Specific fractionation of ginsenosides based on activated carbon fibers and online fast screening of ginseng extract by mass spectrometry.

Ginseng is beneficial in the prevention of many diseases and provides benefits for proper growth and development owing to the presence of various useful bioactive substances of diverse chemical heterogeneity (e.g., triterpenoid saponins, polysaccharides, volatile oils, and amino acids). As a result, understanding the therapeutic advantages of ginseng requires an in-depth compositional evaluation employing a simple and rapid analytical technique. In this work, three types of surface-activated carbon fibers (ACFs) were prepared by gas-phase oxidation, strong acid treatment, and Plasma treatment to obtain CO2-ACFs, acidified-ACFs, and plasma-ACFs, respectively. Three prepared ACFs were compared in terms of their physicochemical characterization (i.e., surface roughness and functional groups). A separation system was built using a column with modified ACFs, followed by mass spectrometry detection to investigate and determine substances of different polarities. Among the three columns, CO2-ACFs showed the optimum separation effect. 13 strong polar compounds (12 amino acids and1 oligosaccharide) and 15 lesser polar compounds (ginsenosides) were separated and identified successfully within 4 min in the ginseng sample. The data obtained by CO2-ACFs-TOF-MS/MS and UHPLC-TOF-MS/MS were compared. Our approach was found to be faster (4 min vs. 36 min) and greener, requiring much less solvent (1 mL vs. 10.8 mL), and power (0.06 vs. 0.6 kWh). The developed methodology can provide a faster, eco-friendly, and more reliable tool for the high-throughput screening of complex natural matrices and the simultaneous evaluation of several compounds in diverse samples.

Controlled assembly of photosensitizers through directional interactions for effective photooxidation.

Despite the fact that effective photosensitizers (PSs) can be achieved through rational molecular design, controlling the hierarchical assemblies of individual PSs with distinct function and morphological nanoscopic architectures remains a challenge. Here, very ordered one-dimensional PS polymers and their hollow tubular structures are presented from aqueous assembly of organic PS-based di- or tri-blocked supramolecules. Di-blocked PSs were interdigitated into 1D fibrils, significantly quenching photooxidation. Meanwhile, tri-blocked PSs were tilted with respect to each other to generate hollow tubules, showing remarkable photo-activities as well as photo-stability, which are particularly suited for green chemistry due to their unusual rapid photo-oxidation.

Fabrication of ionic liquid-mesoporous silica/platinum electrode with high hydroelectric stability for electric-field-assisted particle separation.

Surface chemistry of electrodes plays a critical role in the fields of electrochemistry and electric-field-assisted separation. In this study, making ingenious use of the ordered mesoporous structure of silica materials and the electrochemical stability of ionic liquids (ILs) when integrated with polyvinylpyrrolidone (PVP), the PVP-modified IL-mesoporous silica/platinum wire (Pt/PVP@meso-SiO2@IL) was fabricated to increase hydroelectric stability and avoid the problem of electrode polarization. The effect of different amounts of mesoporous silica material used to modify the surface of the Pt electrode was systematically investigated. As a result, we successfully obtained a highly ordered mesoporous Pt/PVP@meso-SiO2 material with smooth surface. Because pentyl triethylamine bis(trifluoromethylsulfonyl) imide exhibits a wide electrochemical window between -3 to 3 V, this IL was chosen to modify mesopores under vacuum. Even after repeatedly applying electric field on Pt/PVP@meso-SiO2@IL 100 times, this working electrode remained stable and showed high hydroelectric stability. After verifying the feasibility of this method, it was successfully applied in the electric-field-assisted separation of 2.0 and 3.0 µm polystyrene particles without any impediment from electrode polarization problems. This work provides a brand-new insight for resolving the problem of electrode polarization by developing a versatile tool for the electroseparation of micro-objects.

Efficient and reusable ordered mesoporous WO x /SnO2 catalyst for oxidative desulfurization of dibenzothiophene.

