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    22 April 2021, Volume 51 Issue 4 Previous Issue    Next Issue
    Basic research
    Study on the behavior and mechanism of pyrolysis of lauric acid bymodel-fitting and model-free methods
    ZHANG Gong-yan,ZHANG Yan-song,CHEN Kun,ZHANG Xin-yan,HUANG Xing-wang
    2021, 51 (4):  265-271.  doi: 10.3969/j.issn.1001-1803.2021.04.001
    Abstract ( 310 )   HTML ( 61 )   PDF (2851KB) ( 771 )  

    The pyrolysis kinetics of lauric acid powder in nitrogen and air was studied by comprehensive thermal analysis. The experimental results showed that 30 µm lauric acid powder was rapidly pyrolyzed and gasified in nitrogen atmosphere without exothermic combustion reaction. At different heating rates, the pyrolysis of lauric acid powder in air included two stages: fast pyrolysis and slow pyrolysis. The kinetic parameters of lauric acid pyrolysis in nitrogen and air atmosphere were solved by means of Coats-Redfern method, and the pyrolysis mechanism was described. The results showed that, the rapid pyrolysis of lauric acid in nitrogen and air atmosphere followed the one-dimensional reaction model at phase interface (R1 model); the apparent activation energy (9.1 kJ/mol) and pre-exponential factor (8.606 1) of lauric acid pyrolysis in nitrogen atmosphere were relatively low, indicating that the oxidation and exothermic behavior of lauric acid inhibited the pyrolysis reaction, but had no obvious effect on its pyrolysis mechanism; when the heating rate was 15 ℃/min, at the same temperature, the conversion of lauric acid pyrolysis in nitrogen atmosphere was higher than that in air atmosphere. The apparent activation energy of lauric acid for different conversion α in air atmosphere was also calculated by using the methods of model-free functions (Flynn-Wall-Ozawa method and Kissinger-Akahira-Sunose method). The results obtained by the two methods were close to those by the model-fitting method. The average apparent activation energy of lauric acid in air atmosphere was 14.82 kJ/mol; in the range of 10%~80% conversion, the apparent activation energy in the oxidation stage of rapid pyrolysis showed a gentle change with the conversion, which verified that the pyrolysis of lauric acid followed the one-dimensional phase-interface reaction mechanism.

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    Lecture of science and technology
    Cosmetic emulsions and new technologies of emulsification (II) Construction and application of water-in-water emulsions
    CHEN Feng-feng,QI Jia-yue,NI Xin-jiong,LI Yun-xing,YANG Cheng,SUN Ya-juan
    2021, 51 (4):  272-280.  doi: 10.3969/j.issn.1001-1803.2021.04.002
    Abstract ( 795 )   HTML ( 41 )   PDF (1467KB) ( 1813 )  

    The development of preparation technology of water-in-water emulsions has been reviewed. Firstly, the research status of water-in-water emulsions is briefly summarized, then the modulation of morphology and particle size of water-in-water emulsions is introduced, and the stability of the reinforced water-in-water emulsions is discussed. Finally, the potential applications of water-in-water emulsions in preparation of microgels and drug delivery are introduced, and the future development direction of water-in-water emulsions is prospected. This review might provide some reference for the preparation and application of water-in-water emulsions.

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    Development and application
    Performance and influencing factors of four kinds of lipopeptide biosurfactants
    FU Jun-wei,WU Juan,MEI Ping
    2021, 51 (4):  281-287.  doi: 10.3969/j.issn.1001-1803.2021.04.003
    Abstract ( 402 )   HTML ( 16 )   PDF (2077KB) ( 487 )  

