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IONICS · 2018 ·Vol. 25 ·期 4 ·1669-1677 · IF 2.347

Hierarchical carbon-free NiCo2O4 cathode for Li–O2 batteries

Yuan Jiashu,Liu Zhihao,Wen Yandi,Hu Huili,Zhu Yongming,Thangadurai Venkataraman

Li–oxygen battery provides much higher specific energy density compared to conventional Li–ion batteries, but there is a lack of desired cathodes which show lower over-potential during the charging cycle. Here, we report the effect of surface morphology of carbon-free spinel-like NiCo 2 O 4 nanowires and nanosheets on Ni foam on cathode performance in Li–O 2 battery. Two hierarchical structured NiCo 2 O 4 cathodes were synthesized by using a hydrothermal method. Physical, chemical, and electrochemical properties of NiCo 2 O 4 were characterized using powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, BET surface area, electrochemical AC impedance spectroscopy, and linear sweep voltammetry. Scale-like NiCo 2 O 4 electrode showed the highest specific capacity, compared to that of rod-like morphology, which seems due to a superior catalytic activity for oxygen reduction reaction, with lower charging over-potential, high discharge capacity, and excellent cycle performance.

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2018 ·Vol. 29 ·期 19 ·16469-16477 · IF 2.324

Navy-to-transmissive electrochromic polymer based on 3,4-propylenedioxythiophene

Chen Xiaoming,Zhang Jingyan,Yang Mingdi

A novel conjugated polymer PProDOTCBDEM based on propylenedioxythiophene (ProDOT) with diethyl malonate (DEM) pendant group and a cyclobutane spacer between ProDOT and DEM was successfully synthesized through electrochemical polymerization. The polymer film exhibits reversible electrochromism switching between navy neutral state (− 0.1 V) and transmissive oxidized state (0.7 V). The symmetric double short chain ester substitution pattern was utilized to realize the navy color of the polymer film. The electrochemistry, spectroelectrochemistry and electrochromic switching properties of the polymer film were studied in detail.

CAS / MDL: 7791-03-9
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JOURNAL OF MATERIALS SCIENCE · 2018 ·Vol. 53 ·期 22 ·15487-15499 · IF 2.993

Enhanced adsorption performance of hierarchical S-doped Ni(OH)2 hollow nanocomposites for the removal of Congo red

Yang Ming,Rao Richuan

In this work, nonmetallic S was doped into hierarchical Ni(OH) 2 hollow microspheres by ethanol solvothermal method using thiourea as sulfur source. Although the morphology of precursor Ni(OH) 2 is maintained, the surface states and pore properties had greatly changed after S doping. Using the as-prepared S-doped Ni(OH) 2 as adsorbents for the removal of Congo red (CR), the S-doped Ni(OH) 2 exhibited much better adsorption capacity compared with undoped Ni(OH) 2 . The adsorption behavior of both Ni(OH) 2 and S-doped Ni(OH) 2 followed the pseudo-second-order kinetic model and intraparticle diffusion model. The equilibrium data of Ni(OH) 2 could be better fitted by Langmuir model, while Freundlich model could be better used to describe the S-doped Ni(OH) 2 with a much larger adsorption capacity toward CR. The tuned microstructure and changed surface states of adsorbent after S doping may be responsible for the enhanced adsorption performance. Therefore, the doping of S species into hierarchical Ni(OH) 2 paves a new way to tune the microstructure and surface states of Ni-based materials.

CAS / MDL: 100-97-0
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MICROCHIMICA ACTA · 2018 ·Vol. 185 ·期 8 ·1-8 · IF 5.705

Highly sensitive fluorometric determination of thrombin by on-chip signal amplification initiated by terminal deoxynucleotidyl transferase

Wen Dongxiao,He Minhui,Ma Kefeng,Cui Ying,Kong Jinming,Yang Huaixia,Liu Qingyun

The article describes an on-chip amplification scheme initiated by a terminal deoxynucleotidyl transferase (TdT) for highly sensitive fluorometric determination of protein. Two thrombin-binding aptamers were designed to capture thrombin as they can form a sandwich structure for improved specificity. An amino-modified aptamer (TBA29) was first immobilized on a silicon chip. After capture of thrombin, a second aptamer (TBA15) was conjugated to the second binding site of thrombin. The 3’-terminal of aptamer TBA15 is exposed on the chip surface, and then fluorescein-labeled 12-dATP associates to the 3’-terminal with the help of TdT. This results in signal amplification, and eventually leads to highly sensitive detection. Under optimal conditions, fluorescence intensity is linearly related to the logarithm of thrombin concentration in the range of 100 fM - 0.1 μM, and the detection limit is as low as 2.0 fM. The assay is sensitive and selective even over potentially interfering proteins and in the presence of human serum. Schematic strategy for thrombin detection. Two thrombin-binding aptamers were designed to capture thrombin to form a sandwich structure for improved specificity. The protein detection is based on TdT initiated on-chip fluorescent amplification.

