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2018年, 第48卷, 第5期　刊出日期：2018-05-20 上一期    下一期

基础研究

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OPEO表面活性剂在油/水界面的分子动力学模拟 Molecular dynamics simulation of OPEO surfactants at oil-water interface 候孟蝶, 李惠萍, 胡子昭, 宋宏伟 2018 (5):  243-246.  doi: 10.13218/j.cnki.csdc.2018.05.001 摘要 ( 341 )   PDF(2741KB) ( 399 )   辛基酚聚氧乙烯醚(OPEO)是常用的非离子型表面活性剂,可以显著降低油水体系的界面张力。选择醋酸乙烯酯/水体系,通过改变OPEO中氧乙烯基的数量,采用MS7.0软件中的分子动力学(MD)模拟方法,在常温常压下对油/表面活性剂/水体系的界面生成能、界面厚度等指标进行测定,结果表明,氧乙烯基数量为12时,OPEO的界面生成能较高,降低醋酸乙烯酯/水体系界面张力的能力较好。 Polyoxyethylene octylphenol ether (OPEO) is a commonly used nonionic surfactant that can significantly reduce the interfacial tension of oil-water systems.The vinyl acetate/water system was chosen as the oil-water system.Molecular dynamics (MD) simulation methods in MS7.0 software was used.By changing the number of oxyethylene groups in OPEO,the interface formation energy,interface thickness and other parameters for the oil/surfactant/water system were measured at normal temperature and pressure.Results show that when the number of oxyethylene groups is 12,the interface formation energy of OPEO is relatively high,and its ability to reduce the interfacial tension of vinyl acetate/water system is relatively good. 参考文献 | 相关文章 | 计量指标

科技讲座

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化妆品功效评价(Ⅴ)——舒缓功效宣称的科学支持 Efficacy evaluation of cosmetics (Ⅴ) Scientific support for soothing skin efficacy claims 王欢, 盘瑶 2018 (5):  247-254.  doi: 10.13218/j.cnki.csdc.2018.05.002 摘要 ( 1319 )   PDF(762KB) ( 1205 )   概述了敏感性皮肤的表现和形成机制,介绍了物理化学法、生物化学法、细胞生物学法、三维重组皮肤模型替代法、动物实验法、主观评价法、半主观评价法、客观仪器评价法等舒缓化妆品功效的评价方法,提供了舒缓功效评价的新思路,展望了舒缓化妆品功效评价方法的未来发展方向。 The performance and formation mechanism of sensitive skin were summarized.Various evaluation methods for soothing skin cosmetics such as physical and chemical methods,biochemical methods,cell biological methods,three dimensional recombinant skin model substitution method,animal experiment method,subjective evaluation,semi subjective evaluation and objective instrument evaluation method were introduced.The new idea of soothing efficacy evaluation was proposed and put forward the development direction of it. 参考文献 | 相关文章 | 计量指标

