Synthesis of oxindoles through trifluoromethylation of N-aryl acrylamides by photoredox catalysis.

Mild and direct intramolecular oxidative aryltrifluoromethylations of activated alkenes have been established through visible light photocatalysis, affording a range of CF3-containing oxindoles or isoquinolinediones in the presence of an organic fluorophore-type photocatalyst 4CzIPN, oxygen and visible light irradiation under strong oxidant and transition metal free conditions. A variety of frequently encountered functional groups are well tolerated in this transformation.

Study of the role of oxygen vacancies as active sites in reduced graphene oxide-modified TiO2.

In recent years, substantial efforts have been devoted to exploring reduced graphene oxide/TiO2 (RGO/TiO2) composite materials; however, there is still a paucity of reports on the construction of reduced graphene oxide/TiO2 with oxygen vacancies (RGO/TiO2-OV) via a facile two-step wet chemistry approach. In this work, we show a proof-of-concept study follow RGO introduced into TiO2 with oxygen vacancies, the role of oxygen vacancies as active sites in reduced graphene oxide-modified TiO2. The photocatalytic performance and related properties of blank-TiO2, blank-TiO2 with oxygen vacancies (blank-TiO2-OV), RGO/TiO2, and RGO/TiO2-OV were comparatively studied. It was found that due to the incorporation of RGO, RGO/TiO2 and RGO/TiO2-OV exhibit a higher photocatalytic performance under simulated solar light irradiation than their counterparts without rGO. More importantly, it was found that blank-TiO2 has a higher photocatalytic activity than blank-TiO2-OV under simulated solar light irradiation. However, RGO/TiO2 shows a lower photocatalytic activity than rGO/TiO2-OV. By a series of combined techniques, we found that the introduction of a component, such as RGO, with the matched energy band to TiO2 could lead to the formation of a long-lived electron-transfer state, thus prolonging the lifetime of the photogenerated charge carriers. Furthermore, during the photocatalytic process, RGO could tune the role of oxygen vacancies in TiO2 from recombination centers to active sites. These findings are of great significance for the design of effective photocatalytic materials in the field of solar energy conversion.

Carbon dots and chitosan composite film based biosensor for the sensitive and selective determination of dopamine.

A simple, sensitive and reliable dopamine (DA) biosensor was developed based on a carbon dots (CDs) and chitosan (CS) composite film modified glassy carbon electrode (CDs-CS/GCE). Under optimal conditions, the CDs-CS/GCE showed a better electrochemical response for the detection of DA than that of the glassy carbon electrode (GCE). The oxidation peak current (Ipa) of DA was linear with the concentration of DA in the range from 0.1 µM to 30.0 µM with the limit of detection as 11.2 nM (3S/N). The CDs-CS/GCE was applied to the detection of DA content in an injection solution of DA with satisfactory results.

Visible-Light-Enabled Lanthanum-Mediated Intramolecular Epoxy-Ring Opening/Dehydrogenative Lactonization.

Catalytic C(sp3)-H functionalization has afforded great opportunities to prepare organic substances, facilitating the derivatization of complex drugs and natural molecules. This letter describes an efficient and practical protocol for lanthanum-catalyzed continuous epoxy-ring opening and oxidative dehydrogenative lactonization under visible-light irradiation. Notably, the lanthanum catalyst also acts as a photocatalyst while acting as a Lewis acid in this reaction; therefore, no additional photocatalyst is required. We can conveniently prepare a series of diverse isochromanones with oxygen-containing spirocyclic structural units under a balloon-oxygen atmosphere at room temperature. Mechanistic studies and control experiments reveal that the in situ-generated lanthanum bromide should be crucial in the reaction.

Preparation of hydrogels based on pectin with different esterification degrees and evaluation of their structure and adsorption properties.

In this study, pectin (Pe) with different esterification degrees was used as raw materials to prepared hydrogel adsorbents via free radical polymerization. The effect of Pe esterification degree on hydrogel structure and adsorption performance was studied by FTIR, SEM and XPS characterization and copper ion adsorption experiment. The results demonstrated that the carboxyl group in the hydrogels was bonded to Cu2+ through electrostatic force and coordination, which was an important factor in its adsorption capacity. The hydrogels prepared from Pe with low esterification degree had finer pores and higher carboxyl content, so the adsorption capacity on both water and Cu2+ was stronger. The preparation of hydrogels from low-ester Pe was more conducive to the adsorption of copper ions. Besides, the adsorption behavior of the hydrogels on Cu2+ was investigated through the adsorption thermodynamics and kinetics. The results indicated that the adsorption kinetics of the hydrogels was in accordance with the quasi-second-order model. The adsorption of Cu2+ by hydrogels was the result of physical and chemical adsorption, which was endothermic under natural condition, and a higher temperature will result in more favorable spontaneous adsorption.

