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    2022年, 第52卷, 第9期 刊出日期:2022-09-22 上一期    下一期
    基础研究
    消防减阻用聚合物/表面活性剂复配体系实验探索
    Experimental exploration on applicability of the mixture of polymer and surfactant as the drag reduction additives for firefighting system
    贺文云,徐娜,李小坤,张瑾渊,吕耀东,张兴芳
    2022 (9):  913-919.  doi: 10.3969/j.issn.1001-1803.2022.09.001
    摘要 ( 2346 )   HTML ( 34 )   PDF(1712KB) ( 532 )  

    在全球能源紧张的背景下,“过程节能”手段的探索具有重要意义。消防工作在国民经济和社会发展中占据重要地位,将添加剂湍流减阻技术引进到消防系统,在不额外增大能耗的前提下能直接提高消防水的射出速度和射程,在提高灭火效率的同时节省水泵功耗。根据消防水流特点,初步选定聚氧乙烯/十八烷基三甲基氯化铵/水杨酸钠的聚合物/表面活性剂复配体系作为研究对象,通过测试该体系的减阻性能和表面张力,证实此体系可以用作消防系统减阻添加剂,但需控制聚合物浓度。研究发现复配体系的减阻性能及表面张力表现主要依赖于聚、表分子之间的相互作用,因此聚、表分子间相互作用强的体系,才更适合用作消防减阻聚/表复配添加剂。

    With the global energy scarcity, the exploration of process energy conservation method is of great significance. The fire fighting plays an important role in the national economy and social development. If the techniques of drag reduction by additives are applied to the firefighting system, the jet velocity and range of firefighting water can be directly increased without additional energy consumption, and consequently, the firefighting efficiency will be improved, and the power consumption of fire pumps will be reduced. According to the characteristics of fire water flow, polyethylene oxide (PEO), octadecyl trimethyl ammonium chloride (OTAC) and sodium salicylate (NaSal) were chosen to be mixed as the drag reduction additives for the firefighting system. The drag reduction ability and surface tension of the mixed PEO/OTAC/NaSal solution were experimentally tested under different conditions. The results show that the PEO/OTAC/NaSal mixture is suitable for the firefighting system as the drag reduction additives, however, the PEO concentration must be controlled. Meanwhile, it is found that the drag reduction ability and surface tension of PEO/OTAC/NaSal solution mainly depend on the interactions between PEO and OTAC. Therefore, the mixture with strong interactions between polymer and surfactant molecules is more suitable for the firefighting system as drag reduction additives.

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    洗发水体系低温“果冻”现象流变学研究及改善
    “Jelly” phenomenon rheology study and improvement in shampoo system
    梁亦欢,杜晶
    2022 (9):  920-929.  doi: 10.3969/j.issn.1001-1803.2022.09.002
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    从流变分析的角度上,运用动态温度扫描和动态频率扫描的方式了解低温凝胶现象,也就是俗称的“果冻”现象,在两种常见的透明洗发水表面活性剂体系中的表现。该现象在能形成虫状胶束并伴随盐屏蔽效应而加剧增稠的体系中容易产生,且随着Versathix(PEG-150季戊四醇四硬脂酸酯/PPG-2羟乙基椰油酰胺)锚定类型增稠剂的加入而加剧,在不易形成虫状胶束而仅依靠增稠剂形成三维网络结构增稠的体系中没有发现。冷冻透射电镜(Cryo-TEM)表征,确认了相似网络结构中虫状胶束和Versathix增稠的微观差异。同时探究在洗发水体系应用中有效改善凝胶的尝试方法。通过筛选,发现0.5%用量的水溶性赋脂剂Cromollient SCE(二PPG-2肉豆蔻油醇聚醚-10己二酸酯)的应用,使配方可以在不影响洗发水常温表观黏度范围的前提下有效改善体系低温下产生的凝胶现象。而该油脂更是一款能带来额外调理利益和提升配方温和性的原料,具有实际参考价值。

    “Jelly” phenomenon of two combined surfactant systems (SLES+CAPB and LS+CAPB) within temperature range of 0 ℃ to 40 ℃ were studied via two types of dynamic rheology tests, temperature sweep and frequency sweep. The results show that the phenomenon is mainly caused by the mechanism of wormlike micelles self-thickening structure. They both happen to appear in SLES+CAPB bases and LS+CAPB bases. The gelation range demonstrated by dynamic temperature constant frequency sweep appears in the systems which generates capability to form wormlike micelles. And the addition of Versathix (PEG-150 Pentaerythrityl Tetrastearate (and) PPG-2 Hydroxyethyl Cocamide) can intensify the phenomenon because its anchor chemical structure helps to build up the 3D network in between wormlike micelles and to consolidate its entangled transient interspace micellar structure. The systems with wormlike micelles can be verified by dynamic frequency constant temperature sweep and draw the graph of ‘Cole-Cole’ curve with the result of Maxwell trend. All over the trials, viscosity of SLES+CAPB systems could be thickened by sodium chloride with salt shielding effect to form wormlike micelles self-thickening structure. However, viscosity of LS+CAPB system can only form wormlike micelles with a certain low pH range. On the other hand, systems which can only form spherical micelles do not show gelation range according to temperature sweep results, even in those systems using a large use level of Versathix. The systems containing spherical micelles thickened by Versathix show Maxwell trend in ‘Cole-Cole’ curve transferred from the results of dynamic frequency constant temperature sweep as well. This is due to the network effect provided by the thickener. The microstructural difference of wormlike micelles and Versathix thickening systems were confirmed via characterization with Cryo-TEM images. In shampoo formulations, applying 0.5% use level of emollients with good solubilities may help to reduce “jelly” phenomenon during low temperature condition. However, some of those emollients may influence on viscosity at room temperature. According to the study results, Cromollient SCE (Di-PPG-2 Myreth-10 Adipate) out of other ingredients can help to reduce this phenomenon with practical applying significance. Cromollient SCE does not influence much on system viscosity within room temperature range. And it can keep good clarity even using in surfactant systems. In addition, this ingredient can work as hair conditioning agent and help to reduce irritation mitigation in surfactant-based systems with additional benefits.

