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    2021年, 第51卷, 第12期 刊出日期:2021-12-22 上一期    下一期
    基础研究
    基于聚集诱导发光现象检测十二烷基三甲基溴化铵
    Detection of dodecyltrimethylammonium bromide based on aggregation-induced emission phenomenon
    孙庆,方银军,刘雪锋
    2021 (12):  1163-1170.  doi: 10.3969/j.issn.1001-1803.2021.12.001
    摘要 ( 261 )   HTML ( 85 )   PDF(1400KB) ( 232 )  

    阳离子表面活性剂对土壤和水系微生物具有明显的毒性,快捷而灵敏的阳离子表面活性剂分析检测方法是监控阳离子表面活性剂排放的重要工具,而利用聚集诱导发光(AIE)现象分析检测表面活性剂是一种新兴的快捷方法。但是,尚未见有基于AIE现象分析阳离子表面活性剂的报导。为此,利用一种水溶性的AIE探针1,1,2,2-四[4-(3-磺酸丙氧基)苯基]乙烯盐(TSTPE)并以十二烷基三甲基溴化铵(DTAB)为模型物,建立了基于AIE现象检测水体中DTAB的“turn-on”荧光分析方法。结果表明:游离的TSTPE在水中只有微弱的荧光发射;与DTAB以静电相互作用结合后,其荧光发射强度(F)显著增强,并且随DTAB浓度(c)增加而进一步地增强;当TSTPE的浓度为4.5×10-5 mol/L时,Fc的线性响应范围约为1.05×10-4~1.7×10-4 mol/L,检测限约为5.7×10-7 mol/L;在pH为3~10范围内TSTPE-DTAB混合体系的荧光发射具有较好的稳定性,NaCl,KCl和NaNO3三种无机盐对TSTPE-DTAB混合体系的荧光发射干扰较小,在模拟水样中DTAB的回收率不低于95%。

    Cationic surfactants have obvious toxicity to microorganisms in soil and water. Methods for fast and sensitive analysis and detection of cationic surfactants are important tools for monitoring the discharge of cationic surfactants. Aggregation-induced emission (AIE) phenomenon analysis is an emerging and fast method to detect surfactants. However, the analysis of cationic surfactants based on AIE phenomenon has not been reported. Therefore, a “turn-on” fluorescence method for detecting dodecyltrimethylammonium bromide (DTAB) in water was established by using a water-soluble AIE probe, 1, 1, 2, 2-tetrakis[4-(3-sulfonatopropoxyl)phenyl] ethylene salt (TSTPE), and using DTAB as the model. The results showed that free TSTPE was only weakly emissive in water; after binding with DTAB by electrostatic interaction, its fluorescence emission intensity (F) was significantly enhanced and was further increased with the increase of DTAB concentration (c). When the concentration of TSTPE was 4.5×10 -5 mol/L, the linear response range of F vs. c was around 1.05×10 -4~1.7×10-4 mol/L, and the detection limit was approximately 5.7×10-7mol/L. The fluorescence emission of TSTPE-DTAB mixed system had good stability in the pH range of 3~10; three inorganic salts, NaCl, KCl and NaNO3, had little interference with the fluorescence emission of the TSTPE-DTAB mixture, and the recovery rate of DTAB in simulated water samples was not less than 95%.

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    科技讲座
    化妆品乳液及乳化新技术(Ⅵ)——液体弹珠与化妆品
    Cosmetic emulsions and new technologies of emulsification (Ⅵ) Liquid marbles and cosmetics
    陈凤凤,龚穗菁,陈文静,孙亚娟,杨成,李云兴
    2021 (12):  1171-1178.  doi: 10.3969/j.issn.1001-1803.2021.12.002
    摘要 ( 660 )   HTML ( 30 )   PDF(1219KB) ( 454 )  

    液体弹珠是一种由疏液固体颗粒在液滴表面形成吸附层而兼具液体和固体性质的特殊软物质。虽然结构简单,但是这种新型软物质呈现出众多独特的物理化学性质,使其在许多不同的领域都展现出良好的应用前景,特别是在化妆品领域,应该是最有前景和最具可行性的。然而,液体弹珠在目前的使用过程中仍然存在一些缺点,例如,内部液滴挥发速度快和外壳机械强度不可控。本文首先回顾液体弹珠的制备方法、形成原理和使用材料,进而论述液体弹珠的物理化学性质,主要针对液体弹珠内部液滴的挥发速度和外壳的机械强度,最后概述液体弹珠在化妆品领域的应用现状和存在的挑战。

    Liquid marbles are a type of unusual soft matter that combines properties of liquid and solid by producing a lyophobic adsorbed layer of solid particles on the surface of liquid droplets. Despite the simple structure thereof, this novel soft matter has numerous unique physical and chemical properties, making it promising in a wide range of applications, particularly in cosmetics, which should be the most promising and feasible. However, there are still some disadvantages to using liquid marbles, e.g., quick evaporation of the interior droplet and uncontrollable mechanical strength of the outer shell. Herein, the preparation methods, formation mechanism and material selection have been reviewed, followed by a discussion of the physical and chemical properties of liquid marbles, with a focus on the evaporation rate of the interior droplet and the mechanical strength of the outer shell. Finally, the current state of application and the challenges of liquid marbles in cosmetics have been summarized.

