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          Volume 40,  2023 Issue 12
            Review and monographs
          • ZHUANG Yu, PENG Gang-yang, DUAN Xiao-jun, ZHU Yan-an, QU Jin-qing

            2023,40(12), DOI:

            Abstract:

            Due to its excellent performance, polyurethane emulsion is widely used in painting, protection and protection in construction, leather, metal anti-corrosion and other fields. Most of the existing polyurethane emulsions are petroleum-based products, and out of the need for sustainable development, with the rapid development of bio-based raw materials and large-scale commercialization, bio-based polyurethane emulsions have achieved rapid development. In this paper, the bio-based raw materials and additives for the synthesis of polyurethane emulsions, including bio-based isocyanates, polyols, chain extenders and other modified raw materials, analyze the new progress of lignin-based, vegetable oil-based, unnatural monomer-based and other bio-based polyurethane emulsions, point out the main problems faced by bio-based polyurethane emulsions, including insufficient raw material supply, high cost and insufficient product performance, and look forward to the development prospects of bio-based polyurethane emulsions in solvent-free, high bio-based content and multi-functional products.

          • FENG Ying, ZHANG Hong, YU Han-zhe, LI Ke-xin, ZHANG Jian-wei, DONG Xin

            2023,40(12), DOI:

            Abstract:

            Chitosan stabilized nanoscale zero-valent iron (CS-NZVI) is a novel composite material with both reducing and adsorption ability, which can be used for the removal of metal ions and arsenates in water and the degradation of aromatic dyes. This paper introduces the main methods and characteristics of CS-NZVI preparation, summarizes the mechanism and application research progress of CS-NZVI treatment of heavy metal ions, arsenic ions, aromatic organic compounds, etc. On this basis, the modification methods, material properties and application progress of several chitosan stabilized nano ferritic derivatives, such as chitosan modified CS-NZVI, metal catalyst modified CS-NZVI and composite modified CS-NZVI, were reviewed. Finally, suggestions and prospects for optimizing the preparation process of CS-NZVI, broadening the application conditions and improving the material properties were put forward, which provided ideas for further research.

          • YU Xiuming, ZHU Wentao, YANG Bin, HU Hao, YANG Jinhui, ZHOU Shukui

            2023,40(12), DOI:

            Abstract:

            The number and variety of solid waste have increased as a result of socioeconomic growth and human activity, and resourcization of solid waste has gained popularity across the globe. Waste resourcization has a lot of space for improvement against the backdrop of double carbon, which emphasizes the growth of the circular economy. Uranium(VI)-containing radioactive wastewater is produced by the nuclear industry's rapid advancement of nuclear technology, and it can be treated with adsorbent materials made of solid waste to achieve the goal of "treating waste with waste", reducing environmental pollution issues and promoting sustainable development. This paper introduces the preparation and modification methods of solid waste adsorbent materials, the mechanism of uranium removal, and summarizes some of the main solid waste adsorbent materials that can be used in uranium removal, such as agricultural and forestry solid waste, industrial solid waste, and municipal solid waste. It also provides an outlook on the future research direction of uranium adsorbent materials. It is pointed out that the uranium adsorption materials will be developed in the direction of efficient adsorption, green environmental protection and high added value.

          • CHEN Xiang-li, ZHANG Tian, LI Qian-qian, LI Biao, LI Kangkang

            2023,40(12), DOI:

            Abstract:

            Self-healing conductive gels have been widely used in electronic skin, flexible robots and wearable devices due to their excellent mechanical properties, good biocompatibility and extended material life. The structural adjustability of gel matrix and the diversity of conductive material selection also provide the possibility for the preparation of flexible sensors with different functions. In this paper, the research progress of self-healing gel in the mechanical, photoelectric and biological aspects of flexible sensors is reviewed. The classification, forming mechanism and properties of self-healing gel were introduced. Finally, the paper discusses the existing problems in this field and gives a brief outlook on its future development.

