI (OR = 1.848, p = 0.001). Additionally, patients with MCI and the CC genotype of CYP46A1 rs754203 showed the highest plasma level of 24-OHC even though the difference was not statistically significant, and they obtained low scores in both the verbal fluency test and Stroop color and word test A (p = 0.008 and p = 0.029, respectively). CONCLUSION: In patients with T2DM, high plasma level of 24-OHC and the CC genotype carrier of CYP46A1 rs754203 may portend a high risk of developing early cognitive impairment, including attention and executive deficits.

Synthesis and biological evaluation of fluorescent hyaluronic acid modified amorphous calcium phosphate drug carriers for tumor-targeting.

Cancer is becoming a major threat to national public health security. The integration of disease diagnosis and monitoring with treatment has become a hot spot for researchers. The amorphous calcium phosphate (ACP) nanoparticles prepared by the group in the previous stage could not precisely treat the lesion without tumor targeting and imaging characteristics. In this paper, water-soluble hyaluronic acid fluorescent carbon nanoparticles (HA-FCNs) were prepared and co-interacting with ACP nanoparticles to form hyaluronic acid fluorescent carbon/amorphous calcium phosphate (HA-FCNs/ACP) nanoparticles. The basic characteristics were characterized and the biological characteristics before and after drug loading were evaluated. HA-FCNs/ACP nanoparticles have good hemocompatibility, pH responsiveness, and enzymatic release. HA-FCNs and HA-FCNs/ACP nanoparticles are dispersed in the cytoplasm through the overexpressed CD44 receptors, which are actively targeted into A549 cells. Besides, the migration of A549 cells would be inhibited after cells were treated with drug-loaded nanomaterials. Therefore, the as-prepared nanoparticles can be used to monitor and treat focal sites through tumor-targeting bioimaging, pH-responsive, and enzymatic drug release properties, thus enabling integrated diagnosis and treatment.

Hydrophobin-enhanced stability, dispersions and release of curcumin nanoparticles in water.

Most chemotherapeutic drugs commonly suffer from low aqueous solubility that can potentially limit drugs absorption. Drug nanomerization is an advanced approach to overcoming their poor water-solubility. In this study, class I hydrophobin recombinant HGFI (rHGFI)-based curcumin (Cur) nanoparticles (rHGFI-Cur) were prepared by freeze-drying method. The rHGFI-Cur nanocomposites were characterized by contact angle, transmission electron microscopy, fluorescence microscopy and dynamic light scattering. The results showed that rHGFI could lead to the wettability conversion and stability improved of Cur in water. X-ray photoelectron spectroscopy and Fourier transform infrared suggested that rHGFI could non-covalently bind to Cur to render them hydrophilic through hydrophobic forces. Additionally, drug release and cytotoxicity assays illustrated that rHGFI-Cur nanoparticles could facilitate Cur release and exhibited higher cytotoxicity than free Cur for human esophageal cancer cells TE-1. Thus, it suggested that rHGFI has a great potential application for hydrophobic drug delivery without toxicity.[Formula: see text].

In vitro and in vivo release of diclofenac sodium-loaded sodium alginate/carboxymethyl chitosan-ZnO hydrogel beads.

To control release of drugs sensitive to gastrointestinal (GI) environmental effects or irritating to stomach, such as diclofenac sodium (DS), sodium alginate (SA) hydrogel beads are gaining considerable attention gradually. However, due to high swelling ratio, the sustained release performance of SA hydrogel is still far from satisfactory. The objective of this research was to develop new drug delivery device based on SA and ZnO nanoparticles (ZnO NPs). ZnO NPs were prepared by direct precipitation method, and carboxymethyl chitosan (CMCS) acted as stabilizing agent to dominate the preparation of ZnO NPs. The incorporation of CMCS-ZnO NPs resulted in slower and sustained release of DS in vitro. In vivo pharmacokinetics studies showed the bioavailability of DS was better after oral administration of DS-loaded SA/CMCS-ZnO hydrogel beads. These results suggested that SA/CMCS-ZnO hydrogel beads will be a prospective material for loading drugs sensitive to GI environmental effects or irritating to stomach.

Structure-Activated Copper Photosensitisers for Photocatalytic Water Reduction.

A series of phenanthroline-based ligands have been synthesised and their influence as bidentate nitrogen ligands in heteroleptic [Cu(P^P)(N^N)]+ photosensitisers in light-driven water reduction has been studied. In this noble-metal-free Cu-Fe-based photocatalytic water reduction system, the structural effects of the nitrogen ligands have been explored, including the steric and electronic effects of substituents at the 2,9- and 4,7-positions of phenanthroline. Ligands were prepared that led to increased hydrogen generation, with turnover numbers (TONCu ) of up to 1388 being observed. All the new complexes were electrochemically and photophysically characterised. We demonstrate for the first time that the presence of fluorine in nitrogen ligands increases the efficacy of copper complexes in photocatalytic hydrogen production.

Iodine-Promoted Construction of Polysubstituted 2,3-Dihydropyrroles from Chalcones and ß-Enamine Ketones (Esters).

A novel approach for the synthesis of a variety of polysubstituted trans-2,3-dihydropyrroles from a wide range of chalcones and ß-enamine ketones (esters) via iodine-promoted tandem Michael/cyclization sequence has been developed, affording the desired products in moderate to excellent yields. This methodology is a highly efficient, convenient way to access functionalized 2,3-dihydropyrroles from readily accessible substrates under mild reaction conditions.

Iodine-catalyzed 1,3-dipolar cycloaddition/oxidation/aromatization cascade with hydrogen peroxide as the terminal oxidant: general route to pyrrolo[2,1-a]isoquinolines.

We report a novel molecular iodine-catalyzed 1,3-dipolar cycloaddition/oxidation/aromatization cascade process with hydrogen peroxide as the terminal oxidant for the construction of pyrrolo[2,1-a]isoquinolines. The product pyrrolo[2,1-a]isoquinolines were obtained from reactions between simple, readily available dipolarophiles and tetrahydroisoquinolines in moderate to excellent yields without the need for a metal catalyst.

The synthesis of benzo[f]isoindole-1,3-dicarboxylates via an i2-induced 1,3-dipolar cycloaddition reaction.

An I2-induced 1,3-dipolar cycloaddition reaction has been developed for the synthesis of benzo[f]isoindole-1,3-dicarboxylates from quinones and N-substituted amino esters. The reaction proceeds in good to excellent yields in one step from 3 equiv of amino ester to react with the quinone structure. The utility of this transformation has been highlighted by its use for the construction of benzo[f]isoindole-1,3-dicarboxylates, which have been identified in natural products exhibiting important biological activities.

X-ray structure of 1,3,4-tri-O-acetyl-2-deoxy-beta-d-erythro-pentopyranose.

Peracetylated 2-deoxy-d-erythro-pentose (2-deoxy-d-ribose) was synthesized through the acetylation of 2-deoxy-d-ribose with acetic anhydride in pyridine, and the products (including all four ring forms) exist in form of either a white solid or a syrup. A single crystal of 1,3,4-tri-O-acetyl-2-deoxy-beta-d-erythro-pentopyranose was obtained from the syrup and its structure was determined by X-ray diffraction. The crystal adopts the (1)C(4) conformation, presenting an orthorhombic system, space group P2(1)2(1)2(1) with Z=4, unit cell dimensions a=7.2274 (3)A, b=8.0938 (5)A, and c=22.0517 (11)A.