• Volume 38,Issue 9,2021 Table of Contents
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    • >Functional materials
    • Construction of pH-responsive HMSN nanocomposites for combinatory therapy of tumor

      2021, 38(9).

      Abstract (63) HTML (0) PDF 4.62 M (92) Comment (0) Favorites

      Abstract:Hollow mesoporous silica nanoparticles (HMSN) with a diameter of about 100 nm were fabricated from tetraethyl orthosilicate. HMSN were used as drug nanocarrier to load chemotherapeutic drug doxorubicin (DOX) and manganese dioxide by physical embedding method and in situ reduction of KMnO4 to produce manganese dioxide. Then, a pH-responsive nano-drug delivery system (DOX/MnO2@HMSN-imide-PEG-R7-RGDS) was constructed by forming Schiff base between tamino group at the terminal of tumor-targeting functional peptide (PEG-R7-RGDS) and the aldehyde-modified nanoparticles (HMSN-CHO). The morphology, particle size, structure and composition of the nanomaterials were characterized by TEM, laser particle size analyzer, FTIR and XRD. The results showed that the synthesized spherical HMSN possessed hollow nanostructure. DOX/MnO2@HMSN-imide-PEG-R7-RGDS nanoparticles exhibited higher drugrelease rate under the simulated acidic tumor environment (pH 5.0) than that in the simulated physiological environment (pH 7.4). In addition, the results of in vitro cell experiments indicated that DOX/MnO2@HMSN-imide-PEG-R7-RGDS could target to cervical cancer cells (HeLa) and release DOX efficiently. At the same time, MnO2 in nanoparticles reacted with high concentration of glutathione (GSH) in tumor cells to produce Mn2+ with Fenton-like effect. Subsequently, Mn2+ would  catalyze endogenous H2O2 into highly toxic ·OH via Fenton-like chemistry. The cytotoxicity experiments revealed that the combination of chemodynamic therapy and chemotherapy of DOX/MnO2@HMSN-imide-PEG-R7-RGDS could produce high cytotoxicity against HeLa cells.

    • >Dyeing and finishing auxiliaries
    • Preparation of Azo Dyes Based on Succinimide and Their Dyeing of Wool in Supercritical CO2

      2021, 38(9).

      Abstract (58) HTML (0) PDF 2.06 M (66) Comment (0) Favorites

      Abstract:Four kinds of reactive disperse dyes Ⅰ~Ⅳ were prepared by the diazo coupling reaction in which succinimide ester was introduced into precursors. The data of absorption spectrum, photo-thermal stability, process of supercritical carbon dioxide (scCO2) dyeing wool fibers were tested. The results show that four dyes have good photo-thermal stability, and the maximum absorption wavelengths for dyes Ⅰ, Ⅲ and Ⅳ are observed at the range of 360-370 nm, and the maximum absorption wavelength for dye II has a red shift to 400-450 nm. Thus, the dyes are suitable for scCO2 dyeing. The optimal dyeing conditions for dyes are as follows: 2 h, 80 ℃ and 15 MPa for Ⅰ and Ⅲ, 1.5 h, 80℃ and 15 MPa for dye Ⅱ, and 1.5 h, 80 ℃ and 24 MPa for dye Ⅳ. The soaping fastness to soaping and light of the dyed wool fibers can reach 4-5 grade, and the fixation rate can reach up to 86%. Compared with un-activated precursor, the color fastness to soaping improves 2~3 grades, and the fixation rate increases 63%. Scanning electron microscopy (SEM) and microscopy images show that four dyes have good dyes’ permeability, evenly adhere to the surface and interior of the fibers. The test of mechanical parameters shows that the dyed wool fibers can basically maintain the original mechanical properties.

    • >Rubber and plastics auxiliaries
    • Synthesis and Application of Oligohydroxypropyl ethyl phosphate Flame Retardant

      2021, 38(9).

      Abstract (64) HTML (0) PDF 967.26 K (70) Comment (0) Favorites

      Abstract:Phosphorus pentoxide, propylene oxide, etc. were used as raw materials to synthesize oligomeric hydroxypropyl ethyl phosphate flame retardant. The effects of dropping temperature and dosage of propylene oxide, reaction temperature, reaction time, reaction pressure on the acid value of the target product were studied. The results showed that the optimum conditions were as follows: mass ratio of propylene oxide to intermediate Ⅱ was 0.67:1, propylene oxide dropping temperature 15 ℃, reaction pressure 0.5 MPa, reaction temperature 70 ℃, reaction time 1.5 h, the acid Value of target product reached 0.6 mgKOH/g . Its structure and performance were characterized by FTIR, GPC, TGA and chemical titration. Subsequently, the synthesized flame retardant was then used to modify polyurethane rigid foam. TGA data showed the composite containing 10% product Ⅲ, the residual mass at 900 ℃ increased from 7.9% to 20.71%; its flame-retardant performance test data showed the composite containing 30% product Ⅲ achieved UL-94 V-0 rating with a LOI value of 27.1% and retained the basic mechanical properties of RPUF

    • >Review and monographs
    • Recent advances in transition metal catalyzed late-stage C–H functionalization in medicinal chemistry

      2021, 38(9).

