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    2019年, 第49卷, 第5期 刊出日期:2019-05-22 上一期    下一期
    基础研究
    非对称Gemini离子液体表面活性剂的制备及表面活性
    Synthesis and surface activities of asymmetrical Gemini ionic liquid-based surfactants
    杨许召,王军,方云
    2019 (5):  279-285.  doi: 10.3969/j.issn.1001-1803.2019.05.001
    摘要 ( 468 )   HTML ( 108 )   PDF(1132KB) ( 580 )  

    以咪唑、溴代烷、1,3-二溴丙烷和长链烷基N,N-二甲基叔胺分别经取代反应和季铵化反应制备出非对称Gemini离子液体表面活性剂[CnIMC3N11n][Br]2n=10,12,14,16),并通过 1H NMR、 13C NMR和元素分析确定其化学结构。测定了其Krafft点,发现随着疏水链链长的增加,Krafft点逐渐升高。采用吊片法测定了产物的表面活性,结果表明,所制备的Gemini离子液体表面活性剂具有优良的表面活性,其γcmc在35 mN/m左右,cmc在10 -4~10 -3 mol/L范围内,比普通阳离子表面活性剂的cmc低1~2个数量级。通过电导率法测定了[CnIMC3N11n][Br]2的cmc和反离子结合度(β),由电导率法测得的cmc值稍高于吊片法测得的数据,表明形成了无表面活性的预胶束聚集体;同时随着温度的增加,cmc值增加、β值降低,这是因为温度的升高降低了其形成胶束的能力和已形成胶束的稳定性。

    Asymmetrical Gemini ionic liquid-based surfactants,[CnIMC3N11n][Br]2n=10, 12, 14, 16), were prepared with imidazole, bromoalkane, 1,3-dibromopropane and long-chain alkyl N,N-dimethyl tertiary amine as raw materials through substitution reaction and quaternization reaction, respectively. The chemical structures of these Gemini ionic liquid-based surfactants were characterized and identified by 1H NMR, 13C NMR and elemental analysis. The Kraff points were determined and it was found that the Krafft points gradually increased as the hydrophobic chain length increased. Surface activities of[CnIMC3N11n][Br]2 were measured by Wilhelmy plate method. The results show that[CnIMC3N11n][Br]2 display good surface active performance. The values of γcmc of [CnIMC3N11n][Br]2 are approximately 35 mN/m and those of cmc are between 10 -4 mol/L and 10 -3 mol/L, which are 1 to 2 orders of magnitude lower than the traditional cationic surfactants. The values of cmc and counterion binding degree(β)were determined by electrical conductivity method. The cmc values measured by conductivity method were slightly higher than that measured by Wilhelmy plate method, indicating the existence of nonsurface-active premicellar aggregates. Meanwhile, cmc values increase and β values decrease as the temperature increases because of the reduction of the ability to form micelles and the stability of the formed micelles.

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    科技讲座
    弱相互作用调控表面活性剂自组装(V)——在纳米材料制备方面的应用
    Self-assembly of surfactants regulated by weak interactions(V)Application in the preparation of nanomaterials
    吴奥丽,郑利强,孙继超
    2019 (5):  286-292.  doi: 10.3969/j.issn.1001-1803.2019.05.002
    摘要 ( 472 )   HTML ( 12 )   PDF(1808KB) ( 642 )  

    通过调节表面活性剂之间,表面活性剂与前驱体之间以及表面活性剂与溶剂之间的弱相互作用,可以制备形貌和功能多样的介孔二氧化硅、贵金属纳米材料和超分子材料。除了传统的以表面活性剂形成的聚集体(胶束、囊泡、液晶等)作为模板制备纳米材料外,还可以利用表面活性剂中引入的响应性基团简化制备过程,提高材料的循环使用。采用有机-无机共组装的方法制备超分子材料更是具有广阔的应用前景。

    Mesoporous silica, noble metal nanomaterials and supramolecular materials with various morphologies and functions can be prepared by adjusting the weak interactions between surfactants, surfactants and precursors or surfactants and solvents. In addition to the traditional surfactant-forming aggregates(micelles, vesicles, liquid crystals, etc.)as templates for the preparation of nanomaterials, the responsive groups introduced in the molecule can be used to simplify the preparation process and improve the recycling of the materials. The preparation of composite nanomaterials by organic-inorganic co-assembly method has broad application prospects.

