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    2024年, 第54卷, 第3期 刊出日期:2024-03-22 上一期    下一期
    基础研究
    甜菜碱/AOS/Gemini季铵盐三元复合型泡排剂的研制与性能评价
    Preparation and performance of betaine/AOS/Gemini ternary surfactant foam for gas well deliquification
    张志升, 沈产量, 李建勋, 刘延强, 韩薇薇, 董三宝
    2024 (3):  239-249.  doi: 10.3969/j.issn.2097-2806.2024.03.001
    摘要 ( 196 )   HTML ( 24 )   PDF(2759KB) ( 91 )  

    泡沫排液技术是保障气井产量的重要手段,研发高性能的泡排剂极其关键。为适应高矿化度、高凝析油含量及高温等苛刻气井环境,以椰油酰胺丙基羟基磺基甜菜碱(CHSB)作为主剂,α-烯基磺酸钠(AOS)和合成的Gemini阳离子表面活性剂CAGB作为辅剂制备了一种高效环保的三元泡排体系。结果表明,三元复配体系AOS/CAGB/CHSB在摩尔比为12∶3∶35、总量为20 mmol/L时性能最优,泡沫体积和半衰期分别达到360 mL和30.27 min;在含有30%甲醇的泡排剂溶液中,测得的携液率最高可达31%,发泡率为95%;在含有0%~50%凝析油的泡排剂溶液中,三元泡沫体系表现出良好的性能,其中在凝析油含量为20%时,测得的携液率最高可达38%,发泡率为95%;优选的三元复配体系AOS/CAGB/CHSB对盐离子耐受性较差,加入螯合剂(氨三乙酸三钠(NTA))后,三元复配体系在矿化度为150 g/L的溶液中仍能稳定发泡和携液;温度大于50 ℃时,泡沫的携液率也逐渐增加,温度在90 ℃时,携液率在95%以上。此外,通过表面张力测试、泡沫微观结构观察也证实了该泡排剂体系存在的协同效应使其起泡、稳泡和泡沫携液能力得到有效提升。

    Foam-based deliquification is important to ensure the production of gas wells, therefore, there is no doubt that the development of high-performance foaming agents is extremely critical for the gas wells with high salinity, high condensate oil content and high temperature. For this reason, a highly efficient and environmentally friendly ternary foaming mixture was prepared by coconut oil amide propyl hydroxy sulfobetaine (CHSB), sodium α-olefin sulfonate (AOS) and synthetic Gemini cationic surfactant (CAGB) in this study. The results showed that the AOS/CAGB/CHSB mixture had the best performance when the molar ratio was 12∶3∶35 at the total amount of 20 mmol/L. The foam volume and half-life reached 360 mL and 30.27 min, respectively. In the foaming agent solution containing 30% methanol, the measured liquid unloading efficiency was 31%, and the foaming efficiency was 95%. With 0%-50% condensate oil, the ternary foaming mixture showed good performance. With 20% condensate oil, the liquid unloading efficiency was up to 38% and the foaming efficiency was 95%. The optimized AOS/CAGB/CHSB exhibited poor tolerance to salt ions. However, with trisodium aminotriacetate (NTA), the ternary complex system was still effective at a salinity of 150 g/L. At temperatures higher than 50 ℃, the liquid unloading efficiency of the foam also gradually increased, and the liquid unloading efficiency was above 95% at 90 ℃. In addition, the surface tension test and foam microstructure observation also confirmed the presence of synergy in foaming, foam stabilization and foam liquid unloading.

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    页岩油藏渗吸驱油剂体系性能评价
    Performance evaluation of a system of imbibition oil displacement agent in shale reservoir
    李国峰, 刘凯楠, 莫文龙, 马腾
    2024 (3):  250-258.  doi: 10.3969/j.issn.2097-2806.2024.03.002
    摘要 ( 92 )   HTML ( 12 )   PDF(2881KB) ( 75 )  

    由于页岩油藏的超低渗透率和复杂的孔隙结构,从页岩油储层中采油仍然是一个重大挑战。表面活性剂作为一种潜在的解决方案,通过降低界面张力和改变润湿性来提高非常规油藏的原油采收率。本研究旨在通过研究页岩油储层的自发渗吸行为,评价表面活性剂在页岩油藏中的应用潜力。结果表明,复配渗吸驱油体系0.15 wt% CA-90+0.15 wt% SDS,在地层条件下界面张力降低至1.03×10-2 mN/m;亲油岩心片润湿接触角降低了86°,岩石润湿性由油湿转变为水湿,毛管力由油渗吸驱油阻力转变为渗吸驱油动力;在含水率为70%时,乳状液黏度降低至23.4 mPa·s,其黏度接近原油黏度,但流动性更强,更有利于提高采收率;0.15 wt% CA-90和0.15 wt% SDS的动态吸附量分别为0.85和0.97 mg/g,具有较好的抗吸附能力,对页岩渗透率伤害率低于8%;滑溜水+复配体系的渗吸采收率可以达到31.27%,相比滑溜水体系中自发渗吸采收率(19.43%)提高了11.84%,渗吸驱油效率提高了60.94%,极大地提高了页岩油藏的采收率。

    The recovery of crude oil from shale oil reservoirs remains a significant challenge due to the ultra-low permeability and complex pore structures. Surfactants have been increasingly investigated as a potential method to enhance oil recovery in unconventional reservoirs by reducing interfacial tension and altering wettability. In this work, the performance of surfactants for potential application in shale oil reservoirs was evaluated by investigating spontaneous imbibition behavior. The results showed that the interfacial tension of 0.15 wt% CA-90+0.15 wt% SDS was reduced to 1.03×10-2 mN/m under formation conditions. The wetting contact angle of the oil-wet core sheet was reduced from 135.5° to 49.5°, i.e., the wettability of the rock was changed from oil-wet to water-wet, and the capillary force was thus changed from resistance for oil imbibition to driving force. When the water content was 70%, the viscosity of the emulsion decreased to 23.4 mPa·s which was close to the viscosity of crude oil, but the fluidity was higher, which was more conducive to improving oil recovery. The dynamic adsorption capacities of 0.15 wt% CA-90 and 0.15 wt% SDS were 0.85 mg/g and 0.97 mg/g, respectively, which had good anti-adsorption ability, and the damage rate of shale permeability was less than 8%. The imbibition recovery of slick water+compounded system could reach 31.27%, which was much higher than that of spontaneous imbibition recovery in slick water system (19.43%), and the imbibition oil displacement efficiency was thus increased by 60.94%, which greatly improved the oil recovery for shale reservoirs.

