Loading...

Table of Content

    01 August 2019, Volume 35 Issue 4
    Contents
    Chemical Research in Chinese Universities Vol.35 No.4 August 2019
    2019, 35(4):  0-0. 
    Abstract ( )   PDF (827KB) ( )  
    Related Articles | Metrics
    Articles
    Carboxylate-induced Various Structures of Ni(Ⅱ) Complexes with Fluorescence Sensing and Bifunctional Electrochemical Properties
    LU Xue, LIU Guocheng, WANG Xiang, LIN Hongyan, WANG Xiuli
    2019, 35(4):  549-555.  doi:10.1007/s40242-019-9015-7
    Abstract ( )  
    References | Related Articles | Metrics
    We synthesized three new Ni(Ⅱ) coordination polymers[Ni(L)(HIP)(H2O)2]·H2O(CP1),[Ni(L)(NIP)]·2H2O(CP2) and[Ni(L)(NDC)(H2O)2](CP3)[L=N,N'-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, H2HIP=5-hydroxyisophthalic acid, H2NIP=5-nitroisophthalic acid, H2NDC=2,6-naphthalenedicarboxylic acid] by hydrothermal method, which were characterized by means of infrared spectra(IR), TG analyses, PXRD and single-crystal X-ray diffraction. The CP1 is a 1D tubular structure based on[Ni-HIP]2 loops and pairs of L ligands. CP2 is a 2D 3,5-connected architecture, which consists of Ni-L linear chains and (Ni-NIP)2 double chains. CP3 is a 2D network, which features 4-connected topology. Solid-state luminescent behaviours of CP1-CP3 were investigated. The CP1 can detect Fe3+ ions through luminescence quenching. The electrochemical properties of CP1 buk-modified carbon paste electrode(CP1-CPE) has also been investigated, which has bifunctional electrocatalytic activity for oxidation of ascorbic acid and reduction of NO2-.
    Synthesis and Characterization of 3-Phenyl-adamantane-1-carboxylic Acid
    FENG Wei, YE Kaiqi, JIANG Yang, HOU Ruibin
    2019, 35(4):  556-559.  doi:10.1007/s40242-019-9134-1
    Abstract ( )  
    References | Related Articles | Metrics
    Adamantane and its derivatives have been introduced into many drugs for current clinical research and some of them are used for the treatment of neurological disease and/or used as the antiviral agents as well as the agents against type-2 diabetes. Recently, there have been many relevant research reported for developing medicinal chemistry by employing the adamantyl group. In this paper, a new adamantane-based compound (3-phenyl-adaman-tane-1-carboxylic acid, PACA) was synthesized and characterized by X-ray diffraction(XRD), thermogravimeric analysis(TGA), Fourier transform infrared spectroscopy(FTIR), etc., which should be a beneficial complement or extension to the existing adamantyl-based materials.
    Solvothermal Syntheses and Characterization of Three One-dimension Cadmium Selenidoarsenates[Ni(1,2-dap)3] [As2CdSe4],[Zn(1,2-dap)3] [As2CdSe4] and[Ni(en)3] [As2CdSe4]
    DU Cuixia, CHEN Juan, BAIYIN Menghe
    2019, 35(4):  560-563.  doi:10.1007/s40242-019-9011-y
    Abstract ( )  
    References | Related Articles | Metrics
    Three new cadmium selenidoarsenates,[Ni(1,2-dap)3] [As2CdSe4](1)(1,2-dap=1,2-diaminopropane),[Zn(1,2-dap)3] [As2CdSe4](2) and[Ni(en)3] [As2CdSe4](3)(en=ethylenediamine), were synthesized under solvothermal conditions. And they are isostructural and monoclinic crystalls. As seen from their structures,they exhibited one-dimensional(1D) chains composed of[As2CdSe4]2- anions and[TM(amine)3]2+(TM=Ni, Zn; amine=1,2-dap, en) cations. Their absorption edges are 2.32, 1.84 and 2.38 eV, and they show the properties of the semiconductor. These compounds were also characterized by means of single-crystal X-ray diffraction(XRD), powder X-ray diffraction (PXRD), solid-state optical absorption spectrometry, and so on.
    Facile Synthesis of Fe-b ased MOFs(Fe-BTC) as Efficient Adsorbent for Water Purifications
    HAN Qian, WANG Zumin, CHEN Xiaoyu, JIAO Chuangwei, LI Haiyan, YU Ranbo
    2019, 35(4):  564-569.  doi:10.1007/s40242-019-8415-z
    Abstract ( )  
    References | Related Articles | Metrics
    Fe-based metal-organic frameworks(Fe-BTC) were successfully synthesized in a large scale by using a simple one-pot method at room temperature. To understand its composition, texture and morphology, the as-synthesized material was analyzed systematically. Moreover, based on the adsorption property for anionic organic dyes(methyl orange, Congo red), cationic organic dyes(methylene blue, rhodamine B) and heavy metal ions(Pb2+) in aqueous solutions, it was revealed that the obtained Fe-BTC showed excellent capacities and adsorption rates for different adsorbates. Besides the general adsorption effect derived from the numerous pores and large specific surface area, the electrostatic forces and π-π interactions between benzene rings are believed to play significant roles in the large uptakes of this Fe-BTC sample. And the existence of mesopores in Fe-BTC might accelerate the adsorption.
