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    2021年, 第51卷, 第11期 刊出日期:2021-11-22 上一期    下一期
    基础研究
    动态亚胺型pH开关表面活性剂的合成及性能研究
    Synthesis and properties of pH-switchable surfactants based on dynamic imine bond
    李欢,方银军,刘雪锋
    2021 (11):  1039-1044.  doi: 10.3969/j.issn.1001-1803.2021.11.001
    摘要 ( 283 )   HTML ( 65 )   PDF(1411KB) ( 203 )  

    基于动态亚胺键特殊的pH响应特性,构筑具有pH可逆响应的表面活性剂及其自组装体系是近年来表面活性剂物理化学领域的热点之一,但是两性离子型的动态亚胺键表面活性剂尚未见报导。为此,设计并合成一种带有磺基甜菜碱亲水基的芳香醛(FPSA,(CHO)C6H4OCH2CH2N+(CH32CH2CH2CH2SO3-)的前驱体,并与脂肪辛基伯胺(OA)在水溶液中原位形成动态亚胺键型表面活性剂FPSA-OA(C8H17N=CH-C6H4OCH2CH2N+(CH32CH2CH2CH2SO3-)。通过表面张力(γ)曲线得到25 ℃时FPSA-OA的临界胶束浓度(cmc)为3.43×10-3 mol/L,γcmc为30.89 mN/m;此外,FPSA-OA可以将石油醚-水的界面张力降低至4.87 mN/m,表现出良好的表(界)面活性。结果表明,FPSA-OA具有pH响应性,其pH开关窗口为8~12;对于2×10-3 mol/L FPSA-OA溶液而言,当pH分别在8和12可逆变化时,其γ在70和37 mN/m之间相应可逆改变;如此循环5次,FPSA-OA水溶液的表面张力均表现出良好的响应可逆性。

    Based on the particular pH-response of dynamic imine bonds, constructing pH-responsive surfactants and the self-assemblies thereof has been one of the hotspots recently in the field of physical chemistry of surfactants. However, the reports on amphoteric surfactants containing dynamic imine bonds with simple structure have been rarely seen. Herein, an aromatic aldehyde containing sulfobetaine group (FPSA, (CHO)C6H4OCH2CH2N+(CH32CH2CH2CH2SO3-) was designed and synthesized. FPSA and octylamine (OA) were used as the precursors to form an amphoteric dynamic imine surfactant (FPSA-OA, C8H17N=CH-C6H4OCH2CH2N+(CH32CH2CH2CH2SO3-) in situ in the aqueous solution. The critical micelle concentration (cmc) and the surface tension (γ) at cmc were 3.43×10-3mol/L and 30.89 mN/m at 25 ℃, respectively. In addition, the interfacial tension at the interface of petroleum ether-water was reduced to 4.87 mN/m. All of these results indicate that the interfacial activities of FPSA-OA are quite well. The pH-response of FPSA-OA was observed, and the pH-responsive window was in the range of 8 to 12. For a sample solution of FPSA-OA (2×10-3mol/L), the value of γ was reduced from approximately 70 mN/m to 37 mN/m when the pH was changed from 8 to 12, and then restored to approximately 70 mN/m if the pH was changed back to 8. This transition could be steadily and reversibly carried out over 5 cycles without any remarkable variation, which implies that FPSA-OA has an excellent pH-reversibility.

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    固载过氧化氢酶微球清除家庭漂白后残留过氧化氢的研究
    Removal of residual hydrogen peroxide after bleaching by microspheres containing catalase
    陈佳琳,刘刚,孙梦梦,郭婷,孟涛
    2021 (11):  1045-1051.  doi: 10.3969/j.issn.1001-1803.2021.11.002
    摘要 ( 201 )   HTML ( 10 )   PDF(1494KB) ( 252 )  

    利用仿生矿化法制备了固载过氧化氢酶的碳酸钙微球,研究了该载酶微球的包封情况、在苛刻环境中的稳定性和清除漂白纱布后残留过氧化氢的效果。结果表明,该载酶微球粒径约11 μm,孔径为5.53 nm,能有效封装住过氧化氢酶;在过氧化氢酶质量浓度为0.15 mg/mL的条件下,该微球对过氧化氢酶具有最高负载量为24.26 mg/g,此时酶包封率为98%,酶活力保留率为72%。该载酶微球与游离酶相比提升了热稳定性(80 ℃条件下仍能保留38.99%的相对酶活力)、改变了过氧化氢酶对不同pH环境耐受能力的趋势(最适酶活力pH值由pH 8偏移至pH 11),提升了耐表面活性剂性质(在十二烷基硫酸钠环境中仍保留了85.82%的相对酶活力)。且该载酶微球能在25 min完全清除漂白纱布后残留的过氧化氢。

    Calcium carbonate microspheres containing catalase were prepared by the method of bionic mineralization. The size and pore size of the enzyme-carrying microspheres were measured; the encapsulation efficiency, loading capacity and stability of the enzyme-carrying microspheres in harsh environments were studied; the removal of residual hydrogen peroxide from the gauze after bleaching was studied. The results show that the enzyme-carrying microspheres have a particle size of approximately 11 μm. From the nitrogen adsorption-desorption isotherm and pore size distribution diagram, it can be seen that CAT@CaCO3 microspheres have uniformly distributed pores (approximately 5.53 nm), which can well encapsulate catalase (approximately diameter 6 nm×10 nm), allowing the substrate H2O2 and the product H2O to diffuse freely. Under the condition that the mass concentration of catalase is 0.15 mg/mL, the microsphere has a maximum load of 24.26 mg/g for catalase. Meanwhile, the enzyme encapsulation rate is 98%, and the enzyme activity retention rate is 72%, indicative of the mildness of the method of enzyme immobilization. Compared with free enzymes, the enzyme-carrying microspheres have improved thermal stability (38.99% of relative enzyme activity can still be retained at 80 ℃) and have changed the trend of catalase tolerance to different pH environments (the optimal pH for the enzyme activity shifts from pH 8 to pH 11). This phenomenon may be ascribedto the mineralization and fixation of calcium carbonate changing the conformation of the enzyme. To a certain extent, the conformation of CAT is changed, resulting in a different tendency of pH tolerance from free enzymes. In addition, the anti-surfactant performance of the enzyme-carrying microspheres is improved (85.82% of relative enzyme activity remains in the presence of sodium lauryl sulfate). The reasons might be that the calcium carbonate mineral shell can stabilize the three-dimensional structure of the enzyme during the process of immobilizing the enzyme, resulting in the enhanced stability of the immobilized enzyme. Finally, the enzyme-carrying microspheres can completely remove the residual hydrogen peroxide from the gauze after bleaching within 25 min, which has a faster removal rate than the free enzyme (35 min).

