Construction of Flexible Amine-linked Covalent Organic Frameworks by Catalysis and Reduction of Formic Acid via the Eschweiler-Clarke Reaction.

Compared to the current mainstream rigid covalent organic frameworks (COFs) linked by imine bonds, flexible COFs have certain advantages of elasticity and self-adaptability, but their construction and application are greatly limited by the complexity in synthesis and difficulty in obtaining regular structure. Herein, we reported for the first time a series of flexible amine-linked COFs with high crystallinity synthesized by formic acid with unique catalytic and reductive bifunctional properties, rather than acetic acid, the most common catalyst for COF synthesis. The reaction mechanism was demonstrated to be a synchronous in situ reduction during the formation of imine bond. The flexibilities of the products endow them with accommodative adaptability to guest molecules, thus increasing the adsorption capacities for nitrogen and iodine by 27 % and 22 %, respectively. Impressively, a novel concept of flexibilization degree was proposed firstly, which provides an effective approach to rationally measure the flexibility of COFs.

Effects of curcumin on the pharmacokinetics of amlodipine in rats and its potential mechanism.

Context: Hyperlipidaemia and hypertension are often treated together with curcumin and amlodipine. It is necessary to investigate the drug-drug interaction between curcumin and amlodipine.Objective: The interaction between curcumin and amlodipine was investigated in rats and with rat liver microsomes.Methods: The pharmacokinetics of amlodipine (1 mg/kg) was investigated in rats with or without curcumin pre-treatment (2 mg/kg), six rats in each group. The metabolic stability of amlodipine was investigated with rat liver microsomes.Results: Curcumin significantly increased the Cmax (26.19 ± 2.21 versus 17.80 ± 1.56 µg/L), AUC(0-t) (507.27 ± 60.23 versus 238.68 ± 45.59 µg·h/L), and t1/2 (14.69 ± 1.64 versus 11.43 ± 1.20 h) of amlodipine (p < 0.05). The metabolic stability of amlodipine was significantly increased with the half-life time in rat liver microsomes increased from 34.23 ± 3.33 to 44.15 ± 4.12 min, and the intrinsic rate decreased from 40.49 ± 3.26 to 31.39 ± 2.78 µL/min/mg protein.Discussion and conclusions: These results indicated that drug-drug interaction might appear during the co-administration of curcumin and amlodipine. The potential mechanism may be due to the inhibition of CYP3A4 by curcumin. Thus, this interaction should be given special attention in the clinic and needs further experiments to characterize the effect in humans.

Redox-Active Two-Dimensional Covalent Organic Frameworks (COFs) for Selective Reductive Separation of Valence-Variable, Redox-Sensitive and Long-Lived Radionuclides.

We report the first example of 2D covalent organic framework nanosheets (Redox-COF1) for the selective reduction and in situ loading of valence-variable, redox-sensitive and long-lived radionuclides (abbreviated as VRL nuclides). Compared with sorbents based on chemical adsorption and physical adsorption, the redox adsorption mechanism of Redox-COF1 can effectively reduce the impact of functional group protonation under the usual high-acidity conditions in chemisorption, and raise the adsorption efficiency from the monotonous capture by pores in physisorption. The adsorption selectivity for UO2 2+ reaches up to unprecedented ca. 97 % at pH 3, more than for any analogous adsorbing material.

Colyliform Crystalline 2D Covalent Organic Frameworks (COFs) with Quasi-3D Topologies for Rapid I2 Adsorption.

Constructing three-dimensional (3D) structural characteristics on two-dimensional (2D) covalent organic frameworks (COFs) is a good approach to effectively improve the permeability and mass transfer rate of the materials and realize the rapid adsorption for guest molecules, while avoiding the high cost and monomer scarcity in preparing 3D COFs. Herein, we report for the first time a series of colyliform crystalline 2D COFs with quasi-three-dimensional (Q-3D) topologies, consisting of unique "stereoscopic" triangular pores, large interlayer spacings and flexible constitutional units which makes the pores elastic and self-adaptable for the guest transmission. The as-prepared QTD-COFs have a faster adsorption rate (2.51 g h-1 ) for iodine than traditional 2D COFs, with an unprecedented maximum adsorption capacity of 6.29 g g-1 . The excellent adsorption performance, as well as the prominent irradiation stability allow the QTD-COFs to be applied for the rapid removal of radioactive iodine.

Health literacy and self-management among middle-aged and young hypertensive patients: a parallel mediation effect of illness perception and self-efficacy.