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    开发与应用
    稠油流量监测涡轮表面超双疏涂层的构筑与性能研究
    Study on the preparation and performance of water and oil super-phobic coating on the surface of the turbine for monitoring the flow of heavy oil
    宋海,张梦华,安鹏,武元鹏
    2021 (12):  1179-1185.  doi: 10.3969/j.issn.1001-1803.2021.12.003
    摘要 ( 191 )   HTML ( 8 )   PDF(1414KB) ( 249 )  

    以正硅酸乙酯和氟硅酸水解产物为基体,加入结构控制剂,制得具有微纳结构的双疏液涂层前驱体,喷涂固化后,可形成具有双疏液性的涂层。利用高氟硅材料和表面微结构控制剂,通过改变表面自由能和固体表面形貌来控制固体表面的浸润性。考察了结构控制剂的种类、含量及喷涂条件(喷涂量、基底温度、喷涂距离)对涂层双疏液性能的影响。实验结果表明,用纤维状二氧化硅纳米管作为微结构控制填料,制备的双疏液涂层性能最佳。在氟硅聚合物中加入5 g/L的自制二氧化硅纳米管,可使涂层对重油介质的接触角明显增大,对重油介质的滚动角减小。将二氧化硅纳米管的质量浓度提高到15和20 g/L时,对其表面微观结构和双疏液性没有明显影响,所形成的双疏液涂层能在160 ℃下长时间使用,且不受盐腐蚀。最优的喷涂条件为二氧化硅纳米管质量浓度10 g/L,喷涂量10 mL,底温150 ℃,喷距6 cm。双疏液材料涂覆后的涡轮能够满足稠油工况下的测速要求,保证了涡轮流量计在稠油开发监测中的正常工作,解决了稠油粘着涡轮机的难题。

    The water and oil super-phobic coating precursor with a micro-nano structure was produced by adding structure control agents to the substrate which was composed of the hydrolysis products of ethyl orthosilicate and fluorinated decyl trimethoxysilane, and after spraying and curing, a coating with water and oil super-phobicity could be formed. Using highly fluorinated silicon materials and surface microstructure control agents, the wettability of the solid surface has been controlled by changing the surface free energy and surface morphology. The effects of the type and content of structure control agents and the spraying conditions (spraying volume, substrate temperature, and spraying distance) on the properties of the coatings were investigated. The silica nanotubes made by ourselves with natural halloysite (nanotube), sepiolite (nanofilament) and montmorillonite (nanoflake) were selected as microstructure control fillers. The experimental results showed that the water and oil super-phobic coating with the best performance was prepared by using fibrous silica nanotubes as the microstructure control filler. By adding 5 g/L of silica nanotubes to the fluorosilicone polymer, the coating obtained could significantly increase the contact angle of heavy oil and decrease the roll angle of heavy oil. Increasing the mass concentration of silica nanotubes to 15 and 20 g/L had no significant effect on the surface microstructure and water and oil super-phobicity. During its formation, a large number of Si-Si bonds formed and the coating could be used for a long time at 160 ℃ and was not subject to salt corrosion. The optimal spraying conditions were silica nanotube mass concentration of 10 g/L, spraying volume of 10 mL, substrate temperature of 150 ℃, and spraying distance of 6 cm. The turbine coated with the water and oil super-phobic material could meet the speed measurement requirements under thick oil conditions, ensuring the normal operation of the turbine flowmeter in the monitoring and development of thick oil and solving the problem of thick oil sticking to the turbine.

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    CLAA@CaCO3纳米颗粒稳定双水相Pickering乳液
    Aqueous two-phase Pickering emulsions stabilized by the CLAA@CaCO3 nanoparticles
    胡佳雯,樊晔,方云,王红
    2021 (12):  1186-1191.  doi: 10.3969/j.issn.1001-1803.2021.12.004
    摘要 ( 249 )   HTML ( 13 )   PDF(1358KB) ( 264 )  

    双水相体系在生物物质的分离纯化领域具有较好应用前景,但是水-水界面极低的界面张力和较大的界面厚度导致两亲分子无法在界面吸附,因此难以获得稳定的双水相乳液。以共轭亚油酸(CLA)在CaCO3纳米颗粒表面吸附,在80 ℃下引发CLA分子进行自交联制备得到CLAA@CaCO3纳米颗粒,并通过紫外(UV)、红外(FT-IR)和热重(TG)表征手段证实CLA双层吸附在CaCO3纳米颗粒表面。绘制了由硫酸钠(Na2SO4)和聚乙二醇20000(PEG 20000)组成的双水相体系的相图,并以CLAA@CaCO3纳米颗粒稳定Na2SO4/PEG 20000双水相Pickering乳液,结果表明:以质量分数0.1%的CLAA@CaCO3纳米颗粒即可稳定PEG-in-Na2SO4双水相Pickering乳液;在同一条系线上,不同两相质量比的乳液均可保持稳定;体系中两种溶质的浓度都必须大于临界浓度(介于系线TL-3和TL-4之间)才可以得到稳定的双水相Pickering乳液。

    Aqueous two-phase system (ATPS) with the advantages of low toxicity, environmental friendliness, and good biocompatibility is often used in the field of separation and purification of biological substances. However, ATPS emulsions (the most common name is water-in-water emulsion) are much less known than oil-in-water or water-in-oil emulsions, since amphiphiles such as surfactants are difficult to adsorb on the water-water interface due to the large thickness of the water-water interface and the corresponding ultralow interfacial tension. Therefore, it is a challenge to develop effective stabilizers for water-in-water emulsions. Colloidal particles are one of the commonly used emulsifiers to stabilize water-in-water emulsion. Herein, CLAA@CaCO3 nanoparticles (NPs) were prepared via adsorbing conjugated linoleic acid admicelle (CLAA) on the surface of CaCO3 nanoparticles followed by stabilizing CLA molecules through self-crosslinking of conjugated double bonds in the CLA molecules by thermal polymerization at 80 ℃, which was confirmed by UV, FT-IR and TG analyses. The phase diagram of the ATPS composed of sodium sulfate and polyethyleneglycol 20000 (PEG 20000) was drawn and the binodal curve and tie lines were established. Subsequently, the CLAA@CaCO3 NPs were used as emulsifiers to stabilize the Pickering emulsions of Na2SO4/PEG 20000 ATPS. The results show that the CLAA@CaCO3 NPs can stabilize the PEG-in-Na2SO4 Pickering emulsions of ATPS when the mass fraction of the CLAA@CaCO3 NPs is 0.1%. Emulsions with different two-phase mass ratios on the same tie line (TL) can remain stable and the droplet size is around 50 μm. Moreover, the PEG-in-Na2SO4 Pickering emulsions with two-phase mass ratios on TL-1, TL-2 and TL-3 respectively have good long-term stability. It is found that the concentrations of the two solutes in the system should be greater than a lowest threshold concentration as indicated between TL-3 and TL-4 in order to obtain the stable Pickering emulsions of ATPS.