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    科技讲座
    化妆品植物原料(VI)——在抗衰老化妆品中的研究与开发
    Botanical cosmetic ingredients (VI)Research and development of anti-aging skincare ingredients from plants
    张雨彤,魏梦雅,任倩倩,吴华,金建明
    2021 (11):  1052-1059.  doi: 10.3969/j.issn.1001-1803.2021.11.003
    摘要 ( 554 )   HTML ( 45 )   PDF(1285KB) ( 577 )  

    随着年龄的增长,皮肤会发生一些变化,衰老是最明显的迹象之一。在皮肤衰老过程中,皮肤表皮慢慢变薄,固有修复能力逐渐减弱,胶原蛋白和弹性蛋白逐渐减少,皮肤慢慢失去弹性。皮肤衰老是不可避免的,但可以采用多种方法延缓皮肤衰老。本文介绍影响皮肤衰老的内外因素,以及皮肤衰老的机制和抗衰老方法。植物提取物可以通过多种途径对皮肤产生抗衰老作用:可以通过防晒作用防止皮肤光老化,可以作为各种活性物延缓和抑制皮肤衰老,也可以通过剥脱作用促进角质细胞的更新和新陈代谢而减少皮肤的皱纹和黑斑等。本文主要介绍有助于胶原蛋白、弹性蛋白和透明质酸合成与抑制降解的抗皮肤衰老的植物活性成分;多酚、黄酮、维生素和类胡萝卜素等,以及作为剥脱剂的植物羟基酸类成分。通过对植物提取物的皮肤抗衰老成分的详细阐述,以期为植物原料更好地应用到抗衰老化妆品中提供借鉴。

    Among the changes of skin with age, skin aging is one of the most obvious evidence. During this process, the epidermis gradually becomes thinner, and its self-repairing capability is gradually weakened. In addition, the amounts of collagen and elastin in the skin gradually reduce, and thus the skin loses elasticity. Skin aging is inevitable, but a varity of anti-aging strategies can be adopted. Herein, the intrinsic and extrinsic factors leading to skin aging have been introduced, as well as some skin anti-aging strategies. Some of plant extracts can exhibit skin anti-aging effects via multiple ways, such as preventing skin photoaging by sun-screening ingredients, inhibiting skin aging by various bioactive components, and reducing skin wrinkles and pigment spots by skin peeling which activates the proliferation and metabolism of keratinocytes. The anti-aging skincare ingredients from plants have been introduced, including polyphenols, flavonoids, vitamins and carotenoids which promote the biosynthesis (or inhibit the degradation) of collagen, elastin and hyaluronic acid. Plant hydroxy acids used for skin peeling have also be introduced. The description of the anti-aging skincare ingredients from plants may provide a reference for the application of plant extracts in anti-aging cosmetics.

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    开发与应用
    基于动态亚胺键构筑的pH响应型囊泡
    pH-responsive vesicles based on dynamic covalent bond
    穆蒙,张星,蒋焱,李建兵,陆娉娉,张永民
    2021 (11):  1060-1066.  doi: 10.3969/j.issn.1001-1803.2021.11.004
    摘要 ( 751 )   HTML ( 20 )   PDF(1669KB) ( 541 )  

    基于动态亚胺键构筑pH响应型表面活性剂及自组装体已成为刺激响应型胶体体系的研究热点之一。然而,传统的亚胺型表面活性剂只能在表面活性剂与非表面活性剂的前体之间可逆开关,无法实现表面活性剂结构对称度的调控。本文利用含醛基的表面活性剂N-十六烷基-N,N-二甲基-N-(2-(4-甲酰基-苯氧基)乙基)溴化铵(HOBAB)与廉价的正辛胺(OA),通过简单的席夫碱反应,原位合成了一种结构近似对称的单头双尾表面活性剂。该表面活性剂可自发形成半径约为70 nm的囊泡状聚集体,且表现出明显的pH响应特性。当pH值低于8.0后,亚胺键断裂,原位产生的动态双尾表面活性剂结构瓦解,HOBAB重新生成,体系中的囊泡随之解离,形成了球形胶束。随着体系pH值在酸性(pH=5.0)与碱性(pH=10.0)之间的循环调控,溶液中的主表面活性剂结构可在高度不对称与近似对称之间可逆切换,同时伴随着聚集体在球形胶束与囊泡之间的可逆转变。