    A Novel Fluorescence Sensor Towards Hydrazine in Living Cells
    WANG Jinjin, GUO Jing, DOU Lili, WANG Rui, SONG Yan, YANG Qingbiao, DU Jianshi, LI Yaoxian
    2019, 35(4):  570-576.  doi:10.1007/s40242-019-9109-2
    Abstract ( )  
    References | Related Articles | Metrics
    By a simple one-step reaction, a new fluorescein-based probe, 3'-hydroxy-3-oxo-3H-spiro[isobenzofu-ran-1,9'-xanthen]-6'-yl-4-bromobutanoate(FLB), was designed and synthesized. Relative to other cations, anions or amines, the probe exhibited high sensitivity and specificity towards hydrazine with approximate 40-fold fluorescence enhancement at 515 nm. The detection limit(DL) was calculated to be 2.87×10‒8 mol/L, which was about 10 times lower than maximum allowable level of hydrazine(3.12×10‒7 mol/L) in drinking water permitted by the US Environment and Protection Association(EPA). Simultaneously, through mass spectroscopy and proton nuclear magnetic resonance titration, the detection mechanism was further confirmed. Eventually, due to the low cytotoxicity and excellent water solubility, FLB could be employed to detect hydrazine in living cells.
    Nitrogen-doped Carbon Dots: Application of Hg Ions Detection in Rannasangpei
    WU Lili, LIU Huirong, LIU Tonghua, LI Caolong
    2019, 35(4):  577-580.  doi:10.1007/s40242-019-9098-1
    Abstract ( )  
    References | Related Articles | Metrics
    Nitrogen-doped carbon dots(N-CDs) were hydrothermally synthesized by folic acid, which revealed excited wavelength-dependent blue emission and the specific recognition of Hg ions by fluorescence quenching. A wide range response and a fitted linear relationship for Hg ions detection were established to show that these blue-emission N-CDs achieved a satisfying Hg ions detection in Chinese traditional herb, Rannasangpei(RSNP). The results from the N-CDs FL quenching gave the similar outcomes with those from ICP-OES measurement, which exhibited the possibility of the simple FL method of Hg ions detection by N-CDs in Chinese traditional herbs.
    DNA-silver Nanocluster Binary Probes for Ratiometric Fluorescent Detection of HPV-related DNA
    YUAN Yan, LI Shaoyuan, LUO Lei, WANG Qing, FANG Hongmei, HUANG Jin, LIU Jianbo, YANG Xiaohai, WANG Kemin
    2019, 35(4):  581-585.  doi:10.1007/s40242-019-9085-6
    Abstract ( )  
    References | Related Articles | Metrics
    Herein, we described a ratiometric strategy based on "chameleon" DNA-silver nanoclusters(DNA-AgNCs) fluorescent binary probes. The strategy was applied to detect high-risk human papillomavirus(HPV) DNA sequences, HPV-16. First, DNA-AgNCs were synthesized by a simple reduction method. The obtained nanoprobes showed typical yellow and red fluorescence of AgNCs. Upon the addition of HPV-16 DNA, the yellow fluorescence of AgNCs was reduced greatly, whereas the red fluorescence of AgNCs was increased. The concentration of HPV-16 DNA in the samples was characterized by the ratio of fluorescence intensity at 570 and 630 nm. The ratiometric nanoprobes showed good selectivity for HPV-16 DNA, and the detection limit was 2 nmol/L. In addition, the practical applicability of this strategy was demonstrated by analysing the HPV-16 DNA in human serum, illustrating its potential promise for clinical diagnosis.
    FTIR Spectroscopy in Cultural Heritage Studies: Non-destructive Analysis of Chinese Handmade Papers
    YAN Yueer, WEN Chenqing, JIN Ming, DUAN Lian, ZHANG Ruohong, LUO Chan, XIAO Jianfang, YE Zhaoqi, GAO Boxu, LIU Peng, TANG Yi
    2019, 35(4):  586-591.  doi:10.1007/s40242-019-9026-4
    Abstract ( )  
    References | Related Articles | Metrics
    Chinese handmade papers have been the carriers of paper-based documents, paintings and calligraphies, which are of great importance for historical and cultural heritage studies. This research developed the attenuated total reflectance-Fourier transform infrared(ATR-FTIR) spectroscopic technique for the analysis of Chinese handmade papers. The test was applied to Chinese handmade papers taken from bark, hemp and bamboo groups, followed by papers from ancient books and arts collected in library and museum. Our study indicated that FTIR was an efficient analytical method to identify fiber types of library/museum papers of unknown origin. Moreover, information about degree of crystallinity and state of deterioration of cellulosic fibers was learned from FTIR spectra. This research provides a non-destructive method to study the molecular structure of cellulosic fibers, and guides the selection of appropriate Chinese handmade papers for the restoration of cultural heritage objects.
