2020 Volume 37 Issue 11

Recent Progress of Metal Organic Frameworks-Based Hollow Materials
CHEN Jiaqi , ZHOU Yan , SUN Jingwen , ZHU Junwu , WANG Xin , FU Yongsheng
2020, 37(11): 1221-1235  doi: 10.11944/j.issn.1000-0518.2020.11.200208
[Abstract](2998) [FullText HTML] [PDF 1074KB](78)
Abstract:
Metal organic frameworks (MOFs) hollow materials, such as hydroxide, phosphide and sulfide, have attracted great attention in the applications of energy storage and conversion owing to their advantageous features of large specific area, low density, high loading capacity and excellent ion permeability. This review summarizes various synthetic strategies and formation mechanism for different structural MOFs-derived hollow materials. The promising electrochemical applications in the supercapacitors, lithium ion battery, and electrocatalysis are prominently elucidated. An outlook of development prospects and challenges for MOFs hollow structured derivatives is also discussed.
Advances in Synthetic Methods of (R)-α-Lipoic Acid
HAN Xiu , KANG Chuanqing
2020, 37(11): 1236-1248  doi: 10.11944/j.issn.1000-0518.2020.11.200151
[Abstract](2426) [FullText HTML] [PDF 840KB](61)
Abstract:
The methods for the effective synthesis of (R)-α-lipoic acid have been widely investigated since (R)-α-lipoic acid can be widely used for the treatment of diabetes and diabetic complications. It is also extensively used in health care products. Therefore, asymmetric synthesis of (R)-α-lipoic acid has attracted broad interests from the community of both academia and industry. To date, the reported routes for the synthesis of (R)-α-lipoic acid include asymmetric synthesis catalyzed by the enzymatic and chemical catalysts, chiral resolution, and chiral substrate-controlled synthesis. Based on this classification, this paper summarizes the advances of the methods for asymmetric synthesis of (R)-α-lipoic acid and predicts future prospects.
Research on the Enhanced Activity of Hemin/G-Quadruplex DNAzyme and Its Application in Biosensors
MO Yanhong , LI Hui , WANG Bin , XU Xiaohui , LIU Sisi , ZENG Dongdong
2020, 37(11): 1249-1261  doi: 10.11944/j.issn.1000-0518.2020.11.200153
[Abstract](4407) [FullText HTML] [PDF 718KB](171)
Abstract:
Hemin/G-quadruplex DNAzyme is a type of DNA molecule with peroxidase-like activity. Because of its excellent activity, easy modification and programmability, it has been widely used in biosensors and other fields. This article first briefly introduces the structure of G-quadruplex, and then reviews the strategies for enhancing hemin/G-quadruplex DNAzyme activity and application of biosensors based on hemin/G-quadruplex DNAzyme in the detection of biomarkers, microorganisms, biotoxins and metal ions. We also prospect the development trend of hemin/G-quadruplex DNAzyme.
Synthesis and Anti-colorectal Cancer Activity of Amphipathic Trimethine Indocyanine Dyes
QIU Na , SHI Xiao , YANG Yiyi , SONG Nannan , LI Jiajia , GE Zhenying , ZHANG Lei
2020, 37(11): 1262-1267  doi: 10.11944/j.issn.1000-0518.2020.11.200126
[Abstract](632) [FullText HTML] [PDF 637KB](3)
Abstract:
The improvement of the amphipathicity of cyanine dyes is conducive to the improvement of its own antitumor activity. In this paper, the feasibility of converting trimethine indocyanine dye (Cy3) into multifunctional small-molecule chemotherapy drug was explored for the first time. Two amphipathic trimethine indocyanine dyes of Cy3-DIPEG and Cy3-SO3-DIPEG containing polyethylene glycol(PEG) chains on the indol "N" were designed and synthesized in yields of about 40%. The structure of the product was identified by 1H NMR and 13C NMR spectroscopy and mass spectroscopy. The maximal fluorescence emission wavelengths of Cy3-DIPEG and Cy3-SO3-DIPEG in water are about 570 nm, and their fluorescence quantum yields (Ф) are 0.06 and 0.13, respectively. The antitumor activities of two dyes on human colorectal cancer cell lines (SW480 and HCT-116) were tested in vitro by the thiazole blue (MTT) assay and the antitumor mechanism was initially explored by subcellular localization experiments. The results show that Cy3-DIPEG can accumulate in mitochondria through the tumor cell membrane, and significantly inhibit the proliferation of human colorectal cancer cells, but Cy3-SO3-DIPEG cannot penetrate into the tumor cell and has no antitumor activity.