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    科技讲座
    化妆品植物原料(Ⅶ)——抗真菌的植物原料的研究与开发
    Botanical cosmetic ingredients (VII)Research and development of plant antifungal
    柳婧璇, 金建明, 吴华
    2024 (3):  259-266.  doi: 10.3969/j.issn.2097-2806.2024.03.003
    摘要 ( 138 )   HTML ( 15 )   PDF(1458KB) ( 1221 )  

    文章介绍了皮肤真菌及其相关皮肤疾病,总结了植物提取物的抗真菌作用机理及其相应作用靶点。植物中具有抗真菌的活性成分主要为酚类、生物碱、黄酮、萜类、甾体和精油等。这些植物抗真菌活性成分的作用机制主要通过破坏真菌细胞壁和细胞膜结构而产生抗真菌功效:破坏细胞壁结构的作用靶点是抑制β-葡聚糖合酶、几丁质合酶和甘露聚糖合酶活性;作用于细胞膜的靶点是细胞膜的结构组分麦角甾醇和鞘脂,通过抑制其相关合成酶麦角甾醇合酶、丝氨酸软脂酰辅酶A转移酶、神经酰胺合酶和肌糖磷脂酰神经酰胺合酶,以及直接靶向结合麦角甾醇和鞘脂来破坏真菌细胞膜结构;另外,酚类、生物碱、黄酮、萜类和精油也可以靶向作用于线粒体,通过诱导活性氧积累、抑制ATP合成和质子泵,破坏线粒体呼吸和代谢系统,而产生抗真菌作用。文章通过对植物中的不同抗真菌活性成分和作用机制的阐述,希望能为抗真菌植物原料在化妆品中的开发提供借鉴,更好地维持皮肤健康。

    This paper describes skin fungi and fungal skin infections, and summarizes the antifungal mechanism and the corresponding drug targets of the bioactive compounds from plants. The active antifungal compounds from plants include polyphenols, alkaloids, flavonoids, terpenoids, steroids and essential oils, etc. The main antifungal mechanism is inhibition of fungal cell wall and cell membrane biosynthesis. The target of cell wall biosynthesis inhibition is via inhibiting the activities of β-glucan synthetase, chitin synthase and mannan synthase. And the target of cell membrane biosynthesis inhibition is via inhibiting the synthesis of the structural components, ergosterol and sphingolipids. By inhibiting ergosterol synthetase, serine palmitoyltransferase, ceramide synthase and myo-inositol phosphatidyl ceramide synthase, the active components from plants can also directly bind to ergosterol and sphingolipids and destruct the cell membrane. In addition, phenols, alkaloids, flavonoids, terpenoids and essential oils also target mitochondrion to display antifungal activity, by inducing reactive oxygen species (ROS) accumulation, inhibiting ATP biosynthesis and proton pumps, and disrupt the mitochondrial respiration and metabolic system. This paper has reviewed the antifungal mechanisms of bioactive compounds from plants, hoping to provide a reference for the applications of plant materials in cosmetics, for a better maintaining of skin health.

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    开发与应用
    放射性污染衣物洗涤剂去污效果评价
    Evaluation of decontamination effect of a laundry detergent for radioactive contaminants
    高志婷, 郭丽潇, 陈崔冬慧, 张宇航, 罗丹, 武明亮, 台秀梅
    2024 (3):  267-272.  doi: 10.3969/j.issn.2097-2806.2024.03.004
    摘要 ( 53 )   HTML ( 8 )   PDF(2149KB) ( 27 )  

    核工业日常放射性污染衣物的去污可以实现废物最小化,资源重复利用,同时减少辐射对人体健康的损害。一般商用的洗衣液/洗衣粉可以满足对油污及汗渍的去除,但是对放射性核素如锶、铀难以去除。为了解决这些问题,采用自制的配方制备了去污剂,参考GB/T 13174和GB/T 14057.2建立了去污效果评价方法并对其进行去污性能评价,且与常用的商用市售的洗衣液进行对比。结果表明,该去污剂对放射性污染具有良好的去污效果,达到80%以上,综合去污性能优于商用市售的洗衣液产品。对模拟的油、灰尘渍、人体油脂渍具有良好的去污能力,对蛋白渍去污效果较差,可以满足对核工业日常操作中放射性污染、工作人员的汗渍污染和机械设备的油污污染衣服的去污,使其有望成为一种去除核工业日常衣物放射性污染的新型产品。

    Decontamination of the radioactively contaminated daily clothing in nuclear industry can minimize waste, reuse resources, and reduce the radiation damage to human health. Normal commercial laundry detergents can meet the requirements for removing oil and sweat stains, but they are difficult to remove radioactive nuclides such as strontium and uranium. Currently, many foreign companies have specialized products for radioactively contaminated clothing, such as HAKA and FEVDI, but there are few in China. To solve this problem, in this work, a detergent was prepared using a self-made formula. The evaluation method on decontamination effect was established with reference to GB/T 13174 and GB/T 14057.2, and the decontamination performance of the detergent was evaluated. The homemade detergent was compared with commercially available laundry detergents. The results showed that the detergent had good decontamination effects on radioactive pollutants, reaching over 80%, and its comprehensive decontamination performance was superior to commercial laundry detergents. It had good detergency for simulated stains of oil, dust and sebum. But it had poor detergency for protein stains. This detergent could meet the requirements in daily operations of nuclear industry for decontamination of radioactive contaminants, sweat stains of workers, and oil stains of machinery and equipment, which was expected to become a new product for removing radioactive contamination from daily clothing in nuclear industry.

