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    2023年, 第53卷, 第6期 刊出日期:2023-06-22 上一期    下一期
    基础研究
    十四酸单乙醇酰胺醚磺酸盐与烷醇酰胺的复配性能研究
    Properties of mixtures of tetradecanoic acid monoethanolamide ether sulfonate and tetradecanoic acid diethanolamide
    易晓, 田富全, 郑延成, 王帅栋, 蔡小军, 罗芳草, 常世腾
    2023 (6):  609-616.  doi: 10.3969/j.issn.2097-2806.2023.06.001
    摘要 ( 187 )   HTML ( 18 )   PDF(1326KB) ( 192 )  

    以十四酸单乙醇酰胺为原料,通过乙氧基化、磺化反应得到了十四酸单乙醇酰胺醚磺酸盐(C14NE3S),测定了C14NE3S的溶解性,C14NE3S与C14酸二乙醇酰胺(C14DN)复配体系的表面张力以及与长庆原油的界面张力。实验结果表明,C14NE3S具有良好的耐盐性,C14NE3、C14NE3S在蒸馏水中cmc分别为0.07和0.158 mmol/L。溶液热力学理论研究表明,C14NE3S与C14DN摩尔比为1∶4和2∶3时在形成混合胶束时具有中等程度的相互作用。不同比例的复配体系界面张力为超低时对应的NaCl质量分数不同。随着复配体系中C14NE3S含量的增加,达到低或超低界面张力(10-2或10-3 mN/m数量级)的盐质量分数范围及最高无机盐质量分数越来越大。n(C14NE3S) ∶n(C14DN)=1∶4达到低界面张力时的盐质量分数为0.3%~1% NaCl,n(C14NE3S) ∶n(C14DN)= 2∶3和3∶2的复合体系达到超低界面张力时所对应的盐质量分数分别为0.3%~3% NaCl和5%~10% NaCl,体现出表面活性剂极性增强和矿化度增加有利于界面活性的提高。

    To meet the requirements of oil production in high-salinity reservoirs, tetradecanoic acid monoethanolamide ether sulfonate (C14NE3S) was prepared from tetradecanoic acid monoethanolamide by ethoxylation and sulfonation. The solubility and the surface tension of the product were measured. The properties of C14NE3S when mixed with tetradecanoic acid diethanolamide (C14DN) were investigated. The interfacial activity between the binary mixed system and Changqing crude oil in mineralized water was also measured. The results showed that the aqueous solution of C14NE3S remained clear in 30% NaCl at above 30 ℃. The critical micelle concentrations of tetradecanoic acid monoethanolamide polyoxyethylene ether (C14NE3) and C14NE3S in distilled water were 0.07 and 0.158 mmol/L, respectively, indicative of the enhancement of hydrophilicity of C14NE3S due to the multiple hydrophilic groups. The theoretical study on solution thermodynamics showed that C14NE3S had synergism with C14DN for the formation of mixed micelles, especially when the molar fractions of C14NE3S were fixed to 0.2 and 0.4, the mixed systems showed moderate interaction. The interfacial tension of mixed surfactants in which the molar fraction of C14NE3S was 0.2 could be ultra-low to low (i.e., 10-3-10-2 mN/m) in the presence of 0.3%-10% NaCl. The interfacial tension of mixed surfactant systems when n(C14NE3S) ∶n(C14DN) = 2∶3 and 3∶2 could be ultra-low (order of magnitude, 10-3 mN/m) at 0.3%-3% NaCl and 5%-10% NaCl, respectively. The mixed system withn(C14NE3S) ∶n(C14DN) of 1∶4 could show ultra-low interfacial tension at 0.3%-1% NaCl. This work could have a certain guiding role for the development of temperature- and salt-resistant oil-displacement surfactant systems.

    数据和表 | 参考文献 | 相关文章 | 计量指标
    CO2对长庆采出油水物性影响及乳状液稳定机理
    Effect of CO2 on physical properties of produced oil and water in Changqing and emulsion stabilization mechanism
    王华正, 张亮, 康鑫, 康万利, 李哲, 杨红斌
    2023 (6):  617-624.  doi: 10.3969/j.issn.2097-2806.2023.06.002
    摘要 ( 129 )   HTML ( 13 )   PDF(2322KB) ( 323 )  

    二氧化碳(CO2)驱作为一项日益完善的采油技术,已经成为提高低渗油田采收率的重要手段,具有适用范围广、开采成本低和洗油效率高等优点。然而,由于CO2特殊的物理和化学性质,其采出液稳定性较常规水驱明显增强,为采出液处理带来了困难。通过光学显微镜、动态光散射、流变学等方法,研究了在不同压力下CO2处理对长庆原油和采出水的物性以及所形成的油包水(W/O)型乳状液稳定性的影响,探究了CO2驱采出液乳化和稳定的影响因素。结果表明,随着CO2压力的增大,CO2驱采出水中Ca2+和Mg2+质量浓度均有所下降,而CO32-与HCO3-总体含量有所增加,水相pH值略下降,从弱碱性转变为弱酸性。CO2处理导致原油中轻质组分减少,胶质沥青质等重质组分的含量升高,原油极性增强。CO2处理后油的反常温度和析蜡点均升高,原油黏度增加。CO2处理后W/O型乳状液的液滴粒径变小,均一性增强,粒径由2.14 μm减小至0.61 μm。由于乳状液体系黏度上升以及胶质、沥青质和水中颗粒在油/水界面膜上吸附成膜,从而提高油/水界面膜强度,使得乳状液的稳定性增强。为CO2驱采出液处理工艺提供理论指导和技术支撑。