    Over the past decades, stimuli-responsive colloidal materials based on dynamic covalent bonds (especially imine bonds) have aroused significant interest due to the combination of the stability of covalent bonds and the tunability of non-covalent bonds. However, conventional imine-type surfactants are usually switched between active and inactive states. Tuning the symmetry of surfactants using the dynamic imine bonds has barely been reported to date. Herein, a novel imine-type surfactant bearing approximately symmetrical double tails was fabricated utilizing a simple Schiff base reaction by mixing aldehyde-containing surfactant ((N-alkyl-N,N-di-methyl-N-(2-(4-formyl-phenoxy)ethyl) ammonium bromides, HOBAB) and n-octylamine (OA) at a fixed stoichiometric ratio of 1∶1 in water. Both the results of 1H NMR and FT-IR manifested the formation of dynamic imine bonds, and the conversion rate from aldehyde to imine was as high as 80.75%. With alternatively adding HCl (pH=5.0) and NaOH (pH=10.0), the surfactant could be reversibly switched between highly asymmetrical HOBAB and approximately symmetrical imine-type double-tail amphiphile because of the breakage and formation of imine bonds. Surface tension experiment showed that the critical micelle concentration of the sample at pH=10.0 was decreased by at least one order of magnitude compared to that at pH=5.0, owing to the presence of imine-type double-tail surfactant. Furthermore, in contrast with HOBAB, the presence of imine-type double-tail amphiphiles remarkably improved the surface/interfacial properties (larger pc20 values and more compact packing at the air/solution interface). More importantly, this imine-type double-tail surfactant could spontaneously self-assemble into vesicles with radius being approximately 70 nm in aqueous solution, because of the favorable molecular geometry. When the pH value was decreased to 5.0, vesicles had disappeared and spherical micelles with radius being ~2.5 nm re-dominated in the solution, which was mainly ascribed to the change of molecular geometry originated from the breakage of imine bonds. As pH value was increased to 10.0 again, small spherical micelles re-evolved into large vesicles due to the re-formation of imine-type double-tail surfactant. In a word, upon cyclically changing the pH value between 5.0 and 10.0, the aggregates that dominate the solution can be reversibly changed between spherical micelles and vesicles because of the reversible change in molecular geometry between high asymmetry and approximate symmetry. The current research may facilitate the design of new stimuli-responsive soft materials based on dynamic covalent bonds.

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    鼠李糖脂纳米乳液的构建及性能研究
    Preparation and performance evaluation of the nanoemulsion based on rhamnolipid
    张峙,胡徐彦,袁辉,李彦闯
    2021 (11):  1067-1072.  doi: 10.3969/j.issn.1001-1803.2021.11.005
    摘要 ( 331 )   HTML ( 13 )   PDF(1750KB) ( 241 )  

    为了解决低渗透油藏开发中原油采收率低的问题,采用微乳液稀释法制备了具有纳米尺寸的鼠李糖脂乳液体系,研究了表面活性剂与助表面活性剂的质量比(Km)、温度和无机盐对上述体系拟三元相图和纳米乳液粒径的影响规律,最后对纳米乳液的驱油效率进行了评价。结果表明,随着Km的增加,单相微乳区面积先增加后减少;当Km=3时,单相微乳区面积最大。随着温度的升高,单相微乳区面积先增加后减小;在323.15 K时,单相微乳区面积最大。相图中单相微乳区面积随着NaCl和CaCl2质量浓度的增加而增加,无机盐的加入降低了鼠李糖脂的临界胶束浓度,因此能增加油相和水相的互溶程度。当水的质量分数小于80%时,鼠李糖脂/异丙醇/柠檬烯/水纳米乳液的粒径随放置时间增长略微增加,表现出良好的稳定性。并通过考察温度和无机盐对粒径的影响,发现上述纳米乳液体系具有较好的耐温性能和耐盐性能。驱替实验结果表明纳米乳液的注入明显降低了水驱注入压力,且采收率提高了17%以上,因此纳米乳液在低渗透油藏采收率提高方面应用前景广阔。

    To enhance the low oil production rate in low-permeability reservoir development, the nanoemulsion based on rhamnolipid was prepared by diluting the microemulsion. The effects of the mass ratio of surfactant to cosurfactant (Km), temperature, and inorganic salts on the pseudo-ternary phase diagram and the droplet diameter were studied. Finally, the oil displacement efficiency of the nanoemulsion was evaluated. The results show that the area of the monophase microemulsion zone is first increased and then decreased with the increase of Km. The area of the monophase microemulsion zone reaches a maximum at Km=3. With the increase of temperature, the area of the monophase microemulsion zone is also first increased and then decreased. The maximum area of the monophase microemulsion zone is observed at 323.15 K. The area of the monophase microemulsion zone is increased with the concentrations of NaCl and CaCl2. The addition of inorganic salts has reduced the critical micelle concentration of rhamnolipid and thus increased the miscibility of oil and water phases. When the mass fraction of water is lower than 80%, the droplet diameter is slightly increased with the increase of the storage time. In addition, the nanoemulsion shows excellent temperature and salt resistance. Core displacement experiment shows that nanoemulsion flooding can decrease the injection pressure of water flooding and can improve the recovery by 17%. Therefore, the nanoemulsion has the potential in enhancing oil recovery of low-permeability reservoirs.

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    表面活性剂起泡及润湿性能的影响研究
    Research on the influence of surfactant on foaming and wetting performance
    龚佳怡,乔建江
    2021 (11):  1073-1079.  doi: 10.3969/j.issn.1001-1803.2021.11.006
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    通过单因素法,配制不同体系的表面活性剂溶液,研究亲水亲油平衡值(HLB值)、表面张力、黏度、复配组分对溶液起泡、泡沫携液和润湿性能的影响。实验结果表明:在吐温85、吐温40、烷基糖苷(APG)构成的表面活性剂体系中,溶液HLB值对起泡和润湿能力无明显影响。在十二烷基硫酸钠(SDS)和APG构成的表面活性剂体系中,表面张力的降低有利于溶液起泡和润湿;当质量分数大于临界胶束浓度(cmc)时,随着质量分数增加,溶液起泡能力先增加后平稳,泡沫稳定性降低,润湿性能提升。在SDS、APG、黄原胶构成的复配体系中,溶液黏度的增加有利于泡沫稳定和携液,但降低了起泡和润湿性能。表面活性剂复配的协同作用与组分及配比质量分数有关,月桂醇聚醚硫酸酯钠(SLES)与十二烷基二甲基甜菜碱(BS)复配组分有明显增效作用,在质量分数比为5∶5的条件下综合性能最佳。