Design and Synthesis of Chalcone-Based Derivative for Sensing Cu(Ⅱ) Ion
LI Di , SUN Jianqiang , XU Bingsong , CHEN Hao , ZHOU Le , HU Lei , WANG Hui
2020, 37(11): 1268-1275  doi: 10.11944/j.issn.1000-0518.2020.11.200120
[Abstract](708) [FullText HTML] [PDF 795KB](2)
Abstract:
A novel chalcone derivative (E)-3-(1-butyl-1H-indol-3-yl)-1-(pyridin-2-yl)prop-2-en -1-one (L) was designed and synthesized from 1-butyl-1H-indole-3-carbaldehyde and 1-(pyridin-2-yl)ethan-1-one by condensation reaction. Compound L was characterized by nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and Fourier transform infrared (FT-IR) spectrometry. It is found that probe L exhibits a specific selectivity and high sensitivity to Cu2+ with a limit of detection (LOD) at 27.8 nmol/L, giving a noticeable color change from light yellow to red, which demonstrates that probe L can be used to recognize Cu2+ by "naked-eye". Probe L binds to Cu2+ by a 1:1 stoichiometry. The mechanism for sensing Cu2+ was investigated using 1H NMR titration and theoretical calculations.
Catalytic Conversion of γ-Valerolactone to 1, 4-Pentanediol on CuZn/Al2O3 Catalyst
LIU Qiang , ZHAO Zhenbo , ZHANG Chao , ZHAO Fengyu
2020, 37(11): 1285-1292  doi: 10.11944/j.issn.1000-0518.2020.11.200109
[Abstract](650) [FullText HTML] [PDF 869KB](1)
Abstract:
Biomass conversion is one of the most effective ways for alleviating the energy and environmental crisis. A series of CuZn/Al2O3 catalysts was prepared by co-precipitation method and the structure and properties of the catalysts obtained were characterized by several techniques such as inductively coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM), and CO2-temperature programmed desorption (TPD). We focused our attention on the effects of reduction temperature on the catalytic performances of CuZn/Al2O3 catalysts in γ-valerolactone hydrogenation. It is found that reduction of temperature significantly influences the activity and selectivity of CuZn/Al2O3 catalysts, that is, the larger reduction temperature benefits for the formation of 1, 4-pentanediol, and a high selectivity of 98% is achieved over the catalyst at 440℃, while it is only 71% on the catalyst reduced at 200℃. Based on the structure analysis of the catalyst, it is concluded that the high reduction temperature can promote the reduction of ZnO and generate new surface active sites and vary the surface basic-acid properties, thus result in the improvement of 1, 4-pentanediol selectivity.
Catalytic Decomposition of Ozone by Manganese Oxide Supported on Cordierite Honeycomb Ceramics
CHEN Chonglai , ZHANG Wenxia , QIU Jianping , JIA Aiping , LUO Mengfei
2020, 37(11): 1293-1300  doi: 10.11944/j.issn.1000-0518.2020.11.200143
[Abstract](1043) [FullText HTML] [PDF 821KB](12)
Abstract:
A series of different manganese oxides was mixed with aluminum gel and coated to cordierite honeycomb ceramics to produce monolithic catalysts for improving the application ability of catalysts. The performances of these monolithic catalysts in the decomposition of ozone at ambient temperature and pressure were investigated. The structures of these catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), BET specific surface area method and H2-programmed temperature reduction (H2-TPR) techniques. The results show that the activities of different manganese oxide supported monolithic catalysts are arranged in the following order:OMS-2 (Manganese oxide octahedral molecular sieve) > MnO2 > Mn2O3 > Mn3O4 > MnO. Compared with other manganese oxides, OMS-2 supported cordierite honeycomb ceramics monolithic catalyst has the highest activity to decompose ozone, probably due to the fact that OMS-2 has a larger specific surface area and better reducibility, which are favorable for the oxygen vacancy formation on the surface and participation in the decomposition of ozone. The results of this paper provide a theoretical basis for improving the performance of cordierite honeycomb ceramic supported monolithic catalyst for ozone decomposition.