开发与应用

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改性蜡质玉米淀粉稳定Pickering乳液的制备及应用 Preparation and application of Pickering emulsion stabilized by modified waxy maize starch 钱鑫, 梁蓉, 杨成, 曹光群 2018 (5):  255-259.  doi: 10.13218/j.cnki.csdc.2018.05.003 摘要 ( 339 )   PDF(2907KB) ( 324 )   采用辛烯基琥珀酸酐(OSA)对蜡质玉米淀粉(WS)疏水改性制得辛烯基琥珀酸酐改性蜡质玉米淀粉(OSA-WS),以不同取代度OSA-WS制备了稳定的Pickering乳液。测定了OSA-WS取代度(DS)、反应效率(RE)及三相接触角,对其进行了FT-IR、XRD和SEM表征。结果表明,OSA通过与淀粉表面羟基反应对其进行改性并未改变淀粉颗粒结构;随着取代度的增大,淀粉颗粒乳化性增加,制得Pickering乳液稳定性增强;以OSA-WS为乳化剂制得包埋辅酶Q10的Pickering乳液,通过透皮运输实验可知,与辅酶Q10的油溶液相比,包埋辅酶Q10的Pickering乳液更有利于辅酶Q10的透皮运输。 The waxy maize starch (WS) was hydrophobically modified by octenyl succinic anhydride (OSA) to prepare the modified waxy maize starch (OSA-WS).Stable Pickering emulsions were prepared by using OSA-WS with different degree of substitution (DS).The DS,reaction efficiency (RE) and three-phase contact angle of OSA-WS were measured.The OSA-WS was characterized by FT-IR,XRD and SEM.The results show that,by reacting with the hydroxyl groups on the surface of starch,OSA has been successfully grafted without changing the granule of starch.The emulsifying ability of OSA-WS becomes stronger with larger DS,thus the storage stability of Pickering emulsion is also increased with DS.The Pickering emulsion emulsified by OSA-WS was then applied in the transdermal transport of coenzyme Q10.Compared with the oil solution of coenzyme Q10,the Pickering emulsion containing coenzyme Q10 is more favorable for transdermal transport of coenzyme Q10. 参考文献 | 相关文章 | 计量指标

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壳聚糖的接枝改性及其CO2/N2响应乳化性能研究 Study on the modification of chitosan and its CO2/N2-switchable emulsification 任冬寅, 尚志新, 王启宝 2018 (5):  260-265.  doi: 10.13218/j.cnki.csdc.2018.05.004 摘要 ( 240 )   PDF(1997KB) ( 287 )   通过化学反应将甲基丙烯酸二甲氨基乙酯(DMAEMA)接入壳聚糖(CTS)的分子结构中,获得改性产物CTS-g-DMAEMA。使用红外光谱和核磁氢谱对其进行了结构表征。向CTS-g-DMAEMA的聚集体分散液中依次通入CO2和N2后,其外观形态、透光率和电导率发生了明显的循环变化,证实了CTS-g-DMAEMA的CO2/N2刺激响应性。水-液体石蜡的乳化实验证明,与原料CTS相比,CTS-g-DMAEMA具有更好的稳定乳液的能力;并且在CO2/N2作用下,由CTS-g-DMAEMA制备的乳液可以发生破乳和再乳化的循环。 2-(Dimethylamino) ethyl methacrylate (DMAEMA) was grafted onto the molecular structure of chitosan by chemical reaction.FT-IR and 1H NMR were used to characterize the structure of the modified product (CTS-g-DMAEMA).The appearance,conductivity and transmittance of the dispersion of CTS-g-DMAEMA aggregates are repeatedly changed in the stimulation of CO2 and N2,which shows the CO2/N2-switchable behavior of CTS-g-DMAEMA.The emulsification experiment of water-liquid paraffin illustrates that the CTS-g-DMAEMA shows better emulsification capability than the raw chitosan.Moreover,under the action of CO2/N2,the emulsion prepared by CTS-g-DMAEMA can be demulsified and re-emulsified circularly. 参考文献 | 相关文章 | 计量指标