    POMs as Active Center for Sensitively Electrochemical Detection of Bisphenol A and Acetaminophen
    DONG Pengfei, LI Na, ZHAO Haiyan, CUI Min, ZHANG Cong, HAN Hongyan, REN Jujie
    2019, 35(4):  592-597.  doi:10.1007/s40242-019-8370-8
    Abstract ( )  
    References | Related Articles | Metrics
    A new type of electrochemical sensor based on multi-walled carbon nanotubes(MWCNTs), K2H4SiW11CuO39·6H2O(SiW11Cu) and gold nanoparticles(AuNPs) was prepared for the simultaneous detection of bisphenol A and acetaminophen. Differential pulse voltammetry(DPV), cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) were used for electrochemical characterization, and Fourier transform infrared spectroscopy(FTIR) was used to characterize the structure of polyoxometalates. Electrochemical experimental results show that the composite modified electrodes have good electrochemical activity as well as current response values of bisphenol A and acetaminophen when pH=7.0. At the same time, the modified electrode exhibits good stability and reproduction, and has good anti-interference ability to other substances. In practical application, the sensor obtained satisfactory results.
    Naked Eye and Selective Detection of Copper(Ⅱ) in Mixed Aqueous Media Using a Cellulose-based Support
    FETTOUCHE Souad, BOUKHRISS Aicha, TAHIRI Mohamed, CHERKAOUI Omar, BAZI Fathallaah, GMOUH Said
    2019, 35(4):  598-603.  doi:10.1007/s40242-019-8313-4
    Abstract ( )  
    References | Related Articles | Metrics
    A new colorimetric sensor based-azo dye for Cu2+ detection was synthesized and characterized by FTIR and NMR spectroscopies. The results showed that the azo dye had a high selective and sensitive recognition toward Cu2+. The solution containing the sensor changed color from pink to pale yellow with a hypsochromic shift in the presence of Cu2+. The sensor selectivity and sensitivity toward Cu2+ions were investigated by colorimetry and UV-Vis spectroscopy. For practical applications, a cellulosic textile test strip for high-selectivity detection of Cu2+ ions in aqueous solution was developed using the synthesized azo dye as chromogenic chemosensor molecule, while using a solid cellulose textile as a substrate. As a result, a spectacular color change of the test strip was observed depending on the amount of copper ions in contact with the strip, which allows an estimation of Cu2+ concentration by naked eye.
    Enantioselective Addition of Allyltrichlorosilane to Bulky-substituted Aldehydes Catalyzed by Axial N,N'-Dioxide Pivalate
    WANG Jie, WU Shijie, WANG Xiaoke, LI Longfei, YANG Kan, ZHU Huajie, LI Wan, LIU Li
    2019, 35(4):  604-608.  doi:10.1007/s40242-019-9046-0
    Abstract ( )  
    References | Related Articles | Metrics
    Allylation of bulky-substituted aromatic aldehydes with allyltrichlorosilanes were catalyzed by axial biscarboline N,N'-dioxide esters with high enantioselectivities up to 92% e.e. for 1-(4-chlorophenyl)-9-methyl-9H-pyrido[3,4-b]indole-3-carbaldehyde and 90% e.e. for 1-(3-methoxyphenyl)-9-methyl-9H-pyrido[3,4-b]indole-3-carbaldehyde, respectively. Total 22 aldehydes were tested with good yields and enantioselectivities. Catalyst 4f exhibited good catalytic enantioselectivity.
    Synthesis and Herbicidal Activity of 3-Acetyl-4-hydroxy-2,1-benzothiazine Derivatives
    LEI Kang, LIU Yang, WANG Shiben, SUN Bin, HUA Xuewen, XU Xiaohua
    2019, 35(4):  609-615.  doi:10.1007/s40242-019-9029-1
    Abstract ( )  
    References | Related Articles | Metrics
    In order to develop a novel herbicide containing the 2,1-benzothiazine motif, a series of 3-acetyl-4-hydroxy-2,1-benzothiazine derivatives was synthesized. All the target compounds were confirmed by 1H NMR, 13C NMR, and high-resolution mass spectrometry(HRMS). In addition, the crystal structure of compound T27 was determined by single crystal X-ray diffraction. The bioassay results showed that some of the 3-acetyl-4-hydroxy-2,1-benzothiazine derivatives(T13, T15, T22, and T24) showed good herbicidal activity at a dosage of 100 µg/mL. Among them, compounds T22 and T24 showed promising post-emergent herbicidal activities against Brassica campestris and Amaranthus retroflexus even at a dosage of 375 g/ha(1 ha=104 m2) in the greenhouse test. Studies on the structure-activity relationship demonstrated that the type of acetyl group played an important role in the herbicidal activity, and that the introduction of a phenoxyacetyl group at the 3-position of 2,1-benzothiazine was beneficial in improving the herbicidal activity. The present study also indicated that 3-phenoxyacetyl-4-hydroxy-2,1-benzothiazine could be a potential lead compound for further development of novel 2,1-benzothiazine-containing herbicides.
