Photocatalytic Cr(VI) sequestration and photo-Fenton bisphenol A decomposition over white light responsive PANI/MIL-88A(Fe)

Polyaniline (PANI)/MIL-88A(Fe) (Px@M88) composites were constructed through a simple one-pot hydrothermal method. The photocatalytic and photo-Fenton activities of Px@M88 composites toward reduction of Cr(VI) and degradation organic pollutants were explored by white light irradiation. PANI, as a conductive polymer, can improve MIL-88A(Fe)’s conductivity and the efficiency of photogenerated e⁻–h⁺ pair separation. In the presence of H₂O₂, a photo-Fenton reaction occured to boost the degradation efficiency of organic pollutants like bisphenol A. In addition, P9@M88 showed excellent recycling and stability in cycling experiments. Finally, a possible reaction mechanism for photocatalytic degradation was proposed and verified by X-ray photoelectron spectroscopy and electron spin resonance determination and electrochemical characterizations.     

Asymmetric synthesis of novel spirocycles via a chiral phosphoric acid catalyzed desymmetrization

A straightforward method for the asymmetric preparation of novel lactone and lactam spirocycles is described. An initial desymmetrization via a chiral Brønsted acid yields enantioenriched lactones which readily undergo a second cyclization to give the desired spirocycle.     

Synthesis of enantiomerically pure glycerol derivatives containing an organochalcogen unit: In vitro and in vivo antioxidant activity

We describe here the synthesis of enantiomerically pure chalcogenoethers obtained through the reaction of nucleophilic species of chalcogen (S, Se and Te), generated in situ from the respective diorganyl dichalcogenides, with (R)- and (S)-tosyl solketal. Furthermore, some of the chalcogenoethers were treated with acidic cation exchange resin Dowex-(H⁺) leading to the respective deprotected enantiomerically pure 3-phenylchalcogenyl-1,2-diols. In order to explore the biological potential of these molecules, the antioxidant activity of some organochalcogens was evaluated by several in vitro assays. Overall, the chalcogenoethers containing Te were better scavengers of DPPH and ABTS⁺ radicals, had higher ferric reducing capacity and prevented lipid peroxidation. To analyze the effects of these compounds in vivo, we used the alternative model Caenorhabditis elegans. Chalcogenoethers treatment, especially (S)- and (R)-2,2-dimethyl-4-(phenylselanylmethyl)-1,3-dioxolane, conferred protection against the mortality-induced by hydrogen peroxide. Accordingly, these chalcogenoethers were able to modulate the antioxidant enzyme catalase. Notably, the compounds did not present toxicity in worm’s reproduction. To sum up, our study demonstrated that Te- containing chalcogenoethers were promising in vitro scavengers, while Se molecules were more prone to protect against a stressor in vivo. In this sense, the antioxidant activity of chalcogenoethers, especially with Se and Te, indicates that these molecules may have biological application in an attempt to reduce the oxidative stress.     

Multi-band giant circular dichroism based on conjugated bilayer twisted-semicircle nanostructure at optical frequency

Plasmonic circular dichroism (CD) effect has been drawn great attention increasingly for its wide application in the fields of bio-sensing, biological detection, pharmaceuticals, and analytical chemistry. In this paper, we propose a chiral metasurface (CMS) to achieve strong multi-band CD effect at optical frequency. The designed CMS is composed of a periodic array of conjugated bilayer twisted-semicircle nanostructures. The numerical simulation results show that the CMS can produce strong multi-band CD effect due to the different coupling resonance modes under the excitations of left-handed circular polarization (LCP) light and right-handed circular polarization (RCP) light. It is shown that the chiral-selective absorption peaks can reach 89.4% and 95% for LCP light, 79% and 78.2% for RCP light, and the maximum CD is about 0.69 and −0.61 at 198.75 THz and 352.25 THz, 0.69 and −0.54 at 291.75 THz and 402.25 THz, respectively. The mechanism of the giant CD effect of the CSM has been revealed by analyzing the coupling mode of electric dipoles on the top and bottom layer through surface current distributions. Furthermore, the geometric parameter dependences of CD effect in the proposed CMS have been also studied numerically. The present results will guide the design of plasmonic chiral nanostructures for enhancing the CD effect.     

Cyclodextrin derivatives functionalized highly sensitive chiral sensor based on organic field-effect transistor

Novel highly sensitive chiral organic field-effect transistors(COFET)were developed by directly assembling imidazolium3,5-dimethylphenylcabamoylated-β-cyclodextrin(lm^+-Ph-β-CD)and 3,5-dimethylphenylcarbamoylated-β-CD(Ph-β-CD)respectively onto the semiconductor layer as sensing units.The Im+-Ph-β-CD/COFET afforded better enantioselectivity and a lowest detection concentration of10^-18 L/mol as well as the potentiality in quantitative analysis of commercial medicines.     