Construction of double-network hydrogel based on low methoxy pectin/polyvinyl alcohol and its structure and properties.

In this study, an interpenetrating double-network hydrogel (LMP/AA/PVAH) was prepared based on low methoxy pectin (LMP), acrylic acid (AA) and polyvinyl alcohol (PVA). The first rigid network of chemical crosslinking was constructed via free radical polymerization of LMP and AA, and the second of ductile physical crosslinking network was constructed via cyclic freeze-thaw of PVA. The first cycle hardness and elasticity of the LMP/AA/PVAH significantly increased from 13.08 N and 0 to 24.28 N and 0.79, respectively, when the second network structure was constructed in the hydrogel by PVA. Besides, the PVA network might enhance the ductile and limit the swelling of hydrogel. In addition, the adsorption properties of LMP/AA/PVAH were evaluated by adsorption of methylene blue (MB). The adsorption behavior of MB by LMP/AA/PVAH conformed to the pseudo-second-order kinetic model. Besides, after 4 cycles of adsorption, there was no significant difference in adsorption capacity of LMP/AA/PVAH. The results showed that LMP/AA/PVAH had good reusability.

Microwave synthesis of 3D rambutan-like CuO and CuO/reduced graphene oxide modified electrodes for non-enzymatic glucose detection.

A novel type of cupric oxide (CuO) particles-reduced graphene oxide (r-GO) modified electrode has been fabricated through a facile, simple and fast microwave method. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), and X-ray diffraction (XRD) were employed to characterize the morphologies and structures of the as-prepared samples. The results reveal that the CuO/r-GO composite was a porous 3D rambutan-like microstructure with high surface area. Then the CuO and CuO/r-GO electrodes were constructed for their use as non-enzymatic glucose biosensors owing to their high-performance and sensitivity under alkaline conditions. The proposed biosensor exhibits glucose concentrations in the range from 0.50 µM to 3.75 mM. Besides, chronoamperometry demonstrates a desirable sensitivity of 52.1 µA mM-1 at an applied potential of 0.50 V (vs. Ag/AgCl), with a detection limit of 0.10 µM (signal/noise = 3). Most importantly, this non-enzymatic glucose biosensor has highly stable characteristics and can be manufactured into a long-term stability electrode for its application in various complicated circumstances. All these results confirm that this CuO/r-GO biosensor is a promising active material with excellent analytical properties for non-enzymatic glucose detection.

Designed self-assembled hybrid Au@CdS core-shell nanoparticles with negative charge and their application as highly selective biosensors.

A novel and general strategy for the synthesis of a monodispersed Au@CdS core-shell structure with uniform morphology and size through a self-assembly process is proposed here. The obtained negatively charged Au@CdS hybrid core-shell nanoparticles (NPs) are highly selective to dopamine (DA), in the presence of oxidation of ascorbic acid (AA) and uric acid (UA), based on electrostatic interaction. The fabricated biosensor shows a wide linear range from 0.002 to 800 µmol L-1, with a lower detection limit of 0.55 nmol L-1 (n = 5, S/N = 3), revealing the high-sensitivity properties. Electrostatic charge plays an important role in the selective electrocatalytic activity of Au@CdS hybrid core-shell nanoparticles, that is the formation of an electrostatic system between the negatively charged Au@CdS hybrid core-shell NPs and the DA cation. The modified electrode is used to achieve the real-time quantitative detection of DA for biological applications, and satisfactory results are obtained. Due to the advantages of the biosensor, its selectivity, sensitivity and stability, it will have a bright future in the field of medical diagnosis.

Nafion covered core-shell structured Fe3O4@graphene nanospheres modified electrode for highly selective detection of dopamine.

