Interplay between Cation–π and Coinage‐Metal–Oxygen Interactions: An Ab Initio Study and Cambridge Structural Database Survey

The interplay between cation–π and coinage‐metal–oxygen interactions are investigated in the ternary systems N???PhCCM???O (N=Li⁺, Na⁺, Mg²⁺; M=Ag, Au; O=water, methanol, ethanol). A synergetic effect is observed when cation–π and coinage‐metal–oxygen interactions coexist in the same complex. The cation–π interaction in most triads has a greater enhancing effect on the coinage‐metal–oxygen interaction. This effect is analyzed in terms of the binding distance, interaction energy, and electrostatic potential in the complexes. Furthermore, the formation, strength, and nature of both the cation–π and coinage‐metal–oxygen interactions can be understood in terms of electrostatic potential and energy decomposition. In addition, experimental evidence for the coexistence of both interactions is obtained from the Cambridge Structural Database (CSD).     

Separation of isorhamnetin 3‐sulphate and astragalin from Flaveria bidentis (L.) Kuntze using macroporous resin and followed by high‐speed countercurrent chromatography

D4020 resin offered the best dynamic adsorption and desorption capacity for total flavonoids based on the research results from ten kinds of macroporous resin. A column packed with D4020 resin was used to optimize the separation of total flavonoids from Flaveria bidentis (L.) Kuntze extracts. The content of flavonoids in the product was increased from 4.3 to 30.1% with a recovery yield of 90%. After the treatment with gradient elution on D4020 resin, the contents of isorhamnetin 3‐sulfate and astragalin were increased from 0.49 to 8.70% with a recovery yield of 74.1% and 1.16 to 30.8%, with a recovery yield of 92.2%, respectively. Further purification was carried out by one‐run high‐speed countercurrent chromatography yielding 4.5 mg of isorhamnetin 3‐sulfate at a high purity of 96.48% and yielding 24.4 mg of astragalin at a high purity of over 98.46%.     

Preparation of novel curcumin‐imprinted polymers based on magnetic multi‐walled carbon nanotubes for the rapid extraction of curcumin from ginger powder and kiwi fruit root

A novel molecularly imprinted polymer based on magnetic phenyl‐modified multi‐walled carbon nanotubes was synthesized using curcumin as the template molecule, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross‐linker. The phenyl groups contained in the magnetic imprinted polymers acted as the assisting functional monomer. The magnetic imprinted polymers were characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy and vibrating sample magnetometry. Adsorption studies demonstrated that the magnetic imprinted polymers possessed excellent selectivity toward curcumin with a maximum capacity of 16.80 mg/g. Combining magnetic extraction and high‐performance liquid chromatography technology, the magnetic imprinted polymer based on magnetic phenyl‐modified multi‐walled carbon nanotubes was applied for the rapid separation and enrichment of curcumin from ginger powder and kiwi fruit root successfully.     

Determination of neuroprotective oxysterols in Calculus bovis,human gallstones,and traditional Chinese medicine preparations by liquid chromatography with mass spectrometry

So far, the components responsible for the neuroprotective effects of Calculus bovis are unclear. Cholesterol, one of the major components in Calculus bovis, is easily oxidized into oxysterols, which possess direct or indirect neuroprotective effects proved by our and others’ previous studies. Therefore, a liquid chromatography with mass spectrometry method coupled with ultrasonic extraction and solid‐phase extraction was developed for the determination of neuroprotective oxysterols in Calculus bovis, human gallstones, and traditional Chinese medicine preparations. Chromatographic separation was achieved on a C₁₈ column with isocratic elution at a flow rate of 1 mL/min. The established method showed good linearity (R² > 0.998), sensitivity with low limits of detection (0.06–0.39 μg/g), acceptable precisions (relative standard deviations ≤ 7.4%), stability (relative standard deviations ≤ 5.9%), and satisfactory accuracy (92.4–102.9%) for all analytes identified by different retention times, which could be applied for the determination of oxysterols. Five kinds of oxysterols proved to function as neuroprotectants were detected at different concentrations. Among them, 7β‐hydroxycholesterol and cholestane‐3β,5α,6β‐triol were rather abundant in the samples. It could be concluded that the potential neuroprotective components in Calculus bovis may be these oxysterols.     

Infinite Horizon Controlled Diffusions with Randomly Varying and State-Dependent Discount Cost Rates

This work focuses on optimal controls of diffusions in an infinite horizon. It has several distinct features in contrast to the existing literature. The discount factor is allowed to be randomly varying and state dependent. The existence and uniqueness of the viscosity solution to the associated Hamilton–Jacobi–Bellman equation are established. The verification theorem is also obtained. Because closed-form solutions are virtually impossible to obtain in most cases, we develop numerical methods. Using the Markov chain approximation methods, numerical schemes are constructed; viscosity solution methods are used to prove the convergence of the algorithm. In addition, examples are given for demonstration purpose.     