      Abstract (76) HTML (0) PDF 1.56 M (78) Comment (0) Favorites

      Abstract:Transition metal catalyzed C–H bond direct activation has gradually developed as one of the most effective tools in synthetic chemistry and is an essential part of drug research and development, which can provide functionalized bioactive molecules in an efficient and selective fashion. The research progress of transition metal-catalyzed C–H bond late-stage functionalization of bioactive molecules in the past decade is summarized from three aspects: C–C, C–O and C–N bond formation. The limitations and future development are reviewed and prospected.

    • >Functional materials
    • Preparation of nitrogen-containing macromolecular adsorbent and its adsorption mechanism for Cd(II)

      2021, 38(9).

      Abstract (75) HTML (0) PDF 1.74 M (77) Comment (0) Favorites

      Abstract:Water—insoluble macromolecular particle adsorbents, which were adopt to treat Cd(II) in water, were synthesized at low temperature though the nucleophilic substitution between polyethylene polyamine and cyanuric chloride due to the temperature gradient reaction activity of cyanuric chloride. In this system, the triazine ring of cyanuric chloride served as connection point to combine polyethylene polyamine and cyanuric chloride. The synthesized particulate adsorbent was characterized by elemental analysis, FTIR and SEM. At the same time, the adsorption kinetics, isothermal adsorption model fitting and adsorption mechanism of Cd(II) were studied. The effect of pH on Cd(II) was investigated and the effect of adsorption performance, the performance and structural stability of the adsorption-desorption regeneration cycle of the adsorbent were also studied. The results showed that the adsorption mechanism of the adsorbent was to utilize the coordination complexation of the nitrogen lone pair electrons on the secondary amine on the surface of the particulate adsorbent with the heavy metal ion Cd(II) for adsorption. Which was in line with the pseudo—second—order kinetic equation and the Langmuir adsorption model. The maximum adsorption capacity reached 539.1 mg/g, and the adsorption of Cd(II) was relatively easy, and the adsorption capacity was strong. The initial concentrations of Cd(II) were 3636.5 mg/L and 70.0 mg/L, and the removal rate of Cd(II) can reach 97.5% and 99.9%, respectively, and the adsorption effect remains unchanged during the 10 adsorption—desorption regeneration cycles. The adsorption rate was maintained at about 97.0%~98.2%, the desorption rate was above 97.6%, the recovery rate of the adsorbent was above 92.0%, and the adsorbent can reach 100% recovery after 7 cycles.

    • >Modernization technology of traditional Chinese medicines
    • GC-MS analysis and antitumor activity of the volatile oils from Arisaema decipiens Schott from various habitats

      2021, 38(9).

      Abstract (94) HTML (0) PDF 417.95 K (95) Comment (0) Favorites

      Abstract:The compositions of the volatile oil of Arisaema decipiens Schott from two habitats were extracted by simultaneous distillation extraction (SDE) method, analyzed by gas chromatography–mass spectometry (GC–MS) and In vitro cytotoxic activities of both essential oils were explored by MTT test. 12 and 11 kinds of volatile components were identified from Guangxi and Sichuan respectively and the relative contents calculated by GC peak areas were 90.96% and 94.68%. 5 kinds of common components were (Z,Z)-9,12-Octadecadienoic acid, n-Hexadecanoic acid, Pentadecanoic acid, 5-Octadecyne and Z-11- Hexadecenoic acid. The main components of two volatile oils from Arisaema decipiens Schott were fatty acids, but they were different in the composition and relative amounts. Both essential oils inhibited cellular proliferation significantly against A549, Hela, HepG2 and HCT-116 cell lines with IC50 ranged from 43.66 μg/mL to 105.04 μg/mL.

    • >Review and monographs
    • Research progress in chitosan and its metal particle composite materials for biological antibacterial

      2021, 38(9).

      Abstract (494) HTML (0) PDF 4.19 M (70) Comment (0) Favorites

      Abstract:Diseases caused by microbial infections such as bacteria and fungi have been a problem in public health. Antibacterial materials that can effectively kill bacteria and have no side effects have become one of the current research hotspots and focuses. However, microbes widely appear drug resistance, which has become a difficult point in the treatment of microbial infections. In recent years, chitosan as a green material with high antibacterial activity, good biocompatibility and wide source has attracted wide attention. Chitosan and Ag, Au and Zn nanoparticles would produce synergistic antibacterial effects after being compounded. More importantly, it is difficult for nanoparticles to develop resistance. They can be used in wound dressing films, dressing antibacterial additives and other fields. In this paper, according to the antibacterial properties of chitosan, we summarize its antibacterial mechanism and the factors of activity, and review the current research status of antibacterial materials combined with nanoparticles of Ag, Au and Zn. At last, we provide the development trend of the field and information support for further research on biological antibacterial materials.

