In-situ grown metal organic framework synergistic system for the enantioseparation of three drugs in open tubular capillary electrochromatography

Metal organic frameworks have received great attention as the chiral stationary phase for racemic drug separation because of their fascinating structures and properties. However, the most homochiral metal organic frameworks were constructed by rare and precious chiral organic ligands. In this work, an achiral metal organic framework, together with a natural chiral selector carboxymethyl β-cyclodextrin built a synergistic separation system in the open tubular capillary electrochromatography. The novel coated columns were developed by inducing metal organic framework nanoparticles to grow on the imidazolyl functional capillary inner wall. The baseline separations of hydroxychloroquine, ofloxacin, and atenolol were achieved in the synergistic separation system. The effects of the concentration of chiral selector, pH, voltage, and the concentration of organic additives were studied. Compared with chiral selector auxiliary bare capillary, the resolutions of three drugs were remarkably improved. The relative standard deviations for the retention time of intraday (n = 6), interday (n = 6), and column-to-column were less than 2.1, 2.6, and 5.2%, respectively. These results demonstrate that affordable synergistic separation systems are prospective for racemic drug enantioseparation in capillary electrochromatography.     

Convergent architecting of multifunction-in-one hydrogels as wound dressings for surgical anti-infections

Surgical procedures are susceptible to the cause of infections, which could induce delayed wound healing, oxidative stress and tissue ischemia. Multifunctional wound dressings (e.g., hydrogels) without the induction of antibiotics is promising for the elimination of surgical site infections and the associated complications. Herein, we report a reductionism approach for the fabrication of bioactive hydrogels to recapitulate antibacterial functions as well as antioxidant, pro-angiogenic and hemostatic properties in surgical infection treatments. The hydrogels composed of naturally derived Cirsium setosum extracts (CE, a traditional medicinal herb) and carboxymethyl chitosan (CS) show their capacity for surgical anti-infections on three different models (i.e., infectious random skin flap model, infectious skin defect model and infectious femur fracture model). Due to the innate bioactivities of CE and CS, CECS hydrogels can also reduce the bleeding loss (85% reduction) on a hemorrhaging liver model and improve the vascularization for skin flap regeneration. Overall, bioactive CECS hydrogels integrated with the ease and scalability of assembly process and biological activities without the addition of antibiotics is promising to act as multifunctional wound dressings for surgical anti-infections.     

Recent Progress in High-Performance Lithium Sulfur Batteries: The Emerging Strategies for Advanced Separators/Electrolytes Based on Nanomaterials and Corresponding Interfaces

Lithium-sulfur (Li−S) batteries, possessing excellent theoretical capacities, low cost and nontoxicity, are one of the most promising energy storage battery systems. However, poor conductivity of elemental S and the “shuttle effect” of lithium polysulfides hinder the commercialization of Li−S batteries. These problems are closely related to the interface problems between the cathodes, separators/electrolytes and anodes. The review focuses on interface issues for advanced separators/electrolytes based on nanomaterials in Li−S batteries. In the liquid electrolyte systems, electrolytes/separators and electrodes system can be decorated by nano materials coating for separators and electrospinning nanofiber separators. And, interface of anodes and electrolytes/separators can be modified by nano surface coating, nano composite metal lithium and lithium nano alloy, while the interface between cathodes and electrolytes/separators is designed by nano metal sulfide, nanocarbon-based and other nano materials. In all solid-state electrolyte systems, the focus is to increase the ionic conductivity of the solid electrolytes and reduce the resistance in the cathode/polymer electrolyte and Li/electrolyte interfaces through using nanomaterials. The basic mechanism of these interface problems and the corresponding electrochemical performance are discussed. Based on the most critical factors of the interfaces, we provide some insights on nanomaterials in high-performance liquid or state Li−S batteries in the future.     