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    开发与应用
    一类以对苯二胺为联接基的双子表面活性剂的合成及性能
    Synthesis and properties of a series of Gemini surfactants with p-phenylenediamine as a spacer
    王晨,许虎君
    2019 (5):  293-297.  doi: 10.3969/j.issn.1001-1803.2019.05.003
    摘要 ( 310 )   HTML ( 25 )   PDF(1043KB) ( 1028 )  

    以环氧氯丙烷,对苯二胺和N,N-二甲基烷基胺为原料,分两步合成了一系列具有不同疏水链长的新型双子表面活性剂C12、C16和C18,通过FT-IR和 1H NMR对产物结构进行表征,测定了苯二胺型表面活性剂的临界胶束浓度(cmc)和表面张力(γcmc)以及Krafft点、乳化、泡沫和抗菌性能。结果表明,在25 ℃时C12、C16和C18的cmc分别为3.29×10 -3,2.53×10 -4和3.14×10 -4 mol/L,γcmc分别为28.24,31.95和35.06 mN/m;C12和C16的Krafft点均小于0 ℃,C18的Krafft点为10 ℃;C12的发泡性优于C16和C18;C18的乳化性能强于C12和C16;C12、C16和C18均具有优异的抗微生物活性。

    A series of novel Gemini surfactants C12, C16, and C18 with the hydrophobic groups of different lengths were synthesized with epichlorohydrin, N, N-dimethylalkyl amine and p-phenylenediamine as materials in two steps. The products were characterized by FT-IR and 1H NMR. The critical micelle concentration(cmc)and the corresponding surface tension(γcmc)of the phenylenediamine surfactants in aqueous solution were measured at 25 ℃ by surface tensiometer. The Krafft points and the emulsifying, foaming and antimicrobial properties of the aqueous solutions were also determined. The results show that the cmc of C12, C16 and C18 at 25 ℃ are 3.29×10 -3, 2.53×10 -4 and 3.14×10 -4 mol/L, respectively, and the γcmc are 28.24, 31.95 and 35.06 mN/m, respectively. The Krafft points of C12 and C16 are both below 0 ℃, and the Krafft point of C18 is 10 ℃. The foaming properties of C12 are better than those of C16 and C18. The emulsifying properties of C18 are better than those of C12 and C16. C12, C16 and C18 have shown excellent antimicrobial activities.

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    含刚性基团的Gemini表面活性剂的制备及其与SDS复配性能研究
    Preparation of Gemini surfactants containing rigid groups and their properties after mixed with sodium dodecyl sulfate
    张文哲,李盼,侯琳熙
    2019 (5):  298-303.  doi: 10.3969/j.issn.1001-1803.2019.05.004
    摘要 ( 387 )   HTML ( 6 )   PDF(934KB) ( 398 )  

    以邻苯二甲酸酐、环氧氯丙烷以及N,N-二甲基十四烷基胺为原料合成了含有刚性联接基团的Gemini表面活性剂G14,通过电喷雾质谱以及核磁共振氢谱对其结构进行了表征。研究了G14和十二烷基硫酸钠(SDS)复配体系的表面活性以及应用性能。发现复配体系比单一组分拥有更低的临界胶束浓度(cmc)、更强的乳化能力以及更好的润湿性能。其中当n(G14)∶n(SDS)=1∶2时,cmc为3.19×10 -5 mol/L,γcmc为22.3 mN/m,Amin为0.57 nm 2,pc20为5.01,Гmax为2.92 μmol/m 2;在65 ℃时对柴油的清洗率能达到91.67%。