    Improved Synthesis of Icaritin and Total Synthesis of β -Anhydroicaritin
    TONG Jie, LIU Chang, WANG Bo
    2019, 35(4):  616-620.  doi:10.1007/s40242-019-9012-x
    Abstract ( )  
    References | Related Articles | Metrics
    Natural products icaritin and β-anhydroicaritin with P-glycoprotein(P-gp) inhibitory activities were efficiently synthesized in nine steps from commercially available phloroglucinol. A modified Algar-Flynn-Oyamada cyclization and relay Claisen-Cope rearrangement were employed in this concise route. Our synthesis offers opportunities to synthesize various icariin analogues for biological and pharmacological investigations.
    Tandem Approach to Functionalized Pyrrolo[3,4-a]carbazole-1,3-diones via a Pd-catalyzed Indole-to-carbazole Transformation
    GUO Lianghua, XU Mei, JIAN Yong, LIU Sheng, PAN Weidong, DUAN Lian
    2019, 35(4):  621-626.  doi:10.1007/s40242-019-8399-8
    Abstract ( )  
    References | Related Articles | Metrics
    A one-pot and efficient three-component reaction of indoles, acrylates and maleimides for the synthesis of pyrrolo[3,4-a]carbazole-1,3-dione derivatives was developed. Three C-C bonds and one ring were created in a single step via an indole-to-carbazole transformation triggered by Pd(Ⅱ)-catalyzed direct C3-alkenylation of indoles.
    Excited State Properties of Fucoxanthin Aggregates
    ZUO Jialing, TAN Liming, XU Yi, MA Yingchao, DONG Jia, WANG Peng, ZHANG Jianping
    2019, 35(4):  627-635.  doi:10.1007/s40242-019-9097-2
    Abstract ( )  
    References | Related Articles | Metrics
    The structure and excited state properties of the H-and J-aggregates of the marine carbonyl carotenoid, fucoxanthin(Fx), were studied by various spectroscopic methods, and compared with those of Fx monomers in polar organic solvents. The fluorescent analysis indicated that the higher vibronic states of S2 contribute more to populating the S1 state, from which fluorescent emission mainly originates. Resonance Raman and density functional theory calculations confirmed the ‘card-packed’ and ‘head-to-tail’ structures of the H-and J-aggregates of Fx, respectively. An fs time-resolved absorption study proved the coexistence of S1 and intramolecular charge transfer relaxation pathways upon excitation to the S2 state for both the monomers and aggregates.
    Reduction of 4-Nitrophenol Using Ficin Capped Gold Nanoclusters as Catalyst
    WU Han, CAI Huiwu, QIAO Juan, QI Li
    2019, 35(4):  636-640.  doi:10.1007/s40242-019-9070-0
    Abstract ( )  
    References | Related Articles | Metrics
    Conversion of nitroarenes to aminoarenes has attracted great attention in pharmaceutical industry, agricultural production, environmental protection and chemical catalysis area. In this work, ficin capped gold nanoclusters(ficin@AuNCs) were prepared for the reduction of 4-nitrophenol to 4-aminophenol. The proposed catalyst was characterized by transmission electron microscopy, dynamic light scattering, fluorescence spectra and UV-Vis spectra. With NaBH4 as the reducing agent, the reduction reaction could carry out completely within 10 min at 25℃. Interestingly, the resultant catalyst exhibited size-related properties in the reduction, smaller ficin@AuNCs exhibited higher catalytic activity. Its present pseudo-first-order rate constant was found to be 2.95×10‒3 s‒1 and the catalytic activation energy was 27.7 kJ/mol. Moreover, ficin@AuNCs-based catalyst displayed good stability, heading to 4-nitrophenol conversion of 98.5%-100.0% after six consecutive cycles. It has shown a great potential in construction of unique catalysts based on AuNCs for reduction reaction.
    Enhanced Corrosion Resistance and Discharge Performance of Mg-MnO2 Battery by Na2SiO3 Additive
    XU Jing, HU Jie, HU Sibo
    2019, 35(4):  641-646.  doi:10.1007/s40242-019-9049-x
    Abstract ( )  
    References | Related Articles | Metrics
    Corrosion resistance and delayed action are major obstacles that severely limit the practical application of Mg alloy in battery fields. In this work, the effects of Na2SiO3 on the electrochemical behavior of the AZ31B Mg alloy in MgSO4-Mg(NO3)2 composite solution[0.14 mol/L MgSO4, 1.86 mol/L Mg(NO3)2] were investigated. Electrochemical tests were carried out using electrochemical impedance spectroscopy, galvanostatic discharge, and linear sweep voltammograms. The results indicate that the impedance value increases by nearly fourfold, and the delayed time decreases from 2.1 s to 0.6 s. Battery performance test reveals that the addition of Na2SiO3 significantly improves the discharge specific capacity of Mg-MnO2. The surface morphology and composition of corrosion products from Mg alloys were studied by scanning electron microscopy(SEM) and Fourier transform infrared spectroscopy(FTIR), respectively. The SEM images of the AZ31B Mg alloys in composite solution with or without Na2SiO3 additive have an evident distinction due to the formation of new insoluble compound. FTIR result confirms that the corrosion products accumulated on the alloy surface in the electrolyte containing Na2SiO3 are mainly composed of Mg(OH)2, MgCO3, and MgSiO3.