    Carbon dioxide (CO2) flooding has become an important means to improve the recovery efficiency of low-permeability oil fields, with the advantages including wide range of application, low production cost and high oil-washing efficiency. However, due to the special physical and chemical properties of CO2, the stability of corresponding produced liquid is significantly enhanced compared with that of conventional water flooding, which brings many difficulties to the treatment of produced liquid. By means of optical microscope, dynamic light scattering, rheology and other methods, the effects of CO2 treatment on the physical properties of Changqing crude oil and produced water under different pressures and the stability of the water-in-oil (W/O) emulsion were studied, and the factors affecting the emulsification and stability of the produced liquid from CO2 flooding were studied. The results showed that, with the increase of CO2 pressure, the mass concentrations of Ca2+and Mg2+ ions in produced water for CO2 flooding were decreased, while the overall content of CO32- and HCO3- ions was increased, and the pH value of the water phase was slightly decreased, changing from weak alkalinity to weak acidity. CO2 treatment led to the decrease of light components and the increase of heavy components (such as resins and asphaltenes) in crude oil, and the enhancement of crude oil polarity. The abnormal temperature and wax precipitation point of the crude oil after CO2 treatment were both increased, and the viscosity of the crude oil was increased. After CO2 treatment, the droplet size of W/O emulsion became smaller, and its homogeneity was enhanced. The particle size changed from 2.14 μm to 0.61 μm. As the viscosity of the emulsion was increased and the resins, asphaltenes and the particles in water adsorbed on the oil-water interface to form a film, the strength of the interfacial film was improved and the stability of the emulsion was thus enhanced. The clarification of emulsion stabilization mechanism could provide theoretical guidance and technical support for treatment process to the produced liquid from CO2 flooding.

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    基于水/辛酸异戊酯-白油反相乳液体系合成压裂液增稠剂及性能
    Properties of a fracturing fluid thickener synthesized by inverse emulsion polymerization based on water/isoamyl octanoate-white oil
    高党鸽, 李随荣, 王历历, 吕斌, 赵静
    2023 (6):  625-633.  doi: 10.3969/j.issn.2097-2806.2023.06.003
    摘要 ( 115 )   HTML ( 9 )   PDF(2175KB) ( 223 )  

    反相乳液聚合过程中通常采用饱和烷烃的混合物白油作为分散介质,但是白油在使用过程中会存在污染环境的问题。本文以可降解化合物辛酸异戊酯替代了部分白油作为混合油相,丙烯酰胺(AM)和丙烯酰氧乙基三甲基氯化铵(DAC)为单体,通过反相乳液聚合法合成了W/O型聚丙烯酰胺-丙烯酰氧乙基三甲基氯化铵(P(AM-DAC)),通过1H NMR、FT-IR和SEM对其结构进行表征。考察了乳化剂用量和辛酸异戊酯用量对预乳液稳定性、黏度和油-水界面张力的影响,引发剂用量和反应温度对P(AM-DAC)水溶液黏度的影响。结果表明:当乳化剂用量为10%,辛酸异戊酯用量为50%时,引发剂用量为0.8%,反应温度为38 ℃时,P(AM-DAC)水溶液黏度达到最大值,为129 mPa·s。考察了P(AM-DAC)与以白油作为油相合成的聚丙烯酰胺-丙烯酰氧乙基三甲基氯化铵(P(AM-DAC)-W)的性能对比,P(AM-DAC)和P(AM-DAC)-W的粘均分子量分别为5.019×106和5.045×106;质量分数为1%的水溶液黏度分别为129和132 mPa·s;当Na+质量浓度为3 000 mg/L时,1%的水溶液黏度分别为65和67 mPa·s;在90 ℃,170 s-1剪切速率下持续剪切45 min后,1%的水溶液黏度分别为36.9和43.1 mPa·s;陶粒在1%的水溶液中的沉降速度分别为0.049和0.053 mm/s;破胶液表面张力分别为27.8和28.9 mN/m;残渣含量分别为1.63和1.76 mg/L。该研究表明辛酸异戊酯代替部分白油制备压裂液用增稠剂是可行的,不仅不影响增稠性能,而且对耐盐、耐温耐剪切、携砂、破胶和残渣含量等性能没有造成明显的影响。

    In the process of inverse emulsion polymerization, white oil, which is a mixture of saturated paraffins, is usually used as the oil phase, but white oil will pollute the environment during the process of use. In this work,W/O-type poly(acrylamide-acryloxyethyl trimethyl ammonium chloride) (P(AM-DAC)) was synthesized by inverse emulsion polymerization. A biodegradable compound, isoamyl octanoate, was used to replace part of the white oil as mixed oil phase, and acrylamide (AM) and acryloxyethyl trimethyl ammonium chloride (DAC) were monomers. The structure of P(AM-DAC) was characterized by 1H NMR, FT-IR and SEM. The effects of the dosages of emulsifier and isoamyl octanoate on the stability, viscosity and interfacial tension of the pre-emulsion were studied, and the effects of initiator dosage and reaction temperature on the viscosity of aqueous P(AM-DAC) solution were investigated. The results showed that, when the dosage of emulsifier was 10%, the dosage of isoamyl octanoate was 50%, the initiator dosage was 0.8%, and the reaction temperature was 38 ℃, the viscosity of aqueous P(AM-DAC) solution reached the maximum value of 129 mPa·s. The properties of P(AM-DAC) were compared with that of poly(acrylamide-acryloxyethyl trimethylammonium chloride) synthesized by using white oil as oil phase (P(AM-DAC)-W). The viscosity-average molecular weights of P(AM-DAC) and P(AM-DAC)-W were 5.019×106 and 5.045×106, respectively. The viscosities of 1% aqueous solutions were 129 and 132 mPa·s, respectively. When the mass concentration of Na+ was3 000 mg/L, the viscosities of 1% aqueous solutions were 65 and 67 mPa·s, respectively. After continuous shear at 90 ℃ and 170 s-1 for 45 min, the viscosities of 1% aqueous solutions were 36.9 and 43.1 mPa·s, respectively. The settling velocities of ceramsite in 1% aqueous solutions were 0.049 and 0.053 mm/s, respectively. The surface tension of the gel-breaking fluids was 27.8 and 28.9 mN/m, respectively. The residue contents were 1.63 and 1.76 mg/L, respectively. Therefore, partial substitution of white oil by isoamyl octanoate in the preparation of the thickening agent for fracturing fluid is feasible, without any negative influence on the thickening performance, salt resistance, temperature resistance, shear resistance, sand carrying, gel breaking and residue content.

