Abstract:The Al-modified Cu/ZnO catalysts were studied by deposition precipitation method, and the catalysts were characterized by XRD, BET and NH₃-TPD.At the same time, the preparation of N,N-dimethylaniline (N,N-DMA) by N-methylation of aniline and methanol was studied. The calcination conditions of the catalysts prepared by the deposition precipitation method were investigated and the process conditions were optimized for the N-methylation reaction. The results show that when pseudo-boehmite is the aluminum source, the molar ratio of Cu/Zn/Al is 1:3:1, the calcination temperature is 400 ℃, the calcination time is 3 h, the reaction temperature is 250 ℃, and the reaction pressure is 1.5 MPa, When the feed space velocity is 0.3 h^_-1, the nitrogen flow rate is 150 mL/min, and the molar ratio of aniline to methanol is 1:7, the N-methylation reaction of aniline was the best, and the conversion rate of aniline reaches 99.8%, N,N -DMA selectivity reaches 92.8%. The catalyst has undergone a 720h stability test. The aniline conversion rate is stable above 99%, and the N,N-DMA selectivity is stable above 90%. The catalyst has good stability.

Abstract:Dendritic transition metal catalysts are transition metal active centers loaded on dendritic macromolecular. Therefore, these catalysts not only have the unique artistic structure of dendrimers, but also have the functional performance of transition metal complexes, so that they can work together, and have the characteristics of homogeneous and heterogeneous catalytic systems, It has high catalytic activity and good catalytic stability in catalytic olefin polymerization. It has attracted much attention in recent years, and catalytic ethylene polymerization is one of the research hotspots. This paper is classified by their transition metal active center and summarizes the progress of dendritic transition metal catalysts in this ethylene polymerization at home and abroad in recent years, expounds the causes of various dendritic effects, and looks forward to the development prospect of dendritic transition metal catalysts for ethylene polymerization

Abstract:Popularity of green and sustainable development among people encourages them to pursue safe, harmless and side-effect free products. No toxicity and irritation, coupled with superior biodegradability and bio-compatibility, are attributable for people’s growing attention on biomass particle emulsifier. This paper reviews the research progress of Pickering emulsions stabilized with naturally derived solid particles, including polysaccharide-based particles such as starch, chitosan, cellulose, cyclodextrin, etc., and protein-based particles such as whey protein, soy protein, and zein. etc., and other types of particles such as flavonoids, polyphenols, natural pearl powder, etc. In addition, the paper reviews the application of Pickering emulsions stabilized with natural solid particles in cosmetics, including enhancing emulsion system stability, loading bio-active ingredients and synergistic effect. Finally, the application prospect of Pickering emulsions stabilized with naturally derived solid particles is prospected.

Abstract:The schiff base containing aromatic disulfide bond was successfully synthesized by the reaction of salicylic aldehyde and 2, 2-diaminodiphenyl disulfide ether. The schiff base was reacted with polytetrahydrofuranediol, isophorone diisocyanate,2, 2-dihydroxymethyl butyric acid and 1, 4-butanediol. The characterization of the schiff base and polyurethane film was performed by 1HNMR and FTIR. The results showed that the self-healing waterborne polyurethane with aromatic Schiff base and aromatic disulfide bond was successfully synthesized. The self-healing ability of polyurethane was characterized by scratch test and healing test. The results showed that swPU-2 had the best scratch healing effect and self-healing rate. After 12h healing at room temperature, swPU-2 film's scratch disappeared, and after 24h healing at room temperature, the self-healing rate of polyurethane film could reach 95.8%

