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    2022年, 第52卷, 第2期 刊出日期:2022-02-25 上一期    下一期
    基础研究
    耐酸纳米微球的研发及CO2驱封窜性能研究
    Preparation and CO2 flooding plugging channeling performance of acid resistant nanospheres
    马丽萍,刘笑春,杨棠英,吕伟,周博博,杨红斌
    2022 (2):  109-115.  doi: 10.3969/j.issn.1001-1803.2022.02.001
    摘要 ( 237 )   HTML ( 56 )   PDF(1556KB) ( 399 )  

    针对长庆低渗透油藏CO2驱出现的窜流难题,以丙烯酰胺(AM)、4-苯乙烯磺酸钠(SSS)和二甲基二烯丙基氯化铵(DMDAAC)为共聚单体,N,N’-亚甲基双丙烯酰胺(MBA)为交联剂,亚硫酸氢钠(SHS)和过硫酸铵(APS)为引发剂,通过反相微乳液聚合法研发了一种耐酸纳米微球(AR-NS)。采用红外光谱(FTIR)、扫描电镜(SEM)、热重(TG)及流变仪对产物的结构、形貌和性能进行了分析。结果表明,合成产物在乳液中为高分散度的纳米微球,其平均初始粒径为255 nm。在酸性地层水条件下,耐酸纳米微球的膨胀倍数为13.8倍而普通微球膨胀倍数仅为3.7倍;油藏温度85 ℃条件下、质量浓度为5 000 mg/L时耐酸纳米微球悬浮液黏度仅为0.56 mPa·s,具有优异的注入性;低渗裂缝岩心超临界CO2驱封窜实验表明,耐酸纳米微球注入后裂缝性岩心的封堵率达95.41%,采收率提高了21.03%,耐酸纳米微球在低渗CO2驱油藏中具有优异的封窜效果。

    Aimed at the channeling problem of CO2 flooding in low permeability reservoir of Changqing, acid resistant nanospheres (AR-NS) were prepared by inverse microemulsion polymerization using acrylamide (AM) as monomer, 4-styrene sulfonate (SSS) and dimethyl diallyl ammonium chloride (DMDAAC) as functional monomers, N, N’-methylene bis acrylamide (MBA) as crosslinking agent, sodium bisulfite and ammonium persulfate as initiators. The results show that the smooth microspheres with high dispersion are found in the emulsion, with an average particle size of 255 nm. The mass retention rate of the acid resistant nanospheres is still about 20%, when the temperature is 450 ℃. It has good temperature resistance. Under the condition of acid formation water, the expansion ratio of the acid resistant nanospheres is 13.8 times, while that of the ordinary nanospheres is only 3.7 times. When the reservoir temperature is 85 ℃ and the concentration is 5 000 mg/L, the viscosity of the suspension is only 0.56 mPa·s, and it has good injectability. The plugging experiment of supercritical CO2 flooding in low permeability heterogeneous fractured core shows that the plugging efficiency of fractured core is 95.41% and the recovery efficiency is increased by 21.03% after acid resistant nanospheres injection. Acid resistant nanospheres have excellent plugging channeling effect in low permeability CO2 flooding reservoirs.

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    有机反离子十六烷基三甲基铵的表面活性及应用性能
    Study on the surface activity and application properties of cetrimonium salts with organic counterions
    王亚魁,鞠洪斌,耿涛,曹玉朋,杨伟光,丁慧,姜亚洁
    2022 (2):  116-123.  doi: 10.3969/j.issn.1001-1803.2022.02.002
    摘要 ( 420 )   HTML ( 30 )   PDF(1265KB) ( 355 )  

    研究了十六烷基三甲基甲酸铵(HTAF)、十六烷基三甲基乙酸铵(HTAA)和十六烷基三甲基丁酸铵(HTAE)的表面活性、抗静电性、耐盐和耐酸碱性、金属腐蚀性、抑菌性和生物降解性,并对HTAF与脂肪醇聚氧乙烯醚硫酸钠(AES)、脂肪醇聚氧乙烯醚羧酸钠(AEC-9Na)和非离子表面活性剂烷基糖苷(APG1214)二元复配体系的抑菌性和去污洗涤效果进行了测试。结果表明:HTAE的临界胶束浓度(cmc)和表面张力(γcmc)皆低于HTAF和HTAA;HTAF和HTAA的抗静电性能与传统抗静电剂十八烷基二甲基羟乙基硝酸铵(SN)处于一个数量级,HTAE的抗静电性较差;三种有机反离子季铵盐对一价Na+和二价Ca2+,Mg2+都具有优良的耐盐性(>200 g/L),并且耐酸碱性能较好;有机反离子季铵盐对金属的腐蚀性明显低于十六烷基三甲基氯化铵(HTAC);三种有机反离子季铵盐的7天初级生物降解度都大于98%;在20 mg/kg含量下,HTAF对金黄色葡萄球菌(S. aureus)和大肠杆菌(E. coli)仍表现出较好的抑菌效果(>95%)。二元复配体系表明:AES/HTAF混合体系相比标准洗衣液具有更好的去污效果,但基本无抑菌性能;AEC-9Na/HTAF混合体系兼具优异的抑菌和去污洗涤性能;APG1214/HTAF混合体系抑菌性能较好,但去污效果较差。

    The surface activity, antistatic performance, salt resistance, acid and alkali resistance, metal corrosion, antimicrobial properties and biodegradability of cetrimonium formate (HTAF), cetrimonium acetate (HTAA) and cetrimonium butyrate (HTAE) were investigated, and the antibacterial properties and detergency of binary mixed systems of HTAF mixed with sodium alkylpolyoxyethylene sulphate (AES), sodium polyoxyethylene alkyl ether carboxylate (AEC-9Na) and alkyl glucoside (APG1214) were measured. The results are as follows: the critical micelle concentration (cmc) and the surface tension at cmc (γcmc) of HTAE are lower than that of HTAF and HTAA; the antistatic performance of HTAF and HTAA is basically at the same order of magnitude as traditional antistatic agent octadecyl dimethyl hydroxyethyl ammonium nitrate (SN), while the antistatic performance of HTAE is poor; three cetrimonium salts with organic counterions have exhibited strong salt resistance (>200 g/L) against either monovalent Na+or divalent Ca2+ and Mg2+, and have good acid and alkali resistance; their corrosiveness to metals is significantly lower than that of cetrimonium chloride (HTAC) ; the primary biodegradability after 7 days for three surfactants is greater than 98%; HTAF shows good antibacterial activity against Staphylococcus aureusS. aureus) and Escherichia coli E. coli) (>95%) even at a content of 20 mg/kg. The results of binary mixed systems show that, AES/HTAF mixed system has better detergency than that of standard laundry detergent, but has no antibacterial activity; AEC-9Na/HTAF mixed system has both excellent antibacterial performance and detergency; APG1214/HTAF mixed system has good antibacterial activity but poor detergency.