    This paper is intended to explore the influence of the surfactant solution physical parameters and compound components on the foaming and wetting performance by preparing surfactant solutions of different systems. Physical parameters includes the HLB value of surfactant, solution surface tension, and its viscosity. The HLB value of the solution was measured by water counting, and its surface tension and viscosity were measured by the surface tension instrument and rotational viscometer, respectively. Foaming ability of the solution was determined by the shaking method and Warning-Blender method, while foam stability was determined by the foam volume attenuation method. The wetting time was determined by the immersion method. The nonionic-nonionic surfactant system solution was formulated from Tween 85, Tween 40, alkyl glycoside (APG) to change the HLB value of the solution. Results show that the HLB value has no obvious effect on the foaming and wetting performance. Within the test range, when the APG concentration is the same, the solution has similar foaming and wetting performance, indicating that the foaming and wetting performance of the solution mainly depends on the effect of APG concentration. The anionic-nonionic surfactant system solution is formulated from sodium dodecyl sulfate (SDS) and APG to change the surface tension of the solution. Results show that the decrease of surface tension is conducive to the improvement of foaming and wetting performance. When the concentration is greater than the critical micelle concentration (0.011 6%), the surface tension is almost constant. With the increase of concentration, foaming ability of the solution increases first and then stabilizes, the foam stability decreases and the wetting performance improves. In the compound solution of SDS, APG and xanthan gum, the concentration of xanthan gum is different to change the viscosity of the solution. Results show that the increase of solution viscosity is beneficial to the improvement of foam stability, and the foam can carry more solutions in the initial stage of formation. The foaming ability of the solution is slightly reduced, and the wetting performance decreases. The synergistic effect of surfactant compounding is related to the composition and ratio concentration. The combination of sodium lauryl polyoxyethylene ether sulfate (SLES) and dodecyl dimethyl betaine (BS) has a synergistic effect, and the comprehensive performance is the best when the concentration ratio is 5∶5.

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    环氧大豆油基水溶性醇酸树脂的合成、表征及酯化动力学研究
    Synthesis, characterization and esterification kinetics of epoxidized soybean oil based water soluble alkyd resin
    马百峰,甄卫军,欧阳辰光,阿不拉江·玉素甫,欧全胜
    2021 (11):  1080-1087.  doi: 10.3969/j.issn.1001-1803.2021.11.007
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    以环氧大豆油(ESO)、三羟甲基丙烷(TMP)、邻苯二甲酸酐(PA)和水性单体偏苯三酸酐(TMA)作为主要原料,采用醇解、酯化和中和等工艺路线合成水溶性醇酸树脂。以静态接触角为目标函数,通过正交试验设计优化水溶性醇酸树脂的较优合成条件,并对树脂的结构进行表征。结果表明:油度为40%,醇超量为1.2,TMA和PA的摩尔比为0.5∶1,最终酸值控制在60~80 mg KOH/g,水溶性醇酸树脂表现出优异的水溶性和稳定性。酯化动力学分析表明酯化反应符合二级反应动力学模型,由阿伦尼乌斯方程求得酯化反应活化能Ea为88.081 kJ/mol。

    Epoxidized soybean oil (ESO), trimethylolpropane (TMP), phthalic anhydride (PA) and water-soluble monomer trimellitic anhydride (TMA) were used as the main raw materials to prepare water-soluble alkyd resin by alcoholysis, esterification and neutralization. With the static contact angle as the objective function, the synthesis conditions of water-soluble alkyd resin were optimized by the orthogonal experiment. The structure of the water-soluble alkyd resin was characterized. The results of Fourier transform infrared (FTIR) show that the water-soluble alkyd resin is successfully synthesized. The optimum conditions obtained by orthogonal test are as follows: the oil content is 40%; the alcohol excess is 1.2; the molar ratio of TMA to PA is 0.5∶1; the final acid value is controlled at 60-80 mg KOH/g. Through the transmittance testing and storage stability testing, the prepared water-soluble alkyd resin shows excellent water solubility and stability, indicating that epoxidized soybean oil can be used as the raw material for manufacture of waterborne alkyd coatings. The rotational rheological analysis shows that the water-soluble alkyd resin has good rheological properties and conforms to the pseudoplastic fluid. Esterification kinetics analysis shows that temperature has significant effect on the esterification reaction. With the increase of temperature, the reaction rate and conversion rate are significantly improved. The study on esterification kinetics finds that it conforms to the second-order reaction kinetics model, and the activation energy Ea of esterification reaction is 88.081 kJ/mol according to Arrhenius equation.

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    6种常用防晒剂的透皮吸收和安全评估
    Transdermal absorption and safety assessment of six commonly used sun-screening agents
    柳亚锋,刘岱拯,谢珍茗
    2021 (11):  1088-1094.  doi: 10.3969/j.issn.1001-1803.2021.11.008
    摘要 ( 485 )   HTML ( 29 )   PDF(1297KB) ( 388 )  

    以猪耳皮肤为模型,利用静态Franz垂直扩散池法,探究皮肤状态、涂抹量、接收液等因素的影响,完善体外透皮实验方法,得到6种不同结构防晒原料二苯酮-3、对甲氧基肉桂酸异戊酯、4-甲基卞亚基樟脑、丁基甲氧基二苯甲酰甲烷、乙基己基三嗪酮、双-乙基己氧苯酚甲氧苯基三嗪的透皮吸收值,比较其透皮吸收性能,结果表明使用法规允许最高限10%的二苯酮-3涂抹在冷冻储存的猪耳皮肤24 h后,经皮吸收率达到36.66%,高出其它准用防晒剂,安全边际值为96.15;新鲜与冷冻储存的皮肤的渗透系数在0.47~0.88之间;透皮吸收量随涂抹量的增加而增加,但非线性关系。总体来讲,在法规允许剂量下使用防晒剂,经皮吸收的量占比较小,带来的健康风险较低。