Abstract:Monolayer tungsten trioxide nanosheets (ML-WO₃) were prepared via the space-confined strategy and then compounded with TiO₂ to obtain ML-WO₃/TiO₂ nanomaterials, which were used for the photocatalytic degradation of rhodamine B under simulated solar light. The compositional structure and optical features of ML-WO₃/TiO₂ were characterized by means of SEM, TEM, HRTEM, XRD, UV-Vis and PL. The results showed that the ML-WO₃/TiO₂ overcame the defect of large band gap of pure TiO₂ and exhibited stronger absorption performance than ML-WO₃ and TiO₂ in the full wavelength solar light, and there was a remarkable synergistic relationship between ML-WO₃ and TiO₂. The active species capture experiments showed that .OH and .O_2^- free radicals were the main active species for RhB degradation. The Z-scheme heterojunction charge transfer pathway constructed between ML-WO₃ and TiO₂ can ensure efficient separation and recombination of photogenerated carriers. The photocatalytic activity of the ML-WO₃/TiO₂ composites could still approach 80% after 5 cycles of experiments, with good photochemical stability. The possible degradation pathway of RhB was speculated by the detection of RhB intermediates by HPLC-MS.

Abstract:Based on solid agglomeration or stacking of organic fluorescent dyes, which leads to fluorescence quenching, luminescence, and weakening of stability, the method of exfoliation and supramolecular assembly is used to prepare solid fluorescent ultra-thin film emitters. First, vermiculite nanosheets were prepared by shear exfoliation, and their particle size distribution was controlled at 30-300 nm. Then, vermiculite organic-inorganic vermiculite was obtained by layer-by-layer supramolecular assembly with organic fluorescent dyes (rhodamine 6G and rhodamine B). fluorescent film. It was found by comparative experiments that a uniform luminescent fluorescent film could not be obtained without adding vermiculite nanosheets. The SEM of the vermiculite organic-inorganic fluorescent film shows that the organic fluorescent dyes and vermiculite are evenly distributed, which overcomes the fluorescence quenching of the agglomeration or stacking of the organic fluorescent dyes, and realizes the controllable fluorescence brightness.

Abstract:The Zein/chitosan (CS) composite film with high content of Zein was prepared by casting method, and the film was blended and modified by composite additives [m(glycerol):m(polyethylene glycol 400)=1:1]. The effects of the additive amount of the composite additives (0, 0.5%, 1.0%, 1.5%, 2.0%, respectively, based on the total solution mass) on the mechanical, optical and thermal properties of the film were studied. The morphology and structure of the film were characterized by SEM and FTIR. The results showed that the composite additives could achieve the plasticizing effect by weakening the intermolecular force between Zein and CS, and the comprehensive mechanical properties of the film are improved. With the increase of the additive amount of the composite additives, the elongation at break of the film gradually increased, and the tensile strength decreased and then increased, the WVP increased gradually, the water contact angle decreased gradually, and the hydrophilicity of the film increased. Compared with the film without composite additives, when the concentration of composite additives reached 1.5%, the tensile strength decreased by 27.40%, the breaking elongation increased by 39.87%. The barrier performance decreased, and the WVP increased by 29.10%. Through the observation of SEM and DSC, the compatibility between Zein and CS was improved after adding composite additives, and the surface of the prepared film was more flat and smooth. with high content of Zein, the Zein/CS film has the best performance when the concentration of the composite additive is 1.5%. Adding curcumin to zein/cs composite membrane could effectively improve the oxidation resistance of the film, and with the increase of curcumin content, the proportion of bound water in the film increased, and the mechanical properties of the composite membrane were better than those without curcumin.

Abstract:The effects of pretreatment methods of wheat straw on sophorolipids (SLs) fermentation by Starmerella bombicola were investigated, and the fermentation parameters were optimized. Dilute acid pretreatment (DAP), sodium hydroxide pretreatment (SHP) or sulfur trioxide microthermal explosion pretreatment (STMEP) were chosen to pretreat wheat straw to enhance the following enzymatic saccharification. Then, the saccharification liquids were used for SLs fermentation, respectively. Glucose supplement and activated carbon detoxification were used to improve SLs production. The results showed that SHP was the most favorable method for enzymatic saccharification of wheat straw, and the glucose content reached 61.30 g/L, followed by STMEP and DAP, with glucose content of 48.33 g/L and 40.00 g/L, respectively. The total content of inhibitors in STMEP saccharification liquid was the lowest, followed by SHP and DAP. S. bombicola could directly use the above saccharification solution to produce SLs, but the fermentation characteristics were different. Compared to the control chemical synthesis medium, SHP and STMEP saccharification medium were more conducive to acidic sophorolipid (ASL) accumulation, and the yield increased by 74.27% and 92.33% to 100.45 g/L and 110.86 g/L. Glucose addition and activated carbon detoxification could further improve SLs production. For SHP saccharification medium, glucose addition combined with activated carbon detoxification further increased ASL production to 124.49 g/L; For STMEP saccharification medium, lactonic sophorolipid (LSL) production was further increased to 32.02 g/L, which was similar to the LSL fermentation level of chemical synthesis medium. Therefore, wheat straw had potential for SLs production, and different pretreatment methods and fermentation methods can be used to obtain different types of SLs. The present study is benificial to reduce the production cost of SLs and expand its application field.