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    一种抗光老化组合物的药效学研究及凝胶面膜的制备
    Pharmacodynamic study of an anti-photoaging composition and preparation of a gel mask
    吴淇,金鑫,杨小倩,郅慧,吴楠,张辉
    2021 (12):  1192-1201.  doi: 10.3969/j.issn.1001-1803.2021.12.005
    摘要 ( 279 )   HTML ( 16 )   PDF(1938KB) ( 390 )  

    以人参皂苷、鹿茸肽、透明质酸钠和鳕鱼胶原蛋白为组合物,探究其抗光老化的功效,并制备凝胶面膜。通过紫外线(UVB)诱导人永生化角质细胞(HaCaT)和人真皮成纤维细胞(HDF-α)建立光损伤模型,MTT法测定不同质量浓度组合物对细胞活性的影响;酶联免疫法测定细胞上清液中超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GSH-Px)及基质金属蛋白酶(MMP-9)的含量。将该组合物制备成凝胶面膜,以卡波姆用量、载药量、pH值为考察因素,以综合评分为指标,利用响应面法优化其最佳工艺参数。实验结果表明,与模型组相比,50 μg/mL组合物可以显著提高HaCaT细胞和HDF-α细胞活性,增加SOD和GSH-Px的分泌水平,降低MMP-9的分泌水平,对HaCaT细胞和HDF-α细胞光损伤具有一定的保护作用。通过响应面法的实验优化,得到凝胶面膜的最优工艺参数为:卡波姆用量0.6%,载药量1.3 g,pH=6;按最优工艺参数制备的凝胶面膜外观光滑平整、均匀细腻、黏稠度适中、涂展性良好,为产品的进一步开发提供了基础研究。

    Ginsenosides, velvet antler peptides, sodium hyaluronate and cod collagen are used to make a composition to explore its anti-aging effect and prepare a gel mask. Through ultraviolet (UVB) induced human immortalized keratinocytes (HaCaT) and human dermal fibroblasts (HDF-α) to establish a light injury model, MTT method was used to determine the effects of different concentrations of compositions on cell viability, and enzyme-linked immunosorbent assay was used to determine the contents of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px) and matrix metalloproteinase (MMP-9) in the cell supernatant. The composition was prepared into a gel mask, and the carbomer dosage, drug loading, and pH value were used as the inspection factors, and the comprehensive score of the gel mask was used as the evaluation index. The response surface method was used to screen the optimal process parameters to obtain the best preparation process for the gel mask. The test results show that compared with the blank group, the cell viability of the model group is significantly reduced (P<0.01). Compared with the model group, when the mass concentration of the composition reaches 50 μg/mL, the survival rate of HaCaT cells is 89.47%±1.81%, SOD content is (39.56±0.29) ng/mL, GSH-Px content is (41.62±0.40) ng/mL, MMP-9 content is (5.46±0.21) ng/mL. While the survival rate of HDF-α cells is 81.04%±4.09%, SOD content is (38.76±0.29) ng/mL, the content of GSH-Px is (44.28±0.05) ng/mL, and the content of MMP-9 is (4.91±0.13) ng/mL. Therefore, 50 μg/mL composition can significantly increase the activity of HaCaT cells and HDF-α cells, promote the secretion level of SOD and GSH-Px, reduce the secretion level of MMP-9, and it has a certain protective effect on HaCaT cells and HDF-α cells against light injury. Through the experimental optimization of the response surface method, the optimal process parameters of the gel mask are as follows: the dosage of carbomer is 0.6%, the drug loading is 1.3 g, and the pH=6. The gel mask prepared according to the optimal process parameters has a smooth appearance, uniformity and fineness, moderate viscosity, and good spreadability, which provides basic research for the further development of the product.

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    灯盏花化妆品原料的抗氧化活性及质量控制研究
    Antioxidant activity analysis and quality control of cosmetic ingredients from Erigeron breviscapus
    李倩,徐明,肖茹月,罗春,李战国,梅双喜
    2021 (12):  1202-1207.  doi: 10.3969/j.issn.1001-1803.2021.12.006
    摘要 ( 225 )   HTML ( 10 )   PDF(1115KB) ( 241 )  

    对灯盏花化妆品原料(EBCI)的抗氧化活性进行研究,同时建立其中两种指标成分的含量测定方法。采用DPPH、ABTS、·OH清除法考察EBCI的自由基清除活性,同时用H2O2诱导HHF-1细胞氧化损伤模型考察EBCI对细胞存活率和细胞中谷胱甘肽(GSH)含量的影响;建立了HPLC法同时测定EBCI中野黄芩苷和4,5-二-O-咖啡酰奎宁酸的含量测定方法。结果显示EBCI具有DPPH、ABTS和·OH自由基清除能力,IC50分别为46.93、91.36和89.37 μg/mL,在4、20 μg/mL质量浓度下能显著提高氧化损伤HFF-1细胞的存活率且能显著提高细胞中GSH含量。野黄芩苷和4,5-二-O-咖啡酰奎宁酸分别在0.009 3~0.372 2、0.008 5~0.340 9 mg/mL范围内呈现良好线性关系,加样回收率分别为103.47%、103.38%(RSD均小于2%)。结果表明EBCI具有抗氧化作用;所建立的含量测定方法简便、稳定、准确可靠,可用于EBCI质量控制。