          • ZHENG Shu-fang, WANG Yu-yin, ZHANG Ze-kai, JIN Yu-ling

            2023,40(12), DOI:

            Abstract:

            Due to the advantages of lightweight, high sensitivity, wide pressure range, low cost and scalability, conductive polymer composites (CPCs) based on graphene/polymers with three-dimensional porous structures have been the optimal choice for the wearable and flexible strain sensors. In this article, the sensing mechanisms of the flexible strain sensors were first summarized, including crack propagation, overlapping-disconnection and tunneling effect. Meanwhile, three kinds of construction processes of CPCs with porous structures were introduced, including on the basis of polymer foam, graphene/polymer mixed dispersion and graphene foam, respectively. Furthermore, the sensing performances of the flexible strain sensors with porous structures prepared by the above-mentioned three techniques have been summarized, and the relevant examples of flexible strain sensors with porous structures in human motion monitoring fields were presented. Finally, the challenges and development prospects of porous and flexible strain sensors based on graphene/polymers were prospected.

          • WANG Ziwen, ZHANG Tongtong, HUANG Nengkun, ZHU Xinbao, TAN Jihuai

            2023,40(12), DOI:

            Abstract:

            Vegetable oil-based plasticizers are regarded as the most promising bio-based environmental plasticizers owing to the their wide source of raw materials, adjustable structure, excellent plasticity, non-toxicity and biodegradability. However, the high proportion of long chain alkyl in the structure of vegetable oil-based plasticizer results in poor compatibility with PVC resin, which is typically used as an auxiliary plasticizer, and the application value has not been fully incarnated. In recent years, domestic and foreign scholars have chemically modified the vegetable oil-based plasticizer structure and developed a series of multifunctional vegetable oil-based plasticizers (such as solubilizationt, heat tolerance, flame retardant, suppressed migration, etc.) to achieve the "improvement of quality and efficiency" of vegetable oil-based plasticizer. In this paper, beginning with the molecular structure design of vegetable oil, the existing literature was compiled, analyzed and summarized through the combination of molecular simulation, micro and macro analysis methods, and the "structure-activity" relationship between the structure of plasticizer and the performance of plasticized PVC products was established, aiming to provide a theoretical basis for the structural design and industrial production of high-performance and multi-functional vegetable oil-based plasticizer.

          • Functional materials
          • WANG Qian, YAN Yuting, ZHOU Fangfang, HUANG Yue

            2023,40(12), DOI:

            Abstract:

            Enrofloxacin is widely used in the treatment of animal and plant diseases due to its strong antibacterial activity and broad antibacterial spectrum. However, overuse and even abuse of enrofloxacin can lead to excessive residues in animal and plant food and harm human health through the food chain, so it is crucial to develop efficient methods for enrofloxacin detection. In this work, a novel electrochemical method for enrofloxacin detection is established based on the signal amplification strategy designed by collaborating terminal deoxynucleotidyl transferase (TdT) with G-quadruplex ribozyme. The binding of target enrofloxacin with specific aptamer triggers the extension reaction of TdT on the electrode surface, resulting in the formation of G-quadruplex ribozyme nanowires, which can play horseradish peroxidase activity to catalyze signal amplification, finally achieving highly sensitive and specific detection of enrofloxacin. The linear detection range of enrofloxacin is 0.5 ~ 50 ng/mL, and the limit of detection is as low as 0.043 ng/mL. In addition, the label free electrochemical biosensor is simple, fast and low cost, and has been successfully applied to the analysis of real food samples, showing good application potential.

          • XU Jing, XIANG Zhou-yang, WANG Qiang, SONG Tao

            2023,40(12), DOI:

            Abstract:

            A superhydrophobic surface was fabricated via a non-induced phase separation method by combination of two polymers (polyvinylidene fluoride and polydimethylsiloxane) enhanced with cellulose nanocrystals (CNCs). The aggregation of the polymers and particle sizes were both effectively reduced during the phase separation owing to the electrostatic repulsion between CNCs and their high surface area, which led to a construction of a fine and uniform micro - and nano-structures on the surface of the substrates, correspondingly endowed them a stable superhydrophobicity. The morphology and structure of the CNCs and superhydrophobic surfaces were characterized by FTIR, SEM, AFM, contact angle measuring instrument and 3D optical profilometer. It was found that the surface of the substrates had uniform micro-nano rough structure. The water contact angle was up to 158°, and the lowest rolling angle is 2°, indicating obvious superhydrophobic characteristics. After mechanical friction (over 500 times), acid-base treatment (pH 1 ~ 13), temperature change (-40 ~ 40°C) and ultraviolet irradiation (0 ~ 320 h), the superhydrophobicity of the substrate surface was not reduced obviously. In addition, the substrates had excellent self-cleaning and oil-water separation efficiency. The maximum separation efficiency of the super hydrophobic cotton cloth was up to 98.4%.