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    科技讲座
    常用化妆品成型技术(Ⅲ)——液固飞扬:气雾剂和喷雾剂
    Common cosmetic preparation technologies (Ⅲ)Liquid, solid floating: Aerosol and spray
    于昕琪,隋振全,徐桂云,范金石
    2022 (9):  930-936.  doi: 10.3969/j.issn.1001-1803.2022.09.003
    摘要 ( 1424 )   HTML ( 28 )   PDF(1047KB) ( 635 )  

    气雾剂和喷雾剂是一类使用方便、应用范围广泛、发展前景广阔的精细化工产品制剂,通过压力装置使液(固)态功效成分分散为分散度高、表面积巨大的细小液滴(颗粒),使功效成分均匀地分布在应用场所的立体空间里或作用对象的表面上以充分发挥其功能效用。本文介绍了气雾剂和喷雾剂的发展历程、产品特性、工作原理、装置构件、关键材料、制备方法和使用注意事项,有选择地介绍了近年来气雾剂和喷雾剂在个人护理、卫生保健、家用清洁和生物药剂等方面的典型应用情况,并简析了气雾剂和喷雾剂未来的研发重点和发展趋势。

    Aerosols and sprays are widely used in industry, agriculture, scientific research and people’s daily life in virtue of their advantages such as small volume, light weight, easy to carry and use, excellent function, and suitable for application for open, close and semi-close applicable spaces. Aerosols and sprays atomize functional active components into very fine droplets/particles via pressure device, which can easily spread throughout the whole application space, or evenly distribute on the object surfaces, to make full use of the valuable active components. Herein, the development history, product characteristics, working principle, device structure, key components, production process and application notices of aerosols and sprays were introduced. Furthermore, the typical applications of aerosols and sprays in hair and body care, household cleaning, medical products with natural active components, and biological pharmaceutical preparations in recent years were mentioned. Finally, the possible priorities and directions for research and development of aerosols and sprays in the future were also briefly pointed out.

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    开发与应用
    高产生物表面活性剂鼠李糖脂的制备及性能研究
    The production of high yield biosurfactant rhamnolipid and performance research
    郑兰健,臧颖,林潼,谢懿雯,王红蕾
    2022 (9):  937-944.  doi: 10.3969/j.issn.1001-1803.2022.09.004
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    为降低生物表面活性剂使用成本且缓解厨余油带来的环境压力,从实验室前期原油污染土壤筛选保存的菌株出发,通过原油培养基初筛和乳化指数、表面张力测定等复筛,筛选具有较高表面活性的菌株。同时通过单因素实验优化生物表面活性剂A产量,并对其理化性质、乳化性和增溶性进行表征。实验结果表明,通过筛选获得一株具有较高表面活性的菌株铜绿假单胞菌AY-1(Pseudomonas aeruginosa AY-1)。该菌株在35 ℃、pH 8.0、摇床转速180 r/min、厨余油50 g/L、硝酸钠2 g/L发酵96 h产生5.86 g/L鼠李糖脂,其临界胶束质量浓度(cmc)为200 mg/L,且在温度4~120 ℃、pH 2~12和NaCl含量0~20%(w/%)等条件下均具有较高表面张力稳定性。同时进一步研究了该菌株产生的鼠李糖脂对不同疏水化合物(甲苯、正己烷、环己烷、庚烷和十六烷)的乳化性能和多环芳烃(菲和芘)的增溶效果,结果表明该菌株产生的鼠李糖脂对十六烷的乳化效果最好且对多环芳烃中的菲和芘具有明显的增溶效果。