    Four biosurfactants (A8, A10-EA, A10-MeOH and B3) were extracted from petroleum bacteria cultured in laboratory. They were all identified as anionic lipopeptide biosurfactants. The curves of equilibrium surface tension and dynamic interfacial tension of A8, A10-EA, A10-MeOH and B3 were determined employing the platinum plate and droplet shape analysis methods, respectively. The emulsifying performance of biosurfactants and their leaching performance on pyrene-polluted soil were studied. The experimental results showed that the critical micelle concentrations (cmc’s) of A8, A10-EA, A10-MeOH and B3 were 1.014 g/L, 5.417 g/L, 0.717 g/L and 0.689 g/L, respectively. Four biosurfactants showed good surface activity in the temperature range of 25~70 ℃. In addition, they had good resistance to monovalent and bivalent salts. The results showed that A8 had the best emulsifying performance for formation of emulsion composed of water and n-decane with the emulsifying coefficient of 65% after 48 h. The interfacial tension could be reduced to lower than 10 mN/m within the studied concentration range. The aqueous solutions of A8 and A10-MeOH at their cmc’s had good leaching effect on pyrene in soil.

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    Green synthesis and application of a condensating agent with short fluorocarbon chain
    WANG Qin-qin,LI Yan-li,ZOU Wei,YAN Jie,LIU Bo,LI Hui
    2021, 51 (4):  288-293.  doi: 10.3969/j.issn.1001-1803.2021.04.004
    Abstract ( 290 )   HTML ( 7 )   PDF (1421KB) ( 383 )  

    A triazine-type condensating agent with high activity, 1-chloro-3,5-bis((octafluoropentyl)oxy)-triazine(DFCT), was synthesized by one-pot two-step method, in which cyanuric chloride(TCT)was used as reactive group and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol(OFP)was used as the source of short fluorocarbon chain. The intermediate(2,4-dichloro-6-((octafluoropentyl)oxy)-triazine, DCFT)and the target product(DFCT)were characterized by FT-IR,1H NMR,13C NMR,19F NMR and mass spectrometry. The reaction conditions were optimized according to the yield of product: Dichloromethane was used as the solvent; sodium hydroxide was used as acid binding agent; n(TCT)∶n(OFP)=1∶2.2; the reaction temperature was 0 ℃ to generate DCFT, and then 30 ℃ to obtain the target product DFCT, and the yield of DFCT was 96%. DFCT was used as a condensating agent to activate carboxylic acid which would react with amines/alcohols to produce amides(Ⅰa-Ⅰc)/esters(Ⅱa-Ⅱc). It showed that DFCT could be used as a condensating agent for amidation and esterification reactions, and the reaction conditions were mild and easy to operate.

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    Study of degreasing and fatliquoring properties of PEG fatty acid glycerides
    WANG Zi-han,XU Hu-jun
    2021, 51 (4):  294-298.  doi: 10.3969/j.issn.1001-1803.2021.04.005
    Abstract ( 384 )   HTML ( 18 )   PDF (1208KB) ( 474 )  

    The measurement system for the skin-surface degreasing and fatliquoring properties of surfactants was established by independently designing experiments based on Sebumeter method using pigskin as the subject skin for quantificationally measuring sebum content. In this system, the washing effects of aqueous solutions of PEG-7 lauric acid glycerides on the skin surfaces containing three oils that were commonly used in cosmetics (white oil, olive oil and simethicone, respectively) were tested, the results of which showed that the sebum decrease rate is increased first and then decreased with the increase of mass fraction. The washing effects of aqueous solutions of PEG-7 lauric acid glycerides on the skin surfaces without lipid were tested, and the skin surfaces were observed by electron microscopy. The results showed that the sebum content after washing is increased first and then remained constant with the increase of mass fraction, and a lipid film was formed on the skin surfaces. The washing effects of the aqueous mixture of sodium laurate/PEG-7 lauric acid glycerides on the skin surfaces containing olive oil were tested, the results of which showed that the sebum decrease rate is decreased first and then remained constant with the increase of amount of PEG-7 lauric acid glycerides. The experiments above proved that PEG fatty acid glycerides possessed good degreasing and fatliquoring properties. They could clean mildly when applied to related products and achieve a fatliquoring effect when compounded with soap base to improve the dry and tight feelings of skin after washing by soap base. Therefore, they had broad application prospect in makeup remover products and soap-based washing products.