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    科技讲座
    头发与头皮护理的科学基础(Ⅵ)——头皮油脂的特点及调控手段
    Scientific foundations of hair and scalp care (Ⅵ)Characteristics and regulation of scalp sebum
    万凯波, 马玲, 陈殿松, 常宽, 王靖
    2023 (6):  634-641.  doi: 10.3969/j.issn.2097-2806.2023.06.004
    摘要 ( 416 )   HTML ( 34 )   PDF(1932KB) ( 423 )  

    头皮健康日益成为消费者选择发用产品时的关注重点,而头皮油脂是影响头皮健康的关键因素之一。皮脂本身是头皮屏障的重要组分部分,起着保护皮肤、保存水分、维持皮肤稳态等作用,由皮脂腺分泌。皮脂腺位于真皮层,通过全浆分泌产生皮脂,皮脂腺上存在着大量受体,受多种机制调控,其功能的异常会导致多种皮脂腺疾病,引发一系列的头皮健康问题。本文概述了皮脂和皮脂腺的功能及特点,介绍了当前几种皮脂调控理论,并对皮脂分泌的实验评价方法进行概述,总结了市面上控油产品原料及其机理,旨在为皮脂腺相关功能的皮肤护理问题和控油产品的开发解决提供参考依据。

    Scalp health has been increasingly focused by the consumers while choosing hair products. Scalp sebum is one of the key factors affecting scalp health. Sebum is an important component of the scalp barrier, which plays the roles of protecting the skin, preserving moisture and maintaining skin homeostasis. It is secreted by the sebaceous glands. Sebaceous glands are located in the dermis and produce sebum through holocrine secretion. There are a large number of receptors on sebaceous glands, which are regulated by a variety of mechanisms. Abnormality in functions of sebaceous glands can lead to a variety of diseases and a series of scalp health problems. Herein, the functions and characteristics of sebum and sebaceous glands are summarized. Several current theories of sebum regulation are introduced. The experimental evaluation methods of sebum secretion are summarized. The raw materials of oil-control products on the market and their mechanisms are also summarized, which might provide reference both for the skin care problems related to the functions of sebaceous glands and the development of oil-control products.

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    开发与应用
    CaCO3纳米晶体稳定非水相泡沫实验研究
    Experimental study on non-aqueous foams stabilized by CaCO3 nanocrystals
    张佩亮, 燕永利, 吕博, 曹玉霞, 吴春生, 贺炳成
    2023 (6):  642-648.  doi: 10.3969/j.issn.2097-2806.2023.06.005
    摘要 ( 97 )   HTML ( 3 )   PDF(2097KB) ( 355 )  

    非水相泡沫在油田开发、功能材料、食品工业和日化等领域有着广泛的应用,对非水相泡沫性能的调控在相关行业的发展中发挥着重要的影响。然而,由于非水相溶剂具有的低界面张力和低介电常数,导致其发泡难度较大。为解决非水相溶剂发泡困难的问题,文章通过制备CaCO3纳米晶体,并经TEM,FT-IR及XRD等对晶体颗粒进行了表征,采用1H,1H,2H,2H-全氟癸基三乙氧基硅烷对CaCO3纳米晶体的润湿性进行了调控,研究CaCO3纳米晶体对非水相溶剂发泡性能的影响。研究发现:随CaCO3纳米晶体质量分数的增加,不同接触角的CaCO3纳米晶体所产生的泡沫体积呈现先增后减的趋势,当晶体质量分数为5%时,非水相溶剂发泡性能最佳,泡沫体积最高可达到120 mL;非水相泡沫的稳定性随CaCO3纳米晶体接触角的增加呈现先增强后减弱的趋势,当接触角范围在47.5°~73.9°时,非水相泡沫的稳定性最佳,排液半衰期最高可达到100 h。

    Non-aqueous foams are widely used in fields such as oilfield development, functional materials, food industry and daily chemicals. The regulation of the properties of non-aqueous foams plays an important role in the development of related industries. Due to the low interfacial tension and low dielectric constant of non-aqueous solvents, foaming is difficult. Therefore, in this work, to solve the problems in non-aqueous solvent foaming, CaCO3 nanocrystals were prepared. The crystal particles were characterized by TEM, FT-IR and XRD. 1H, 1H, 2H, 2H-perfluorodecyl triethoxy silane was used to regulate the wettability of CaCO3 nanocrystals. The effects of CaCO3 nanocrystals on the foaming performance of non-aqueous solvents were studied. It was found that, with the increase of mass fraction of CaCO3 nanocrystals, the foam volume produced by CaCO3 nanocrystals with different contact angles first increased and then decreased. When the crystal mass fraction was 5%, the foaming performance of non-aqueous solvent was the best, and the foam volume could reach 120 mL. The stability of the non-aqueous foam first increased and then decreased with the increase of the contact angle of CaCO3 nanocrystals. When the contact angle was in the range from 47.5° to 73.9°, the stability of the non-aqueous foam was the best, and the draining half-life was up to 100 h.