    • Research progress of modified electrodes in microbial fuel cell for simultaneously enhancing electricity generation and organic pollutants degradation

      2021, 38(9).

      Abstract (492) HTML (0) PDF 8.69 M (76) Comment (0) Favorites

      Abstract:As the acceleration of urbanization, the organic pollutants in wastewater have been more complex and persistent. However, these toxic materials could not be effectively removed by conventional wastewater treatment, posing a serious threat to the eco-environment and human health. Microbial fuel cell (MFC), an emerging renewable technology, can directly convert the chemical energy from organic compounds into electricity by microbial catalysis. Electrode design is one of the most important factors in affecting the pollutants degradation and power output capacity. Hence, this review demonstrates the latest developments of organic pollutants removal along with electricity generation by the anode/cathode modification in MFC. Furthermore, the applications of MFC electrode materials in wastewater treatment field are prospected.

    • Research Progress of Oil Water Separation Materials with Special Wettability

      2021, 38(9).

      Abstract (506) HTML (0) PDF 9.52 M (204) Comment (0) Favorites

      Abstract:Frequent oil spill accidents have seriously harmed the ecological environment. Special wettability materials are widely used in the field of oil-water separation because of their different wettability to oil-water two phases. In this paper, the preparation methods of special wetting oil-water separation materials are briefly introduced. According to the different ways of oil removal, they are divided into filter-type, adsorption-type and selective separation intelligent materials. And introduced in detail the various substrates of filter-type materials, including metal mesh, textiles, polymer membranes, etc., and various substrates of adsorption-type materials such as sand, sponge, foam, and aerogel. Finally, the development of this field is prospected. It is pointed out that special wetting oil-water separation materials must be directed towards green, self healing and multi-functional response.

    • Research progress on the application of plant-based biomass resources in self-healing materials

      2021, 38(9).

      Abstract (793) HTML (0) PDF 3.50 M (71) Comment (0) Favorites

      Abstract:In recent years, plant-based biomass resources have become a research hotspot due to their wide range of sources, renewable, biodegradable and so on. The preparation or modification of polymers can further alleviate the petrochemical resource crisis and improve the environmental adaptability of polymer materials; meanwhile, the active functional groups and hydrogen bonds are rich in its molecular structure, it has attracted much attention for its application in the preparation and modification of self-healing materials. In this paper, taking cellulose and lignin as examples, the application of plant matrix resources in self-repairing materials in recent years are reviewed, and their natural characteristics and their important roles in the preparation of self-healing materials are introduced in detail. In addition, the application principles of dynamic chemical bonds such as Diels-Alder reaction, sulfur—sulfur bond and hydrogen bond in self-healing materials are discussed in detail from the point of view of molecular structure. Finally, the main challenges and potential solutions for the preparation of plant-based self-repairing material resources by polymer engineering are put forward, and the research direction of the application of plant biomass materials in non-repair materials is prospected.

    • >Functional materials
    • Preparation and characterization of schiff base modified Fe3O4 hybrid material

      2021, 38(9).

      Abstract (406) HTML (0) PDF 1.34 M (80) Comment (0) Favorites

      Abstract:A Fe3O4 hybrid material (Fe3O4@SiO2-S2) modified by schiff base was prepared by grafting methyl acrylate (MA), ethylenediamine (EDA) and salicylaldehyde (SA) onto the prepared magnetic hybrid material Fe3O4@SiO2-NH2 successively, what's more, the structure was characterized by IR, XRD, SEM ,TEM and VSM. The results showed that the Fe3O4@SiO2-S2 has an abvious core-shell structure and a saturation magnetization of 45.9 emu/g. Study on the adsorption of aqueous heavy metal ions showed that Fe3O4@SiO2-S2 posed selective adsorption for Hg2+ with the saturated adsorption capacity of 362 mg/g(1.12 mmol/g), which was superior to Fe3O4@SiO2-NH2, Fe3O4@SiO2-HO-S and other adsorbents, at the condition of pH=6, 45 ℃, the adsorption capacity remained 89% after 5 cycles of adsorption-desorption, what's more, adsorption equilibrium was reached at about 300 min and the adsorption isotherm conformed to the Langmuir isotherm adsorption model.

    • Preparation and performance of 2D MoSe2 and its flexible photodetector

      2021, 38(9).