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    科技讲座
    天然生物质材料的制备、性质与应用(Ⅱ)——pH敏感型功能海洋多糖:海藻酸钠
    Preparation, properties and applications of natural biomass materials (Ⅱ)pH-sensitive functional marine polysaccharide: sodium alginate
    毛金超,隋振全,徐桂云,范金石
    2022 (2):  124-133.  doi: 10.3969/j.issn.1001-1803.2022.02.003
    摘要 ( 913 )   HTML ( 25 )   PDF(1614KB) ( 699 )  

    海藻酸钠是一种提取自海藻的pH敏感型多功能海洋多糖。因具有无毒、水溶、生物相容、可生物降解、成膜、胶凝、增稠、抗过敏、絮凝、螯合、促植物生长、阻燃等优良特性,且分子结构中含有可进行化学改性的羟基、羧基、糖苷键等活性基团,使得海藻酸钠及其衍生物、复合物、掺混物在食品、医药、化妆品、纺织印染、水处理、农业和功能材料等多个行业领域得到广泛关注与应用。本文阐述了海藻酸钠的名称、来源和结构,以及理化性质、制备方法和近期的应用进展情况,并指出了这种天然海洋生物质材料的发展方向和前景。

    Sodium alginate is a kind of typical, widely used, pH-sensitive functional marine polysaccharide, which is extracted from the abundant seaweed in ocean. Sodium alginate is composed of β-D-mannuronic acid (M) and α-L-gulonic acid (G) linked by 1 → 4 glycosidic bonds and can be chemically modified due to the presence of reactive hydroxyl group, carboxyl group and glucosidic bond in the molecular structure, via oxidation, reductive amination, sulfation, copolymerization of hydroxyl group, esterification, Ugi reaction, amidation of carboxyl group, and degradation of glucosidic bond. For possessing many excellent properties including non-toxic, water-soluble, biocompatible, biodegradable, film-forming, gelling, thickening, anti-allergy, flocculation, chelation, plant growth promotion and flame retardant, sodium alginate and its derivatives, composites and blends have been extensively studied and applied in food, medicine, cosmetics, textile printing and dyeing, water treatment, agriculture, functional materials and other industrial fields. Herein, the name, source, structure, physical and chemical properties and conventional production methods of sodium alginate, and the current application status of sodium alginate and sodium alginate-based materials were introduced. The research trend and development prospect of this valuable natural marine biomass material were also pointed out.

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    开发与应用
    复合促渗剂对当归水溶性成分阿魏酸的体外透皮性能影响研究
    Study on the effect of compound penetration enhancer on the permeability of Angelica’s water-soluble component ferulic acid in vitro
    冉鑫,王继龙,刘晓霞,何红杰,魏舒畅,冯晓莉,李真真
    2022 (2):  134-139.  doi: 10.3969/j.issn.1001-1803.2022.02.004
    摘要 ( 246 )   HTML ( 18 )   PDF(1103KB) ( 292 )  

    选用立式透皮扩散试验仪,以离体小鼠皮为透皮屏障进行体外透皮实验,研究了促渗剂氮酮、薄荷脑和冰片对当归水溶性成分阿魏酸的体外透皮性能影响,并优选出了较佳复合促渗剂。实验结果表明,三种促渗剂单用时,对阿魏酸透皮性能的影响大小顺序为:薄荷脑>冰片>氮酮,而联合使用时,顺序为:冰片>薄荷脑>氮酮。且优选出的较佳复合促渗剂为2%冰片+2%薄荷脑,结果显示二者联合使用优于氮酮、冰片、薄荷脑单独使用,其24 h单位面积累积透过量(Q24)可达34.32 µg/cm2,增渗倍数(ER)可达64.195,分别为单用薄荷脑和冰片的8倍和25倍,且滞后时间在2 h以内,协同作用明显,即优选出的复合促渗剂对当归水溶性成分阿魏酸的促渗效果很好,可为当归及以当归为主药方剂的经皮给药制剂开发提供促渗剂。

    By using vertical transdermal diffusion tester and HPLC to determine the content of index components in the receiving solution, the in vitro transdermal absorption experiment was carried out by using isolated mouse skin as the transdermal barrier. The effects of classical penetration enhancers Azone, menthol and borneol on the in vitro transdermal penetration of ferulic acid, a water soluble component of Angelica sinensis, were studied, and the best compound penetration enhancer was selected. The experimental results show that the three penetration enhancers have a good effect on the penetration of ferulic acid in vitro, and the cumulative permeability of ferulic acid increases gradually within 24 hours. When used alone, the effect on the transdermal permeability of ferulic acid is menthol>borneol>azone., while used in combination, the effect on the transdermal permeability of ferulic acid is borneol>menthol>azone. And the best compound penetration enhancer is 2% borneol+2% menthol. The results show that the combination of them is better than azone, borneol and menthol alone. The cumulative permeability per unit area (Q24) in 24 hours is 34.32 μg/cm 2, and the multiple (ER) is 64.195, which is 8 times and 25 times higher than that of menthol and borneol alone, respectively, with the lag time less than 2 hours. The synergistic effect is obvious. In other words, the optimized compound penetration enhancer has a good effect on the penetration of ferulic acid, a water-soluble component of Angelica sinensis, and can provide a penetration enhancer for the development of Angelica sinensis and transdermal drug delivery preparations with Angelica sinensis as the main prescription. At the same time, by comparing the permeability of mouse skin and Strat-M TM membrane to ferulic acid, it is found that although the permeability of the two kinds of transdermal barrier is the same, the lag time of Strat-MTM membrane is much shorter than that of mouse skin, indicating that the barrier effect of Strat-MTM membrane on ferulic acid is less than that of mouse skin. Because the permeability of mouse skin is higher than that of human skin, if Strat-MTMmembrane is used in ferulic acid transdermal experiment in vitro, the transdermal lag time may be much different from the real situation.