Background: Hypertension is increasingly prevalent among young and middle-aged populations in rural China, accompanied by suboptimal self-management. Given that this population forms the backbone of the labor force, enhancing their self-management capabilities is crucial for improving overall population health. Studies indicate that individuals with good health literacy are more likely to effectively manage their health. Methods: Grounded in the health literacy skills framework, a model was constructed in this study to examine the impact of health literacy on self-management among young and middle-aged hypertensive patients in rural China. Meanwhile, the mediating roles of illness perception and self-efficacy were also verified. Using a multi-stage stratified random sampling method, 338 patients were recruited to participate in the study. Structural equation modeling was utilized to establish the relationship model, and bootstrap tests were carried out to examine the mediating effects. Results: The average self-management score was 70.45 ± 11.36. Health literacy exhibited a positive correlation with self-management (standardized ß = 0.372, p < 0.001). The mediating effects through illness perception and self-efficacy were 0.040 and 0.236, constituting 6.68 and 39.31% of the total effect, respectively. Conclusion: Illness perception and self-efficacy serve as parallel mediators amid the association between health literacy and self-management. Implementing psychological counseling and health education is imperative for augmenting self-management competence and cultivating an adaptive coping mentality.

Clinical Value of Circulating ZFAS1 and miR-590-3p in the Diagnosis and Prognosis of Chronic Heart Failure.

Long non-coding RNAs (lncRNAs) have been reported to be involved in the development of various cardiovascular diseases, including chronic heart failure (CHF). In this study, we aimed to investigate the role of ZFAS1/miR-590-3p axis in the diagnosis and prognosis of CHF. The expression of ZFAS1 and miR-590-3p in the serum samples of CHF was measured using quantitative real-time polymerase chain reaction. Pearson correlation coefficient was applied to analyze the correlation between ZFAS1 and miR-590-3p. The receiver operating characteristic (ROC) curve was used to examine the diagnostic accuracy of ZFAS1, miR-590-3p, and brain natriuretic peptide (BNP). The Kaplan-Meier curve and Cox regression analysis were used to assess the prognostic value of ZFAS1 and miR-590-3p in CHF. This study found that the serum levels of ZFAS1 were significantly higher, while miR-590-3p levels were significantly lower in CHF. ROC results indicated that the combined diagnostic accuracy of ZFAS1 + miR-590-3p + BNP was significantly higher than that of these indicators used alone. Kaplan- Meier results showed that patients with low expression of miR-590-3p or high expression of ZFAS1 had poor prognosis. In conclusion, CHF patients had increased ZFAS1 and decreased miR-590-3p expression. ZFAS1 and miR-590-3p might serve as novel non-invasive diagnostic and prognostic markers for patients with CHF.

A fully conjugated organic polymer via Knoevenagel condensation for fast separation of uranium.

Design and preparation of a kind of pore-free adsorbent with abundant active sites is favorable for fast separation of uranium. Here, a two-dimensional olefin-linked conjugated organic polymer was prepared via the Knoevenagel condensation reaction. The product owns good stability and excellent fluorescence property due to the fully conjugated skeleton. Moreover, owning to the high content of N atom, it shows excellent performance in adsorption and separation of uranium, and more importantly, it is constructed with nearly pore-free structure because of the irregular staggered stacking, which makes it exhibit fast adsorption behavior towards uranium. These results confirm the feasibility of pore-free material for fast adsorption.

Crystalline quantum dots of covalent organic frameworks for fast and sensitive detection of uranium.

A crystalline quantum dot of a COF was prepared for the first time by the original BRB method and a novel pathway for online monitoring of the COF reaction rate was proposed. The quantum dot can respond to uranyl ion quickly and sensitively and is of great potential in uranium detection.

Laminated self-standing covalent organic framework membrane with uniformly distributed subnanopores for ionic and molecular sieving.

The preparation of subnanoporous covalent-organic-framework (COF) membranes with high performance for ion/molecule sieving still remains a great challenge. In addition to the difficulties in fabricating large-area COF membranes, the main reason is that the pore size of 2D COFs is much larger than that of most gas molecules and/or ions. It is urgently required to further narrow their pore sizes to meet different separation demands. Herein, we report a simple and scalable way to grow large-area, pliable, free-standing COF membranes via a one-step route at organic-organic interface. The pore sizes of the membranes can be adjusted from >1 nm to sub-nm scale by changing the stacking mode of COF layers from AA to AB stacking. The obtained AB stacking COF membrane composed of highly-ordered nanoflakes is demonstrated to have narrow aperture (∼0.6 nm), uniform pore distribution and shows good potential in organic solvent nanofiltration, water treatment and gas separation.

