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    2024年, 第54卷, 第2期 刊出日期:2024-02-22 上一期    下一期
    基础研究
    烷基羧酸甜菜碱驱油机理研究
    Study on oil displacement mechanism of alkyl carboxyl betaine
    张晓杰, 张明哲, 徐志成, 宫清涛, 张磊, 张路
    2024 (2):  123-130.  doi: 10.3969/j.issn.2097-2806.2024.02.001
    摘要 ( 119 )   HTML ( 16 )   PDF(3507KB) ( 99 )  

    为了探究不同甜菜碱的微观驱油机理,文章选取三种具有不同疏水烷基链长度的羧酸甜菜碱表面活性剂进行微观可视化驱油实验,并测定了界面张力和乳化性能。实验结果表明,烷基羧酸甜菜碱能够高效降低油水界面张力,促进原油原位乳化。随着烷基链长增加,界面张力进一步降低,乳化效果增强。十六烷基羧酸甜菜碱提高采收率机制包括以下两个方面:0.3% C16BC可以将界面张力降至10-2 mN/m数量级,通过乳化和弱剪切作用有效启动孔道中原油,将柱状、多孔和簇状剩余油分解形成水包油乳化油滴,提高洗油效率。同时,由于乳化油滴产生的贾敏效应叠加,C16BC可产生稳定的堵塞通道效果,使残余油的水相波及效率提高了20%。C16BC作为一种可以原位乳化协同自调剖的驱油剂,驱油效率较地层水驱提高42%以上,可以用于低渗油藏化学驱提高采收率。

    To explore the oil displacement mechanism of betaine surfactants, three alkyl carboxyl betaines with different alkyl chain lengths were selected for microscopic visualization oil displacement experiments. The oil-water interfacial tension (IFT) and the emulsification of crude oil were also measured. The experimental results showed that alkyl carboxyl betaines could effectively reduce the IFT and promote the in-situ emulsification of crude oil. With the increase of alkyl chain length, the IFT decreased and the emulsifying effect was enhanced. The mechanism of enhanced oil recovery by cetyl carboxyl betaine (C16BC) included the following two aspects: 0.3% C16BC could reduce the IFT to the order of magnitude of 10-2 mN/m, effectively mobilize the crude oil in the pores through emulsification under weak shear, and break the columnar, porous and cluster remaining oil into oil droplets by formation of oil-in-water emulsion, which improved the oil washing efficiency. At the same time, due to the superposition of the Jamin effect generated by emulsified oil droplets, C16BC could stably produce a channel blockage effect, which increased the sweep efficiency by 20%. As an oil displacement agent exhibiting in-situ emulsification synergistic self-profile control, the oil displacement efficiency of C16BC was 42.1% higher than that of formation water flooding, which could be used to improve the recovery of chemical flooding in low-permeability reservoirs.

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    多阳离子位点季铵盐与AEC复配体系的应用性能研究
    Application properties of the mixed system of AEC and a quaternary ammonium salt with multiple cationic sites
    侯仕达, 王志飞, 王亚魁, 李俊, 姜亚洁, 耿涛
    2024 (2):  131-138.  doi: 10.3969/j.issn.2097-2806.2024.02.002
    摘要 ( 104 )   HTML ( 13 )   PDF(2481KB) ( 85 )  

    将含多阳离子位点双子季铵盐表面活性剂(TC-GS)与脂肪醇聚氧乙烯醚羧酸钠(AE9C)以不同比例复配,并测试了不同复配比例下混合体系的浸润、去污、乳化、抗静电和活性炭分散性能。结果表明,不同复配比例下的TC-GS/AE9C体系都为均一透明溶液,表现出优异的复配稳定性。复配体系对帆布片的浸润能力优于单一表面活性剂,其中αTC-GS为0.4时浸润性能最好。复配体系在乳化液体石蜡的过程中表现出协同增效作用。AE9C溶液对炭黑污布和油脂污布都具有较好的去污能力,但与TC-GS复配后去污性能有所下降,可能由于TC-GS在污布表面的吸附阻碍了污渍的洗涤剥离。TC-GS溶液和复配体系溶液均表现出较好的抗静电性能,能够将聚酯织物表面电阻降低至≤1010 Ω。最后,大部分复配比例下的TC-GS/AE9C体系溶液都具有良好的分散活性炭的能力;但当复配比与理论等电摩尔比一致时,复配溶液对活性炭的分散稳定性能较差。

    A quaternary ammonium surfactant (TC-GS) containing multiple cationic sites was mixed with sodium fatty alcohol polyoxyethylene ether carboxylate (AE9C) in different ratios, and the wetting, detergency, emulsification, antistatic and activated-carbon-dispersing properties of the mixed systems were tested. The results showed that the TC-GS/AE9C system was homogeneous and transparent solution at different mixing ratios, indicative of excellent compatibility and stability. The mixed system showed better wetting ability for canvas cloth than single surfactant, with the best wetting performance at αTC-GS of 0.4. The mixed surfactants showed synergistic effect in the process of emulsifying liquid paraffin. The AE9C solution had good detergency for both carbon-black-stained cloth and grease-stained cloth, but the detergency was decreased after mixed with TC-GS, probably due to the adsorption of TC-GS on the surface of stained cloths, which hindered the washing and stripping of stains. Both TC-GS solution and the solution of TC-GS/AE9C system exhibited good antistatic performance and could reduce the surface resistance of polyester fabric to≤1010 Ω. The TC-GS/AE9C system at most mixing ratios had good ability to disperse activated carbon; however, when the mixing ratio was consistent with the theoretical isoelectric molar ratio, the mixture had poor dispersion stability for activated carbon.