Cu Doping-Induced Transformation from [Ag62S12(SBut)32]2+ to [Ag62−xCuxS12(SBut)32]4+ Nanocluster

The change in the valence state of nanocluster can induce remarkable changes in the properties and structure. However, achieving the valence state changes in nanoclusters is still a challenge. In this work, we use Cu²⁺ as dopant to “oxidize” [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ (4 free electrons) to obtain the new nanocluster: [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ with 2 free electrons. As revealed by its structure, the [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ (x=10∼21) has a similar structure to that of [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ precursor and all the Cu atoms occupy the surface site of nanocluster. It′s worth noting that with the Cu atoms doping, the [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ nanocluster is more stable than [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ at higher temperature and in electrochemical cycle. This result has laid a foundation for the subsequent application and exploration. Overall, this work reveals crystals structure of a new Ag−Cu nanocluster and offers a new insight into the electron reduction/oxidation of nanocluster.     

MIL-101(Cr) Microporous Nanocrystals Intercalating Graphene Oxide Membrane for Efficient Hydrogen Purification

Graphene oxide (GO) is a promising two-dimensional building block for fabricating high-performance gas separation membranes. Whereas the tortuous transport pathway may increase the transport distance and lead to a low gas permeation rate, introducing spacers into GO laminates is an effective strategy to enlarge the interlayer channel for enhanced gas permeance. Herein, we propose to intercalate CO₂-philic MIL-101(Cr) metal-organic framework nanocrystals into the GO laminates to construct a 2D/3D hybrid structure for gas separation. The interlayer channels were partially opened up to accelerate gas permeation. Meanwhile, the intrinsic pores of MIL-101 provided additional transport pathways, and the affinity of MIL-101 to CO₂ molecules resulted in higher H₂/CO₂ diffusion selectivity, leading to a simultaneous enhancement in gas permeance and separation selectivity. The MIL-101(Cr)/GO membrane with optimal structures exhibited outstanding and stable mixed-gas separation performance with H₂ permeance of 67.5 GPU and H₂/CO₂ selectivity of 30.3 during the 120-h continuous test, demonstrating its potential in H₂ purification application.     

Polyoxygenated Klysimplexane- and Eunicellin-Based Diterpenoids from the Gorgonian Briareum violaceum

Three new polyoxygenated diterpenoids with a rare 4-isopropyl-1,5,8a-trimethylperhydrophenanthrane structure of the klysimplexane skeleton, briarols A‒C (1‒3), and one eunicellin-based diterpenoid, briarol D (4), were isolated from Briareum violaceum, a gorgonian inhabiting Taiwanese waters. The chemical structures of these compounds were determined by employing extensive analyses of NMR and high-resolution electrospray ionization mass spectrometry (HRESIMS) data. Metabolites 1‒3 were found to possess the rarely found skeleton of the diterpenoid klysimplexin T. All isolated compounds showed very weak cytotoxic activity against the growth of three cancer cell lines. A plausible biosynthetic pathway for briarols A‒C from the coexisting eunicellin diterpenoid briarol D (4) was postulated.     

Enhanced Oral Absorption of Icaritin by Using Mixed Polymeric Micelles Prepared with a Creative Acid-Base Shift Method

The purpose of this study was to develop mixed polymeric micelles with high drug loading capacity to improve the oral bioavailability of icaritin with Soluplus^® and Poloxamer 407 using a creative acid-base shift (ABS) method, which exhibits the advantages of exclusion of organic solvents, high drug loading and ease of scaling-up. The feasibility of the ABS method was successfully demonstrated by studies of icaritin-loaded polymeric micelles (IPMs). The prepared IPMs were characterized to have a spherical shape with a size of 72.74 ± 0.51 nm, and 13.18% drug loading content. In vitro release tests confirmed the faster release of icaritin from IPMs compared to an oil suspension. Furthermore, bioavailability of icaritin in IPMs in beagle dogs displayed a 14.9-fold increase when compared with the oil suspension. Transcellular transport studies of IPMs across Caco-2 cell monolayers confirmed that the IPMs were endocytosed in their intact forms through macropinocytosis, clathrin-, and caveolae-mediated pathways. In conclusion, the results suggested that the mixed micelles of Soluplus^® and Poloxamer 407 could be a feasible drug delivery system to enhance oral bioavailability of icaritin, and the ABS method might be a promising technology for the preparation of polymeric micelles to encapsulate poorly water-soluble weakly acidic and alkaline drugs.     