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    二葡糖基没食子酸的合成及其性能研究
    Study on the synthesis and performance of diglucosyl gallic acid
    张凯强,许虎君
    2022 (2):  140-146.  doi: 10.3969/j.issn.1001-1803.2022.02.005
    摘要 ( 758 )   HTML ( 20 )   PDF(1714KB) ( 512 )  

    以没食子酸甲酯和五乙酰基葡萄糖为原料,经过乙酰化反应、成盐、酸化等过程合成了美白剂二葡糖基没食子酸,并通过IR,MS,1H NMR和13C NMR确认了最终产物的结构。同时考察了美白剂二葡糖基没食子酸对酪氨酸酶活性的影响、酪氨酸二酚酶的抑制作用机制以及抗氧化能力。研究表明:以L-酪氨酸为底物时,二葡糖基没食子酸对酪氨酸单酚酶的半抑制浓度IC50为1.46 mg/mL,以L-多巴为底物时,二葡糖基没食子酸对酪氨酸二酚酶的半抑制浓度IC50为2.68 mg/mL,而且从Lineweaver-Burk图获得的抑制机理表明二葡糖基没食子酸对酪氨酸二酚酶的抑制作用表现为竞争性抑制,抑制常数Ki为2.43 mg/mL。没食子酸相比于同质量浓度下的VC对DPPH自由基的清除效果更好,而二葡糖基没食子酸相比于同质量浓度下的VC,其对DPPH自由基仍存在一定的清除作用。

    A whitening agent, diglucosyl gallic acid, was synthesized through acetylation reaction, salt formation, acidification and other processes using methyl gallate and pentaacetyl glucose as raw materials. The structure of the final product was confirmed by IR, MS, 1H NMR and 13C NMR. The effect of diglucosyl gallic acid on tyrosinase activity, the inhibitory mechanism of tyrosine diphenolase activity and the antioxidant capacity were investigated. The results show that when L-tyrosine is used as a substrate, diglucosyl gallic acid can not only prolong the lag time of the tyrosine monophenolase reaction, but also cause a further increase in the lag time with the increase of concentration, and its half-inhibitory mass concentration IC50 is 1.46 mg/mL; When L-dopa is used as a substrate, the progress curve of the inhibitory effect of diglucosyl gallic acid at different mass concentrations on tyrosine diphenolase all passes through the origin of the coordinate axis, indicating that the progress has occurred and shows a retardation effect, and the IC50 of diglucosyl gallic acid against tyrosine diphenolase is 2.68 mg/mL; the enzyme activity was plotted against the enzyme concentration. As the mass concentration of diglucosyl gallic acid increases, the slope of the straight line continues to decrease and all straight lines intersect at the origin, which indicates that the inhibitory effect of diglucosyl gallic acid on tyrosine diphenolase is a reversible process, namely the inhibitory effect is through the binding of diglucosyl gallic acid with the enzyme to inhibit the activity of tyrosine diphenolase, thereby reducing the efficiency of the enzyme to catalyze the oxidation of L-dopa to produce dopa pigment, rather than reducing the effective enzyme amount; Lineweaver-Burk double reciprocal mapping method was used to judge the inhibitory effect type and inhibitory constant of diglucosyl gallic acid. As the mass concentration of diglucosyl gallic acid increases, the vertical intercept of all straight lines is 2.645. Moreover, the slope of the straight line (Michaelis constant Km) also shows an increasing trend, while Vmax remains basically unchanged, which can indicate that the type of inhibitory effect of diglucosyl gallic acid on tyrosine diphenolase is competitive inhibition. Gallic acid has a better scavenging effect on DPPH free radicals than VC does under the same mass concentration, while diglucosyl gallic acid still has a certain scavenging effect on DPPH free radicals compared to VC under the same mass concentration.

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    时间效应在悬滴法测定表面张力中的影响
    Discussion on the time effect in surface tension measurement by pendant drop method
    叶丹妮,邢捷,李纪晖,梁丽,张豫红,姚永毅
    2022 (2):  147-151.  doi: 10.3969/j.issn.1001-1803.2022.02.006
    摘要 ( 300 )   HTML ( 18 )   PDF(1189KB) ( 255 )  

    表面张力是流体重要的物理性质,测定表面张力的方法通常包括毛细管上升法、最大气泡压力法、拉环法、旋滴法和悬滴法等。目前,最普遍的表面张力的测定方法为国家标准推荐的平板法或拉环法。然而,悬滴法作为一项成熟的表面张力测定方法且具备静态表面张力及动态表面张力测定功能,目前使用该法测定的较少。文章使用悬滴法测定较低含量的表面活性剂溶液静态表面张力时发现结果与拉环法差异较大,而测定单组分液体及含量较大的表面活性剂溶液,悬滴法与拉环法的测定数据差异较小,这种情况的相关报道较少。另外,使用动态表面张力测定探索了静态测定时出现差异的原因,并对应用悬滴法进行表面张力测定的适用范围进行了总结。使用悬滴法测定表面张力时,应注意时间效应的影响。