    In order to reduce the cost of biosurfactant in various industries and alleviate the environmental pressure caused by kitchen waste oil, a strain with higher surface activity was screened out through preliminary screening of crude oil medium and re-screening of emulsification index and surface tension measurement from preserved strains with crude oil-contaminated soil in the early stage. In addition, biosurfactant produced by this strain was extracted by acid precipitation-organic solvent extraction, such as acid precipitation-ethyl acetate and acid precipitation-(VchloroformVmethanol=2∶1). Further, the biosurfactant production of this bacteria was optimized by single factor experiment and physical-chemical properties, emulsification and solubilization of biosurfactant were characterized. The experimental results show that a strain with higher surface activity, Pseudomonas aeruginosa AY-1, is obtained through screening. This strain is fermented to produce 5.86 g/L biosurfactant which are characterized as rhamnolipids when the fermentation conditions are 35 ℃, pH=8.0, shaker speed 180 r/min, kitchen waste 50 g/L, sodium nitrate 2 g/L and fermentation time 96 h. The critical micelle mass concentration (cmc) of rhamnolipid produced by this strain is 200 mg/L, and the surface tension of rhamnolipids changes little when rhamnolipid is in all kinds of conditions such as temperature (4-120 ℃), pH=2-12 and the content of NaCl (0-20%, w/%). At the same time, the emulsification performance on different hydrophobic compounds (methylbenzene, n-hexane, cyclohexane, heptane and n-hexadecane) and solubilization effect on polycyclic aromatic hydrocarbons (phenanthrene and pyrene) of rhamnolipids produced by this strain were further studied. Results show that the rhamnolipids produced by this strain have the best emulsification effect on n-hexadecane and significant solubilization effect on polycyclic aromatic hydrocarbons (phenanthrene and pyrene).

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    凝胶软物质体系的超分子结构多样性分析
    Analysis of supramolecular structure diversity of gel soft matter system
    窦欣
    2022 (9):  945-950.  doi: 10.3969/j.issn.1001-1803.2022.09.005
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    采用TEMPO介导氧化方法分析凝胶软物质体系的超分子结构多样性。以TEMPO氧化细菌纤维素基纳米复合凝胶作为实验样品。通过FT-IR、SEM、XRD、TEM和Raman光谱测试获取超分子结构多样性分析结果。结果表明,不同类型凝胶的FT-IR光谱伸缩振动峰值、X射线衍射峰数量、Raman光谱振动峰数量均表现出较大差异,在添加剂、光照条件等干扰因素的作用下,SEM图像显示的超分子结构出现明显转变。而TEM图像也说明,纤维素含量不同的凝胶超分子结构也不一致。

    The supramolecular structure diversity of gel soft matter system was analyzed by TEMPO-mediated oxidation method, TEMPO-oxidized bacterial cellulose nanocomposite gel was used as the experimental sample. The analysis results of supramolecular structure diversity were obtained by FT-IR, SEM, XRD, TEM and Raman spectroscopy. The results showed that, there were great differences in FT-IR stretching vibration peaks, X-ray diffraction peaks and Raman vibration peaks between different types of gel. Under the influences of additives, light conditions and other interference factors, the supramolecular structure showed by SEM images changed significantly. When the cellulose content in the gel was 10%, the molecules in the structure piled up with each other, indicative of an obvious uneven dispersion, while the pore distribution distance in the gel was kept at several nanometers. TEM images also showed that the supramolecular structures of gel with different cellulose content were inconsistent. With the increase of calcination temperature, the number of vibration peaks in the Raman spectrum of gel was continuously increased, indicative of the change in supramolecular structure, which could reflect the diversity of supramolecular structure.

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    表面活性剂结构对细粒煤过滤脱水的影响及其机理研究
    Effect of surfactant structure on filtration dewatering of fine coal and its mechanism research
    赵珂,刘生玉,张素红
    2022 (9):  951-959.  doi: 10.3969/j.issn.1001-1803.2022.09.006
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    为降低细粒煤的水分,选取具有不同疏水基的聚氧乙烯型非离子表面活性剂AEO9,LAE9,OP9和不同亲水基的AEO4,AEO7,AEO9,AEO15,AEO20表面活性剂分别进行了细粒煤的过滤脱水试验。选取滤饼水分、过滤速度、滤饼比阻、滤饼渗透率为脱水效果评价指标。进行了表面张力、红外、润湿热、吸附量、Zeta电位的测试表征。细粒煤脱水实验结果表明,不同疏水基表面活性剂中的AEO9表现较好的过滤脱水性能,不同亲水基的AEO系列表面活性剂中AEO7具有较好的过滤脱水性能。针对表面活性剂AEO7进行了细粒煤的过滤脱水的机理研究,发现在药剂用量为120 mg/L时,含氧官能团减弱程度最大,润湿热最低,表明煤表面的疏水性增强最显著,此时滤饼水分降低4.66%。同时滤液表面张力在AEO7药剂用量超过120 mg/L几乎不再降低。吸附量测试结果表明表面活性剂用量在超过120 mg/L后,可能煤表面发生双层吸附使得煤表面变得亲水,从而减弱过滤脱水性能。

    In order to reduce the moisture content of fine coal, both nonionic polyoxyethylene surfactants with different hydrophobic groups such as AEO9, LAE9, OP9 and surfactants with different hydrophilic groups including AEO4, AEO7, AEO9, AEO15, and AEO20 were selected for fine coal filtration dewatering experiments. The filter cake moisture, filter speed, filter cake specific resistance and permeability were used as the evaluation indexes for the dewatering effect. The surface tension, infrared spectroscopy, wetting heat, adsorption capacity and Zeta potential were employed. The results of the fine coal dewatering experiments show that AEO9 among the surfactants with different hydrophobic groups has best performance, and AEO7 among AEO series surfactants with different hydrophilic groups has best performance. The mechanism of the surfactant AEO7 in the filtration and dewatering of fine coal was studied. The obtained results show that when the dosage of AEO7 is 120 mg/L, the maximum amount of oxygen-containing functional groups have been decreased and the lowest wetting heat of the fine coal treated by AEO7 indicating that the hydrophobicity of the coal surface has significantly been enhanced. At this time, the moisture content of the filter cake is reduced by 4.66%. The surface tension of the filtrate solution hardly decreases when the dosage of AEO7 agent exceeds 120 mg/L. The adsorption capacity results show that when the surfactant dosage exceeds 120 mg/L, it is possible that double-layer adsorption on the coal surface may make the coal surface hydrophilic, thereby weaken the filtration and dewatering performance.