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    乳化热固性树脂体系构建及其封堵性能评价
    Construction and plugging performance evaluation of emulsified thermosetting resin system
    甄恩龙, 张雯, 钱真, 杜若彤, 王洋
    2023 (6):  649-657.  doi: 10.3969/j.issn.2097-2806.2023.06.006
    摘要 ( 91 )   HTML ( 4 )   PDF(1707KB) ( 135 )  

    随着高温(储层温度130 ℃)裂缝油藏开展水驱作业,注入水沿裂缝窜进问题日益突出。环氧树脂高温条件下固化后具有强度高、耐老化的特点,是一种有潜力的高温堵剂。针对环氧树脂不易注入、潮湿条件下难固化的问题,采用相反转法乳化环氧树脂,初选多种乳化剂分别以自来水和模拟地层水为水相,对环氧树脂E-44进行乳化,筛选出同时适用于两种水相的乳化剂;然后进行单因素实验,分别研究搅拌速度、乳化温度、加水速度、乳化剂质量分数、油水体积比工艺因素对环氧树脂相反转过程及乳状液性能的影响;最后采用正交试验综合分析各因素的影响水平并确定较优乳化工艺参数,建立乳化体系。差示扫描量热实验结果表明,该体系的固化温度为129.5 ℃,在储层温度下固化后具有良好的封堵效果。

    With the development of water flooding in fractured reservoirs with high temperature (reservoir temperature of 130 ℃), the problem of fracture channeling by water injected becomes more and more prominent. Epoxy resin has the characteristics of high strength and aging resistance after curing at high temperature, which is a potential high-temperature plugging agent. Since epoxy resin is not easy to be injected and difficult to cure under wet conditions, the epoxy resin was emulsified by the phase inversion method. A variety of emulsifiers were selected to emulsify epoxy resin (E-44) with tap water and simulated formation water as the water phase, and the emulsifiers suitable for both kinds of water were screened out. Then single-factor experiments were carried out to study the effects of stirring speed, emulsifying temperature, water adding speed, mass fraction of emulsifier, and oil-water volume ratio on the phase inversion process of epoxy resin and the properties of emulsion. Finally, the orthogonal experiment was used to analyze the level of each factor and determine the optimal emulsifying process. The results of differential scanning calorimetry showed that the curing temperature of the system was 129.5 ℃, and it had good plugging effect after curing at reservoir temperature.

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    乙烯基吡咯烷酮/乙烯基咪唑聚合物的制备及其防沾染性
    Preparation and anti-staining properties of N-vinyl pyrrolidone/N-vinyl imidazole polymers
    张森林, 孙旭东, 张凌飞, 王云
    2023 (6):  658-664.  doi: 10.3969/j.issn.2097-2806.2023.06.007
    摘要 ( 216 )   HTML ( 9 )   PDF(2817KB) ( 467 )  

    以N-乙烯基吡咯烷酮(NVP)和N-乙烯基咪唑(NVI)为原料合成了三种不同单体比例的N-乙烯基吡咯烷酮/N-乙烯基咪唑聚合物(VP/VI聚合物),采用乌氏黏度计、傅里叶变化红外光谱(FT-IR)、凝胶渗透色谱(GPC)对聚合物的结构进行了表征,结果表明三种聚合物的K值均在30左右,重均分子量(MW)分别为37 848,22 656,8 111。通过紫外可见光光谱(UV-Vis)和防沾染实验对三种VP/VI聚合物的防沾染性进行测试,结果表明,加入VPVI-P,VPVI-5和VPVI-7后,直接大红染液的最大吸收波长(λmax)从499 nm分别升至520,527和531 nm,λmax处的吸光度从0.30升至0.39左右;直接深蓝染液的λmax从558 nm升至576 nm左右,λmax处的吸光度从0.15升至0.35,三种聚合物均与直接大红、直接深蓝染料分子有明显相互作用。随着聚合物中NVI组分的增加,VP/VI聚合物的防串色性能得到提升。

    Three kinds of N-vinyl pyrrolidone (NVP)/N-vinyl imidazole (NVI) polymers (VP/VI polymers) with different monomer ratios were synthesized, and all samples were characterized and analyzed by Ubbelohde viscometer, Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The results showed that the K values of the three copolymers were around 30, and the weight average molecular weights (MW) of the three copolymers were 37 848, 22 656 and 8 111, respectively. The anti-staining properties of the VP/VI polymers were tested by ultraviolet-visible spectrophotometer (UV-vis) and anti-staining experiments. With the addition of VPVI-P, VPVI-5 and VPVI-7,the maximum absorption wavelength (λmax) of the Direct Red 28solution was red shifted from 499 nm to 520 nm, 527 nm and 531 nm, respectively. The absorbance value at λmax was increased from 0.30 to 0.39 as the mass concentration of the VP/VI polymer was increased from 0 g/L to 5.0×10-2 g/L. The λmax of the Direct Dark Blue solution was red shifted from 558 nm to approximately 576 nm and the absorbance at λmax was increased from 0.15 to around 0.35 as the mass concentration of the VP/VI polymer was increased. It indicated obvious interactions between the VP/VI polymers and the dye molecules (Congo red and direct blue). It showed better performance in the anti-staining experiments as the content of NVI component was increased in the polymers.