Abstract:The effects of n-butanol content and oil-water ratio on the microemulsion phase behavior of diesel oil and distillate oil at 350~395℃, 395~450℃ and 450~500℃ were investigated using isoctyl polyoxyethylene ether-5 (E1305) as surfactants. The results showed that the phase of microemulsion system changed from Winsor I →Winsor III →Winsor II with the increase of n-butanol content.The optimum solubilizing parameter (SP*) decreases while the optimum alcoholicity (A*) increases with the increase of oil phase distillation temperature. For the system with low contents of N-butanol and E1305, the phase changes from micelle solution type → Winsor-like II → Winsor IV→Winsor I with the increase of oil-water ratio. For the system with lower n-butanol content and higher E1305 content, the phase changes directly from micelle solution to Winsor I microemulsion with the increase of oil-water ratio. For the system with higher n-butanol content, the phase states change from Winsor II →Winsor III →Winsor I with the increase of oil-water ratio. The oil-water ratio required for phase transformation is related to the surfactant content and the distillation temperature of the oil phase.

Abstract:Cordyceps militaris is rich in protein, polysaccharide, cordycepin and other active components, with anti-cancer and anti-oxidation functions. In order to improve the economic value of Cordyceps militaris, the protein was extracted from its fruiting body by alkali solution and acid precipitation method, and the extraction conditions were optimized by orthogonal test. The polypeptide was obtained by digesting those protein with protein complex enzyme. And the antimicrobial and anticancer activities of those polypeptides were evaluated by measuring inhibitory zone and cytotoxicity. The results showed that the optimal extraction conditions of protein were as follows: pH 8.5, solid-liquid ratio 1:28, extraction time 210 min, extraction three times, the highest protein yield was 45.06%. The optimum enzymatic hydrolysis process of Cordyceps militaris polypeptide solution was as follows: the ratio of alkaline protease to papain was 4:3; The optimum temperature of enzymolysis was 55℃, pH 7.2, the enzyme dosage was 7000 U/mL, the enzymolysis time was 210 min, and the highest yield of peptide was 16.73%. Under these conditions, the polypeptides prepared from Cordyceps militaris (< 3.0×103 Da) showed good antibacterial activity against Escherichia coli, Bacillus subtilis and Staphylococcus aureus, with inhibitory zones of (12.08 ± 0.22), (6.67 ± 0.12) and (10.32 ± 0.23) mm, respectively. The results showed that the SAO-S (IC50 = 0.49 mg/L) and T24 (IC50 = 0.23 mg/L) were significantly inhibited by Cordyceps militaris polypeptide.

Abstract:We developed a superheated steam distillation (SSD) strategy for the extraction of Chinese fir essential oil with Chinese fir root cuttings as raw materials. The conditions were listed as follows: feed 350 g, steam flow 650 mL/h, distillation for 4 hours, different extraction temperatures as 130 ± 5 ℃, 160 ± 5 ℃, 190 ± 5 ℃, 220 ± 5 ℃, 250 ± 5 ℃ and 280 ± 5 ℃ respectively. The results showed that the yield of superheated steam was increased 2-4 folds comparing with that of atmospheric steam distillation (SD). The essential oil of Cunninghamia lanceolata has the smell of wood and ointment. However, the compounds with low boiling point in the components of the essential oil decrease with the increase of extraction temperature. Also, acidic compounds were observed in the mixture with acidic smell. On the other hand, increasing the steam temperature led to the decrease of cedanol in essential oil from 49.99% to 25.41%, increase of α-cedrene from 16.61% to 30.14%, and increase of β-cedrene from 4.10% to 11.92%. This SSD strategy could dramatically improve the oil yield from Chinese fir essential oil. Furthermore, variation of the extraction temperature could provide the oil with different chemical components, which can meet the different needs of the product.

