One-dimensional GdVO4:Ln (Ln=Eu, Dy, Sm) nanofibers: Electrospinning preparation and luminescence properties

One-dimensional GdVO₄:Ln³⁺ (Ln=Eu, Dy, Sm) nanofibers have been prepared by a combination method of sol-gel process and electrospinning technology. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL), quantum efficiency (QE), and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The XRD, FT-IR, and TG-DTA results show that GdVO₄:Ln³⁺ nanofibers samples crystallize at 700 °C. SEM images indicate that the as prepared precursor fibers are smooth. After being calcined at 700 °C for 4 h, the fibers still maintain their fiberlike morphology with rough surface. TEM image further manifests that the GdVO₄:Ln³⁺ nanofibers consist of nanoparticles. Under ultraviolet excitation and low-voltage electron beam excitation, GdVO₄:Ln³⁺ phosphors showed their strong characteristic emission due to an efficient energy transfer from vanadate groups to dopants. The optimum doping concentration of Ln³⁺ in the GdVO₄ nanofibers also has been investigated.     

Experimental Evidence for Ion Accumulation Time Affecting Qualitative and Quantitative Analysis of Ophiopogons in Ophiopogon Extract by Hybrid Ion Trap Time-of-Flight Mass Spectrometry

The qualitative and quantitative capability of the ion trap mass analyzer could be greatly affected by the accumulation time. However, the importance of the accumulation time has not so far been thoroughly explored. Here, the influence of ion accumulation time on qualitative and quantitative analysis of complicated components was systematically investigated based on the case study of 40 ophiopogonins in Ophiopogon extract by hybrid ion trap time-of-flight mass spectrometry (LCMS-IT-TOF). In this process, the accumulation time was set at 10, 25, 50, 100, and 200 ms, respectively. The effect of accumulation time on qualitative analysis of ophiopogonins was studied by comparing the total ion current (TIC) of MS¹, TIC of MS², and the number and signal of fragmental ions. The results demonstrated that the signal could be greatly influenced by varying the accumulation time. The number and signal of the fragmental ions were increased significantly with a longer accumulation time in the range of 10–100 ms. Also, the effect of accumulation time on quantitative analysis of ophiopogonins was investigated by comparing the linearity, accuracy, and precision measured on LCMS-IT-TOF. Importantly, quantitative parameters could all be significantly improved by choosing an appropriate accumulation time.

     

Microfluidic synthesis of tunable poly-(N-isopropylacrylamide) microparticles via PEG adjustment

We present a microfluidic droplet method to synthesize a series of tunable poly(N-isopropylacrylamide) (PNIPAM) microparticles by the addition of polyethylene glycols (PEGs). The PEGs are used as porogens and could be removed simply by washing step. By varying molecular weights and concentrations of the PEGs, morphologies and temperature-sensitive properties of the formed PNIPAM microparticles are flexibly tuned. It is found that PEG of lower molecular weight induces smaller micropore sizes, and results in faster response rate. The volume changes prior to and after shrinkage can also be regulated by the addition of PEGs due to tuned homogeneities of micropores. The microparticles tuned by PEG1000 with ratio of added PEGs to NIPAM of 2:1 respond the fastest (120 s), whereas with ratio of added PEGs to NIPAM of 1:1 display largest volume change (1/γ=12.12). This simplicity and controllability of tunable microparticles synthesis are appealing for various applications ranging from chemical delivery, drug release control, to optical applications.     

Theoretical study on the alkaline hydrolysis of methyl thioacetate in aqueous solution

A base-catalyzed hydrolysis reaction of thiolester has been studied in both gas and solution phases using two ab initio quantum mechanics calculations such as Gaussian09 and CPMD. The free-energy surface along the reaction path is also constructed using a configuration sampling technique, namely, the metadynamics method. While there are two different reaction paths obtained for the potential profile of the base-catalyzed hydrolysis reaction for thiolester in the gas phase, a triple-well reaction path is computed for the reaction in the solution phase by two quantum mechanics calculations. Unlike the S(N)2 mechanism (a concerted mechanism) found for the gas-phase reaction, a nucleophilic attack from the hydroxide ion on the carbonyl carbon to yield a tetrahedral intermediate (a stepwise mechanism) is observed for the solution-phase reaction. Moreover, the energy profiles computed by these two theoretical calculations are found to be very comparable with those determined experimentally.     