    Surface tension is an important physical property of fluid. The methods for measuring surface tension usually include capillary rising method, maximum bubble pressure method, ring method, plate method, spinning drop method and pendant drop method. At present, the most common method to measure surface tension is plate method or ring method as recommended by the national standard. However, as a mature method of surface tension measurement, pendant drop method has the functions of static and dynamic surface tension measurement, but it is seldom used. In this work, when the static surface tension of surfactant solution with relatively low concentration was measured by pendant drop method, it was found that the results were quite different from that of ring method, while the data of pure liquids and those surfactant solutions with higher concentrations were essentially in agreement with those results obtained by ring method. In addition, dynamic surface tension measurement was used to explore the reasons for the differences between the two methods in static measurement. The application scope of surface tension measurement by pendant drop method was also summarized. Regarding the accuracy of surface tension test by pendant drop method, the influence of time must be paid close attention to. For the samples of low efficiency to reduce the surface tension, especially at relatively low concentrations, it is recommended to use dynamic surface tension measurement rather than static surface tension measurement. As a mature method, pendant drop method has been applied to the determination of surface tension. Most of the current studies have focused on the determination of pure liquids, and most of them are static determination. In practical applications, surfactant solutions are multicomponent systems, and sometimes it is necessary to rapidly reduce surface tension at lower concentrations. Therefore, in such kind of research, it is very necessary to use pendant drop method to study dynamic surface tension of the mixed surfactant system. Pendant drop method, as a method with simple operation, less sample amount, rapid determination and accurate results, has both static surface tension and dynamic surface tension measurement, and will be applied to a wider range.

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    双亲性聚合物调理剂在护发素中的应用研究
    Research on the amphiphilic polymer applied in hair conditioner
    秦志昂,张云,刘冬,曹玉华
    2022 (2):  152-158.  doi: 10.3969/j.issn.1001-1803.2022.02.007
    摘要 ( 321 )   HTML ( 22 )   PDF(1497KB) ( 286 )  

    研究了双亲性聚合物作为调理剂成分在无硅油护发素中的应用。以溶液自由基聚合法合成了双亲性无规聚合物聚(苯乙烯-co-丙烯酸)。利用阳离子表面活性剂山嵛基三甲基氯化铵与聚合物之间的阳离子-π电子作用,将双亲性无规共聚物聚(苯乙烯-co-丙烯酸)吸附到头发表面起到顺滑作用。通过调节聚合物中苯环与山嵛基三甲基氯化铵的摩尔比、山嵛基三甲基氯化铵的浓度以及使用量,制备具有优异梳理性能的护发素,对护发素效果进行评价,并与含硅护发素进行比较。结果表明:最优条件下,双亲性聚合物在头发上的残留量为102 μg/g头发;在护发素中添加双亲聚合物后能够显著改善湿梳理性能,其湿梳性优于市售含硅护发素;经护发素处理后的头发毛鳞片规整、无翘起,且双亲聚合物在头发上无累积效应。

    The amphiphilic polymer was used as a conditioner in a silicone-free hair conditioner. The amphiphilic random copolymer poly (styrene-co-acrylic acid) was synthesized by free radical polymerization. Through the cation-π electron interaction between the cationic surfactant behenyl trimethyl ammonium chloride and the benzene ring in the copolymer, the amphiphilic random copolymer poly (styrene-co-acrylic acid) would be adsorbed on the hair surface to give more smoothness to hair. The hair conditioner with excellent combing performance was prepared by adjusting the molar ratio of styrene in poly (styrene-co-acrylic acid) to behenyl trimethyl ammonium chloride, the concentration of behenyl trimethyl ammonium chloride as well as the dosage. The prepared conditioner was evaluated and compared with silicone conditioner. The results show that, the amphiphilic random polymer poly(styrene-co-acrylic acid) is successfully synthesized; the molecular weight of the polymer is 11 824 and the polydispersity coefficient is 1.67; the optimized molar ratio is close to the feeding ratio of 7∶3. The residual amount of the amphiphilic polymer on the hair is positively correlated with the viscosity of the compound solution, i.e., the greater the viscosity of the compound solution, the greater the cation-π electron interaction, and thus the more easily the amphiphilic polymer would stay on the hair surface. The optimized conditions are as follows: the usage amount of BTAC is 1 mL; the mass fraction is 2.0%; the molar ratio is 1.2. Under this condition, the residual amount of the amphiphilic polymer on the hair is 102 μg/ghair. The analysis of the significant difference in the maximum friction force and the combing work show that the wet combing performance is significantly improved by adding the amphiphilic polymer into the hair conditioner, and the wet combing performance of the self-made conditioner is better than that of the commercially available silicone-containing conditioners. SEM images show that the hair scales after treatment with the prepared conditioner are regular and without curling. The amphiphilic polymer has no cumulative effect on hair.

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    桃树脂提取物的抗衰老功效研究
    Study of the anti-aging efficacy of Prunus persica (peach) resin extract
    黄少勇,周利丹,寻伟,施雪梅,卢伊娜
    2022 (2):  159-165.  doi: 10.3969/j.issn.1001-1803.2022.02.008
    摘要 ( 2424 )   HTML ( 59 )   PDF(1551KB) ( 546 )  

    皮肤老化由多种因素引起,主要包括年龄导致的自然老化和暴露于环境导致的光老化。大气中的紫外线、雾霾中的多环芳烃均能造成皮肤炎症、细胞活性和功能下降,最终导致皮肤松弛、老化,形成皱纹、斑点。本研究以桃树脂提取物(PG)为研究对象,通过多种方法对其紧致、抗皱的功效进行研究。结果显示,在成纤维细胞衰老模型上,PG在质量分数为0.3%~10%的范围下能剂量依赖性地促进成纤维细胞增殖、Ⅰ型胶原蛋白合成,降低β-半乳糖苷酶的活性。在紫外线(UVA)和雾霾类似物苯并芘(BaP)造成的角质形成细胞衰老模型上,质量分数为0.1%~10%的PG可以抑制细胞因子前列腺素E2和基质金属蛋白酶1表达,恢复细胞活性,并降低β-半乳糖苷酶的活性。在人体临床评价上,质量分数为2%~10%的PG具有显著的即时提升皮肤含水量、降低经皮失水率、提升紧肤感、减少皱纹效果。PG作为一种天然来源的活性原料,可应用于皮肤保湿、紧致、抗皱系列产品中。