The oxidative desulfurization (ODS) of organic sulfur compounds over tungsten oxide supported on highly ordered mesoporous SnO2 (WO x /meso-SnO2) was investigated. A series of WO x /meso-SnO2 with WO x contents from 10 wt% to 30 wt%, were prepared by conventional wet impregnation. The physico-chemical properties of the WO x /meso-SnO2 catalysts were characterized by X-ray diffraction (XRD), N2 adsorption-desorption isotherms, electron microscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, and the temperature-programmed reduction of hydrogen (H2-TPR). The characterization results indicated that these catalysts possessed mesoporous structures with uniform pores, high specific surface areas, and well-dispersed polyoxotungstate species on the surface of meso-SnO2 support. The ODS performances were evaluated in a biphasic system (model oil/acetonitrile, S initial = 2000 ppm), using H2O2 as an oxidant, and acetonitrile as an extractant. Dibenzothiophene (DBT) in the model oil was removed completely within 60 min at 50 °C using 20 wt% WO x /meso-SnO2 catalyst. Additionally, the effect of reaction temperature, H2O2/DBT molar ratio, amount of catalyst and different sulfur-containing substrates on the catalytic performances were also investigated in detail. More importantly, the 20 wt% WO x /meso-SnO2 catalyst exhibited 100% surfur-removal efficiency without any regeneration process, even after six times recycling.

Open-tubular radially cyclical electric field-flow fractionation (OTR-CyElFFF): an online concentric distribution strategy for simultaneous separation of microparticles.

An open-tubular radially cyclical electric field-flow fractionation technique which achieves the online separation of microparticles in a functional annular channel is proposed in this study. The system was set up by using a stainless steel tube and a platinum wire modified with ionic liquid/mesoporous silica materials as the external and internal electrodes. The feasibility for online separation of various particles was experimentally demonstrated. Particles in the channel were affected by a radial electric field and field-flow fractionation (FFF). On the cross section, different particles showed distinctive migration distances depending on their own properties and the different magnitudes of forces being exerted. The same kind of particles form an annular distribution within the same annulus while different particles form annular distributions at varied concentric annuli through electrophoresis. Under a laminar flow of FFF, different sizes of particles formed a conical arrangement within the annular separation channel. With the joint influence of electric field and flow field, different trajectories were obtained and the particles were eventually separated. Voltage, frequency and duty cycle value are the main parameters affecting the separation of particles. By adjusting these parameters, particles migrate in a zigzag trajectory on one side of the electrodes (mode I) and reach both sides of the electrodes (mode II). Six polystyrene particles were completely separated with high resolution within several minutes. Our system offers numerous advantages of label-free, high-resolution and online separation without tedious operations, and it is a promising tool for the effective separation of various micro-objects.

Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes.

Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g(-1) for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems.

An etched stainless steel wire/ionic liquid-solid phase microextraction technique for the determination of alkylphenols in river water.

In this study, a stainless steel wire/ionic liquid-solid phase microextraction technique was developed for the direct extraction of APs from water samples. Some parameters were optimised, such as selection of the substrate and ILs, extraction time, extraction temperature, stirring rate and sample pH, etc. The experimental data demonstrated that the etched stainless steel wire was a suitable substrate for IL-coated SPME. The coating was prepared by directly depositing the ILs onto the surface of the etched stainless steel wire, which exhibited a porous structure and a high surface area. The [C8MIM][PF6] IL exhibited maximum efficiency with an extraction time of 30 min, and the aqueous sample was maintained at 40 °C and adjusted to pH 2 under stirring conditions. The enrichment factor of the IL coating for the four APs ranged from 1382 to 4779, the detection limits (LOD, S/N=3) of the four APs ranged from 0.01 to 0.04 ng mL(-1) and the RSD values for purified water spiked with APs ranged from 4.0 to 11.8% (n=3). The calibration graphs were linear in the concentration range from 0.5 to 200 ng mL(-1) (R(2)>0.9569). The optimised method was successfully applied for the analysis of real water samples, and the method was suitable for the extraction of APs from water samples.

Catalytic properties of highly ordered crystalline nanoporous tungsten oxide in butanol dehydration.

Highly ordered mesoporous tungsten oxide (meso-WO3) was successfully synthesized using mesoporous silica KIT-6 as a hard template via the nanoreplication method. The physicochemical properties of meso-WO3 were characterized by X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed desorption of ammonia, and infra-red spectroscopy of adsorbed pyridine. No oxidation state other than WO3 was observed in the meso-WO3 sample. Lewis acid sites were dominant in meso-WO3, which could be confirmed by infra-red spectroscopy of pyridine and temperature-programmed desorption of ammonia. Its catalytic behavior in 2-butanol dehydration was investigated in a fixed bed reactor and compared with that of the WO3/MCM-41 catalyst prepared by the atomic layer deposition method. The meso-WO3 catalyst exhibited higher 2-butanol dehydration activity than that of the WO3/MCM-41 catalyst, which is ascribed to the stronger acidity as well as higher amount of acid sites that are mainly composed of Lewis acid sites in the meso-WO3 catalyst.