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    多孔氮化硼材料的制备及其吸附性能研究
    Preparation and adsorption properties of porous boron nitride materials
    段玉婷, 赵樱淼, 沈绥, 卢振西, 梁兵, 龙佳朋
    2024 (3):  273-281.  doi: 10.3969/j.issn.2097-2806.2024.03.005
    摘要 ( 67 )   HTML ( 3 )   PDF(1946KB) ( 37 )  

    以二甲胺、三氯化硼、氨气和甲胺为原料,通过多步反应得到氮化硼前驱体三(甲胺基)环硼氮烷,经高温烧结后得到多孔氮化硼材料。通过FTIR、NMR对氮化硼前驱体中间体二氯(二甲胺基)硼烷和三(二甲胺基)环硼氮烷以及前驱体三(甲胺基)环硼氮烷的结构进行表征。利用XRD和SEM对多孔氮化硼结构和形貌进行表征。结果表明:通过反应合成前驱体中间物,最终能够合成出含碳量较低的氮化硼前驱体三(甲胺基)环硼氮烷。研究了多孔氮化硼材料对重金属离子的吸附能力,确定了多孔氮化硼材料对各种金属离子的吸附能力。研究发现:利用前驱体中间物制备出的多孔氮化硼具有较高的比表面积,吸附性能优异,能够有效的去除掉溶液中的重金属离子。使用有机前驱体法制备氮化硼弥补了无机制备中元素分布不均,易吸潮,易粉化的缺点。

    By using the precursor conversion method, one-dimensional boron nitride fibers, two-dimensional boron nitride films and coatings, and three-dimensional boron nitride composite materials have been prepared, which cannot be prepared by traditional preparation methods. Dimethylamine, boron trichloride, ammonia and methylamine were used as raw materials to obtain the boron nitride precursor tri(methylamino) borazine by multi-step reaction, and the boron nitride porous materials were obtained by high temperature sintering. The structures of the intermediates dichlorodimethylamino borane and tri(dimethylamine) borazine and the precursor tri(methylamino) borazine were characterized by FTIR and NMR. The porous boron nitride structures and morphologies were characterized by XRD and SEM. The results show that tri(methylamino) borazine with low carbon content can be synthesized through the synthesis of precursor intermediates. The adsorption capacity of porous boron nitride materials for various metal ions was determined by investigating the adsorption capacity of porous boron nitride materials for metal ions. The results show that the porous boron nitride prepared by using precursor intermediates has high specific surface area and excellent adsorption performance, which can effectively remove the metal ions from the solution and provide new ideas for the preparation of boron nitride adsorption materials. This method solves the problems of low industrialization yield and high difficulty. The use of organic precursor method to prepare boron nitride compensates for the shortcomings of uneven element distribution, easy moisture absorption, and easy pulverization in inorganic preparation, providing new ideas for the preparation of adsorbents.

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    中药复方MHC-20的抗化脓性链球菌功效与作用机制探究
    Efficacies and mechanisms of a formula of Chinese medicinal plants (MHC-20) against Streptococcus pyogenes
    胡翠翠, 周代红, 陈欣菀, 钟佳伶, 茆灿泉
    2024 (3):  282-289.  doi: 10.3969/j.issn.2097-2806.2024.03.006
    摘要 ( 69 )   HTML ( 4 )   PDF(1938KB) ( 54 )  

    以化脓性链球菌(Streptococcus pyogenes)为研究对象,探究了MHC-20的抑菌性能及作用机制。通过微量肉汤稀释法以及常量稀释法测得MHC-20对化脓性链球菌的MIC值为31.25 μg/mL或0.31%,并且对金黄色葡萄球菌以及白色念珠菌等均有较强杀伤作用。瞬时杀菌活性结果表明:MHC-20在5 min时可以完全杀死化脓性链球菌。定量生物膜与疏水性测定结果表明:MHC-20能够极显著降低化脓性链球菌细胞表面疏水性(P<0.000 1)以及极显著抑制生物膜的形成(P<0.01)。细胞膜通透性测定结果表明:MHC-20作用下菌液相对电导率、碱性磷酸酶均上升、蛋白严重泄露,并且呈浓度依赖性。扫描电子显微镜结果表明:MHC-20对菌体形态有很强的破坏作用。最后,构建了小鼠化脓性链球菌皮肤感染模型,结果表明:复方MHC-20可以促进创口恢复,极显著抑制创口的细菌(P<0.01),5% MHC-20与20% MHC-20均极显著降低小鼠血清以及创口炎症因子IL-6表达(P<0.001),20% MHC-20极显著降低白细胞的表达(P<0.01),综上所述,MHC-20有望成为广谱抗菌剂以及抗化脓性链球菌皮肤感染的有效药物。

    The antimicrobial properties and mechanisms of a formula of Chinese medicinal plants (MHC-20) against Streptococcus pyogenes were studied. The MIC of MHC-20 against S. pyogenes was 31.25 μg/mL or 0.31% as measured by broth micro-or macro-dilution. MHC-20 was also found to have strong killing effects on Staphylococcus aureus, Escherichia coli and Candida albicans. The results of instantaneous bactericidal activity showed that MHC-20 was able to kill S. pyogenes completely in 5 min. It could also significantly reduce the cell surface hydrophobicity and inhibit the formation of biofilm. Cell membrane permeability test showed that MHC-20 could induce the increase of relative conductivity and alkaline phosphatase, as well as the protein leakage, in a concentration-dependent manner. The results of scanning electron microscopy further confirmed that MHC-20 had a strong destructive effect on cell morphology. Finally, a mouse model of cutaneous infection with S. pyogenes was established. It was shown that MHC-20 could promote wound healing and significantly inhibit the loading concentration of S. pyogenesP<0.01); 5% MHC-20 and 20% MHC-20 significantly decreased the expression of IL-6 in serum and tissue of the mice (P<0.001). 20% MHC-20 significantly decreased the expression of leukocytes (P<0.01). In conclusion, MHC-20 had the potential to be developed into a broad-spectrum antibiotic and an effective drug for cutaneous infection with S. pyogenes.