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    Molecular dynamics simulation of protease PB92 for washing before and after substrate binding
    GUO Yu-fei,ZHANG Jian,YU Wen
    2021, 51 (4):  299-305.  doi: 10.3969/j.issn.1001-1803.2021.04.006
    Abstract ( 269 )   HTML ( 21 )   PDF (1653KB) ( 366 )  

    Based on the structure of protease PB92, molecular dynamics (MD) simulations were performed on protease PB92 without substrate binding and with substrate binding to study its dynamic characteristics, and the structure of protease PB92 with or without substrate binding was obtained. Properties and comparisons were made to evaluate a series of changes in the structural characteristics and stability of protease PB92 after binding to the substrate. The experimental results show that during the kinetic simulation process, the conformation of protease PB92 with substrate binding is more compact and stable than the conformation of protease PB92 without substrate binding, showing a pattern that conforms to the “induced fit” reaction. The article provides a theoretical basis and guidance for the development of protease properties and structures that are more suitable for the detergent industry in the future.

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    Effects of glycerol on the storage stability of the chitosan solution
    CHEN Si-jia,YI Ya,ZHANG Da-wei
    2021, 51 (4):  306-311.  doi: 10.3969/j.issn.1001-1803.2021.04.007
    Abstract ( 272 )   HTML ( 7 )   PDF (1286KB) ( 387 )  

    The effects of glycerol (GL) on the storage stability of the chitosan (CS) solution were investigated by studying the variation of the viscosity of CS dissolved in GL/water mixed solvent with storage temperature and storage time. The results showed that, at room temperature, GL could effectively improve the decreasing trend of storage stability of CS solution caused by heating. Compared with room temperature, the specific viscosity of CS solution with GL as stabilizer was almost unchanged within 6.5 h at 1 ℃. After standing for 99 h, the specific viscosity of the CS solution containing GL was decreased by only 3.8%, less than half of the specific viscosity decrease in aqueous solution at the same temperature. The addition of GL could effectively improve the storage stability of CS. When the storage temperature was 1 ℃, the CS solution had better storage stability in the presence of GL.

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    Study on the clinical efficacy of a soothing gel
    SUN Jin-yuan,CHEN Yi-qi,ZHAO Hua
    2021, 51 (4):  312-318.  doi: 10.3969/j.issn.1001-1803.2021.04.008
    Abstract ( 746 )   HTML ( 21 )   PDF (1160KB) ( 511 )  

    Self-developed soothing gel was tested on the clinical efficacy and its soothing effect was evaluated. At the inception of the study, 30 healthy volunteers at the age of 18-55 were selected. Their skin barriers had been destroyed by means of repeatedly tearing the adhesive tapes and the skin models was built by the stimulation of histamine solution. Then the medial forearm photos and skin erythema index (EI values) after using the soothing gel for 15, 40, 60 and 90 minutes were collected. The redness, swelling, stinging and itching could be evaluated by expert evaluation and self-evaluation. The results show that the soothing gel can effectively improve the redness and swelling of skin after stimulation. It also relieves itching and pain, and its effect is significantly better than that of skin self-repair. This indicates that soothing repair gel has a certain effect on soothing irritation.

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    Formulation design and efficacy study of dihydroxyacetone sunless tanner gel
    YANG Yi,XU Jian,ZHAO Meng-tian,CAO Gao
    2021, 51 (4):  319-323.  doi: 10.3969/j.issn.1001-1803.2021.04.009
    Abstract ( 728 )   HTML ( 14 )   PDF (1176KB) ( 815 )  

    The effects of the types and dosage of thickener, the ratio of solvent, the content of dihydroxyacetone and the preparation technology on the formulation design of dihydroxyacetone sunless tanner gel were studied. Through sensory evaluation such as appearance, spreading property, stability and efficacy evaluation, the better formulation was determined synthetically, which laid a theoretical foundation for the development of dihydroxyacetone sunless tanner gel. The results show that 2% hydroxyethyl cellulose should be used as the thickener of dihydroxyacetone tanner gel. The solvent is ethanol, propylene glycol and glycerol with a mass ratio of 10︰5︰3. The better process is heating to dissolve the thickener, then adding dihydroxyacetone after cooling. The color of tanning can be obtained when the content of dihydroxyacetone is 3%~17%.