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    增稠定型二合一流变改性剂的合成及应用研究
    Study on the synthesis and application of thickening-fixing hybrid rheology modifier
    麦景璋,李琳,何金清,李泽勇
    2022 (9):  960-968.  doi: 10.3969/j.issn.1001-1803.2022.09.007
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    通过沉淀聚合法分别合成了丙烯酸(AA)/N-乙烯基吡咯烷酮(NVP)、AA/NVP/N-叔丁基丙烯酰胺(BAA)、AA/NVP/N-叔辛基丙烯酰胺(OAA)的交联共聚物,并对其进行了结构及性能表征。通过DSC测定其玻璃化转变温度(Tg),发现随着BAA和OAA的引入,Tg依次升高。润湿分散性能及聚合物水凝胶测试结果表明,AA/NVP/OAA交联共聚物的润湿分散性能、增稠性能、水凝胶透光率和头发定型能力均较为理想。选取该聚合物进一步考察其流变学性能和发胶应用性能,并对其流变特性和定型机理进行了探讨。水凝胶的流变测试结果表明,该聚合物表现出与传统卡波树脂和市售AA/NVP共聚物流变改性剂不同的流变特性,且其可黏取性能与市售成品发胶接近。发胶应用实验结果表明,该聚合物用于发胶配方中,能同时起到增稠剂和定型剂的作用,其发胶透光率、定型能力优于市售AA/NVP共聚物流变改 性剂。

    Acrylic acid (AA)/N-vinyl-2-pyrrolidinone (NVP) crosspolymer, AA/NVP/N-tert-butyl acrylamide (BAA) crosspolymer and AA/NVP/N-tert-octyl acrylamide (OAA) crosspolymer were synthesized via precipitation polymerization. The polymers were characterized by FT-IR, 1H NMR and differential scanning calorimetry (DSC). Glass transition temperature (Tg) of the polymers were measured by DSC. As the introduction of BAA and OAA, polymers’ Tg rise from 120.50 ℃ to 123.66 ℃ and 129.23 ℃, respectively, while the neutralized polymers’ Tg rise from 97.99 ℃ to 111.76 ℃ and 112.74 ℃, respectively. The viscosity, transmittance, hair curl retention, wetting time and dispersing performance of these samples were characterized to determine their thickening, fixing and dispersing performances. The AA/NVP/OAA crosspolymer shows the best parameters. This polymer sample was selected for further study, such as rheological test and hair gel application. Commercial hair gels usually can stick to the user’s fingers so that it can be picked up easily. The G' (0.1 rad/s)and G'' (100 rad/s) of various samples were determined by rotary rheometer so that rheological properties and pick up performance can be characterized. The G' (0.1 rad/s)and G'' (100 rad/s) of AA/NVP/OAA crosspolymer’s aquogel are comparable with the commercial hair gels, while the commercial carbomers and commercial AA/NVP copolymer show the opposite. These results indicate that AA/NVP/OAA crosspolymer’s aquogel can be easily picked up by users as the commercial hair gels. Hair gel formulation study was also carried out. Formula A is the hair gel prepared by AA/NVP/OAA crosspolymer, which shows comparable performance with the hair gel prepared by carbomer and PVP-K90 (Formula D). The transmittance of Formula A is 93.82%, viscosity is 59 000 mPa·s and the curl retention is 96.5%. Hair bending strength of Formula A is also comparable with Formula D. These results indicate that AA/NVP/OAA crosspolymer can act as both rheology modifier and hair fixing agent in the formula. Even though commercial AA/NVP polymer can also provide thickening and fixing functions, it shows poorer transmittance, lower curl retention and weaker bending strength in formula. The introduction of NVP and OAA can also improve the compatibility with PVP-K90.

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    鹿茸提取物对UVB诱导光老化小鼠皮肤的保护作用
    Protective effect of pilose antler extracts against UVB-induced skin photoaging in mice
    唐靖惠,王毅,马淑骅,孙娅楠,贺改英,何忠梅
    2022 (9):  969-974.  doi: 10.3969/j.issn.1001-1803.2022.09.008
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    研究鹿茸提取物(PAEs)对UVB诱导光老化小鼠皮肤的保护作用。通过HE染色和含水量测试仪检测光老化小鼠皮肤形态和含水量变化,采用双光子激发荧光(TPEF)和液晶偏光影像技术研究小鼠皮肤胶原纤维病理变化,RT-qPCR方法分析不同类型胶原蛋白、基质金属蛋白酶及基质金属蛋白酶抑制剂的表达。结果发现PAEs显著抑制UVB引起的小鼠皮肤厚度,增加光老化小鼠皮肤角质层和深层含水量。PAEs明显提高光老化小鼠真皮胶原纤维荧光信号强度,降低胶原纤维方位角的变异程度,促进光老化小鼠真皮Ⅰ型和Ⅲ型胶原蛋白mRNA表达,调控MMP-1和TIMP-2 mRNA表达。结果表明PAEs可以明显保护UVB引起皮肤的光老化,在抗衰老产品中具有重要的应用价值。

