Redox Reactions of Organic Molecules Using Rotating Magnetic Field and Metal Rods.

In recent years, redox reactions have harnessed light or mechanical energy to enable the formation of chemical bonds. We postulated a complementary approach that electromagnetic induction could promote the redox reaction of organic molecules using a rotating magnetic field and metal rods. Here, we report that electromotive force activates the redox-active trifluoromethylating reagents. This magnetoredox system can be applied to the trifluoromethylation of heteroarenes with high regioselectivity and hydrotrifluoromethylation of alkenes without the need for catalysts and organic additives.

Enhanced ammonia sensing response based on Pt-decorated Ti3C2Tx/TiO2composite at room temperature.

Herein, we report a Pt-decorated Ti3C2Tx/TiO2gas sensor for the enhanced NH3sensing response at room temperature. Firstly, the TiO2nanosheets (NSs) arein situgrown onto the two-dimensional (2D) Ti3C2Txby hydrothermal treatment. Similar to Ti3C2Txsensor, the Ti3C2Tx/TiO2sensor has a positive resistance variation upon exposure to NH3, but with slight enhancement in response. However, after the loading of Pt nanoparticles (NPs), the Pt-Ti3C2Tx/TiO2sensor shows a negative response with significantly improved NH3sensing performance. The shift in response direction indicates that the dominant sensing mechanism has changed under the sensitization effect of Pt NPs. At room temperature, the response of Pt-Ti3C2Tx/TiO2gas sensor to 100 ppm NH3is about 45.5%, which is 13.8- and 10.8- times higher than those of Ti3C2Txand Ti3C2Tx/TiO2gas sensors, respectively. The experimental detection limit of the Pt-Ti3C2Tx/TiO2gas sensor to detect NH3is 10 ppm, and the corresponding response is 10.0%. In addition, the Pt-Ti3C2Tx/TiO2gas sensor shows the fast response/recovery speed (23/34 s to 100 ppm NH3), high selectivity and good stability. Considering both the response value and the response direction, the corresponding gas-sensing mechanism is also deeply discussed. This work is expected to shed a new light on the development of noble metals decorated MXene-metal oxide gas sensors.

Hierarchical SnO2nanoflower sensitized by BNQDs enhances the gas sensing performances to BTEX.

In this study, the SnO2nanoflowers with hierarchical structures sensitized by boron nitride quantum dots (BNQDs) were prepared through a simple hydrothermal method. It was applied for the detection of the BTEX vapors. Further investigation showed that the response value of SnO2sensitized by different amounts of BNQDs to the BTEX gases have a certain improvement. Especially 10-BNQDs/SnO2gas sensor exhibited a significant improvement in gas sensing performance and its response values to different BTEX gases was increased up to 2-4 folds compared with the intrinsic SnO2sensor. In addition, SnO2nanoflowers based gas sensor showed surprisingly fast response and recovery time for BTEX gases with 1-2 s. That can be attributed to the sensitization of BNQDs and the hierarchical structure of SnO2nanoflowers, which provided an easy channel for the gas diffusion. An economically viable gas sensor based on BNQDs sensitized SnO2nanoflowers exhibited a great potential in BTEX gas detection due to the simple synthesis method, environmentally friendly raw materials and excellent gas sensing performance.

Novel Ag3PO4/boron-carbon-nitrogen photocatalyst for highly efficient degradation of organic pollutants under visible-light irradiation.