    A Gemini surfactant containing the rigid linking group(G14)was synthesized from phthalic anhydride, epichlorohydrin and N,N-dimethyltetradecylamine. The structure was characterized by electrospray mass spectrometry and 1H NMR. The surface activity and application properties of the mixtures of G14 and sodium dodecyl sulfate(SDS)were studied. The mixed systems have exhibited a lower critical micelle concentration(cmc), a stronger emulsifying ability, and better wetting properties than a single component. When n(G14)∶n(SDS)=1∶2, the cmc is 3.19×10 -5 mol/L; γcmc is 22.3 mN/m; Amin is 0.57 nm 2; pc20 reaches 5.01; Гmax reaches 2.92 μmol/m 2; the cleaning rate of diesel can reach 91.67% at 65 ℃.

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    红花活性成分的提取及其改善皮肤微循环的功效评价
    Extraction of active components from Carthamus tinctorius and evaluation of its effect on improving skin microcirculation
    聂园进泽,罗元,李欣洋,尹雅婷,易帆,孟宏
    2019 (5):  304-309.  doi: 10.3969/j.issn.1001-1803.2019.05.005
    摘要 ( 612 )   HTML ( 18 )   PDF(1407KB) ( 567 )  

    为探究红花及其与桃胶复合提取物对皮肤微循环的影响及化妆品原料应用前景。在提取了红花及其与桃胶复合物活性成分后,采用以激光多普勒检测技术为主,生物红外热成像等检测技术为辅的检测方法,对比受试者使用前后血流灌注量、红外温度、皮肤粗糙度、水分含量和水分散失量的数据变化,以及受试者皮肤状态变化情况。结果显示涂抹红花提取物及红花与桃胶的提取复合物7 d后,受试者的皮肤血流灌注量、面部温度、皮肤水分含量、水分散失量和皮肤鳞屑指数均有提高;红花提取物降低了细胞脱落数量,而红花和桃胶的复合提取物使细胞脱落数量增加。表明红花含有能够改善并促进皮肤微循环的活性物质,与桃胶制成复合物之后具有促进皮肤微循环的功效,可用作化妆品添加剂。

    In order to explore the effect of safflower and its compound extract with peach gum on skin microcirculation and the application prospect of cosmetics raw materials, after extracting the active components of safflower and its complex with peach gum, laser Doppler detection technique and biological infrared thermal imaging technique were adopted in order to compare the data changes of blood perfusion, infrared temperature, skin roughness, moisture content, transepidermal water loss and skin condition of the subjects before and after use. The results show that the amount of skin blood flow, facial temperature, skin moisture content, transepidermal water loss and skin scale index of the subjects are increased after 7 days with the application of safflower extract and the extract complex of safflower and peach gum. In addition, the extract of safflower decreases the amount of cell shedding, while the compound extract of safflower and peach gum increased the amount of cell shedding. It indicates that safflower contains an active substance capable of improving and promoting skin microcirculation, and has a function of promoting skin microcirculation after being compounded with peach gum, which can be used as a cosmetic additive.

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    凝胶分散法用于TiO2紫外屏蔽能力的测定
    Gel dispersion method for determination of UV shielding capability of TiO2
    景盼盼,谭笑,张迪,田青平
    2019 (5):  310-314.  doi: 10.3969/j.issn.1001-1803.2019.05.006
    摘要 ( 315 )   HTML ( 4 )   PDF(1013KB) ( 545 )  

    利用胶凝作用使颗粒均匀分散于凝胶介质,建立一种测定TiO2紫外吸收的新方法。研究表明,质量分数为0.15%的卡波姆980凝胶可使锐钛型TiO2在3 h内稳定分散。TiO2在UVA和UVB波段无最大吸收,吸光度值随波长增大略有增大。吸光度的均值与其质量浓度在25~70 mg/L范围内线性关系良好,回归方程为A=0.009 7ρ+0.042 5,R 2=0.999,精密度高(RSD=0.20%~1.16%),准确度好(回收率为88.10%~110.3%,RSD=0.58%~1.24%)。该方法用于自制TiO2防晒乳中TiO2的质量浓度定量,相对误差<5%。研究结果可为颗粒型物质分光光度法定量测定提供方法借鉴。

