Graphene‐based solid‐phase extraction disk for fast separation and preconcentration of trace polycyclic aromatic hydrocarbons from environmental water samples

Graphene has great potentials for the use in sample preparation due to its ultra high specific surface area, superior chemical stability, and excellent thermal stability. In our work, a novel graphene‐based SPE disk was developed for separation and preconcentration of trace polycyclic aromatic hydrocarbons from environmental water samples. Based on the strong π–π stacking interaction between the analytes and graphene, the analytes extracted by graphene were eluted by cyclohexane and then determined by GC‐MS. Under the optimized conditions, high flow rate (30 mL/min) and sensitivity (0.84–13 ng/L) were achieved. The proposed method was successfully applied to the analysis of real environmental water samples with recoveries ranging from 72.8 to 106.2%. Furthermore, the property of anticlogging and reusability was also improved. This work reveals great potentials of graphene‐based SPE disk in environmental analytical.     

Optimization of microwave‐assisted extraction for anthocyanins,polyphenols, and antioxidants from raspberry (Rubus Coreanus Miq.) using response surface methodology

Anthocyanins (Acys), polyphenols, and antioxidants were extracted from raspberry (Rubus Coreanus Miq.) using a highly efficient microwave‐assisted extraction technique. Different solvents, including methanol, ethanol, and acetone, were tested. The colors of the extracts varied from light yellow to purple red or dark red. SEM and other nutrient analyses verified that ethanol was the most favorable medium for the microwave‐assisted extraction of raspberry due to its high output and low toxicity. Effects of process parameters, including microwave power, irradiation time, and solvent concentration, were investigated through response surface methodology. Canonical analysis estimated that the highest total Acys content, total polyphenols content, and antioxidant activity of raspberry were 17.93 mg cyanidin‐3‐O‐glucoside equivalents per gram dry weight, 38.57 mg gallic acid equivalents per gram dry weight, and 81.24%, respectively. The polyphenol compositions of raspberry extract were identified by HPLC with diode array detection, and nine kinds of polyphenols were identified and quantified, revealing that chlorogenic acid, syringic acid, and rutin are the major polyphenols contained in raspberry fruits. Compared with other fruits and vegetables, raspberry contains higher Acy and polyphenol contents with stronger antioxidant activity, suggesting that raspberry fruits are a good source of natural food colorants and antioxidants.     

Ligand‐Functionalization of BPEI‐Coated YVO4:Bi3+,Eu3+ Nanophosphors for Tumor‐Cell‐Targeted Imaging Applications

In this study, surface‐functionalized, branched polyethylenimine (BPEI)‐modified YVO₄:Bi³⁺,Eu³⁺ nanocrystals (NCs) were successfully synthesized by a simple, rapid, solvent‐free hydrothermal method. The BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs with high crystallinity show broad‐band excitation in the λ=250 to 400 nm near‐ultraviolet (NUV) region and exhibit a sharp‐line emission band centered at λ=619 nm under excitation at λ=350 nm. The surface amino groups contributed by the capping agent, BPEI, not only improve the dispersibility and water/buffer stability of the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs, but also provide a capability for specifically targeted biomolecule conjugation. Folic acid (FA) and epidermal growth factor (EGF) were further attached to the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs and exhibited effective positioning of fluorescent NCs toward the targeted folate receptor overexpressed in HeLa cells or EGFR overexpressed in A431 cells with low cytotoxicity. These results demonstrate that the ligand‐functionalized, BPEI‐coated YVO₄:Bi³⁺, Eu³⁺ NCs show great potential as a new‐generation biological luminescent bioprobe for bioimaging applications. Moreover, the unique luminescence properties of BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs show potential to combine with a UVA photosensitizing drug to produce both detective and therapeutic effects for human skin cancer therapy.     

Vitrifolin A: A Norlabdane Diterpenoid from the Fruits of Vitex trifolia Linn. var. simplicifolia Cham

A new norlabdane diterpenoid, named vitrifolin A, was isolated from the fruits of Vitex trifolia Linn. var. simplicifolia Cham. Its structure was elucidated by mean of spectroscopic methods, including HRESIMS, IR, 1D and 2D NMR. The inhibitory effect of vitrifolin A on nitric oxide production in lipopolysaccarideactivated mouse macrophages was also evaluated.     