Activity Guided Isolation of Phenolic Compositions from Anneslea fragrans Wall. and Their Cytoprotective Effect against Hydrogen Peroxide Induced Oxidative Stress in HepG2 Cells

Anneslea fragrans Wall., commonly known as “Pangpo Tea”, is traditionally used as a folk medicine and healthy tea for the treatment of liver and intestine diseases. The aim of this study was to purify the antioxidative and cytoprotective polyphenols from A. fragrans leaves. After fractionation with polar and nonpolar organic solvents, the fractions of aqueous ethanol extract were evaluated for their total phenolic (TPC) and flavonoid contents (TFC) and antioxidant activities (DPPH, ABTS, and FRAP assays). The n-butanol fraction (BF) showed the highest TPC and TFC with the strongest antioxidant activity. The bio-guided chromatography of BF led to the purification of six flavonoids (1–6) and one benzoquinolethanoid (7). The structures of these compounds were determined by NMR and MS techniques. Compound 6 had the strongest antioxidant capacity, which was followed by 5 and 2. The protective effect of the isolated compounds on hydrogen peroxide (H₂O₂)-induced oxidative stress in HepG2 cells revealed that the compounds 5 and 6 exhibited better protective effects by inhibiting ROS productions, having no significant difference with vitamin C (p > 0.05), whereas 6 showed the best anti-apoptosis activity. The results suggest that A. fragrans could serve as a valuable antioxidant phytochemical source for developing functional food and health nutraceutical products.     

Structural Insights into the Interactions of Digoxin and Na+/K+-ATPase and Other Targets for the Inhibition of Cancer Cell Proliferation

Digoxin is a cardiac glycoside long used to treat congestive heart failure and found recently to show antitumor potential. The hydroxy groups connected at the C-12, C-14, and C-3′a positions; the C-17 unsaturated lactone unit; the conformation of the steroid core; and the C-3 saccharide moiety have been demonstrated as being important for digoxin’s cytotoxicity and interactions with Na⁺/K⁺-ATPase. The docking profiles for digoxin and several derivatives and Na⁺/K⁺-ATPase were investigated; an additional small Asn130 side pocket was revealed, which could be useful in the design of novel digoxin-like antitumor agents. In addition, the docking scores for digoxin and its derivatives were found to correlate with their cytotoxicity, indicating a potential use of these values in the prediction of the cancer cell cytotoxicity of other cardiac glycosides. Moreover, in these docking studies, digoxin was found to bind to FIH-1 and NF-κB but not HDAC, IAP, and PI3K, suggesting that this cardiac glycoside directly targets FIH-1, Na⁺/K⁺-ATPase, and NF-κB to mediate its antitumor potential. Differentially, digoxigenin, the aglycon of digoxin, binds to HDAC and PI3K, but not FIH-1, IAP, Na⁺/K⁺-ATPase, and NF-κB, indicating that this compound may target tumor autophagy and metabolism to mediate its antitumor propensity.     

From borophosphate to fluoroborophosphate: a rational design of fluorine-induced birefringence enhancement

The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_2BP_3O_(11)with the monoclinic space group P2_1/c has been synthesized in the sealed system.Ba_2BP_3O_(11)exhibits a rare P–O–P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_4]~(3-)with[BO_3F]~(4-),the first alkaline-earth metal/lead fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) with the same space group were designed.Since the scissors effect of fluorine,in M_2BP_2O_8F (M=Ba and Pb),a BO_3F tetrahedron corner-sharing with three PO_4tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_n(M=Ba/Pb,n=5,6,8) distorted polyhedra.The first principles calculation shows that the borophosphate Ba_2BP_3O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.