CAS / MDL: 919-30-2
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AMB Express · 2018 ·Vol. 8 ·期 1 ·1-16 · IF 1.719

Comprehensive investigation of a dye-decolorizing peroxidase and a manganese peroxidase from Irpex lacteus F17, a lignin-degrading basidiomycete

Duan Zihong,Shen Rui,Liu Binjie,Yao Mengwei,Jia Rong

Irpex lacteus F17 is well-known for its ability to degrade recalcitrant aromatic pollutants, which mainly results from the action of the manganese peroxidase (MnP) that it is able to produce. Recently, the genome sequencing and annotation of this strain provided comprehensive picture of the ligninolytic peroxidase gene family. In addition to revealing the presence of 13 MnPs, genes for five dye-decolorizing peroxidases (DyPs) were also discovered in the I. lacteus F17 genome, which are unrelated to the fungal class II peroxidases. In the present study, amino acid sequences of five DyPs and 13 MnPs, representing two different families of heme peroxidases, were analyzed. Of these, two enzymes, a DyP (Il-DyP4) and a MnP (Il-MnP6) were expressed respectively in Escherichia coli, and were characterized by comparing their molecular models, substrate specificities, and catalytic features. The results showed that Il-DyP4 possessed a higher catalytic efficiency for some representative substrates, and a stronger decolorizing ability to a wide range of synthetic dyes in acidic conditions. Based on electrochemical measurements, Il-DyP4 was found to have a high redox potential of 27 mV at pH 3.5, which was superior to that of Il-MnP6 (− 75 mV), thereby contributing to its ability to oxidize high redox potential substrates, such as veratryl alcohol and polymeric dye Poly R-478. The results highlighted the potential of Il-DyP4 for use in industrial and environmental applications.

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JOURNAL OF MATERIALS SCIENCE · 2018 ·Vol. 53 ·期 21 ·15118-15129 · IF 2.993

Building an interpenetrating network of Ni(OH)2/reduced graphene oxide composite by a sol–gel method

Liu Hao,Xu Jü,Liu Guanxi,Wang Meiri,Li Jing,Liu Yuanyuan,Cui Hongtao

Herein, a facile sol–gel strategy for building the ordered interpenetrating network of Ni(OH) 2 and reduced graphene oxide (rGO) was proposed. In this strategy, rGO nanosheets were homogeneously fixed inside composite utilizing the pores of Ni(OH) 2 gel as template, forming rGO-interpenetrated gel network. It was found that the rGO nanosheets could effectively reduce the internal resistant of composites and provide mechanical support for the gel network of Ni(OH) 2 . Therefore, the composite presented high electrochemical performance, especially high-rate performance, due to the interpenetrating of rGO nanosheets plus the supplementary role of acetylene black. It had high specific capacitance of 2163 F g −1 at low current density of 2.9 A g −1 and 733 F g −1 at high current density of 86.8 A g −1 .

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Nature Biomedical Engineering · 2018 ·Vol. 2 ·期 8 ·611-621 · IF 0

Combined local immunostimulatory radioisotope therapy and systemic immune checkpoint blockade imparts potent antitumour responses

Chao Yu,Xu Ligeng,Liang Chao,Feng Liangzhu,Xu Jun,Dong Ziliang,Tian Longlong,Yi Xuan,Yang Kai,Liu Zhuang

Radiation therapy for cancer can lead to off-target toxicity and can be ineffective against hypoxic solid tumours and distant metastases. Here, we show that intratumoral injection, in mouse and rabbit xenografts and in patient-derived mouse xenografts, of a sodium alginate formulation containing catalase (Cat) labelled with the therapeutic 131 I radioisotope enables long-term relief of tumour hypoxia and complete tumour elimination at low radioactivity doses. On injection, the soluble polysaccharide rapidly transforms into a hydrogel in the presence of endogenous Ca 2+ , fixing 131 I-Cat within the tumours. We also show that local radiotherapy with a formulation that includes the immunostimulatory CpG oligonucleotide combined with systemic checkpoint-blockade therapy using an anti-CTLA-4 antibody leads to metastasis inhibition and protection against tumour rechallenge. The local therapy, which uses only biocompatible components, might enable new strategies for local tumour treatments that can be combined with systemic therapeutic responses, for the inhibition of tumour metastasis and the prevention of tumour recurrence in patients with advanced-stage cancer.