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    人参红景天乳液的制作及其抗氧化、美白作用研究
    Preparation of a lotion containing Rhodiola rosea and Panax ginseng and its antioxidant and whitening effects
    韩雨迪, 金莉英, 孙熙浛, 林长青, 崔承弼
    2023 (6):  665-672.  doi: 10.3969/j.issn.2097-2806.2023.06.008
    摘要 ( 229 )   HTML ( 21 )   PDF(1578KB) ( 236 )  

    试验确定了红景天提取物与人参提取物的最佳复配比并以其为原料制成人参红景天乳液,采用正交试验确定了其最佳工艺,并采用1,1-二苯基-2-三硝基苯肼(DPPH)、2,2'-联氨-双(3-乙基苯并噻唑啉)二胺盐(ABTS)、3-氧代-2-苯基-4,4,5,5-四甲基咪唑啉-1-氧(PTIO)自由基清除试验及乳液中总黄酮含量的测定、小鼠B16黑色素瘤细胞实验、酪氨酸酶及黑色素抑制实验、黑色素细胞氧化应激相关蛋白表达实验研究其抗氧化和美白作用。结果表明:人参红景天乳液中红景天提取物与人参提取物的体积分数比为5∶3时配方最佳,乳化温度为80 ℃、乳化时间为20 min、乳化速度为4 000 r/min为最佳工艺,此条件下乳液的总黄酮含量为1.84 mg/mL,其对DPPH,ABTS,PTIO自由基的清除率分别为40.17%,48.27%,38.22%,酪氨酸酶抑制率与黑色素抑制率分别为40.49%和35.64%,且在中、高剂量组中氧化应激相关蛋白表达量较高,人参红景天乳液具有良好的抗氧化活性及美白功效。

    The best mixing ratio of Rhodiola rosea extract and Panax ginseng extract was determined, and this mixture was used as a raw material to prepare a lotion. The process was optimized by orthogonal experiment. The antioxidant and whitening effects of the lotion were studied by DPPH, ABTS, PTIO free radical scavenging tests, measurement of total flavonoid content, mouse B16 melanoma cell test, tyrosinase and melanin inhibition tests, and melanocyte oxidative stress-related protein expression test. The results showed that, when the ratio of Rhodiola rosea extract to Panax ginseng extract in the lotion was 5∶3, the optimal formula was obtained. The optimized conditions were emulsification temperature of 80 ℃, emulsification time of 20 min, and emulsification speed of 4 000 r/min. The total flavonoid content of the lotion thus obtained was 1.84 mg/mL.The scavenging rates for DPPH, ABTS and PTIO free radicals were 40.17%, 48.27% and 38.22%, respectively. The inhibition rates on tyrosinase and melanin were 40.49% and 35.64%, respectively. The expression of oxidative stress-related proteins was high in the middle- and high-dose groups. Therefore, the lotion containing Rhodiola rosea and Panax ginseng had good antioxidant activity and whitening efficacy.

    数据和表 | 参考文献 | 相关文章 | 计量指标
    专论与综述
    化妆品原料标准现状及缺失分析
    Analysis on the current situation and deficiency of cosmetic rawmaterial standards
    顾宇翔, 刘恕, 周羽
    2023 (6):  673-678.  doi: 10.3969/j.issn.2097-2806.2023.06.009
    摘要 ( 223 )   HTML ( 9 )   PDF(1007KB) ( 264 )  

    化妆品的质量很大程度上取决于所用原料,通过分析和整理化妆品原料标准,发现目前国家和行业化妆品原料标准主要包括《化妆品安全技术规范》限用、准用物质,可能含有害杂质的原料、基础原料和功效成分这几类,团体标准更侧重于制订基础成分的原料标准和植物提取物的原料标准。有不少常用原料虽然没有化妆品专用的标准,但是可以参考、借鉴其他行业的标准。总体而言,有质量标准的原料仅占《已使用化妆品原料目录》中的小部分,热门的纳米成分标准缺失,植物提取物原料标准中的特征性指标设定也有所欠缺。缺乏统一的化妆品原料标准给企业的质量控制、政府部门的监督带来了不小的困难,今后建议加强可能含有害杂质的化妆品原料、功效性成分、纳米成分和植物提取物的原料标准制订,完善化妆品原料标准化体系。

    The quality of cosmetics greatly depended on the quality of raw materials. Through the analysis and sorting of cosmetics raw material standards, it was found that the existing national and industrial cosmetics raw material standards included limited and permitted substances in “Safety and Technical Standards for Cosmetics”, basic materials and raw materials that might contain harmful impurities. The number of preservative standards accounted for more than 1/4 of all national and industrial cosmetic raw material standards. There are some raw materials that might contain harmful impurities, such as methanol, asbestos and diethylene glycol, in ethanol, talc powder and glycerol, respectively. If the amount of these impurities is not controlled, it might cause health damage to the consumers. Different from the concerns of government departments, the group standard focuses on the raw material standards of basic raw materials and plant extracts. Although there are many common raw materials without special standards for cosmetics, they could refer to the standards of other industries. However, the attention should be paid to the applicability of these standards. For example, only a few standards of colorant food additives could fully meet the requirements of “Safety and Technical Standards for Cosmetics”. Nowadays, the raw materials standards only account for a small part of raw materials allowed in “Catalogue of used cosmetic raw materials”. The popular nano component standard is missing, and the setting of characteristic indicators in the raw material standards of plant extracts is also insufficient. The lack of unified cosmetic raw material standards brings great difficulties to the quality control of enterprises and the supervision of government. In the future, it is suggested to strengthen the draft of raw material standards for cosmetic raw materials that may contain harmful impurities, functional components, nano components and plant extracts, to improve the standardization system of cosmetic raw materials.