    Skin aging is an irreversible physiological process. Many factors, such as long-term UVB radiation, can accelerate skin aging and lead to a series of skin problems, whose symptoms include irregular pigmentation, wrinkles, dryness, loss of elasticity and capillary dilation. Herein, the protective effects of pilose antler extracts (PAEs) on skin photoaging induced by UVB in mice were investigated. The changes of epidermal thickness in photoaged skin were observed by H&E staining, while the changes of skin water content in photoaged mice were detected by a stratum corneum water content tester and a subcutaneous 0.05 mm water content tester. The fluorescence signal intensity of collagen fibers was detected in vivo by two-photon excitation fluorescence (TPEF) imaging technique, while the azimuth angle changes of collagen fibers were studied by liquid crystal polarized light imaging. RT-qPCR was used to analyze the expression of different types of collagen, matrix metalloproteinases and matrix metalloproteinase inhibitors. The results showed that, PAEs significantly inhibited UVB-induced hyperproliferation in mouse skin and increased the water content in the stratum corneum and deep layers of photoaged mouse skin. PAEs significantly increased the fluorescence signal intensity of dermal collagen fibers in photoaged mice, decreased the variability of collagen fiber azimuth, promoted the expression of dermal type I and III collagen mRNA in photoaged mice, and regulated MMP-1 and TIMP-2 mRNA expression. The experimental results showed that PAEs could significantly improve UVB-induced skin photoaging and have important applications in anti-aging products.

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    玉米秸秆木聚糖的硫酸化修饰及抗氧化活性研究
    Study on the synthesis and antioxidant activities of a sulfated cornstalk xylan
    米浩宇,刘婉怡,段虹钰,张天春,韩鲁平
    2022 (9):  975-980.  doi: 10.3969/j.issn.1001-1803.2022.09.009
    摘要 ( 220 )   HTML ( 13 )   PDF(1209KB) ( 295 )  

    以玉米秸秆为原料采用碱提醇沉法提取木聚糖,通过筛选合适的酯化体系(ClSO3H/C5H5N法、C5H5N·SO3/C5H5N法、氨基三磺酸钠法)制备了玉米秸秆木聚糖硫酸酯,产物结构特征经IR、13C NMR确证,进一步考察了其抗氧化活性。通过碱提醇沉法获得木聚糖,经氨基三磺酸钠法酯化体系(反应时间2.5 h,反应温度45 ℃),所获得的产物硫酸取代度(DS)为1.566。体外抗氧化实验表明,玉米秸秆木聚糖硫酸酯对·OH有较好的清除能力,具有剂量依赖性,并且硫酸酯化可以提高玉米秸秆木聚糖的抗氧化活性。

    Cornstalk was used as raw material, from which cornstalk xylan was obtained by alkaline extraction and alcohol precipitation. Then a sulfated cornstalk xylan was synthesized by three sulfating methods (chlorosulfuric acid-pyridine method, sulfur trioxide-pyridine method and sodium sulfamate method). The structure of sulfated cornstalk xylan were characterized by IR and 13C NMR, and its antioxidant activity in vitro was further investigated. Structural characterization revealed that sulfate groups were successfully grafted onto cornstalk xylan. The results indicated that, the optimal conditions for sulfating were sodium sulfamate method at a reaction temperature of 45 ℃ for a sulfating time of 2.5 h. The degree of substitution (DS) of the sulfated cornstalk xylan thus obtained was 1.566. The results of in vitro antioxidant activities showed that, sulfated cornstalk xylan had scavenging ability on hydroxyl radicals in a dose-dependent manner, and sulfation could improve the antioxidant activity of cornstalk xylan.

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    牛奶外泌体对皮肤屏障的影响研究
    Study on the effect of bovine milk exosomes on skin barrier
    柏玮,韩春乐,王淼,杜焕青,董凤伟,葛啸虎
    2022 (9):  981-989.  doi: 10.3969/j.issn.1001-1803.2022.09.010
    摘要 ( 593 )   HTML ( 26 )   PDF(1280KB) ( 715 )  

    通过密度梯度离心的方法纯化得到了牛奶外泌体,并研究了牛奶外泌体对皮肤屏障的影响。结果表明,制备的牛奶外泌体呈现出典型的外泌体形态、粒径和标志物特征;分析牛奶外泌体的蛋白组数据,聚类显示,它对细胞间粘附的生物学过程的影响是显著的,提示了牛奶外泌体可能具有修护皮肤屏障的潜能。进一步分析牛奶外泌体对人永生化角质形成细胞(HaCat)的蛋白表达的影响,蛋白质谱数据显示,细胞的紧密联接蛋白Claudin-1和Claudin-6表达上调,紧密联接通路相关的负调控因子PPP2R1A和PPP2R2A下调。细胞实验发现,牛奶外泌体上调HaCat中Claudin-1基因的转录水平和翻译水平。动物实验进一步验证了牛奶外泌体对小鼠皮肤中Claudin-1的表达影响,发现48 h后,Claudin-1的表达显著提升。