      Abstract (761) HTML (0) PDF 2.51 M (125) Comment (0) Favorites

      Abstract:Due to their excellent electrical, optical, mechanical and other physical and chemical properties, two-dimensional transition metal chalcogenide compounds have important application prospects in the fields of electronics and optoelectronics. The MoSe2 material was successfully prepared by the hydrothermal method. The prepared MoSe2 was characterized by SEM and TEM, and the prepared MoSe2 was flower-shaped microspheres with a particle size of about 200-300 nm. The MoSe2 photodetector was prepared by the vacuum filtration method with flexible organic nylon membrane as the substrate, and its photoelectric characteristics were tested under different laser wavelengths and different laser powers. The results showed that the highest responsivity at 520 nm was 7.5×10 -5A/W; when the laser power is 0.5mW, the maximum light detection rate is 1×107 cm·Hz1/2/W; the light responsivity and light detection rate increase with the increase of laser power, and the response time is faster. The rising response time is 4.6 ms, and the falling response time is 1.3 ms.

    • Modified titanium dioxide powder by fluorine-hydrovinyl polysiloxane and investigation on its superhydrophobic properties

      2021, 38(9).

      Abstract (690) HTML (0) PDF 1.66 M (157) Comment (0) Favorites

      Abstract:In order to improve the hydrophobicity property of titanium dioxide and solve the problems in its low dispersibility and compatibility in organic solvents, the surface of titanium dioxide powder was modified by using fluorine-hydrovinyl polysiloxane (F-PMHS). The structures and superhydrophobic properties of the modified TiO2 were studied by FT-IR, TGA, SEM, contact angle tests and sedimentation experiments. The formation mechanism of the superhydrophobic surface was also analyzed in detail. The results showed that when the mass fraction of F-PMHS relative to TiO2 is only 8%, the static contact angle between the modified TiO2 coating and water can reach 152.4 ° with good superhydrophobic properties, and the dispersion and compatibility of TiO2 in organic solvents are significantly improved.

    • Preparation and thermal properties of stearyl alcohol @ Co3O4/Expanded Graphite composite phase change material for heat storage

      2021, 38(9).

      Abstract (413) HTML (0) PDF 1.58 M (88) Comment (0) Favorites

      Abstract:A novel stearyl alcohol @ Co3O4/Expanded graphite composite phase change material (PCM) was prepared. Stearyl alcohol (SAL) and Co3O4/Expanded Graphite were selected as phase change material and supporting material, respectively. Expanded Graphite (EG), which was used to improve the thermal conductivity of PCM, was chemically modified using Co3O4. Co3O4 derived from ZIF-67 has abundant pore structure and large specific surface area. The structure of Co3O4/EG additive was characterized by SEM analyzing method. The prepared Co3O4/EG has the three-dimensional coupled network and hierarchical porous structure. Meanwhile, EG can effectively prevent the structural collapse and aggregation of Metal-Organic Framework (MOF) derivatives. The morphology and thermal properties of composite PCMs were analyzed with SEM, DSC and infrared imager. These results showed that the melting temperature of SAL@ Co3O4 /EG-8% composite phase change material was 51.25℃, and its latent heat was 191.63 kJ/kg. As the ratio of Co3O4 to EG increased from 1:1 to 1:8, the thermal conductivity of the composite phase change material SAL@Co3O4 /EG showed an increasing trend. When Co3O4: EG was 1:8, the thermal conductivity of PCM was about 47 times that of pure SAL(0.248 W/(m?K)).The infrared imaging results confirmed that the transient temperature variation of the composite phase change material sample was closely related to its thermal conductivity. All the test results showed that the new composite was a promising phase change material, because of its excellent thermal properties, it had a great potential application value in the field of heat storage.

    • Effect of counter anions on the electromagnetic properties of graphene oxide/polyaniline

      2021, 38(9).

      Abstract (459) HTML (0) PDF 1.32 M (68) Comment (0) Favorites

      Abstract:The graphene oxide/polyaniline composites were synthesized by in-situ chemical oxidation polymerization using Cl-, CSA- (camphor sulfonic anion group) and SO42- as counter anions, with 1 mol/L proton concentration and ammonium persulfate as initiator. SEM, FTIR and XRD analyses were conducted to characterize the morphologies and structures, four-probe method and vector network analyzer were employed to determine the electromagnetic parameters. The impedance and reflection loss (RL) were calculated. The results indicated that the three types of composites appear to be sandwich-like structure with graphene oxide layer coated by polyaniline nanocones. The electronic conductivity reaches 5.500 S/cm portending higher dielectric loss capacity, when the para-anion is SO42-. While the standing-wave ratio of CSA doping composite is up to 1.1 at 14.2 GHz and much closer to a traveling wave state suggesting the best impedance matching, whose minimum RL reaches -30 dB (9.925 GHz, 2.75 mm) and effective absorbing bandwidth (RL<-10 dB) reaches 4.845 GHz (12.305~17.15 GHz, 2 mm).

    • >功能材料
    • Synthesis of 2-indolyl methanamine derivatives catalyzed by diphenyl phosphate

      2021, 38(9):0-0.