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餐厨废弃油脂合成的生物油磺酸盐与碱复配的界面性能 Interfacial properties of compounded system of alkali and bio-oil sulfonate synthesized from waste cooking oil 龙运前, 黄小荷, 王永政, 汪勇, 宋兴兴, 宋付权 2018 (5):  266-271.  doi: 10.13218/j.cnki.csdc.2018.05.005 摘要 ( 229 )   PDF(790KB) ( 358 )   利用餐厨废弃油脂经磺化反应合成了生物油磺酸盐,并与碳酸钠进行复配,测定了复配体系的界面活性、动态界面张力、界面张力稳定性和分配性能。结果表明,生物油磺酸盐的平均分子量为393,属于水溶性;生物油磺酸盐与碳酸钠的复配体系具有较宽的界面活性范围和较好的界面张力稳定性。在碳酸钠质量分数为0.4%~0.8%范围内,能降低油水界面张力至10-3 mN/m。随着碳酸钠质量分数增加,复配体系与原油的最低界面张力呈现先减小后增大的趋势,碳酸钠最佳质量分数为0.6%。放置90 d后,最低界面张力基本上保持在10-3 mN/m。碳酸钠质量分数一定时,随着生物油磺酸盐质量分数增加,生物油磺酸盐在油水两相中的分配系数降低,当质量分数大于0.25%后,分配系数降幅变小。生物油磺酸盐质量分数一定时,随着碳酸钠质量分数增加,生物油磺酸盐在油水两相中的分配系数增大,增幅较小。 A bio-oil sulfonate was synthesized by sulfonation of waste cooking oil.A compounded system of bio-oil sulfonate and sodium carbonate was prepared.The interfacial activity,dynamic interfacial tension,interfacial tension stability and partition property of the blended system were measured.Results show that the bio-oil sulfonate is water soluble and its average molecular weight is 393.The blended system of bio-oil sulfonate and sodium carbonate has a wide range of interfacial activity and relatively good interfacial tension stability.The interfacial tension between oil and water can be reduced to 10-3 mN/m when sodium carbonate is in the mass fraction range of 0.4%-0.8%.The minimum interfacial tension between crude oil and compounded solution decreases first and then increases with the increase of mass fraction of sodium carbonate.The optimum mass fraction of sodium carbonate is 0.6%.The minimum interfacial tension is still maintained at 10-3 mN/m after 90 d.For a given mass fraction of sodium carbonate,the oil/water partition coefficient of bio-oil sulfonate is decreased as the mass fraction of bio-oil sulfonate increases.The decline of partition coefficient becomes smaller when the mass fraction of bio-oil sulfonate is greater than 0.25%.For a given mass fraction of bio-oil sulfonate,the oil/water partition coefficient of bio-oil sulfonate has a small increase with the increase of mass fraction of sodium carbonate. 参考文献 | 相关文章 | 计量指标

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耐腐蚀超疏水超亲油不锈钢网的制备及其在油水分离过程中的应用 Preparation of anti-corrosion superhydrophobic/superoleophilic stainless steel mesh and its application in oil/water separation 丁鹏, 台秀梅, 杜志平 2018 (5):  272-277.  doi: 10.13218/j.cnki.csdc.2018.05.006 摘要 ( 279 )   PDF(3369KB) ( 494 )   以不锈钢网为基底,通过化学刻蚀法制备微米级粗糙表面,通过一步浸泡法将stöber法制得的疏水亲油纳米SiO2颗粒沉积到粗糙的不锈钢网表面,制备了具有微纳二级粗糙结构的超疏水超亲油不锈钢网。利用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FT-IR)和接触角测量仪(CA)表征了超疏水超亲油不锈钢网的表面形貌、化学组成和润湿性能,并将其用于油水分离过程中。结果表明,疏水亲油纳米SiO2颗粒成功的沉积到不锈钢网表面;水滴在超疏水超亲油不锈钢网上的接触角最大为151°,煤油的接触角为0°;制备的超疏水超亲油不锈钢网不仅能高效的分离不同种类油和水的混合物,还能高效的分离油和腐蚀性液体(强酸或强碱水溶液)的混合物,其耐腐蚀特性可满足复杂环境下的油水分离要求。 Using stainless steel mesh as substrate,a superhydrophobic/superoleophilic stainless steel mesh with micro/nano hierarchical structure was prepared.The surface with micron-sized roughness was obtained through chemical etching and was then coated with hydrophobic/oleophilic nano-SiO2 (the nano-SiO2 was obtained by stöber method) through one step immersing method.The surface morphology,chemical composition and wettability of the superhydrophobic/superoleophilic stainless steel mesh were characterized by scanning electron microscopy (SEM),fourier transform infrared spectroscopy (FT-IR) and contact angle measurement (CA).The mesh was used in oil/water separation process.Results show that hydrophobic/oleophilic nano-SiO2 was coated on the surface of chemical etched stainless steel mesh.The surface of the prepared mesh exhibited superhydrophobicity and superoleophilicity with a water contact angle of 151° and kerosene contact angle of 0°.The prepared mesh could efficiently separate not only the mixtures of water and different kinds of oil but also the mixtures of oil and corrosive aqueous solutions (containing strong acid or alkali).The anti-corrosion ability could meet the requirements of oil/water separation in complex environments. 参考文献 | 相关文章 | 计量指标