    Separation and Purification of Glufosinate Through Combination of an Electrodialysis Membrane and a Macroporous Adsorption Resin
    CUI Menglong, DU Xiaohua
    2019, 35(4):  647-653.  doi:10.1007/s40242-019-9045-1
    Abstract ( )  
    References | Related Articles | Metrics
    Glufosinate is a nonselective organophosphorus herbicide with low toxicity and high efficiency that is widely used in forestry, agriculture and other industries. In the process of manufacturing glufosinate, large amounts of ammonium chloride and coloured organic impurities are generated. Because of its high solubility in water, separation of glufosinate from inorganic salts is extremely difficult. Hence, a co-separation method combining an electrodialysis membrane and a macroporous adsorption resin was developed to obtain glufosinate with higher purity. For the electrodialysis process, a glufosinate reaction solution was placed in a dilute chamber and desalinated. The concentration of inorganic salts in the resultant glufosinate aqueous solution was only 0.99 g/L under the optimal conditions of an operating voltage and a volume ratio of 9 V and 1:1, respectively. For the macroporous resin adsorption/desorption process, the sample solution treated by electrodialysis was pumped into the resin-filled column, which was eluted to obtain the eluent when the adsorption reached equilibrium. Consequently, nearly all the coloured organic impurities were removed under the optimal conditions, in which the resin type, pH value, flow rate, glufosinate concentration, temperature, ratio of ethanol and volume of eluent were LX-300C, 3, 0.5 mL·cm-2·min-1, 20 mg/mL, 25℃, 50% and 400 mL, respectively. After the electrodialysis and adsorption/desorption process, the purity of the glufosinate was increased to 95.14%, and its recovery rate was as high as 98%. The advantages of this process included its ease of operation, environmental friendliness and low cost, which provided strong potential for its use in industrial applications.
    Impregnated Sulfur in Carbonized Nitrogen-containing Porous Organic Frameworks as Cathode with High Rate Performance and Long Cycle Life for Lithium-sulfur Batteries
    DONG Yan, BEN Teng
    2019, 35(4):  654-661.  doi:10.1007/s40242-019-9038-0
    Abstract ( )  
    References | Related Articles | Metrics
    The undesirable cycling performance caused by soluble polysulfides shuttling between anode and cathode has been considered as the main challenge that has hindered its practical applications for lithium-sulfur(Li-S) batteries. To solve this issue effectively, a nitrogen-containing porous carbon, namely JUC-Z2-900, developed from a porous organic framework, namely JUC-Z2, bearing a high surface area(805 m2/g), small pore size(0.5 nm) and nitrogen doping(2.15%, mass fraction), has been used as a host material for Li-S batteries. The micropores of JUC-Z2-900 can confine the smaller sulfur molecules S2-4, which can essentially alleviate the critical problem of polysulfide dissolution. Furthermore, nitrogen-containing JUC-Z2-900 can promote chemical adsorption of sulfur. The above two factors can improve the electrochemical performance of Li-S batteries effectively. To compare the effects of sulfur contents and melt-diffusion strategy in JUC-Z2-900/S composites, a series of JUC-Z2-900/S composites was synthesized and their electrochemical performances were explored, indicating good rate performance and excellent cycling stability of the composites contributed by both appropriate mass percentage of sulfur and its confinement in the micropores.
    In-situ Reduction Synthesis of Bi/BiOI Heterostructure Films with High Photoelectrochemical Activity
    LIU Yanfei, CHU Yu, DU Zhuoyang, SUN Yan, CAO Feng
    2019, 35(4):  662-666.  doi:10.1007/s40242-019-9023-7
    Abstract ( )  
    References | Related Articles | Metrics
    The Bi/BiOI heterostructure films grew perpendicular to the FTO substrates were synthesized in-situ through an electrochemical deposition and hydrogen reduction method. The metallic Bi nanoparticles were decorated onto the surface of BiOI nanosheets via an in-situ reduction, induced 6.3 times improvement of photocurrent density, compared to the pristine BiOI at 1.23 V vs. reversible hydrogen electrode(RHE). The enhancement of photoelectrochemical performance was attributed not only to the efficient separation of charge resulted from surface plasmon resonance effect, but also to the fast charge transfer at the interface due to the in-situ reduction of the films. This work provided a simple and facile strategy to in-situ construct heterostructure films, and showed an effective method to improve the photoelectrochemical activity of Bi-based semiconductors.