Ag3PO4 is an indirect bandgap semiconductor with excellent photocatalytic activity. However, it has not been widely used so far for the treatment of polluted wastewaters. This scarce use in wastewater treatment can be mainly attributed to its large crystallite size, which would be due to rapid agglomeration during the synthesis process, as well as to the photo-corrosion problem affecting this material. Hence, it would be crucial to develop a photocatalytic system involving Ag3PO4 nanoparticles with enhanced properties, such as higher specific surface area and excellent photocatalytic stability. To meet this demand, a novel Ag3PO4/boron carbon nitrogen (Ag3PO4/BCN) composite photocatalyst was successfully prepared in the present study via electrostatically driven self-assembly and ion exchange processes. After characterization and assessment, it was shown that the as-prepared Ag3PO4/BCN nanocomposite photocatalyst not only contains smaller Ag3PO4 nanoparticles, but also exhibits an enhanced visible-light photocatalytic activity for Rhodamine B (RhB) Methyl Orange (MO) and Tetracycline (TC) and improved stability, without decrease after 5 cycles, compared with pure Ag3PO4 nanoparticles. Positive synergy between Ag3PO4 nanoparticles and BCN nanosheets, including the increase in the number of active adsorption sites, and the restriction of the formation of Ag due to the recombination of photogenerated electron-hole pairs in Ag3PO4 nanoparticles, are mainly responsible for the enhanced properties of the prepared catalyst. This study shows that Ag3PO4/BCN composite photocatalyst would be promising for wastewater treatment, which would be of clearly environmental and public health relevance.

Cytosine Methylation Enhances DNA Condensation Revealed by Equilibrium Measurements Using Magnetic Tweezers.

CpG methylation of DNA is common in mammalian cells. In sperm, the DNA has the highest level of CpG methylation and is condensed into toroidal structures. How CpG methylation affects DNA structures and interactions is important to understand its biological roles but is largely unknown. Using an RNA-DNA-RNA structure, we observed the equilibrium hopping dynamics between the condensed and extended states of DNA in the presence of polyamines or polylysine peptide as a reduced model of histone tails. Combing with the measured DNA elasticities, we report that CpG methylation of each cytosine nucleotide substantially increases DNA-DNA attraction by up to 0.2 kBT. For the DNA with 57% GC content, the relative increase caused by CpG methylation is up to 32% for the spermine-induced DNA-DNA attraction and up to 9% for the polylysine-induced DNA-DNA attraction. These findings help us to evaluate the energetic contributions of CpG methylation in sperm development and chromatin regulation.

Fabrication of ZnO Nanoparticles Modified by Uniformly Dispersed Ag Nanoparticles: Enhancement of Gas Sensing Performance.

Zinc oxide (ZnO) nanoparticles modified with uniformly dispersed silver (Ag) nanoparticles (Ag-ZnO) were prepared in one step by calcining precursor electrospun nanofibers. The molar ratios of Ag to Zn in the precursor solutions were 0, 1, 3, and 5%. The microstructure of the Ag-ZnO sensor was characterized by scanning electron microscopy and transmission electron microscopy. The existence of metallic Ag was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy, and the gas sensing properties of Ag-ZnO were investigated. The results showed that the ZnO nanoparticles after Ag nanoparticles modification exhibited excellent gas sensing performance to ethanol and hydrogen sulfide (H2S). The optimal working temperature of the Ag-ZnO sensor significantly decreased for ethanol compared with pure ZnO. The 3% Ag-ZnO sensor exhibited the fastest response to ethanol with the response/recovery times of only 5 and 9 s, respectively. However, all the Ag-ZnO-based gas sensors showed a high response value to H2S, especially the 3% Ag-ZnO gas sensor exhibited a maximum response value of 298 at 10 ppm H2S. These results could be attributed to the spillover effect and electron sensitization effect of Ag nanoparticles, which led to more absorbed oxygen species and active sites, and thereby can further enhance the gas sensing performances of ZnO-based gas sensors.

In Situ Growing Double-Layer TiO2 Nanorod Arrays on New-Type FTO Electrodes for Low-Concentration NH3 Detection at Room Temperature.