    The widespread use of sunscreen has caused great concern about its safety. Using sunscreen products can protect the skin from UV radiation, meanwhile, it may cause damage to the human body if it intervenes the circulatory system through the skin. In this study, the transdermal absorption of six sun-screening agents in full-thickness porcine ear skin was examined. The effects of skin condition, application dose, composition of receptor fluid, and retention of sun-screening agents at different skin depths were investigated. The results show that skin condition can affect the transdermal absorption of sun-screening agents, and the sun-screening agents can penetrate through frozen skin more easily. The penetration coefficient of each sun-screening agent was from 0.47 to 0.88. When the dosages were 0.5 mg and 2 mg, the transdermal absorption values of the sun-screening agents were different and increased with the increase of dosage, but the relationship was not linear. Adding different nonionic additives into the receptor fluid had little effect on the transdermal absorption of the sun-screening agents. The retention of the sun-screening agents in each layer of skin was related to their physical and chemical properties, such as molecular weight, water-oil balance coefficient, etc. Twenty-four hours after application, the transdermal absorption rate of BP-3 was 36.66%, higher than other sun-screening agents, and the margin of safety was 96.15. In general, the amounts of the sun-screening agents absorbed through the skin are relatively small and the health risks are low when the legally permitted dosages are used.

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    龙脑樟精油的化学成分、抗氧化活性和认知改善作用研究
    Study on chemical components, antioxidant activity and cognitive improvement of borneol essential oil
    唐寅,吕晓帆,王莹,吴亚妮
    2021 (11):  1095-1101.  doi: 10.3969/j.issn.1001-1803.2021.11.009
    摘要 ( 347 )   HTML ( 13 )   PDF(1303KB) ( 186 )  

    利用气相色谱-质谱(GC-MS)技术检测龙脑樟精油化学成分,通过1,1-二苯基苦基苯肼(DPPH)和2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)法测定龙脑樟精油体外抗氧化能力,采用Morris水迷宫实验和免疫组化实验判断小鼠嗅吸精油后的认知功能,检测小鼠嗅吸精油后脑组织中超氧化物歧化酶(SOD)、谷胱甘肽过氧化物(GSH-PX)和丙二醛(MDA)体内氧化指标。结果显示,龙脑樟精油鉴定出龙脑、右旋柠檬烯、桉叶素等43种主要化学成分;龙脑樟精油对DPPH和ABTS自由基的IC50分别是1.65和2.27 g/L;龙脑樟精油组小鼠在Morris水迷宫中的逃避潜伏期、穿越原平台次数等指标改善,在免疫组化切片中发现β-淀粉样蛋白减少;龙脑樟精油组小鼠脑组织的SOD和GSH-PX活力提高,MDA含量减少。综上,龙脑樟精油具有一定的体外、体内抗氧化活性,对小鼠认知功能障碍具有一定的改善作用。

    Gas chromatography-mass spectrometry (GC-MS) technology was used to detect chemical compositions and their relative contents of borneol essential oil. By analyzing scavenging activity of 2,2-Diphenyl-1-picrylhydrazyl (DPPH) free radical and 2,2'-azinobis[3-ethylbenzothiazoline-6-sulfonicacid]-diammonium salt (ABTS) free radical, the antioxidant activity of borneol essential oil and trolox were determined in vitro. In order to explore the effect of borneol essential oil on behavior of mice with learning and memory impairment, Morris water maze test and immunohistochemistry experiment were used to judge the cognitive function of mice in normal group, model group, borneol essential oil group and positive group. In addition, after completing the animal behavior experiment, the levels of superoxide dismutase (SOD), glutathione peroxidase (GSH-PX) and malondialdehyde (MDA) of brain tissue were measured. The results show that there are 43 main chemical components in borneol essential oil, such as borneol, d-limonene and 1,8-cineole. Free radical scavenging experiment finds that a certain concentration of borneol essential oil can effectively clean up DPPH and ABTS free radical, but its scavenging ability is less than trolox. The half maximal inhibitory concentration (IC50) of borneol essential oil on DPPH and ABTS free radical are 1.65 and 2.27 g/L, respectively. In Morris water maze, compared to mice in model group, the escape latency and crossing times of mice in borneol essential oil group are improved, and the performance of mice in borneol essential oil group is close to that in positive group. In immunohistochemistry experiment, the immunohistochemical section indicates that compared to mice in model group, the β-amyloid protein of mice in borneol essential oil group decreases, and the situation of mice in borneol essential oil group is close to that in positive group. Compared to mice in model group, the activities of SOD and GSH-PX increase, and the content of MDA decreases in brain tissue of mice in borneol essential oil group. In conclusion, borneol essential oil has certain antioxidant activity in vitro and in vivo, and can improve cognitive impairment in mice.

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    异阿魏酸酰胺类衍生物的合成及其美白活性的研究
    Study on synthesis and whitening activity of isoferic acid amides
    罗天骥,梅子坤,宋京九,祝钧
    2021 (11):  1102-1108.  doi: 10.3969/j.issn.1001-1803.2021.11.010
    摘要 ( 236 )   HTML ( 9 )   PDF(1202KB) ( 359 )  