      Abstract (621) HTML (0) PDF 454.56 K (93) Comment (0) Favorites

      Abstract:Friedel-Crafts reaction of 3-methylindoles and imines catalyzed by diphenyl phosphate can be used to synthesize 2-indolyl methanamines in one step, which has a wide range of pharmacological activities. The reaction conditions were optimized and the optimal reaction conditions were obtained as follows: n (3-methylindoles) ∶ n (imines) ∶ n(diphenyl phosphate) = 1.0 : 2.0∶0.1, the amount diphenyl phosphate is 0.0025 mmol, 1 mL anhydrous dichloromethane as solvent, room temperature, reaction time 0.5 h. 2-indolyl methanamine derivatives can be obtained in good yields (85~90%). The structures of the products were confirmed by 1HNMR, 13CNMR and HRMS.

    • High safety fullerene cosmetic raw materials and their whitening, anti-inflammatory and repairing effects

      2021, 38(9):0-0.

      Abstract (623) HTML (0) PDF 891.35 K (108) Comment (0) Favorites

      Abstract:Two kinds of water-soluble fullerenes〔fullerene sodium hyalornate(MHAF60 and fullenene polyvinylpyrrolidone (PPF60)〕were prepared and tested for skin care .The results of GC UV-Vis and FTIR showed that fullerenes still keep their characteristic absorption .The results of DLS showed that the particle sizes of the two materials are 368.5nm and 500.6nm, respectively The results of GC showed that there was no residual organic solvent in the two materials. EPR detection showed that the free radical quenching ability of MHAF60 was significantly better than that of PPF60, vitamin C and water-soluble astaxanthin. HEK-A cells was used to test the ability of fullerene to repair oxidative damage. The results show that MHAF60 has significant protective and repairing effects on cell injury, and the effect was significantly better than that of vitamin C and water-soluble astaxanthin. The results of zebrafish experiment showed that fullerene could significantly inhibit melanin production, inhibit inflammation and promote wound healing, and higher security.

    • Synergistic Effects of Polyethylene Oxide on Polypropylene Oxide of Extended Surfactants

      2021, 38(9):0-0.

      Abstract (509) HTML (0) PDF 620.67 K (118) Comment (0) Favorites

      Abstract:Sodium lauryl polyoxypropylene-polyoxyethylene ether sulfate (SLP3E3S) was synthesized from lauryl alcohol by propoxylation, ethoxylation, sulfation and neutralization, and characterized by FTIR, ESI-MS and 1HNMR. The interfacial and application properties of SLP3E3S were tested and compared with those of sodium lauryl sulfate (SDS), sodium laureth sulfate (SLE3S) and sodium lauryl polyoxypropylene ether sulfate (SLP3S). The synergistic effects of polyoxyethylene (PEO) and polypropylene chain (PPO) of extended surfactants were investigated. The results showed that the synergistic effects of PEO and PPO led to SLP3E3S displaying the best low foamability (49 mL), emulsifying power of polar oil (19.4 min) and lime soap dispersing power (55.8 mol/mol) among four surfactants, and the electrolyte tolerance (especially the calcium ion tolerance) of SLP3E3S is as good as that of SLE3S while much better than SDS and SLP3S.

    • Green and effective synthesis of N,N,N-trimethyladamantan-1-aminium hydroxide

      2021, 38(9):0-0.

      Abstract (548) HTML (0) PDF 531.60 K (91) Comment (0) Favorites

      Abstract:In this paper, a green process for the synthesis of N,N,N-trimethyladamantan-1-aminium hydroxide was reported. Firstly, the precursor N,N,N-trimethyladamantan-1-aminium salt was obtained by using 1-adamantanamine as raw material, dimethyl carbonate (DMC) as methylating reagent. Then, the precursor was reacted with calcium hydroxide to achieve the final product N,N,N-trimethyladamantan-1-aminium hydroxide. The structures of ammonium salt and hydroxide were characterized by 1H NMR and 13C NMR spectra. After investigating the effects of catalyst, mole ratio of reactants, reaction temperature and time on the yield of N,N,N-trimethyladamantan-1-aminium salt, the optimum reaction conditions were obtained as follows: N,N-dimethyl formamide (DMF) was used as the catalyst, m(DMF):m(1-adamantanamine) = 0.25, n(1-adamantanamine):n(DMC) = 1:8, reaction temperature and time were 140 ℃ and 5 h, respectively. Under these conditions, the yield of N,N,N-trimethyladamantan-1-aminium salt could be up to 97.3%. Compared with the traditional process using dimethyl sulfate (DMS) as the methylation reagent, this process is more safe, green and efficient.

    • >Electronic chemicals
    • Preparation of perfluoropolyether with double terminal functional groups by fluorination of hydrogen-containing fluoropolyether

      2021, 38(9).