    Pd/TiO2 Nanospheres with Three-dimensional Hyperstructure for Enhanced Photodegradation of Organic Dye
    WANG Huan, XIAO Liguang, WANG Chao, LIN Bin, LYU Sa, CHU Xuefeng, CHI Yaodan, YANG Xiaotian, WANG Xinyan
    2019, 35(4):  667-673.  doi:10.1007/s40242-019-9014-8
    Abstract ( )  
    References | Related Articles | Metrics
    Pd/TiO2 nanospheres assembled from nanorods with three-dimensional hyperstructure for enhanced photodegradation of organic dye was prepared by a sample solvothermal method. Further, it was used for degradation of methyl orange(MO) under the illumination of visible-light(simulated). The results show that Pd/TiO2 with 2%(mass fraction) Pd exhibits the noticeable activity in photodegrading of MO. The detailed analysis shows that this enhancement is attributed to the reduction of the rate of electron-hole recombination and surface plasmon resonance of Pd. The high activity and good stability of the obtained Pd/TiO2 nanospheres make it a promising photocatalyst for solving the environmental pollution problems.
    Converting Thiophene in Simulated Coking Crude Benzene to N,N-Dimethyl-2-thiophenecarboxamide by Dimethylcarbamyl Chloride Under Mild Conditions
    SHEN Xizhou, SONG Hao, FANG Liuya, DENG Hang, GAN Feng, SHEN Zhi
    2019, 35(4):  674-679.  doi:10.1007/s40242-019-8414-0
    Abstract ( )  
    References | Related Articles | Metrics
    Since the content of thiophene in coking crude benzene is high, it is necessary to remove it from coking crude benzene for efficient utilization. In this study, an important intermediate, N,N-dimethyl-2-thiophenecar-boxamide, was synthesized from thiophene and dimethylcarbamyl chloride. The influences of the dosages of dimethylcarbamyl chloride and ZnCl2 catalyst, reaction temperature and time on the removal rate were further explored based on the reaction kinetics. The structure of the target product was characterized by means of MS, 1H NMR and 13C NMR. The removal rate of thiophene was 98.14% after the reaction for 2 h and thiophene was almost removed after the reaction for 3 h under the optimal reaction conditions[a molar ratio of n(thiophene):n(dimethylcarbamyl chloride):n(ZnCl2)=1:12:10, 300 r/min, 318 K and 101.325 kPa]. The acylation of thiophene with dimethylcarbamyl chloride was approximately in accord with the first order kinetic equation at 303-323 K. The activation energy was 53.9850 kJ/mol and the pre-exponential factor was 1.4521×109 h-1.
    Research on Chemical Reactivity of Nitrotriazolam in Its Process of Preparation
    YANG Bowen, AN Qiufeng, ZHAO Zhigang, SHAO Kaiyuan, HU Wenxiang
    2019, 35(4):  680-685.  doi:10.1007/s40242-019-8339-7
    Abstract ( )  
    References | Related Articles | Metrics
    Chemical reaction possibility was described quantitatively for the case of nitrotriazolam preparation with 2-clonazepam by using the data of two quantum chemical reactivity indices:net electrophilicity index and Wiberg bond order. Furthermore, relevant reaction mechanism was derived from the aspect of quantum chemistry. The results show that the indices used can quantitatively explain the chemical reactivity and reaction mechanism of the nitrotriazolam preparation. To validate the universal applicability of the proposed approach, the authors continued to use the quantum chemical reactivity indices to describe some classic chemical reactions, expecting to predict major issues related to physical organic chemistry, such as new chemical reactions and their mechanisms.
    Fabrication and In vitro Bioactivity of Robust Hydroxyapatite Coating on Porous Titanium Implant
    DUAN Mengna, WU Xiaofeng, YUAN Long, ZHANG Zhiying, ZHANG Yan, ZHOU Yanmin
    2019, 35(4):  686-692.  doi:10.1007/s40242-019-9101-x
    Abstract ( )  
    References | Related Articles | Metrics
    Compared with the traditional dental implant, TixOs® manufactured by direct laser metal forming(DLMF) technology exhibits improved capability for bone osteointegration due to its porous surface structure, and has achieved remarkable clinical effect. However, like the traditional titanium and other alloyed implants, the porous titanium implant TixOs® also has relatively weak bioactivity. To address this issue, a proper surface modification method may be needed. Hydroxyapatite(HA) has been widely used in implant surface coating for its similar chemical composition to bone tissue and its osteoconductive properties. Thus, combining TixOs® implants with hydroxyapatite can be an efficient way to enhance their bioactivity. We herewith reported a competent pulsed laser deposition(PLD) method of coating nano-sized HA thin film onto the porous TixOs® implant. The HA coatings were characterized by means of scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS) and focused ion beam(FIB) method, and nanocrystal sized thin HA films were identified on the surface of TixOs® implants. The low cytotoxicity and improved cell proliferation ability of HA coated implants were further tested and verified using MC 3T3 E1 cells with the consideration of the controlling group. Our results show that a stable and bioactive HA thin film is able to form on the surface of the porous titanium implant by PLD method. This may benefit the further clinical application of TixOs® implants.