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    三乙烯四胺固化单宁吸附剂制备及性能研究
    Preparation and adsorption performance of tannin cured with triethylenetetramine
    金绍娣, 许雪儿, 顾东雅
    2024 (3):  290-297.  doi: 10.3969/j.issn.2097-2806.2024.03.007
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    利用曼尼希反应将三乙烯四胺固化到单宁表面,制备得到胺化改性单宁吸附剂TETA-TA,并通过正交实验优化制备工艺。采用红外光谱、扫描电镜、比表面积及孔隙度分析仪对TETA-TA进行了结构表征,探讨了其对Cd2+和Pb2+的吸附性能,研究不同pH值、时间、金属离子初始质量浓度对吸附的影响。正交结果表明反应最佳条件为:反应温度为80 ℃,反应时间为4 h,醋酸用量为4%(w/%),n(TA)∶n(TETA)∶n(甲醛)=1∶2∶2.5。吸附实验表明:pH值对吸附平衡影响显著,Cd2+和Pb2+最佳pH值均为5.0;TETA-TA对Cd2+的吸附在60 min内能快速达到平衡,对Pb2+能持续24 h的吸附,吸附动力学符合准二级反应动力学模型,为化学吸附;提高金属离子初始质量浓度可以增大平衡吸附量,Cd2+的等温线数据对Langmuir模型线性拟合系数能达到0.995,理论吸附最大值为150.41 mg/g,Pb2+的等温线数据对Sips模型线性拟合较好,理论吸附最大值为210.45 mg/g,推测对Pb2+的吸附除了螯合、氧化还原等化学反应,还存在静电和离子交换作用,氨基和酚羟基为主要参与官能团;TETA-TA对Cd2+和Pb2+可以实现同时吸附,再生5次后仍具有较强的吸附性能。

    An amine-modified tannin adsorbent (TETA-TA) was prepared by Mannich reaction, in which triethylenetetramine (TETA) was used to cure tannin, and its preparation process was optimized by orthogonal experiment. The structure of TETA-TA was characterized by FT-IR, SEM and BET, and the adsorption properties of the adsorbent to Cd2+ and Pb2+ were investigated at different pH, different adsorption time and different initial concentrations of metal ions. The results of orthogonal experiment showed that, when the molar ratio of tannin to TETA to formaldehyde was 1∶2∶2.5, the reaction temperature was 80 ℃, the reaction time was 4 h and the dosage of acetic acid was 4%, the experiment had the best preparation conditions. The results of adsorption indicated that, the adsorption capacity for Cd2+ and Pb2+ greatly depended on the pH, and the optimal pH values for Cd2+ and Pb2+ were both 5.0. The adsorption of Cd2+ was rapid, which could quickly reach adsorption equilibrium within 60 min, but the adsorption of Pb2+ could continue for 24 h. The adsorption process of Cd2+ and Pb2+ by TETA-TA conformed to the pseudo-second-order kinetic model, which was a chemical adsorption process. Higher initial concentrations of metal ions could lead to higher equilibrium adsorption capacity. The adsorption isotherm of Cd2+ could be well described by Langmuir equation (R2=0.995), and the theoretical maximum adsorption capacity was 150.41 mg/g. The adsorption isotherm of Pb2+ could be well fitted with Sips equation, and the theoretical maximum adsorption capacity was 210.45 mg/g. The main adsorption mechanism for Pb2+was speculated to be chelation and redox reaction between Pb2+ and hydroxyl/amine groups on the surface of the adsorbent, which were accompanied with ion exchange and electrostatic adsorption. It was also found that when more than one kind of metal ions coexisted in aqueous solution, the equilibrium adsorption capacity for each was not affected by others, implying that the TETA-TA adsorbent was effective in simultaneous removal of these ions. The test results of regeneration and reusability indicated that the TETA-TA adsorbent was suitable for repeated use for more than five times.

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    Fe3O4基核壳纳米结构材料的制备及顺磁性研究
    Preparation and paramagnetic study of Fe3O4-based core-shell nanostructured materials
    胡可云
    2024 (3):  298-304.  doi: 10.3969/j.issn.2097-2806.2024.03.008
    摘要 ( 213 )   HTML ( 2 )   PDF(2013KB) ( 66 )  

    以Fe3O4为磁核,SiO2为外壳,制备了Fe3O4@SiO2核壳纳米结构材料,使用三乙氧基硅烷对Fe3O4@SiO2进行表面亲水改性,研究了亲水改性对Fe3O4@SiO2顺磁性能和催化性能的影响。结果表明:立方相结构的Fe3O4是核壳材料中主要的晶体相,表面的SiO2为非晶态,表面亲水处理后未改变Fe3O4@SiO2的晶格结构,Fe3O4@SiO2为80~110 nm的不规则颗粒状,SiO2包覆在Fe3O4外部,亲水处理后改善了颗粒的分布均匀性。亲水处理的Fe3O4@SiO2的饱和磁化强度降低至20.31 emu/g,具有超顺磁性。以含Cd2+的金属废水为吸附降解对象,表面亲水处理后的Fe3O4@SiO2去除率提高至94.2%,二级动力学模型更适合于Fe3O4@SiO2对Cd2+的吸附,模型的相关系数为0.994 3,拟合效果更好,表明了Fe3O4@SiO2对Cd2+的吸附速率受化学吸附的影响较大。

    Fe3O4@SiO2 core-shell nanostructured materials were prepared with Fe3O4 as magnetic core and SiO2 as shell. Surface hydrophilic modification of Fe3O4@SiO2 was carried out with triethoxysilane. The effects of hydrophilic modification on its paramagnetism and catalytic properties were studied. The results showed that Fe3O4 with cubic structure was the main crystal phase in the core-shell materials. The SiO2 at surface was amorphous, and the crystal structure of Fe3O4@SiO2 remained unchanged after surface hydrophilic modification. The Fe3O4@SiO2 material was irregular particles of 80-110 nm, in which the Fe3O4 was coated with SiO2. The saturated magnetization of the Fe3O4@SiO2 after hydrophilic treatment was reduced to 20.31 emu/g, indicative of superparamagnetism. This nanomaterial was applied to the wastewater containing Cd2+ for adsorption and degradation, where the removal rate was increased to 94.2%. The second-order kinetic model was more suitable for the adsorption of Cd2+ with Fe3O4@SiO2, and the correlation coefficient of the model was 0.994 3, showing good fitting. The results showed that the adsorption rate of Cd2+ by Fe3O4@SiO2 was greatly affected by chemisorption.