      Abstract (484) HTML (0) PDF 2.52 M (100) Comment (0) Favorites

      Abstract:Using hydrofluoropolyether (E10H) as raw material and fluorinating with a mixture of fluorine and nitrogen, a double-terminated hydroxyl perfluoropolyether (F-E10H-AL) was prepared. Three fluorination processes were explored, including normal temperature fluorination, low temperature fluorination, and first low temperature and then normal temperature fluorination. Then it is combined with lithium bistrifluoromethanesulfonate (LiTFSI) to prepare a lithium-ion electrolyte. The structure of the fluorinated product was analyzed by infrared spectroscopy, hydrogen nuclear magnetic spectroscopy and fluorine spectroscopy. The impedance and chronoamperometry(CA) were tested by electrochemical workstation. The results show that the low-temperature fluorination process has high fluorination efficiency. After direct fluorination of E10H at -10°C for 12 hours, 21.0% of H atoms in the molecular chain is replaced by F atoms, but more CF3O- are produced. When the hydroxyl group on E10H was protected by hexafluoropropylene oxide dimer, the fluorination process of low temperature followed by normal temperature was adopted, and 48.3% of H atoms in the molecular chain were replaced by F atoms. Finally, the fluorinated product is reduced to obtain F-E10H-AL with a CF3O- content of 0.7% at the end of the molecular chain. Combining the impedance and CA datas, lithium-ion transference number of F-E10H-AL/LiTFSI is calculated to be 0.32, which is higher than that of PFPE-OH/LiTFSI (0.07).

    • >Catalysis,separation and purification technology
    • Preparation of polyporphyrin and its application in photocatalysis

      2021, 38(9).

      Abstract (369) HTML (0) PDF 1.70 M (98) Comment (0) Favorites

      Abstract:A library of cross-linked poly-porphyrins with porous and network structures were prepared via the Sonogashira polymerization method to address the issues of the porphyrin monomers in separation, recycling and purification during the photocatalytic process. Two types of porphyrin monomers (dibromodiacetylenic porphyrin and tetrabromoporphyrin) were designed and the porphyrin-based porous organic polymer (PPOP-1) was obtained through self-polymerization of dibromodiacetylenic porphyrin and three poyporphyrins were obtained through the copolymerization of tetrabromoporphyrin and various linkers containing dialkynes (1, 7-octadiyne, p-phenylenediyne, and biphenyl). The surface morphology and pore structure of the polymers are characterized by scanning electron microscopy and physical adsorption. All four polymers had uniform ellipsoid morphology and microporous structures. PPOPs were used as metal-free heterogeneous photocatalysts and the photocatalytic activity for C-N and C-S bonds were confirmed through the visible light-induced oxidation of dibenzylamine, bisaminothioketal and dibenzyl sulfide. The PPOPs maintained excellent catalytic activity after five cycles.

    • Effection of Si and Al Sources on Hydroalkylation of Benzene to Cyclohexylbenzene over Ni-Pd-La/Hβ

      2021, 38(9).

      Abstract (291) HTML (0) PDF 1.71 M (87) Comment (0) Favorites

      Abstract:Hβ zeolites were synthesized by hydrothermal crystallization with different Si and Al sources. Correspondingly, the multifunctional catalysts (Ni-Pd-La/Hβ) with Ni, Pd and La supported on these synthesized Hβ zeolites were prepared by impregnation method. These catalysts were characterized by XRD, BET, NH3-TPD, HR-TEM, and were used for catalytic hydroalkylation of benzene (BZ) to cyclohexylbenzene (CHB). The results showed that Ni-Pd-La/Hβ-2 (HAC-2) prepared using tetraethyl silicate and aluminum powders as Si and Al sources had higher activity and higher CHB selectivity than Ni-Pd-La/Hβ-3 (25) (HAC-3) (25 represents the molar ratio of Si to Al) prepared by the classical method using silica sol and NaAlO2 as Si and Al sources. HAC-2 showed good stability, which was attributed to the higher specific surface area of Hβ-2 and more uniform distribution of aluminum atoms in its frameworks. Under the conditions of HAC-2 (25) as catalyst, reaction temperature 190 ℃, hydrogen pressure 2.0 MPa and reaction time 90 min, the conversion rate of BZ and the selectivity of CHB were 46.8% and 79.6%. After reused after 10 times, the activity of the catalyst decreased by 2.0% and the carbon deposit was only 0.21%.

    • Thermoregulated phase-separable Pd nanocatalyst for selective hydrogenation of α, β-unsaturated ketones

      2021, 38(9).

      Abstract (357) HTML (0) PDF 1.11 M (92) Comment (0) Favorites

      Abstract:Thermoregulated phase-separable Pd nanocatalyst exhibited high performance in the selective hydrogenation of α, β-unsaturated ketones at atmospheric hydrogen pressure. Under optimized reaction conditions, the conversion and hydrogenation selectivity of the C=C bond for chalcone were >99%. The catalyst can be easily separated from the product and recycled seven times remaining >99% conversion and selectivity. The turnover frequency (TOF) was up to 1470 h-1, which exceeds the value reported in literatures for the selective hydrogenation of chalcone catalyzed by transition metal nanocatalysts under atmospheric hydrogen pressure.