    Photoaging or premature aging of skin is caused by a variety of factors, including hormone imbalance and exposure to ultraviolet radiation. Both ultraviolet light and polycyclic aromatic hydrocarbons in haze can cause skin aging and inflammation. Peach resin is a gum substance secreted from the bark of Rosaceae Prunus persica (L.) Batsch or Prunus davidiana (Carr.) Franch, which is beneficial to health. It also has the advantages of being natural and non-toxic, large in yield, and low in price. Peach gum is a kind of polysaccharide, which has the characteristics of swelling in water and slow release. At present, peach gum has been widely used in food and health care, but the basic research is still relatively weak. Peach gum is a natural cosmetic raw material with great potential for development and application. In this study, a Prunus persica (Peach) resin extract (PG) was prepared and its anti-aging effect was detected by several methods. The results suggested that, based on the model of fibroblast cell aging, PG could promote cell proliferation, Collagen Ⅰ expression and inhibit the activity of beta-GAL in a dosage-dependent manner in the mass fraction range of 0.3% to 10%. In the cell damage model induced by UVA and BaP, PG at the mass fraction between 0.1% to 10% could inhibit the expression of inflammatory factors Prostaglandin E2 and Matrix metallopeptidase 1. The results of clinical study showed that 5% and 10% PG had significantly increased skin tightening effect. In human clinical evaluation, PG at the mass fraction range of 2% to 10% could significantly increase skin moisture content, reduce transepidermal water loss, improve skin firmness, and reduce wrinkles. As a natural material with anti-aging effect, PG can be used in skin anti-wrinkle products.

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    珍珠灵芝复配物美白功效与机理初步研究
    Whitening efficacy and mechanism study of compound of Ganoderma atrum (mushroom) extract and pearl extract
    金佳颖,陈露,王欣之,刘睿,吴皓
    2022 (2):  166-171.  doi: 10.3969/j.issn.1001-1803.2022.02.009
    摘要 ( 372 )   HTML ( 24 )   PDF(1293KB) ( 315 )  

    为研究珍珠灵芝提取物复配在美白类化妆品中开发的优势,采用体外酪氨酸酶活性和小鼠B16黑色素瘤细胞模型实验,分别对黑灵芝提取物、珍珠提取物及其复配物的美白功效进行评价,测定三者对体外酪氨酸酶活性、B16细胞相对黑色素含量、酪氨酸酶(TYR)和酪氨酸酶相关蛋白-1(TRP1)mRNA表达水平的影响。结果表明,1%黑灵芝提取物、2%珍珠提取物及二者组成的复配物均可显著抑制酪氨酸酶活性(P<0.05)、降低细胞内黑色素含量(P<0.05),其中复配物组对酪氨酸酶活性、细胞内黑色素生成抑制率分别达32.87%、68.27%,均优于单用组(P<0.05);此外,复配物组可显著下调TRP1 mRNA表达水平(P<0.05),而单用组无显著下调TRP1 mRNA表达水平的效果,提示复配物组较单用组有更好地抑制真黑色素生成的功效,具有开发成为化妆品功效添加剂加入美白化妆品的潜力。

    The literature reported that both pearl and Ganoderma lucidum had whitening effects, and both of them had products in cosmetics field, but the compound of pearl and Ganoderma lucidum was seldom reported. The purpose of this article was to study the advantages of the compound of pearl extract and Ganoderma lucidum extract in the development of whitening cosmetics. The whitening effects of Ganoderma atrum (mushroom) extract, pearl extract and their compound extracts were evaluated by in vitro tyrosinase and B16 cell model. The effects on tyrosinase activity in vitro, B16 cell viability, relative melanin content in B16 cells, expression level of tyrosinase (TYR) and tyrosinase-related protein 1(TRP1) mRNA were studied. The results of B16 cell viability show that Ganoderma atrum (mushroom) extract, pearl extract and their compound extracts have no cytotoxicity, and they can be used to B16 cells to next step. The results of tyrosinase activity and relative melanin content in B16 cells show that 1% Ganoderma atrum (mushroom) extract, 2% pearl extract and the compound extract can significantly inhibit tyrosinase activity (P<0.05) and reduce melanin content in B16 cells(P<0.05). Inhibition rate of tyrosinase activity of the compound extract reaches 32.87%, and inhibition rate of melanin synthesis of the compound extract reaches 68.27%. Compared the compound extract with Ganoderma atrum (mushroom) extract and pearl extract, the compound extract has better effect of reducing the melanin content in B16 cells (P<0.05). The results of the mRNA expression levels of tyrosinase (TYR) and tyrosinase-related protein 1(TRP1) show that the group of the compound extract can significantly reduce mRNA expression levels of TYR and TRP1 (P<0.05), while single groups can only significantly reduce TYR mRNA expression levels. TRP1 can regulate the production of eumelanin, which is a species of melanin. The results show that the compound extract has better effect on inhibiting the formation of eumelanin, indicating that 2% pearl extract combined with 1% Ganoderma atrum (mushroom) extract have better effect on inhibiting the formation of melanin and it is related with its significant reduction of TRP1 mRNA expression. The compound extract has potential to develop as a cosmetic efficacy additive into whitening cosmetics.

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    白梅花提取物抗氧化及美白功效评价
    Evaluation of antioxidant and whitening efficacy of Prunus mume extract
    查雨锋,黄加文,詹易,李婷,颜宏,吴德松
    2022 (2):  172-179.  doi: 10.3969/j.issn.1001-1803.2022.02.010
    摘要 ( 472 )   HTML ( 19 )   PDF(1440KB) ( 378 )  

    采用体外评价方法对白梅花提取物进行抗氧化及美白功效研究。通过测定白梅花提取物对超氧阴离子及羟自由基清除的半数抑制浓度(IC50),以及在H2O2诱导人皮肤成纤维细胞株(HFF-1细胞)氧化损伤模型中,考察白梅花提取物对细胞形态学、细胞存活率、丙二醛(MDA)含量、活性氧自由基(ROS)含量、超氧化物歧化酶(SOD)活力、谷胱甘肽(GSH)活力、Ⅰ型胶原蛋白(Col Ⅰ)以及基质金属蛋白酶1(MMP-1)含量的影响,评价其抗氧化功效。采用酪氨酸酶活性抑制实验以及小鼠黑色素瘤细胞株(B16-F10细胞)黑色素含量测定实验评价白梅花提取物的美白功效。结果表明白梅花提取物具有自由基清除作用,且白梅花60%醇提物、白梅花90%醇提物可明显提高HFF-1细胞活力、SOD活力、GSH活力以及Col Ⅰ含量,下调ROS、MDA及MMP-1含量,并明显降低B16-F10细胞中的黑色素含量,表现出明显的抗氧化及美白功效。