A novel double-layer TiO2 nanorod array (NRA) gas sensor for room-temperature detection of NH3 was fabricated by employing etched fluorine-doped tin dioxide (FTO) glass as the in situ growing substrate and the new-type gas-sensing electrode via the facile droplet-coating and hydrothermal methods. Due to the synergistic effect of forces, special double-layer TiO2 NRAs with a cross-linked and bridgelike structure is formed, in which adequate point junctions can be generated to construct self-assembled electron pathways required for gas-sensing tests. Gas-sensing tests indicate that all samples obtained at different growth times have an excellent gas-sensing response to low-concentration NH3 at room temperature. Among them, the TiO2 NRAs obtained at 6 h (S2) exhibit the highest gas-sensing response to 100 ppm NH3 with a value of 102%. In addition, the growth mechanism, the gas reaction mechanism, and the effect of humidity on the gas-sensing performance are also discussed in the present paper.

Low-temperature operating ZnO-based NO2 sensors: a review.

Owing to its excellent physical and chemical properties, ZnO has been considered to be a promising material for development of NO2 sensors with high sensitivity, and fast response and recovery. However, due to the low activity of ZnO at low temperature, most of the current work is focused on detecting NO2 at high operating temperatures (200-500 °C), which will inevitably increase energy consumption and shorten the lifetime of sensors. In order to overcome these problems and improve the practicality of ZnO-based NO2 sensors, it is necessary to systematically understand the effective strategies and mechanisms of low-temperature NO2 detection of ZnO sensors. This paper reviews the latest research progress of low-temperature ZnO nanomaterial-based NO2 gas sensors. Several efficient strategies to achieve low-temperature NO2 detection (such as morphology modification, noble metal decoration, additive doping, heterostructure sensitization, two-dimensional material composites, and light activation) and corresponding sensing mechanisms (such as depletion layer theory, grain boundary barrier theory, spill-over effects) are also introduced. Finally, the challenges and future development directions of low-temperature ZnO-based NO2 sensors are outlined.

The 2D Porous g-C3N4/CdS Heterostructural Nanocomposites with Enhanced Visible-Light-Driven Photocatalytic Activity.

In this study, the 2D porous graphitic carbon nitride (g-C3N4) nanosheets were successfully fabricated via a facile thermal decomposition polymerization method without any help of templates, and then novel porous g-C3N4/CdS complex catalysts of different mass fractions were is situ synthesized by a simple solvothermal process. The results of photocatalytic experiments demonstrate that the coupling g-C3N4/CdS cocatalysts exhibit significant enhanced visible-light-driven photocatalytic activity for the decolorization of methyl orange (MO) compared with individual porous g-C3N4 and CdS. In particular, an optimal porous g-C3N4 content in the hybridized composite has been determined to be 70 wt.%, corresponding to pseudo-first-order rate constant of 0.046 min-1, which is 7 and 11 times faster than that of pure porous g-C3N4 and CdS, respectively. Photoluminescence (PL) spectroscopy measurements clearly confirmed that the recombination of photoproduced electrons and holes in g-C3N4/CdS composites was efficiently inhibited due to the formation of heterojunctions. Furthermore, the possible mechanism of enhanced photocatalytic activity and photostability of prous g-C3N4/CdS are also tentatively proposed.

Improving Photocatalytic Degradation Activity of Organic Pollutant by Sn4+ Doping of Anatase TiO2 Hierarchical Nanospheres with Dominant {001} Facets.

Herein, high-energy {001} facets and Sn4+ doping have been demonstrated to be effective strategies to improve the surface characteristics, photon absorption, and charge transport of TiO2 hierarchical nanospheres, thereby improving their photocatalytic performance. The TiO2 hierarchical nanospheres under different reaction times were prepared by solvothermal method. The TiO2 hierarchical nanospheres (24 h) expose the largest area of {001} facets, which is conducive to increase the density of surface active sites to degrade the adsorbed methylene blue (MB), enhance light scattering ability to absorb more incident photons, and finally, improve photocatalytic activity. Furthermore, the SnxTi1-xO2 (STO) hierarchical nanospheres are fabricated by Sn4+ doping, in which the Sn4+ doping energy level and surface hydroxyl group are beneficial to broaden the light absorption range, promote the generation of charge carriers, and retard the recombination of electron-hole pairs, thereby increasing the probability of charge carriers participating in photocatalytic reactions. Compared with TiO2 hierarchical nanospheres (24 h), the STO hierarchical nanospheres with 5% nSn/nTi molar ratio exhibit a 1.84-fold improvement in photodegradation of MB arising from the enhanced light absorption ability, increased number of photogenerated electron-hole pairs, and prolonged charge carrier lifetime. In addition, the detailed mechanisms are also discussed in the present paper.