    Bovine milk exosomes were purified by density centrifugation, and their effect on skin barrier was studied. TEM, nanoFCM, Western-blot, LC-MS and BCA test showed that, the obtained bovine milk exosomes were highly pure exosome product whose appearance, particle size and markers were consistent with the typical characteristics of exosomes. Proteomics was then employed. The results showed that, the bovine milk exosomes contributed to cell-cell adhesion, indicative of an effect of skin barrier repair. HaCat cells were then incubated with bovine milk exosomes, and the cell proteomics analysis proved that tight junction proteins such as Claudin-1 and Claudin-6 were upregulated by bovine milk exosomes at all dosages, while some negative regulatory factors like PPP2R1A and PPP2R2A were downregulated. Molecular analysis identified with the proteomics results showed that Claudin-1 was upregulated at both transcription and translation levels. The bovine milk exosomes were then labeled with fluorescent dye and topically applied on mouse skin. Trans-epidermal trace of labeled bovine milk exosomes was demonstrated by fluorescence confocal microscopy. Immunohistochemical detection further verified that Claudin-1 was enhanced after 48 hours’ topical application on mouse skin.

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    专论与综述
    化妆品中化学性风险物质及其检测研究进展
    Research progress on chemical risk substances and related detection methods in cosmetics
    顾宇翔,杨保刚,陆壹
    2022 (9):  990-998.  doi: 10.3969/j.issn.1001-1803.2022.09.011
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    概述了化妆品安全评估所涉及的化学性风险物质,包括《化妆品安全技术规范》规定的限用、准用物质中的杂质要求,化妆品原料标准和国内外研究、文献所报道的原料中可能存在的风险物质。结果表明准用着色剂中的风险物质较多,而且大多没有相应的检测方法;其他常用原料中可能含有的杂质不少是化妆品中的禁用物质,来源于降解、生产用原料带入、化学反应的副产物等多个途径,目前基本有配套的测定标准或文献方法可供参考。今后随着原料安全评估的深入开展,还会发现越来越多的风险物质,因此建议加强化妆品原料标准尤其是准用着色剂质量标准和所含风险物质检测方法标准的研究,充实化妆品标准体系。

    The chemical risk substances involved in the safety assessment of cosmetics were summarized. The requirements for impurities in restricted and approved substances were specified in the “Safety and Technical Standards for Cosmetics”, and the possible risk substances in raw materials in the standards of cosmetics raw materials, domestic and foreign research and literature were presented. It is concluded that many approved colorants contain risk substances, however, there are little detection methods of these impurities. Although there are many product standards of dyes or food additives, no cosmetic raw material standard of approved colorants is released. The quality indicators of most dyes or food additives do not match the requirements of “Safety and Technical Standards for Cosmetics”. It is indicated that many risk substances that may be contained in common raw materials are prohibited substances in cosmetics, which come from degradation, introduction of raw materials, by-products of chemical reaction, et al. Most of these impurities have determination standards or literature testing methods. Since there are no residue requirements in standard or assessment for chlorotoluene, nitromethane and other risk substances which rare prohibited substances in cosmetics, it is necessary to calculate the MoS, LCR or AEL according to their toxicological data and exposure dose during the safety assessment, in order to judge the safety of the product. In the future, with the in-depth development of raw material safety assessment, more and more risk substances would be found. It is suggested to strengthen the research of cosmetics raw materials, especially the quality standards of approved colorants and the detection methods of their risk substances, so as to enrich the system of cosmetics standards.

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    肽在个人护理用品中的应用现状与展望
    Application status and prospect of peptides in personal care products
    燕欣,凌峰,魏少敏
    2022 (9):  999-1004.  doi: 10.3969/j.issn.1001-1803.2022.09.012
    摘要 ( 530 )   HTML ( 29 )   PDF(1158KB) ( 553 )  

    活性肽是一类具有皮肤护理功效的功效成分,近几年为市场和消费者所推崇。为了解全球肽原料在个人护理用品中的应用现状,文章回顾了肽的简短应用历史,以及在个人护理用品中所应用肽的定义,比较了我国《已使用化妆品原料目录(2021年版)》和《国际化妆品原料字典和手册(2018版)》中肽原料的情况,调研了2016—2020年全球个人护理用品市场上含有肽成分的产品情况及肽应用广泛的企业。进一步研究了使用频率较高的14种肽,并按其作用机理分为三类:信号肽、神经递质抑制肽、载体肽,还简述了其他一些活性肽。文章还对肽在个人护理用品中的应用趋势进行了展望,以期为功效性肽原料的进一步研究开发和应用提供一定的参考价值。

    Peptides are a kind of active ingredient with skin care effect, which has been highly praised by the market and consumers in recent years. To understand the current situation of peptide application in personal care products globally, the brief history of peptide applications and their naming rules were reviewed. The peptide materials in Inventory of Existing Cosmetic Ingredients in China (2021 edition) and International Cosmetic Ingredient Dictionary and Handbook (2018 edition) were compared, and the products containing peptides and the companies with extensive use of peptides in the global market of personal care products from 2016 to 2020 were surveyed. 14 peptides that were frequently used were further studied and divided into three categories according to their action mechanism: signal peptide, neurotransmitter inhibitory peptide and carrier peptide. Some other active peptides were also briefly described. The application trend of peptides in personal care products was also prospected to provide reference for their further research, development, and application.