    In vitro evaluation method was used to study the anti-oxidation and whitening effects of Prunus mume extract. Preliminary evaluation of its antioxidant activity was conducted by measuring the IC50 of Prunus mume extract on superoxide anion and hydroxyl radical scavenging. And in the H2O2-induced oxidative damage model of human skin fibroblast cell line (HFF-1 cells), the antioxidant activity of Prunus mume extract was evaluated by examining the cell morphology, cell survival rate, malondialdehyde (MDA) content, reactive oxygen radical (ROS) content, superoxide dismutase (SOD) activity, glutathione (GSH) activity, type I collagen (ColⅠ) content and matrix metalloproteinase 1 (MMP-1) content. The tyrosinase activity inhibition experiment and the melanin content determination experiment of B16-F10 cells were used to evaluate the whitening effect of the Prunus mume extract. The results show that the Prunus mume extract has free radical scavenging effect, and the 60% and 90% alcohol extract of Prunus mume can significantly increase the activity of HFF-1 cells, SOD activity, GSH activity and Col Ⅰ content, and decrease the content of ROS, MDA and MMP-1. And it can also significantly reduce the melanin content in B16-F10 cells. To sum up, the white plum extract has obvious antioxidant and whitening effects.

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    专论与综述
    碱性蛋白酶洗涤稳定性提高的研究进展
    Research progress in improving the washing performance of alkaline protease
    王朋辉,王伟贤,曾晖,芮泽宝
    2022 (2):  180-189.  doi: 10.3969/j.issn.1001-1803.2022.02.011
    摘要 ( 500 )   HTML ( 12 )   PDF(1204KB) ( 460 )  

    碱性蛋白酶是液体洗涤剂中使用量最大的一类酶制剂,应用于洗涤剂行业的碱性蛋白酶占碱性蛋白酶市场的60%以上。不同于粉状洗涤剂中的酶制剂被造粒所包裹,液体洗涤剂中的碱性蛋白酶直接暴露于溶液中,与洗涤剂成分如表面活性剂、洗涤助剂及漂白剂直接接触作用,使得蛋白酶洗涤稳定性下降。除此之外,蛋白酶在液体洗涤剂环境中存在普遍的自溶失活现象,对其洗涤性能造成不利影响。如何提升碱性蛋白酶的稳定性是液体洗涤剂领域中的一个热点问题。本文介绍了碱性蛋白酶的催化与失活机制,综述了几种常用于稳定碱性蛋白酶的策略,即添加稳定剂、分子改造和化学修饰,重点介绍了化学修饰中的聚乙二醇化修饰与多糖修饰,对比了两种修饰方法的过程与效果,并在最后对碱性蛋白酶稳定性提高策略进行了展望。

    Alkaline protease is the most widely used enzyme in liquid detergents. The alkaline protease used in detergent industry accounts for more than 60% of the alkaline protease market. Different from the enzyme in powder detergents, which is wrapped due to granulation, the alkaline protease in liquid detergent is directly exposed to the solution and interacts with various deactivators such as surfactants, builders and bleaching agents. Anionic surfactants can cause significant changes in the conformation of alkaline protease, bleaching agents can partially oxidize the active center of protease, and chelators will compete with protease for Ca2+ to stabilize its active conformation, all resulting in the decline of washing stability of alkaline protease. In addition, the alkaline protease in liquid detergents suffers from the autolysis which can be enhanced by other deactivation factors, leading to an adverse effect on its washing performance. The stabilization of alkaline protease has been a hot topic. Researchers have made a lot of efforts on improving the stability of protease, which can improve the performance of enzyme preparation, reduce production costs and improve economic benefits. Extremozymes isolated from high or low temperatures, high salinity or alkaline environment have great potential in detergent industry, but it still needs a long time for industrial application because of the high cost of separation and cultivation. Herein, the catalytic and inactivation mechanisms of alkaline protease have been introduced, and the Ser-His-Asp catalytic triad is the key to the peptide bond hydrolysis activity of alkaline protease. Typical strategies for the stabilization of alkaline protease have been reviewed, including adding stabilizers, molecular modification and chemical modification. Adding stabilizers is the simplest but effective way to stabilize protease, and the stabilization effect of multi-component system is often better than that of a single stabilizer. Molecular modification is a new method of enzyme stabilization with high technical threshold, and the modification is not targeted at the enzyme itself, but involved in the process of enzyme translation, synthesis and expression. Chemical modification is a traditional strategy to improve the stability of enzyme, but seldom used for the enzymes for washing. Special attention has been paid to the introduction and comparison of polyethylene glycol modification and glycosylation modification. Finally, future perspectives of the stabilization stratagies for alkaline protease have been provided.

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    国际化妆品监管模式对比分析与启示
    Comparative analysis and enlightenment of international cosmetics supervision modes
    曹爔,陈坚生,刘佐仁,谢志洁,陈旻
    2022 (2):  190-198.  doi: 10.3969/j.issn.1001-1803.2022.02.012
    摘要 ( 515 )   HTML ( 27 )   PDF(918KB) ( 526 )  

    研究美国、欧盟、日本和中国化妆品监管模式的异同,借鉴国外化妆品监管模式的先进经验,为促进中国化妆品监管创新,寻找更多的新方法、新工具、新标准、新制度,推进化妆品治理体系和治理能力的现代化提供参考。采用文献研究法和对比分析法,通过相关文献和网站等查找化妆品监管模式相关文件,对美国、欧盟、日本和中国四个国家地区化妆品的定义、监管部门、法律法规、相关社会组织及监管方法等方面进行对比分析。美国和欧盟监管体系较为成熟完备,监管模式又有各自不同的特点,日本和中国都向美欧接轨。欧盟采用市场主导模式,实施化妆品责任人制度和备案制度,相对弱化目前生产准入的事前监管,强化事中事后的政府监管,行业协会制定标准和规范行业自律等作用都处于世界领先水平。