Ultrasound-aided rapid and enhanced adsorption of anionic dyes from binary dye matrix onto novel hematite/polyaniline nanocomposite: Response surface methodology optimization

In recent times, polyaniline (PANI), a conducting polymer, has been studied widely for environmental remediation application due to its controllable electric conductivity with high surface area, which makes it a suitable adsorbent material. But lower mechanical stability of PANI is considered to be a serious drawback for its large-scale industrial application. To improve the mechanical strength of PANI, in this study, hematite nanoparticles were impregnated onto PANI by oxidative polymerization method in order to fabricate a novel organometallic nanocomposite (hematite-PANI-NC). The hematite-PANI-NC was used as adsorbent for removal of methyl orange (MO) and eosin yellow (EY) dye from binary dye matrix under ultrasonic-assisted adsorption. Excellent MO and EY dye removal (more than 98%) was observed from binary matrix at a wide solution pH from 2.0 to 6.0, and under ultrasound wave the adsorption equilibrium was achieved within 15 min only. Both MO and EY dyes adsorption experimental data strictly followed Langmuir isotherm, and maximum monolayer adsorption capacity of 126.58 mg/g and 112.36 mg/g was observed for MO and EY dye, respectively. The uptake mechanism of MO and EY dyes onto hematite-PANI-NC is governed by electrostatic interaction, π-π bonding and hydrogen bonding between dye molecules and nanocomposite. Response surface methodology analysis reveals maximum MO and EY removal of 98.43% and 99.35% at optimum experimental conditions. This study implies that the hybrid organometallic material hematite-PANI-NC has high potential for quick and enhanced sono-assisted uptake of anionic dyes from water near neutral solution pH.     

Chirality and Magnetic Properties of One-dimensional Ln (Ln = Gd,Dy) Polymers

The usage of the achiral ligand, in lanthanide chemistry, successfully obtained two series of chiral lanthanide complexes, formulated d - and l -{Gd[IN][HIN][CH₂OCH₂O]}_n (abbreviated as Gd ) and d - and l -{Dy[IN][HIN][CH₂OCH₂O]}_n (abbreviated as Dy , HIN = isonicotinic acid). Crystallographic researches determined that four compounds are all one-dimensional (1D) chain structures and crystallized in a chiral space group. In addition, CH₂OHCH₂OH acts as not only solvent but also the bridge ligand. Besides, single crystal circular dichroism (CD) spectra conformed compounds Gd-_L and Gd-_D , Dy-_L and Dy-_D are enantiomers respectively. Magnetically, compound Gd showed predominant magnetocaloric effect (MCE) of 26.20 J · kg^–1 · K^–1 at 2.5 K for ΔH = 7 T, while there is ferromagnetic interactions in compound Dy .     

Highly Sensitive Enzyme-free Sensor Based on a Carbon Paste Electrode Modified with Binary Zinc Oxide/Polyaniline Nanocomposites for Dopamine,Ascorbic Acid and Uric Acid Sensing

Hybrid composites ZnO/PANI were facily synthesized by a sonication process at room temperature. This procedure is non-expensive, time/energy saving and environmentally safe. The as-prepared ZnO/PANI were characterized by FTIR, UV-vis spectroscopies and SEM in order to investigate the structure and morphology of the studied composites. The samples were used to modify carbon paste electrode (CPE) in order to develop electrochemical biosensors (ZnO/PANI/CPE). The sensing properties of the nanoparticles were evaluated for dopamine, ascorbic acid and uric acid non-enzymatic detection. The effect of percentage of polyaniline in the composites and the effect of calcination on the biosensor's response were also examined in the present study. It was revealed that the existence of PANI in ZnO/PANI/CPE largely enhanced the electroactive surface area and therefore the sensitivity for electrochemical sensing. A good electrochemical behavior was noted for ZnO/40 wt% PANI-cal/CPE modified electrode toward DA, AA and UA oxidation. The electroactive surface area of the previously mentioned modified electrode (0.235 cm²) was two times higher than that of the bare electrode (0.117 cm²). The liner relationships between current intensities and concentrations were found to be 0.01–1.4 mM, 0.1–1.3 mM and 0.01–0.12 mM, with detection limit of 0.029 mM, 0.063 mM and 0.007 mM, for DA, AA and UA respectively. In the mixtures of ascorbic acid (AA), dopamine (DA) uric acid (UA) and glucose (Glu) the sensor showed high selectivity of DA with low interference of ascorbic acid by a current change of 14 %. The as-prepared ZnO/PANI/CPE biosensor displayed a good reproducibility and stability.     

Highly Sensitive Electrochemical Immunosensor Based on Mesoporous PdPt Nanoparticles Anchored on a Three-dimensional PANI@CNTs Network as Nanozyme Labels

In this study, a novel strategy to amplify electrochemical signals by mesoporous PdPt nanoparticles with core-shell structures anchored on a three-dimensional PANI@CNTs network as nanozyme labels (PdPt/PANI@CNTs) was proposed for the sensitive monitoring of α-fetoprotein (AFP, Ag). First, the mesoporous PdPt nanoparticles prepared by a facile chemical reduction method had excellent biocompatibility with biomolecules, which could capture a large amount of AFP-Ab₂ (Ab₂) and exhibit plentiful pores to entrap more thionine (Thi) into mesoporous PdPt nanoparticles with enhanced loading and abundant active sites. Furthermore, the resulting mesoporous PdPt nanoparticles were abundantly dotted on the surface of a three-dimensional PANI@CNTs network with excellent conductivity and a high specific surface area through the bonding of the amino group to form PdPt/PANI@CNTs nanozyme labels. Most importantly, the as-prepared PdPt/PANI@CNTs nanozyme labels exhibited unexpected enzyme-like activity towards the reduction of hydrogen peroxide owing to the highly indexed facets, enhancing the current response to realize signal amplification. In view of the advantages of nanozyme labels and the involvement of gold nanoparticles (AuNPs, which behave as electrode materials) for the sensitive determination of AFP, the as-developed immunosensor could obtain a dynamic working range of 0.001 ng mL^−1–100.0 ng mL⁻¹ at a detection limit of 0.33 pg mL⁻¹ via DPV (at 3σ). Furthermore, the nanozyme-based electrochemical immunosensor exhibited remarkable analytical performance, which brought about feasible ideas for disease diagnosis in the future.