Self‐Assembly and Disassembly of Vesicles as Controlled by Anion–π Interactions

Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self‐assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self‐assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self‐assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO₃^?, Cl^?, and Br^?, or by changing the pH value of the medium.     

Real-time tracking of hydrogen peroxide secreted by live cells using MnO2 nanoparticles intercalated layered doubled hydroxide nanohybrids

We report a facile and green method for the fabrication of new type of electrocatalysts based on MnO₂ nanoparticles incorporated on MgAl LDH P-type semiconductive channel and explore its practical applications as high-performance electrode materials for electrochemical biosensor. A series of MgAl layered doubled hydroxide (LDH) nanohybrids with fixed Mg/Al (M²⁺/M³⁺ atomic ratio of 3) and varied amount of MnCl₂.4H₂O are fabricated by a facile co-precipitation method. This approach demonstrates the combination of distinct properties including excellent intercalation features of LDH for entrapping nanoparticles and high loading of MnO₂ nanoparticles in the host layers of LDH. Among all samples, Mn5–MgAl with 0.04% loaded manganese has a good crystalline morphology. A well-dispersed MnO₂ nanoparticles encapsulated into the host matrix of hydrotalcite exhibit enhanced electrocatalytic activity towards the reduction of H₂O₂ as well as excellent stability, selectivity and reproducibility due to synergistic effect of good catalytic ability of MnO₂ and conductive MgAl LDH. Glass carbon electrode (GCE) modified with Mn5–MgAl possesses a wide linear range of 0.05–78 mM, lowest detection limit 5 μM (S/N = 3) and detection sensitivity of 0.9352 μAmM⁻¹. This outstanding performance enables it to be used for real-time tracking of H₂O₂ secreted by live HeLa cells. This work may provide new insight in clinical diagnosis, on-site environmental analysis and point of care testing devices.     

Syntheses,Structures, and Luminescent Properties of d10 Coordination Polymers with 2‐(4‐Carboxyphenyl)‐imidazo[4, 5‐f]‐1, 10‐phenanthroline and 1, 3‐Benzenedicarboxylate Derivatives

Four Zn^II/Cd^II coordination polymers (CPs) based on 2‐(4‐carboxy‐phenyl)imidazo[4, 5‐f]‐1, 10‐phenanthroline (HNCP) and different derivatives of 5‐R‐1, 3‐benzenedicarboxylate (5‐R‐1, 3‐BDC) (R = NO₂, H, OH), [Zn(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 1 ), [Cd(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 2 ), [Zn(HNCP)(1, 3‐BDC)(H₂O)₂]_n ( 3 ), and {[Zn(HNCP)(5‐OH‐1, 3‐BDC)(H₂O) · H₂O}_n ( 4 ) were synthesized under hydrothermal conditions. Compounds 1 – 4 were determined by elemental analyses, IR spectroscopy, and single‐crystal and powder X‐ray diffraction. Compounds 1 and 2 are isomorphous, presenting a 4‐connected uninodal (4, 4)‐sql 2D framework with threefold interpenetration, which are further extended into the three‐dimensional (3D) supramolecular architecture through π ··· π stacking interactions between the aryl rings of 5‐NO₂‐1, 3‐BDC. Compared to compound 1 , 3 is obtained by using different reaction temperatures and metal‐ligand ratios, generating a 3D framework with –ABAB– fashion via π ··· π stacking interactions. Compound 4 is a 1D chain, which is further extended into a 3D supramolecular net by hydrogen bonds and π ··· π stacking interactions. The thermogravimetric and fluorescence properties of 1 – 4 were also explored.     

Syntheses,Structures, and Magnetic Properties of Two Cobalt(II) Metal‐Organic Frameworks Based on Y‐shaped 3,5,4′‐Azobenzenetricarboxylic Acid and Different N‐donor Ligands

Two metal‐organic frameworks, [Co₂(ABTC)(bimh)(OH)] · 2H₂O ( 1 ) and [Co₃(ABTC)₂(dimb)₄]_n ( 2 ) [H₃ABTC = 3,4′,5‐azobenzenetricarboxylic acid, bimh = 1,1′‐(1,4‐hexanediy)bis(imidazole), dimb = 1,4‐bis(1H‐imidazol‐1‐yl)benzene], were prepared under solvothermal conditions and structurally characterized. Complex 1 demonstrates a complicated 3D (3,8)‐connected tfz‐d net with (4³)₂(4⁶.6¹⁷.8⁵) topology. The framework of 2 can be classified as a rare 3D (3,6,6)‐connected net with the Schäfli symbol of (4.6²)₂(4².6¹⁰.8³)(4⁴.6¹⁰.8), and exhibits an intriguing self‐penetrating motif. Meanwhile, the thermal stabilities and magnetic properties for 1 and 2 were also probed.     

Colorimetric method for determination of bisphenol A based on aptamer-mediated aggregation of positively charged gold nanoparticles

A sensitive, specific and rapid colorimetric aptasensor for the determination of the plasticizer bisphenol A (BPA) was developed. It is based on the use of gold nanoparticles (AuNPs) that are positively charged due to the modification with cysteamine which is cationic at near-neutral pH values. If aptamers are added to such AuNPs, aggregation occurs due to electrostatic interactions between the negatively-charged aptamers and the positively-charged AuNPs. This results in a color change of the AuNPs from red to blue. If a sample containing BPA is added to the anti-BPA aptamers, the anti-BPA aptamers undergo folding via an induced-fit binding mechanism. This is accompanied by a conformational change, which prevents the aptamer-induced aggregation and color change of AuNPs. The effect was exploited to design a colorimetric assay for BPA. Under optimum conditions, the absorbance ratio of A ₅₂₇/A ₆₈₀ is linearly proportional to the BPA concentration in the range from 35 to 140 ng∙mL⁻¹, with a detection limit of 0.11 ng∙mL⁻¹. The method has been successfully applied to the determination of BPA in spiked tap water and gave recoveries between 91 and 106 %. Data were in full accordance with results obtained from HPLC. This assay is selective, easily performed, and in our perception represents a promising alternative to existing methods for rapid quantification of BPA.