    以异阿魏酸和氨基酸乙酯盐酸盐为原料,1-(3-二甲基氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC·HCl)和1-羟基苯并三唑(HOBt)为催化剂,采用EDC缩合的方法合成异阿魏酰丙氨酸乙酯(a)、异阿魏酰苯丙氨酸乙酯(b)、异阿魏酰亮氨酸乙酯(c)、异阿魏酰异亮氨酸乙酯(d)、异阿魏酰缬氨酸乙酯(e)、异阿魏酰蛋氨酸乙酯(f)。利用核磁共振氢谱(1H NMR)和高效液相色谱-质谱(HPLC-MS)对产物结构进行表征,并对比研究了异阿魏酸与异阿魏酰氨基酸乙酯对DPPH自由基清除率和酪氨酸酶活性抑制率的影响,发现6种异阿魏酰氨基酸乙酯均呈现良好的清除DPPH自由基和抑制酪氨酸酶活性的效果,其中异阿魏酰丙氨酸乙酯抑制效果较强,清除DPPH自由基IC50值为1.13 mg/mL,酪氨酸酶活性抑制率为95.43%。B16黑素瘤细胞水平结果表明,2 mg/mL质量浓度下异阿魏酰丙氨酸乙酯、异阿魏酰苯丙氨酸乙酯和异阿魏酰蛋氨酸乙酯对黑色素抑制效果比异阿魏酸单体更强,且刺激性有所降低。

    Using isoferulic acid and amino acid ethyl ester hydrochloride as raw materials, 1- (3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC HCl) and 1-hydroxybenzotriazole (HOBt) as catalysts, isoferuloyl-alanine ethyl ester (a), isoferuloyl-phenylalanine ethyl ester (b), isoferuloyl-leucine ethyl ester (c), isoferuloyl-isoleucine ethyl ester (d), isoferuloyl-valine ethyl ester (e), isoferuloyl-methionine ethyl ester (f) were synthesized by EDC condensation. The structure of the products was characterized by nuclear magnetic resonance (1H NMR) and high performance liquid chromatography-mass spectrometry (HPLC-MS). The whitening activity of ethyl isoferulyl-amino acid was detected by two in vitro non-cellular experiments of scavenging DPPH free radicals and inhibiting tyrosinase activity. It can be seen from the experimental results that the six isoferulyl amino acids have a good ability to scavenge DPPH free radicals, which are higher than that of isoferulic acid. Isoferulyl-alanine ethyl ester has the strongest ability to scavenge DPPH free radicals. Its IC50 value reaches 1.13 mg/mL. It also has a certain inhibitory effect on tyrosinase activity, of which isoferulyl-alanine ethyl ester has the best effect, with the inhibition rate of 95.43%. The results of B16 melanoma cells show that isoferulyl-alanine ethyl ester, isoferulyl-phenylalanine ethyl ester and isoferulyl-methionine ethyl ester have better inhibitory effects on melanin than isoferulic acid at 2 mg/mL mass concentration and its irritation is reduced. The differences in the efficacy of the six products may be due to the different types of side chain amino acids on each substance. In the follow-up investigation, the biological activity of isoferulyl amino acid derivatives can be analyzed to clarify the relationship between the molecular structure of the substance and the physiological activity, and to increase the transdermal absorption effect and safety of the substance in animal experiments.

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    专论与综述
    碱性蛋白酶洗涤性能的影响因素
    Influencing factors on washing performance of alkaline protease in liquid detergent
    王朋辉,王伟贤,杨涛,曾晖,芮泽宝,李东华,黄平
    2021 (11):  1109-1117.  doi: 10.3969/j.issn.1001-1803.2021.11.011
    摘要 ( 379 )   HTML ( 20 )   PDF(1330KB) ( 407 )  

    碱性蛋白酶是液体洗涤剂中使用量最大的一类酶制剂,它具有广泛的肽键水解选择性,能够降解多种蛋白类污垢。不同于生物体内环境,碱性蛋白酶在液体洗涤剂中因受到各种失活因素干扰而变性,降低了去污效率,增加了使用成本。探究在复杂多变液体洗涤剂环境中影响蛋白酶洗涤性能的影响因素是提升现有蛋白酶洗涤性能的前提。文章将从碱性蛋白酶的自溶失活,螯合剂、漂白剂以及表面活性剂对碱性蛋白酶的作用四个方面揭示碱性蛋白酶在液体洗涤剂中失活的主要原因,重点讨论了表面活性剂与碱性蛋白酶的相互作用,并对未来液体洗涤剂配方中的表面活性剂种类及复配技术的发展进行了展望。

    Alkaline protease is one of the most widely used enzymes in liquid detergents. It has a wide range of peptide bond hydrolysis selectivity and can degrade a variety of protein souls. However, unlike the biological environment, various inactivation factors in the harsh liquid detergent environment may lead to the denaturation, performance degradation and cost increase of alkaline protease. Understanding these influencing factors in the complex liquid protease environment is necessary for further improving the washing performance of alkaline protease. This paper firstly addresses the main inactivation factors of alkaline protease in liquid detergent, such as autolysis inactivation and the effect of chelating agent, bleaching agent and surfactant. Special attention is paid to the interaction between surfactant and alkaline protease. Finally, the development of surfactant types and compounding technology in liquid detergent formulation in the future is prospected.

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    非生理性脱发种类及其发生机理研究进展
    Research progress on the types and mechanisms of non-physiological alopecia
    于笑乾,马宇晨,丁文玉,胡艺琼,贾焱,何聪芬
    2021 (11):  1118-1124.  doi: 10.3969/j.issn.1001-1803.2021.11.012
    摘要 ( 411 )   HTML ( 27 )   PDF(1223KB) ( 670 )  

    非生理性脱发是指头发大量异常脱落导致头发稀疏或发际线后移等严重影响患者外表形象的现象。根据其发生原因不同分为:雄激素性脱发(AGA)、免疫缺陷性脱发(IDA)、损伤性脱发(SDA)、营养异常性脱发(NAA)和药物性脱发(DIA)。不同类型脱发发生原因均是各种因素直接或间接作用于毛囊引起毛囊异常。其中AGA和IDA的病理学发病过程报道较多,AGA是毛囊对于雄激素敏感导致生长周期紊乱,IDA是毛囊免疫赦免机制崩溃,免疫细胞攻击毛囊。SDA和NAA的原因较为直观,分别是皮肤损伤和营养异常导致毛囊的状态异常或生理周期紊乱。DIA影响因素较多,根据药物不同脱发机理也有所不同。本文将简述各种不同原因导致非生理性脱发的发生机理,以期将有关非生理性脱发的研究成果进行集中体现,使研究人员可以更好地了解非生理性脱发发生的原因和机理并找到脱发防治的方法。