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    基于网络药理学的化妆品原料粉防己抗敏作用机制分析
    Analysis of the mechanism of anti-sensitive skin effect of cosmetic raw material Stephania tetrandra based on network pharmacology
    毕武, 潘小红, 涂晓琴, 殷帅, 孙辉
    2024 (3):  305-312.  doi: 10.3969/j.issn.2097-2806.2024.03.009
    摘要 ( 109 )   HTML ( 12 )   PDF(2549KB) ( 64 )  

    采用网络药理学方法探索化妆品原料粉防己对敏感肌肤的抗敏作用机制。通过TCMSP、中国知网、PubMed等数据库收集粉防己的主要化学成分,并利用SwissTargetPrediction预测其靶点,与从Genecards数据库获得的疾病靶点取交集后采用String数据库构建蛋白质相互作用(PPI)网络,采用Cytoscape3.9.1软件分析获得核心靶点,再运用DAVID在线数据库对核心靶点进行基因GO功能分析和KEGG通路富集分析,Cytoscape3.9.1软件构建粉防己活性成分-靶点交互网络。共筛选出粉防己潜在活性成分50个及相应靶点682个,敏感肌肤疾病相关靶点2 389个,交集靶点295个,其中核心靶点39个。GO富集分析结果显示,39个核心靶点主要涉及蛋白磷酸化、信号转导、转录调控、基因表达等多种生物学过程。KEGG通路富集分析结果显示,粉防己发挥抗敏作用可能与VEGF信号通路、HIF-1信号通路、ErbB信号通路、PI3K-Akt信号通路密切相关。粉防己中荷包牡丹碱、千金藤素、防己诺林碱等活性成分可能是通过作用于JAK2、JAK3、SYC等靶点发挥抗敏作用,体现了粉防己多成分-多靶点-多通路的作用特点。

    Explore the mechanism of anti-sensitive skin effect of cosmetic raw material Stephania tetrandra on sensitive skin using a network pharmacological approach. The main chemical components of Stephania tetrandra were collected through TCMSP, CNKI, PubMed and other databases, and their targets were predicted using Swiss Target Prediction, intersected with the disease targets obtained from Genecards database and then used String database to construct protein interaction (PPI) network. Cytoscape3.9.1 software was used to analyze the core targets, and the DAVID online database was used to perform GO functional analysis and KEGG pathway enrichment analysis on the core targets. The results of GO enrichment analysis show that the 39 core targets are mainly involved in various biological processes such as protein phosphorylation, signal transduction, transcriptional regulation and gene expression. The results of KEGG pathway enrichment analysis show that the anti-sensitive skin effect of Stephania tetrandra may be closely related to VEGF signaling pathway, HIF-1 signaling pathway, ErbB signaling pathway and PI3K-Akt signaling pathway. The active ingredients in Stephania tetrandra, such as Dicentrined, Cepharanthine and Fangchinoline, may exert their anti-sensitive skin effects by acting on the targets of JAK2, JAK3 and SYC, reflecting the multicomponent-multitarget-multipathway action characteristics of Stephania tetrandra.

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    异橙黄酮的抗衰老及抗氧化功效研究
    Study on the anti-aging and antioxidant effects of isosinensetin
    李瑶瑶
    2024 (3):  313-319.  doi: 10.3969/j.issn.2097-2806.2024.03.010
    摘要 ( 133 )   HTML ( 17 )   PDF(1770KB) ( 78 )  

    考察异橙黄酮(Isosinensetin,ISO)经皮给药对D-半乳糖(D-gal)诱导的皮肤衰老小鼠的抗衰老和抗氧化功效。将小鼠分为6组(n=12):分别为C组、D-gal组、D-gal+L-ISO组、D-gal+M-ISO组、D-gal+H-ISO组和D-gal+H-ISO+ML385组。在小鼠背部连续6周皮下注射1 g/ (kg·d)的D-gal建立皮肤衰老小鼠模型。D-gal注射当天开始,C组和D-gal组小鼠背部脱毛区域涂抹雪花膏,D-gal+L-ISO组、D-gal+M-ISO组和D-gal+H-ISO组小鼠分别涂抹50,100和200 mg/kg的异橙黄酮乳膏。D-gal+H-ISO+ML385组小鼠涂抹200 mg/kg的异橙黄酮乳膏,并腹腔注射30 mg/ (kg·d)核因子E2相关因子2(Nrf2)抑制剂ML385。涂抹量为2 mg/cm2。经皮给药6周后,检测小鼠的体重、皮肤含水量、皮肤抗氧化指标、羟脯氨酸(HYP)和透明质酸(HA)水平。采用苏木素伊红(HE)染色观察皮肤形态。采用RT-qPCR检测皮肤中COL1A1、COL3A1、基质金属蛋白酶(MMP)-1和MMP-3的转录水平。采用Western blotting检测皮肤中Nrf2(细胞核)、Kelch样ECH相关蛋白1(Keap1)和血红素加氧酶-1(HO-1)的蛋白水平。结果显示,3个剂量的异橙黄酮经皮给药均升高了皮肤衰老小鼠的皮肤含水量,改善了皮肤形态,升高了超氧化物歧化酶(SOD)、过氧化氢酶(CAT)和谷胱甘肽过氧化物酶(GSH-Px)水平,降低了丙二醛(MDA)水平,升高了HYP和HA水平,升高了COL1A1和COL3A1转录水平,降低了MMP-1和MMP-3转录水平,升高了Nrf2(细胞核)和HO-1蛋白水平,降低了Keap1蛋白水平(P<0.05)。ML385减弱了异橙黄酮的抗衰老及抗氧化功效(P<0.05)。总之,异橙黄酮经皮给药通过激活Nrf2通路提高D-gal诱导的皮肤衰老小鼠的抗衰老和抗氧化能力。