Abstract:Bi12TiO20 photocatalyst doped with Fe element was prepared by hydrothermal method, and the structure of Bi12TiO20 was modified by X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance (UV-Vis DRS), scanning electron microscope (SEM), nitrogen adsorption and desorption, X-ray photoelectron spectroscopy (XPS) to characterize the morphology, microstructure and chemical valence state of the photocatalyst, and apply it to the photocatalytic degradation of methylthionine chloride (MB).The experimental results show that When the doping amount of Fe is 5%,the catalyst dosage is 0.05g, and the degradation rate of 10mg/L MB reaches 98.949%. After Fe doping, the Fe-Bi12TiO20 photocatalyst forms a new hybrid energy level, and the absorption band boundary is red-shifted, thereby improving the photocatalytic activity of the catalyst. Fe is a crystal doped in Bi12TiO20 with +3 and +2 valences middle.Fe-Bi12TiO20 photocatalyst, after repeated use for 5 times, the degradation rate of MB can still reach more than 88%, and it has excellent photocatalytic stability performance.Both h+ and·O2-are the main active species during photocatalytic degradation.This paper provides a reference for the doping modification of Bi12TiO20 materials.

Abstract:A series of CeO₂/g-C₃N₄ composite catalytic materials were prepared by microwave-assisted double template method and soft template method, and the materials were characterized by XRD, N2 adsorption-desorption, XPS, SEM and TEM, and their wet catalytic properties were investigated. The results showed that the D-CeO₂/g-C₃N₄ composites prepared by the double-template method exhibit the characteristics of cubic-phase CeO₂ and laminated g-C₃N₄, with large specific surface area and pore size, which are mesoporous structures and the presence of Ce^₃₊ and Ce^₄₊ on the surface, which are favorable to the formation of oxygen vacancies. The D-CeO₂/g-C₃N₄(7.5) sample obtained after adding 1 g of block copolymer F127, using anhydrous ethanol solution as the solvent and adjusting the mixture to be alkaline, and microwave radiation reaction for 120 min had a complete and homogeneous structure with the best morphological characteristics. The COD removal rate of 100 mg/L phenol solution could reach more than 80% when the reaction temperature was controlled at 75 ℃, D-CeO₂/g-C₃N₄(7.5) was injected at 0.7 g, H₂O₂ was injected at 0.5 mL, and the initial pH was 5. The D-CeO₂/g-C₃N₄(7.5) composite catalytic material could still achieve more than 60% catalytic degradation after five times of use.

Abstract:Subnano-Pd@SiO2 core shell materials were prepared by a one-pot method in a microemulsion made up of cetyltrimethyl ammonium bromide/n-butanol/cyclohexane with newly prepared Pd(NO3)2 solution as raw material. Pd subnanoclusters with an average size of 0.7 nm are uniformly dispersed in the entire SiO2 nanospheres with a high loading amount of 4% on the basis of the mass of SiO2. The physico-chemical properties of the Subnano-Pd@SiO2 were characterized by TEM, XRD, XPS, and N2 adsorption-desorption. The catalytic performances of Subnano-Pd@SiO2 for the hydrogenation reaction of aromatic nitro compounds were investigated. The results showed a 99.5% yield of aniline was achieved through the hydrogenation of nitrobenzene under mild reaction conditions of 50 ℃ and 1.0 MPa H2 for 4 h. Meanwhile, Subnano-Pd@SiO2 was efficient for the hydrogenation of various aromatic nitro compounds to give high yields (98.5%~100%) of arylamines. The activity of Subnano-Pd@SiO2 did not decrease significantly even after being recycled for 4 times.