Growth of high-quality covalent organic framework nanosheets at the interface of two miscible organic solvents.

Stronger covalent bonds between monomers, relatively more complex growth processes (polymerization, crystallization, assembly, etc.) and π-π stacking interactions between adjacent layers make it extremely difficult to obtain highly ordered crystalline 2D covalent organic framework (COF) nanosheets. So more effective solutions have to be developed to push the methods reported so far beyond their inherent limitations. Herein, we report the first example of growing high-quality 2D COF nanosheets (NS-COF) at the interface of two miscible organic solvents. The novel approach, which is named as a buffering interlayer interface (BII) method, can be achieved by simply adding a low-density solvent interlayer, as a buffer layer, between the two miscible main solvents based on the self-propelled directed motion of the interface driven by the density differences among the solvents involved. The as-synthesized NS-COF exhibits a super-large size and a relatively regular shape with a smooth surface, which have not been observed before. The proposed strategy offers a facile and effective approach for growing well-structured 2D COF nanosheets and also other kinds of nanosheets.

Graphene-synergized 2D covalent organic framework for adsorption: A mutual promotion strategy to achieve stabilization and functionalization simultaneously.

Most of current absorbents are difficult to hold favorable stability and functionality simultaneously when used in condition of high acidity and strong radiation existing in nuclear industry. Herein, a new graphene-synergized 2D covalent organic framework (GS-COF) was obtained via an in-situ loading of a covalent organic framework (TDCOF) on graphene sheets based on a mutual promotion strategy proposed in this work. The corresponding oximation products, o-GS-COF, and also o-TDCOF as a reference object, were respectively prepared subsequently. The results of experiments confirmed that o-GS-COF possesses better acid and irradiation stability than that of o-TDCOF. Adsorption experiments showed that the adsorption capacity of o-GS-COF for uranium is 144.2 mg g-1, higher than that of GO (92.5 mg g-1) and o-TDCOF (105.0 mg g-1), and the maximum adsorption capacity reaches 220.1 mg g-1. In the multi-ions system, o-GS-COF also displayed good selective adsorption property for uranium with SFU/M 35-100 for 5 coexisting divalent metal ions and 14-18 for 5 coexisting trivalent lanthanide ions. The proposed strategy successfully achieved the synergistic improvement of both stability and functionality for the desired adsorbing materials and is of considerable practical utility in the field of design and preparation of reliable high-performance absorbents.

Synthesis of Microporous Covalent Phosphazene-Based Frameworks for Selective Separation of Uranium in Highly Acidic Media Based on Size-Matching Effect.

On the basis of high stability of phosphorus-oxygen linkage, we constructed two microporous covalent phosphazene-based frameworks (CPFs), for the first time, by choosing hexachlorocyclotriphosphazene as a core unit and polyhydroxy aromatic compounds (hydroquinone or phloroglucinol) as monomers, named CPF-D and CPF-T, respectively. Characterization studies by using Fourier transform infrared, nuclear magnetic resonance, thermal gravimetric analysis, 60Co γ-ray irradiation, and so forth, demonstrated that both of the CPF materials have excellent acid and radiation stability and relatively higher thermal stability. The results of batch adsorption experiments show that CPF-T is significantly more capable of sorbing uranium than CPF-D. In a pure uranium system with higher acidity (pH 1), the uranium sorption amount of CPF-T can reach up to 140 mg g-1. Distinctively, in mixed-metal solution with 12 coexisting cations, CPF-T shows relatively stable and excellent uranium adsorption capability over a wide range of acidity (pH 4 to 3 M HNO3), and the difference in uranium sorption amounts is less than 30% with the maximum of 0.26 mmol g-1 at pH 4 and the minimum of 0.20 mmol g-1 at 3 M HNO3, which is far superior to that of the conventional solid-phase extractant (SPE) materials previously reported. The research results suggested that the sorption model based on the speculated mechanism of size-matching plus hydrogen bond network has played a dominant role in the process of uranium adsorption. The proposed strategy for the one-pot fabrication of an acid-resistant microporous framework materials by bridging the aromatic monomers via P-O bonds provides an alternative approach for the design and synthesis of new SPE materials with size-matching function desired for effective separation of uranium or other valuable metals from highly acidic environments.