    The study aimed to investigate the anti-aging and antioxidant effects of isosinensetin (ISO) on skin aging mice induced by D-galactose (D-gal). The mice were divided into 6 groups (n=12): C group, D-gal group, D-gal+L-ISO group, D-gal+M-ISO group, D-gal+H-ISO group and D-gal+H-ISO+ML385 group. The skin aging mouse model was established by subcutaneous injection of D-gal of 1 g/ (kg·d) into the back of mice for 6 weeks. From the day of D-gal injection, mice in C group and D-gal group were applied with snow cream on their back depilation area, while mice in D-gal+L-ISO group, D-gal+M-ISO group and D-gal+H-ISO group were applied with 50, 100 and 200 mg/kg isosinensetin cream, respectively. The mice in D-gal+H-ISO+ML385 group were applied with 200 mg/kg isosinensetin cream and intraperitoneally injected with 30 mg/(kg·d) nuclear factor E2 related factor 2 (Nrf2) inhibitor ML385. The application amount was 2 mg/cm2. After 6 weeks of transdermal administration, the body weight, skin water content, skin antioxidant index, hydroxyproline (HYP) and hyaluronic acid (HA) levels were measured. The skin morphology was observed by HE staining. The transcriptional levels of COL1A1, COL3A1, matrix metalloproteinase (MMP) -1 and MMP-3 in skin were detected by RT-qPCR. The protein levels of Nrf2 (nucleus), Kelch-like ECH associated Protein 1 (Keap1) and heme oxygenase-1 (HO-1) in skin were detected by Western blotting. The results show that all three doses of isosinensetin increases skin water content, improves skin morphology, increases superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px) levels, decreases malondialdehyde (MDA) levels, increases HYP and HA levels, increases COL1A1 and COL3A1 mRNA levels, decreases MMP-1 and MMP-3 mRNA levels, increases Nrf2 (nucleus) and HO-1 protein levels, and decreases Keap1 protein levels in skin aging mice (P<0.05). ML385 attenuates the anti-aging and antioxidant effects of isosinensetin (P<0.05). In short, transdermal administration of isosinensetin can improve the anti-aging and antioxidant ability of D-gal-induced skin aging mice by activating Nrf2 pathway.

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    专论与综述
    4-取代酚诱导化学性白斑的机制及研究进展
    Mechanism and research progress of chemical leukoderma induced by 4-substituted phenols
    张婉萍, 彭祺, 张冬梅, 郑时莲, 蒋汶, 顾理浩
    2024 (3):  320-328.  doi: 10.3969/j.issn.2097-2806.2024.03.011
    摘要 ( 71 )   HTML ( 10 )   PDF(1406KB) ( 100 )  

    4-取代酚是一类广泛应用于制药、农药、染料、食品添加剂以及化妆品中的有机化合物。4-取代酚在化妆品中的应用主要是由于其与酪氨酸的结构上的相似性,使其具有独特的抑制酪氨酸酶活性以及抑制皮肤中黑色素形成的效果,因此包括熊果苷、白藜芦醇等化学物质在内,已有多种4-取代酚作为美白成分用于化妆品中。但包括杜鹃醇在内的4-取代酚同时也具有一定安全风险,大量研究表明许多4-取代酚具有黑素细胞毒性,且不同的取代基也会对黑素细胞毒性的诱导途径、毒性强弱等产生不同的影响,使用不当可能会诱发白癜风(Vitiligo)和白斑病(Leukoderma)的产生,对消费者的健康造成损害。本文综述了4-取代酚及杜鹃醇的美白及黑素细胞毒性机制,以及不同国家发生白斑病的案例,以期为开发更安全的有美白效果的化学物质提供参考。

    4-substituted phenols are a class of organic compounds widely used in pharmaceuticals, pesticides, dyes, food additives and cosmetics. The application of 4-substituted phenols in cosmetics is mainly due to its structural similarity with tyrosine, which makes it have a unique effect of inhibiting tyrosinase activity and inhibiting melanin formation in the skin. Therefore, including chemical substances such as arbutin and resveratrol, there are many 4-substituted phenols used as whitening ingredients in cosmetics. However, 4-substituted phenols including hydroquinone also have certain safety risks. A large number of studies have shown that many 4-substituted phenols have melanocyte toxicity, and different substituents will also induce different pathways and toxicities of melanocyte toxicity. The improper use of them may induce the occurrence of vitiligo and leukoderma, causing harm to the consumers’ health. This article reviews the whitening and melanocyte toxicity mechanisms of 4-substituted phenols and hydroquinone, as well as the cases of leukoderma in different countries, in order to provide reference for the development of safer whitening chemicals.