The negatively-charged anti-BPA aptamers can absorb onto the positively-charged cysteamine-capped AuNPs (cysteamine-AuNPs) via electrostatic interactions, which can cause the aggregation of AuNPs accompanied by a red-to-blue color change. In the presence of BPA, the specific binding of BPA to the aptamers induces the conformation changes of anti-BPA aptamers, which can release the aptamers from cysteamine-AuNPs and thus prevent the aggregation and color change of cysteamine-AuNPs.

     

New 19-oxygenated steroid from the South China Sea gorgonian Dichotella gemmacea

A new 19-oxygenated steroid, 25-acetate-nebrosteroid K (1), and five known steroids (2–6), along with one known 19-hydroxy steroidal glycoside (7) were obtained from the gorgonian Dichotella gemmacea collected from the South China Sea. The structure and relative configuration of 1 were elucidated by using comprehensive spectroscopic data including NOESY spectra. Compound 1 represents the first example of 19-oxygenated steroid with a 19-oic acid methyl ester group isolated from gorgonians. All of the isolated compounds were evaluated for lethal activity to brine shrimp Artemia salina and cytotoxicity against A549 and HL-60 cell lines. Among them, 1 showed strong lethality towards A. salina.     

Lipophilic constituents from two processed products and three different parts of Changium smyrnioides Wolff.

This article reports the lipophilic chemical composition of different processed products (Changii Radix, Changii Radix Alba) and parts (root bark, leaf and fruit) of Changium smyrnioides Wolff.. The lipophilic constituents were extracted with petroleum ether in Soxhlet apparatus, subsequently identified and determined by gas chromatography–mass spectroscopy (GC–MS). Yield of lipophilic constituents from Changii Radix (3.65%) was about three times more than Changii Radix Alba's (1.07%), which indicated processing by boiling in water had an impact on the content of lipophilic constituents. Moreover, the major compounds in different processed products and parts were found to be fatty acids and sesquiterpenes. The results are a contribution for the lipophilic chemical composition and can serve as a reference for product development of Changium smyrnioides Wolff..     

Preparation and Electrochemical Properties of Tin–Iron–Carbon Nanocomposite as the Anode of Lithium‐Ion Batteries

Tin–iron–carbon nanocomposite is successfully prepared by a sol–gel method followed by a chemical vapor deposition (CVD) process with acetylene gas as the carbon source. The structural properties, morphology, and electrochemical performances of the nanocomposite are comprehensively studied in comparison with those properties of tin–carbon and iron–carbon nanocomposites. Sheet‐like carbon architecture and different carbon contents are induced thanks to the catalytic effect of iron during CVD. Among three nanocomposites, tin–iron–carbon demonstrates the highest reversible capacity of 800 mA h g^?1 with 96.9 % capacity retention after 50 cycles. It also exhibits the best rate capability with a discharge capacity of 420 mA h g^?1 at a current density of 1000 mA g^?1. This enhanced performance is strongly related to the carbon morphology and content, which can not only accommodate the large volume change, but also improve the electronic conductivity of the nanocomposite. Hence, the tin–iron–carbon nanocomposite is expected to be a promising anode for lithium‐ion batteries.     

Selective adsorption of metronidazole on conjugated microporous polymers

Conjugated microporous polymers (CMPs) have recently received extensive attention in oil/organic solvent-water separation field as a kind of ideal porous absorbents with tunable porosity, large surface areas, and super-hydrophobicity. However, reports on the application of CMPs in adsorption of hydrophilic contaminants from water are very few. In this work, we studied the adsorption of metronidazole (MNZ), a polar antibiotic, by two kinds of CMPs. The adsorption characteristics of MNZ by the CMPs, including adsorption kinetics, mechanism, and isotherm parameters were calculated. The adsorption kinetics of MNZ was well expressed by the pseudo-second-order model, and the adsorption process was found to be mainly controlled by film diffusion. The adsorption isotherm data agreed well with the Langmuir isotherm model, and the values of free energy E indicated that the adsorption nature of MNZ on the CMPs was physisorption. Increasing dispersion degree of the CMPs in MNZ solution resulted in greater adsorption. This work may provide fundamental guidance for the removal of antibiotics by CMPs.     

Quantum entanglement generation on magnons assisted with microwave cavities coupled to a superconducting qubit

We present protocols to generate quantum entanglement on nonlocal magnons in hybrid systems composed of yttrium iron garnet (YIG) spheres, microwave cavities and a superconducting (SC) qubit. In the schemes, the YIGs are coupled to respective microwave cavities in resonant way, and the SC qubit is placed at the center of the cavities, which interacts with the cavities simultaneously. By exchanging the virtual photon, the cavities can indirectly interact in the far-detuning regime. Detailed protocols are presented to establish entanglement for two, three and arbitrary N magnons with reasonable fidelities.