"Stereoscopic" 2D super-microporous phosphazene-based covalent organic framework: Design, synthesis and selective sorption towards uranium at high acidic condition.

So far, only five primary elements (C, H, O, N and B) and two types of spatial configuration (C2-C4, C6 and Td) are reported to build the monomers for synthesis of covalent organic frameworks (COFs), which have partially limited the route selection for accessing COFs with new topological structure and novel properties. Here, we reported the design and synthesis of a new "stereoscopic" 2D super-microporous phosphazene-based covalent organic framework (MPCOF) by using hexachorocyclotriphosphazene (a P-containing monomer in a C3-like spatial configuration) and p-phenylenediamine (a linker). The as-synthesized MPCOF shows high crystallinity, relatively high heat and acid stability and distinctive super-microporous structure with narrow pore-size distributions ranging from 1.0-2.1nm. The results of batch sorption experiments with a multi-ion solution containing 12 co-existing cations show that in the pH range of 1-2.5, MPCOF exhibits excellent separation efficiency for uranium with adsorption capacity more than 71mg/g and selectivity up to record-breaking 92%, and furthermore, an unreported sorption capacity (>50mg/g) and selectivity (>60%) were obtained under strong acidic condition (1M HNO3). Studies on sorption mechanism indicate that the uranium separation by MPCOF in acidic solution is realized mainly through both intra-particle diffusion and size-sieving effect.

Nano-diamond particles functionalized with single/double-arm amide-thiourea ligands for adsorption of metal ions.

Separation efficiency of solid-phase extractant is greatly subjected to the spatial configurations of functional ligands attached to the matrix, which has not been studied efficiently till now. In order to further understand the relationship between spatial configurations of the attached functional ligand and the adsorption ability of the extractant, two novel molecules (single-armed ligand, SA and double-armed ligand, DA) with identical coordination unit (amide-thiourea) but different spatial configurations (single/double arms) were designed and synthesized. The corresponding extractants, ND-SA and ND-DA were obtained by modification of nanodiamond (ND) with SA and DA and both the extractants displayed good chemical and thermal stabilities. The batch adsorption experiments showed that ND-SA and ND-DA possess large adsorption capacities (∼200 mg g(-1)), very fast adsorption kinetics (reaching equilibrium within 2 min) and excellent selectivities (up to 82% and 72%, respectively) for uranium. The study of the possible mechanism indicated that ND-DA tends to utilize its tweezer-like double arms to "clamp" metal ions and the stronger chelate interaction could to some extent weaken the coordination selectivity of attached DA ligand. In contrast, single-armed adsorbent ND-SA unexpectedly exhibited better adsorption selectivity for uranium than ND-DA owing to its more flexible spatial configuration and moderate complexing ability.

Pore-Free Matrix with Cooperative Chelating of Hyperbranched Ligands for High-Performance Separation of Uranium.

A new strategy combining a pore-free matrix and cooperative chelating was proposed in the present paper in order to effectively avoid undesired nonselective physical adsorption and intraparticle diffusion caused by pores and voids in porous sorbents, and to greatly enhance uranium-chelating capability based on hyperbranched amidoxime ligands on the surface of nanodiamond particles. Thus, a pore-free, amidoxime-terminated hyperbranched nanodiamond (ND-AO) was designed and synthesized. The experimental results demonstrate that the strategy endows the as-synthesized ND-AO with the following expected features: (1) distinctively high uranium selectivity (SU = qe-U/qe-tol × 100%) from over 80% to nearly 100% over the whole weak acidity range (pH < 4.5); especially, the SU can reach up to unprecedented >91% at pH 4.5, more than 20% of selectivity increment over any analogous sorbent materials reported so far, with a uranium sorption capacity of 121 mg/g in simulated nuclear industry effluent samples containing 12 coexistent nuclide ions; (2) superfast equilibrium sorption time of <30 s; and (3) one of the highest distribution coefficients (Kd) of ∼3 × 106 mL/g for U(VI) as well as a fairly high sorption capacity of 212 mg/g at pH 4.5 in pure uranium solution. The strategy could also provide an optional approach for the design and fabrication of other new high-performance sorbing materials with prospective applications in selective separation of other interested metal ions.

[Preparation and characterization of polyclonal antibodies against rat sodium pump alpha 2 subunit M1-M2 extra membrane fragment].