Flexibility and thermal dynamic stability increase of dsDNA induced by Ru(bpy)2dppz2+ based on AFM and HRM technique.

Ru(bpy)2dppz2+ has been widely used as a probe for exploring the structure of double-stranded DNA (dsDNA). The flexibility change of DNA helix is important in many of its biological functions but not well understood. Here, flexibility change of dsDNA helix caused by intercalation with Ru(bpy)2dppz2+ was investigated using the atomic force microscopy. At first, the interactions between ruthenium complex and dsDNA helix were characterized and the binding site size (p = 2.87 bp) and binding constant (Ka = 5.9 * 107 M-1) were determined by the relative extension of DNA helix using the equation of McGhee and von Hippel. By measuring intercalator-induced DNA elongation and the mean square of end-to-end distance at different molar ratios of Ru(bpy)2dppz2+ to dsDNA, the changes of persistence length under different ruthenium concentrations were determined by the worm-like chain model. We found that the persistence length of dsDNA decreased with increasing Ru(bpy)2dppz2+ concentration, demonstrating that the flexibility of dsDNA obviously enhanced due to the intercalation. Especially, the persistence length changed greatly from 54 to 34 nm on changing the molar ratio of ruthenium to dsDNA from 0 to 0.2. We speculated that the intercalation of dsDNA with Ru(bpy)2dppz2+ resulted in local deformation or bending of the DNA duplex. In addition, the thermal dynamic stability of DNA helix was measured with high resolution melting method which revealed the increase in thermal dynamic stability of DNA helix due to the ruthenium intercalation.

Low-Cost and High-Performance ZnO Nanoclusters Gas Sensor Based on New-Type FTO Electrode for the Low-Concentration H2S Gas Detection.

A low-cost and high-performance gas sensor was fabricated by the in-situ growing of ZnO nanoclusters (NCs) arrays on the etched fluorine-doped tin dioxide (FTO) glass via a facile dip-coating and hydrothermal method. Etched FTO glass was used as a new-type gas-sensing electrode due to its advantages of being low cost and having excellent thermal and chemical stability. ZnO NCs are composed of multiple ZnO nanorods and can provide adequate lateral contacts to constitute the paths required for the gas-sensing tests simultaneously, which can provide many advantageous point junctions for the detection of low-concentration gases. The gas-sensing tests indicate that the ZnO NCs gas sensor has good selectivity and a high response for the low-concentration H2S gas. The sensing response has reached 3.3 for 500 ppb H2S at 330 °C. The excellent gas-sensing performances should be attributed to the large specific surface area of in-situ grown ZnO NCs, the perfect ohmic contact between ZnO NCs and FTO electrode and the variation of grain boundary barrier at the cross-linked junctions of multiple nanorods. In addition, the detailed effect of work temperature and gas concentration on gas-sensing, the stability of gas sensors and the corresponding response mechanism are also discussed in the present paper.

Recent Developments in the Interactions of Classic Intercalated Ruthenium Compounds: [Ru(bpy)2dppz]2+ and [Ru(phen)2dppz]2+ with a DNA Molecule.

[Ru(bpy)2dppz]2+ and [Ru(phen)2dppz]2+ as the light switches of the deoxyribose nucleic acid (DNA) molecule have attracted much attention and have become a powerful tool for exploring the structure of the DNA helix. Their interactions have been intensively studied because of the excellent photophysical and photochemical properties of ruthenium compounds. In this perspective, this review describes the recent developments in the interactions of these two classic intercalated compounds with a DNA helix. The mechanism of the molecular light switch effect and the selectivity of these two compounds to different forms of a DNA helix has been discussed. In addition, the specific binding modes between them have been discussed in detail, for a better understanding the mechanism of the light switch and the luminescence difference. Finally, recent studies of single molecule force spectroscopy have also been included so as to precisely interpret the kinetics, equilibrium constants, and the energy landscape during the process of the dynamic assembly of ligands into a single DNA helix.