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    科技讲座
    新型乳化体系及其在化妆品中的应用(Ⅵ)——微乳液
    New emulsion system and its application in cosmetics (VI)Microemulsion
    周康夫, 支奕轩, 王飞飞, 尚亚卓
    2024 (2):  139-148.  doi: 10.3969/j.issn.2097-2806.2024.02.003
    摘要 ( 206 )   HTML ( 26 )   PDF(2113KB) ( 149 )  

    微乳液(ME)是水、油、表面活性剂及助表面活性剂按照一定的比例自发形成的各向同性、热力学稳定的分散体系。微乳液粒径小,能自发形成,且具有优异的增溶作用,对增溶的成分能起到良好的保护、缓释作用的同时,还能有效促进其透皮吸收,改善其生物利用度。微乳液被认为是一种理想的活性成分的保存及输送体系,在化妆品、生物医药等诸多领域具有广阔的应用空间。基于此,本文详细介绍了微乳液及其形成机理;并简述了微乳液的制备方法,总结了影响微乳液形成及性质的关键因素;概括了微乳液的性能优势,并简单介绍了几种特殊微乳液,包括无表面活性剂微乳液、离子液体微乳液以及低共熔溶剂微乳液等。在此基础上,阐述了微乳液在化妆品领域的研究及应用现状。最后,对微乳液在化妆品领域实际应用中面临的问题及未来需要开展的研究工作提出了个人观点,希望能为微乳液在化妆品领域发挥其实际应用价值提供参考,也为性能优异的功效化妆品的开发提供依据。

    Microemulsion (ME) is an isotropic and thermodynamic stable dispersion system formed spontaneously by water, oil, surfactant and cosurfactant in a certain proportion. The particle size of microemulsion is very small (usually 10-100 nm) and microemulsion has excellent solubilization. It can not only protect the solubilized components but also slow release the solubilized components. At the same time, microemulsion apt to promote the transdermal absorption of solubilized components and thus improve their bioavailability. Thus the microemulsion is considered as an ideal system for the preservation and transportation of active ingredients. The microemulsion has wide application in many fields, such as cosmetics, biomedicine and so on. In this paper, the microemulsion and its formation mechanism are introduced in detail firstly. Then the preparation methods of microemulsion are summarized and the key factors of affecting the formation and properties of microemulsion are stated. Furthermore, the performance advantages of microemulsion are listed and the special microemulsions, including surfactant-free microemulsion, ionic liquid microemulsion as well as low-eutectic solvent microemulsions were introduced. On this basis, the research and application of microemulsion in the field of cosmetics were reviewed. Finally, the limitations of the application of microemulsion in the field of cosmetics are put forward and personal views on the problems to be solved are proposed, hoping to provide reference for the practical application of microemulsion in the field of cosmetics and basis for the development of functional cosmetics with excellent performance.

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    开发与应用
    [芥酰胺苯甲酸][胆碱]离子液体表面活性剂的合成及性能研究
    Synthesis and properties of a choline-fatty-acid-based ionic liquid surfactant
    张红梅, 张永民
    2024 (2):  149-155.  doi: 10.3969/j.issn.2097-2806.2024.02.004
    摘要 ( 92 )   HTML ( 4 )   PDF(1863KB) ( 133 )  

    鉴于简单易得的原料和潜在的环境友好性,脂肪酸型离子液体表面活性剂近年来引起了人们极大的兴趣。以菜籽油加工过程中的下脚料芥酸(二十二碳-13-烯酸)为原料,制备了一种超长碳链的脂肪酸基离子液体表面活性剂[芥酰胺苯甲酸][胆碱](EABCho)。通过傅里叶红外光谱仪、核磁共振氢谱、碳谱确认了其分子结构。利用表面张力、电导率、偏光显微镜和流变研究了该离子液体表面活性剂水溶液的表面活性、胶束化热力学以及溶液的相行为等基础性能。结果表明超长碳链和苯环结构的引入赋予了EABCho极强的自组装能力。EABCho的临界胶束浓度仅为0.01 mmol/L,胶束化自由能达到了-59.852 kJ/mol,均远低于短碳链的[月桂酰胺苯甲酸][胆碱]。随着浓度的增大,EABCho水溶液依次呈现出胶束相、六方液晶相和层状液晶相,均表现出显著的类凝胶性质。

    Ionic liquid surfactants (ILSs) are advantageous over traditional amphiphiles because of their adjustable structure and physicochemical properties. However, the improvement of common ILSs in terms of self-assembly and thickening remains a significant challenge. Compared with conventional cationic ILSs, anionic ILSs composed of a long alkyl anion and a relatively small cation have been rarely reported. Due to the simple and readily available raw materials and potential environmental friendliness, fatty-acid-based ionic liquid surfactants have attracted great interest in recent years. In this work, an ILS based on ultra-long-chain fatty acid, namely [erucamide benzoic acid] [choline] (EABCho), was designed and synthesized using erucic acid as raw material. Erucic acid is a leftover material in the processing of rapeseed oil. The molecular structure was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. Its fundamental properties including surface activity, thermodynamics of micellization, and phase behavior of aqueous solution were investigated by surface tension, conductivity, polarized optical microscopy and rheology. The results indicated that, EABCho had a critical micelle concentration of only 0.01 mmol/L and a micellization free energy of -59.852 kJ/mol, i.e., the introduction of an ultra-long carbon chain (C22) and benzene ring structure endowed EABCho with strong self-assembly ability which was much stronger than that of the corresponding analogue with short carbon chain. With the increase of concentration, the aqueous solution of EABCho presented micellar phase, hexagonal liquid crystal phase and lamellar liquid crystal phase in sequence, all showing significant gel-like properties. Therefore, it was expected to be used as a rheology regulator in daily chemicals, oil exploration, etc.