          • LIN Jiao-pan, GAO Jun-kai, PENG Hui-ting, SHI Qian, HAN Zhi, CHEN Yan

            2023,40(12), DOI:

            Abstract:

            PDA nanosheets were prepared by in-situ coating magnesium hydroxide nanosheets with hydrophobic cotton cloth as the substrate, polydopamine (PDA) as the raw material and magnesium hydroxide as the template, and then PDA nanosheets composite filter membrane (referred to as composite filter membrane) was prepared with hydrophobic cotton cloth as the substrate. The structure of the composite filter membrane was characterized by SEM, TEM, BET, FTIR, XPS, XRD and contact angle tester. The separation performance, recycling performance and anti-pollution performance of the composite filter membrane for oil-water mixture and emulsified oil were measured. The results showed that the introduction of PDA nanosheets significantly increased the surface roughness of the composite membrane. Under the condition of self-weight, the permeation fluxes of the composite membrane for oil-water mixture and emulsified oil were 2866.24 and 1015.13 L/(m2?h), respectively, and the separation efficiency was 99.1%. The permeation flux of the composite membrane for emulsified oil was 789.11 L/(m2?h) and the separation efficiency was 98.1% after repeated use for 10 times. In addition, PDA nanosheets also have universality and can cover different substrates for emulsified oil separation, which has good application prospects.

          • TAN Chunyu, YE Xiangdong, XI Changqin, LI Ji, WANG Quandai

            2023,40(12), DOI:

            Abstract:

            In order to improve the current situation of curtain wall glass through complex surface treatment process to reduce the light transmittance and light pollution of glass, and at the same time make it have excellent self-cleaning and anti-fog performance. In this paper, tannic acid (TA), carbon nanotubes (CNTs), dendritic nano-SiO2, ethyl orthosilicate (TEOS) and other basic raw materials were used to spray the solution onto the blank glass substrate through a low-cost spraying process. After curing at room temperature, TA-CNTs / SiO2 coated glass with self-cleaning and anti-fogging was obtained, which can be applied to glass curtain walls. The carbon nanotubes before and after modification were analyzed by Fourier transform infrared (FT-IR) and thermogravimetry (TG). The morphology of the samples was characterized by scanning electron microscope (SEM) and water contact angle (WCA). The effect of TEOS hydrolysate content on the contact angle and the effect of modified carbon nanotube content on the transmittance of the coating were investigated. Finally, the samples were tested for anti-fog, self-cleaning and wear resistance.The results show that when the TEOS hydrolysate is 6 g and the TA-CNTs is 0.16 g, the coating has super-hydrophilic effect ( CA, 2.5 ° ), and has excellent self-cleaning and anti-fogging effects. The addition of carbon nanotubes makes the surface of the coating more rough, which is conducive to reducing light reflection and reducing light pollution. When the content of TA-CNTs in the coating reached 0.002 g / cm2, the transmittance of the coating decreased to 60 %. At this time, the coating can maintain a certain transparency while having privacy. After 120 friction experiments, it still maintains superhydrophilicity and has good wear resistance.

          • LIU Yali, ZHANG Sufeng, HU Xuxu, LI Lei, LI Nan, LIU Ye

            2023,40(12), DOI:

            Abstract:

            Based on the three-dimensional porous and flexible scaffold structure of bacterial cellulose (BC) and the excellent conductivity of carbon nanotubes (MWCNT), a self-supporting conductive substrate was fabricated, and then manganese dioxide (MnO2) was electrodeposited on the substrate to construct a novel BC/MWCNT/MnO2 thin film electrode. Among them, the two components are closely combined through hydrogen bonds, synergistically endowing the composite substrate with excellent electrical conductivity and mechanical properties. The porous structure, electrolyte absorption characteristics and bridging structure of the honeycomb active MnO2 nanosheets of the BC/MWCNT composite membrane endow it with excellent electrochemical performance (at a current density of 1 mA cm-2, its areal and mass specific capacitances reach 1.17 F cm-2 and 200 F g-1, respectively) and remarkable cycling stability (the specific capacitance retention is stable at 96% after 10,000 cycles at a current density of 20 mA cm-2). Such binder-free thin-film electrodes are facile and inexpensive to prepare, and have great potential in the development of flexible energy storage devices.