    The aim is to study the similarities and differences of cosmetics supervision modes in the United States(US), European Union(EU), Japan, and China, and learn from the advanced experience of foreign cosmetics supervision modes, so as to provide reference for promoting the innovation of China’s cosmetics supervision, looking for more new methods, tools, standards and systems, and promoting the modernization of cosmetics management system and management ability. Literature research method and comparative analysis method were adopted to find documents related to cosmetics supervision mode through relevant literature and websites, and comparative analysis was conducted on cosmetics definitions, regulatory departments, laws and regulations, relevant social organizations and supervision methods in the US, EU, Japan and China. The regulatory systems of US and EU are relatively mature and complete, and the supervision modes have their own different characteristics. Japan and China are in line with US and EU. The EU adopts a market-oriented model, implements a cosmetics responsible person system and a filing system,relatively weakens the current pre-regulation of production access, strengthens the government’s supervision during and after the event, and the role of industry associations in formulating standards and regulating industry self-discipline is at the world’s leading level.

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    面部皮肤衰老的外观变化及形成因素
    Appearance changes and formation factors of facial skin aging
    杜克斯,李泽巧,张宝江,郑玉梅,任晗堃,程建华
    2022 (2):  199-206.  doi: 10.3969/j.issn.1001-1803.2022.02.013
    摘要 ( 665 )   HTML ( 37 )   PDF(936KB) ( 568 )  

    皮肤会随年龄发生有规律地渐近变化,表现出一些特定的衰老迹象,如皮肤皱纹、松弛和色素沉着,影响人的外观吸引力。从衰老机理出发,开发有效延缓皮肤衰老的产品备受企业的关注。综述了面部皮肤衰老的外观变化和相关外观衰老迹象对感知年龄的影响,以及皮肤主要衰老迹象的内在机制和外在环境影响因素。近年来,研究发现,无论性别、种族或地域,皮肤衰老外观最明显的迹象是皱纹和下垂,也是影响感知年龄最主要的因素,与皮肤结构的变化有关;其余主要是色素沉着相关问题。光老化、环境污染等环境因素会显著促进皮肤的衰老外观变化,提高衰老迹象的阈值。皮肤衰老是多种因素综合作用的结果,基于皱纹、下垂、色素沉着等不同皮肤衰老迹象的对应机制和影响因素开发抗衰老产品,将更有针对性地解决消费者的需求,实现精准护肤。本文为研究人员多维度开发抗衰老化妆品提供理论支持和建议。

    Skin tends to show regular asymptotic changes with age, showing some specific aging signs, such as skin wrinkles, sagging and pigmentation. These aging changes affect physical attractiveness and perceived age, contradicting people’s desire to look younger. How to develop effective anti-aging products based on the mechanism of skin aging is the focus of enterprises. This paper summarized the appearance changes of skin aging, the influence of appearance signs of aging on perceived age, and the internal mechanism and external influencing factors of the skin aging signs. The most obvious and dominant skin aging signs are wrinkles and sagging, which are associated with changes in skin structure, regardless of gender, race or region, and the rest are mainly pigmentation problems. The severity of these aging problems and cultural background together affect people’s subjective judgment of age and health. The formation of wrinkles is more like the double result of muscle contraction and tissue defect, and skin softness and moisture content also play an important role. The decrease of skin thickness, extracellular matrix composition and water content associated with aging are the main contributing factors to the formation of wrinkles. The mechanism of skin sagging involves skin deformation (mechanics) caused by progressive stretching of skin by gravity, atrophy of dermis and subcutaneous adipose tissue, weakening of support force of adipose muscle and damage of elastic fibers. The appearance of “faded old woman” is related to carbonylation and glycosylation of dermal protein. Sun exposure and environmental pollution can worsen the appearance of aging, increase perceived age, and present premature aging. Skin aging signs are the result of comprehensive factors. The development of anti-aging products based on mechanisms of different skin aging signs of wrinkles, sagging, and pigmentation will be more targeted to solve consumer’s needs. This paper provides suggestions and directions for researchers to develop multi-dimensional skin anti-aging products.

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    分析与检测
    UPLC-ESI-Q-TOF/MS法测定化妆品中倍他米松及其8种类似物
    Determination of betamethasone and eight analogues in cosmetics by UPLC-ESI-Q-TOF/MS
    贾昌平,张斌,张珊珊,郑佳新,郑梅,陈卫
    2022 (2):  207-213.  doi: 10.3969/j.issn.1001-1803.2022.02.014
    摘要 ( 373 )   HTML ( 11 )   PDF(1356KB) ( 313 )  

    建立了同时分析倍他米松及其8种类似物的超高效液相色谱-高分辨质谱联用仪(UPLC-ESI-Q-TOF/MS)的定性、定量检测方法。采用小颗粒色谱柱,梯度洗脱,电喷雾离子源正离子模式(ESI+),利用TOF采集的化合物母离子推测分子组成,子离子推测结构,并借助对照品加以确证,利用质谱一级准分子离子建立含量测定方法。对建立的检测方法进行方法学验证,发现考察范围内线性关系良好,检出浓度为0.05~0.34 mg/kg,回收率为93.1%~103.7%,相对标准偏差普遍小于6%。在对10批化妆品的分析中,有5批检出激素,并首次发现了2种新的激素添加物:倍他米松17-丙酸酯、倍他米松21-丙酸酯。

    A method of ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-ESI-Q-TOF/MS) was developed for simultaneous determination of betamethasone and its 8 analogues. The separation was executed on a small particle column, and gradient elution was used. The mass spectrometer was performed in positive ion mode, and the identification was performed by MS2 scan with aid of standards, and the determination was carried out in MS scan mode by the external standard method. The analysis method developed was validated. The linear relationship in the linear range was satisfactory, the detection limit was between 0.05 and 0.34 mg/kg. The recovery was 93.1%-103.7%, and the relative standard deviation was less than 6%. In the analysis of 10 batches of cosmetics, glucocorticoids were detected in five batches. Furthermore, two glucocorticoids additives were found for the first time, i.e., betamethasone 17-propionate and betamethasone 21-propionate.