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    应用DPRA替代方法评价3种香豆素类化合物的皮肤致敏性
    Using DPRA alternative method to evaluate the skin sensitization of 3 coumarins
    张红菱, 程琳, 王海燕, 罗飞亚, 张会亮, 孙磊
    2024 (2):  156-160.  doi: 10.3969/j.issn.2097-2806.2024.02.005
    摘要 ( 75 )   HTML ( 6 )   PDF(1356KB) ( 60 )  

    应用直接多肽反应试验(DPRA)方法,对化妆品植物提取物原料中存在的蛇床子素、滨蒿内酯、东莨菪内酯3种未知致敏性的香豆素类化合物进行评价。3种香豆素类化合物与半胱氨酸多肽和赖氨酸多肽模拟的皮肤蛋白共同孵育,使用高效液相色谱法检测3种化合物的多肽消耗率。在标准色谱条件下,蛇床子素和滨蒿内酯与两种多肽的反应体系峰型均正常,东莨菪内酯与赖氨酸反应体系峰型异常,以体积分数0.1%的甲酸水-乙腈流动相体系对标准流动相体系进行优化后检测。结果表明:蛇床子素与半胱氨酸反应体系在反应24 h前产生沉淀,致敏性结果为不确定;滨蒿内酯多肽消耗率均值为6.95%,判定致敏性为阳性,反应等级为弱反应;东莨菪内酯的半胱氨酸多肽消耗率为75.82%,优化色谱条件后的赖氨酸多肽消耗率为80.46%,判定致敏性为阳性,反应等级为中度反应。阳性和阴性对照化合物的结果均与小鼠淋巴结试验(LLNA)致敏性结果一致,实验结果可为3种香豆素类化合物的致敏性提供参考和依据。

    Three coumarins with unknown sensitization in plant extracts of cosmetic were evaluated by direct peptide reaction assay (DPRA). Three coumarins were incubated with skin proteins simulated by cysteine polypeptide and lysine polypeptide. The percentage of peptide consumption of the three coumarins was detected by HPLC. Under standard chromatographic conditions, the peak type of the reaction system of osthole and escoparone with the two peptides was normal, while the peak type of the reaction system of scopoletin with lysine was abnormal. The standard mobile phase system was optimized by 0.1% formic acid-acetonitrile mobile phase system. The results show that the reaction system of osthole and cysteine precipitates 24 h before the reaction, and the sensitization result is uncertain. The average percentage of peptide consumption of escoparone is 6.95%, which indicates that the sensitization is positive and the reaction grade is weak. The cysteine peptide consumption of scopoletin is 75.82%, and the lysine peptide consumption is 80.46% after the optimized chromatographic conditions. It is determined that the sensitization is positive and the reaction grade is moderate. The results of positive and negative control compounds are consistent with the results of LLNA sensitization. The experimental results can provide reference and basis for the sensitization of 3 coumarins.

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    化妆品眼刺激性评价中角膜损伤生物标志物研究
    Study on biomarkers of corneal injury in the evaluation of eye irritation of cosmetics
    谢珍, 黄微, 张劲松, 陈舒怀, 瞿霖吉, 匡荣
    2024 (2):  161-167.  doi: 10.3969/j.issn.2097-2806.2024.02.006
    摘要 ( 87 )   HTML ( 8 )   PDF(3536KB) ( 57 )  

    针对离体兔眼(IRE)试验只适用于筛选严重眼刺激性(UN GHS第1类)的缺陷,建立IRE试验结合基于细胞活性生物标记物的荧光染色方法用于评价化妆品眼刺激性。通过IRE试验条件的探索,包括测试浓度和后暴露时间,对市售化妆品进行眼刺激性检测,同时对角膜进行冰冻切片并染色,鬼笔环肽对丝状肌动蛋白进行染色,DAPI染色胞核后,测量损伤深度(depth of injury,DOI),并比较体外DOI、体内DOI及Draize试验结果,建立预测模型。结果显示通过DOI检测,可对化妆品无刺激性至中刺激性进行检测,表明在离体兔眼中,基于细胞活力的DOI测量可作为角膜损伤的生物标志物,适用于化妆品眼刺激性的评价。