    Erigeron breviscapus (vant.) Hand. Mazz. is one of the most important traditional Chinese medicinal plants for cardiopathy. Erigeron breviscapus mainly contains flavonoids and caffeic acids, which have obvious antioxidant activities. To study the possibility of developing Erigeron breviscapus as a cosmetics material, the antioxidant activity of Erigeron breviscapus cosmetic ingredients (EBCI) was studied and a method for simultaneous determination of two index compounds therein was established. The scavenging activities of EBCI against DPPH, ABTS and ·OH radicals were evaluated by in vitro method. The effects of EBCI on cell viability and glutathione (GSH) content were investigated by using H2O2-induced damage in HHF-1 cells. HPLC method for simultaneous determination of scutellarin and 4,5-dicaffeoylquinic acid in EBCI was established. The results show that EBCI have scavenging activities against DPPH, ABTS and ·OH radicals, with IC50 values being 46.93, 91.36 and 89.37 μg/mL, respectively. The cell viability of H2O2-induced injury in HFF-1 cells and the GSH content in the cells could be significantly increased at the concentrations of 4 and 20 μg/mL. 4,5-Dicaffeoylquinic acid and scutellarin showed good linearity in the linear ranges of 0.008 5-0.340 9 mg/mL and 0.009 3-0.372 2 mg/mL, respectively. Average recoveries of scutellarin and 4,5-dicaffeoylquinic acid were 103.47% and 103.38% (RSD<2%), respectively. This method is accurate, simple and well reproducible, and can be used for the quality control of EBCI. It shows the antioxidant activity of EBCI in this study.

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    余甘子提取物抗衰老和防脱生发功效的研究
    Study on the effects of Phyllanthus emblica extract on anti-aging and hair growth promotion
    吴启,王晓晴,崔挺,章漳,王风楼,马钢
    2021 (12):  1208-1214.  doi: 10.3969/j.issn.1001-1803.2021.12.007
    摘要 ( 896 )   HTML ( 71 )   PDF(1537KB) ( 511 )  

    通过测试余甘子提取物的总抗氧化能力和其对弹性蛋白酶的抑制能力,在生化层面考察其抗衰老的功效;人体内的睾酮在5α-还原酶的作用下还原成二氢睾酮,其含量过高是导致雄激素性脱发的首要原因。开发抑制5α-还原酶的植物提取物以降低二氢睾酮含量是缓解雄激素性脱发的有效方式。真皮毛乳头(DP)不仅是毛发生长的信号中心,还表达丰富的5α-还原酶,是毛囊中睾酮发挥作用的靶位点。体外3D培养人毛囊真皮毛乳头细胞(HFDPC)是检测植物提取物防脱生发功效理想的细胞模型。通过测试余甘子提取物的5α-还原酶抑制率、对3D培养HFDPC细胞活性和离体人毛囊生长的影响,在生化、细胞和体外组织层面验证其防脱生发的功效。结果表明,一定质量浓度的余甘子提取物具有抗氧化和弹性蛋白酶抑制作用,还具有抑制5α-还原酶和β-半乳糖苷酶活性、促进HFDPC细胞增殖、增强HFDPC的毛发诱导能力以及促进离体人毛囊生长的功效。

    Herbal extracts which are safer and more acceptable compared with chemical compounds and hormone products, may contain agonists in the Nrf-2/HO-1 pathway that mobilize the body to produce effective endogenous antioxidant capacity delaying aging and reducing elastase content to keep skin elastic and firm. Antioxidant capacity and elastase inhibition rate of P. emblica extract were tested to obtain its effects on anti-aging. Under the action of 5α-reductase, testosterone is reduced to DHT, whereas high content of DHT is the primary cause of the AGA. Inhibiting 5α-reductase by plant extracts to reduce DHT content is an effective way to alleviate AGA. DP is the signal center of hair growth and the target of testosterone in the hair follicle which expresses rich 5α-reductase. In vitro 3D cultivation of HFDPC, an ideal detection model, can not only agglomerate them into balls to resemble growth environment in vivo, but also maintain hair induction ability. The 5α-reductase inhibiting ability, the cell viability of HFDPC after 3D cultivation and in vitro human hair growth rate were examined to acquire its effects on hair growth promotion. The results suggest that P. emblica extract is supposed to delay senescence through inhibition of oxidization and elastase activity, and to facilitate hair growth through inhibition of 5α-reductase and β-galactosidase, enhancement of HFDPC proliferation and inductivity, and promotion of in vitro human hair follicle growth. We evaluate the anti-aging and hair growth promotion effect of the P. emblica to provide reference for further researches.

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    驱蚊凝胶的制备及效能评价
    Preparation and efficacy evaluation of mosquito repellent gel
    赵梦恬,杨艺,徐建,金家骅,丁礼琴,曹高
    2021 (12):  1215-1220.  doi: 10.3969/j.issn.1001-1803.2021.12.008
    摘要 ( 573 )   HTML ( 16 )   PDF(1278KB) ( 281 )  

    研究了不同增溶剂的复配、增稠剂和驱避剂种类和用量等对驱蚊凝胶的影响。通过耐寒耐热等理化指标和感官相结合的方法评价驱蚊凝胶的稳定性及肤感,从而确定较优配方,并对其进行了驱蚊效能和安全性评价。结果表明:30% PEG400和15%丙二醇增溶的凝胶稳定性较好且能够有效地增加驱避剂在水中的溶解性;选用0.8%卡波姆940作为增稠剂,其增稠性能好,且能达到理想的肤感;驱避剂的添加量为7.5%时所制成的避蚊胺、驱蚊酯和埃卡瑞丁驱蚊凝胶有效驱蚊时间分别为6.8、8.0和9.3 h。对该凝胶的理化性能进行检测,显示其各项指标均符合相关标准,且性能稳定,预期拥有较好的应用前景。

    We aimed to prepare a mosquito repellent gel with suitable consistency, refreshing skin feeling, safe and convenient use and long effective mosquito repellent time. In this paper, the effects of the mixture of different solubilizers, the dosage of different thickeners and the types and dosage of repellent on mosquito repellent gel were studied. The stability, appearance and skin sensation of mosquito repellent gel were evaluated by the combination of physical and chemical indexes such as cold and heat resistance and sensation, so as to determine the better basic formula. The mosquito repellent efficacy and safety of the better basic formula were evaluated. Then, in order to meet the needs of different target users, plant extracts with antibacterial and antioxidant activities were added to the basic gel formulation, and its effect on gel stability was observed. The results show that the gel prepared by the combination of 30% PEG400 and 15% propylene glycol can not only effectively increase the solubility of the repellent in water, but also has good stability and refreshing skin feeling. 0.8% carbomer 940 is used as the thickening agent of the mosquito repellent gel, which has good thickening performance and can achieve ideal skin feeling. The effective mosquito repellent time of DEET, BAAPE and Ecaritin repellent gel with 7.5% repellent addition is 6.8, 8.0 and 9.3 h, respectively, and the effect of the three self-made mosquito repellent gels is better than that of the mosquito repellent toilet water containing 12.5% mosquito repellent ester on the market. The animal skin irritation and eye irritation experiments show that the prepared mosquito repellent gel has no obvious irritation to the skin, but has slight irritation to the eyes. When the plant extract with antibacterial and antioxidant efficacy is added to the basic formula of the mosquito repellent gel, the transparency of the mosquito repellent gel decreases, especially with mosquito repellent ester as repellent. The physical and chemical properties of the mosquito repellent gel were tested, and the results show that all the indexes of the mosquito repellent gel meet the relevant requirements. The performance is relatively stable, and it is expected to have a good application prospect.

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    一种抗敏修护组合物对敏感性皮肤的舒缓修护功效的研究
    Study on soothing and repair effects of “Franicshield” on sensitive skin
    陈庆生,孟潇,刘婷,李楚忠,周兆芳,龚盛昭
    2021 (12):  1221-1227.  doi: 10.3969/j.issn.1001-1803.2021.12.009
    摘要 ( 471 )   HTML ( 30 )   PDF(1043KB) ( 485 )  

    研究一种抗敏修护组合物对敏感性皮肤的舒缓修护功效。采用LPS诱导RAW264.7小鼠巨噬细胞释放TNF-a实验及红细胞溶血实验对其抗炎作用、眼刺激性进行评估。采用人体临床测试,基于研究者评估、仪器测量以及受试者自评等三个维度对其进行测试评价。结果显示,该组合物质量分数在20%及以内,对RAW264.7小鼠巨噬细胞的活力无显著影响,对LPS诱导下的TNF-a的生成具有明显的抑制作用;红细胞溶血实验显示为无刺激性;使用该组合物4周后,受试者皮肤红斑、脱屑、光滑度以及粗糙度较使用前皆有改善,差异有统计学意义(P<0.05)。综合受试者使用前后皮肤角质层含水量、TEWL值、红区面积变化、乳酸刺激性以及对刺痛、瘙痒、紧绷和灼热等皮肤问题的缓解率等,表明该组合物具有显著的舒缓和修护功能,差异有统计学意义(P<0.05)。4周的试验期间未出现任何皮肤不良反应,表明其对敏感性皮肤人群具有良好的安全性,适用于敏感性皮肤人群。

    The soothing and repair functions of “Franicshield” on sensitive skin were studied. The anti-allergy &repair composition “Franicshield” was composed of ceramide, squalane and other skin lipid components to repair the skin barrier function; sodium hyaluronate and aloe leaf water were used to replenish water and moisturize the skin; natural active extracts such as Centella asiatica, Polygonum hydropiper and Inonotus obliquus were used to reduce skin inflammation and soothe skin. The anti-inflammatory effect and eye irritation were evaluated by TNF-a release induced by LPS from mouse macrophages (RAW264.7) and erythrocyte hemolysis test. Human clinical test was used for evaluation based on three dimensions: researcher evaluation, instrument measurement and subject self-assessment. The results showed that it had no significant effect on the activity of RAW264.7 mouse macrophages, and significantly inhibited the production of TNF-a inflammatory factor induced by LPS when the mass fraction of “Franicshield” was within 20%. The erythrocyte hemolysis test showed no irritation. After using “Franicshield” for 4 weeks, the subjects’ skin erythema, scaling, smoothness and roughness were improved, and the difference was statistically significant (P<0.05). The water content of stratum corneum, TEWL value, red area change, lactic acid irritation and the relief rate of skin problems such as tingling, itching, tension and burning before and after use showed that “Franicshield” had good soothing and repair functions, and the difference was statistically significant (P<0.05). No adverse skin reactions occurred during the 4-week test, indicating that it had good safety and was suitable for people with sensitive skin.

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    皂基/氨基酸复配型洁面产品的性能研究
    Study on the performance of facial cleansers based on the mixture of a soap and an amino acid surfactant
    何广文,颜少慰,曾一帆,闫加雷,钱景茹,王靖
    2021 (12):  1228-1234.  doi: 10.3969/j.issn.1001-1803.2021.12.010
    摘要 ( 791 )   HTML ( 38 )   PDF(1421KB) ( 575 )  

    根据洁面的开发需求,筛选了合适的皂基型表面活性剂和氨基酸型表面活性剂,制得纯皂基型、纯氨基酸型以及皂基/氨基酸复配型(简称皂氨型)洁面产品,采用人体法评测,结合皮肤染色残留实验,皮肤天然保湿因子和脂质溶出实验,对3种产品的保湿、控油、温和性等性能进行对比研究。结果表明:皂氨型洁面对皮肤的保湿锁水能力优于纯皂型洁面,而控油能力优于纯氨基酸型洁面,且使用感方面皂氨型洁面整体上优于皂基型和氨基酸型洁面。此外,皂氨型洁面在人体皮肤上的残留少于纯氨基酸型,同时对皮肤的温和性优于纯皂基型。总体而言,皂氨型洁面产品实现了洗净力、温和性和使用感的良好平衡。

    According to the demand for development of facial cleansers, the suitable soap based surfactant and the amino acid surfactant were selected to prepare facial cleansers based on pure soap, pure amino acid surfactant and the mixture of soap and amino acid surfactant. The moisturizing, sebum control and mildness of the three kinds of facial cleansers were compared by volunteer evaluation, skin dyeing residue test and skin natural moisturizing factor/lipid extraction tests. The results showed that the ability of moisturizing of soap-amino acid surfactant based cleanser was higher than that of pure-soap based cleanser, and its sebum controlling property was better than that of pure-amino-acid-surfactant based cleanser. Moreover, the soap-amino acid surfactant based cleanser was the favourite one according to the volunteer evaluation. In addition, the residue of soap-amino acid surfactant based cleanser on the skin was less than that of pure-amino-acid-surfactant based cleanser, and its skin mildness was much better than that of pure-soap based cleanser. In general, the soap-amino acid surfactant based cleanser developed in this study achieves a better balance among cleansing ability, mildness and skin feeling.

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    专论与综述
    化妆品原料吡硫鎓锌毒理学及风险评估研究进展
    Research progress on toxicology and risk assessment of zinc pyrithione as cosmetics ingredient
    黄湘鹭,卢家灿,邢书霞,孙磊
    2021 (12):  1235-1241.  doi: 10.3969/j.issn.1001-1803.2021.12.011
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    吡硫鎓锌(Zinc Pyrithione,ZPT)是化妆品中常用的去屑剂,因欧盟ZPT禁令引起化妆品行业高度关注。ZPT急性经口/吸入毒性为中等毒性,对眼睛有严重刺激性和腐蚀性,未见皮肤致敏性,口服吸收率较高,在体内代谢较快,生物蓄积能力较低,不具有致突变性/遗传毒性和致癌潜力,具有一定生殖毒性,对水域生态环境存在较大负面影响。欧盟SCCS评估认为ZPT作为去屑剂在淋洗类发用产品最大用量1%是安全的,课题组初步评估认为在其作为去屑剂我国发用产品中最大用量1.5%是安全的。鉴于欧盟ZPT禁令对我国化妆品行业的影响,建议相关部门积极关注吡硫鎓锌国际法规调整及其安全性,做好技术储备,完善我国化妆品监管体系。同时,多途径开展风险交流以引导行业进行配方调整,综合考虑对产品过渡期的设置,鼓励行业积极开展去屑新原料的研究开发工作,增加可选原料的品种,推动化妆品行业健康发展。

    Zinc pyrithione (ZPT) is a commonly used anti-dandruff ingredient in cosmetics, which have attracted great attention in the cosmetic industry because of the ban on ZPT in the EU. It could be demonstrated that the acute as well as the sub-chronic toxicity of both ZPT alone or incorporated in market formulation is moderate to low in animal experiments or after practical application to humans. ZPT is-at least-a mild skin irritant but a severe eye irritant and corrosive. ZPT is considered not to be a skin sensitizer based on guinea pig studies. Concerning human data, ZPT (or PT moiety part) has a low potential to induce contact hypersensitivity when tested per se or as part of a cosmetic formulation. ZPT is rapidly and extensively absorbed after oral dosing, is distributed throughout the body, and is not concentrated in any particular tissue. The primary route of excretion of ZPT is via the urine. In a combined chronic toxicity/carcinogenicity study, the dose of 0.5 mg/kg bw/d is considered as NOAEL by the SCCS. It considers ZPT as a non-genotoxic and non-mutagenic compound in vivo. From the studies performed by the oral or dermal route with ZPT, there is no evidence of carcinogenic potential up to dermal doses of 100 mg/kg bw/d and up to oral doses of 2.5 mg/kg bw/d.It is not indicated any potential concern to humans regarding adverse effects on fertility but on development which is most likely attributable to maternal toxicity. It is under a significant adverse impact on the aquatic ecological environment. The SCCS considers ZPT as safe when used as an anti-dandruff in rinse-off hair products up to a maximum content of 1%, while the preliminary evaluation of the research group believes that the maximum content of 1.5% in hair products in China as an anti-dandruff agent is safe. In view of the impact of the EU ZPT ban on China’s cosmetics industry, it is suggested to continuously track the legislative formulation and safety of ZPT in cosmetics and to make good technical reserves, so as to provide reference for perfecting the supervision system of cosmetics in China. Meanwhile, multi-channel risk communication should be made to guide the improvement of the product formula, and the setting of product transition period should be comprehensively considered. The industry should be encouraged to carry out research and development of new cosmetic ingredients and increase the variety of optional cosmetics ingredients to promote the healthy development of the cosmetics industry.

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    自然环境中能否出现可有效降解碳氟链的微生物
    Analysis about whether microorganisms that can effectively degrade fluorocarbon chains would appear in the natural environment
    肖子冰,邢航,窦增培,肖进新
    2021 (12):  1242-1249.  doi: 10.3969/j.issn.1001-1803.2021.12.012
    摘要 ( 304 )   HTML ( 8 )   PDF(1161KB) ( 337 )  

    全氟或多氟烷基物质(PFAS)的碳氟链具有很强的化学惰性,随着环境保护和健康观念的不断加强,PFAS的大量使用引发了公众的担忧。PFAS在很多应用领域中是不可替代的,尤其是高技术领域或外部条件苛刻的场合,因此最积极的应对策略是探索可行的后处理方法。与物理或化学法处理相比,生物降解在实施条件的便利性以及能源消耗、经济成本方面更具优势。然而,迄今尚未发现能“有效”降解PFAS的微生物,这里的“有效”是指在令人满意的时间内破坏PFAS的C-F键以实现彻底的降解。这意味着微生物要满足降解程度和降解效率的双重要求。本文详细论述了自然环境中能否产生有效降解碳氟链的微生物,以及实验室模拟这一过程可以采取的策略。同时列出了当前微生物降解PFAS的若干证据,未来,期待人类能研制培育出可有效降解碳氟链的微生物品种。

    The fluorocarbon chains of PFAS (per- and polyfluoroalkylated substances) are highly chemically inert. With the increasing awareness of protection of environment and health, the extensive use of PFAS has aroused public concern. PFAS are irreplaceable in many application fields, especially in the cases of high-tech applications or harsh conditions. Therefore, the most active coping strategy should be to explore feasible treatment methods. Compared with physical or chemical treatment, biodegradation is advantageous in convenient applied conditions and being energy-saving and cost-effective. However, up to now, no microorganisms have been found to be qualified to “effectively” degrade PFAS, i.e., to completely break down PFAS in a satisfactory range of time by destroying the C-F bonds. It means that a desired species of microorganisms must meet the dual requirements of degradation degree and degradation efficiency. Herein, we have discussed whether microorganisms, that can effectively break down the fluorocarbon chain, could appear in the natural environment, as well as the strategies that can be adopted to simulate this process in laboratory. Some evidence of the microbial degradation of PFAS has also been listed. In the future, it is expected that human beings can develop and cultivate microbial species that can effectively break down fluorocarbon chains.

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    分析与检测
    超高效液相色谱-串联质谱法同时测定化妆品中23种抗生素
    Determination of 23 illegally added antibiotics by UPLC-ESI-Q-TOF/MS in cosmetics
    郑佳新,贾昌平
    2021 (12):  1250-1258.  doi: 10.3969/j.issn.1001-1803.2021.12.013
    摘要 ( 238 )   HTML ( 7 )   PDF(1304KB) ( 253 )  

    建立了超高效液相色谱-串联质谱法同时测定化妆品中23种抗生素的检测方法。样品采用乙腈超声提取,经色谱柱分离,以0.1%甲酸溶液和0.1%甲酸-乙腈梯度洗脱,采用电喷雾离子源正离子模式(ESI+),利用Q-TOF获得的母离子建立含量测定方法,保留时间和二级质谱碎片用于进一步定性确证。结果表明,23种抗生素在线性范围内线性关系良好,相关系数均大于0.995;检出限为0.05~1.36 μg/g,平均回收率为74.1%~125.5%,RSD为2.3%~13.2%。应用该方法对22批次样品进行筛查,首次检出了甲氧苄啶。该方法操作简便,具有良好的选择性、灵敏度及准确度,能够用于化妆品中抗生素类成分的测定。

    The aim of the study is to develop an ultra high performance liquid chromatography-tandem mass spectrometry method for the identification and determination of 23 antibiotics in cosmetics. The samples were extracted by ultrasonic machine with acetonitrile, and the separation was executed on a column using a mobile phase consisting of 0.1% formic acid (A), and 0.1% formic acid- acetonitrile (B). The mass spectrometer was operated in positive ion mode, the determination was conducted in MS scan mode by the external standard method, and confirmatory analysis for target compounds was performed with the retention time and MS2 scan. The result show that the linear relationship of the 23 antibiotics in the linear range is good, and the correlation coefficient is greater than 0.995. The detection limit are between 0.05-1.36 μg/g, and the average recovery rate is in the range of 74.1%-125.5%, with RSD within 2.3%-13.2%. One batch of positive sample is detected in 22 batches of the samples. Trimethoprim is detected in cosmetics for the first time. The established method is simple, selective, sensitive and accurate, and can be used for determination of antibiotics in cosmetics.

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    UHPLC-MS/MS法同时测定面膜类化妆品中63种激素
    Simultaneous determination of 63 hormone drugs in facial masks by UHPLC-MS/MS
    乔亚森,董亚蕾,黄传峰,王海燕,孙磊
    2021 (12):  1259-1268.  doi: 10.3969/j.issn.1001-1803.2021.12.014
    摘要 ( 513 )   HTML ( 16 )   PDF(1152KB) ( 299 )  

    建立了准确测定面膜类化妆品中63种激素类药物的超高效液相色谱-串联质谱(UHPLC-MS/MS)检测方法。对样品前处理条件进行了优化,采用乙腈为提取试剂进行超声辅助液液萃取。对色谱和质谱条件进行考察,在Scheduled MRM模式下,通过正负离子同时采集,建立了面膜类化妆品中63种糖皮质激素和性激素的检测方法。对该方法进行方法学考察,63种激素在线性范围之内的线性相关系数均不低于0.99。加标回收试验结果表明,各化合物的平均回收率范围为71.5%~119.5%,RSD均小于19.2%,证明本方法具有灵敏度高、测定准确、结果可靠的优点,能用于市售面膜类化妆品中63种激素的检测,满足化妆品中禁用物质高通量检测的要求。

    An UHPLC-MS/MS method for the determination of 63 hormone drugs in facial mask cosmetics was established. The pretreatment conditions and mass spectrometry parameters were optimized. The samples were extracted with acetonitrile by ultrasonic-assisted liquid-liquid extraction. Acetonitrile and water were employed as mobile phases and gradient elution was performed. The UHPLC separation was carried out on a Shim-pack XR-ODSⅢ column (2.0 mm×150 mm). The samples were detected by tandem mass spectrometry detector with scheduled multiple reaction monitoring (Scheduled MRM) scanning method. And 63 kinds of glucocorticoids and sex hormones were scanned through simultaneous collection of positive and negative ions. Quantitative analysis was carried out by matrix standard curve with the peak areas of the daughter ions on high intensity. The detection limit, quantitative limit and linear equation of 63 hormone drugs were confirmed. The average recoveries are 71.5%-119.5%, and the RSD are less than 19.2%, indicating good recovery and high precision. This method is simple, sensitive and accurate, which can be employed to simultaneously detect illegal addition of hormone drugs in facial mask cosmetics. It is suitable for high through-put detection of prohibited substances in cosmetics. This research work provides technical support for the safety and quality supervision of facial mask cosmetics.