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10-十一烯酸四氟丙酯的合成及表征 Synthesis and characterization of 10-undecenoic acid tetrafluoropropyl ester 郭睿, 韩双, 张瑶, 王宁 2018 (5):  278-282.  doi: 10.13218/j.cnki.csdc.2018.05.007 摘要 ( 203 )   PDF(1637KB) ( 319 )   以四氟丙醇和10-十一烯酸为原料,采用直接酯化法合成了10-十一烯酸四氟丙酯(UATE),通过FT-IR和1H NMR对UATE进行了结构表征,考察了反应温度、四氟丙醇用量、催化剂用量、甲苯用量及反应时间5个因素对UATE酯化率的影响。通过响应面实验设计对UATE合成工艺进行优化,确定其最佳合成工艺条件为:n(四氟丙醇)∶n(10-十一烯酸)＝3∶1,催化剂浓硫酸用量为0.5%,甲苯用量为7.6 mL,反应时间10 h,反应温度为138 ℃,在该条件下UATE酯化率最大为78.6%。 10-Undecenoic acid tetrafluoropropyl ester (UATE) was synthesized from 2,2,3,3-tetrafluoro-1-propanol and 10-undecenoic acid by direct esterification.The UATE was characterized by FT-IR and 1H NMR.The effects of the reaction temperature,the amounts of tetrafluoropropanol,catalyst and toluene and the reaction time on the yield of UATE were studied.The synthesis process of UATE was optimized through the response surface experimental design.Thus the optimal conditions of synthesis are determined:n (2,2,3,3-tetrafluoro-1-propanol)∶n (10-undecenoic acid) = 3∶1;the amount of concentrated sulfuric acid is 0.5%;the amount of toluene is 7.6 mL;the reaction time is 10 h;the reaction temperature is 138 ℃.Under such condition,the maximum yield of UATE is 78.6%. 参考文献 | 相关文章 | 计量指标

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氟化铵对纳米金红石型钛硅复合氧化物表面改性研究 Surface modification of rutile titania-silica nanocomposites by ammonium fluoride 赵淑芳, 侯磊鑫, 柳丹丹, 方莉, 程芳琴 2018 (5):  283-287.  doi: 10.13218/j.cnki.csdc.2018.05.008 摘要 ( 240 )   PDF(4208KB) ( 417 )   以硫酸氧钛为钛源、硅酸钠为硅源,采用改进的水解沉淀法制备了纳米金红石型钛硅复合氧化物(TiO2-SiO2),以氟化铵(NH4F)为表面改性剂,采用水热法在不同溶剂中对TiO2-SiO2进行改性,并通过X-射线衍射仪、傅里叶红外光谱仪、扫描电镜、原子力显微镜和接触角测量仪等,研究了不同溶剂对改性效果的影响。结果表明,以异丙醇为溶剂进行NH4F改性时,由于表面Si-F键的形成、异丙醇表面自组装和表面微纳分层粗糙结构的形成等因素的协同作用,改性后的纳米金红石型TiO2-SiO2比表面积大,具有良好的表面性能,其比表面积达332 m2/g,水和二碘甲烷接触角分别达到147.1°和147.2°。 Rutile-TiO2-SiO2 nanocomposites were synthesized by an improved hydrolysis-coprecipitation method using sodium metasilicate and titanium oxysulfate as precursors.Using hydrothermal method,the obtained nanocomposites were further modified by ammonium fluoride (NH4F) in different solvents.The effects of solvents on modification were studied by characterization of the modified nanocomposites by X-ray diffraction,fourier transform infrared spectra,scanning electron microscopy,atomic force microscope and contact angle (CA) measurements.Results show that,the rutile-TiO2-SiO2 modified by NH4F in isopropanol exhibits large specific surface area and has good surface properties,due to the cooperative factors happening at the surface,such as the formation of Si-F bonds,the micro/nano hierarchical rough structure and the self-assembly of isopropanol.Its specific surface area is 332 m2/g,and the contact angles of water and diiodomethane are 147.1° and 147.2°,respectively. 参考文献 | 相关文章 | 计量指标

