Optimizing Photochirogenic Performance by Solvent-Driven Conformational Fixation in Enantiodifferentiating Photoisomerization of (Z)-Cyclooctene Mediated by Sensitizing ß-Cyclodextrin Hosts.

Catalytic enantiodifferentiating photoisomerization of cyclooctene (1Z) included and sensitized by regioisomeric 6-O-(o-, m-, and p-methoxybenzoyl)-ß-cyclodextrins (CDs) was performed under a variety of solvent conditions for higher enantioselectivities. The enantiomeric excess (ee) of chiral (E)-isomer (1E) produced was a critical function of all the internal and external factors examined, in particular, the sensitizer structure and the solvent conditions, to afford (R)-1E in record-high ee's of up to 67% upon sensitization with the meta-substituted ß-CD host in water and salt solutions but neither in 50% aqueous ethanol nor with the ortho- and para-substituted hosts. The mechanistic origin of the sudden ee enhancement achieved under the specific conditions is discussed on the basis of the circular dichroism spectral behaviors upon substrate inclusion and the compensatory enthalpy-entropy relationship of the activation parameters for the enantiodifferentiating photoisomerization.

Simultaneous electrochemical sensing of serotonin, dopamine and ascorbic acid by using a nanocomposite prepared from reduced graphene oxide, Fe3O4 and hydroxypropyl-ß-cyclodextrin.

Reduced graphene oxide containing Fe3O4 nanoparticles was decorated with hydroxypropyl-ß-cyclodextrin (HP-ß-CD) to construct a novel nanocomposite (3D-rGO/Fe3O4/HP-ß-CD). The composite was placed on a glassy carbon electrode (GCE) to design an electrochemical sensor for detecting simultaneously serotonin (5-HT), dopamine (DA), and ascorbic acid (AA). The interconnected porous reduced graphene oxide framework tightly anchored to the Fe3O4 magnetic nanoparticles warrants good electrical conductivity and efficient catalytic activity. The HP-ß-CD acts as a supramolecular host with high recognition ability for 5-HT, DA and AA. Well-separated oxidation peaks and increased peak currents were observed for 5-HT, DA, and AA individually and in mixtures by differential pulse voltammetry (DPV). The following figures of merit were found for simultaneous electrochemical determination of 5-HT, DA, and AA: (a) Well separated peaks at around 0.316, 0.16 and - 0.044 V; (b) linear responses in the 0.01 - 25 µM, 0.02 - 25 µM and 10 - 350 µM; (c) detection limits of 3.3 nM, 6.7 nM and 3.3 µM (S/N = 3), and (d) recoveries of 96.9-103%, 97.3%-102% and 96.3-105% from spiked serum samples, respectively. All relative standard deviation (RSD) are less than 4%. Graphical abstractSchematic representation of simultaneous detecting serotonin (5-HT), dopamine (DA) and ascorbic acid (AA) for three-dimensional reduced-graphene oxide/Fe3O4/hydroxypropyl-ß-cyclodextrin (3D-rGO/Fe3O4/HP-ß-CD) by differential pulse voltammetry (DPV) approach.

Supramolecular recognition enhanced electrochemical sensing: ß-cyclodextrin and Pd nanoparticle co-decorated 3D reduced graphene oxide nanocomposite-modified glassy carbon electrode for the quantification of ractopamine.

Ractopamine (RAC) is universally known for improving lean meat percentage in livestock and thus is widely introduced as a feed additive. However, it is difficult to eliminate the RAC residue in animal tissues from the biological system and will inevitably harm human health. Hence, detecting RAC molecules in biological samples is extremely significant. Herein, a novel strategy of supramolecular recognition-enhanced electrochemical sensing is presented. This platform was constructed by coupling ß-cyclodextrin (ß-CD) with palladium nanoparticles (Pd NPs)-functionalized three-dimensional reduced graphene oxide (3D-rGO) to form a nanocomposite (3D-rGO/Pd/ß-CD), which was further used to modify a glassy carbon electrode (GCE) for RAC detection. Benefiting from the attractive electrical conductivity and catalytic activity of 3D-rGO/Pd, as well as the unique small-molecule-recognition ability of ß-CD demonstrated by 1H NMR spectrum, which revealed the 1 : 2 binding mode of RAC with ß-CD, increased peak current signals of RAC were observed in the cyclic voltammetry (CV) test. Under optimized conditions, the wide linear concentration range spanned 1-95 µM, along with a relatively low detection limit of 0.12 µM (S/N = 3), as evidenced by the differential pulse voltammetry (DPV) approach. The platform also exhibited satisfactory stability and fine reproducibility, as well as high selectivity and good anti-interference capability. Moreover, this as-obtained sensor was efficiently applied in pork samples with a high recovery rate (96.44-103.99%), which provides a promising view of its electrochemical biosensing ability in practical applications.

Tailoring carboxylatopillar[5]arene-modified magnetic graphene oxide nanocomposites for the efficient removal of cationic dyes.

A carboxylatopillar[5]arene-embellished (CP5) magnetic graphene oxide nanocomposite (MGO@CP5) was smoothly constructed via a mild layer-by-layer method. The morphology, structure, and surface characteristics of this nanocomposite was investigated by field-emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, zeta potential, and other techniques. Benefiting from a high capture ability for small molecules of CP5 as a supramolecular host molecule, along with a negative surface charge and large surface area of MGO@CP5, this nanocomposite exhibits an ultrafast, efficient adsorption property for representative cationic dyes: methylene blue (MB) and basic fuchsin (BF). The removal efficiency of MB and BF can reach nearly 99% within 3 min, while the maximum adsorption capacity of the two dyes reaches 240 mg g-1 for MB and 132 mg g-1 for BF. Furthermore, owing to excellent magnetic responsiveness from the tight loading of Fe3O4 nanoparticles on graphene oxide, MGO@CP5 could be easily and magnetically separated, regenerated, and reused four times without an evident reduction in the removal efficiency (>95%). Impressively, the adsorption property of MGO@CP5 reveals a strong tolerance to pH changes and ionic strength interference, which renders it a promising adsorbent in the field of water treatment.

ß-Cyclodextrin functionalized 3D reduced graphene oxide composite-based electrochemical sensor for the sensitive detection of dopamine.

A three-dimensional reduced graphene oxide nanomaterial with ß-cyclodextrin modified glassy carbon electrode (3D-rGO/ß-CD/GCE) was constructed and used to detect the electrochemical behavior of dopamine (DA). The nanocomposite materials were characterized by scanning electron microscopy (SEM), infrared spectrometry (FT-IR), Raman spectrogram and thermogravimetric analysis (TGA), which showed that ß-CD was well modified on 3D graphene with a porous structure. The electrochemical properties of different modified electrodes were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), proving the highest electron transfer rate of the 3D-rGO/ß-CD modified electrode. The experimental conditions such as scan rate, pH, enrichment time and layer thickness were optimized. Under the best experimental conditions, DA was detected by differential pulse voltammetry (DPV) by 3D-rGO/ß-CD/GCE with excellent electrocatalytic ability and satisfactory recognition ability, resulting in a wide linear range of 0.5-100 µM and a low detection limit (LOD) of 0.013 µM. The modified electrode based on 3D-rGO/ß-CD nanocomposites is promising in the field of electrochemical sensors due to its high sensitivity and other excellent properties.