          • SHENG Xiao, SHEN Yalong, ZHANG Chen, ZHANG Yiwen, LIU Shuling, WANG Shouxin

            2023,40(12), DOI:

            Abstract:

            Based on coumarin as fluorophore, 4-bromobutyryl as recognition group, a ratiometric fluorescent probe COCB for hydrazine was designed and synthesized. Its structure was confirmed by 1H NMR, 13C NMR and HRMS. The selective deprotection of the 4-bromobutyryl of COCB by hydrazine led to the recovery of the intramolecular charge transfer (ICT) process. COCB exhibited an attenuation of blue emission at 420 nm and an enhancement of cyan emission at 480 nm, indicating that it can be used as a ratiometric chemosensor for hydrazine. The probe COCB showed high selectivity, high sensitivity and strong anti-interference ability for hydrazine, and could detect hydrazine in a wide linear range (0-250 μmol/L) and pH range (6-11) with a detection limit as low as 0.15 μmol/L. In addition, COCB was easy to synthesize and had low cytotoxicity, and had been successfully used for the detection of hydrazine in actual water samples, soils and living cells.

          • Electronic chemicals
          • WANG Tian-yu, QI Duo, SHI Ying, LIU Li-zhi, CAI Yi-fei

            2023,40(12), DOI:

            Abstract:

            A multifunctional sodium alginate crosslinked polyethyleneimine (SAPEI) water-based binder with cross-linked network structure for lithium sulfide battery cathode was created using sodium alginate (SA) and polyethyleneimine (PEI) as the raw materials. The ability of the SAPEI binder for adhesion and polysulfide adsorption, as well as its effects on the composition and electrochemical functionality of the lithium sulfur battery cathode, were investigated. The findings demonstrate that the SAPEI binder has a stronger binding capacity than conventional commercial (PVDF) binder, and that the reaction's amide bond has an adsorption impact on polysulfide ions. After cycling, the lithium-sulfur battery with SAPEI binder had a more consistent microstructure and improved electrochemical performance. The specific discharge capacity is still 620 mA·h/g after 200 cycles of charging and discharging at a rate of 0.2 C, and the capacity retention rate can reach 72.5%, which is higher than that of a lithium-sulfur battery employing PVDF binder.

          • Biological engineering
          • XIAO Zhi-wei, ZHOU Ke-meng, AN Yu-meng, DAI Jian-ying, XIU Zhi-long, DANG Yan-yan, QUAN Chun-shan

            2023,40(12), DOI:

            Abstract:

            Liquorice residue, the residue of liquorice after the extraction of active ingredients, is rich in lignocellulose. The liquorice residue was pretreated with two dilute basic solutions (Na2CO3 aqueous solution and NaOH aqueous solution) and the mixtures of dilute basic solution (Na2CO3 aqueous solution or NaOH aqueous solution) and ethanolamine acetate, and the effects of different base concentrations and pretreatment temperatures on the composition and enzymatic hydrolysis of liquorice residue were studied. The results showed that the lignin removal reached 54.1% and cellulose recovery rate was 77.2% when the liquorice residue was pretreated with 2% (mass fraction) NaOH aqueous solution with a solid-liquid ratio (w/v) of 1:10 (i.e., 10 ml of solvent per gram of liquorice residue) for 1.5 h at 100 ℃, and the glucose yield was 53.5% after 24-h enzymatic digestion which was 4.0 times higher than that without pretreatment (10.6%). When the pretreated liquorice residue was subjected to high solid enzymatic digestion at a solid-liquid ratio of 3:10 with an enzyme dosage of 45 FPU/g of biomass for 72 h, the glucose concentration reached 86.2 g/L and xylose was 18.9 g/L. Using this hydrolysate as the carbon source for fermentation, the total production of 2,3-butanediol and acetoin was 43.9 g/L after 96-h fermentation, and the conversion rate was 0.42 g/g. Compared with the control group, the hydrolysate was more favorable to the growth of the bacteria, and the productivity of 2,3-butanediol and acetoin was increased, while the conversion rate was slightly lower.