Effect of Surfactants on the Microstructures of Hierarchical SnO2 Blooming Nanoflowers and their Gas-Sensing Properties.

Hierarchical SnO2 blooming nanoflowers were successfully fabricated via a simple yet facile hydrothermal method with the help of different surfactants. Here we focus on exploring the promotion effects of surfactants on the self-assembly of 2D SnO2 nanosheets into 3D SnO2 flower-like structures as well as their gas-sensing performances. The polyporous flower-like SnO2 sensor exhibits excellent gas-sensing performances to ethanol and H2S gas due to high porosity when polyvinyl pyrrolidone is added into the precursor solution as a surfactant. The response/recovery times were about 5 s/8 s for 100 ppm ethanol and 4 s/20 s for 100 ppm H2S, respectively. Especially, the maximum response value of H2S is estimated to be 368 at 180 °C, which is one or two orders of magnitude higher than that of other test gases in this study. That indicates that the sensor fabricated with the help of polyvinyl pyrrolidone has good selectivity to H2S.

Development of an Immunochromatographic Strip Test for the Rapid Detection of Alternariol Monomethyl Ether in Fruit.

A rapid, portable, and semi-quantitative immunochromatographic strip was developed for rapid and visual detection of alternariol monomethyl ether (AME). For this purpose, the anti-AME monoclonal antibody (mAb) was prepared and identified. AME coupled to bovine serum albumin (BSA) via methyl 4-bromobutanoate was prepared as immunogen. The recoveries of AME in spiked cherry and orange fruits determined by competitive ELISA were 86.1% and 80.7%, respectively. A colloidal gold nanoparticle (CGN) and CGNs-mAb conjugate were synthesized, and on this basis, a competitive colloidal gold immunochromatographic strip was developed and applied to the detection of AME toxin in fruit samples. The intensity of red density of the test line (T line) is inversely proportional to AME concentration in the range 0.1-10 ng/mL. The visual limit of detection (LOD) of AME was found to be about 10 ng/mL. The semi-quantitative detection can be completed in 10 min. Moreover, the immunochromatographic strip has lower cross-reactivity with AME analogues, and it has a good stability performance (following 3 months of storage). Hence, the colloidal gold immunochromatographic strip could be used as a semi-quantitative tool for the on-site, rapid, and visual detection of AME in fruit.

Flexibility of short ds-DNA intercalated by a dipyridophenazine ligand.

We use Förster Resonant Energy Transfer (FRET) in order to measure the increase of flexibility of short ds-DNA induced by the intercalation of dipyridophenazine (dppz) ligand in between DNA base pairs. By using a DNA double strand fluorescently labeled at its extremities, it is shown that the end-to-end length increase of DNA due to the intercalation of one dppz ligand is smaller than the DNA base pair interdistance. This may be explained either by a local bending of the DNA or by an increase of its flexibility. The persistence length of the formed DNA/ligand is evaluated. The described structure may have implications in the photophysical damages induced by the complexation of DNA by organometallic molecules.

Complexation of DNA with ruthenium organometallic compounds: the high complexation ratio limit.

Interactions between DNA and ruthenium organometallic compounds are studied by using visible light absorption and circular dichroism measurements. A titration technique allowing for the absolute determination of the advancement degree of the complexation, without any assumption about the number of complexation modes is developed. When DNA is in excess, complexation involves intercalation of one of the organometallic compound ligands between DNA base pairs. But, in the high complexation ratio limit, where organometallic compounds are in excess relative to the DNA base pairs, a new mode of interaction is observed, in which the organometallic compound interacts weakly with DNA. The weak interaction mode, moreover, develops when all the DNA intercalation sites are occupied. A regime is reached in which one DNA base pair is linked to more than one organometallic compound.