    • Photocatalytic properties of Bi2S3 /CNFs composite photocatalyst and its preparation

      2021, 38(9).

      Abstract (409) HTML (0) PDF 1.17 M (76) Comment (0) Favorites

      Abstract:Bismuth sulfide (Bi2S3) and activated carbon nanofiber doped bismuth sulfide composites (Bi2S3/CNFs) were prepared by the hydrothermal method to remove metronidazole (MTZ) from the aqueous solution. The photocatalyst was specified by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy(FT-IR), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance and photoluminescence(PL). The results show that the introduction of active carbon nanofibers (CNFs) into Bi2S3 can reduce the recombination rate of the photogenerated-electron-hole pairs and improve the photocatalytic activity. The photocatalytic degradation of MTZ by Bi2S3/CNFs composite was assessed under visible light irradiation. It was found that the photocatalytic activity of Bi2S3/CNFs composite was excellent when the CNFs content was 47% (based on the mass of Bi2S3, the same below), and the removal rate of MTZ was 92% within 3 h. Bi2S3/CNFs composites also showed strong stability and recoverability after three cycles. In addition, the experimental results of active group capture showed that hydroxyl radical (·OH), photogenerated hole (h+) and superoxide radical (·O2-) were involved in the degradation of MTZ on Bi2S3/CNFs, and·OH and h+ were the main active components of the system.

    • Ultrathin metal-organic framework nanosheets as precursors for efficient electrocatalysts for oxygen evolution reaction

      2021, 38(9).

      Abstract (432) HTML (0) PDF 3.42 M (72) Comment (0) Favorites

      Abstract:Metal-organic frameworks (MOFs), as promising precursors for specific morphologies nanomaterials for oxygen evolution reaction (OER), become a new research focus. Ultrathin NiCoFe-MOF nanosheets are synthesized on the Ni foam substrate by solvothermal method and becomes converted into metal hydrogen (hydroxy) oxide on the basis of retaining the morphology of the nanosheets under the In-situ electrochemical conditions. The overpotential of 189 mV at a current density of 10 mA?cm-2 and a Tafel slope of 35 mV/dec in 1 M KOH electrolyte, long-term electrolysis experiment also signifies its excellent stability. In-situ Raman spectroscopic reveals that the high activity of the OER derives from the "active oxygen" species intermediates.

    • >Drug and cosmetic materials
    • Synthesis of furoxan and chlorin e6 conjugate and evaluation of photodynamic antitumor activity

      2021, 38(9).

      Abstract (397) HTML (0) PDF 653.04 K (90) Comment (0) Favorites

      Abstract:Photodynamic therapy (PDT) is a non-invasive method of treating tumors.It is characterized by using light of a specific wavelength to excite the photosensitizer enriched in tumor cells to produce cytotoxic reactive oxygen species (ROS), and induce cell damage and death. However, the low oxygen concentration near the tumor tissue limits the level of active oxygen produced by the photosensitizer and affects the therapeutic effect of PDT. Using phenylpropenol as a raw material, 4-phenyl-3-hydroxymethyl-furoxan was synthesized, and it was esterified with chlorin e6 to obtain a chlorin e6 conjugate containing furazan. The results of the activity evaluation showed that the introduction of furazan group can significantly increase the level of intracellular NO, increase the number of intracellular ROS, and synergistically increase the photodynamic inhibitory activity of tumor cell proliferation by about 20 times. The results of this study indicate that the introduction of furoxan-like NO donor structure in the photosensitizer structure can significantly improve the photosensitizer’s activity in inhibiting tumor cell proliferation, providing a new idea for the synthesis of new and efficient photosensitizing anti-tumor therapeutic agents .

    • Improved Synthesis of β- Decitabine

      2021, 38(9).

      Abstract (431) HTML (0) PDF 594.79 K (105) Comment (0) Favorites

      Abstract:Starting from 2-deoxy-D-ribose, ethanol/acetyl chloride was used instead of methanol/HCl to prepare 1-ethoxy-2-deoxyribose. And its 3,5-dihydroxyl group was protected by p-chlorobenzoyl chloride rather than p-methylbenzoyl chloride, taking dichloromethane as the solvent. Thus 1-Ethoxy-2-deoxy-3,5-di-p-chlorobenzoyloxy-D-ribofuran was obtained with 100% conversion rate. While the extra p-chlorobenzoyl chloride was removed by low-temperature crystallization. Followed by condensation of glycosides with 5’-azacytosine, deprotection by ammonia methanol, and isomer isolation, β-decitabine was synthesized. Structures of the products and intermediates were rigorously solved using 1HNMR, 13CNMR,MS(ESI), IR and X-ray diffraction. The yields of trial batch and kilogram-level scale-up batch were 30.61 % and 30.00 %, respectively.