          • Catalysis,separation and purification technology
          • YANG Jianguo, LI Jin-zhu, XU Yan, ZHAI Liu-bin, Zhang Hong-bo

            2023,40(12), DOI:

            Abstract:

            A carbamate organocatalyst (TEPA-EC) for the synthesis of methyl ethyl carbonate (EMC) was synthesized by the addition reaction between tetraethylenepentamine (TEPA) and ethylene carbonate (EC). The structure of TEPA-EC was characterized by FTIR and NMR, and the catalytic mechanism was analyzed. The effects of synthesis and application conditions of TEPA-EC were investigated on its catalytic activity and transesterification efficiency, respectively. The stability and water resistance of TEPA-EC were also assessed. The results shows that the hydroxyethyl tert-aminoformate group of TEPA-EC can facilitate the transesterification between dimethyl carbonate (DMC) and ethyl alcohol (EtOH) via synergistic hydrogen-bonding. The TEPA-EC catalyst of high catalytic activity can be obtained when EC reacts with TEPA at 140℃ for 2 hours by a molar ratio of 5∶1. When DMC reacts with EtOH by a molar ratio of 2∶1 at 78℃ for 7 hours and the amount of TEPA-EC accounts for 1% of the total mass of raw materials, the conversion of EtOH and selectivity of EMC are 59.50% and 83.77% respectively. The catalytic efficiency of TEPA-EC is comparable to that of sodium ethoxide used in industrial applications. For the transesterification under the same conditions as above, the conversion of EtOH and selectivity of EMC fluctuate around 62.35%, 86.03% and 57.33%, 87.91% respectively during 8 times of repeated use and 14 times of circulated use with water, when the amount of TEPA-EC catalyst is 3% of the total mass of raw material. TEPA-EC shows much better stability and water resistance than sodium ethoxide.

          • JIANG Chunyue, ZHANG Haitao, RONG Zeming

            2023,40(12), DOI:

            Abstract:

            Compared with the traditional process, the preparation of caprolactam by butadiene has the green, economical and environmentally friendly characteristics in which the partial hydrogenation of adiponitrile (ADN) to produce 6-aminohexonitrile (ACN) is the core step of the process. Ni/CaO ADN Ni-Fe/CaO catalysts were prepared by the deposition-precipitation method using urea as precipitant ADN applied to the partial hydrogenation of adiponitrileto prepare 6-aminohexanenitrile. XRD showed that FeNi3 alloy phase was formed in the catalyst after Fe doped, and TEM showed that the metal Ni became more dispersed after Fe doped. The effect of reaction temperature ADN reaction pressure on the hydrogenation performance of ADN was investigated. The experimental results showed that the ADN conversion was 87.5% and the ACN selectivity was 74.4% under mild conditions of 80 ℃, 4 MPa and 0.1 g of catalyst for 2h. ADN it was found that the catalyst could be regenerated after hydrogen reduction.

          • Shao Yuemei, Li Tingting, Wu Cai-e, Duan Yi-fan, Wang Xian-rong, Chen Lin, LI Xu, Wang Lei

            2023,40(12), DOI:

            Abstract:

            In order to investigate the optimal extraction process of Osmanthus fragrans flavonoids and their antifungal effect on Candida albicans (C. albicans), the following experiments were conducted. The extraction rates of Osmanthus fragrans flavonoids by ultrasonic extraction, ultrasonic-assisted enzyme extraction and ultrasonic-assisted double aqueous phase extraction were compared, the method with the highest extraction rate was selected for process optimization experiments of single factor and response surface; the components of four varieties of Osmanthus fragrans flavonoids were identified by liquid chromatography-mass spectrometry (UPLC-MS/MS). The inhibition effects of four varieties of Osmanthus fragrans flavonoids on C. albicans in terms of minimum inhibitory concentration (MIC), cell membrane integrity and biofilm formation were determined. The results showed that after the single-factor and response surface optimization experiments, the best extraction process of cinnamon flavonoids was 50 ℃, the liquid-solid ratio was 17 mL/g, and the ethanol concentration was 52%, and the best extraction rate were 13.88% for Thunbergii group, 8.79% for Latifolius group, 13.16% for Aurantiacus group, and 10.28% for Semperflorens group under these conditions. Under these conditions, the extraction rates of thunbergii group, latifolius group, aurantiacus group and semperflorens group were 13.88%, 8.79%, 13.16% and 10.28%, respectively. The antifungal effect of different varieties of Osmanthus fragrans flavonoids on C. albicans was different, among which, Osmanthus fragrans var. thunbergii had the best antifungal effect with MIC value of 1.5 mg/mL, which could significantly improve the permeability of the cell membrane of C. albicans within 24 h, leading to the efflux of cell contents, and the inhibition rate of biofilm formation could reach up to 46.59%. Therefore, cinnamon flavonoids can be studied and developed as natural antibacterial agents in depth.