    Non-physiological alopecia refers to a phenomenon that severely affects the appearance of patients, such as a heavy loss of hair leading to thinning hair or receding hairline. According to the different causes, it can be categorized into androgenic alopecia (AGA), immunodeficiency alopecia (IDA), skin damage alopecia (SDA), nutritional abnormalities alopecia (NAA) and drug-induced alopecia (DIA). All these types of hair loss are caused by corresponding factors that directly or indirectly act on hair follicles. Among them, the pathological processes of AGA and IDA have been reported a lot. As for AGA, hair follicles are sensitive to androgens, leading to disorder of growth cycle; as for IDA, the breakdown of hair follicle immune pardon mechanism makes immune cells attack hair follicles. The reasons for SDA and NAA are relatively straightforward. They are caused by skin damage and nutrient deficiency, respectively, which lead to disorder of the physiological cycle of hair follicles and affect hair growth. There are many factors influencing DIA, which vary according to different drugs. Herein, the mechanisms of non-physiological alopecia caused by various reasons have been briefly described. Research results of non-physiological alopecia are focused on. It may provide a better understanding of the causes and mechanisms of non-physiological alopecia, which might help researchers to find a way to prevent hair loss.

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    ICCR关注议题:技术差异和趋势分析
    Technical comparison and trend analysis on the topics that ICCR are concerned with
    苏哲,罗飞亚,邢书霞,王钢力
    2021 (11):  1125-1133.  doi: 10.3969/j.issn.1001-1803.2021.11.013
    摘要 ( 234 )   HTML ( 11 )   PDF(1083KB) ( 344 )  

    综述了2008~2020年期间国际化妆品监管合作组织(ICCR)在化妆品监管和技术领域的关注议题、技术性文件及研究进展,对其技术趋势进行分析,并比较其与我国的主要差异,展望了我国化妆品科学的未来发展方向。提出对我国化妆品技术法规持续动态修订以不断提高技术标准,重点追踪ICCR在安全性评价、纳米原料、ISO标准评议、致敏物质等方面的技术进展,加快替代方法的开发验证以及组合策略的研究应用,建立健全我国化妆品纳米原料和纳米技术相关监管和技术体系,并关注ICCR在下一代风险评估、微生物组学等专业领域的前瞻性研究。为配合《化妆品监督管理条例》的发布实施,加快相应的技术支撑和技术储备。

    The topics of concern that the International Cooperation on Cosmetics Regulation (ICCR) has focused on from 2008 to 2020 have been reviewed. Corresponding technical documents and research progress in regulations and technologies of cosmetics have also been reviewed. Trend analysis and technical comparison have been completed. The prospects of future cosmetic science in China have been discussed. It is proposed to revise the technical regulations dynamically to continuously improve the standards. Technical progress of ICCR in several directions can be followed up, especially in safety evaluation, nanomaterials, ISO standard evaluation and allergens. The development and verification of alternative methods, as well as the study and application of integrated strategies, should be accelerated. The regulatory system for nanomaterials and the technical system for nanotechnology in cosmetics should be established and improved in China. In addition, attentions can also be paid to some advanced research work of ICCR, for example, the next generation risk assessment and microbiome. To implement the Regulations on the Supervision and Administration of Cosmetics, corresponding technical support and technical preparation should be speeded up.

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    分析与检测
    电感耦合等离子体质谱法(ICP-MS)测定牙膏中多种元素
    Determination of multiple elements in toothpaste by inductively coupled plasma mass spectrometry (ICP-MS)
    吴莉,周娟娟,方方,冯有龙,曹玲
    2021 (11):  1134-1141.  doi: 10.3969/j.issn.1001-1803.2021.11.014
    摘要 ( 227 )   HTML ( 12 )   PDF(988KB) ( 297 )  

    建立了电感耦合等离子体质谱法(ICP-MS)测定牙膏中多种元素的含量。采用微波消解法消解样品,选用铑(Rh)、铼(Re)作为内标,ICP-MS法同时测定牙膏中镁(Mg)、铝(Al)、钾(K)、钙(Ca)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、镍(Ni)、铜(Cu)、锌(Zn)、砷(As)、硒(Se)、锶(Sr)、钼(Mo)、银(Ag)、镉(Cd)、锡(Sn)、锑(Sb)、钡(Ba)、汞(Hg)、铊(Tl)、铅(Pb) 23种元素的含量,以内标法计算。结果表明,对于所测元素,标准曲线相关系数r≥0.998 8。重复性试验的相对标准偏差(RSD)在2.5%~9.5%(n=6)。低、中、高浓度加样回收率(n=9)范围为85.6%~105.9%。该方法灵敏度高、专属性强、简便、快速、准确,适用于牙膏中多种元素的含量测定。

    A method for the determination of multiple elements in toothpaste by ICP-MS was established. Microwave digestion was used for sample pre-treatment. Rh and Re were used as the internal standard. The contents of 23 kinds of elements in toothpaste, including Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Sr, Mo, Ag, Cd, Sn, Sb, Ba, Hg, Tl and Pb were determined by ICP-MS. The internal standard method was used for quantitative analysis. The results show that the correlation coefficient of the calibration curve is over 0.998 8 for all the analyzed elements. RSD of repeatability test ranges from 2.5% to 9.5% (n=6). The recovery of low, medium and high concentration (n=9) ranges from 85.6% to 105.9%. The method is sensitive, specific, simple, rapid and accurate. It is suitable for the determination of multiple elements in toothpaste.