    To address the shortcomings of the isolated rabbit eyes (IRE) assay which is only suitable for screening for severe eye irritation (UN GHS Category 1), an IRE test combined with a fluorescent staining method based on the biomarkers of cell viability was developed for evaluating the eye irritation potential of cosmetic products. Cosmetic products all contain surfactants and other ingredients, and the surfactants may cause damage in a different way compared to other chemicals, in which the exposure procedures for eye irritation evaluation may be different. The IRE test conditions are explored, including the test concentration and post-exposure time. Eye irritation of the commercially available cosmetics were tested by the optimized IRE assay, processed for cryosectioning and staining using phalloidin to detect F-actin and DAPI staining to detect nuclei, and the depth of injury (DOI) were measured. To evaluate the applicability of eye irritation classification of cosmetics based on the measurement of DOI by live cell fluorescent staining, the correlation between in vitro and in vivo DOI measurements was evaluated, and pearson correlation analysis shows a good correlation between the above two methods (r=0.851 1, p<0.001). Finally, we compared the in vitro DOI, in vivo DOI and Draize test results to establish a prediction model. The results show that the classification of eye irritation of cosmetic products from non-irritating to moderate level can be distinguished by DOI measuring, suggesting that in isolated rabbit eyes, DOI measurements based on cell viability can be used as a biomarker of corneal damage, and suitable for the evaluation of cosmetic eye irritation.

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    化妆品防晒黑功效评价方法研究
    Evaluation of cosmetics in melanin inhibition efficacy
    李慧怡, 周悦, 吴谦, 杜丽镝, 谢嘉颖, 谭建华
    2024 (2):  168-174.  doi: 10.3969/j.issn.2097-2806.2024.02.007
    摘要 ( 120 )   HTML ( 17 )   PDF(1596KB) ( 106 )  

    建立了一种新型防晒黑功效的化妆品人体功效评价方法。基于皮肤晒黑的光生物学反应机理,通过系统探索皮肤黑化特征及客观测试指标变化趋势,构建了一种紫外诱导-黑化前产品干预的新型防晒黑评价模型。以2倍MED单次紫外照射诱导,照射后即刻起连续9天涂抹测试产品,测试时间点为照射前、第5天、第7天、第10天,以皮肤肤色(ITA°值)和皮肤黑色素值(MI值)为评价指标。通过对比不同部位、不同紫外照射剂量等实验条件的影响,对防晒黑评价方法进行了优化。该方法已成功应用于祛斑美白功效化妆品功效评价,并与我国现有祛斑美白功效评价方法进行对比。结果表明,该方法能有效评估祛斑美白化妆品的防晒黑功效,且具有试验周期短、成本较低等特点。

    The stimulation to melanosomes from ultraviolet (UV) irradiation in sunlight plays a crucial role in the formation of skin pigmentation and color spots. The current practice of anti-freckle and skin-whitening efficacy evaluation in our country basically lies in reducing the pigmentation that have been formed, which is unable to assess the influence of cosmetics on the melanin formation. In this study, a new human efficacy evaluation method was established to assess the effectiveness of cosmetics on inhibiting melanin production and blocking melanin transport. Based on the photobiological reaction mechanism of skin tanning, the influences of body regions and UV irradiation doses on skin pigmentation were investigated during the establishment and optimization of the anti-tanning model. The test areas on the skin were induced by single UV irradiation with 2 fold minimal erythema dose (MED). The test products were applied for 9 consecutive days immediately after UV irradiation. The skin color (shown as individual type angle, ITA°) and melanin index (MI) were recorded on the day 0 (before irradiation), day 5, day 7, and day 10. This method is successfully applied in the cosmetic anti-freckle and skin-whitening efficacy evaluation. Compared with the existing evaluation methods in China, this method is able to effectively evaluate the anti-tanning efficacy of the anti-freckle and skin-whitening cosmetics with shorter test period and lower cost.

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    BaTiO3-TiO2复合光催化剂降解盐酸四环素及机理研究
    Degradation of tetracycline hydrochloride by BaTiO3-TiO2 composite photocatalyst and its mechanism
    汤艳娜, 陈子珍
    2024 (2):  175-180.  doi: 10.3969/j.issn.2097-2806.2024.02.008
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    以钛酸丁酯(TBOT)和钛酸钡(BaTiO3)为原料,采用水热法制备了BaTiO3-TiO2复合光催化剂,研究了不同煅烧温度(400,500,600,700 ℃)对复合光催化剂结构、形貌及对盐酸四环素(TCH)光催化性能的影响。结果表明:煅烧温度的升高促进了部分TiO2向BaTiO3的转变,BaTiO3的衍射峰增强,晶粒尺寸逐渐增大,球状颗粒的生长成型更为完全。BaTiO3-TiO2复合光催化剂的禁带宽度为3.03 eV,煅烧温度的变化没有改变BaTiO3-TiO2的吸收带边,复合光催化剂的吸收强度随煅烧温度的升高先增大后减小,600 ℃退火处理的BaTiO3-TiO2光催化剂吸收强度最高。在180 min时,600 ℃退火的BaTiO3-TiO2光催化剂对TCH的降解率最高可达92.80%,相比400 ℃退火,降解率提高了24.08%,重复使用5次对TCH的降解率逐次衰减幅度小于7%,重复使用第5次时对TCH的降解率为70.11%,在pH=6.2的条件下180 min时BaTiO3-TiO2的降解率最高为93.19%。