Effects of Ethyl Orthosilicate on the Electrochemical Performance of High-Voltage Lithium Nickel Manganese Oxide-Based Full-Cell
CAI Min , WU Chunyan , XIE Yishun , BAN Gui , LAI Feiyan , HUANG Xiaoying , ZHANG Xiaohui
2020, 37(11): 1301-1308  doi: 10.11944/j.issn.1000-0518.2020.11.200099
[Abstract](831) [FullText HTML] [PDF 796KB](8)
Abstract:
In order to improve the electrochemical performance of LiNi0.5Mn1.5O4 lithium ion batteries, a physical mixing method was used to add ethyl orthosilicate (TEOS) to the negative electrode slurry with the mass ratios of TEOS to graphite of 0:100, 5:100, 10:100, 16:100 and 20:100. A 502030-type flexible packaging lithium-ion battery was assembled by using LiNi0.5Mn1.5O4 as the positive electrode and graphite as the negative electrode. The battery was tested for constant current charge and discharge and internal resistance. The test results show that the internal resistance of the 0TEOS(m(TEOS):m(graphite)=0:100) and 16TEOS(m(TEOS):m(graphite)=16:100) batteries are 159 mΩ and 105 mΩ, respectively. After 200 cycles, the capacity retention rates are 52.6% and 65.7%, and the specific discharge capacities are 46 mA·h/g and 62.9 mA·h/g, respectively. The addition of TEOS to the negative electrode slurry through a physical mixing method is beneficial to the formation of a structurally stable artificial solid electrolyte interface(SEI) film on the surface of the negative electrode, and improves the cycling and rate performance of LiNi0.5Mn1.5O4.
Analysis of High Current Acceleration Battery Cycle Test
WEN Yun , WANG Lei , CHENG Cheng , WANG Zhou , PEI Feng , JIA Lulu , LI Zhimei , DENG Ruihong
2020, 37(11): 1309-1315  doi: 10.11944/j.issn.1000-0518.2020.11.200110
[Abstract](1024) [FullText HTML] [PDF 697KB](11)
Abstract:
In order to improve the operational stability and life of the new substation engineering fixed valve-controlled lead-acid battery, the battery performance was analyzed by using the high current acceleration cycle test, disassembly test and flame retardant test. The results show that at 50℃ after 18 high-current charge and discharge cycles (time-consuming 10 d), the capacity holding rate is 80.22%, reducing from the initial 701.93 A·h to 563.12 A·h, and the battery internal structure is still maintained. It is shown that the high temperature and high current circulation charge and discharge test can quickly destroy the internal structure and thus reduce the capacity. The research results can be used as a new test method and exploration for rapid evaluation and analysis of the performance and life of lead-acid batteries, and provide a basis for battery quality assessment.
Synthesis of Magnetic CuS Composite Nanomaterial and Its Specific Adsorption of Hg(Ⅱ) in Water
WANG Qiushi , HE Junhui
2020, 37(11): 1316-1323  doi: 10.11944/j.issn.1000-0518.2020.11.200119
[Abstract](776) [FullText HTML] [PDF 807KB](3)
Abstract:
Design and synthesis of adsorption/enrichment materials with rapid adsorption rate and good adsorption selectivity are significant for high-efficiency uptake and precise detection of Hg2+ ions. In this work, a magnetic CuS composite nanomaterial (Fe3O4@SiO2@CuS) was successfully synthesized by a facile and economic strategy, and a series of adsorption experiments was carried out to investigate the adsorption performance of core-shell structured Fe3O4@SiO2@CuS towards Hg2+ ions in aqueous solution. The results show that Fe3O4@SiO2@CuS exhibits fast adsorption kinetics and excellent adsorption capacity. It also displays a superior selective capture of Hg2+ in the presence of other co-existing metal ions, and the removal efficiency of Hg2+ is as high as 99.9%. In addition, Fe3O4@SiO2@CuS can be separated easily and fastly from samples under an external magnetic field, which is attributed to its magnetic property. These results demonstrate that magnetic metal sulfide composite nanomaterials have great application prospects in the areas of adsorption, enrichment and detection.