    A new method for determining UV absorption of TiO2 was established by using gelation to uniformly disperse particles in a gel medium. The results show that 0.15% Carbomer 980 gel can make anatase TiO2 disperse stably within 3 hours. TiO2 has no maximum absorption in the UVA and the UVB bands, and the absorbance value slightly increases with increasing wavelength. The mean absorbance has a good linear relationship with its mass concentration within 25-70 mg/L range, and the regression equation is A=0.009 7ρ+0.042 5, with R 2=0.999, and the precision is high(RSDs=0.20%-1.16%)and the accuracy is good(recoveries 88.10%-110.3%, RSD=0.58%-1.24%). The method was applied to quantify the mass concentration of TiO2 in self-made TiO2 sunscreen lotions, and the relative error is less than 5%. The research results can provide a reference for quantitative determination of granular materials by spectrophotometry.

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    藏荆芥提取物对酪氨酸酶活性及其动力学研究
    The effect of extract of Nepeta angustifolia C.Y.Wu on tyrosinase activity and kinetics
    王飞飞,王敏竹,王晗,黄山,旦增江白,李斌
    2019 (5):  315-319.  doi: 10.3969/j.issn.1001-1803.2019.05.007
    摘要 ( 386 )   HTML ( 5 )   PDF(1160KB) ( 374 )  

    L-酪氨酸和L-多巴为底物,采用酶促反应动力学方法研究藏荆芥提取物对酪氨酸单酚酶和二酚酶活性的影响以及抑制动力学。结果表明,藏荆芥提取物对酪氨酸单酚酶和二酚酶均有抑制作用,单酚酶和二酚酶活力下降50%的藏荆芥提取物质量浓度(IC50)分别为0.138 8和0.533 2 g/L。藏荆芥提取物对酪氨酸二酚酶的抑制作用属于可逆过程,Lineweaver-Burk图显示其作用类型表现为竞争性抑制,抑制常数为504.846 mg/L。藏荆芥提取物对酪氨酸酶有明显的抑制作用,具有开发成天然酪氨酸酶抑制剂的潜力。

    The effect of extract of Nepeta angustifolia C.Y.Wu on tyrosine monophenolase and diphenolase activity and inhibition kinetics were studied by enzymatic reaction using L-tyrosinase and L-DOPA as substrates. Experimental results show that the extract of Nepeta angustifolia C.Y.Wu, has inhibitory effect on tyrosine monophenolase and diphenolase, and the concentrations of the extract of Nepeta angustifolia C.Y.Wu leading to 50% decrease in monophenolase and diphenolase activity(IC50)are calculated to be 0.138 8 and 0.533 2 g/L, respectively. The inhibition of tyrosine diphenolase by the extract of Nepeta angustifolia C.Y.Wu is a reversible process. The Lineweaver-Burk plots show that the type of action is competitive inhibition with an inhibition constant of 504.846 mg/L. The extract of Nepeta angustifolia C.Y.Wu has a significant inhibitory effect on tyrosinase and has the potential to be developed into a natural tyrosinase inhibitor.

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    山茶籽油对D-半乳糖亚急性小鼠皮肤的影响
    Effect of Camellia oil on the skin of D-galactose induced aging mice model
    王姝畅,吴亚妮
    2019 (5):  320-327.  doi: 10.3969/j.issn.1001-1803.2019.05.008
    摘要 ( 394 )   HTML ( 6 )   PDF(1251KB) ( 534 )  