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    Study on the skin care effect of oat β-glucan extracted by bidirectional fermentation
    FU Hao,WU Di,BING Xue,ZHANG Jia-chan,WANG Chang-tao,LI Meng
    2021, 51 (4):  324-330.  doi: 10.3969/j.issn.1001-1803.2021.04.010
    Abstract ( 430 )   HTML ( 18 )   PDF (1769KB) ( 606 )  

    Using oats as a culture medium, the β-glucan in oats was extracted by a bidirectional fermentation method, and its efficacy of cosmetic skin care was studied. Three fungi, i.e., Pholiota adiposa, Clitocybe maxima and Grifola frondose, were used for bidirectional fermentation with oats. The experimental results showed that the cytotoxicity of oats is significantly reduced after fermentation. By measuring the content of reactive oxygen species (ROS), type I collagen (Col I) and matrix metalloproteinase (MMP-1) in fibroblasts, it was found that the fermentation broth had certain anti-aging effect, and the effect was better than that of unfermented oats. Compared with those before fermentation, the fermentation broth and purified fermented oat β-glucan showed relatively reduced content of active oxygen, relatively high content of Col I, and relatively low content of MMP-1in fibroblasts. By measuring the melanin content and tyrosinase activation rate in mouse melanoma cells(B16 cells), it was found that the melanin content in the cells after being treated with the fermentation broth was lower, and the Pholiota adiposa/oat fermentation broth had the best effect. Franz diffusion cell transdermal absorption experiments had showed that the cumulative permeation amount of the fermentation broth is higher.

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    Safety and scalp care efficacy evaluation of shampoos containing tea saponins
    YANG Jing-guo,SHEN Hu-chi,CHEN Dian-song,ZHAO E,CAI Zhen-zi,WANG Jing
    2021, 51 (4):  331-337.  doi: 10.3969/j.issn.1001-1803.2021.04.011
    Abstract ( 685 )   HTML ( 37 )   PDF (1343KB) ( 771 )  

    In this study, the skin irritation and eye irritation of tea saponin were studied by using alternative models (including EpiskinTM reconstructed human epidermal model and chicken embryo chorioallantoic membrane test). The results show that 2%-10% tea saponin solution shows no skin irritation, and tea saponin solution less than 2% (mass fraction) does not exhibit eye irritation. Then, a shampoo containing 5.0% (mass fraction) tea saponin was prepared. By combined sensory evaluation, microscopic scalp observation and instrument test, the efficacy of tea saponin shampoo on scalp care was evaluated. The results show that the shampoo containing tea saponin shows good efficacy in removing dandruff, controlling sebum, relieving itching, lowering scalp sensitivity and improving barrier function. The above effects may be related to the biological activities of tea saponin, such as antibacterial, anti-inflammatory and anti-oxidation. This study can provide basic data for the safety and scalp care efficacy of tea saponin in shampoo.

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    Reviews
    Advances in research and application of quaternary ammonium Gemini surfactants and their modified clay
    FU Duo-jiao,ZHOU Yin,CHEN Han-yu,LIU Hong-qin,XU Bao-cai
    2021, 51 (4):  338-347.  doi: 10.3969/j.issn.1001-1803.2021.04.012
    Abstract ( 330 )   HTML ( 17 )   PDF (1806KB) ( 327 )  

    The synthesis of quaternary ammonium Gemini surfactants and their application in adsorption of organic pollutants in water by modified clay were reviewed. Starting from the synthesis of alkyl quaternary ammonium Gemini surfactants, emphasis was given on the introduction of different types of quaternary ammonium Gemini surfactants and their synthetic routes from four aspects, i.e. changing the structures of the spacer group, hydrophobic group, cationic connection point and counterion. The application of quaternary ammonium Gemini surfactants to modify different kinds of natural clay was also reviewed. Finally, based on the development background of green chemistry, the development direction of Gemini surfactants in the future and the opportunities and challenges of their application in water pollution control were discussed.