Phenolic constituents from <Emphasis Type="Italic">Alisma plantago</Emphasis>-<Emphasis Type="Italic">aquatica</Emphasis> Linnaeus and their anti-chronic prostatitis activity

Background

The plant Alisma plantago-aquatica Linnaeus, which is widely distributed in southwest of China, is the main material of traditional Chinese medicine “Zexie”. It was used as folk medicine for immune-modulation, anti-tumor, anti-inflammatory and antibacterial. Previous chemical studies on A. plantago-aquatica reported the identification of triterpenes, diterpenes, sesquiterpenes, steroids, alkaloids and phenolic acid. Terpenes and phenolic acid were regard as major secondary metabolites from this medicine plant.

Results

A new phenolic acid, plantain A (1), along with four known compounds (2–5) were isolated and identified from A. plantago-aquatica by extensive chromatographic and spectrometric methods. In the present study, the levels of TNF-α, IL-1β, COX-2, PEG2 and TGF-β1 were increased in model group rats, whereas on treatment with the isolated compound (1 and 4) at 50 mg/kg, there was a significant decrease in the cytokine levels. Therefore, the anti-CNP effect of 1 and 4 may be related to their anti-inflammatory properties.

Conclusions

A new phenolic acid and four known phenolic compounds were isolated from A. plantago-aquatica. Moreover, compounds 1 and 4 shows significant anti-chronic prostatitis activity in rats.

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Exploring the Interactions of Atomic Oxygen on Silver Clusters with Hydrogen

The interactions between Ag_nO^-(n=1-8) and H₂ (or D₂) were explored by combination of the mass spectroscopy experiments and density function theory (DFT) calculations. The experiments found that all oxygen atoms in Ag_nO^-(n=1-8) are inert in the interactions with H₂ or D₂ at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation (PROX) of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between Ag_nO^-(n=1-8) and H₂ were explored using DFT calculations. The results indicated that adsorption of H₂ on any site of Ag_nO^-(n=1-8) is extremely weak, and oxidation of H₂ by any kind of oxygen in Ag_nO^-(n=1-8) has an apparent barrier strongly dependent on the adsorption style of the "O". These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.     

Encapsulation of RNA by negatively charged human serum albumin via physical interactions

Human serum albumin (HSA) is the most abundant plasma protein and has an inherent ability to target tumor cells. It is an excellent candidate for drug delivery. However, HSA cannot form complex with DNA or RNA, because it is negatively charged under physiological conditions. In this work, we reported a simple method to prepare HSA/RNA nanoparticles mainly by physical interaction. Firstly, the solution pH is adjusted to 4.0, under which condition HSA is positively charged. It forms complex with RNA via electrostatic interaction. The solution is then heated at 75 oC for 15 min to stabilize the structure and the size of the formed complex. The HSA/RNA nanoparticle prepared by this method has a diameter about 110 nm and a narrow distribution. It is also stable for days under physiological conditions. Cellular essays demonstrate that these particles exhibit a high cellular uptake efficiency and non-toxicity to HeLa cells.     

Structural versatility and electrochemical properties of four copper(II) complexes based on 1<Emphasis Type="Italic">H</Emphasis>-indazole-3-carboxylic acid

Copper (Cu)(II) complexes were synthesized by Ind-3-COOH combined with N-containing auxiliary ligands via a combinatorial strategy involving hydrothermal and solvent-evaporation method. The synthesized complexes had the following formulas: [Cu(Ind-3-COO)₂] (1), [Cu(PHEN)(Ind-3-COO)]₂·2H₂O (2), [Cu₂(DPP)(Ind-3-COO)₂(H₂O)]·H₂O, (3) and [Cu(BPY)(Ind-3-COO)₂]·4H₂O (4). Meanwhile, the symbol abbreviations were listed as follows: Ind-3-COOH = 1H-indazole-3-carboxylic acid, 1,3-bis(4-pyridyl)propane (DPP), 1,10-phenanthroline (PHEN) and 4,4′-bipyridine (BPY). The crystalline structure and spectroscopy of each complex were characterized by single-crystal X-ray diffraction, elemental analysis, Fourier transform infrared spectroscopy and powder X-ray diffraction. The redox reactions in the complexes were then investigated by performing cyclic voltammetry under nitrogen conditions at room temperature. Two pairs of distinctive irreversible reduction potentials were identified, which could be attributed to the processes of Cu(II)–Cu(I) and Cu(I)–Cu(0).     

Self-catalytic synthesis of hydrophilic polypyrrole/tellurium nanocomposite and its capacitance performance

Journal of Solid State Electrochemistry - A hydrophilic polypyrrole/tellurium (PPy/Te) nanocomposite was synthesized by a facile approach in which H2TeO3 was used as the oxidizing agent of pyrrole...