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欢迎访问《日用化学工业(中英文)》,今天是

当期目录

    2021年, 第51卷, 第4期 刊出日期:2021-04-22 上一期    下一期
    基础研究
    模式拟合法和无模式函数法对月桂酸热解行为及机理的研究
    Study on the behavior and mechanism of pyrolysis of lauric acid bymodel-fitting and model-free methods
    张公妍,张延松,陈昆,张新燕,黄兴旺
    2021 (4):  265-271.  doi: 10.3969/j.issn.1001-1803.2021.04.001
    摘要 ( 310 )   HTML ( 61 )   PDF(2851KB) ( 771 )  

    通过综合热分析实验研究了月桂酸粉体在氮气及空气气氛下的热解动力学行为。实验结果表明,氮气气氛中30 µm月桂酸粉体快速热解气化,无燃烧放热反应。而不同升温速率条件下,空气气氛中月桂酸粉体的热解包括快速热解氧化及残余物质缓慢热解氧化两个阶段。运用模式拟合法(Coats-Redfern法)求解氮气与空气气氛中月桂酸主要热解阶段的动力学参数,并描述其热解反应机理。结果表明氮气与空气气氛中月桂酸的快速热解阶段均遵循一维相界面反应模型(R1模型),且氮气气氛中月桂酸热解的表观活化能(9.1 kJ/mol)和指前因子(8.606 1)均较低,表明月桂酸的氧化放热行为抑制了热解反应,但对其热解机理无明显影响,且在升温速率为15 ℃/min时,相同温度条件下,月桂酸在氮气气氛中热解的转化率高于空气气氛。同时运用无模式函数法(Flynn-Wall-Ozawa法和Kissinger-Akahira-Sunose法)对空气气氛中月桂酸不同转化率α下的表观活化能进行解算,两种方法的计算结果与模式拟合法计算结果较为接近,可得空气气氛下月桂酸的平均表观活化能为14.82 kJ/mol;且在10%~80%转化率范围内,月桂酸快速热解氧化阶段的表观活化能随转化率的变化趋势较为平缓,进而验证了月桂酸热解遵循一维相界面反应机理的可靠性。

    The pyrolysis kinetics of lauric acid powder in nitrogen and air was studied by comprehensive thermal analysis. The experimental results showed that 30 µm lauric acid powder was rapidly pyrolyzed and gasified in nitrogen atmosphere without exothermic combustion reaction. At different heating rates, the pyrolysis of lauric acid powder in air included two stages: fast pyrolysis and slow pyrolysis. The kinetic parameters of lauric acid pyrolysis in nitrogen and air atmosphere were solved by means of Coats-Redfern method, and the pyrolysis mechanism was described. The results showed that, the rapid pyrolysis of lauric acid in nitrogen and air atmosphere followed the one-dimensional reaction model at phase interface (R1 model); the apparent activation energy (9.1 kJ/mol) and pre-exponential factor (8.606 1) of lauric acid pyrolysis in nitrogen atmosphere were relatively low, indicating that the oxidation and exothermic behavior of lauric acid inhibited the pyrolysis reaction, but had no obvious effect on its pyrolysis mechanism; when the heating rate was 15 ℃/min, at the same temperature, the conversion of lauric acid pyrolysis in nitrogen atmosphere was higher than that in air atmosphere. The apparent activation energy of lauric acid for different conversion α in air atmosphere was also calculated by using the methods of model-free functions (Flynn-Wall-Ozawa method and Kissinger-Akahira-Sunose method). The results obtained by the two methods were close to those by the model-fitting method. The average apparent activation energy of lauric acid in air atmosphere was 14.82 kJ/mol; in the range of 10%~80% conversion, the apparent activation energy in the oxidation stage of rapid pyrolysis showed a gentle change with the conversion, which verified that the pyrolysis of lauric acid followed the one-dimensional phase-interface reaction mechanism.

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    科技讲座
    化妆品乳液及乳化新技术(Ⅱ)——水包水乳液的构建及其应用
    Cosmetic emulsions and new technologies of emulsification (II) Construction and application of water-in-water emulsions
    陈凤凤,齐佳悦,倪鑫炯,李云兴,杨成,孙亚娟
    2021 (4):  272-280.  doi: 10.3969/j.issn.1001-1803.2021.04.002
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    在水包油和油包水乳液的基础上,综述了水包水乳液制备的技术发展。首先简单概述了水包水乳液的研究现状,并介绍了水包水乳液在形貌、粒径上的调控,深入探讨了乳液增强水包水乳液的稳定性。最后介绍了水包水乳液在制备微凝胶、活性物包载递送等领域的应用前景,展望了水包水乳液未来的发展方向。文章为基于水包水乳液的制备和应用提供一定的参考和借鉴。

    The development of preparation technology of water-in-water emulsions has been reviewed. Firstly, the research status of water-in-water emulsions is briefly summarized, then the modulation of morphology and particle size of water-in-water emulsions is introduced, and the stability of the reinforced water-in-water emulsions is discussed. Finally, the potential applications of water-in-water emulsions in preparation of microgels and drug delivery are introduced, and the future development direction of water-in-water emulsions is prospected. This review might provide some reference for the preparation and application of water-in-water emulsions.

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    开发与应用
    4种脂肽类生物表面活性剂的性能及其影响因素研究
    Performance and influencing factors of four kinds of lipopeptide biosurfactants
    符军伟,吴娟,梅平
    2021 (4):  281-287.  doi: 10.3969/j.issn.1001-1803.2021.04.003
    摘要 ( 402 )   HTML ( 16 )   PDF(2077KB) ( 487 )  

    实验室培养石油耐生菌并分离出4种阴离子脂肽类生物表面活性剂A8、A10-EA、A10-MeOH和B3。采用铂金板法和液滴形状分析法分别测定其平衡表面张力和动态界面张力,并研究生物表面活性剂的乳化性能及其对芘污染土壤的淋洗作用。结果表明:A8、A10-EA、A10-MeOH和B3的临界胶束浓度(cmc)分别为1.014,5.417,0.717和0.689 g/L。 4种生物表面活性剂在25~70 ℃温度范围内均表现出良好的表面活性,且具有很强的耐单价及二价盐性能。A8表面活性剂对水和正癸烷的乳化效果最佳,48 h后乳化系数保持在65%;在研究浓度范围内,界面张力均可低于10 mN/m。临界胶束浓度下的A8和A10-MeOH溶液对土壤中芘具有良好的淋洗效果。

    Four biosurfactants (A8, A10-EA, A10-MeOH and B3) were extracted from petroleum bacteria cultured in laboratory. They were all identified as anionic lipopeptide biosurfactants. The curves of equilibrium surface tension and dynamic interfacial tension of A8, A10-EA, A10-MeOH and B3 were determined employing the platinum plate and droplet shape analysis methods, respectively. The emulsifying performance of biosurfactants and their leaching performance on pyrene-polluted soil were studied. The experimental results showed that the critical micelle concentrations (cmc’s) of A8, A10-EA, A10-MeOH and B3 were 1.014 g/L, 5.417 g/L, 0.717 g/L and 0.689 g/L, respectively. Four biosurfactants showed good surface activity in the temperature range of 25~70 ℃. In addition, they had good resistance to monovalent and bivalent salts. The results showed that A8 had the best emulsifying performance for formation of emulsion composed of water and n-decane with the emulsifying coefficient of 65% after 48 h. The interfacial tension could be reduced to lower than 10 mN/m within the studied concentration range. The aqueous solutions of A8 and A10-MeOH at their cmc’s had good leaching effect on pyrene in soil.

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    短碳氟链缩合剂的绿色合成与应用
    Green synthesis and application of a condensating agent with short fluorocarbon chain
    汪琴琴,李颜利,邹伟,颜杰,刘波,李慧
    2021 (4):  288-293.  doi: 10.3969/j.issn.1001-1803.2021.04.004
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    以2,2,3,3,4,4,5,5-八氟-1-戊醇(OFP)作为短碳氟链来源,三聚氯氰(TCT)为反应活性基团,通过一锅两步法合成了一种高活性的三嗪类缩合剂1-氯-3,5-双((八氟-1-戊基)氧基)-三嗪(DFCT),采用傅里叶变换红外光谱(FT-IR)、核磁共振(1H NMR、13C NMR、19F NMR)对目标产物(DFCT)进行了表征,通过质谱对中间体2,4-二氯-6-((八氟-1-戊基)氧基)-三嗪(DCFT)和目标产物DFCT进行了表征;同时对缩合试剂合成条件进行研究,确定了合成的较佳工艺:二氯甲烷为溶剂,氢氧化钠为中和试剂,n(TCT)∶n(OFP)=1∶2.2,先在0 ℃反应生成中间体DCFT,然后在30 ℃反应生成目标产物DFCT,收率为96%。用制备的DFCT作为缩合试剂,以羧酸和胺/醇为原料,分别合成了酰胺类目标产物(Ⅰa~Ⅰc)和酯类目标产物(Ⅱa~Ⅱc),说明DFCT可应用于酰胺化、酯化反应的缩合试剂,且反应条件温和,易于操作。

    A triazine-type condensating agent with high activity, 1-chloro-3,5-bis((octafluoropentyl)oxy)-triazine(DFCT), was synthesized by one-pot two-step method, in which cyanuric chloride(TCT)was used as reactive group and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol(OFP)was used as the source of short fluorocarbon chain. The intermediate(2,4-dichloro-6-((octafluoropentyl)oxy)-triazine, DCFT)and the target product(DFCT)were characterized by FT-IR,1H NMR,13C NMR,19F NMR and mass spectrometry. The reaction conditions were optimized according to the yield of product: Dichloromethane was used as the solvent; sodium hydroxide was used as acid binding agent; n(TCT)∶n(OFP)=1∶2.2; the reaction temperature was 0 ℃ to generate DCFT, and then 30 ℃ to obtain the target product DFCT, and the yield of DFCT was 96%. DFCT was used as a condensating agent to activate carboxylic acid which would react with amines/alcohols to produce amides(Ⅰa-Ⅰc)/esters(Ⅱa-Ⅱc). It showed that DFCT could be used as a condensating agent for amidation and esterification reactions, and the reaction conditions were mild and easy to operate.

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    PEG脂肪酸甘油酯的脱脂、赋脂性能研究
    Study of degreasing and fatliquoring properties of PEG fatty acid glycerides
    汪子涵,许虎君
    2021 (4):  294-298.  doi: 10.3969/j.issn.1001-1803.2021.04.005
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    使用猪皮作为受试皮,采用Sebumeter法定量测定皮脂含量,以此为基础自主设计实验,建立了表面活性剂对皮肤表面脱脂、赋脂性能的测定体系。在该体系中,通过测试PEG-7月桂酸甘油酯水溶液对分别含3种化妆品常用油类(白油、橄榄油、二甲基硅油)皮肤表面的洗涤效果,结果表明皮脂减少率随其质量分数的增大先升高后降低;通过测试PEG-7月桂酸甘油酯水溶液对无脂质皮肤表面的洗涤效果,并使用电子显微镜观察皮肤表面,结果表明洗涤后皮脂含量随其质量分数的增大先增加后不变,且在皮肤表面形成了脂质膜;通过测试月桂酸钠/PEG-7月桂酸甘油酯复配体系水溶液对含橄榄油皮肤表面的洗涤效果,结果表明皮脂减少率随PEG-7月桂酸甘油酯添加量的增大先降低后不变。上述实验证明了PEG脂肪酸甘油酯具有良好的脱脂性能和赋脂性能,其应用于相关产品中能温和清洁,与皂基复配能产生赋脂作用,从而改善皂基洗后皮肤的干涩、紧绷感,因此在卸妆产品和皂基型洗护产品中具有广阔的应用前景。

    The measurement system for the skin-surface degreasing and fatliquoring properties of surfactants was established by independently designing experiments based on Sebumeter method using pigskin as the subject skin for quantificationally measuring sebum content. In this system, the washing effects of aqueous solutions of PEG-7 lauric acid glycerides on the skin surfaces containing three oils that were commonly used in cosmetics (white oil, olive oil and simethicone, respectively) were tested, the results of which showed that the sebum decrease rate is increased first and then decreased with the increase of mass fraction. The washing effects of aqueous solutions of PEG-7 lauric acid glycerides on the skin surfaces without lipid were tested, and the skin surfaces were observed by electron microscopy. The results showed that the sebum content after washing is increased first and then remained constant with the increase of mass fraction, and a lipid film was formed on the skin surfaces. The washing effects of the aqueous mixture of sodium laurate/PEG-7 lauric acid glycerides on the skin surfaces containing olive oil were tested, the results of which showed that the sebum decrease rate is decreased first and then remained constant with the increase of amount of PEG-7 lauric acid glycerides. The experiments above proved that PEG fatty acid glycerides possessed good degreasing and fatliquoring properties. They could clean mildly when applied to related products and achieve a fatliquoring effect when compounded with soap base to improve the dry and tight feelings of skin after washing by soap base. Therefore, they had broad application prospect in makeup remover products and soap-based washing products.

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    洗涤用蛋白酶PB92的分子动力学模拟
    Molecular dynamics simulation of protease PB92 for washing before and after substrate binding
    郭雨飞,张剑,于文
    2021 (4):  299-305.  doi: 10.3969/j.issn.1001-1803.2021.04.006
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    以蛋白酶PB92结构为基础,分别对无底物结合和有底物结合的蛋白酶PB92进行了分子动力学(MD)模拟来研究其动力学特性,研究得到了有、无底物结合的蛋白酶PB92的结构性质,并进行了比较,进而评估与底物结合后蛋白酶PB92在结构性特征以及稳定性上发生的一系列变化。实验结果表明,在动力学模拟过程中,有底物结合的蛋白酶PB92的构象比无底物结合的蛋白酶PB92的构象更加致密稳定,表现出符合“诱导契合”反应的模式。对未来更适用于洗涤用品工业的蛋白酶性能和结构的开发提供理论基础和指引。

    Based on the structure of protease PB92, molecular dynamics (MD) simulations were performed on protease PB92 without substrate binding and with substrate binding to study its dynamic characteristics, and the structure of protease PB92 with or without substrate binding was obtained. Properties and comparisons were made to evaluate a series of changes in the structural characteristics and stability of protease PB92 after binding to the substrate. The experimental results show that during the kinetic simulation process, the conformation of protease PB92 with substrate binding is more compact and stable than the conformation of protease PB92 without substrate binding, showing a pattern that conforms to the “induced fit” reaction. The article provides a theoretical basis and guidance for the development of protease properties and structures that are more suitable for the detergent industry in the future.

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    丙三醇对壳聚糖溶液储存稳定性的影响
    Effects of glycerol on the storage stability of the chitosan solution
    陈思佳,易亚,张大伟
    2021 (4):  306-311.  doi: 10.3969/j.issn.1001-1803.2021.04.007
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    研究了溶解在丙三醇(GL)/水混合溶剂中的壳聚糖(CS)黏度随储存时间、储存温度的变化规律,探讨了GL对CS溶液储存稳定性的影响。结果表明,室温时,GL的加入可以有效改善温度升高导致的CS溶液储存稳定性的下降趋势;相比于室温,1 ℃时,使用GL作为稳定剂的CS溶液体系在6.5 h内增比黏度几乎不变,放置99 h后,含有GL的CS溶液增比黏度也仅下降了3.8%,小于同等温度下水溶液中的CS增比黏度下降比例的1/2。GL的加入可以有效提高CS的储存稳定性,1 ℃下储存时,GL使CS溶液达到较佳的储存稳定性能。

    The effects of glycerol (GL) on the storage stability of the chitosan (CS) solution were investigated by studying the variation of the viscosity of CS dissolved in GL/water mixed solvent with storage temperature and storage time. The results showed that, at room temperature, GL could effectively improve the decreasing trend of storage stability of CS solution caused by heating. Compared with room temperature, the specific viscosity of CS solution with GL as stabilizer was almost unchanged within 6.5 h at 1 ℃. After standing for 99 h, the specific viscosity of the CS solution containing GL was decreased by only 3.8%, less than half of the specific viscosity decrease in aqueous solution at the same temperature. The addition of GL could effectively improve the storage stability of CS. When the storage temperature was 1 ℃, the CS solution had better storage stability in the presence of GL.

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    一款舒缓凝胶的临床功效评测研究
    Study on the clinical efficacy of a soothing gel
    孙金媛,陈奕齐,赵华
    2021 (4):  312-318.  doi: 10.3969/j.issn.1001-1803.2021.04.008
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    对实验室自制的舒缓凝胶进行临床功效测试,评价其舒缓刺激的效果。选择30名18~55岁有效健康志愿者作为研究对象,使用胶带重复撕拉破坏皮肤屏障后,用组胺溶液刺激建立皮肤模型,分别在使用舒缓凝胶15、40、60和90 min后,采集受试者前臂内侧照片和皮肤红斑指数(EI值),并通过专家评估和自我评估对泛红、红肿、刺痛和瘙痒进行评估。结果显示,自制舒缓凝胶可有效改善皮肤因刺激而产生的泛红和红肿,同时能缓解瘙痒、疼痛和灼热感,其效果显著好于皮肤自身改善效果,说明其对皮肤具有一定的舒缓刺激的功效。

    Self-developed soothing gel was tested on the clinical efficacy and its soothing effect was evaluated. At the inception of the study, 30 healthy volunteers at the age of 18-55 were selected. Their skin barriers had been destroyed by means of repeatedly tearing the adhesive tapes and the skin models was built by the stimulation of histamine solution. Then the medial forearm photos and skin erythema index (EI values) after using the soothing gel for 15, 40, 60 and 90 minutes were collected. The redness, swelling, stinging and itching could be evaluated by expert evaluation and self-evaluation. The results show that the soothing gel can effectively improve the redness and swelling of skin after stimulation. It also relieves itching and pain, and its effect is significantly better than that of skin self-repair. This indicates that soothing repair gel has a certain effect on soothing irritation.

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    二羟基丙酮免晒美黑凝胶的配方设计与功效研究
    Formulation design and efficacy study of dihydroxyacetone sunless tanner gel
    杨艺,徐建,赵梦恬,曹高
    2021 (4):  319-323.  doi: 10.3969/j.issn.1001-1803.2021.04.009
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    研究了二羟基丙酮美黑凝胶中增稠剂的种类和用量、溶剂配比、二羟基丙酮的含量和制备工艺对配方的影响,通过外观、铺展性等感官评价和稳定性、功效性研究,综合确定较优配方,为二羟基丙酮免晒美黑凝胶的开发提供理论依据。结果表明,二羟基丙酮免晒美黑凝胶的增稠剂宜用2%质量分数的羟乙基纤维素;溶剂以乙醇、丙二醇和丙三醇质量比为10︰5︰3复配;较优工艺为加热溶解增稠剂,冷却后再添加二羟基丙酮;二羟基丙酮的含量为3%~17%时能够呈现类似晒黑的着色。

    The effects of the types and dosage of thickener, the ratio of solvent, the content of dihydroxyacetone and the preparation technology on the formulation design of dihydroxyacetone sunless tanner gel were studied. Through sensory evaluation such as appearance, spreading property, stability and efficacy evaluation, the better formulation was determined synthetically, which laid a theoretical foundation for the development of dihydroxyacetone sunless tanner gel. The results show that 2% hydroxyethyl cellulose should be used as the thickener of dihydroxyacetone tanner gel. The solvent is ethanol, propylene glycol and glycerol with a mass ratio of 10︰5︰3. The better process is heating to dissolve the thickener, then adding dihydroxyacetone after cooling. The color of tanning can be obtained when the content of dihydroxyacetone is 3%~17%.

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    双向发酵提取燕麦β-葡聚糖的护肤功效研究
    Study on the skin care effect of oat β-glucan extracted by bidirectional fermentation
    付豪,吴迪,邴雪,张佳婵,王昌涛,李萌
    2021 (4):  324-330.  doi: 10.3969/j.issn.1001-1803.2021.04.010
    摘要 ( 430 )   HTML ( 18 )   PDF(1769KB) ( 606 )  

    以燕麦作为培养基,通过双向发酵法提取燕麦中的β-葡聚糖,进行化妆品护肤功效研究。选用黄伞、大杯伞和灰树花3种真菌与燕麦进行双向发酵,实验结果表明,燕麦发酵后细胞毒性明显的降低。通过对成纤维细胞内活性氧(ROS)含量、Ⅰ型胶原蛋白(Col Ⅰ)含量及基质金属蛋白酶(MMP-1)含量进行测定发现,与发酵前相比,发酵液及纯化燕麦β-葡聚糖所作用的成纤维细胞内活性氧含量相对降低,Col I含量相对升高,MMP-1含量相对降低,证明发酵液具有一定的抗衰老功效,且比未经发酵处理的燕麦效果要好。通过对小鼠黑素瘤细胞(B16细胞)内黑色素含量及酪氨酸酶激活率的测定发现,发酵液处理后的细胞内黑色素含量更低,其中黄伞燕麦发酵液的效果最好。Franz扩散池透皮吸收实验证明发酵液的累积透过量更高。

    Using oats as a culture medium, the β-glucan in oats was extracted by a bidirectional fermentation method, and its efficacy of cosmetic skin care was studied. Three fungi, i.e., Pholiota adiposa, Clitocybe maxima and Grifola frondose, were used for bidirectional fermentation with oats. The experimental results showed that the cytotoxicity of oats is significantly reduced after fermentation. By measuring the content of reactive oxygen species (ROS), type I collagen (Col I) and matrix metalloproteinase (MMP-1) in fibroblasts, it was found that the fermentation broth had certain anti-aging effect, and the effect was better than that of unfermented oats. Compared with those before fermentation, the fermentation broth and purified fermented oat β-glucan showed relatively reduced content of active oxygen, relatively high content of Col I, and relatively low content of MMP-1in fibroblasts. By measuring the melanin content and tyrosinase activation rate in mouse melanoma cells(B16 cells), it was found that the melanin content in the cells after being treated with the fermentation broth was lower, and the Pholiota adiposa/oat fermentation broth had the best effect. Franz diffusion cell transdermal absorption experiments had showed that the cumulative permeation amount of the fermentation broth is higher.

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    含茶皂素洗发水的安全性及头皮护理功效评价
    Safety and scalp care efficacy evaluation of shampoos containing tea saponins
    杨井国,沈胡驰,陈殿松,赵锷,蔡臻子,王靖
    2021 (4):  331-337.  doi: 10.3969/j.issn.1001-1803.2021.04.011
    摘要 ( 685 )   HTML ( 37 )   PDF(1343KB) ( 771 )  

    采用替代模型(包括EpiSkinTM重组人表皮模型和鸡胚绒毛尿囊膜试验)研究了茶皂素的皮肤刺激性和眼刺激性,结果表明质量分数2%~10%的茶皂素水溶液无皮肤刺激性,而质量分数小于2%的茶皂素水溶液无眼刺激性。在此基础上配制了含茶皂素(质量分数5.0%)的洗发水,结合志愿者感观评价、头皮显微观察和仪器测试,对茶皂素洗发水的头皮护理功效进行了评价,结果显示含茶皂素的洗发水具有较好的去屑、控油、止痒、改善头皮敏感性和屏障功能的功效。上述功效可能与茶皂素的抑菌、抗炎、抗氧化等生物活性相关。本研究可为茶皂素应用于洗发水的安全性及头皮护理功效提供基础数据。

    In this study, the skin irritation and eye irritation of tea saponin were studied by using alternative models (including EpiskinTM reconstructed human epidermal model and chicken embryo chorioallantoic membrane test). The results show that 2%-10% tea saponin solution shows no skin irritation, and tea saponin solution less than 2% (mass fraction) does not exhibit eye irritation. Then, a shampoo containing 5.0% (mass fraction) tea saponin was prepared. By combined sensory evaluation, microscopic scalp observation and instrument test, the efficacy of tea saponin shampoo on scalp care was evaluated. The results show that the shampoo containing tea saponin shows good efficacy in removing dandruff, controlling sebum, relieving itching, lowering scalp sensitivity and improving barrier function. The above effects may be related to the biological activities of tea saponin, such as antibacterial, anti-inflammatory and anti-oxidation. This study can provide basic data for the safety and scalp care efficacy of tea saponin in shampoo.

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    专论与综述
    季铵盐型双子表面活性剂及其改性黏土的研究和应用进展
    Advances in research and application of quaternary ammonium Gemini surfactants and their modified clay
    富多娇,周银,陈晗宇,刘红芹,徐宝财
    2021 (4):  338-347.  doi: 10.3969/j.issn.1001-1803.2021.04.012
    摘要 ( 330 )   HTML ( 17 )   PDF(1806KB) ( 327 )  

    综述了季铵盐型双子表面活性剂的合成及其在改性黏土吸附水中有机污染物中的应用。从烷基季铵盐型双子表面活性剂的合成出发,重点从改变连接基结构、疏水基结构、阳离子连接点结构及反离子四个方面举例介绍了不同类型的季铵盐型双子表面活性剂的合成。同时概述了季铵盐型双子表面活性剂在改性不同种类的天然黏土中的应用。最后基于绿色化学的发展背景,阐述了未来双子表面活性剂的发展方向及其应用于治理水污染中的机遇与挑战。

    The synthesis of quaternary ammonium Gemini surfactants and their application in adsorption of organic pollutants in water by modified clay were reviewed. Starting from the synthesis of alkyl quaternary ammonium Gemini surfactants, emphasis was given on the introduction of different types of quaternary ammonium Gemini surfactants and their synthetic routes from four aspects, i.e. changing the structures of the spacer group, hydrophobic group, cationic connection point and counterion. The application of quaternary ammonium Gemini surfactants to modify different kinds of natural clay was also reviewed. Finally, based on the development background of green chemistry, the development direction of Gemini surfactants in the future and the opportunities and challenges of their application in water pollution control were discussed.

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    微纳米晶体对于泡沫形成和稳定的影响机制研究进展
    Research progress in effects of micro- and nanocrystals on the foam formation and stability
    吕博,燕永利,杜春保,朱西柱,吴春生,于长龙
    2021 (4):  348-355.  doi: 10.3969/j.issn.1001-1803.2021.04.013
    摘要 ( 313 )   HTML ( 12 )   PDF(1516KB) ( 327 )  

    采用常规表面活性剂或多相体系所形成的泡沫稳定性较差而难以满足众多工业领域的应用。近年来,利用微纳米晶体以形成具有超稳定特性的泡沫体系受到学术界的重视。因此,着重论述了晶体颗粒对泡沫的形成机制和稳定机制以及影响因素,如晶体颗粒的浓度、环境温度、粒径大小、溶剂性质等,并简要概括了晶体颗粒形成的泡沫在食品和材料领域的应用,同时指出了该领域今后的研究方向。

    The foams formed by conventional surfactants or multiphase systems have poor stability and they are difficult to be applied in many fields. In recent years, the use of micro- and nano-crystals to form super-stable foam systems has attracted much attention from the academic community. Therefore, the forming mechanism, stabilizing mechanism and influencing factors of crystal particles on the foams have been emphatically discussed, such as the concentration of crystal particles, temperature, size and solvent properties. The application of foams formed by crystal particles in food and materials has been briefly summarized, and the future research direction in this field has been pointed out.

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    硫辛酸酯的实验室制备方法及其在化妆品中的应用进展
    Laboratory preparation of lipoic acid esters and their application prospect in cosmetics
    宋京九,郭晓丹,王东,祝钧
    2021 (4):  356-362.  doi: 10.3969/j.issn.1001-1803.2021.04.014
    摘要 ( 513 )   HTML ( 31 )   PDF(1152KB) ( 1007 )  

    硫辛酸既是药品,也是一种多功能抗氧化剂。以硫辛酸为原料的化妆品虽性能优秀,但也存在不少问题,如不易保存、刺激性强等。且硫辛酸的不稳定性和弱水溶性也给实验人员带来研究上的不便。将硫辛酸和其他功效性原料结合为硫辛酸酯,可以改善硫辛酸的不足,同时增进功效。酯化反应是化学界最经典的反应之一,催化方式多而繁杂,且各自具有独特的优缺点。但据统计,只有其中几种方法使用频次最高,许多优秀的酯化方法常常被忽视。该文从化学催化和生物酶催化两个方面综述了硫辛酸酯的实验室制备方法,对每种方法的优劣加以分析,并对硫辛酸酯在化妆品方面的应用前景进行了展望。

    Lipoic acid is both a drug and a multi-functional antioxidant. The cosmetics using lipoic acid as raw material have excellent performance, but they also have many problems, such as being not easy to preserve and strong irritation. The instability and poor water solubility of lipoic acid also bring inconvenience to professionals in research. The combination of lipoic acid with other functional materials as lipoic acid esters can improve the deficiency of lipoic acid and enhance the efficacy. The esterification reaction is one of the most classic reactions in the chemical world. There are many catalytic methods, and each method has unique advantages and disadvantages. However, according to statistics, only a few of them were most frequently used, and many excellent esterification methods had often been ignored. The laboratory preparation methods of lipoic acid esters were summarized from the aspects of chemical catalysis and biological enzyme catalysis. The advantages and disadvantages of each method were analyzed, and the application prospect of lipoic acid esters in cosmetics was discussed.

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    分析与检测
    超高效液相色谱法测定液态水基类化妆品中22种性激素
    Determination of 22 sex hormones in water-based cosmetics by ultra-high performance liquid chromatography
    胡贝,李丽霞,吴茜,刘红,黄伟,丁晓萍
    2021 (4):  363-369.  doi: 10.3969/j.issn.1001-1803.2021.04.015
    摘要 ( 214 )   HTML ( 9 )   PDF(1153KB) ( 493 )  

    建立了液态水基类化妆品中22种性激素的超高效液相色谱分析方法。样品经80%乙腈水溶液超声提取,离心后上清液经PRiME HLB固相萃取柱净化。采用CORTECS C18+ (2.1 mm×100 mm,2.7 μm)色谱柱分离,以乙腈-水为流动相进行梯度洗脱,PDA检测器多波长检测,外标法定量。结果表明,22种性激素在各自的质量浓度范围内线性关系良好(相关系数r>0.99),检出限(LOD)和定量下限(LOQ)分别为0.03~0.1 μg/mL和0.1~0.4 μg/mL。在5,25和50 μg/g 3个加标水平下的回收率为80.3%~99.6%,相对标准偏差(RSD,n=6)为0.3%~7.7%。该方法前处理简单、灵敏度高、准确性好,适用于液态水基类化妆品中性激素的测定。

    An ultra-high performance liquid chromatography method was established for determination of 22 sex hormones in water-based cosmetics. The sample was ultrasonically extracted with 80% acetonitrile solution. After centrifugation, the supernatant was purified by PRiME HLB column. Chromatographic separation was achieved on an CORTECS C18+ (2.1 mm×100 mm, 2.7 μm) column by gradient elution using acetonitrile-water as mobile phases. PDA detector was used to test samples by multiple wavelengths, and external standard method was used for quantification. The results show that there are good linear relationships for 22 sex hormones in the respective concentration range with their correlation coefficients (r) all above 0.99. The limits of detection (LOD) and limits of quantitation (LOQ) for 22 sex hormones are in the range of 0.03-0.1 μg/mL and 0.1-0.4 μg/mL, respectively. Average recoveries at three levels of 5,25,50 μg/g are in the range of 80.3%-99.6%, with relative standard deviations(RSD, n=6) of 0.3%-7.7%. With the advantages of simplicity, sensitivity and accuracy, this method is suitable for the analysis of sex hormones in water-based cosmetics.

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    化学不稳定染发剂分子衍生物的液-质联用分析
    LC-MS analysis of molecular derivatives of chemically unstable hair colorants
    肖静,李若绮,魏学冰,孙莺,刘婷媛,李莉
    2021 (4):  370-374.  doi: 10.3969/j.issn.1001-1803.2021.04.016
    摘要 ( 204 )   HTML ( 7 )   PDF(1133KB) ( 285 )  

    染发剂成分化学性质不稳定,分析重现性差,根据《化妆品安全技术规范》(2015年版)溶液中染发剂禁、限用成分标准品的稳定性最多可维持48 h,难以用于大批量样品检验。为提高标准品的化学稳定性,选用结构简单的高反应活性亲核取代试剂(溴化苄)将苄基键合到7种苯胺类染发剂分子上(2-硝基对苯二胺、4-硝基邻苯二胺、对氨基苯酚、 4-氨基间甲酚、2-氨基-3羟基吡啶、2,6-二氨基吡啶、N-苯基对苯二胺),以得到化学性质稳定的衍生化产物,提高分析结果的准确性和灵敏度。结果表明7种染发剂成分的衍生化产物在10 d内稳定。该研究为保化产品中化学不稳定禁、限用成分分析提供了新的思路。

    Chemical properties of hair dye ingredients are unstable, and the reproducibility of analysis is poor. According to the “safety technical specification for cosmetics”, the chemical standards of prohibited or restricted ingredients in hair dyes could be maintained in solution for 48 hours at most. Thus, it is difficult to conduct analysis on a large number of samples. In order to maintain the chemical stability of standards, benzyl bromide, a nucleophilic substitution reagent with a simple structure and high reactivity, was used to introduce benzyl groups to seven aniline-type hair dye molecules (i.e. 2-nitro-p-phenylenediamine, 4-nitro-o-phenylenediamine, p-aminophenol, 4-amino-m-cresol, 2-amino-3-hydroxypyridine, 2,3-hydroxypyridine), to obtain derivatives with stable chemical properties and improve the accuracy and sensitivity of the analytical results. The results show that the derivatives of 7 hair dyes are stable within 10 days. This project provides a new idea for the analysis of chemical labile components, which are banned or restricted in chemical products.

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