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.     

过渡金属-配体σ键键能在碳-氢键活化中的应用

过渡金属催化的碳-氢(C-H)键活化因其优异的原子经济性及步骤简便性在过去几十年间蓬勃发展,已成为当前构建复杂化合物最常用的策略之一.对该过程中活性中间体的热力学研究有助于加深人们对反应机理的理解,指导新催化剂、新反应的理性设计.然而,近年来该领域的发展颇为缓慢,相应的报道十分零散,缺少系统的归纳和总结.本综述简要梳理了过渡金属-配体σ键键能的研究历程,并举例阐述了这些热力学参数在分析反应可行性、判断反应选择性等方面的应用,旨在推动过渡金属络合物相关的热力学研究的快速发展.     

Form-stable and tough paraffin-Al2O3/high density polyethylene composites as environment-friendly thermal energy storage materials: preparation,characterization and analysis

Journal of Thermal Analysis and Calorimetry - In this study, we focus on important global issue containing both environmental pollution control and energy saving. High density polyethylene (HDPE)...     

Crystallization kinetics of a commercial poly(lactic acid) based on characteristic crystallization time and optimal crystallization temperature

Journal of Thermal Analysis and Calorimetry - A model is proposed to fit differential scanning calorimetry (DSC) isothermal crystallization curves obtained from the molten state at different...