CAS / MDL: 9001-05-2
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2018 ·Vol. 29 ·期 17 ·14971-14980 · IF 2.324

Facile synthesis of Cu nanoparticles on different morphology ZrO2 supports for catalytic hydrogen generation from ammonia borane

Zhu Jianjun,Ma Lirong,Feng Jin,Geng Tianli,Wei Wei,Xie Jimin

In this paper, the X% Cu–ZrO 2 (X = 0, 1, 5, 10, 15 and 20) xerogel catalysts have been successfully synthesized via a facile two-step approach involving epoxide-driven sol–gel method followed by chemical reduction. The series xerogel catalysts were characterized using XRD, SEM–EDS, TEM, XPS, H 2 -TPR, N 2 adsorption–desorption and FT-IR. The results showed that the morphologies of ZrO 2 partly have changed from bulk to nanorods with the increase in Cu loading from 0 to 20%. The catalysts exerted Cu content-dependent activities towards the catalytic hydrolysis of ammonia borane (AB). Among them, the 15% Cu–ZrO 2 showed the best catalytic activity that the maximum hydrogen generation rate was 0.384 mol min −1 . The hydrolysis reaction towards AB was proved to the first order by the 15% Cu–ZrO 2 xerogel by kinetic studies. The activation energy was calculated to be 22.34 kJ mol −1 . Even after five recycle experiment, the catalysts also showed a good recycle stability in aqueous solution.

CAS / MDL: 13774-81-7
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BIOMEDICAL MICRODEVICES · 2018 ·Vol. 20 ·期 3 ·1-8 · IF 2.077

A magnetic beads-based portable flow cytometry immunosensor for in-situ detection of marine biotoxin

Pan Yuxiang,Wei Xinwei,Liang Tao,Zhou Jie,Wan Hao,Hu Ning,Wang Ping

Okadaic acid (OA), a representative diarrhetic shellfish poisoning toxin, mainly produced by toxigenic dinoflagellates, has significant hazard to public health. Traditional methods for detection of OA can not give the consideration to the need of rapid, high sensitive, quantitative and in-situ detection at the same time. Herein, a new effective detection method of OA was developed based on fluorescence immunosensor and flow cytometry (FCM). In this assay, Streptavidin-coated magnetic beads (MBs) were used as the supporter to immobilize the biotinylated OA. Modified MBs competed with the free OA in the sample solution to bind with the anti-OA monoclonal antibody (OA-MAb). The R-phycoerythrin (R-PE) dye labeled IgG was served as a secondary antibody to perform fluorescence detection. A portable flow cytometry was applied for the in-situ fluorescence quantification. The results showed that the OA concentration was inversely proportional to the R-PE fluorescence intensity. The detection method took within 50 min with a limit of detection (LOD) was 0.05 μg/L and range from 0.2 to 20 μg/L for OA detection. Moreover, the matrix effect and the recovery rate were assessed during real sample measurement, showing a high recovery. Performance features such as high sensitivity, low LOD, speediness and simplicity of the analysis protocol, shows this biosensing-systems as a promising tool for routine use.

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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2018 ·Vol. 25 ·期 26 ·26617-26624 · IF 2.8

Development of immunochromatographic assays for the detection of imidacloprid in soil chemical barrier

Yang Jiachuan,Yang Qian,Deng Jiaqi,Tao Zhexuan,Hua Xiude,Wang Minghua

A soil chemical barrier is the most important and common way to control termites; fast and on-site detection methods are significant tools to verify pesticide content meeting the standard requirements. In this study, conventional and enhanced immunochromatographic assays (ICAs) containing two test lines (TLs) were developed to semi-quantitatively detect imidacloprid in soil chemical barrier, and detection results were quantified by a smart phone. According to the results, the disappearance concentrations of first TL (TL-1) and second TL (TL-2) in an enhanced ICA and conventional ICA were 5 and 20 ng/mL and 20 and 80 ng/mL with the naked eye. The sensitivity of TL-2 was four times that of TL-1 in both ICAs, consistent with the maximum and minimum concentration differences for imidacloprid in Jiangsu province’s “the technical regulation of assay and evaluation on chemical soil barrier of termite prevention treatment in buildings”. The results of TLs can be used to judge whether the amount of imidacloprid in soil chemical barrier meets the standard. Enhanced and conventional ICAs were available for further quantitative testing with a smart phone, and the limit of detection (LOD) was 0.74 and 3.17 ng/mL, respectively. Moreover, some soil chemical barrier samples from several areas in Wuxi, Jiangsu province, were used to test by ICAs and high-performance liquid chromatography (HPLC), and the results of ICAs correlated well with HPLC.