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    超高效液相色谱-串联质谱法测定化妆品中38种抗感染药
    Determination of 38 anti-infective drugs in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry
    陆林玲,钱叶飞,张斌,鲁辉,陈丽波,闵春艳,陈卫
    2022 (2):  214-223.  doi: 10.3969/j.issn.1001-1803.2022.02.015
    摘要 ( 345 )   HTML ( 11 )   PDF(1600KB) ( 277 )  

    建立了同时测定2种不同基质类型化妆品中非法添加38种抗感染禁用药的超高效液相色谱-串联质谱方法。样品经溶剂提取后,采用Waters Acquity BEH C18(50 mm×2.1 mm,1.7 μm)色谱柱,流动相A为0.1%乙酸铵缓冲液(pH=4.0),流动相B为0.1%甲酸甲醇,梯度洗脱;使用三重四极杆质谱多反应监测模式(MRM)检测,以保留时间和相对离子丰度定性,外标法定量。结果表明,氯霉素在质量浓度100~1 000 μg/L范围内,其余37种抗感染药在质量浓度15~150 μg/L范围内均呈现良好的线性关系,相关系数均大于0.99;方法检出限和定量限分别为0.3~240.4 μg/kg和1.1~801.2 μg/kg。3个不同浓度加标水平下,38种抗感染化合物的加标回收率为79.0%~119.8%,相对标准偏差为0.3%~9.7%(n=6)。该方法准确、灵敏、快速,适用于水剂和膏霜化妆品中38种抗感染药的同时测定。

    An ultra high performance liquid chromatography-tandem mass spectrometric method was established for the determination of 38 forbidden anti-infective drugs in 2 matrixes of cosmetics. The cosmetic samples were extracted with solvent and performed on a Waters BEH C18 (2.1 mm×100 mm, 1.7 μm) column with binary mobile phase consisting of 0.1% ammonium acetate pH=4.0 (solvent A) and 0.1% formic acid methanol solution (B) with gradient elution. Samples were analyzed by electronic spray ionization under a positive ion or negative ion mode with multiple reaction monitoring (MRM), and then quantified by an external standard curve. The calibration curve of chloramphenicol is linear within the range of 100-1 000 μg/L and the calibration curves of the other 37 target compounds are linear within the range of 15-150 μg/L with the correlation coefficients above 0.99. The limits of detection (LOD) and limits of quantitation (LOQ) are in the ranges of 0.3-240.4 μg/kg and 1.1-801.2 μg/kg, respectively. The recoveries for 38 prohibited anti-infective drugs at three spiked levels are in the range of 79.0%-119.8% with the relative standard deviations (RSD) of 0.3%-9.7%(n=6). The method is simple, rapid and accurate, and quite suitable for the simultaneous determination of illegally added anti-infective drugs in aqueous and cream cosmetics.

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    微波消解-电感耦合等离子体质谱法测定儿童爽身粉中微量硼
    Determination of trace boron in talcum powder for children by microwave digestion and ICP-MS
    郭珊珊,顾昉,肖紫芬,陈旭,卢端萍
    2022 (2):  224-228.  doi: 10.3969/j.issn.1001-1803.2022.02.016
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    利用微波消解前处理法,通过优化前处理和检测条件,针对儿童爽身粉(三岁以下)中不得检出硼酸和硼酸盐的规定,探索了一种电感耦合等离子体质谱(ICP-MS)法测定儿童爽身粉中的微量硼,实现了对硼元素在低质量浓度0~20 ng/mL范围内的准确定量。通过优化,最终选择HNO3-H2O2消解体系,消解程序为最终温度185 ℃,保持30 min,仪器分析模式为Nogas模式;同时考察了样品中共存离子的干扰情况。结果表明,Na+、K+、Ca2+、Mg2+、Fe2+、Al3+、Pb2+、Zn2+对硼的测定不产生干扰。该方法中硼的线性相关系数(r)为0.999 9,检出限为0.02 µg/g,定量限为0.07 µg/g。在低、中、高三个质量浓度水平下的加标平均回收率为99.2%~101.4%。在阳性样品中,测定值的相对标准偏差RSD (n=6)为1.3%。实验结果表明,该方法准确、可靠、灵敏度高,适用于儿童爽身粉中硼酸和硼酸盐的测定,有助于加强对儿童爽身粉中硼酸和硼酸盐的风险管控。

    In this paper, according to the regulation that boric acid and borate should not be detected in talcum powder for children (under 3 years old), an inductively coupled plasma mass spectrometry (ICP-MS) method was explored to determine trace boron in children’s talcum powder. In exploratory stage, operation parameters of ICP-MS, microwave digestion pre-treatment, interference of coexisting ions were studied. By optimizing the microwave digestion system, HNO3-H2O2 digestion solvent system was selected, and the temperature of the digestion procedure was raised to 185 ℃ for 30 minutes. In the process of optimizing instrument conditions, Nogas analysis mode was selected as the instrumental analysis mode, and yttrium (Y) was used as the internal standard element. Meanwhile, the test of interference with coexisting ions indicated that the common coexisting ions in talcum powder such as Na+, K+, Ca2+, Mg2+, Fe2+, Al3+, Pb2+, Zn2+ had no effects on the determination of boron. Under the best experimental conditions, the boron in the range of 0-20 ng/mL can be quantified accurately. The linear correlation coefficient (r) of the method is 0.999 9. The detection limit of boron is as low as 0.02 µg/g and the limit of quantitation of boron is 0.07 µg/g. The recoveries of boron range from 99.2% to 101.4% at low, medium and high mass concentration spiked levels with 2, 4, 20 times of the quantitative concentration. The specific spiked concentrations are 25, 50 and 250 ng and the relative standard deviations (RSDs) (n=3) of recovery experiments are between 2.2% and 5.4%. The RSD (n=6) of positive samples is 1.3%. The data above show that the method is accurate, reliable and sensitive. Applying the method to control quality of 30 batches of children’s talcum powder available in the market, trace boron are detected in 24 batches of the products. Boric acid is obtained through the conversion of the mass number of boron. The results are in accordance with the requirement of current standards. This method can be used for the accurate quantification of trace boron, which is conducive to strengthen the risk control of boric acid and borate in children’s talcum powder.

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