Microporous organic network hollow spheres: useful templates for nanoparticulate Co(3)O(4) hollow oxidation catalysts.

Hollow microporous organic networks (H-MONs) were prepared by a template method using silica spheres. The shell thickness was delicately controlled by changing the synthetic conditions. The H-MONs were used as a template for the synthesis of nanoparticulate Co3O4 hollows which showed excellent catalytic performance in H2O2 oxidation.

A new mussel-inspired polydopamine sensitizer for dye-sensitized solar cells: controlled synthesis and charge transfer.

The efficient electron injection by direct dye-to-TiO(2) charge transfer and strong adhesion of mussel-inspired synthetic polydopamine (PDA) dyes with TiO(2) electrode is demonstrated. Spontaneous self-polymerization of dopamine using dip-coating (DC) and cyclic voltammetry (CV) in basic buffer solution were applied to TiO(2) layers under a nitrogen atmosphere, which offers a facile and reliable synthetic pathway to make the PDA dyes, PDA-DC and PDA-CV, with conformal surface and perform an efficient dye-to-TiO(2) charge transfer. Both synthetic methods led to excellent photovoltaic results and the PDA-DC dye exhibited larger current density and efficiency values than those in the PDA-CV dye. Under simulated AM 1.5 G solar light (100 mW cm(-2)), a PDA-DC dye exhibited a short circuit current density of 5.50 mW cm(-2), corresponding to an overall power conversion efficiency of 1.2 %, which is almost 10 times that of the dopamine dye-sensitized solar cell. The PDA dyes showed strong adhesion with the nanocrystalline TiO(2) electrodes and the interface engineering of a dye-adsorbed TiO(2) surface through the control of the coating methods, reaction times and solution concentration maximized the overall conversion efficiency, resulting in a remarkably high efficiency.

In situ-generated metal oxide catalyst during CO oxidation reaction transformed from redox-active metal-organic framework-supported palladium nanoparticles.

The preparation of redox-active metal-organic framework (ra-MOF)-supported Pd nanoparticles (NPs) via the redox couple-driven method is reported, which can yield unprotected metallic NPs at room temperature within 10 min without the use of reducing agents. The Pd@ra-MOF has been exploited as a precursor of an active catalyst for CO oxidation. Under the CO oxidation reaction condition, Pd@ra-MOF is transformed into a PdOx-NiOy/C nanocomposite to generate catalytically active species in situ, and the resultant nanocatalyst shows sustainable activity through synergistic stabilization.

Mesoporous inverse opal TiO2 film as light scattering layer for dye-sensitized solar cell.

The light harvesting efficiency of dye-sensitized solar cells was enhanced by using a scattering layer. Such as sphere type TiO2, inverse photonic crystal TiO2, hollow spherical TiO2. Among these materials, the TiO2 with inverse photonic crystal (IPC) structure, synthesized by self-assembly using spherical templates, has attracted much attention due to their photonic crystal characteristics and light scattering effects. However, when applied in the DSSCs, the surface area of IPC is very low that caused insufficient adsorption amount of dye molecules. In the present work, a scattering layer with mesoporous inverse photonic crystal (MIPC) TiO2 film was fabricated by the sol-gel reactions with surfactant-assisted sol-gel method using poly(methyl methacrylate) as the template and titanium (IV) isopropoxide as the TiO2 precursor. After removing the PMMA and surfactant, a highly ordered macroporous structure with mesopores were successfully obtained. The surface area and total pore volume of the MIPC were 82 m2/g and 0.31 cm3/g, respectively, which is much larger than those of the IPC. The DSSCs with the scattering layer of MIPC film exhibited 18 and 10% higher photo-conversion efficiency than those of cells only with a nano-crystalline TiO2 film and with scattering layer of IPC film. From UV-visible spectra of dye solutions, the MIPC film showed a higher amount of absorbed dye molecules than those of the reference and IPC films. Accordingly, an increase in the photo-current density through abundant adsorption of the dye, coupled with inherent light scattering ability can improve overall photo-conversion efficiency.