Abstract:In order to study the effect of mixing condition on the thermo-sensitivity of chitosan/ sodium β-glycerophosphate (β-GP) solutions. The β-GP solution (50 wt%) was added dropwise in the chitosan solution(2 wt%), and the viscoelastic properties of the solutions were studied by off-line rheology. It is found that the system has thermal induced sol - gel transition character when the volume ratio of chitosan solution/β-GP solution is 8/2. When more β-GP solution was added, the sol-gel transition temperatures of the chitosan/β-GP solutions are similar, but the gel structure loose. Temperature is the important influence factor for the chitosan/β-GP solution. The solution is stable at the temperature of 4 °C and forms weak gel at 25 °C after a certain time. When the temperature is above 30 °C, sol-gel transition occurs quickly.

Abstract:2-Amino-4,5-dimethylthiophene-3-carbonitrile was first obtained through the modified Gewald reaction with butan-2-one, malononitrile and elemental sulfur as raw materials. Then sixteen fluorinated thieno[2,3-d]pyrimidine derivatives IIIa~IIIp were synthesized by the substitution reaction of substituted benzylamines with the key intermediate 4-chloro-5,6-dimethyl-2-(trifluoromethyl)thieno[2,3-d]pyrimidine, which was prepared directly from 2-amino-4,5-dimethylthiophene-3-carbonitrile and trifluoroacetic acid in the presence of phosphorous oxychloride via one-pot procedure. The structures of these target compounds were confirmed by 1HNMR, 13CNMR, IR, MS and elemental analysis. The crystal structure of compound IIIa was determined by X-ray single-crystal diffraction. The bioassay results suggest that the target compounds IIIa, IIIc and IIIf exhibit good in vitro antitumor activity. The target compounds IIIk~IIIp with an electron-donating substituent in the benzene ring display poor antitumor activity, but the antitumor activity is better (e.g. IIIc, IIIf and IIIi) when the meta-position of the benzene ring was substituted with an electron-withdrawing group, especially a fluorine atom. The half inhibitory concentration (IC50) values of compound IIIa against MCF-7 and HepG2 cells were 2.01 μmol/L and 2.44 μmol/L, respectively, while the IC50 values of IIIc against MCF-7 and HepG2 cells were 1.44 μmol/L and 1.47 μmol/L, respectively. Both of them indicate much better antitumor activity than the control group Gefitinib.

Abstract:To reduce the content of whey protein, heat-set mixed gels of potato protein and whey protein were prepared by partially replacing whey protein with potato protein at the ratio of 50/50 by weight. The physical properties of mixed protein gels at different total protein concentrations (40~80 g/L) were investigated by color, textural properties, moisture distribution and rheological properties. The results showed that the lowest gelation concentration of mixed protein gels was 50 g/L. Compared with whey protein gels formed at the lowest gelling concentration of 80 g/L, consumption of whey protein in those gels decreased by 2.20 times. When the protein concentration increased from 50 to 80 g/L, mixed protein gels exhibited yellow color in the appearance. Hardness and elasticity increased by 5.28 times and 5.90%, respectively, but the content of immobilized water decreased by 3.63%. The storage modulus G' showed weak relation with the frequency. Laser confocal microscopy and scanning electron microscopy showed that the mixed protein gels at the concentration of 80 g/L had uniform and compact gel network, small pore size, and clear spherical particle aggregation morphology, thus it had a higher G'. The results of FT-IR showed that the amount of β-folding and β-turn structures account for about 70% of the secondary structures in mixed protein gels. The results of solubility test showed that hydrogen bond and hydrophobic interaction made more contributions to maintaining the structure of mixed protein gels than disulfide bond.