    数据和表 | 参考文献 | 相关文章 | 计量指标
    化妆品中防腐剂的应用现状及检测技术研究进展
    Recent progress on the application status of cosmetic preservatives and their detection technology
    朱海荣, 孙胜敏, 张娟, 刘爽, 刘倩倩, 邹惠玲
    2023 (6):  679-685.  doi: 10.3969/j.issn.2097-2806.2023.06.010
    摘要 ( 262 )   HTML ( 15 )   PDF(1006KB) ( 464 )  

    化妆品中的防腐剂在抑制微生物生长、延长产品保质期方面发挥了重要作用,但其使用不当会损害人体健康并对环境和生态安全造成潜在危害。随着化妆品安全事件的频发,居民消费安全意识的提升和行业监管法规趋严,防腐剂的添加状况成为社会各界的关注焦点。文章总结了当前化妆品中防腐剂的使用现状,梳理了近年来常规检测技术在化妆品中防腐剂领域的最新应用,介绍了高效液相色谱-电感耦合等离子体质谱法和激光解吸附离子化质谱等新型检测手段。分析了化妆品中防腐剂的市场发展前景和检测技术发展方向,为今后化妆品中防腐剂的监管和高通量快速检测提供借鉴。

    Preservatives in cosmetics play an important role in inhibiting the growth of microbial and maintaining the product quality. With the influence of domestic and foreign residents' consumption level upgrading and the rapid development of Internet and other factors, the market demand of domestic cosmetics is growing steadily. However, the improper use of preservatives could be harmful to human health and cause negative effects on environment and ecological security. With the frequent occurrence of cosmetic safety incidents, the safety awareness of consumers has been improved and the industry regulations has been strengthened. Nowadays, the addition of preservatives has received much attention, which sets a higher request to the market regulations of cosmetics preservatives. The species of the cosmetic preservatives used at home and abroad have significantly increased. Accordingly, the analytical methods for single preservatives are difficult to meet new regulatory requirements. With the rapid upgrade of modern instrumental analysis technology, high-throughput, efficient, high-sensitivity and low-cost detection methods are essential to push the development of the industry. In this review, the current status of cosmetic preservatives is outlined and the up to date applications of conventional instruments for their detections have been summarized. Some novel detection methods are introduced, such as high performance liquid chromatography-inductively coupled plasma mass spectrometry and laser desorption ionization mass spectrometry. The market development of cosmetic preservatives and detection technology on them are analyzed and prospected, which would shed light on the high-throughput rapid detection of cosmetic preservatives in the future.

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    基于in silico技术探究益母草在化妆品中的应用前景
    Research on the application prospect of motherwort in cosmetics based on in silico approach
    刘丽, 尹雅婷, 程康, 李惠, 吕智, 易帆
    2023 (6):  686-697.  doi: 10.3969/j.issn.2097-2806.2023.06.011
    摘要 ( 152 )   HTML ( 14 )   PDF(2080KB) ( 350 )  

    益母草具有行血养血,活血化瘀的作用,临床应用广泛,常用来主治妇科疾病,近年来益母草的美容应用逐渐受到关注。本研究利用in silico技术平台,通过文献计量学对益母草的研究现状和未来的发展态势进行了预测,同时结合网络药理学对益母草皮肤美容的功效及物质基础进行预测,结果表明益母草的活性成分萜类化合物及益母草碱可通过NADPH、PDPK1、MAOB、VEGF2、SIRT2等靶点有效促进血液流动,改善皮肤微循环,调节激素代谢,降低炎症反应,抵御氧化应激,具有延缓皮肤老化,滋养皮肤的功效。本研究为益母草作为化妆品植物功效原料的物质基础及功效机理提供了理论基础,同时证明了益母草作为化妆品功效原料的独特性,具备良好的发展前景。

    Motherwort (Leonurus japonicas Houtt.) is a good gynecological medicine, which has the function of promoting circulation of blood, nourishing blood and activating circulation to remove blood stasis. It is widely used in clinical practice and commonly used to treat gynecological diseases, while the beauty application of motherwort has gradually attracted attention in recent year. This article built an in silico technology platform to present a systematic review of the literature concerning motherwort over the past two decades through bibliometrics to explore current research hotspots and predict the future development trends, and combine with network pharmacology to predict the efficacy and material basis of motherwort for skin beauty. The results show that terpenoids and alkali, the main active ingredient of motherwort, can effectively open blood vessles and expand blood passages to improve the facial skin blood micro-circulation and strengthen the skin's metabolism through NADPH, PDPK1, MAOB, VEGF2, SIRT2. In addition, they can regulate hormone metabolism to maintain the skin barrier, regulate the secretion of inflammatory factors to ease skin inflammation and involve in the regulation of cell-cycle to prevents oxidative stress-mediated skin aging by ER-α,ER-β, AKRAC3, CA2, HSP90AA1, MAPK14, CDK2 and other targets. Our research suggests that motherwort has the effect of delaying skin aging and nourishing skin. This study provides the theoretical basis for the material basis and efficacy mechanism of motherwort as a cosmetic plant efficacy raw material, and proves the uniqueness of motherwort as a cosmetic efficacy raw material, and has good development prospects.

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    西藏特色植物资源在化妆品中的研究与应用
    Research and application of Tibetan characteristic plant resources in cosmetics
    孟宪瑶, 程一丹, 郭苗苗, 凌霄, 虞旦, 李丽
    2023 (6):  698-705.  doi: 10.3969/j.issn.2097-2806.2023.06.012
    摘要 ( 243 )   HTML ( 11 )   PDF(1049KB) ( 191 )  

    国家“鼓励和支持运用现代科学技术,结合我国传统优势项目和特色植物资源研究开发化妆品”的政策导向为国内化妆品开发指明了全新的科研方向。西藏作为我国乃至世界上生物多样性最丰富和最典型的地区之一,孕育了9 600多种野生植物,其中1 075种为西藏特有,各类珍稀濒危保护野生植物383种。其地处青藏高原,海拔高、光照强、空气稀薄、昼夜温差大,导致该地区植物资源具有独特的二次代谢产物与生物活性,近年来,成为中国特色植物资源化妆品研发的热点领域。文章对西藏阿里、那曲、拉萨、日喀则、山南、林芝及昌都等七个地区植物资源的植物组成、区系划分、植物多样性特征进行系统综述,首次系统分析30种西藏特色植物在抗皱、美白、舒缓、祛痘、发用等产品中的应用现状及其发展前景,为西藏植物资源的保护、开发以及在化妆品领域的研究与应用提供可靠的基础理论支持。

