日用化学工业（中英文）

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阴/阳离子表面活性剂自发囊泡的氧化还原响应行为研究
Study on redox response behaviors of spontaneous vesicles formed by anionic/cationic surfactants

李颖,刘炼,刘雪锋

2019 (11): 699-704. doi: 10.3969/j.issn.1001-1803.2019.11.001

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利用一种对氧化还原具有刺激响应的阴离子表面活性剂十二烷基硒丙基硫酸钠（SDSePS）与阳离子表面活性剂十二烷基三甲基溴化铵（DTAB）复配形成SDSePS/DTAB自发囊泡,探究了该囊泡的氧化还原可逆响应行为。结果表明,在H₂O₂的作用下,SDSePS分子中二价硒醚基团（-Se-）可以被氧化成四价硒亚砜基团（-Se=O）,SDSePS/DTAB自发囊泡被瓦解成球状胶束;在Na₂SO₃的作用下,四价硒亚砜基团被还原成二价硒醚基团,SDSePS/DTAB自发囊泡再次形成;在H₂O₂和Na₂SO₃的交替作用下,SDSePS/DTAB自发囊泡可以在胶束和囊泡两种状态下可逆氧化还原循环至少10次,还原再生的SDSePS/DTAB自发囊泡的平均半径稳定在115~130 nm。

Spontaneous vesicles were formed by the combination of sodium dodecylselanylpropyl sulfate （SDSePS）, a redox-responsive anionic surfactant, and a cationic surfactant dodecyltrimethylammonium bromide （DTAB）. Then the redox reversible response behavior of the vesicles was explored. The results show that, under the action of H₂O₂, the divalent selenide group （-Se-） in the SDSePS can be oxidized to a tetravalent selenium sulfoxide group （-Se=O）, and the spontaneous vesicles formed by SDSePS/DTAB are disintegrated into spherical micelles; and then under the action of Na₂SO₃, the tetravalent selenium sulfoxide group is reduced to a divalent selenide group, and the spontaneous vesicles formed by SDSePS/DTAB are regenerated; under the alternating action of H₂O₂ and Na₂SO₃, the spontaneous vesicles formed by SDSePS/DTAB can switch between the two states of micelles and vesicles over 10 times at least. The average radius of the regenerated vesicles formed by SDSePS/DTAB remained in the range of 115-130 nm.

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O/W膏霜流变性和融化感研究
Study on rheological properties and melting sensation of O/W cream

蒋彤,张晨,张志伟,张婉萍,方波

2019 (11): 705-710. doi: 10.3969/j.issn.1001-1803.2019.11.002

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研究了O/W膏霜的流变性,并用Cross模型拟合其流动曲线。结果表明：随着膏霜的融化程度指数增大,第一牛顿区黏度η₀、滞后环面积S、复模量G*等参数减小,且lg η₀、S、lg G*与融化程度指数具有较好的线性关系。同时,考察了O/W膏霜在大振幅振荡剪切（LAOS）流场中的流变性,发现随着融化程度指数增大,弹性Lissajous应力响应曲线的振幅减小,最小应变模量G_M和大应变模量G_L也减小。

The rheological properties of the O/W cream were studied. The flow curves were fitted in Cross equation. The results indicate that with the increase of the melting degree index, the first Newtonian viscosity, the hysteresis loop’s area and complex modulus get smaller. lg η₀, S and lg G* show good linear relationship with melting degree index. Meanwhile, the rheological properties of O/W cream were investigated in large amplitude oscillatory shear （LAOS） flow field. The results show that with the increase of the melting degree index, the amplitude of the elastic Lissajous stress response curve get smaller, as well as G_M and G_L.

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表面活性剂-纳米颗粒相互作用与智能体系的构建（Ⅴ）相同电荷表面活性剂-纳米颗粒相互作用（i）——超低浓度纳米颗粒/表面活性剂构建新型乳状液及其稳定机制
Interactions between surfactants and nanoparticles and the construction of smart systems（V） Interactions between like-charged nanoparticles and ionic surfactants（i） Construction of novel emulsions using ultra-low concentration of nanoparticles/surfactants and their stabilization mechanism

张婉晴,许茂东,蒋建中,崔正刚

2019 (11): 711-720. doi: 10.3969/j.issn.1001-1803.2019.11.003

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利用无机纳米颗粒在水介质中带电以及带相反电荷的离子型表面活性剂对颗粒的可逆原位疏水化作用,可以构建具有多种触发机制的Pickering乳状液和Pickering泡沫等智能分散体系。令人惊奇的是,采用无机纳米颗粒与带相同电荷的离子型表面活性剂,亦可协同稳定O/W型乳状液,其特点是所需颗粒和表面活性剂浓度极低,分别可低至0.001%和0.001cmc,其中微量表面活性剂吸附于油/水界面控制液滴大小,而纳米颗粒并不吸附于油/水界面,而是分布于连续相水膜中,相关的稳定机理难以用经典的DLVO理论、位阻稳定理论以及Pickering稳定理论来解释。为此将这种由带相同电荷的离子型表面活性剂与无机纳米颗粒协同稳定的O/W型乳状液称为新型乳状液。本讲座将简单介绍这种新型乳状液的制备、表征、普适性以及初步探索的稳定机制。

By means of reversible hydrophobization of inorganic nanoparticles with the oppositely charged ionic surfactants in aqueous media, smart dispersion systems such as switchable or stimuli-responsible Pickering emulsions/foams with various triggers can be constructed. Surprisingly, like-charged inorganic nanoparticles and ionic surfactants can also co-stabilize O/W emulsions, in which the concentrations of both particles and surfactants required are extremely low, i.e., the minimum concentration required can be as low as 0.001% and 0.001cmc, respectively. It is found that trace amount of surfactants adsorb at oil/water interface controlling droplet size, whereas the nanoparticles do not adsorb at oil/water interface but distribute in aqueous lamellae of the continuous phase. The O/W emulsions co-stabilized by like-charged nanoparticles and ionic surfactants are called novel emulsions since their stabilization mechanism can not be well interpreted by the classic DLVO, the steric and the Pickering stabilization theories. This lecture will discuss the formation, characterization, universality and preliminary stabilization mechanism of the novel O/W emulsions.

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窄分布脂肪醇醚硫酸钠与十四烷基三甲基溴化铵复配体系相行为的研究
Study on the phase behaviors of the mixtures of narrow-distribution sodium fatty alcohol ether sulfate and tetradecyltrimethylammonium bromide

王新刚,杨效益,孙永强,郭朝华,李萍,李建波

2019 (11): 721-726. doi: 10.3969/j.issn.1001-1803.2019.11.004

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为了探究含不同数目聚氧乙烯基团（EO）的窄分布脂肪醇醚硫酸钠（N-AE_nS）与十四烷基三甲基溴化铵（TTAB）复配体系的相行为及N-AE₅S/TTAB双水相体系（ASTP）的形成机理。通过静态表面张力、宏观相行为及微观聚集体形貌对不同摩尔比及浓度的N-AE_nS/TTAB（n=3,5,7,9）的相行为进行了表征。研究结果表明：随着EO基团数目的增加,N-AE_nS/TTAB（n=3,5,7,9）复配体系的外观依次呈现乳白色液态（n=3）、分层（n=5）、蓝色透明液态（n=7）、无色透明液态（n=9）,其相应的微观形貌依次为球形（n=3）、棒状（n=5）、球形（n=7）,且在N-AE₉S/TTAB复配体系中并未观察到聚集体。静电相互作用力和疏水作用对N-AE₅S/TTAB双水相体系的形成起主要作用。

The phase behaviors of the mixtures of tetradecyltrimethylammonium bromide （TTAB） and narrow-distribution sodium fatty alcohol ether sulfate （N-AE_nS） containing different number of oxyethylene units（EO）（n） were investigated, as well as the mechanism of the formation of aqueous two-phase systems （ASTP） of N-AE₅S/TTAB. The phase behaviors of N-AE_nS/TTAB （n = 3, 5, 7, 9） with different molar ratios and concentrations were studied by static surface tension, macroscopic phase behavior and microscopic aggregate morphology. The results showed that with the increase of EO number, the mixtures of N-AE_nS/TTAB appear to be milky white liquid （n = 3）, phase separation （n = 5） , bluish transparent liquid （n = 7） and colourless transparent liquid （n = 9） . Corresponding microscopic morphologies are spherical aggregates （n = 3） , rod-shaped aggregates （n = 5） , spherical aggregates （n = 7） , and no aggregates in N-AE₉S/TTAB. Electrostatic interaction and hydrophobic interaction play major roles in the formation of ASTP of N-AE₅S/TTAB.

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阳离子植物糖原的制备及性能研究
Preparation and properties of cationic phytoglycogen

张瑞琪,杨成

2019 (11): 727-732. doi: 10.3969/j.issn.1001-1803.2019.11.005

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以2,3-环氧丙基三甲基氯化铵（GTA）为季铵化试剂,通过季铵化反应赋予超支化葡聚糖植物糖原（PG）阳离子性。通过单因素试验得到优化后的条件为：催化剂氢氧化钠质量分数为0.3%,反应温度为（50±2） ℃,反应时间2 h,GTA与PG质量比为1.2:1,此时反应产物阳离子植物糖原（PG-GTA）取代度可达到0.294。研究了PG-GTA与洗发水中的表面活性剂相互作用的絮凝情况,结果表明,当洗发水被稀释至5倍时有良好的絮凝效果。在此基础上,研究了添加PG-GTA的洗发水的梳理性能,与不加PG-GTA的洗发水相比,梳理功降低了31.29%。

2, 3-epoxypropyltrimethylammonium chloride（GTA） was used as a quaternization agent to prepare the cationic hyperbranched dextran phytoglycogen（PG） through quaternization. The optimized conditions were obtained by single-factor experimental experiment as follows: the mass fraction of sodium hydroxide was 0.3%, the reaction temperature was（50±2） ℃, the reaction time was 2 h, and the mass ratio of GTA to PG was 1.2:1. In such condition, the degree of substitution of cationic phytoglycogen（PG-GTA） could reach 0.294. The flocculation of the interaction between PG-GTA and the anionic surfactant in the shampoo was studied. The results show that the shampoo has a good flocculation effect when diluted to 5 times. On this basis, the combing performance of the shampoo added with PG-GTA was studied, and the combing work was reduced by 31.29% compared with the shampoo without PG-GTA.

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碳量子点改性纳米二氧化钛的制备及其光催化降解壬基酚聚氧乙烯醚的性能研究
Preparation and photocatalytic activity of carbon-quantum-dot-modified nano-TiO₂

尹言吉,台秀梅,杜志平

2019 (11): 733-736. doi: 10.3969/j.issn.1001-1803.2019.11.006

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以柠檬酸为碳源,以1-氨丙基-3-甲基咪唑溴盐离子液体为表面修饰剂,一锅热解法制备了离子液体修饰碳量子点（L-CQDs）,再通过简单的水热法将L-CQDs负载到TiO₂纳米颗粒上。以表面活性剂壬基酚聚氧乙烯醚（TX-10）溶液为模拟废水,研究了L-CQDs/TiO₂复合光催化剂的光催化性能。傅立叶变换红外光谱仪（FT-IR）和高分辨透射电子显微镜（HRTEM）表征结果证明L-CQDs负载到TiO₂纳米颗粒的表面上;固体紫外-可见吸收光谱结果表明,L-GQDs/TiO₂相比于TiO₂纳米颗粒在可见光区域的吸收得到了明显增强;光催化结果表明,复合光催化剂3% L-CQDs/TiO₂在500 W氙灯照射下降解0.05 g/L TX-10溶液3 h时,复合光催化剂对TX-10的降解率最高可达83.5%,比TiO₂纳米颗粒高26.6%;重复使用5次后复合光催化剂的光催化活性保持不变。

Ionic-liquid-modified carbon quantum dots （L-CQDs） were prepared by one-pot pyrolysis using citric acid as carbon source and 1-aminopropyl-3-methyl-imidazolium bromide as surface modifier. TiO₂ nanoparticles were loaded with L-GQDs by one-step hydrothermal method. Using a solution of nonylphenol polyoxyethylene ether （TX-10） as the simulated wastewater, the photocatalytic performance of L-CQDs/TiO₂ composite photocatalyst was studied. The characterization results are proved by FT-IR and high-resolution transmission electron microscopy （HRTEM） that L-CQDs are loaded onto the surface of TiO₂ nanoparticles. The UV-visible absorption spectrum show that the absorption of L-GQDs/TiO₂ in the visible region is significantly enhanced compared with TiO₂ nanoparticles. The results of photocatalysis show that the degradation rate of 3% L-CQDs/TiO₂ to 0.05 g/L TX-10 solution could reach 83.5% under illumination of Xenon lamp for 3 h, which is 26.6% higher than that of TiO₂ nanoparticles. The photocatalytic activity of the composite photocatalyst remain unchanged after repeated use for 5 times.

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一种植物复合提取物的抗炎止痒功效研究
Study of anti-inflammatory efficacy of a herb composite extract

卢伊娜

2019 (11): 737-741. doi: 10.3969/j.issn.1001-1803.2019.11.007

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以蔓荆果﹑龙胆﹑何首乌根组成的植物复合提取物（VGP）为研究对象,通过多种方法对其抗炎止痒的功效进行研究。结果显示,在糠秕马拉色菌和过氧化氢（H₂O₂）诱导的角质形成细胞和单核细胞炎症模型上,VGP在质量分数为0.01%~0.125%的范围下能剂量依赖性地抑制白介素6（IL-6）﹑前列腺素E2（PGE-2）、单核细胞趋化蛋白1（MCP-1）和白介素1β（IL-1β）的表达。高浓度H₂O₂造成的人体皮肤损伤模型上,质量分数为0.5%和2%的VGP也能降低红斑及水泡的形成,缓解皮肤刺痛感及痒感。VGP作为一种天然来源的具有抗炎止痒功效的活性原料,可应用于头皮护理及皮肤护理领域。

A herb composite extract VGP which consisted of Vitex trifolia fruit, Gentiana scabra, and Polygonum multiflorum root was prepared and its anti-inflammatory effect was studied by several methods. The results showed that on the model of NHEK and THP1 cell inflammation induced by Malassezia furfur and H₂O₂, VGP could inhibit the expressions of interleukin 6 （IL-6）, prostaglandin E2 （PGE-2）, monocyte chemoattractant protein 1 （MCP-1） and interleukin 1β （IL-1β） in a dosage-dependent manner in the concentration range of 0.01%-0.125%. In the human skin injury model caused by high concentration of H₂O₂, VGP at the concentrations of 0.5% and 2% could reduce the formation of erythema and blisters and relieve pruritus. Therefore, as a natural active ingredient VGP could play a role in scalp care and skin care by targeting inflammation.

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神经酰胺Ⅱ脂质体的制备及在化妆品中的应用
Preparation of ceramide II liposome and its application in cosmetics

王丽,刘瑞学,冷群英,毕凡星

2019 (11): 742-747. doi: 10.3969/j.issn.1001-1803.2019.11.008

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通过乳化均质技术制备得到高含量（10%）神经酰胺Ⅱ脂质体,在偏光显微镜下观察到该脂质体粒径均一,具有大量的马耳他十字液晶结构;该神经酰胺Ⅱ脂质体稠度适宜,细腻光滑,稳定性好,水溶性好,通过简单搅拌即可应用到化妆品中,这在很大程度上解决了神经酰胺水溶性差,易结晶析出等问题。通过人体试验结果表明,使用添加1%神经酰胺Ⅱ脂质体（含10%神经酰胺Ⅱ）的乳霜,受试者的TEWL值（经表皮水分流失）在2 h内可恢复85%,皮肤含水量在1 h内增加39.58%,说明其具有良好的皮肤屏障修复性。

The liposome with high content （10%） of ceramide Ⅱ was prepared by the homogenization technique. A large number of Maltese Cross liquid crystal structures which were uniform in particle size were observed under a polarizing microscope. The ceramide Ⅱ liposomes were smooth, soft and water-soluble, with suitable viscosity and good stability. It could be used in cosmetics by simply stirring, which solved the problems of poor water solubility and easy crystallization and precipitation for ceramide. Human-skin test results showed that the TEWLvalue （transepidermal water loss） of the subjects could recover 85% with the cream containing 1% ceramide Ⅱ liposome （which contained 10% ceramide Ⅱ） in two hours, and the skin moisture content could be increased by 39.58% in an hour, which indicated that it had good repairing ability for skin barrier.

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表面活性剂在植物活性成分提取中的应用
Application of surfactant in the extraction of activeconstituents from plants

李陆军,彭胜,霍延平,王志宏,杨秋玲,王翔,彭密军

2019 (11): 748-752. doi: 10.3969/j.issn.1001-1803.2019.11.009

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综述了表面活性剂在植物活性成分提取中的应用。主要介绍了表面活性剂在辅助提取、微乳体系提取、浊点萃取植物活性成分中的应用及其作用原理和特点,并对表面活性剂在提取植物活性成分中的应用前景进行了展望。

The application of surfactants in the extraction of plant active constituents was reviewed. The application of surfactants in auxiliary extraction, microemulsion system extraction and cloud point extraction of plant active constituents and its principle and characteristics were introduced. The application of surfactants in the extraction of plant active constituents was prospected.

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抗水抗汗型防晒化妆品的研究进展
Research progress on water and sweat resistant sunscreens

曹高,唐新宜,杨艺,徐建,金家骅,丁礼琴

2019 (11): 753-759. doi: 10.3969/j.issn.1001-1803.2019.11.010

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综述了防晒化妆品抗水抗汗性能的体内外评价方法,从配方体系、乳化剂、成膜剂、防晒剂及相互作用力等角度阐述了提高防晒化妆品抗水抗汗性能的方法和途径,并指出了抗水抗汗型防晒化妆品开发时需要注意的问题及发展方向。

The in vivo and in vitro evaluation methods for water and sweat resistance properties of sunscreens were summarized. The methods to improve water and sweat resistance properties of sunscreens were presented from the perspectives of formulasystems, emulsifiers, film-forming agents, sunscreen agents, and interaction forces. Additionally, the problems and development directions that need to be noticed when developing water and sweat resistant sunscreens were pointed out.

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高效液相色谱法测定化妆品中的氨甲环酸
Determination of tranexamic acid in whitening cosmetics by high performance liquid chromatography

代静,高家敏,曹进,王钢力

2019 (11): 760-763. doi: 10.3969/j.issn.1001-1803.2019.11.011

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建立了美白类化妆品中氨甲环酸的高效液相色谱测定方法。采用5%甲醇溶液对化妆品样品中的氨甲环酸进行提取。样品用Shiseido CAPCELL PAK C₁₈ UG120 色谱柱（4.6 mm×250 mm,5 μm）分离,以甲醇与0.05 mol/L KH₂PO₄-0.2% H₃PO₄溶液（体积比为5:95）为流动相,流速为1.0 mL/min,检测波长为210 nm。结果表明,氨甲环酸在5~100 mg/L范围内线性关系良好,相关系数（r）大于0.999。在各化妆品基质中方法检出限为10.7~22.2 μg/g,方法定量限为28.9~48.0 μg/g。回收率为95.23%~110.40%,RSD值为1.24%~3.59%（n=6）。日内稳定性良好,在24 h内峰面积RSD值为0.026%。该方法简便、可靠,可作为美白类化妆品中氨甲环酸的含量测定方法。

A high performance liquid chromatography （HPLC） method for the determination of tranexamic acid in whitening cosmetics was established. The tranexamic acid in cosmetic samples was extracted directly with 5% methanol solution. The separation was performed on a Shiseido CAPCELL PAK C₁₈ UG120 column （4.6 mm×250 mm×5 μm）, with the mobile phase of methanol and 0.05 mol/L KH₂PO₄-0.2% H₃PO₄ solution. The flow rate was 1.0 mL/min and detection wavelength was 210 nm. The detection results show good linearity within the range of 5-100 mg/L （r>0.999）. The limit of detection （LOD） is 10.7-22.2 μg/g and the limit of quantitation （LOQ） is 28.9-48.0 μg/g in the cosmetics matrix. The recoveries range from 95.23% to 110.40%, and the RSD range is 1.24%-3.59%（n=6）. The intraday stability is good, and the peak area RSD value is 0.026% within 24 h. The method is simple and reliable, and can be used for the determination of tranexamic acid in whitening cosmetics.

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微波消解-原子荧光光谱法同时测定化妆品中砷、锑、铅和汞
Simultaneous determination of arsenic, antimony, lead and mercury in cosmetics by microwave digestion-atomic fluorescence spectrometry

周霞,王延华,姜新杰,常澍,孙芬芳

2019 (11): 764-768. doi: 10.3969/j.issn.1001-1803.2019.11.012

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建立了微波消解-原子荧光光谱法同时检测化妆品中砷、锑、铅和汞4种有害元素含量的方法。经微波消解仪消解的样品溶液,在预处理加热仪上120 ℃赶酸后,用氢化物发生双道原子荧光光谱仪以1.0%硝酸为载流,5.0%硫脲-抗坏血酸为还原剂同时测定砷、锑、铅和汞。结果表明,砷、锑、铅和汞4种元素在相应的浓度范围内线性良好,相关系数R ²分别为0.999 3,0.998 4,0.997 3和0.999 7。4种元素的加标回收率为91.7%~101.9%。此方法具有操作简便、快速、线性范围宽、适用性强等优点。

A method for the simultaneous determination of arsenic, antimony, lead and mercury in cosmetics by microwave digestion atomic fluorescence spectrometry was established. After the sample solution was decomposed by microwave digester, acid was removed at 120 ℃ on the pretreatment heater. And then arsenic, antimony, lead and mercury were simultaneous determined by hydride generation dual channel atomic fluorescence spectrometer with 1.0% nitric acid as carrier and 5.0% thiourea-ascorbic acid as reductant. The results show that the linearity of arsenic, antimony, lead and mercury is good in the corresponding concentration range, and the correlation coefficients R ² are 0.999 3, 0.998 4, 0.997 3 and 0.999 7, respectively. The recovery of four elements is 91.7%-101.9%. This method has the advantages of simple operation, fast speed, wide linear range and strong applicability.

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