    Syntheses, Crystal Structures, Magnetic and Near-infrared Luminescence Properties of 3d-4f Coordination Polymers Cu2Pr2, Cu2Eu2 and Cu4Tb2
    ZHONG Liangxuan, LIU Mingyue, ZHANG Bowei, SUN Yaqiu, XU Yanyan
    2019, 35(4):  693-699.  doi:10.1007/s40242-019-9058-9
    Abstract ( )  
    References | Related Articles | Metrics
    Three new 3d-4f heterometallic coordination polymers(CPs), namely,[Pr2(CuL)2(nipt)3(H2O)]×2H2O (Cu2Pr2, 1),[Eu2(CuL)2(nipt)3(H2O)]×2H2O(Cu2Eu2, 2) and[Tb2(CuL)4(nipt)3]·8.3H2O(Cu4Tb2, 3)(CuL, H2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; nipt2‒=5-nitroisophthalate) were obtained by a solvothermal method and structurally characterized by single-crystal X-ray diffraction analyses, elemental analyses, Fourier transform infrared spectra and ultraviolet visible absorption spectra. In Cu2Pr2 and Cu2Eu2, m3-bridged and m5-bridged nipt2‒ ligands alternately linked three Ln3+ and five metal ions(three Ln3+ and two Cu2+ ions) to generate a 2D heterometallic framework with 3,3,4,5-connected (3.4.5)(32.42.5.63.72)(42.63.8)(42.6) topology. In Cu4Tb2, m2-bridged and m4-bridged nipt2- ligands alternately connected two Tb3+ and four metal ions(two Tb3+ and two Cu2+ ions) by carboxylating into a corrugated heterometallic 2D layer with 3-connected (63) topology. The magnetic properties of Cu2Pr2 and Cu2Eu2 were also discussed, the results show that both CPs have a weak antimagnetic interaction. Moreover, the near-infrared luminescence properties of Cu2Pr2 and Cu2Eu2 were also studied.
    Studies on Surface Properties and Cell Adhesion Properties of BSA Modified DBM Scaffold
    SUN Mengjie, FENG Wei, WANG Bowei, HAN Bing, ZOU Jundong, YANG Chunying, LIU Zhihui
    2019, 35(4):  700-707.  doi:10.1007/s40242-019-9020-x
    Abstract ( )  
    References | Related Articles | Metrics
    As a scaffold material for bone tissue engineering, demineralized bone matrix(DBM) has such a limited ability to load cells and growth factors that the surface of the DBM scaffold was modified with bovine serum albumin(BSA) with different concentrations to improve the protein structure and physicochemical properties of the scaffold surface so as to enhance the adhesion of the cells. And the appropriate BSA concentration was explored. Compared with DBM, the scaffold with BSA coating had a smaller pore size and a lower porosity, also, the degradation rate was accelerated and the hydrophilic property was improved. Cells adhesion was observed inside the DBM scaffold before and after it had been modified, and the BSA modified scaffold had a good cell compatibility. When the concentration of BSA was 20 mg/mL, the adhesion ability of the cells to modified scaffold was significantly increased, and the cell proliferation was facilitated.
    Discovery and Characterization of a Novel Method for Effective Improvement of Cyclodextrin Yield and Product Specificity
    HUA Jinghan, ZHANG Hongbin, WU Hao, WANG Jiadong, HU Xueqin, YANG Jingwen
    2019, 35(4):  708-713.  doi:10.1007/s40242-019-8406-0
    Abstract ( )  
    References | Related Articles | Metrics
    Cyclodextrins(CDs) are widely used in food, pharmaceuticals, drug delivery, and chemical industries and in agriculture and environmental engineering. To improve the yield and selectivity of CDs, this work presented a facile, scalable and efficient enzymatic synthesis of β-CD from starch using β-cyclodextrin glycosyltransferase (CGTase, EC 2.4.1.19) from Bacillus cereus. First, we found that the pretreatment of starch dramatically influenced CDs yield that was related to the structure and molecular weight of the substrate starch. Second, alcohol solvents influenced the yield and product selectivity of CDs; tertiary alcohols enhanced CDs yield(from 54.95% to 68.21%) and secondary alcohols increased the product selectivity(β-CD/γ-CD changed from 6.25 to 8.05). Fluorescence quenching analysis showed that the binding constants and entropy of the solvents influenced the yield and product selectivity, respectively. In conclusion, the results demonstrate that this study provides a promising method for the industrial production of β-CD.
    Self-cleaning Anti-fouling TiO2/Poly(aryl ether sulfone) Composite Ultrafiltration Membranes
    GENG Wenzhe, JIANG Hongchuan, YANG Xia, FENG Yong, WANG Xinyu, GENG Zhi, HUO Mingxin
    2019, 35(4):  714-720.  doi:10.1007/s40242-019-8401-5
    Abstract ( )  
    References | Related Articles | Metrics
    A series of novel TiO2/poly(aryl ether sulfone) ultrafiltration membranes with anti-fouling and self-cleaning properties was designed and prepared. First, anti-photocatalytic degraded fluorine contained poly(aryl ether sulfone) matrix(PAES-F) was synthesized. Then the composite membranes were prepared via TiO2 nanoparticles and PAES-F polymer matrix by solution blending and non-solvent induced phase inversion methods. Further, separation efficiency, fouling behavior and self-cleaning property of the composite ultrafiltration(UF) membranes were investigated by dead-end filtration experiments using a polyacrylamide solution. The composite UF membranes exhibited outstanding self-cleaning efficiency and anti-photocatalytic degraded property after exposure to simulated sunlight irradiation. The water flux recovery ratios(FRR) of the optimal composite UF membranes could reach 74.24%, which was attributable to photocatalytic degradation of the organic contaminant by TiO2. And the retention rates of the composite UF membranes could maintain over 97%, which indicated the excellent photocatalytic degradation resistance of the fluorine contained PAES-F matrix. The novel high performance composite UF membranes have a broad application prospect in water treatment.