    In this paper, using butyl titanate (TBOT) and barium titanate (BaTiO3) as raw materials, BaTiO3-TiO2 composite photocatalysts were prepared by hydrothermal method. The effects of different calcination temperatures (400, 500, 600, 700 ℃) on the structure, morphology, and photocatalytic performance of the composite photocatalyst for tetracycline hydrochloride (TCH) were studied. The results show that the increase in calcination temperature promotes the transformation of some TiO2 into BaTiO3, the diffraction peak of BaTiO3 increases, the grain size gradually increases, and the growth and molding of spherical particles become more complete. The band gap width of BaTiO3-TiO2 composite photocatalyst is 3.03 eV, and the change in calcination temperature does not change the absorption band edge of BaTiO3-TiO2. The absorption intensity of the composite photocatalyst first increases and then decreases with the increase in calcination temperature. The BaTiO3-TiO2 composite absorption intensity after annealing at 600 ℃ is the highest. At 180 min, the degradation efficiency of the BaTiO3-TiO2 photocatalyst annealed at 600 ℃ for TCH can reach a maximum of 92.80%, which is 24.08% higher than that of the catalyst annealed at 400 ℃. The gradual attenuation of the degradation rate of TCH after five repetitions is less than 7%. The degradation rate of TCH during the fifth repetitions is 70.11%, and the degradation rate of BaTiO3-TiO2 is 93.19% at pH=6.2 for 180 min.

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    流变调节剂在二元喷雾产品中的影响
    Impact of rheology modifiers on Bag-on-valve spray products
    彭心宇, 梁海燕, 温紫娴, 李美停, 李鑫, 邱晓锋
    2024 (2):  181-187.  doi: 10.3969/j.issn.2097-2806.2024.02.009
    摘要 ( 67 )   HTML ( 7 )   PDF(1453KB) ( 74 )  

    选择了化妆品中常用的5种流变调节剂(卡波姆,丙烯酰二甲基牛磺酸铵/VP共聚物,聚丙烯酸酯交联聚合物-6,黄原胶和纤维素),分别配制含不同质量分数聚合物的水溶液和乳液体系。采用流变仪及马尔文喷雾粒度分析仪研究流变与喷雾行为。利用激光粒度仪测试各流变剂在水中形成的微凝胶粒径分布,并跟踪了乳液体系的稳定性。分析了流变行为及喷雾效果与流变调节剂在水溶液中的微观结构的关系。结果发现,黄原胶因其分子量较大,激光粒度仪测试其水溶液颗粒相对较大,虽然具有较好的剪切变稀性能,但其法向应力较高,不能提供良好的喷雾性能。卡波姆等其他4种聚合物,微凝胶颗粒较小,卡波姆含量较高时,因微凝胶颗粒致密而相互作用,可提供相对较高的黏度与弹性模量,但不利于喷雾,而聚丙烯酸酯交联聚合物-6因其适中的弹性模量,屈服应力和较低的法向应力,可作为辅助流变调节剂帮助乳液体系稳定,同时可以提供优良的喷雾效果。

    The effects of rheology modifiers on the stability and spraying performance of Bag-on-valve spray products were studied. Five rheology modifiers that were commonly used in cosmetics (carbomer, ammonium acryloyldimethyltaurate/VP copolymer, polyacrylate crosspolymer-6, xanthan gum, and cellulose) were studied either alone in water or in a lotion base at different concentrations (0.02%, 0.05%, 0.10%, and 0.20%). The rheological behavior was investigated with a rheometer. The spraying performance was tested on Malven Panalytic Spraytec. The micro-gel size distribution in water was measured on a laser granulometer. The stability of the lotions containing different rheology modifiers was also monitored for 3 months. The results showed that xanthan gum showed bad spraying performance and provided relatively high normal stress. Cellulose had relatively low normal stress and good spraying performance. Carbomer, acryloyldimethyltaurate/VP copolymer, and polyacrylate crosspolymer-6 had relatively small micro-gel size, which proposed a concentration-dependent rheological response. When used at high concentration, the molecules interacted with each other so that higher viscosity was build up. Good elasticity could also be obtained at high concentration. When used at low concentration, the micro-particles were incompact, especially for cellulose and ammonium acryloyldimethyltaurate/VP copolymer, the spraying performance was good, but the rheological behavior was viscous-like, indicative of bad stability.

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    川赤芍总苷及其主成分芍药苷对痤疮相关炎症的抑制作用研究
    Study on the inhibitory effect of total glycosides of Paeonia veitchii and its main component paeoniflorin on acne-associated inflammation
    刘伟兰, 李丽, 何春年, 董银卯, 凌霄, 郭苗苗
    2024 (2):  188-195.  doi: 10.3969/j.issn.2097-2806.2024.02.010
    摘要 ( 87 )   HTML ( 10 )   PDF(1623KB) ( 60 )  

    研究了川赤芍总苷及其主成分芍药苷对痤疮相关炎症的抑制作用。通过制备并基于高效液相色谱分析川赤芍总苷主活性成分含量;建立痤疮丙酸杆菌(Cropionibacterium acnesC.acnes)诱导THP-1细胞炎症模型;采用CCK8法检测细胞相对活力,ELISA法快速检测细胞IL-1β、IL-8的分泌量,并用Western blot法验证。结果表明:在100 μg/mL质量浓度下川赤芍根提取物能显著抑制C.acnes刺激引起的炎症因子IL-1β、IL-8 (p<0.01)。从川赤芍根提取物中提取的川赤芍总苷,在相同浓度下对炎症因子IL-1β抑制率提高了20%。川赤芍总苷中芍药内酯苷、芍药苷、苯甲酰芍药苷含量分别为0.64%,26.3%,1.17%。其中芍药苷的含量最高,且对C.acnes刺激引起的炎症因子IL-1β抑制效果显著(p<0.01)。此外,芍药苷还能降低C.acnes刺激引起的活性氧和乳酸脱氢酶。综上所述,川赤芍总苷及其主成分芍药苷对改善C.acnes引起的皮肤炎症具有潜在的治疗价值。