    • >Electro-organic chemistry and industry
    • Application of pyrolysis carbon from pomelo peel in electrochemical sensors of hydroquinone and catechol

      2021, 38(9).

      Abstract (358) HTML (0) PDF 3.74 M (106) Comment (0) Favorites

      Abstract:In this work, pomelo peel was used as crude material, ammonia, sodium hydroxide and potassium hydroxide was used as activators, then a class of biochar materials were prepared by one-step pyrolysis. The structure and morphology of these materials were characterized by SEM, XRD, and Fully automated surface analyzer; then, the Electrochemical ac impedance technique (EIS) and Cyclic voltammetry (CV) were used to test their electrochemical properties. Compared to other materials, Pyrolytic carbon produced by activation of potassium hydroxide possessed the most abundant pore distribution, while showed the most superior electrochemical properties. This kind of carbon material was modified on the surface of glassy carbon electrode(GCE) by cast. The electrochemical behavior of hydroquinone (HQ) and catechol (CA) at different electrodes were investigated by differential pulse voltammetry (DPV) in PBS solution (pH=7.0). The results indicated that compared to other electrodes, the PC-4/GCE was the most superior to HQ and CA at the same time. Under optimal conditions, when the concentration of HQ and CA were in the range of 0.5~100 μmol/L, a good linear relationship between the PC-4/GCE response current and its concentration has been showed, the detection limits were 0.023μmol/L and 0.040μmol/L, respectively. Meanwhile, the sensor had good stability, and its relative standard deviation values (RSD) were 2.3% and 3.5%, respectively. HQ and CA in tap water samples were detected by standard recovery, and add standard recovery range was 97.8~101.7.

    • >Leather chemicals
    • Tanning performance and mechanism of Coriaria nepalensis bark vegetable tanning agent combined with aluminum salt

      2021, 38(9).

      Abstract (448) HTML (0) PDF 936.06 K (87) Comment (0) Favorites

      Abstract:The vegetable tanning agent extracted from Coriaria nepalensis bark was used as raw material, and the combined tanning of pickled sheep skin was carried out with aluminum salt. The tanning process was optimized to establish a combined tanning method of Coriaria nepalensis bark tanning agent, and the leather performance and tanning mechanism were studied. The results of the experiment show that when the amount of vegetable tanning agent is 15%, the amount of Al3(SO4)2•18H2O is 20%, the penetration pH is 4.0, and the combined pH is 4.5, the shrinkage temperature of the tanned leather can reach 110.5 ℃. The tanned leather has good appearance properties, and thickness increase rate is 82.2%, tensile strength is 10.0 MPa, tear strength is 52.5 N/mm, elongation at break is 76.8%, which is better than the leather tanned by the combination of a commercially available valonia vegetable tanning agent. After tanning, the collagen fibers of the leather become thicker and form a tight network structure. The Coriaria nepalensis bark vegetable tanning agent and aluminum salt can fully penetrate into the collagen fibers of the leather and produce hydrogen bond cross-linking with them. During the combined tanning process, the aluminum salt is complexed with the tannins combined in the leather collagen fibers, which enhances the cross-linking effect, thereby significantly improving the thermal stability and mechanical properties of the tanned leather.

    • >Building chemicals
    • Preparation and application of 1-phenoxy-3-alkoxy-2-propanol film forming auxiliaries

      2021, 38(9).

      Abstract (392) HTML (0) PDF 4.27 M (78) Comment (0) Favorites

      Abstract:1- phenoxy -3- alkoxy -2- propanol film forming auxiliaries were synthesized from benzyl alcohol, isopropyl glycidyl ether and n-butyl glycidyl ether.The optimum process conditions were investigated as follows: N (benzyl alcohol)∶ N (alkyl glycidyl ether)=1∶1.5, reaction temperature 120℃, reaction time 9h, catalyst as compound catalyst (m sodium methoxide∶ m tetrabutylammonium bromide = 2∶1), catalyst dosage 0.8%(total mass ratio).The chemical structure of the film forming auxiliaries was verified by FTIR and 1H NMR spectra.The boiling points of 1-phenoxy-3-isopropoxy-2-propanol film forming assistant and 1-phenoxy-3-n-butoxy-2-propanol film forming assistant were determined as 267℃~270℃ and 276℃~280℃ respectively.Explores the application of synthesis of film forming additives in latex paint, respectively made in the minimum film-forming temperature, coating surface morphology AFM figure, light transmittance of coating, coating hardness, water absorption and heat storage stability of the coating, color and water resistance test, the results said synthesis of film forming additives overall performance is superior to the traditional film forming additives 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.