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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2018 ·Vol. 34 ·期 4 ·571-577 · IF 1.248

Synthesis of 9-Substituted Berberine Derivatives with Microwave Irradiation

Han Xie,Shao Kaiyuan,Hu Wenxiang

Hyperglycemia is frequently accompanying with hyperlipidemia. To explore the potent drugs with dual-activity and dual-site effects that could reduce blood glucose and blood lipid at the same time, fibrate group with lipid-lowering effect on the 9th position of berberine(BBR) was introduced using the drug design combination principle and the multitarget collaborative treatment method. Moreover, the molecular structure of BBR was modified, and six 9-substituted derivatives of BBR were designed and synthesized, among which, five compounds have never been reported before. In addition, the molecular structures of these derivatives were identified using liquid chromatography-mass spectrometry(LC-MS), 1 H nuclear magnetic resonance( 1 H NMR) and 13 C NMR, respectively. Furthermore, the microwave irradiation experimental technique was applied in the synthesis reaction using the novel microwave synthesizer, which accelerated the reaction rate, enhanced the reaction yield, reduced the reaction by-products, and simplified the post-processing steps. In the meantime, the 9-position regioselective demethylation of BBR was explored through quantum chemical calculation during the synthesis of berberrubine. The computations were consistent with the experimental results, which contributed to deducing the mechanism of its selective methylation.

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JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY · 2018 ·Vol. 135 ·期 6 ·3363-3373 · IF 2.209

Investigation on the dissolution behavior of 2HNIW·HMX co-crystal prepared by a solvent/non-solvent method in N,N-dimethylformamide at T = (298.15–318.15) K

Zhang Shijie,Zhang Jiaoqiang,Kou Kaichang,Jia Qian,Xu Yunlong,Zerraza Sofiane,Liu Ning,Hu Rongzu

2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexazisowurtzitane (HNIW)·1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) co-crystal in a 2:1 molar ratio was prepared by a solvent/non-solvent method, and the co-crystal has been characterized by several methods. The enthalpies of dissolution of 2HNIW·HMX co-crystal in N,N -dimethylformamide at different temperatures were measured by a DC08-1 Calvet microcalorimeter under standard atmospheric pressure, and it is indicated that the dissolutions are exothermic process. The empirical formulae for the calculation of the molar enthalpy ( \(\Delta_{\text{diss}} H\) ) of dissolution, relative partial molar enthalpy ( \(\Delta_{\text{diss}} H_{\text{partial}}\) ), relative apparent molar enthalpy ( \(\Delta_{\text{diss}} H_{\text{apparent}}\) ), and enthalpy of dilution ( \(\Delta_{\text{dil}} H_{1,2}\) ) at 298.15 K are obtained. The differential enthalpies ( \(\Delta_{\text{dif}} H\) ) and kinetic equations describing the dissolution process at different temperatures are deduced. Furthermore, the apparent activation energy E  = 10.54 ± 0.22 kJ mol -1 and pre-exponential constant A  = 0.34 ± 0.03 s −1 of 2HNIW·HMX co-crystal are obtained. The standard molar Gibbs free energy of activation ( \(\Delta G_{ \ne }^{\theta }\) ) at different temperatures is 86.44 ± 0.02 kJ mol −1 (298.15 K), 88.02 ± 0.03 kJ mol −1 (303.15 K), 89.61 ± 0.01 kJ mol −1 (308.15 K), 91.18 ± 0.01 kJ mol −1 (313.15 K), and 92.75 ± 0.02 kJ mol −1 (318.15 K), respectively. The standard molar entropy of activation ( \(\Delta S_{ \ne }^{\theta }\) ) and standard molar enthalpy of activation ( \(\Delta H_{ \ne }^{\theta }\) ) are − 262.55 ± 0.72 J mol −1  K −1 and 7.98 ± 0.22 kJ mol −1 , respectively.

CAS / MDL: 68-12-2
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