    In this study, the anti-inflammatory capacity of total paeoniflorin was evaluated by establishing an inflammatory model of Cropionibacterium acnesC.acnes)-induced THP-1 cells and exploring its main active components for anti-inflammation. The results show that at a concentration of 100 μg/mL, the root extract of Paeonia veitchii significantly inhibits the inflammatory factors IL-1β and IL-8 induced by C.acnesp<0.01). Total glucoside of Paeonia veitchii from the root extract of Paeonia veitchii increases the inhibition rate of inflammatory factor IL-1β by 20% at the same concentration. The contents of albiflorin, paeoniflorin and benzoyl paeoniflorin in the total glucoside of Paeonia veitchii are 0.64%, 26.3% and 1.17%, respectively. Among them, paeoniflorin has the highest content and the most significant inhibition of inflammatory factor IL-1β induced by C.acnes. In addition, paeoniflorin reduces the reactive oxygen species and lactate dehydrogenase induced by C.acnes. In conclusion, the total glucoside extract of Paeonia veitchii and its main active ingredient paeoniflorin have potential therapeutic value in improving the skin inflammation caused by C.acnes.

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    基于紫甘蓝色素的智能凝胶材料及其甲醛变色研究
    A smart gel based on red cabbage anthocyanin and its formaldehyde-responsive chromism
    白剑芸, 贲倩岑, 田晶, 潘浩, 孟庆华
    2024 (2):  196-200.  doi: 10.3969/j.issn.2097-2806.2024.02.011
    摘要 ( 60 )   HTML ( 3 )   PDF(1324KB) ( 88 )  

    通过溶剂提取紫甘蓝中的花青苷色素(CabAn),在该色素化学结构的基础上,利用其质子化互变异构形成pH响应变色的特点,设计其与羟胺盐组合为超分子探针,通过甲醛与羟胺盐反应释放质子,而该质子则与花青苷的青绿色醌式体结合转化为紫红色吡喃鎓式,从而实现甲醛变色功能,并将超分子探针溶于琼脂制备成智能凝胶(CabAn_HA@Agar),按照国际照明委员会基于CIELab颜色空间定义色差的方法来测量计算甲醛浓度。

    The red cabbage leaves are found rich in anthocyanins which have antioxidant activity and can reduce the damage of free radicals on human tissues and improve the regeneration ability of tissues. In this work, the anthocyanin pigments were extracted from red cabbage by solvents. Based on the chemical structure, a combination of the pigment and hydroxylammonium salt was designed as a supramolecular probe by taking advantage of its protonation tautomerism to form pH-responsive chromism. The proton was released through the reaction between formaldehyde and hydroxylammonium salt, and the proton would combine with the anthocyanin which was converted from cyan-green quinone form into a purplish red pyrylium form, thus realizing the color-change function by reaction with formaldehyde. A smart gel was prepared by dissolving the supramolecular probe in agar. Scanning electron microscopy (SEM) was used to analyze the micromorphology of the smart gel. The surface of the smart hydrogel was porous (pore size was 100-300 μm), and there were intercommunication channels inside the gel. These pore structures were conducive to the migration of color reaction substances. The formaldehyde concentration was then measured and calculated according to the method of CIE to define color difference based on CIELab color space.

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    专论与综述
    我国化妆品产品稳定性研究与管理现状的探讨
    Discussion on the current situation of research and management on the stability of cosmetic products in China
    潘小红, 高梓琪, 陈真, 殷帅, 黄海萍, 胡斌
    2024 (2):  201-208.  doi: 10.3969/j.issn.2097-2806.2024.02.012
    摘要 ( 113 )   HTML ( 10 )   PDF(1095KB) ( 101 )  

    化妆品的稳定性是评价化妆品质量与安全的重要因素,也是化妆品使用性与功效性的保障。本文对比了全球化妆品稳定性研究的监管体系和稳定性文件情况,梳理了国内化妆品产品有效期、稳定性及监管等相关文件的内容。通过对“监管、协会和企业”三个板块电子问卷调查结果,分析我国目前化妆品产品稳定性研究现状,发现工作开展面临的主要问题。借鉴国外化妆品产品稳定性研究的经验及我国食品药品等行业领域产品稳定性研究情况,对我国化妆品产品稳定性研究方向、技术文件的制定和监管服务提出建议。

    The stability of cosmetics is an important factor to evaluate the quality and safety of cosmetics, and is also the guarantee of the usability and efficacy of cosmetics. This paper compares the regulatory system and stability documents of the global cosmetics stability research, and sorts out the contents of the shelf life, stability and supervision of domestic cosmetics products. Based on the results of the electronic questionnaire survey of “supervision, association and enterprise”, the current situation of the stability of cosmetics products in China is analyzed, and the main problems faced by the work are found. Suggestions of the stability of cosmetic products in China are put forward on the research direction, the formulation of technical documents and the regulatory service, based on the experience of foreign cosmetic product stability research and the research situation of product stability in food and drug industries.