    测定和对比了山茶籽原油和山茶花润肤油的脂肪酸组成、体外抗氧化能力以及对衰老小鼠皮肤的影响。采用气相色谱与质谱联用技术对山茶籽原油与山茶花润肤油的脂肪酸成分进行了分析与对比;获取山茶籽原油与山茶花润肤油的乙醇提取物,采用DPPH(1,1-二苯基苦基苯肼)法和ABTS(2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐)法测定二者的体外抗氧化活性;采用1 g/(kg·d)的D-半乳糖溶液背部皮下注射建立小鼠衰老模型,皮肤涂抹山茶油进行体外干预,观察小鼠皮肤组织的超氧化物歧化酶(SOD)、过氧化物酶(CAT)、谷胱甘肽过氧化物酶(GSH-Px)、羟脯氨酸(Hyp)、丙二醛(MDA)的改变以及小鼠皮肤的形态学变化。结果表明,二者不饱和脂肪酸含量丰富,主要有油酸和亚油酸。在体外抗氧化实验中,二者对化学体系产生的自由基都具有较强的清除作用,并与其质量浓度呈一定的正相关关系。在体内实验中,相较于正常组,模型组小鼠皮肤的SOD、CAT、GSH-Px、Hyp含量降低,MDA含量升高,小鼠表皮和真皮厚度降低,胶原纤维含量下降。体外干预后,小鼠皮肤的SOD、CAT、GSH-Px、Hyp含量升高,MDA含量下降,表皮和真皮厚度升高,胶原纤维含量丰富。对山茶油进行体内、体外相结合的抗氧化实验研究得出山茶油具有一定的延缓皮肤衰老的作用。

    The fatty acid composition of tea seed oil and Camellia emollient oil, its antioxidant capacity in vitro and its effect on the skin of aging mice were determined and compared. The fatty acid composition of tea seed oil and Camellia emollient oil was analyzed and compared by gas chromatography and mass spectrometry. Antioxidant activities of tea seed oil and Camellia emollient oil in vitro were determined by DPPH and ABTS scavenging methods. A mouse aging model was established by subcutaneous injection of 1 g/(kg·d)D-galactose solution in the back. The skin was applied with tea seed oil and Camellia emollient oil to observe superoxide dismutase(SOD), content of malondialdehyde(MDA), hydrogen peroxidase(CAT), content of glutathione peroxidase(GSH-Px), content of hydroxyproline(Hyp)and morphological changes in it. From the results, both unsaturated fatty acids are rich in oleic acid and linoleic acid. Both of them have antioxidant capacity in vitro and these effects are does-dependent. In vivo experiment, compared with the normal group, the SOD, CAT, GSH-Px, Hyp contents of the skin of the model group decrease, the MDA content increases, the thickness of the epidermis and dermis decrease, and the collagen fiber content decreases. After in vitro intervention, the SOD, CAT, GSH-Px, and Hyp contents of the skin of the mice increase, the MDA content decreases, the thickness of the epidermis and dermis increase, and the collagen fibers are abundant. The anti-oxidation experiment on the combination of in vitro and in vivo of tea seed oil and Camellia emollient oil show that they both have certain effect on delaying skin aging.

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    专论与综述
    纳米改性氟碳涂料的研究进展
    Research progress of nano-modified fluorocarbon coatings
    韩明虎,张腊腊,武芸,张琪,胡浩斌
    2019 (5):  328-334.  doi: 10.3969/j.issn.1001-1803.2019.05.009
    摘要 ( 470 )   HTML ( 11 )   PDF(965KB) ( 546 )  

    简述了纳米材料的基本概念和氟碳涂料的类型。归纳介绍了SiO2、TiO2和Al2O3等新型纳米材料改性氟碳涂料的制备、性能和应用,并展望了其未来发展前景。

    The basic concept of nano materials and the types of fluorocarbon coatings are briefly described. The preparation, properties and application of new fluorocarbon coatings modified with nano materials such as SiO2, TiO2 and Al2O3 are introduced. Their future development has also been prospected.

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    敏感肌肤和微生态屏障
    Sensitive skin and skin microbiome
    赵小敏,瞿欣
    2019 (5):  335-340.  doi: 10.3969/j.issn.1001-1803.2019.05.010
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    概览了国内外关于皮肤微生态屏障及其和敏感肌肤的关系,包括微生物在皮肤上的分布,微生物和皮肤的相互关系,敏感皮肤微生态屏障的重要性。论述了角质细胞如何特异性的识别共生菌群,共生菌群通过什么样的机制维护皮肤健康,以及微生态屏障失衡在多种类型敏感皮肤发病中的重要作用。同时提出了从护肤品角度出发,如何调控微生态屏障从而解决敏感肌肤问题。

    This article reviews the recent study and development of skin microbiota and its relationship with sensitive skin. The distribution of the microbes on skin and their interaction with skin, and the impact of skin microbiome barrier on sensitive skin are reviewed and discussed. This content covers how keratinocyte specifically recognize commensal microbes, how they protect skin as immunity barrier and how the disrupted skin ecosystem influences different kinds of sensitive skin. The solution for sensitive skin is also reviewed and discussed based on optimizing skin ecosystems.