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    超高效液相色谱-三重四极杆质谱法同时测定面膜中26种禁用物质
    Simultaneous determination of 26 prohibited substances in masks by ultra performance liquid chromatography-triple quadrupole mass spectrometry
    杜晖,任静
    2021 (11):  1142-1149.  doi: 10.3969/j.issn.1001-1803.2021.11.015
    摘要 ( 156 )   HTML ( 13 )   PDF(1340KB) ( 216 )  

    建立了超高效液相色谱-三重四极杆质谱法(UPLC-MS/MS)同时分离测定市售面膜中包括喹诺酮类、咪唑类及糖皮质激素等26种禁用成分。样品经饱和氯化钠溶液分散后乙腈提取,并利用亚铁氰化钾和乙酸锌沉淀大分子基质和固相萃取净化后,以0.1%醋酸乙腈-0.1%醋酸水溶液二元梯度洗脱,采用多反应监测进行分析。结果显示,26种化合物在各自浓度范围内线性关系良好,相关系数均不低于0.995,检出限为1~80 ng/g,定量限为4~380 ng/g,平均回收率为86.4%~115.2%。本法简单准确,灵敏度高,可用于市售面膜中禁用物质的定量分析。

    An ultra performance liquid chromatography-triple quadrupole mass spectrometric (UPLC-MS/MS) method was developed for simultaneous separation and determination of 26 prohibited substances in commercially available masks, which contained glucocorticoid, quinolones and imidazole derivatives. The samples were dispersed in saturated sodium chloride solution and were extracted with acetonitrile. After removal of macromolecular matrix by potassium ferrocyanide and zinc acetate, the samples were purified by solid phase extraction. The binary gradient elution was performed with acetonitrile (containing 0.1% acetic acid)-0.1% acetic acid solution, and the multi-reaction monitoring was used for analysis. All the 26 compounds show a good linear relationship in their respective concentration ranges, and the correlation coefficients (r) are no less than 0.995. The limits of detection (LODs) range from 1 to 80 ng/g. The limits of quantification (LOQs) are in the range of 4-380 ng/g. The average recoveries of 26 prohibited substances in masks range from 86.4% to 115.2%. The method is simple, accurate and sensitive. It can be used for quantitative analysis of prohibited substances in commercially available masks.

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    HS-SPME/GC-MS法测定北细辛挥发性成分
    Analysis of volatile components in Asarum heterotropoides by HS-SPME/GC-MS
    王风,李楠,李雪,钟灵艳,黄泽甜,胡坪
    2021 (11):  1150-1157.  doi: 10.3969/j.issn.1001-1803.2021.11.016
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    建立了北细辛挥发性成分的顶空固相微萃取/气相色谱-质谱法(HS-SPME/GC-MS)分析方法,并对6个不同产地北细辛进行分析,利用谱库检索和保留指数对挥发性成分进行鉴定,从6个产地的北细辛中共鉴定出68种挥发性成分,挥发性成分中甲基丁香酚的相对含量最高,峰面积百分比为17.20%~33.80%。将HS-SPME/GC-MS法应用于北细辛挥发性成分的研究不仅能反映不同产地北细辛挥发性成分的整体差异,且方法简单快速,为北细辛挥发性的质量评价提供新思路。

    Asarum is a kind of commonly used traditional Chinese medicine, and volatile oil is the main material basis for its efficacy. In traditional studies, the volatile oil is extracted by steam distillation and analyzed by GC-MS. Although the extraction method is easy to operate and has low cost, it is time-consuming, large sample consumption, high extraction temperature and easy thermal decomposition of active components. Moreover, xylene is often added in this method to promote the stratification of volatile oil, which brings great interference to the subsequent GC-MS analysis and component identification of volatile oil. Therefore, Solid Phase Microextration (SPME) technology that integrates extraction, purification, enrichment, and sampling functions was used to analyze the volatile oil of Asarum for the first time. The HS-SPME/GC-MS method was established to analyze Asarum heterotropoides, and the volatile components were identified by the NIST spectral library search and retention index. A total of 68 components are identified from the volatile oil of Asarum heterotropoides from 6 origins. The relative content of methyl eugenol is the highest among the volatile components with peak area percentages ranging from 17.20% to 33.80%. The application of HS-SPME/GC-MS method to the study of the volatile components in Asarum heterotropoides can reflect the overall differences, and the method is simple and rapid, providing new ideas for the quality evaluation of Asarum heterotropoides.

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    本刊专稿
    日化领域学术期刊的发展趋势及应对策略
    Development trend and countermeasures of academic journals in daily chemical field
    刘彦宏,张静,周婷,杨旭,杨玉喜
    2021 (11):  1158-1162.  doi: 10.3969/j.issn.1001-1803.2021.11.017
    摘要 ( 226 )   HTML ( 18 )   PDF(887KB) ( 292 )  

    积极响应习近平总书记关于“办好一流学术期刊和各类学术平台,加强国内国际学术交流”的号召,开展学术期刊发展趋势研究,通过预知风险,把握机遇,提升学术期刊的影响力和经营能力,从而促进学术创新。本文结合日化领域学术期刊的发展现状,总结分析了当前日化领域学术期刊的特点与发展趋势,并着重从媒体融合的制度观念革新、融合路径优化、用户需求体验改良以及编辑人员水平提升4方面提出了未来日化领域学术期刊的发展应对策略。

    In response to a call for President Xi Jinping of “running well first-class academic journals and all kinds of academic platforms, strengthening domestic and international academic exchanges”, carrying out research on the development trend of academic journals, enhancing the influence and management ability of academic journals by predicting risks and seizing opportunities so as to promote academic innovation. This paper stated the current situation of academic journal in the field of daily chemical industry, summarized and analyzed its characteristics and development trend, emphatically put forward countermeasures for the future development of daily chemical academic journals from four aspects including system concept innovation, integration path optimization, user demand experience improvement and editorial staff professional ability improvement.

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