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    王浆酸及其护肤功效的研究进展
    Research progress of royal jelly acid and its skin care efficacy
    杲款款, 杨素珍, 韩婷婷, 李燕, 袁春颖, 毛欣宇
    2024 (2):  209-215.  doi: 10.3969/j.issn.2097-2806.2024.02.013
    摘要 ( 103 )   HTML ( 11 )   PDF(1167KB) ( 73 )  

    王浆酸简称10-HDA(10-Hydroxy-2-Decenoic acid,10-HDA),是蜂王浆中的一种不饱和脂肪酸。在自然界,目前只存在于蜂王浆中,且难以分离获取,生物合成法将有望解决王浆酸原料获取困难、价格昂贵的现状。王浆酸具有很强的生物活性,在抑菌、抗炎、抗癌、抗氧化等功效,在食品、医药、保健品、化妆品方面有广泛的应用前景。目前随着时代的发展与市场的变化,化妆品原料的不断研发将会是提升化妆品品质的关键。文章综述了王浆酸在抗衰、抗炎、美白、抗氧化、抑菌方面的功效,以期为王浆酸在护肤品中的应用提供理论依据,为化妆品公司在开发新型、高效、多种用途的护肤原料上提供新的选择。

    Royal jelly acid (10-hydroxy-2-decenoic acid, 10-HDA) is a kind of trans-unsaturated fatty acid exclusively found in royal jelly. It is difficult to be separated because of its low content in royal jelly. At present, there are three main ways to prepare royal jelly acid, including physical extraction, chemical synthesis and biosynthesis, among which biosynthesis is hopeful to solve its expensive situation. With the in-depth study of royal jelly acid, it has been found that royal jelly acid has strong robust health and medical benefits. These beneficial effects include antimicrobial, anti-inflammatory, antitumor, antioxidant and other effects, and has a wide application prospect in food, medicine, health products and cosmetics. Now, with the development and the changes of the market, cosmetic materials have ushered in new changes, and the cosmetic market needs new high-quality materials. This paper summarizes the effects of royal jelly acid in anti-aging, anti-inflammation, whitening, anti-oxidation and antimicrobial, in order to provide theoretical basis for the application of royal jelly acid in skin care products and provide new choices in cosmetic raw materials.

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    分析与检测
    前体离子扫描超高效液相色谱-三重四级杆串联质谱法快速筛查化妆品中非法添加的磺胺类药物
    Screening for illegal addition of sulfonamides in cosmetic products using ultra-performance liquid chromatographytriple quadrupoletandem mass spectrometry with precursor ion scanning
    芦丽, 方方, 冯有龙, 曹玲
    2024 (2):  216-223.  doi: 10.3969/j.issn.2097-2806.2024.02.014
    摘要 ( 65 )   HTML ( 4 )   PDF(1346KB) ( 58 )  

    磺胺类药物(SAs)为化妆品中禁用物质。采用超高效液相色谱-三重四级杆/复合线性离子阱串联质谱(UPLC-QTrap),利用前体离子-增强子离子扫描(PIS-IDA-EPI)模式,用于快速筛查化妆品中非法添加的SAs。选择三个碰撞诱导解离形成的产物离子m/z 92,m/z 108,m/z 156,对12种化妆品基质中的20个SAs进行PIS-IDA-EPI扫描分析,检出限LODs为0.05~0.1 μg/g,该方法在12批次化妆品加标样品中进行了验证,并测定了60批次化妆品样品,以确保其有效性、灵敏度和选择性。实验结果表明:UPLC-QTrap结合PIS-IDA-EPI采集模式是一种有效的筛查方法,并成功应用于化妆品样品中目标和非目标SAs的快速筛查。

    Sulfonamides (SAs) are prohibited substances in cosmetics. An ultra-performance liquid chromatography-triple quadrupole tandem mass spectrometry (UPLC-QTrap) method using precursor ion-information dependent acquisition-enhanced product ion (PIS-IDA-EPI) scanning mode was developed to screen SAs in cosmetics. Twenty SAs were investigated to identify their common product ions formed by collision-induced dissociation. Three common positive product ions, m/z 92, m/z 108, m/z 156 are selected for PIS analysis. Limits of detection (LODs) are 0.05-0.1 μg/g for all 20 SAs in 12 kinds of cosmetic matrix. Sixty samples are analyzed. An effective screening method using UPLC-QTrap with PIS-IDA-EPI acquisition mode is developed and successfully applied to screen for the targeted and untargeted SAs in cosmetic samples.

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    市售儿童化妆品中苯氧乙醇的测定及初步风险特征评估
    Study on phenoxyethanol content in children’s cosmetics on the mark and preliminary risk assessment
    王任, 吴鸳鸯, 乔佳, 颜琳琦, 陈岑, 张丽媛
    2024 (2):  224-230.  doi: 10.3969/j.issn.2097-2806.2024.02.015
    摘要 ( 96 )   HTML ( 6 )   PDF(1264KB) ( 79 )  

    研究市售儿童化妆品中苯氧乙醇防腐剂的暴露参数,对其进行初步风险特征描述,旨在为完善我国化妆品安全风险评估体系提供参考。本实验依据《化妆品安全技术规范》(2015年版)(国家药品监督管理局2021年第17号通告)检验,测得市售50批儿童化妆品中苯氧乙醇含量,并通过ConsExpo Web暴露评估软件建立数学模型,获得适用中国儿童化妆品中苯氧乙醇的暴露参数。结果表明:实验所测的50批市售儿童化妆品中,苯氧乙醇的使用频率为50%。0~3岁儿童有吸吮行为,会增加苯氧乙醇的安全边际风险。市售儿童化妆品中苯氧乙醇的安全边际(MoS)均大于50。