OBJECTIVE: To prepare polyclonal antibodies against sodium pump alpha 2 subunit M1-M2 extramembrane fragment (NKAα2 EM1) for studying the pathogenesis of hypertension. METHODS: According to the GenBank data, the amino acid sequence of NKAα2 EM1 was obtained and the target peptide (LAAMEDEPSNDN) was synthesized using a peptide synthesizer with Fmoc method and purified with high-performance liquid chromatography. The synthesized peptide was then coupled to KLH for immunizing New Zealand white rabbits for 4 times to obtain the antiserum. The IgG antibodies against the synthetic peptide, after affinity purification with Protein A, were used for detecting NKAα2 EM1 expression in rat aortic vascular smooth muscle cells by enzyme-linked immunosorbent assay and immunocytochemistry (ICC). RESULTS: The synthesized peptide fragment , which consisted of 13 amino acid residues including one derivatized cysteine residue in the N-terminal (LAAMEDEPSNDN-C), had a theoretical relative molecular mass of 1408.48 D with a measured relative molecular mass of 1407.90 D and a purity exceeding 85.5%. The titer of the antiserum was more than 1:512 000, and the purified IgG antibody concentration was 0.965 mg/ml after purification with Protein A. At a 1:1000 dilution (final concentration of 1 µg/ml), the titer of the purified IgG antibody was more than 1:256 000. The purified IgG antibody could be used at 1:100 to 1:200 dilutions for for immunocytological examination of formalin-fixed cells. CONCLUSION: The anti-NKAα2 EM1 polyclonal antibodies obtained can be used in ELISA and immunocytochemistry for detecting the sodium pump alpha 2 subunit in formalin-fixed tissue or cells to facilitate investigation of the relationship between sodium pump and hypertension.

[Effect of ouabain on intracellular Ca(2+) concentration in rat vascular smooth muscle cells in vitro].

OBJECTIVE: To explore the effect of ouabain on intracellular Ca(2+) concentration ([Ca(2+)]i) in thoracic aorta vascular smooth muscle cells (VSMCs) in vitro. METHODS: Primary SD rat thoracic aorta VSMCs were cultured by tissue adherent method and identified by immunochemistry. The binding ability between ouabain and VSMCs was detected by autoradiography, and fluo 3-AM (a Ca(2+) fluorescent probe) was employed to investigate whether ouabain affected VSMCs within a short period of time. The effect of a truncated fragment of the sodium pump α2 subunit was assayed in antagonizing the effect of ouabain on [Ca(2+)]i in the VSMCs. RESULTS: Within the concentration range of 0.1-100 nmol/L, ouabain was found to dose-dependently bind to the VSMCs. Different concentrations of ouabain (0-3200 nmol/L) caused a transient, dose-dependent increase in [Ca(2+)]i in the VSMCs, which was antagonized by the application of the truncated fragment of sodium pump α2 subunit. CONCLUSIONS: Elevations in [Ca(2+)]i in the VSMCs can be the cytological basis of high ouabain-induced hypertension. The truncated fragment of the sodium pump α2 subunit can antagonize ouabain-induced increase of [Ca(2+)]i in the VSMCs, which provides a clue for understanding the pathogenesis of and devising a therapeutic strategy for high ouabain-induced hypertension.

Three novel triazine-based materials with different O/S/N set of donor atoms: One-step preparation and comparison of their capability in selective separation of uranium.

Cyanuric chloride was chosen as a core skeleton which reacted with desired linker molecules, urea, thiourea and thiosemicarbazide, to prepare three novel functional covalent triazine-based frameworks, CCU (O-donor set), CCTU (S-donor set) and CCTS (S, N-donor set) respectively, designed for selective adsorption of U(VI). The products have high nitrogen concentration (>30 wt%), regular structure, relatively high chemical and thermal stability. Adsorption behaviors of the products on U(VI) were examined by batch experiments. CCU and CCTU can extract U(VI) from simulated nuclear industrial effluent containing 12 co-existing cations with relatively high selectivity (54.4% and 54.2%, respectively). Especially, effects of donor atoms O/S on adsorption were investigated, and the outcomes indicate that the difference in coordinating ability between the donor atoms is weakened in large conjugated systems, and the related functional groups with originally very strong coordination abilities may not be the best choice for the application in selective adsorption of uranium and also other metals. The as-proposed approach can easily be expanded into design and preparation of new highly efficient adsorbents for selective separation and recovery of uranium through adjusting the structures, types and amounts of functional groups of adsorbents by choosing suitable linkers.