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    分析与检测
    含推进剂防晒喷雾化妆品取样方式研究
    Study on sampling methods of sunscreen spray cosmetics with propellant
    高家敏,曹进,王钢力
    2019 (5):  341-345.  doi: 10.3969/j.issn.1001-1803.2019.05.011
    摘要 ( 920 )   HTML ( 23 )   PDF(812KB) ( 704 )  

    采用含推进剂和不含推进剂的取样方式,分别测定含推进剂防晒喷雾化妆品样品中防晒剂的含量,比较不同取样方式的测定结果差异,为规范该类产品的取样方式提供参考。结果表明,采用去除推进剂后取样测定得到的防晒剂含量测定结果较不去除推进剂取样测定得到的结果准确,且不含推进剂取样方式的测定结果重现性更好,RSD均小于10%。排完推进剂后取样能准确测定含推进剂防晒喷雾化妆品中防晒剂的含量,平行样测定结果重现性良好。

    The contents of the sunscreen agents in the sunscreen spray cosmetic samples containing propellant were determined respectively by propellant-containing and propellant-free sampling method, and the results of the two methods were compared to provide a reference for standardizing the sampling method for this kind of cosmetic. Results show that the determination of sunscreen contents by sampling after propellant removal are more accurate than those without propellant removal, and the propellant-free sampling method is more reproducible with RSD less than 10%. The content of sunscreen agents in the sunscreen spray cosmetics containing propellant can be accurately determined by sampling after excluding the propellant. The measurement results of parallel samples have good reproducibility.

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    气相色谱法测定烟用香精中的乙醇、1,2-丙二醇和丙三醇
    Determination of ethanol, 1, 2-propylene glycol and glycerol in tobacco flavor with gas chromatography method
    肯生叶,李峰,饶国华,段勤,杨雪燕,邹由
    2019 (5):  346-350.  doi: 10.3969/j.issn.1001-1803.2019.05.012
    摘要 ( 714 )   HTML ( 14 )   PDF(859KB) ( 471 )  

    为了准确测定烟用香精中溶剂的含量,以1,4-丁二醇为内标建立了检测烟用香精中乙醇、1,2-丙二醇和丙三醇的气相色谱法,采用该方法测定了30个烟用香精样品。结果表明:该方法的检出限和定量限范围在0.019~0.088和0.063~0.293 g/L之间;回收率在97.5%~101.6%之间;相对标准偏差(RSD)为0.61%~0.89%。所测样品中均检出1,2-丙二醇,均未检出丙三醇;13个样品中检测出乙醇。该方法前处理简单、灵敏度高、定性定量准确,适用于烟用香精中乙醇、1,2-丙二醇和丙三醇的定性定量分析。

    In order to accurately determine the content of solvents in tobacco flavors, a gas chromatography method was developed for the determination of ethanol, 1,2-propylene glycol and glycerol in tobacco flavor using 1,4-butanediol as an internal standard. Thirty tobacco flavor samples were tested by this method. Results show that the limit of detection and limit of quantitation are 0.019-0.088 and 0.063-0.293 g/L, respectively. The recoveries are 97.5%-101.6% with the relative standard deviations(RSD)ranging from 0.61% to 0.89%. 1,2-propylene glycol is detected, while glycerol is not detected in all samples; ethanol is detected in thirteen samples. This method has the advantages of simple pretreatment, high sensitivity and high accuracy, and is suitable for the determination of ethanol, 1,2-propylene glycol and glycerol in tobacco flavor.

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