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    符号元素特征在化妆品包装设计中的展现
    The representation of symbolic elements in cosmetic packaging design
    闫吉
    2022 (9):  1005-1010.  doi: 10.3969/j.issn.1001-1803.2022.09.013
    摘要 ( 202 )   HTML ( 18 )   PDF(985KB) ( 210 )  

    化妆品行业更新换代较快,品类繁多,为吸引女性受众,需要对产品进行全面包装,使其更具吸引力。为提升化妆品包装的吸引力,本文探索符号元素特征在化妆品包装设计中的展现。首先研究化妆品包装与符号元素特征关系,根据化妆品包装符号元素特征原理,获得符号元素特征的认识性与普遍性,分析了化妆品包装中符号元素特征的应用路径;然后介绍了化妆品包装的功能特性,并且针对各种包装材料所包含的符号元素特征指示性语义开展详细介绍。最后介绍了化妆品包装上符号元素特征应用现状,分析符号元素特征中的造型类符号元素特征、色彩类符号元素特征、图形类符号元素特征以及传统文化符号元素特征在化妆品包装中的应用情况。

    The cosmetics industry is updated rapidly and has a wide range of categories. In order to attract female audiences, it is necessary to fully package the products to make them more attractive. In order to enhance the attractiveness of cosmetic packaging, this article explores the display of symbolic element characteristics in cosmetic packaging design. This article first explores the relationship between cosmetic packaging and symbol element characteristics, and obtains the recognition and universality of symbol element characteristics according to the principle of cosmetic packaging symbol element characteristics, and analyzes the application path of symbol element characteristics in cosmetic packaging; then introduces the functional characteristics of cosmetic packaging. In addition, a detailed introduction is given to the indicative semantics of the symbolic elements contained in various packaging materials. Finally, on this basis, it introduces the current status of the application of symbolic element characteristics on cosmetics packaging, and analyzes the application of the symbolic element characteristics of the modeling symbol element characteristics, color symbol element characteristics, graphic symbol element characteristics and traditional cultural symbol element characteristics in cosmetic packaging.

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    复杂泡沫体系排液动力学研究进展
    Research progress in the dynamics of liquid drainage from complex foam system
    燕永利,蔡雨秀,豆龙龙,曹玉霞
    2022 (9):  1011-1015.  doi: 10.3969/j.issn.1001-1803.2022.09.014
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    看似普通的小气泡,在人们的日常生活、工业生产和医药卫生等领域却发挥着极其重要的作用,而对于含有不同精细结构的复杂泡沫体系而言,其具有更加丰富的流动和稳定特性。本文针对这类复杂泡沫体系,包括表面活性剂聚集体稳定泡沫、纳米颗粒稳定泡沫和油水混相泡沫的排液动力学研究的发展现状做一总结评述。聚焦复杂泡沫体系中精细结构对其排液行为的影响机制,通过文献调研指明了该领域今后的研究方向与手段。

    Bubbles play extremely important roles in our daily life and in the fields of industrial production, medicine, health care, etc. Concerning complex foam systems with different fine structures, they have a variety of flow and stability properties. However, the drainage behavior of complex foam systems has been far less studied compared with simple foams. Herein, the research status and development of dynamics of liquid drainage from complex foam systems are reviewed, including surfactant-aggregate-stabilized foams, nanoparticle-stabilized foams, and oil-water miscible foams. For the surfactant-aggregate-stabilized foam systems, two flow models such as Poiseuille flow and plug flow, and their kinetic equations are introduced. The drainage behaviors of nanoparticle-stabilized foam systems are emphasized in aspects of particle size effects and particle trapping and blocking effects. The two different forms of oil phase (dissolved oil/emulsified oil) have completely different effects on the drainage behavior of oil-water miscible foams. The drainage behaviors of complex foam systems with fine structures have not been well studied yet, and there are many theoretical disagreements and debates. It is necessary to carry out more in-depth research on basic theoretical issues. We believe that the research on the fluid drainage dynamics of complex foam systems will be a research hotspot at present and for a long time in the future.

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    分析与检测
    基于in vitro和in silico技术的化学品眼刺激性评价替代方法研究
    Study on the alternative method for assessing eye irritation of chemicals using in vitro and in silico approaches
    林铌,罗飞亚,曹春然,胡宇驰
    2022 (9):  1016-1022.  doi: 10.3969/j.issn.1001-1803.2022.09.015
    摘要 ( 224 )   HTML ( 16 )   PDF(1001KB) ( 398 )  

    建立基于荧光素漏出试验(Fluorescein Leakage test,FL test)和计算机模拟评价(in silico)技术的化学品眼刺激性初步评估和筛选的替代方法,并探讨其替代整体动物眼刺激性试验(Draize test)的可能性。分别采用FL test和Toxtree软件对经济合作与发展组织(the Organization for Economic Co-operation and Development,OECD)推荐的8种实验室能力验证物质的眼刺激性进行检测,并对结果进行分级。同时,分别比较两种方法测定结果的一致性。FL试验在判断受试物是否为严重刺激性/腐蚀性时和在进一步判定物质是否为严重刺激性/腐蚀性、中度刺激性或轻刺激性/无刺激性时,结果均具有较好的一致性(Kappa值为1,P=0.005;Kappa值为0.579,P=0.035)。Toxtree软件预测结果显示其更适合对“轻刺激性/无刺激性”受试物进行初步筛选。FL test是一种有效的眼刺激性评价体外替代方法,具有良好的应用和推广价值,更适用于判定有严重眼刺激性/腐蚀性的化合物,或作为“自上而下”眼刺激性评价分层组合测试策略中首先开展的实验。Toxtree预测结果可作为眼刺激性综合评估的参考数据。