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基于皮肤模型与THP-1细胞共培养建立皮肤致敏体外检测方法的初步研究 A preliminary study on in vitro skin sensitization test based on skin model and THP-1 cell co-culture 陈健, 柯逸晖, 谈伟君 2018 (5):  288-292.  doi: 10.13218/j.cnki.csdc.2018.05.009 摘要 ( 382 )   PDF(717KB) ( 344 )   建立了皮肤模型与THP-1细胞共培养方法,对石化产品进行了致敏性评价。不同浓度测试物与表皮模型作用15 min,去除受试物后孵育6 h,使用MTT法检测皮肤模型组织活率,利用流式细胞法检测THP-1细胞表面标志物CD86、CD54表达变化情况以及细胞活率。对上述参数进行统计学分析及是否存在剂量效应关系,判定测试物是否具有潜在致敏特性。对SLS、肉桂醛、柠檬醛的测试表明,该方法可以正确区分刺激物和致敏物;对4种未知润滑油添加剂的预测结果表明,HVI60、Cuvan826、ATM PAN为非致敏物,Irgamet30为致敏物,高浓度时可导致表皮组织和THP-1细胞活性降低及表面标志物CD86、CD54的特异性升高。 An in vitro skin sensitization test based on skin model and THP-1 cell co-culture was established,and used to evaluate the sensitizing potency of petrochemicals.Skin model was treated with different concentrations of samples for 15 min,then removing the samples and was incubated for another 6 h.Skin tissue activity was measured by MTT assay,while cell viability and cell surface markers (CD54,CD86) expression levels of THP-1 cells were detected by flow cytometry.The skin sensitization potential of test substances was determined by statistically analyzing the above parameters and reaching a dose-response relationship.The results of SLS,cinnamaldehyde and citral show that this co-culture method can correctly distinguish irritants and sensitizers.The results of 4 unknown lubricant additives show that HVI60,Cuvan826 and ATM PAN are predicted to be non-sensitizers,while Irgamet30 is predicted to be a sensitizer,which at higher concentration can decrease the skin tissue activity and THP-1 cell viability,and specifically increase the expression of surface markers. 参考文献 | 相关文章 | 计量指标