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    化妆品晒后修护功效评价方法研究进展
    Research progress on the evaluation methods of cosmetic after-sun repair efficacy
    许梦然, 赵华
    2024 (3):  329-336.  doi: 10.3969/j.issn.2097-2806.2024.03.012
    摘要 ( 167 )   HTML ( 16 )   PDF(1123KB) ( 112 )  

    人类的日常生活无法避免与紫外线的接触,紫外线照射带来的皮肤问题,如晒黑、晒红、老化等,成为人们常见的困扰,化妆品层面的晒后修护功效也成为人们的日常需求。《化妆品分类规则和分类目录》对“修护”的释义是有助于维护施用部位保持正常状态。根据《化妆品功效宣称评价规范》要求,具有祛斑美白、防晒、防脱发、祛痘、滋养和修护功效的化妆品,应当通过人体功效评价试验方式进行功效宣称评价。本研究简述了紫外线对皮肤的作用机理及晒后表现;晒后修护产品的作用机制;修护的定义及修护化妆品功效宣称的法规要求;化妆品晒后修护功效的人体功效评价试验及辅助评价的体外试验方法和研究进展,并对化妆品晒后修护功效评价体系的建立进行展望。

    Human beings cannot avoid contact with UV rays in their daily lives, and the skin problems caused by UV radiation have become a common problem for people, which leads to a daily demand of the cosmetics claimed after-sun repair effect. The Cosmetics Efficacy Claim Evaluation Code requires that cosmetics with repair efficacy should be evaluated by the means of human efficacy evaluation tests for efficacy claims. In order to improve the research on the evaluation methods of cosmetic after-sun repair efficacy, and to meet the market demand for after-sun repair products from consumers, we provide research on the efficacy evaluation methods of after-sun repair cosmetics, and establish the basis for the establishment of an efficacy evaluation system for after-sun repair cosmetics. It briefly discusses the action mechanism of ultraviolet light on skin and after-sun performance, the action mechanism of after-sun repair products, the definition of repair efficacy and the regulatory requirements for the efficacy claims of repair cosmetics, the methods and research progress of clinical trials and in vitro tests on the efficacy of after-sun repair cosmetics (among which in vitro tests are divided into cell tests and animal tests), and provides an outlook on the establishment of an evaluation system for the efficacy of after-sun repair cosmetics.

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    潜在内分泌干扰风险防晒剂的监管及其使用情况分析
    Supervision and use analysis of sunscreen with potential endocrine disruption risk
    塔娜, 冯孟鑫, 高家敏, 张凤兰, 王钢力
    2024 (3):  337-343.  doi: 10.3969/j.issn.2097-2806.2024.03.013
    摘要 ( 214 )   HTML ( 4 )   PDF(1028KB) ( 97 )  

    欧盟对具有潜在内分泌干扰风险的化妆品原料进行筛查并建立了化妆品原料优先评估清单,该清单包含了4个欧盟化妆品指令准用防晒剂。文章以优先评估清单中的防晒剂为研究对象,对其在欧盟、美国等国家(地区)的监管情况和在我国的使用情况进行概述和分析,并汇总欧盟消费者安全科学委员会的再评估结果。经研究调查发现,优先评估清单中防晒剂在我国的法规限值与美国、日本和韩国规定基本一致,但部分防晒剂限值较欧盟新修订限值高,可能存在安全风险。建议监管部门综合评估上述防晒剂的安全风险、实际使用情况和行业发展等因素,通过进一步评估和细化法规限值,以期更好地保障民众用妆安全。

    The European Union has screened cosmetic ingredients with potential endocrine disrupting risks and established a priority assessment list for cosmetic ingredients, which includes four EU cosmetics directive approved sunscreens. This article focuses on the priority evaluation list of sunscreens, provides an overview and analysis of their regulatory status in countries (regions) such as the European Union and the United States, as well as their use in China. It also summarizes the reevaluation results of the European Union Consumer Safety Scientific Committee. After research and investigation, it is found that the regulatory limits for sunscreen in China on the priority evaluation list are basically consistent with those in the United States, Japan, and South Korea. However, some sunscreen limits are higher than the newly revised limits in the European Union, which may pose safety risks. It is recommended that regulatory authorities comprehensively evaluate the safety risks, actual usage, and industry development of the above-mentioned sunscreen agents, and further evaluate and refine regulatory limits to better ensure the safety of people’s makeup use.

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    O/W乳化体系化妆品感官评价与仪器分析相关性研究进展
    Research progress of the correlation between sensory evaluation and instrumental analysis of cosmetics in O/W emulsion system
    周文瑞, 贺建彪, 焦倩, 王紫迪, 苏芊芊, 贾焱
    2024 (3):  344-352.  doi: 10.3969/j.issn.2097-2806.2024.03.014
    摘要 ( 110 )   HTML ( 7 )   PDF(1341KB) ( 73 )  

    为满足消费者的需求和愿望,在优化产品时,需要做感官评价。以“人”作为测量工具的感官评价需要控制个体差异性,而流变学测量和质构分析等仪器测量方法,操作简单、成本更低、结果客观可重复。文章查阅了国内外化妆品感官评价和仪器分析表征相关的文献,介绍了描述性感官分析中各感官属性的定义,总结与感官属性强相关的仪器参数和测试方法,列出部分感官属性与仪器参数的拟合方程,为化妆品在开发阶段的配方设计和筛选提供科学依据。提出部分感官属性和仪器参数的相关性研究尚不完整,后续研究还应考虑不同皮肤类型的消费者在使用化妆品后感官属性的差异,通过仪器分析对不同皮肤类型感官属性预测的研究方向进行展望。

    With the rapid growth of the cosmetics industry, sensory evaluation is required when designing and optimizing products to meet consumers’ increasing needs and aspirations. Instrumental measurement methods such as rheology measurement and texture analysis have the advantages of simple operation, lower cost, objective and repeatability, which can control individual differences when using “people” as a tool for sensory evaluation. This article reviewed the literature on sensory evaluation and instrumental analysis and characterization of cosmetics in the domestic and overseas, introduced the definitions of various sensory attributes in sensory analysis, summarized instrument parameters and test methods strongly related to sensory attributes, and listed fitting equations for some sensory attributes and instrument parameters, providing a scientific basis for the formulation design and screening of cosmetics during R&D. However, there was an incomplete study of the correlation between certain sensory properties and instrument parameters, such as visual acuity, softness, smoothness, moisture, and other sensory properties. Subsequent studies should also consider the differences in sensory properties of consumers with different skin types after cosmetics use. The information in this paper would help readers to understand the correlation between sensory evaluation and instrumental parameters, providing a scientific reference for the development of cosmetics with good skin sensation.