    The aim of the study was to establish the alternative method for preliminary assessing eye irritation of chemicals using Fluorescein Leakage test (FL test) and Quantitative Structure Activity Relationship (QSAR), to detect and classify the ocular irritation of the recommended substances, and to explore the application value of different alternative methods. Using Toxtree models to predict eye irritation and irritation potency of 8 recommended substances for demonstrating technical proficiency. The test substances were prepared into series of concentrations and exposed with the Madin-Darby canine kidney cell (MDCK) for 1 min to test the percentage of fluorescein leakage (FL/%). The results were categorized according to the classification criteria for assessing eye irritation. Then, the sensitivity, specificity, and accuracy of FL test and Toxtree models were evaluated. Furthermore, the consistency of FL test or Toxtree model was compared with UN-GHS (United Nationas Globally Harmonized System of Classification and Labelling of Chemicals) classification. When FL test is used to distinguish if the test substance belongs to severe irritation/corrosion (GHS Cat. 1), the irritation potency of all test substances is concordant with that in GHS classification (Kappa=1, P=0.005). When FL test is used to distinguish if the test substance is severe irritation/corrosion (GHS Cat. 1), moderate irritation (GHS Cat. 2A) or mild/no irritation (GHS Cat. 2B/No Cat.) substances, the irritation potency of all test substances is concordant with GHS classification in the eye irritant potency (Kappa=0.579, P=0.035). The results predicted by Toxtree software demonstrate that it is more suitable to firstly estimate the possible substances with mild/no ocular irritation. The FL test is an effective and valuable alternative method for evaluating eye irritation, and it is more applicable to identify chemicals with severe irritation/corrosion or to be the study firstly carried out using the “Top-Down approach” of the integrated decision-tree testing strategy for eye irritation. The results predicted by Toxtree software could be reference data for the integrated assessment on eye irritation.

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    高效液相色谱法分析化妆品中苯扎氯铵及苄索氯铵
    Analysis of benzalkonium chloride and benzethonium chloride in cosmetics by HPLC
    王启林,韩晓萍,李镇冰,唐启奎
    2022 (9):  1023-1058.  doi: 10.3969/j.issn.1001-1803.2022.09.016
    摘要 ( 514 )   HTML ( 23 )   PDF(1123KB) ( 397 )  

    建立了高效液相色谱法同时测定化妆品中苯扎氯铵及苄索氯铵含量的方法。选用C8色谱柱对测定结果以苯扎氯铵计的3种二甲基苄基氯化铵的同系物及苄索氯铵进行分离,以甲醇∶0.1 mol/L醋酸铵缓冲溶液(pH=5)为流动相进行等度洗脱,在260 nm波长下经高效液相色谱-二极管阵列检测器同时测定,将《化妆品安全技术规范》(2015年版)中苯扎氯铵的检测方法及劳拉氯铵、苄索氯铵和西他氯铵的检测方法进行优化合并,选用使用范围较广的C8色谱柱实现4种组分同时分离;以苯扎氯铵计的3种二甲基苄基氯化铵的同系物、苄索氯铵在一定质量浓度范围内线性关系良好,相关系数均大于0.999 9,4种不同类型基质低、中、高3个质量浓度梯度下加样回收率为90%~110%,RSD为0.3%~4.4%(n=9)。该方法操作简单、分析时间短,灵敏度和重现性良好,可运用于化妆品中同时快速检测苯扎氯铵、苄索氯铵。

    A method for simultaneous determination of benzalkonium chloride and benzethonium chloride in cosmetics was established by high performance liquid chromatography. Different types of chromatographic columns and mobile phase conditions were screened. Finally, C8 column was used to separate benzethonium chloride and three kinds of homologues of dimethyl benzyl ammonium chlorides calculated with benzalkonium chloride. Methanol : 0.1 mol/L ammonium acetate buffer solution (pH=5) was used as the mobile phase for isocratic elution. The results were simultaneously determined by DAD at the wavelength of 260 nm. Compared with the methods recommended in Technical Specification for Safety of Cosmetics (2015 edition), the detection method of benzalkonium chloride and the detection method of lauralkonium chloride, benzethonium chloride and cetalkonium chloride were optimized and combined. A C8 column with a wide range of use was selected to achieve the simultaneous separation of the four components. Benzalkonium chloride and benzethonium chloride have good linear relationship in a certain mass concentration range, and the correlation coefficients are greater than 0.999 9. The recoveries were 90%-110% with RSD of 0.3%-4.4% (n=9) at three mass concentration gradients of low, medium and high for four different types of matrixes. This method has the advantages of simple operation, short analysis time, good sensitivity and reproducibility, and can be used for the simultaneous determination of benzalkonium chloride and benzethonium chloride in cosmetics.

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