    结论

    儿童化妆品中苯氧乙醇的使用频率较高,市售儿童化妆品中苯氧乙醇的初步风险特征评估为安全。儿童化妆品暴露参数要充分参考到儿童不同年龄段的皮肤特点,儿童特有的行为模式和儿童特定的应用场景,以便更加科学合理地评估儿童化妆品安全。

    The exposure parameters of phenoxyethanol preservative in children’s cosmetics sold in the market was studied, based on which preliminary risk characteristics were described, so as to provide reference to improve the safety risk assessment system of cosmetics in China. This experiment is based on the inspection method of 《Technical Specification for Safety of Cosmetics》(2015 Edition) (Announcement No. 17 of 2021, National Medical Products Administration). The content of phenoxyethanol in 50 batches of children’s cosmetics sold in the market were measured, and the mathematical model was established by the ConsExpo Web exposure assessment software to obtain the exposure parameters of phenoxyethanol. The results show that among the 50 batches of commercial children’s cosmetics tested in the experiment, the frequency of use of phenoxyethanol is 50%. Children aged 0-3 years have sucking behavior, which would increase the marginal risk of safety (MoS), and the margin (MoS) of phenoxyethanol in commercial cosmetics for children is more than 50. This study suggests that phenoxyethanol in children’s cosmetics is used frequently, and the preliminary risk characteristics of phenoxyethanol in children’s cosmetics on the market are evaluated as safe. The exposure parameters of children’s cosmetics should fully take into account the skin characteristics of children at different ages, children’s specific behavior patterns and child-specific application scenarios, so as to scientifically and reasonably evaluate the safety of children’s cosmetics.

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    化妆品中托萘酯、利拉萘酯的高效液相色谱定量及高效液相色谱-串联质谱确证
    Determination of tolnaftate and liranaftate in cosmetics by high performance liquid chromatography and verification by high performance liquid chromatography-tandem mass spectrometry
    鲁毅翔, 伍丽婷, 蒋济民, 陈海露, 黄璇
    2024 (2):  231-238.  doi: 10.3969/j.issn.2097-2806.2024.02.016
    摘要 ( 87 )   HTML ( 8 )   PDF(1500KB) ( 76 )  

    建立了化妆品中托萘酯、利拉萘酯的高效液相色谱法(HPLC)和高效液相色谱-串联质谱(HPLC-MS/MS)确证方法。以乙腈为提取溶剂,经涡旋、超声制成样品溶液。在HPLC方法中,采用5 μm粒径的常规C18色谱柱,以乙腈和0.1%甲酸水为流动相,在258和283 nm波长下进行定量测定,同时结合200~400 nm范围光谱进行定性。HPLC-MS/MS方法所用流动相与HPLC法相同,经粒径为1.8 μm的高效C18柱分离,用ESI源在MRM模式下对目标物进行确证。在HPLC方法中,托萘酯和利拉萘酯的线性范围分别为0.1~10.0 mg/L和0.2~20.0 mg/L (R2>0.99),检出限为3.0和6.0 mg/kg,定量限为10和20 mg/kg,加标回收率为93.3%~107.9% (RSD<5%)。在HPLC-MS/MS方法中,托萘酯和利拉萘酯的线性范围均为0.05~5.00 μg/L (R2>0.99),检出限均为0.002 mg/kg,定量限均为0.005 mg/kg,加标回收率为84.0%~112.8% (RSD<5%)。本研究建立的方法简便、快速、专属性强、准确度高,适用于化妆品中托萘酯和利拉萘酯的测定。

    A method for the determination of tolnaftate and liranaftate in cosmetics by high performance liquid chromatography (HPLC) and verification by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established. Samples (including 5 kinds of matrix: cream, emulsion, liquid, gel, and oil) were extracted with acetonitrile, mixed thoroughly by vortex and ultra-sonication. In HPLC method, the separation was performed by C18 column of 5 μm particle sizes using acetonitrile and 0.1% formic acid water as mobile phases at the wavelength of 258 nm and 283 nm. The HPLC-MS/MS method employed a rapid resolution C18 column of 1.8 μm particle sizes and the same mobile phases as the HPLC method. The target compounds were analyzed by multiple reaction monitoring (MRM) in electro-spray ionization (ESI) mode. Both the HPLC and HPLC-MS/MS methods show good performance in methodology validation. In HPLC method, the linearities of tolnaftate and liranaftate are in the range of 0.1-10.0 mg/L and 0.2-20.0 mg/L, respectively (correlation coefficient, R2>0.99), the limits of detection (LOD) are 3.0 mg/kg and 6.0 mg/kg, the limits of quantitation (LOQ) are 10 mg/kg and 20 mg/kg, and the spiked recoveries are between 93.3% and 107.9% (relative standard deviation, RSD<5%). While in HPLC-MS/MS method, the linearities of tolnaftate and liranaftate both are 0.05-5.00 μg/L (R2>0.99), the LODs are 0.002 mg/kg, the LOQs are 0.005 mg/kg, and the spiked recoveries are between 84.0% and 112.8% (RSD<5%). The method established in this study is simple, rapid, with strong specificity and high accuracy and is suitable for the determination of tolnaftate and liranaftate in cosmetics.

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