    The state encourages and supports the use of modern science and technology, and the policy orientation of research and development of cosmetics in combination with our country's traditional advantageous projects and characteristic plant resources has pointed out a new scientific research direction for the development of domestic cosmetics. As one of the richest and most typical regions of biodiversity in the country and even in the world, Tibet has bred more than 9 600 kinds of wild plants, of which 1 075 are endemic to Tibet, and 383 kinds of rare and endangered wild plants are protected. Because of its location on the Qinghai-Tibet Plateau, high altitude, strong sunlight, thin air, and large temperature difference between day and night, the plant resources in this area have unique secondary metabolites and biological activities. This paper systematically reviews the plant composition, floristic division and plant diversity characteristics of plant resources in seven regions of Tibet, including Ali, Nagqu, Lhasa, Shigatse, Shannan, Nyingchi and Qamdo. Based on the general situation of plant resources in Tibet, the application status and development prospect of 30 kinds of plants with Tibetan characteristics in anti-wrinkle, whitening, soothing, anti-acne, hair care and other products are systematically analyzed for the first time, providing reliable theoretical support for the protection and development of Tibetan plant resources and the research and application in the field of cosmetics.

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    分析与检测
    超高效液相色谱-四级杆/飞行时间高分辨质谱法测定膏霜类化妆品中的阿托品
    Determination of atropine in cream cosmetics by ultra performance liquid chromatography-quadrupole/time-of-flight high-resolution mass spectrometry
    邱倩倩, 路勇, 王欣然, 吴宝金, 王海燕, 孙建博
    2023 (6):  706-713.  doi: 10.3969/j.issn.2097-2806.2023.06.013
    摘要 ( 118 )   HTML ( 5 )   PDF(1523KB) ( 294 )  

    建立了超声辅助提取-超高效液相色谱-四级杆/飞行时间高分辨质谱快速测定膏霜类化妆品中阿托品的分析方法和阿托品数据库。样品经80%乙腈溶液超声提取,离心后过滤。经ACQUITY UPLC® BEH C18 (2.1 mm×100 mm,1.7 μm)色谱柱分离,在电喷雾正离子模式下,采用MSE模式对其进行定性,采用多反应监测(MRM)模式进行数据采集,基质溶剂标准溶液外标法定量。结果显示,阿托品在3.0~100.0 ng/mL的质量浓度范围内线性关系良好,相关系数(R2)>0.999 0,方法的检出限为1.0 ng/mL,定量限为3.0 ng/mL。在质量浓度分别为20,50,80 ng/mL的加标水平下,阿托品的平均回收率分别为107.9%,97.0%,105.3%。RSD分别为4.2%,3.0%,3.2%(n=6)。该方法操作简单,灵敏度高,适用于膏霜类化妆品中阿托品的快速筛查和定量分析。

    A quick method for detecting atropine in cream cosmetics was devised using ultra performance liquid chromatography-quadrupole/time-of-flight high-resolution mass spectrometry (UPLC-QTOF-MS/MS), and a different approach was created for establishing an atropine database. The samples were ultrasonically extracted with 80% (V/V) acetonitrile solution. After centrifugation, the extracts were separated and filtered. The separation was performed on an ACQUITY UPLC® BEH C18 (2.1 mm×100 mm, 1.7 μm) column in electrospray positive ionization mode with MSE mode for characterization, multiple reaction monitoring (MRM) mode for data acquisition and quantification by external standard method of matrix solvent standard solution. The atropine shows a good linearity (R2>0.999 0) in the range of 3.0-100.0 ng/mL. The limit of detection (LOD) of the method is 1.0 ng/mL and the limit of quantification (LOQ) is 3.0 ng/mL. The average recoveries of atropine are 107.9%, 97.0% and 105.3% at the spiked levels of 20, 50 and 80 ng/mL, respectively. The RSDs are 4.2%, 3.0% and 3.2%, respectively (n=6). This method is simple, sensitive and suitable for the rapid screening and quantitative analysis of atropine in cosmetics.

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    高效液相色谱-串联质谱法测定化妆品中17种头孢类抗生素
    Determination of 17 cephalosporins residues in cosmetics by HPLC-MS-MS
    孙小杰, 王玉梅, 刘真, 刘其南
    2023 (6):  714-720.  doi: 10.3969/j.issn.2097-2806.2023.06.014
    摘要 ( 114 )   HTML ( 8 )   PDF(1169KB) ( 121 )  

    建立了高效液相色谱-串联质谱(HPLC-MS/MS)测定化妆品中的17种头孢类抗生素的方法。化妆品中的头孢类药物使用EDTA-Mcllvaine缓冲液提取,经超声和离心后,上清液经PRIME HLB固相萃取柱净化。采用Waters ACQUITY UPLC BEH C18 (2.1 mm×100 mm,1.7 µm)色谱柱分离,流动相为甲醇-0.1%甲酸水溶液,梯度洗脱,电喷雾离子源正离子模式,多反应监测模式(MRM)进行检测。结果表明,17种头孢类药物在此分析方法下分离效果良好,在相应的范围内线性关系良好,相关系数均大于0.99,各加标水平的平均回收率为75.27%~110.32%,相对标准偏差小于10.00%。该方法前处理方便简单,定量准确,适用于化妆品基质中头孢类抗生素的测定。

    There is a huge space in the market of cosmetics, and the quality problem of antibiotics abusage in cosmetics often exists. Cephalosporins as a kind of antibiotic have also been found in cosmetics regulation in recent years. Currently there is no literature on the determination method of cephalosporins in cosmetics. In order to assess the cephalosporins residues in cosmetics, a method was established for the determination of 17 cephalosporins residues in cosmetics by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The cosmetics with liquid water-based, oil-based and cream were investigated. The conditions of extractant solvent, solid phase extraction column and chromatographic conditions were optimized. The samples were ultrasonically extracted with EDTA-Mcllvaine, centrifuged, and then purified with PRIME HLB SPE columns. The target compounds were separated on a Waters ACQUITY UPLC BEH C18 column (2.1 mm×100 mm, 1.7 µm) by gradient elution using methanol and 0.1% formic acid solution as mobile phases. The analysis was carried out using a positive electrospray ion source in the multiple reaction monitoring mode. Results show that under the optimized test conditions the target compounds are separated effectively. There are good linear relationships for 17 cephalosporins in the corresponding ranges, and the linear correlation coefficients are all above 0.99. The average recoveries of the lower limit of quantitation are between 75.27% and 110.32%, and the relative deviations are less than 10.00%. The method is convenient, simple, accurate, and is suitable for the determination of 17 cephalosporins in various kinds of cosmetics.