    Synthesis of Poly (isosorbide carbonate) via Melt Polycondensation Catalyzed by a KF/MgO Catalyst
    SHEN Xiaolong, LIU Shaoying, WANG Qingyin, ZHANG Hua, WANG Gongying
    2019, 35(4):  721-728.  doi:10.1007/s40242-019-8356-6
    Abstract ( )  
    References | Related Articles | Metrics
    MgO loaded with KF was prepared by using the impregnation method and was employed as the catalyst for the direct transesterification of diphenyl carbonate(DPC) with isosorbide to synthesize high-molecular-weight poly(isosorbide carbonate)(PIC). The relationship between physical-chemical properties and catalytic performance for KF/MgO in this melt process was investigated by various characterization techniques. The basic site amount and strength were found to be responsible for this transesterification process, and the medium and strong basic sites tended to promote the polycondensation reaction. 20-KF/MgO-500 exhibited the best catalytic performance, giving PIC with Mw of 84200 and glass transition temperature(Tg) of 173℃ under optimal conditions. Additionally, 20-KF/MgO-500 was found to catalyze the transerification of DPC with isosorbide and other diols to synthesize the corresponding poly(aliphatic diol-co-isosorbide carbonate)s(PAICs). This excellent activity can be ascribed to the presence of an abundance of basic sites and their specific basic strength on the surface of KF/MgO.
    Synthesis and Properties of Poly(butylene carbonate-co-spirocyclic carbonate)
    ZHU Changliang, LIU Shaoying, WANG Qingyin, ZHANG Hua, WANG Gongying
    2019, 35(4):  729-734.  doi:10.1007/s40242-019-8355-7
    Abstract ( )  
    References | Related Articles | Metrics
    Poly(butylene carbonate)(PBC) has significantly promising applications as a degradable material in the field of polymers, while its poor thermal performance and low crystallization rate are its main defects. To overcome these shortcomings, a series of poly(butylene carbonate-co-spirocyclic carbonate)(PBSC) copolymers were synthesized from diphenyl carbonate, 1,4-butanediol and spiroglycol via two-step polycondensation reactions, using magnesium oxide as a catalyst. Differential scanning calorimetry(DSC) results indicated that the glass transition temperature(Tg) values of PBSC copolymers were enhanced from -19℃ to 56℃ with rising the spiroacetal moiety content. Thermogravimetric analysis(TGA) results showed that the resulting PBSCs have a higher thermal stability than that of poly(butylene carbonate). Wide angle X-ray diffraction(WXRD) patterns were characterized to investigate the crystallization behaviour of PBSCs. Tensile testing demonstrated that copolymerization of spiroacetal moieties into PBC chains imparted PBSC with favourable mechanical performance. Typically, PBSC30 had a tensile modulus of (1735±430) MPa, a tensile strength of (42±5) MPa and an elongation of 504%±36%.
    Carboxyl-functionalized Nanocellulose Reinforced Nanocomposite Proton Exchange Membrane
    YANG Xue, WEI Yingcong, CHU Xuefeng, ZHAO Qi, YAN Wenling, DONG Chenjun, LIU Baijun, SUN Zhaoyan, HU Wei, ZHANG Niaona
    2019, 35(4):  735-741.  doi:10.1007/s40242-019-8330-3
    Abstract ( )  
    References | Related Articles | Metrics
    Nanocellulose(NCC) was prepared through the acid hydrolysis of microcellulose(MCC) and was reacted with maleic anhydride to obtain carboxyl-functionized nanocellulose(MA-NCCs). The presence of-OH and-SO3H on the surface of rod-like MA-NCC was confirmed by Fourier transform infrared spectrometry(FTIR). Sulfonated poly(aryl ether ether ketone ketone)(Ph-SPEEKK) was synthesized with bis(4-fluorophenyl-methanone) and 2-phenylhydroquinone as monomer. MA-NCC/Ph-SPEEKK nanocomposite membranes with different MA-NCCs content were prepared, and their properties were characterized. Compared with Ph-SPEEKK, MA-NCC/Ph-SPEEKK nanocomposite membrane showed better mechanical and thermal properties and higher proton conductivity. The proton conductivity of the composite membrane with 4%(mass fraction) MA-NCCs under 80℃ was 0.095 S/cm. And its tensile strength reached 30.3 MPa, which was 21.2% higher than that of Ph-SPEEKK pure polymer membrane.
Editor-in-Chief:
Jihong YU
ISSN 1005-9040
CN 22-1183/O6
Special Issue/Column
Scan and join us
Visited
Total visitors:
Visitors of today:
Now online: