Controllable Fabrication of Vertical Graphene with Tunable Growth Nature by Remote Plasma-Enhanced Chemical Vapor Deposition.

As an important member of the graphene family, vertical graphene (VG) has broad applications like field emission, energy storage, and sensors owing to its fascinating physical and chemical properties. Among various fabrication methods for VG, plasma enhanced chemical vapor deposition (PECVD) is most employed because of the fast growth rate at relatively low temperature for the high-quality VG. However, to date, relations between growth manner of VG and growth parameters such as growth temperature, dosage of gaseous carbon source, and electric power to generate plasma are still less known, which in turn hinder the massive production of VG for further applications. In this study, the growth behavior of VG was studied as functions of temperature, plasma power, and gas composition (or chamber pressure). It was found that the growth behavior of VG is sensitive to the growth conditions mentioned above. Although conditions with high growth temperature, large flow rate of mixed gas of methane and carrier gases, and high plasma power may be helpful for the fast growth of VG, brunching of VG is simultaneously enhanced, which in turn decreases the vertical growth nature of VG. High-quality VG can be achieved by optimizing the growth parameters. It was revealed that the vertical growth nature of VG is governed by the electric field at the interfacial layer between VG and the substrate, for which its strength is influenced by the density of plasma. These findings are important for the general understanding of the VG growth and provided a feasible way for the controllable fabrication of VG using the remote PECVD method which is usually believed to be unsuitable for the fabrication of VG.

ZnO Nanoparticles Modified by Carbon Quantum Dots for the Photocatalytic Removal of Synthetic Pigment Pollutants.

Synthetic pigment pollutants caused by the rapid development of the modern food industry have become a serious threat to people's health and quality of life. Environmentally friendly ZnO-based photocatalytic degradation exhibits satisfactory efficiency, but some shortcomings of large band gap and rapid charge recombination reduce the removal of synthetic pigment pollutants. Here, carbon quantum dots (CQDs) with unique up-conversion luminescence were applied to decorate ZnO nanoparticles to effectively construct the CQDs/ZnO composites via a facile and efficient route. The ZnO nanoparticles with a spherical-like shape obtained from a zinc-based metal organic framework (zeolitic imidazolate framework-8, ZIF-8) were coated by uniformly dispersive quantum dots. Compared with single ZnO particles, the obtained CQDs/ZnO composites exhibit enhanced light absorption capacity, decreased photoluminescence (PL) intensity, and improved visible-light degradation for rhodamine B (RhB) with the large apparent rate constant (k app). The largest k app value in the CQDs/ZnO composite obtained from 75 mg of ZnO nanoparticles and 12.5 mL of the CQDs solution (∼1 mg·mL-1) was 2.6 times that in ZnO nanoparticles. This phenomenon may be attributed to the introduction of CQDs, leading to the narrowed band gap, an extended lifetime, and the charge separation. This work provides an economical and clean strategy to design visible-light-responsive ZnO-based photocatalysts, which is expected to be used for the removal of synthetic pigment pollutants in food industry.

Boosted Inner Surface Charge Transfer in Perovskite Nanodots@Mesoporous Titania Frameworks for Efficient and Selective Photocatalytic CO2 Reduction to Methane.

Exploring high-efficiency and stable halide perovskite-based photocatalysts for the selective reduction of CO2 to methane is a challenge because of the intrinsic photo- and chemical instability of halide perovskites. In this study, halide perovskites (Cs3 Bi2 Br9 and Cs2 AgBiBr6 ) were grown in situ in mesoporous TiO2 frameworks for an efficient CO2 reduction. Benchmarked CH4 production rates of 32.9 and 24.2 µmol g-1 h-1 with selectivities of 88.7 % and 84.2 %, were achieved, respectively, which are better than most reported halide perovskite photocatalysts. Focused ion-beam sliced-imaging techniques were used to directly image the hyperdispersed perovskite nanodots confined in mesopores with tunable sizes ranging from 3.8 to 9.9 nm. In situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy showed that the built-in electric field between the perovskite nanodots and mesoporous titania channels efficiently promoted photo-induced charge transfer. Density functional theory calculations indicate that the high methane selectivity was attributed to the Bi-adsorption-mediated hydrogenation of *CO to *HCO that dominates CO desorption.

Visible light mediated cyclization of tertiary anilines with maleimides using nickel(II) oxide surface-modified titanium dioxide catalyst.

Surface-modified titanium dioxides by highly dispersed NiO particles have an extended absorption in the visible light region and a reduced hole-electron pair recombination than unmodified TiO2. They have now been successfully applied as highly active heterogeneous photocatalysts in the visible light mediated direct cyclization of tertiary anilines with maleimides to give tetrahydroquinoline products in moderate to high yields at ambient temperature. In contrast with unmodified titanium dioxide catalysts that are conventionally used in a stoichiometric amount in combination with UVA light, only a catalytic amount (1 mol %) of the surface-modified TiO2 catalyst is needed along with visible light to efficiently catalyze the reaction. Compared with transition-metal complexes such as Ru(bpy)3Cl2 or Ir(ppy)2(dtbbpy)PF6, advantages of these surface-modified titanium dioxides as photocatalyst include high catalytic activity, low cost, ease of recovering, and being able to be used for at least nine times without significant decay of catalytic activity.

A three-component reaction by photoinduced electron transfer mechanism with N-protected pyrroles as neutral carbon nucleophiles.

A new photoinduced three-component reaction between a cyanoarene, an alkene and an N-protected pyrrole has been developed. This reaction extended the scope of the photo-NOCAS reaction by introducing pyrrole as a neutral carbon-centered nucleophile. The cyanoarenes used include tetracyanobenzene (TCB), 2,3,5,6-tetrafluoro-1,4-dicyanobenzene (TFDCB) and 1,4-dicyanobenzene (DCB). N-Methyl, N-phenyl and N-Boc pyrroles are suitable nucleophiles in the reaction. Taking advantage of the strong electron acceptor ability of the singlet excited TCB, a wide range of alkenes, including the highly electron deficient 4-fluoro-, 4-chloro-, 2,3,4,5,6-pentafluorostyrenes and N-methylmaleimide take part in this reaction, leading to the simultaneous 1,2-diarylation of the alkene and the regioselective 2-alkylation of the pyrrole ring via sequential formation of two new C-C bonds between the three reactants.

Novel monofunctional platinum (II) complex Mono-Pt induces apoptosis-independent autophagic cell death in human ovarian carcinoma cells, distinct from cisplatin.

Failure to engage apoptosis appears to be a leading mechanism of resistance to traditional platinum drugs in patients with ovarian cancer. Therefore, an alternative strategy to induce cell death is needed for the chemotherapy of this apoptosis-resistant cancer. Here we report that autophagic cell death, distinct from cisplatin-induced apoptosis, is triggered by a novel monofunctional platinum (II) complex named Mono-Pt in human ovarian carcinoma cells. Mono-Pt-induced cell death has the following features: cytoplasmic vacuolation, caspase-independent, no nuclear fragmentation or chromatin condensation, and no apoptotic bodies. These characteristics integrally indicated that Mono-Pt, rather than cisplatin, initiated a nonapoptotic cell death in Caov-3 ovarian carcinoma cells. Furthermore, incubation of the cells with Mono-Pt but not with cisplatin produced an increasing punctate distribution of microtubule-associated protein 1 light chain 3 (LC3), and an increasing ratio of LC3-II to LC3-I. Mono-Pt also caused the formation of autophagic vacuoles as revealed by monodansylcadaverine staining and transmission electron microscopy. In addition, Mono-Pt-induced cell death was significantly inhibited by the knockdown of either BECN1 or ATG7 gene expression, or by autophagy inhibitors 3-methyladenine, chloroquine and bafilomycin A 1. Moreover, the effect of Mono-Pt involved the AKT1-MTOR-RPS6KB1 pathway and MAPK1 (ERK2)/MAPK3 (ERK1) signaling, since the MTOR inhibitor rapamycin increased, while the MAPK1/3 inhibitor U0126 decreased Mono-Pt-induced autophagic cell death. Taken together, our results suggest that Mono-Pt exerts anticancer effect via autophagic cell death in apoptosis-resistant ovarian cancer. These findings lead to increased options for anticancer platinum drugs to induce cell death in cancer.

Vaticaffinol, a resveratrol tetramer, exerts more preferable immunosuppressive activity than its precursor in vitro and in vivo through multiple aspects against activated T lymphocytes.

In the present study, we aimed to investigate the immunosuppressive activity of vaticaffinol, a resveratrol tetramer isolated from Vatica mangachapoi, on T lymphocytes both in vitro and in vivo, and further explored its potential molecular mechanism. Resveratrol had a wide spectrum of healthy beneficial effects with multiple targets. Interestingly, its tetramer, vaticaffinol, exerted more intensive immunosuppressive activity than resveratrol. Vaticaffinol significantly inhibited T cells proliferation activated by concanavalin A (Con A) or anti-CD3 plus anti-CD28 in a dose- and time-dependent manner. It also induced Con A-activated T cells undergoing apoptosis through mitochondrial pathway. Moreover, this compound prevented cells from entering S phase and G2/M phase during T cells activation. In addition, vaticaffinol inhibited ERK and AKT signaling pathways in Con A-activated T cells. Furthermore, vaticaffinol significantly ameliorated ear swelling in a mouse model of picryl chloride-induced ear contact dermatitis in vivo. In most of the aforementioned experiments, however, resveratrol had only slight effects on the inhibition of T lymphocytes compared with vaticaffinol. Taken together, our findings suggest that vaticaffinol exerts more preferable immunosuppressive activity than its precursor resveratrol both in vitro and in vivo by affecting multiple targets against activated T cells.

[A rapid nondestructive measurement method for assessing the total plate count on chilled pork surface].

The present paper proposed a method based on the hyperspectral technology for rapidly, nondestructively quantify the total plate count on chilled pork surface. In the research, 50 chilled pork samples stored at 4 degrees C for 1-14 days were used to study the relationship between the total plate count on chilled pork surface and their hyperspectral images collected in 400-1 100 nm. Two models were established using MLR and PLSR methods, and the prediction showed that they can both give satisfactory results with R(v) = 0.886 and 0.863 respectively. The overall research demonstrates that the hyperspectral technology can well quantify the total plate count on chilled pork surface, and so indicates that it is a valid tool to assess the quality and safety properties of chilled pork in the future.