Asymmetric iodoamination of chalcones and 4-aryl-4-oxobutenoates catalyzed by a complex based on scandium(III) and a N,N'-dioxide ligand

Highly diastereo‐ and enantioselective iodoamination of chalcones, 4‐aryl‐4‐oxobutenoates, and a trifluoro‐substituted enone has been accomplished in the presence of a chiral N,N′‐dioxide/[Sc(OTf)₃] complex (0.5–2 mol %), delivering the desired vicinal anti‐α‐iodo‐β‐amino carbonyl compounds regioselectively in high yields (up to 97 %) and with excellent diastereoselectivities (>99:1 d.r.) and enantioselectivities (up to 99 % ee). Enantiopure syn‐α‐iodo‐β‐amino products could also be obtained from the isomerization of particular iodo compounds. TsNHX species (X=Cl, Br, I), generated from the reactions between the halo sources and TsNH₂, were further confirmed as the active species in the haloamination reactions involved in the formation of the key halonium ion intermediates. A typical haloamination dependency was observed, with reactivity decreasing in the order NBS>NIS?NCS.     

Selective supramolecular assembly of multifunctional ligands on a Cu(111) surface: metallacycles, propeller trimers and linear chains

We studied the supramolecular assembly of a multifunctional ligand, cis-bis-terpyridine tetraphenyl ethylene, on a Cu(111) surface by low-temperature scanning tunneling microscopy (STM). Three distinctive supramolecular structures, metallacycles, propeller-shaped clusters and extended linear chains, are formed under specific assembly conditions owing to different inter-molecular binding modes of Cu-coordination, van der Waals interaction and hydrogen bonding, respectively.     

Surface structure and catalytic properties of MoO3/CeO2 and CuO/MoO3/CeO2

XRD, LRS, TPR and in situ NH(3) adsorption FT-IR were used to investigate the dispersion state of the copper oxide and molybdena species of MoO(3)/CeO(2) and CuO/MoO(3)/CeO(2) catalysts as well as their surface acidity. The results showed that the molybdena monolayer modification promoted the dispersion of CuO due to the formation of new tetrahedral vacancies. Meanwhile, CuO changed the structure of molybdenum species and then influenced the surface acidity of the samples. A detail discussion about the possible model of the surface structure of the catalyst was presented. In addition, combining with the in situ NH(3) adsorption FT-IR, the relationships between the activities for 'NO + NH(3) + O(2)' reaction and surface acid properties (Br?nsted and Lewis acid sites) of the catalysts were discussed.     

Molybdenum nitride based hybrid cathode for rechargeable lithium-O2 batteries

Molybdenum nitride/nitrogen-doped graphene nanosheets (MoN/NGS) are synthesized and used as an alternative O(2) electrode for Li-O(2) batteries. In comparison with electrocatalysts proposed previously, this hybrid cathode exhibits a high discharge potential (around 3.1 V) and a considerable specific capacity (1490 mA h g(-1), based on carbon + electrocatalyst).     

Graphene oxide noncovalent photosensitizer and its anticancer activity in vitro

Graphene oxide (GO) was investigated as a potential drug-delivery system due to its special properties and biocompatibility. Thus far, little has been done to use GO as a photosensitive drug-delivery system and to explore its anticancer activity in vitro in photodynamic therapy applications. Here, a novel GO-hypocrellin A (GO-HA) hybrid was prepared by a simple noncovalent method and its photodynamic activity was studied for the first time. The results showed that an efficient loading amount of HA on GO was as high as 1.0 mg mg(-1) and the stability of the hybrid was superior to that of the free hypocrellin A in aqueous solution. Furthermore, GO-HA can be excited by irradiation with light of appropriate wavelength to generate singlet oxygen, and in vitro experiments illustrated that GO-HA was efficiently taken up by tumor cells, and that light irradiation of such impregnated cells resulted in significant cell death. Thus, these properties of GO-HA could possibly make it especially promising for use in clinical photodynamic therapy.