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    高效液相色谱测定化妆品原料羟丙基四氢吡喃三醇的含量及构型比例
    Determination and isomer distribution of a cosmetic raw material hydroxypropyl tetrahydropyrantriol by HPLC
    于海英, 乔振云, 李启艳, 胡德福, 牛水蛟, 王法平
    2023 (6):  721-724.  doi: 10.3969/j.issn.2097-2806.2023.06.015
    摘要 ( 313 )   HTML ( 8 )   PDF(1093KB) ( 274 )  

    建立了高效液相色谱法测定化妆品原料羟丙基四氢吡喃三醇的含量及构型比例的方法。样品以水溶解,经CAPCELL PAK ADME色谱柱分离,示差折光检测器测定,柱温为35 ℃,检测池温度为40 ℃,流速为1.0 mL/min。结果显示,羟丙基四氢吡喃三醇在0.1~2.0 mg/mL范围内线性关系良好,相关系数(r)≥0.999 9,加标回收率为99.3%~99.6%,相对标准偏差(n=3)小于0.76%,方法检出限和定量限分别为0.03%和0.10%。该方法具有操作简单、定量准确、能够有效分离异构体等优点,适用于化妆品原料羟丙基四氢吡喃三醇含量及构型比例的测定。

    A method for determination of the content and isomer distribution of a cosmetic raw material, i.e., hydroxypropyl tetrahydropyrantriol, was established by high performance liquid chromatography. Samples were extracted with water and then were separated by CAPCELL PAK ADME column and determined by differential refractive index detector. The column temperature was 35 ℃, the detector temperature was 40 ℃, and the flow rate was 1.0 mL/min. The results showed that, it had good linearity within the range of 0.1-2.0 mg/mL for hydroxypropyl tetrahydropyrantriol, with the correlation coefficient above 0.999 9. The recoveries were 99.3%-99.6%, with the relative standard deviations (n=3) lower than 0.76%. The limit of detection and the limit of quantitation were 0.03% and 0.10%, respectively. This method is simple, accurate and reproducible, which is suitable for both determination of the content and the isomer distribution of hydroxypropyl tetrahydropyrantriol.

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    高效液相色谱法测定氧化型染发产品中47种染发剂
    Determination of 47 kinds of dyestuffs in oxidative hair dye by high performance liquid chromatography
    高瑞芳, 柴格, 李祥胜
    2023 (6):  725-732.  doi: 10.3969/j.issn.2097-2806.2023.06.016
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    建立了测定氧化型染发产品中47种染发剂含量的高效液相色谱分析方法。样品经无水乙醇-10 g/L亚硫酸氢钠水溶液(体积比7∶3)超声提取后,加入2 g/L亚硫酸氢钠水溶液定容至25 mL。采用Shim-pack GIST C18 (4.6 mm×250 mm,5 μm)色谱柱分离,分别以乙腈-20 mmol/L磷酸二氢钾溶液(pH7.5)、甲醇-20 mmol/L磷酸二氢钾溶液(pH7.5)为流动相梯度洗脱,流速1.0 mL/min,柱温25 ℃,检测波长230和280 nm,标准曲线法定量。结果表明,47种染发剂在相应的浓度范围线性关系良好,相关系数均大于0.999,检出限(LOD)为1~35 μg/g。在3种加标水平下的平均加标回收率为80.4%~110.7%,相对标准偏差为0.25%~5.08%。与现行标准检验方法相比,该方法增加了15种准用染发剂的测定,具有较高的准确度和精密度,能满足实际检测需求,适用于氧化型染发产品中47种染发剂的测定。

    A high performance liquid chromatographic (HPLC) method was developed for the determination of 47 kinds of dyestuffs in oxidative hair dye. The samples were extracted ultrasonically with anhydrous ethanol-10 g/L sodium bisulfite solution (7∶3), and then 2 g/L sodium bisulfite solution was added to a constant volume of 25 mL. If necessary, the extractions were centrifuged at 10 000 r/min for 5 minutes. Chromatographic separation was carried on a Shim-pack GIST C18 (4.6 mm×250 mm, 5 μm) column by gradient elution. Acetonitrile-20 mmol/L dipotassium hydrogen phosphate (pH7.5) and methanol-20 mmol/L dipotassium hydrogen phosphate (pH7.5) were used as the mobile phase, respectively. The flow rate was 1.0 mL/min and the column temperature was 25 ℃. The analysis of 47 kinds of dyestuffs was performed by HPLC with diode array detector at the wavelength of 230, 280 nm, respectively. Quantification analysis was performed by the calibration curve method. The linear ranges of 47 kinds of dyestuffs show good linearity with the correlation coefficients more than 0.999. The limits of detection (LOD) are in the ranges of 1-35 μg/g. The mean recoveries at three different concentration levels are 80.4%-110.7% with the RSDs of 0.25%-5.08%. Compared with the current standard, this method increases the determination of 15 permitted dyes. This method has high accuracy and precision, and can meet the actual detection needs. It is suitable for the determination of 47 kinds of dyestuffs in oxidized hair dyes.

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