Visible‐light photocatalytic activity of Ag@MIL‐125(Ti) microspheres

Ag nanoparticle (NP)‐decorated MIL‐125(Ti) microspheres (Ag@MIL‐125(Ti)) were firstly fabricated via a facile hydrothermal and following photo‐reduction method. The photocatalysts were characterized using X‐ray diffraction, scanning and transmission electron microscopies, X‐ray photoelectron spectroscopy and UV–visible diffuse reflectance spectroscopy. The characterization results indicated that Ag NPs were dispersed on the surface of MIL‐125(Ti) microspheres, and the Ag NPs had a uniform diameter of about 40 nm. The composites exhibited excellent visible‐light absorption, due to the modification with the Ag NPs. The photocatalytic activity for the visible‐light‐promoted degradation of Rhodamine B was improved through the optimization of the amount of Ag loaded as a co‐catalyst, this amount being determined as 3 wt%. Additionally, studies performed using radical scavengers indicated that O₂^? and e^? served as the main reactive species. The catalyst can be reused at least five times without significant loss of its catalytic activity. Furthermore, a photocatalytic mechanism for degradation of organics over Ag@MIL‐125(Ti) is also proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

A green protocol for efficient discovery of novel natural compounds: Characterization of new ginsenosides from the stems and leaves of Panax ginseng as a case study

Exploration of new natural compounds is of vital significance for drug discovery and development. The conventional approaches by systematic phytochemical isolation are low-efficiency and consume masses of organic solvent. This study presents an integrated strategy that combines offline comprehensive two-dimensional liquid chromatography, hybrid linear ion-trap/Orbitrap mass spectrometry, and NMR analysis (2D LC/LTQ-Orbitrap-MS/NMR), aimed to establish a green protocol for the efficient discovery of new natural molecules. A comprehensive chemical analysis of the total ginsenosides of stems and leaves of Panax ginseng (SLP), a cardiovascular disease medicine, was performed following this strategy. An offline 2D LC system was constructed with an orthogonality of 0.79 and a practical peak capacity of 11,000. The much greener UHPLC separation and LTQ-Orbitrap-MS detection by data-dependent high-energy C-trap dissociation (HCD)/dynamic exclusion were employed for separation and characterization of ginsenosides from thirteen fractionated SLP samples. Consequently, a total of 646 ginsenosides were characterized, and 427 have not been isolated from the genus of Panax L. The ginsenosides identified from SLP exhibited distinct sapogenin diversity and molecular isomerism. NMR analysis was finally employed to verify and offer complementary structural information to MS-oriented characterization. The established 2D LC/LTQ-Orbitrap-MS/NMR approach outperforms the conventional approaches in respect of significantly improved efficiency, much less use of drug materials and organic solvent. The integrated strategy enables a deep investigation on the therapeutic basis of an herbal medicine, and facilitates new compounds discovery in an efficient and environmentally friendly manner as well.     

pH/temperature double responsive behaviors and mechanical strength of laponite‐crosslinked poly(DEA‐co‐DMAEMA) nanocomposite hydrogels

A nanocomposite (NC) hydrogel crosslinked by inorganic Laponite XLG was successfully synthesized via in situ free radical polymerization of monomers N,N‐diethylacrylamide and (2‐dimethylamino) ethyl methacrylate (DMAEMA). Polymerization was carried out at room temperature due to the accelerating effect of DMAEMA. The as‐prepared hydrogels displayed controlled transformation in optical transmittance and volume in response to small diversification of environmental factors, such as temperature and pH. The compressive strength of swollen D_6:1G₆ hydrogels was as high as 2219 kPa while compressive strain was 95%. Cyclic compression measurement exhibited good elastic properties of NC hydrogels. This work provides a facile method for fabricating stimuli‐responsive hydrogels with superior mechanical property. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 876–884