          • Perfumes and essences
          • ZHANG Li-hua, LIU Shi-hao, JIN Xue-yuan, FENG Lu-yao, LI Shun-feng, LI Chang-wen, ZONG Wei

            2023,40(12), DOI:

            Abstract:

            Lactic acid bacteria fermentation changed the aroma composition of jujube juice, which may be related to the release of glycosidically bound volatiles (GBVs). The GBVs of fermented jujube juice was obtained by adsorption and elution with Amberlite XAD-2 resin, and the release regularity of GBVs was investigated under three treatment conditions: β-D- glucosidase enzymolysis (38 ℃, 48 h), acid hydrolysis (pH 1.0, 38 ℃, 4 d) and ultrasound treatment (280 W, 30 min), respectively, by electronic nose and headspace solid-phase microextraction-gas chromatography-mass spectrometry (GC-MS). The results showed that the types and contents of GBVs obtained by the three treatments were quite different. The specific manifestations were as follows: in quantity, a total of 16 aroma compounds were identified by ultrasonic treatment, and acids were the most abundant aroma compound. A total of 22 aroma compounds, mainly including acids and other components, were identified after acid hydrolysis of bound components compared to 32 ones with enzymatic hydrolysis, mainly including esters, alcohols and acids. In addition, the valuable aroma components of fermented jujube juice were analyzed by odor activity value (OAV), and it was found that damascenone and nonanal played a major role for the aroma of fermented jujube juice. Aldehydes and ketones were the main aroma components of fermented jujube juice by ultrasonic treatment and acidolysis treatment, while the esters, alcohols, aldehydes and ketones were the main aroma components for enzymatic hydrolysis. Therefore, β-D- glucosidase enzymatic treatment was more conducive to the release of many bonded aroma components in fermented jujube juice.

          • Drug and cosmetic materials
          • HUANG Yue-kun, YANG Cai-xin, FEN Hua-chao, YI Jing, DENG Qing-qing, TANG Ri-yuan

            2023,40(12), DOI:

            Abstract:

            In order to explore new lead compounds against Penicillium italicum(PI) and Penicillium digitatum(PD) on citrus, fifteen 2-(2-cyanophenoxy)-2-fluoroacetamides were designed and synthesized using salicylonitrile, ethyl bromofluoroacetate, and amines as the main starting materials. Their structures were confirmed by 1HNMR, 13CNMR and MS. The antibacterial activity of these compounds against PI and PD was studied by the mycelial growth rate method. The results showed that these compounds had certain antibacterial activity against the tested strains. Among them, six compounds such as Ⅰa[ 2-(2-cyanophenoxy)-2-fluoro-N-phenylacetamide],Ⅰf[2-(2-cyanophenoxy)-2-fluoro-N-(thiazol-2-yl)acetamide] have 80% ~ 100% inhibitory activity against the two bacteria at the mass concentration of 200 mg/L. The antibacterial activity of compound Ⅰh is the best among all compounds. At the mass concentration of 50 mg/L, it’s inhibition rates of PI and PD are 60.96% and 53.95%, respectively. The inhibitions rates are more than 30% at the mass concentration of 25 mg/L. The activity of 2-(2-cyanophenoxy)-2-fluoroacetamides against tested strains is better than 2,4-D(2,4-Dichlorophenoxyacetic acid).

          • Food and feedstuff chemicals
          • ZHANG Luyan, GUO Fengxian, YOU Jieyu, ZHANG Wei, WANG Yaosong

            2023,40(12), DOI:

            Abstract:

            As a gel forming material, ginkgo seed protein isolate (GSPI) was used. Following the addition of γ-aminobutyric acid (GABA) and L-citrulline (L-Cit) to the GSPI solutions and homogenization, the pH of sols was adjusted to pH 5.0, 6.0, and 7.0, respectively. Heat-induced gels were prepared from these pre-treated samples. Physiochemical properties, mechanical mechanics, protein electrophoresis, SEM, and FTIR were used to determine the physiochemical characteristics, gelation, and microstructure of the mixture of GSPI/GABA and GSPI/L-Cit. A hypothesis was proposed to investigate how GABA, L-Cit, and pH influence gelation and potential mechanisms. The results have shown that GABA/L-Cit have no influential effects on protein solubility, but they have the ability to reduce their hydrophobicity; GABA promoted protein aggregation and lowered their ζ-potentials, whereas L-Cit assisted protein dissociation but also increased ζ-potential of the sols at pH 7.0. Moreover, the two amino acids facilitated the folding of hydrophobic groups inside the protein molecule. Additionally, the two amino acids, especially L-Cit, significantly enhanced protein gelation, but significantly decreased it when pH was 6.0. Variations in these changes can be attributed to a pH-dependent manner.

          • Water treatment technology and environmental protection
          • LI Si-yu, ZHANG Quan-guo, WANG Fang, DI lu, ZHANG De-li, ZHANG Zhi-ping, YI Wei-ming, FU Peng

            2023,40(12), DOI:

            Abstract:

            In order to improve the degradation of organics in biogas slurry and electricity production of Microbial Fuel Cell (MFC), the combination of nano-Fe3O4 with MFC was proposed, loading nano-Fe3O4 on anode carbon felt (Fe3O4@carbon felt) and loading nano-Fe3O4 on biochar (Fe3O4@biochar) into the anode chamber. The performance of MFCs were comparatively studied. The results showed that the MFC both loading methods could successfully start, and the power production efficiency was much higher than that of the blank experiment without the intervention of nano-Fe3O4, with the maximum voltage of 699 and 707 mV, respectively, and the both maximum voltage value lasted up to 10 d. The maximum power density was increased by 43% and 31% in the Fe3O4@carbon felt (700 mW/m2) and Fe3O4@biochar (578 mW/m2) approaches, respectively, compared to that MFC without the use of Fe3O4 nanoparticles. The highest chemical oxygen demand (COD) degradation rate of 51.76% was obtained by using Fe3O4@carbon felt as the anode electrode; the direct application of Fe3O4@biochar had the greatest effect on the degradation of ammonium nitrogen, which decreased from (6800.14±57.86) mg/L to (689.14±37.29) mg/L after the application of Fe3O4@biochar, with a degradation rate of 89.87%.The microbial community structure of the MFC with the participation of nano-Fe3O4 tended to be rationalized, and both participation methods stimulated the growth of the main hydrolytic bacteria Clostridia. With the position of nano-Fe3O4 changing, the relative abundance of Clostridia in the MFC with Fe3O4@biochar directly inputting into the anode chamber and the MFC with Fe3O4@carbon felt as the anode electrode reached to 61.11% and 50.98%, respectively. Both had the highest content of Betaproteobacteria in electroactivation and denitrifying bacteria Sporosarcina was found on the post-reaction carbon felt.

          • DENG Yibo, WANG Guohua, XIE Shuibo, ZHANG Lantao, WANG Chenxu, HE Shan

            2023,40(12), DOI:

            Abstract:

            The modified biochar (PMBC+PSB) was produced by modifying pig manure biochar (PMBC) with phosphorus solubilizing bacteria (PSB), and its effect and mechanism of action on U(Ⅵ) removal in water were investigated. The results showed that the biochar modified with PMBC for 24 h(PMBC+PSB24) had the best effect on U(Ⅵ) removal, and the pores in the inner wall of the modified biochar were significantly increased, and the specific surface area and total pore volume of PMBC+PSB24 increased by 88.1% and 39.7%, respectively, compared with those before modification. The maximum adsorption capacity of PMBC+PSB24 for U(Ⅵ) in water was 555.19 mg/g, which was 24.44% higher than that of unmodified U(Ⅵ). The adsorption process was in accordance with the Freundlich isothermal model and the proposed secondary kinetic model. SEM and TEM characterization results showed that PMBC+PSB24 showed radial crystals on the surface and inside the bacterium, and the XRD results indicated that the crystals were metasuranite [K(UO2)(PO4)·3H2O].FTIR and XPS results showed that the abundance of functional groups on the surface of PMBC+PSB24 increased, and the main groups involved in adsorption were hydroxyl and phosphate groups. The main U(Ⅵ) removal mechanism of modified biochar was surface complexation and mineralization precipitation. After five adsorption-desorption cycles, the adsorption capacity of the modified biochar only decreased by 9.4%, which had good regeneration performance.

