Determination of 1-hydroxypyrene in human urine by a multi-wall carbon nanotubes-modified glassy carbon electrode

A multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode (MWNT-GCE) was used to study the electrochemical behaviour of1-hydroxypyrene (1-OHP) and applied to its determination. The results showed that the modified electrode had a strong adsorptive ability to 1-OHP and enhances its electrochemical signal. By square wave voltammetry, the linear relationship of 1-OHP was 6?×?10^?9???8?×?10^?7?mol?L^?1 with a linear correlation coefficient of 0.996, and the detection limit was 1?×?10^?10?mol?L^?1. Compared with other published methods, this newly proposed method possesses many advantages such as very low detection limit, fast response, low cost and simplicity. And this method was applied successfully in the determination of 1‐OHP in real human urine samples.     

Determination of synthetic musks in the sediment of the Taihu lake by using accelerated solvent extraction (ASE) and GC/MS

Synthetic musks, substitutes for natural musks, are widely distributed in environment. They have been detected in water, sludge, fish, shrimp, mussels and other aquatic animals, and even in human's adipose tissue, blood and breast milk. In this study, a new extraction procedure, based on the accelerated solvent extraction (ASE) and in cell clean-up technique was developed and successfully coupled with gas chromatography-mass spectrometry (GC/MS) for the analysis of musks in sediment samples. With this method, the limits of detection as low as 0.03–0.05?ng?g^?1 and the recovery rate of 86.0%–104% are achieved. When compared with soxhlet extraction (SE) and ultrasonic extraction (USE), ASE not only has the best extraction efficiency but also has advantage in extraction time and solvent consumption. Eight synthetic musks, including six polycyclic musks (Tonalide (AHTN), Galaxolide (HHCB), Phantolide (AHDI), Traseolide (ATII), Cashmeran (DPMI) and Celestolide (ADBI)) and two nitro musks (musk xylene (MX) and musk ketone (MK)), were evaluated in sediment samples collected from 15 selected locations of the Taihu lake, one of the largest freshwater lakes in China. The contents of synthetic musks in sediment samples range from 0.336 to 3.10?ng?g^?1 for HHCB, 0.184 to 1.21?ng?g^?1 for AHTN, below detection limit (BDL) to 0.349?ng?g^?1 for MX, and BDL to 0.0786?ng?g^?1 for MK. The contents of DPMI, ADBI, AHMI and ATII are below detection limit in all samples. The results reflect current status of fragrance compound pollution in this area, and provide basic data for environmental policy making.     

Enhancement inhibition efficiency of PBTCA depending on the inclusion complex with hydroxypropyl-β-cyclodextrin

For the first time, hydroxypropyl-β-cyclodextrin (HP-β-CD) has been brought in to include 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) in order to enhance inhibition efficiency of PBTCA, which leads a new approach to study oil–gas field corrosion inhibition in the process of acid treatment. Based on the host–guest inclusion reaction, the inclusion complex of PBTCA with HP-β-CD has been prepared in the laboratory. UV–Vis absorption spectrum was applied to study the inclusion behavior of PBTCA with HP-β-CD. The results revealed that PBTCA with HP-β-CD can form a 1:1 stoichiometry inclusion complex. The 1:1 inclusion complex synthesized by using lyophilization was further characterized by Fourier transform infrared spectroscopy. Besides, inhibition effect of the inclusion complex on the corrosion inhibition of Q235 carbon steel has been investigated in 0.1 M sulfuric acid (H₂SO₄) solution using potentiodynamic polarization, electrochemical impedance spectroscopy techniques and scanning electron microscopy (SEM). It was found that the presence of the inclusion complex better achieved the anti-corrosion property in aggressive medium than was the case with alone PBTCA and the highest inhibition efficiency of the inclusion complex over 90 % was obtained, which are suggestive of the active effect of the inclusion complex for improving inhibition efficiency of PBTCA. Meanwhile, the results obtained from SEM further showed that the inclusion complex acts as a more efficient corrosion inhibitor for Q235 carbon steel in H₂SO₄ medium.     

Synthesis of LiNi1/3Co1/3Mn1/3O2 cathode material by a modified sol–gel method for lithium-ion battery

LiNi_1/3Co_1/3Mn_1/3O₂ was prepared by a modified sol–gel method, selecting ethylene diamine tetraacetic acid and citric acid as the co-chelating agent. The mole ratios of ethylene diamine tetraacetic acid (EDTA) to metal ion (Mⁿ⁺) were 0:1, 1:1 and 2:1. The obtained samples were characterized by XRD, BET and SEM. The XRD showed that LiNi_1/3Co_1/3Mn_1/3O₂ had good crystallinity and well-ordered layered structure. After calcined at 850 °C, the LiNi_1/3Co_1/3Mn_1/3O₂ particles exhibited a three-dimensional space network structure, which was greatly correlated with the ratio of EDTA to metal ion. The LiNi_1/3Co_1/3Mn_1/3O₂ obtained from a mole ratio of 1:1 (EDTA:Mⁿ⁺) had the best electrochemical performance. The reversible capacities were reached 168 and 100 mAh/g at 1C and 10C discharge rate, respectively. The result of the cycling performance showed a high capacity maintenance ratio of 89.3 % at 1C and 25 °C after 50 cycles. The further electrochemical performance was evaluated by electrochemical impedance spectroscopy and cyclic voltammetry.     