Catalytic ozone oxidation of benzene at low temperature over MnOx/Al-SBA-16 catalyst.

The low-temperature catalytic ozone oxidation of benzene was investigated. In this study, Al-SBA-16 (Si/Al = 20) that has a three-dimensional cubic Im3m structure and a high specific surface area was used for catalytic ozone oxidation for the first time. Two different Mn precursors, i.e., Mn acetate and Mn nitrate, were used to synthesize Mn-impregnated Al-SBA-16 catalysts. The characteristics of these two catalysts were investigated by instrumental analyses using the Brunauer-Emmett-Teller method, X-ray diffraction, X-ray photoelectron spectroscopy, and temperature-programmed reduction. A higher catalytic activity was exhibited when Mn acetate was used as the Mn precursor, which is attributed to high Mn dispersion and a high degree of reduction of Mn oxides formed by Mn acetate than those formed by Mn nitrate.

Indoor formaldehyde removal over CMK-3.

The removal of formaldehyde at low concentrations is important in indoor air pollution research. In this study, mesoporous carbon with a large specific surface area was used for the adsorption of low-concentration indoor formaldehyde. A mesoporous carbon material, CMK-3, was synthesized using the nano-replication method. SBA-15 was used as a mesoporous template. The surface of CMK-3 was activated using a 2N H2SO4 solution and NH3 gas to prepare CMK-3-H2SO4 and CMK-3-NH3, respectively. The activated samples were characterized by N2 adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The formaldehyde adsorption performance of the mesoporous carbons was in the order of CMK-3-NH3 > CMK-3-H2SO4 > CMK-3. The difference in the adsorption performance was explained by oxygen and nitrogen functional groups formed during the activation process and by the specific surface area and pore structure of mesoporous carbon.

Effect of Mn precursors on benzene oxidation with ozone over MnOx/MCM-41 at low temperature.

Low temperature benzene oxidation in the presence of ozone on MnOx/MCM-41 catalysts has been studied. MnOx/MCM-41 catalysts were prepared from two different precursors, Mn(NO3)2 and Mn(CH3COO)2, and these samples were characterized by N2 sorption, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction. The characterization results showed that the MnOx/MCM-41 prepared from Mn(CH3COO)2 had higher oxygen mobility and dispersion than the MnOx/MCM-41 from Mn(NO3)2. As a result, the MnOx/MCM-41 obtained from Mn(CH3COO)2 showed higher catalytic activity for the oxidation of benzene using ozone; however, without ozone, the catalytic activity was negligible.

MALDI-TOF-MS analysis of small molecules using modified mesoporous material SBA-15 as assisted matrix.

Mesoporous silica, SBA-15 was successfully functionalized with quinoline moiety, and was applied as a matrix in the MALDI-TOF-MS analysis of small molecules. The modified SBA-15 material [SBA-15-8-(3-(triethoxysilyl)propoxy) quinoline, SBA-15-8QSi] was obtained by using calcined SBA-15 and 8-hydroxy quinoline. The structure of the functionalized mesoporous material was systemically characterized by TEM, the N(2) adsorption-desorption isotherm technique and FT-IR spectra. Compared with DHB and SBA-15, SBA-15-8QSi demonstrated several advantages in the analysis of small molecules with MALDI-TOF-MS, such as less background interference ions, high homogeneity, and better reproducibility. Based on these results, the various analytical parameters were optimized. The ideal operating conditions were (1) methanol used as the dissolving solvent; (2) sample first dropping method; (3) a ratio between the analyte and the matrix of 3.5:10. Under these optimization conditions, a low detection limit (8 pmol for L-Arginine-HCl) and high reproducibility (< or = 29%) were obtained. This technique was successfully applied to the analysis of various types of small molecules, such as saccharides, amino acids, metabolites, and natural honey.

Facile synthesis of highly ordered mesoporous silver using cubic mesoporous silica template with controlled surface hydrophobicity.

Highly ordered mesoporous silver, which exhibits well-defined mesopores, high surface area and pore volume, has been successfully obtained using a cubic mesoporous silica, KIT-6, with controlled surface hydrophobicity as the hard template.