Determination of Aflatoxin B1 in Food by LC-MS/MS Method Based on Magnetic Bead-Aptamer
GU Xinyu , LANG Le , WANG Jianwei , ZHAO Lihui
2020, 37(11): 1324-1332  doi: 10.11944/j.issn.1000-0518.2020.11.200125
[Abstract](879) [FullText HTML] [PDF 797KB](13)
Abstract:
In this study, a magnetic bead-aptamer that specifically recognizes aflatoxin B1 (AFB1) was constructed and coupled with high performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) to establish a quantitative detection method for AFB1 in food. Carboxy magnetic beads were activated by carbodiimide hydrochloride (EDC) and incubated with 5'terminal amino modified aptamers. The aptamers were covalently linked to the surface of the carboxy magnetic beads by amidation reaction and used as capture probes to separate AFB1 in the extracted sample. The qualitative and quantitative analysis of AFB1 was carried out by LC-MS/MS. The results show that the method has a good linear relationship at the concentration of 0.25~25 ng/mL with the correlation coefficient R2=0.999, the quantitative detection limit is 0.25 ng/mL, the recovery is 80.3%~92.5%, and the relative standard deviation (RSD) is less than 8%. The method is simple, fast and convenient, and can detect trace AFB1. The magnetic bead aptamer can be reused, which provides another technical support for the quantitative detection of AFB1.
Rapid Determination of Three Components in Cosmetics by Using Direct Real-time Analysis Ionization Mass Spectrometry
JIANG Tao , DU Lianyun , ZHU Shuang , WANG Huan , ZHAN Yu , YU Ping , ZHANG Zhe , WANG Enpeng , CHEN Changbao
2020, 37(11): 1333-1339  doi: 10.11944/j.issn.1000-0518.2020.11.200202
[Abstract](1097) [FullText HTML] [PDF 690KB](5)
Abstract:
A rapid method for the determination of the contraindicated component urocanic acid(URA), approved sunscreens 2-ethylhexyl 4-methoxycinnamate(EHMC) and butyl-methoxydibenzoylmethane(B-MDM) in cosmetics were developed using direct analysis in real time (DART) of ion sources combined with four-pole flight mass spectroscopy. For qualitative analysis by positive ions, the Full MS/Targeted MS2 mode is applied to obtain the mass spectrum and cosmetics can be directly analyzed in the ionized area. For quantitative analysis, DART parameters are systematically optimized to achieve the best detection performance and the module sampler is used for automatic sampling. The linear range of three kinds of components is 25~1000 mg/L in the calibration curve with a good linear relationship (r>0.99). The lowest limit of detection (S/N=3) is 7.5 mg/L and the minimum quantitative limit (S/N=10) is 25 mg/L. The method recovery is 96.7%~109.2% and the precision RSD (n=6) is 3.59%~11.23%. The method is simple, rapid, efficient and environmentally-friend. It can be widely used in the rapid screening and quantitative detection of banned additives in cosmetics.
Dipeptide-Based Phase-Selective Gelators for Removal of Oils and Toxic Dyes from Water
ZHOU Yao , LUO Ziqing , ZHOU Jialing , YUAN Lin , LI Zhongyan
2020, 37(11): 1276-1284  doi: 10.11944/j.issn.1000-0518.2020.11.200073
[Abstract](582) [FullText HTML] [PDF 840KB](3)
Abstract:
A series of phase-selective gelators (3a-3e) was synthesized and characterized by 1H and 13C nuclear magnetic resonance spectroscopy and mass spectroscopy. The phase-selective activity assay was carried out in organic solvent and water mixture system and the results showed that compound 3c possessed high gelling abilities in the powder form for the removal of benzene, toluene, xylenes and petrol from their biphasic mixtures with water via a shaking process at room temperature. In addition, the efficient purification of toxic dye solutions has been realized by using 3d-benzyl alcohol gel as the adsorbent. Ultraviolet-visible spectroscopy provides the quantification means for the estimation of the purification efficacy. The simple operation and high removal efficiency of the organic solvents from water indicate the promising applicability of these dipeptide gelators in water purification.
Preparation and Release Behavior of Progesterone Nano Micelles in Vitro
QI Yanxin , HUANG Yubin , JIN Ningyi
2020, 37(11): 1340-1342  doi: 10.11944/j.issn.1000-0518.2020.11.200239
[Abstract](972) [FullText HTML] [PDF 607KB](11)
Abstract:
To prepare new controlled-release progesterone nano micelles, polyethylene glycol-polypropylene glycidyl ether polymer (PEG-PAGE), a diblock degradable polymer carrier, micelles carring progesterone were assembled in water. The drug load and encapsulation ratio under different conditions were investigated and the optimal proportion was selected for the in vitro release study. The results show that the micelles can carry progesterone with a drug load of 4.26% and the encapsulation efficiency of 21.30%. The nano micelles can effectively prolong the release of progesterone. This research is an experimental and technical reference for the development of similar dosage forms of steroid hormones.
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