          • Xie Bimei, ZHENG Yan-ning, WANG Ying-bo, SUN Jian-hua, YANG Qi-feng, LIAO Dan-kui

            2023,40(12), DOI:

            Abstract:

            Nanozymes have attracted much attention in the field of environmental remediation due to their excellent catalytic activity. Elemental doping can improve the catalytic performance of nanozymes. A highly active copper-doped manganese dioxide(Cu-MnO2) oxidase-like nanozyme(referred to oxidase-like enzyme) was prepared by a one-step hydrothermal method, and its degradation of rhodamine B (RhB) dye was investigated. It has been shown that the catalytic activity of Cu-MnO2 is enhanced by the synergistic effect of Cu-MnO2 upon copper doping. With a solution pH of 3, an initial mass concentration of RhB of 50 mg/L, and a dose Cu-MnO2 dosage of 0.01 g, RhB was fully degraded within 30 min, and the degradation rate of RhB was still 75% after 5 times the catalyst used. In addition, the degradation rates of ciprofloxacin, ofloxacin, tetracycline, and hydroquinone were 88.86%, 90.47%, 92.62% and 90.99%, respectively. The mechanism of catalytic degradation of RhB by Cu-MnO2 oxidase-like enzyme showed that there were abundant holes (h+) in Cu-MnO2 rich in oxygen vacancies, which was beneficial for adsorbing and catalyzing dissolved oxygen to produce a large amount of singlet oxygen (1O2) and a small number of superoxide radicals (O2·-) and other reactive oxygen species for the rapid degradation of organic pollutants.

          • LU Yan, LUOZhong-qiu

            2023,40(12), DOI:

            Abstract:

            Using copper slag as raw material, NaOH and industrial sodium silicate as alkaline activator, copper slag-based magnetic zeolite-like geopolymer (Fe3O4@GM) was prepared, and then use the as-obtained geopolymer to removal Pb2+, Cu2+ and Zn2+. The effects of initial pH, adsorbent dosage and initial concentration on the adsorption performance were investigated. Meanwhile, adsorption isotherm and adsorption kinetic were analyzed, the adsorption behavior of the F3O4@GM was studied, and the adsorption mechanism was assumed. Moreover, a series of characterizations were employed to analyze the physical and chemical properties of adsorbent, including XRD, FTIR, SEM, BET and XPS. This isothermal adsorption results show that the Langmuir model is more suitable than the Freundlich model to describe the adsorption behavior, and the adsorption capacities for Pb2+, Cu2+, Zn2+ can reach up to 555 mg/g, 489 mg/g and 125 mg/g, respectively. The adsorption process fits the pseudo-second-order kinetic model. The high specific surface area of F3O4@GM improves the adsorption properties of the materials. The adsorption mechanisms are associated with ion exchange, electrostatic attraction, surface complexation and pore fixation. Overall, the F3O4@GM can be used as an eco-friendly, desirable and economic adsorbent in heavy metal polluted water treatment, providing a cheap and convenient choice for the treatment of heavy metal pollution, and realizing the recycling and harmless treatment of copper slag.

          • Fine chemical intermediates
          • ZHAO Ya-min, LI Ze-kun, WEI Li-liang, MA Yu-hao, LIU Rong

            2023,40(12), DOI:

            Abstract:

            Ru59063 is clinically used to treat prostate cancer and has a good effect. In this study, 4-amino-2- ( trifluoromethyl ) benzonitrile was used as raw material to prepare thioisocyanate by thiophosgene, and then [3+2] cycloaddition reaction with 2-aminoisobutyrate methyl ester hydrochloride was carried out to construct thiohydantoin ring, and then Ullmann C-N coupling reaction with halogenated ether was carried out. Finally, a total of 4 steps of hydroxyl deprotection were carried out to obtain Ru59063, with an overall yield of 61.5 %. Compared with the traditional method, the yield of this method is increased by more than 40 %, and no cyanide is used, It is more convenient and safer to prepare Ru59063.

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        Organizers:China Haohua (Dalian) Research & Design Institute of Chemical Industry Co., Ltd.
        Edited Published:
        Editor in Chief:HAN Jianguo
        Associate editor:CHEN Qu
        Address:201 Huangpu Road, Hi-Tech Zone, Dalian
        Phone:86-411-84699773, 84685669
        ISSN:1003-5214
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