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苯乙基间苯二酚抑制黑色素形成的机理研究 Study on the mechanism of inhibition of melanin by phenethyl resorcinol 郝谜谜, 王艳, 刘园园, 鲍炎, 李红艳, 郑琳 2018 (5):  293-298.  doi: 10.13218/j.cnki.csdc.2018.05.010 摘要 ( 546 )   PDF(1486KB) ( 428 )   采用药物替代法,分别阻断黑色素生成过程中的酶催化和非酶催化两个阶段,探究苯乙基间苯二酚抑制黑色素形成的作用机理。在pH=6.8的磷酸盐缓冲溶液中,分别以L-酪氨酸和L-多巴为底物,37 ℃反应后在475 nm处测定吸光度,研究苯乙基间苯二酚对酪氨酸酶催化反应进程的影响,计算抑制动力学参数;通过分子对接技术分析苯乙基间苯二酚抑制酪氨酸酶作用的分子机制。结果表明,苯乙基间苯二酚对黑色素生成过程中的酶催化反应具有抑制作用,是酪氨酸酶抑制剂;对非酶催化过程无影响;对酪氨酸酶单酚酶和二酚酶的半抑制浓度IC50分别为0.28和31 μmol/L;对酪氨酸酶二酚酶的抑制作用表现为非竞争性抑制,抑制常数Km=1.1;分子对接结果显示,苯乙基间苯二酚与酪氨酸酶活性中心的MET A:280形成氢键,并伴有疏水作用。 Using the drug substitution method,the two stages in the process of melanin formation (i.e.enzyme catalysis and nonenzymatic catalysis) were blocked,in order to explore the mechanism of inhibition of melanin formation by phenethyl resorcinol.Using L-tyrosine and L-DOPA as substrates,after the reaction at 37 ℃ in the phosphate buffer solution of pH=6.8,the absorbance was measured at 475 nm.The effect of phenethyl resorcinol on the catalytic reaction of tyrosinase was studied,and the inhibition kinetic parameters were calculated;The mechanism of inhibition of tyrosinase by phenethyl resorcinol was explored by molecular docking analysis.Results show that phenethyl resorcinol is a tyrosinase inhibitor which can inhibit the enzymic catalytic reaction in the process of melanin formation,while it has no effect on nonenzymatic catalysis;phenethyl resorcinol can efficiently inhibit the activities of monophenolase and diphenolase of tyrosinase,with 50% inhibiting concentrations being 0.28 and 31 μmol/L,respectively;it is found that the inhibition of diphenolase is noncompetitive,and the inhibition constant is Km=1.1;molecular docking results show that phenethyl resorcinol forms hydrogen bonds with tyrosinase MET A:280,accompanied by hydrophobic interaction. 参考文献 | 相关文章 | 计量指标

分析与检测

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HPLC-FLD/DAD双检测器串联测定面膜中10种荧光增白剂 Determination of ten fluorescent whitening agents in masks by HPLC- FLD/DAD with series double-detector 刘莹, 王小兵, 李启艳, 于海英, 徐丽华 2018 (5):  299-302.  doi: 10.13218/j.cnki.csdc.2018.05.011 摘要 ( 326 )   PDF(702KB) ( 295 )   建立了一种应用高效液相色谱仪(HPLC)-FLD/DAD双检测器串联测定面膜中10种荧光增白剂的方法。采用Welch Ultimate LP C18(4.6 mm×250 mm,3.5 μm)色谱柱分离,以甲醇-0.05 mol/L磷酸二氢铵水溶液为流动相梯度洗脱,流速1.0 mL/min,柱温35.0 ℃,荧光检测器(FLD)激发波长360 nm,发射波长430 nm,二极管阵列检测器(DAD)测定波长360 nm。结果表明,10种荧光增白剂在各自的线性范围内线性关系良好,相关系数均大于0.999 5。在3个加标水平下,10种荧光增白剂的平均回收率为87.6%~114.2%,RSD均小于5.0% (n=6)。10种荧光增白剂检出限:FLD为0.026~0.40 mg/kg,DAD为0.50~2.7 mg/kg。 To establish a new HPLC-FLD/DAD with series double-detector method for the determination of ten fluorescent whitening agents in masks.The sample was separated by Welch Ultimate LP C18(4.6 mm×250 mm,3.5 μm) column with the gradient elution of methanol-0.05 mol/L ammonium dihydrogen phosphate solution as mobile phase at the flow rate of 1.0 mL/min.The column temperature was set at 35.0 ℃.The excitation wavelength and emission wavelength of fluorescence detector (FLD) were 360 and 430 nm,and the wavelength of diode array detector (DAD) was 360 nm.Results indicate that ten fluorescent whitening agents have good linear relationship in their linear range,with correlation coefficient greater than 0.999 5.At the three spiked levels,the average recoveries of ten fluorescent whitening agents are in the range of 87.6%-114.2% with the relative standard deviations (RSD,n=6) less than 5.0%.The detection limits of these ten fluorescent whitening agents are 0.026-0.40 mg/kg for FLD and 0.50-2.7 mg/kg for DAD. 参考文献 | 相关文章 | 计量指标