Abstract:Peanut hull activated pyrolytic carbon (PHAPC) was prepared from discarded peanut hull with NaCl as activator by a simple one-step molten salt pyrolysis method. The structure, morphology and electrochemical properties of the materials were investigated by SEM, TEM, XRD, XPS, BET, CV and EIS. Compared with peanut hull pyrolysis carbon (PHPC) without molten salt activation, PHAPC presented richer pore structure and larger specific surface area, while exhibiting superior conductibility and electrochemical properties. The PHAPC or PHPC was modified on the surface of the glassy carbon electrode (GCE). The electrochemical behavior of rutin at these electrode (PHAPC/GCE or PHPC/GCE) was investigated by DPV. The results showed that the PHAPC/GCE showed higher electrochemical activity towards rutin than the PHPC/GCE. When the concentration of rutin was within the range of 0.05~10.00 μmol/L, the electrochemical current of rutin on PHAPC/GCE showed a linear relationship, with a detection limit of 0.05 μmol/L (S/N=3) and a sensitivity of 83.61 μA?(μmol/L)-1?cm?2. Moreover, the relative standard deviation (RSD) found 3.06% indicating good reproducibility of the electrode. The standard addition method was used for the detection of rutin in rutin tablets with excellent recovery percentages from 96.0％~101.5％.

Abstract:Microbial fuel cells (MFC) have the potential of generating electricity and removing nitrogen simultaneously in the treatment of nitrate containing wastewater. It is crucial to find a cathode modified material with low cost and improved performance of generating electricity and removing nitrogen for the commercial application of MFC in the field of wastewater treatment. Cuprous oxide/reduced graphene oxide (Cu₂O/rGO) composite which has the advantages of excellent electrochemical properties, hold a wide application prospect in replace of Pt-based material for improving performance of microbial fuel cells (MFCs). In this study, material characterization and oxygen reduction property were conducted to analyze the synthesis of Cu₂O/rGO composite materials after synthesis by reduction method. The electrochemical performance of Cu₂O/rGO cathode was analyzed after it was loaded on the surface of cathode carbon cloth. The enhancement effect of Cu₂O/rGO cathode on the power generation and nitrogen removal performance of MFC were investigated through the output voltage, power density and NO_3^--N removal rate of MFC. The mechanism of Cu₂O/rGO cathode enhancing MFC performance was investigated by measuring denitrifying enzyme activity and extracellular polymer. Results showed that Cu₂O/rGO which has a large number of mesoporous structures, provide more channels for electron transport, and Cu₂O/rGO has better redox reversibility. Compared with Pt/C cathode, the exchange current density of Cu₂O/rGO cathode increases by 33.53%, the electron transfer resistance decreases by 65.53%. The maximum average output voltage (662.54 mV), maximum power density (26.27 mW/cm^₂), NO_3^--N removal rate (83.33 mg NO_3^--N L/h) and average coulomb efficiency (32.02%) of Cu₂O/rGO-MFC were higher than those of Pt/C-MFC (485.33 mV, 16.98 mW/cm^₂, 7.38%, 41.67 mg NO_3^--N L/h). Cu₂O/rGO composite material enhance the activity of key enzymes and the content of protein-like components in denitrification of MFC cathode, improving the performance of electricity generation and nitrogen removal of Cu₂O/rGO-MFC.

Abstract:In order to avoid the harm of capsule raw materials to the environment, degradable ethyl cellulose ether (EC) was selected as the wall material, and essential oil microcapsules were prepared by solvent evaporation. The results showed that the stirring rate had a great influence on the particle size and surface micropores of microcapsules. When the stirring rate was 1200 r/min and the mass of EC and essential oil were 1 g and 1.25 g respectively, the median particle size of the microcapsules was 70.8 μm. The embedding rate was 44.3%. Then, the prepared essential oil microcapsule was used to prepare the hygroscopic and breathable composite fabric through the wet coating process. It could be seen from the SEM that this method retained the original shape of the substrate. The flavor retention rate after 30 days of release was 39.2%. This was due to the fact that the mass fraction of Linalyl Acetate in the encapsulated essential oil increased by 27.09%, which prolonged the storage life of the essential oil. The microcapsules were uniformly and massively distributed on the surface of the stretch coated fabric, making the fragrance value as high as 382. The air permeability of the stretched and un-stretched composite fabrics was more than 600 mm/s, the fragrance retention rate was more than 35% after washing for 5 times, and the quality remains more than 96% after rubbed for 50 times. The preparation method of the composite is simple and can effectively improve the problem that the air permeability and fastness cannot be obtained at the same time.