Oxidant Effect of H2O2 for the Syntheses of Quinoline Derivatives via One-Pot Reaction of Aniline and Aldehyde

A convenient one-pot method for the synthesis of substituted quinolines via the reaction of aniline and aldehyde in the presence of a Lewis acid (AlCl₃) and an oxidant (H₂O₂) has been developed. Hydrogen peroxide was found to promote the reaction by its function as a hydrogen hunter, hindering the formation of by-product N-alkylaniline. The effect of the oxidant on the yield and selectivity was studied. When the molar ratio of aniline, n-butyraldehyde, and H₂O₂ was 1:3:0.5 at 25 °C, the yield of 3-ethyl-2-propylquinoline was improved from 64% (reaction without H₂O₂) to 84% (with H₂O₂), and the quinoline selectivity was improved to almost 100%. Moreover, the reaction time was obviously reduced. The substituent effect was also investigated in this work.     

Extraction Separation of BSA in Aqueous Two-Phase Systems of Anionic and Cationic Surfactant Mixtures

Aqueous two-phase systems (ATPS) are formed in mixtures of sodium dodecylsulfate (SDS), cetyltrimethyl ammonium bromide (CTAB), and sodium bromide (NaBr). Two different kinds of ATPS appear when CTAB and SDS surfactants are in excess, respectively. Such ATPS may provide a new, useful partitioning system for separation of bovine serum albumin (BSA). The partitioning of BSA was studied in these systems. The results show that the partitioning is affected by the electrical property, the hydrophobicity and the structure of liquid crystal (LC), which exists in the top phase of the ATPS. BSA is extracted into the top phase with higher distribution coefficient when LC and BSA are oppositely charged. The hydrophobicity of LC, which can be improved by increasing the length of alkyl group, enhances the distribution coefficient. The hydrophobicity of lamellar LC and hexagonal LC is stronger than that of cubic LC, which causes extractive capability of the former is higher than the latter.     

Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp2)?H and C(sp3)?H Bonds at δ‐ and ε‐Positions

An easily synthesized and accessible N,O‐bidentate auxiliary has been developed for selective C H activation under palladium catalysis. The novel auxiliary showed its first powerful application in C H functionalization of remote positions. Both C(sp²) H and C(sp³) H bonds at δ‐ and ε‐positions were effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium‐catalyzed intramolecular C H amination.     

Study of Cl−(H2O)n (n = 1–4) using basin‐hopping method coupled with density functional theory

Cl^?(H₂O)_n (n = 1–4) clusters were investigated using a basin‐hopping (BH) algorithm coupled with density functional theory (DFT). Structures, energetics, thermodynamics, vertical detachment energies, and vibrational frequencies were obtained from high‐level ab initio calculations. Through comparisons with previous theoretical and experimental data, it was demonstrated that the combination of the BH method and DFT could accurately predict the global and local minima of Cl^?(H₂O)_n (n = 1–4). Additionally, to optimize larger Cl^?(H₂O)_n (n > 4) clusters, several popular density functionals as well as DF‐LMP2 (Schütz et al., J. Chem. Phys. 2004, 121, 737) (second‐order Møller‐Plesset perturbation theory using local and density fitting approximations) were tested with appropriate basis sets through comparisons with MP2 optimized results. DF‐LMP2 will be used in future studies because its overall performance in describing the relative binding energies and the geometrical parameters of Cl^?(H₂O)_n (n = 1–4) was outstanding in this study. © 2013 Wiley Periodicals, Inc.     

Broadband spin‐controlled focusing via logarithmic‐spiral nanoslits of varying width

This work presents analytical, numerical and experimental demonstrations of light diffracted through a logarithmic spiral (LS) nanoslit, which forms a type of switchable and focus‐tunable structure. Owing to a strong dependence on the incident photon spin, the proposed LS‐nanoslit converges incoming light of opposite handedness (to that of the LS‐nanoslit) into a confined subwavelength spot, while it shapes light with similar chirality into a donut‐like intensity profile. Benefitting from the varying width of the LS‐nanoslit, different incident wavelengths interfere constructively at different positions, i.e., the focal length shifts from 7.5 μm (at λ = 632.8 nm) to 10 μm (at λ = 488 nm), which opens up new opportunities for tuning and spatially separating broadband light at the micrometer scale.