Enhancement of critical current density in superconducting YBa2Cu3O7−x films by nanostructure development of substrate surface using sol–gel method

In this paper, a simple sol–gel route has been adopted in developing substrate surface for the first time. Only by adjusting the concentration of precursor solution, LaAlO₃ (LAO) nanodot arrays were directly obtained on LAO single crystal substrate, without incorporating additional processing steps. Subsequently, YBa₂Cu₃O_7?x (YBCO) superconducting films were prepared on the nanodot arrays using a low-fluorine solution process. In contrast, J _c of YBCO films grown on the substrate developed with nanodot arrays is almost three times as large as that of YBCO films grown on undeveloped substrate in an applied magnetic field with the strength of 3 Tesla. The pinning force density (F _p ) of YBCO film on the nanodot arrays developed substrate is 2.7 GN/m³ which exceeds that (1.8 GN/m³) of YBCO films on undeveloped substrate. The results of cross-section transmission electron microscope (TEM) images show that the extended defects along the a–b planes of YBCO, induced by the developed substrate with nanodot arrays, should be the origin of the J _c enhancement.     

From Nitro‐ to Sulfonyl‐Based Chromophores: Improvement of the Comprehensive Performance of Nonlinear Optical Dendrimers

Through the combination of the divergent and convergent approaches, coupled with the utilization of the powerful Sharpless “click‐chemistry” reaction, two series of sulfonyl‐based high‐generation NLO dendrimers were conveniently prepared with high purity and in satisfactory yields. Thanks to the perfect three‐dimensional (3D) spatial isolation from the highly branched structure and the isolation effect of the exterior benzene moieties and the interior triazole rings, these dendrimers exhibited large second harmonic generation coefficient (d₃₃) values up to 181 pm V^?1, which, to the best of our knowledge, is the highest value so far for polymers containing sulfonyl‐based chromophore moieties. Meanwhile, compared with the nitro‐chromophore‐based analogues, their optical transparency and NLO stability were improved in a large degree, due to the lower dipole moment (μ) and the special main‐chain structure of sulfonyl‐based chromophore in these dendrimers.     

A p‐Quinodimethane‐Bridged Porphyrin Dimer

A p‐quinodimethane (p‐QDM)‐bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross‐conjugated keto‐linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel–Crafts alkylation of the diol‐linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one‐photon absorption (OPA, λ_max=955 nm, ε=45400 M ^?1 cm^?1) and a large two‐photon absorption (TPA) cross‐section (σ⁽²⁾_max=2080 GM at 1800 nm) in the near‐infrared (NIR) region due to its extended π‐conjugation and quinoidal character. It also exhibits a short singlet excited‐state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground‐state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto‐linked dimer 8 b . This research has revealed that incorporation of a p‐QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.     

Highly Efficient C?H Oxidative Activation by a Porous MnIII–Porphyrin Metal–Organic Framework under Mild Conditions

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed‐metal–organic framework (M′MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M′MOF of [Zn₂(MnOH–TCPP)(DPNI)] ? 0.5 DMF ? EtOH ? 5.5 H₂O ( CZJ‐1 ; CZJ=Chemistry Department of Zhejiang University; TCPP=tetrakis(4‐carboxyphenyl)porphyrin); DPNI=N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide) has the type of doubly interpenetrated cubic α‐Po topology in which the basic Zn₂(COO)₄ paddle‐wheel clusters are bridged by metalloporphyrin to form two‐dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three‐dimensional porous structure. The porosity of CZJ‐1 has been established by both crystallographic studies and gas‐sorption isotherms. CZJ‐1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94 % to the mixture of cyclohexanone (K) and cyclohexanol (A) (so‐called K–A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M′MOF catalyst.     

Electrochemical‐Reduction‐Assisted Assembly of a Polyoxometalate/Graphene Nanocomposite and Its Enhanced Lithium‐Storage Performance

Herein, we present an electrochemically assisted method for the reduction of graphene oxide (GO) and the assembly of polyoxometalate clusters on the reduced GO (rGO) nanosheets for the preparation of nanocomposites. In this method, the Keggin‐type H₄SiW₁₂O₄₀ (SiW₁₂) is used as an electrocatalyst. During the reduction process, SiW₁₂ transfers the electrons from the electrode to GO, leading to a deep reduction of GO in which the content of oxygen‐containing groups is decreased to around 5 %. Meanwhile, the strong adsorption effect between the SiW₁₂ clusters and rGO nanosheets induces the spontaneous assembly of SiW₁₂ on rGO in a uniformly dispersed state, forming a porous, powder‐type nanocomposite. More importantly, the nanocomposite shows an enhanced capacity of 275 mAh g^?1 as a cathode active material for lithium storage, which is 1.7 times that of the pure SiW₁₂. This enhancement is attributed to the synergistic effect of the conductive rGO support and the well‐dispersed state of the SiW₁₂ clusters, which facilitate the electron transfer and lithium‐ion diffusion, respectively. Considering the facile, mild, and environmentally benign features of this method, it is reasonable as a general route for the incorporation of more types of functional polyoxometalates onto graphene matrices; this may allow the creation of nanocomposites for versatile applications, for example, in the fields of catalysis, electronics, and energy storage.