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    HPLC-MS/MS法测定染发剂中32种染料中间体及其稳定性分析
    Determination of 32 kinds of component in hair dyes by HPLC-MS/MS and stability analysis of dye intermediates
    李若绮,武悦,孙莺,李广宁
    2021 (12):  1269-1277.  doi: 10.3969/j.issn.1001-1803.2021.12.015
    摘要 ( 237 )   HTML ( 15 )   PDF(1320KB) ( 205 )  

    建立了高效液相色谱-串联质谱测定染发剂中32种染料中间体的检测方法,并对染料中间体进行稳定性分析。样品采用甲醇-2 g/L亚硫酸氢钠水溶液(体积比为2∶8)的混合溶液提取,以10 mmol/L甲酸铵水溶液(pH=8)和乙腈-甲醇溶液(体积比为1∶1)为流动相,Atlantis T3色谱柱梯度洗脱分离,采用电喷雾正负离子(ESI+、ESI-)源多反应监测模式进行检测。32种化合物在0.005~50 mg/kg范围内线性关系良好,相关系数r>0.995。样品基质效应为4.1%~44.6%。在0.2、2、10 mg/kg 3个加标水平下,平均回收率为80.2%~109.6%;在0.5、2和5 mg/kg 3个加标水平下,相对标准偏差(RSD)为0.8%~9.8%。方法检出限为0.005 2~2.4 mg/kg,定量限为0.018~7.9 mg/kg。正离子检测模式下染料中间体在10 h峰面积平均增加了30.3%,负离子检测模式下染料中间体在20 h峰面积平均减小了29.6%。该方法简便、快速、灵敏,可为染发剂中染料中间体的检测提供技术支持,同时染料中间体的不稳定性可为定量分析和质量控制提供理论依据。

    A method was developed for the determination of 32 kinds of component in hair dyes using high performance liquid chromatography-tandem mass spectrometry, and the stability analysis of dye intermediates. The samples were extracted with mixed solution with methyl alcohol and 2 g/L sodium bisulfite aqueous solution (V/V=2∶8). The analytes were separated on a Atlantis T3 column with 10 mmol/L ammonium formate aqueous solution (pH=8) and mixed solution with methyl alcohol and acetonitrile (V/V=1∶1) as mobile phases, and finally analyzed using electrospray ionization in positive and negative ion mode (ESI+, ESI-) with multilpe reaction monitoring (MRM). The linear ranges of the 32 dyes are from 0.005-50 mg/kg with correlation coefficients (r) more than 0.995. The matrix effects range from 4.1% to 44.6% in samples. The average recoveries are 80.2%-109.6% at the spiked levels of 0.2, 2 and 10 mg/kg. The average relative standard deviations is 0.8%-9.8% at the spiked levels of 0.5, 2 and 5 mg/kg. The limits of detection and the limits of quantification are 0.005 2-2.4 mg/kg and 0.018-7.9 mg/kg for the 32 dyes. The peak area of dyes increases by an average of 30.3% at 10 h in positive ion detection mode. The peak area of dyes decreases by an average of 29.6% at 20 h in negative ion detection mode. The method is simple, rapid and sensitive, and can provide technical support for dye detection in hair dyes. The instability of dyes can provide theoretical basis for quantitative analysis and quality control. The instability of dye intermediates can provide theoretical basis for quantitative analysis.

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    液质联用法测定甘草组方化妆品中4种标志性成分
    Determination of four characteristic components in Glycyrrhiza uralensis based cosmetics by LC-MS method
    邓映明,陈媛,邓美凌,宋增炫
    2021 (12):  1278-1282.  doi: 10.3969/j.issn.1001-1803.2021.12.016
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    建立液相色谱-质谱法测定宣称含有甘草成分的植物组方化妆品,以饱和氯化钠分散样品,乙腈超声提取,以0.1%甲酸水-乙腈作为流动相梯度洗脱,流速为0.4 mL/min,多反应监测(MRM)模式检测。4种成分在各自范围内线性关系良好,平均加样回收率85%~104%,RSD为1.1%~10.0%,方法检出限在1~15 ng/g之间;12批样品中检出符合率为41.6%。目前市售的植物组方中宣称甘草成分化妆品中,甘草成分检出率和检出含量较低,商家存在一定的概念营销,相关部门应加强监管。

    A LC-MS method was established for determination of botanical cosmetics claimed to contain ingredients from Glycyrrhiza uralensis. The sample was dispersed by saturated solution of sodium chloride and was ultrasonically extracted with acetonitrile. 0.1% formic acid water-acetonitrile was used as the mobile phase for gradient elution at a flow rate of 0.4 mL/min. Multiple reaction monitoring (MRM) mode was used for detection. The four components had good linear relationship within their respective range. The average recovery rate was 85%-104%, the RSD was 1.1%-10.0%, and the detection limit of the method was between 1 and 15 ng/g; 12 batches of samples were tested and the coincidence rate thereof was 41.6%. The test results indicate that the presence and the amount of ingredients from Glycyrrhiza uralensis are actually relatively low in as-claimed cosmetics. In other words, there are conceptual marketing and false publicity and thus relevant supervision should be strengthened.

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