Nafion covered core-shell structured Fe3O4@graphene nanospheres (GNs) modified glassy carbon electrode (GCE) was successfully prepared and used for selective detection dopamine. Firstly, the characterizations of hydro-thermal synthesized Fe3O4@GNs were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Then Fe3O4@GNs/Nafion modified electrode exhibited excellent electrocatalytic activity toward the oxidations of dopamine (DA). The interference test showed that the coexisted ascorbic acid (AA) and uric acid (UA) had no electrochemical interference toward DA. Under the optimum conditions, the broad linear relationship was obtained in the experimental concentration from 0.020 µM to 130.0 µM with the detection limit (S/N=3) of 0.007 µM. Furthermore, the core-shell structured Fe3O4@GNs/Nafion/GCE was applied to the determination of DA in real samples and satisfactory results were got, which could provide a promising platform to develop excellent biosensor for detecting DA.

A sensitive and reliable dopamine biosensor was developed based on the Au@carbon dots-chitosan composite film.

A novel composite film of Au@carbon dots (Au@CDs)-chitosan (CS) modified glassy carbon electrode (Au@CDs-CS/GCE) was prepared in a simple manner and applied in the sensitive and reliable determination of dopamine (DA). The CDs had carboxyl groups with negative charge, which not only gave it have good stability but also enabled interaction with amine functional groups in DA through electrostatic interaction to multiply recognize DA with high specificity, and the Au nanoparticle could make the surface of the electrode more conductive. Compared with the bare GCE, CS/GCE, and CDs-CS/GCE electrodes, the Au@CDs-CS/GCE had higher catalytic activity toward the oxidation of DA. Furthermore, Au@CDs-CS/GCE exhibited good ability to suppress the background current from large excess ascorbic acid (AA) and uric acid (UA). Under the optimal conditions, selective detection of DA in a linear concentration range of 0.01-100.0 µM was obtained with the limit of 0.001 µM (3S/N). At the same time, the Au@CDs-CS/GCE was also applied to the detection of DA content in DA's injection with satisfactory results, and the biosensor could keep its activity for at least 2 weeks.

Determination of trace alpha-fetoprotein variant by affinity adsorption solid substrate-room temperature phosphorimetry and its application to the forecast of human diseases.

In the presence of ion perturber LiAc, 4-generation polyamidoamine dendrimers (4G-D) could emit strong and stable room temperature phosphorescence (RTP) signal at lambda(max)(ex)/lambda(max)(em) = 511.8/675.3 nm on nitrocellulose membrane (NCM), and Triton X-100 could sharply enhance the RTP signal of 4G-D. Triton X-100-4G-D was used to label concanavalin agglutinin (Con A) to get the labeling product Triton X-100-4G-D-Con A. Quantitative specific affinity adsorption (AA) reaction between Triton X-100-4G-D-Con A and alpha-fetoprotein variant (AFP-V) could be carried out on the surface of NCM, whose product Triton X-100-4G-D-Con A-AFP-V could emit strong and stable RTP and its deltaI(p) was proportional to the content of AFP-V. According to the facts above, a new affinity adsorption solid substrate-room temperature phosphorimetry (AA-SS-RTP) for the determination of trace AFP-V by Con A labeled with Triton X-100-4G-D was established. Detection limits of this method were 0.23 fg spot(-1) (direct method, corresponding concentration: 5.8x10(-13) g mL(-1)) and 0.13 fg spot(-1) (sandwich method, corresponding concentration: 3.2x10(-13) g mL(-1)). It has been successfully applied to determine the content of AFP-V in human serum and forecast human diseases, for its high sensitivity, long RTP lifetime, good repeatability, high accuracy and little background perturbation with lambda(max)(em) at the long wavelength area. Meanwhile, the mechanism for the determination of trace AFP-V using AA-SS-RTP was also discussed.

Determination of traces of bismuth by quenching of solid-substrate room-temperature phosphorescence from morin-labeled silicon dioxide nano-particles.

Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin-SiO2) have been synthesized by the sol-gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin-SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (DeltaI(p)) is directly proportional to the concentration of bismuth in the working range 0.16-14.4 ag spot(-1) (sample volume 0.40 muL spot(-1), corresponding to the concentration range 0.40-36.0 fg mL(-1)). The regression equation of the working curve is DeltaI(p)=14.86+5.279x[Bi3+] (ag spot(-1)) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot(-1) (corresponding to a concentration of 6.5 x 10(-17) g mL(-1)).This sensitive, reproducible and accurate method has been used for successful analysis of real samples.