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    分析与检测
    高效液相色谱法测定化妆品中14种α-羟基酸和羟基酸酯
    Determination of 14 kinds of α-hydroxy acids and hydroxy esters in cosmetics
    张丽媛, 颜琳琦, 程巧鸳, 戚绿叶, 王容, 黄柳倩
    2024 (3):  353-359.  doi: 10.3969/j.issn.2097-2806.2024.03.015
    摘要 ( 151 )   HTML ( 4 )   PDF(1221KB) ( 80 )  

    采用高效液相色谱法(HPLC)建立同时测定化妆品中14种α-羟基酸和羟基酸酯含量的方法,并结合高效液相色谱-串联质谱联用法(HPLC-MS/MS)确证结果。采用高效液相色谱法,以0.05 mol/L的磷酸氢二铵水溶液和甲醇为流动相进行梯度洗脱,采用Waters T3-C18 (4.6×250 mm,5 µm)色谱柱分离,采用二极管阵列检测器检测,以214 nm为检测波长,外标法定量。采用高效液相色谱-串联质谱联用法,以0.1%甲酸水溶液和含0.1%甲酸乙腈为流动相进行梯度洗脱,采用Waters T3-C18 (2.1×100 mm,1.8 µm)色谱柱分离,电喷雾电离,正、负离子多反应监测模式定性。14种化合物在各自质量浓度范围内呈良好的线性关系,相关系数R2均大于0.999。4种基质样品,14种化合物平均加标回收率均在85%~115%范围内,相对标准偏差均小于5%,检出限为1~150 μg/g,定量限为3~450 μg/g。对7批含α-羟基酸和酯的样品进行液质确证,结果均为阳性。该方法操作简便、准确度好、灵敏度高,适用于化妆品中14种α-羟基酸及其酯的测定。

    The study aimed to establish a method for simultaneous determination of 14 kinds of α-hydroxy acids and their esters in cosmetics by high performance liquid chromatography (HPLC),and the results were confirmed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). HPLC was used for gradient elution with 0.05 mol/L diammonium hydrogen phosphate-methanol as the mobile phase. The analytes were separated on a Waters T3-C18 (4.6×250 mm, 5 µm) column and detected at the wavelengths of 214 nm. Quantification analysis was performed by the external standard method. HPLC-MS/MS was used for gradient elution with 0.1% formic acid-acetonitrile containing 0.1% formic acid as the mobile phase, and the analytes were separated on a Waters T3-C18 (2.1×100 mm, 1.8 µm) column. Qualitative analysis was performed by electronic spray ionization under a positive ion and negative ion mode with multiple reaction monitoring (MRM). The linearity of the 14 components in the concentration range is good, with the correlation coefficient r≥0.999. The average spiked recoveries of 14 compounds in 4 cosmetic matrices are all in the range of 85%-115%, and the relative standard deviations are all less than 5%. The limits of detections range from 1 μg/g to 150 μg/g. The limits of quantitation range from 3 μg/g to 450 μg/g. Seven batches of samples containing α-hydroxy acid and its ester were confirmed by HPLC-MS/MS and the results are positive. The results indicate that the method is simple, sensitive and accurate, and is suitable for the determination of 14 kinds of α-hydroxy acids and their esters in cosmetics.

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    超高效液相色谱-串联质谱法测定化妆品中36种兴奋剂
    Determination of 36 stimulants in cosmetics by ultra performance liquid chromatography-tandem mass spectrometry
    徐炜, 邹坡, 李长于, 杨铭, 鹿燕, 李慧良
    2024 (3):  360-368.  doi: 10.3969/j.issn.2097-2806.2024.03.016
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    利用超高效液相色谱-串联质谱仪(UPLC-MS/MS),建立了一种同时测定化妆品中蛋白同化制剂、β2激动剂、糖皮质激素、刺激剂、大麻酚类等36种兴奋剂的检测方法。化妆品样品经甲醇超声提取后,以0.1%乙酸水溶液和甲醇-乙腈混合溶液(体积比1∶9)作为流动相,使用Waters ACQUITY UPLC BEH C18色谱柱(3.0 mm×150 mm,1.7 μm)进行梯度分离。目标物在电喷雾正负离子模式下,以多反应监测(MRM)方式进行测定,用外标法定量。结果表明,在1.0~20 ng/mL的质量浓度范围内,36种兴奋剂组分的线性关系良好(r>0.995),检出限为1.0~3.0 μg/kg,定量限为3.3~9.9 μg/kg。3种基质样品在低、中、高3个加标水平下的平均回收率为80.6%~115.3%,相对标准偏差为0.5%~12.9% (n=5)。该方法前处理操作简便,快速,灵敏度高,结果准确,适用于常见化妆品中多类兴奋剂组分的快速检测。

    An ultra performance liquid chromatography-tandem mass spectrometric (UPLC-MS/MS) method was developed for the simultaneous determination of 36 stimulants including anabolic agents, β2 agonists, glucocorticoids, irritants, and cannabinoids in cosmetics. In this study, pretreatment operation and instruments parameters were also optimized. Cosmetic samples were ultrasonically extracted by methanol, and then the separation of 36 stimulants was carried out on a Waters ACQUITY UPLC BEH C18 column (3.0 mm×150 mm, 1.7 μm) by gradient elution, using 0.1% acetic acid solution and methanol-acetonitrile (1∶9, by volume) as the mobile phase. The 36 target compounds were analyzed in positive and negative electrospray ionization mode under multiple reaction monitoring (MRM) mode. Meanwhile, the analytes were quantified by external standard method, and the linear regression analysis data show that there are good linear relationships for 36 target compounds in the mass concentration range of 1.0-20 ng/mL, with their correlation coefficients (r) greater than 0.995. The limits of detection (LOD) and limits of quantitation (LOQ) of the method are in the ranges of 1.0-3.0 μg/kg and 3.3-9.9 μg/kg, respectively. The recoveries for 36 target compounds in three kinds of matrix samples at three spiked levels are between 80.6% and 115.3%, with the relative standard deviations (RSD) of 0.5%-12.9% (n=5). The method is simple, rapid, high sensitivity, accurate and suitable for the rapid detection of many stimulants in cosmetics.

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