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    Research progress in effects of micro- and nanocrystals on the foam formation and stability
    LV Bo,YAN Yong-li,DU Chun-bao,ZHU Xi-zhu,WU Chun-sheng,YU Chang-long
    2021, 51 (4):  348-355.  doi: 10.3969/j.issn.1001-1803.2021.04.013
    Abstract ( 313 )   HTML ( 12 )   PDF (1516KB) ( 327 )  

    The foams formed by conventional surfactants or multiphase systems have poor stability and they are difficult to be applied in many fields. In recent years, the use of micro- and nano-crystals to form super-stable foam systems has attracted much attention from the academic community. Therefore, the forming mechanism, stabilizing mechanism and influencing factors of crystal particles on the foams have been emphatically discussed, such as the concentration of crystal particles, temperature, size and solvent properties. The application of foams formed by crystal particles in food and materials has been briefly summarized, and the future research direction in this field has been pointed out.

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    Laboratory preparation of lipoic acid esters and their application prospect in cosmetics
    SONG Jing-jiu,GUO Xiao-dan,WANG Dong,ZHU Jun
    2021, 51 (4):  356-362.  doi: 10.3969/j.issn.1001-1803.2021.04.014
    Abstract ( 513 )   HTML ( 31 )   PDF (1152KB) ( 1007 )  

    Lipoic acid is both a drug and a multi-functional antioxidant. The cosmetics using lipoic acid as raw material have excellent performance, but they also have many problems, such as being not easy to preserve and strong irritation. The instability and poor water solubility of lipoic acid also bring inconvenience to professionals in research. The combination of lipoic acid with other functional materials as lipoic acid esters can improve the deficiency of lipoic acid and enhance the efficacy. The esterification reaction is one of the most classic reactions in the chemical world. There are many catalytic methods, and each method has unique advantages and disadvantages. However, according to statistics, only a few of them were most frequently used, and many excellent esterification methods had often been ignored. The laboratory preparation methods of lipoic acid esters were summarized from the aspects of chemical catalysis and biological enzyme catalysis. The advantages and disadvantages of each method were analyzed, and the application prospect of lipoic acid esters in cosmetics was discussed.

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    Analytical methods and testing
    Determination of 22 sex hormones in water-based cosmetics by ultra-high performance liquid chromatography
    HU Bei,LI Li-xia,WU Qian,LIU Hong,HUANG Wei,DING Xiao-ping
    2021, 51 (4):  363-369.  doi: 10.3969/j.issn.1001-1803.2021.04.015
    Abstract ( 214 )   HTML ( 9 )   PDF (1153KB) ( 493 )  

    An ultra-high performance liquid chromatography method was established for determination of 22 sex hormones in water-based cosmetics. The sample was ultrasonically extracted with 80% acetonitrile solution. After centrifugation, the supernatant was purified by PRiME HLB column. Chromatographic separation was achieved on an CORTECS C18+ (2.1 mm×100 mm, 2.7 μm) column by gradient elution using acetonitrile-water as mobile phases. PDA detector was used to test samples by multiple wavelengths, and external standard method was used for quantification. The results show that there are good linear relationships for 22 sex hormones in the respective concentration range with their correlation coefficients (r) all above 0.99. The limits of detection (LOD) and limits of quantitation (LOQ) for 22 sex hormones are in the range of 0.03-0.1 μg/mL and 0.1-0.4 μg/mL, respectively. Average recoveries at three levels of 5,25,50 μg/g are in the range of 80.3%-99.6%, with relative standard deviations(RSD, n=6) of 0.3%-7.7%. With the advantages of simplicity, sensitivity and accuracy, this method is suitable for the analysis of sex hormones in water-based cosmetics.

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    LC-MS analysis of molecular derivatives of chemically unstable hair colorants
    XIAO Jing,LI Ruo-qi,WEI Xue-bing,SUN Ying,LIU Ting-yuan,LI Li
    2021, 51 (4):  370-374.  doi: 10.3969/j.issn.1001-1803.2021.04.016
    Abstract ( 204 )   HTML ( 7 )   PDF (1133KB) ( 286 )  

    Chemical properties of hair dye ingredients are unstable, and the reproducibility of analysis is poor. According to the “safety technical specification for cosmetics”, the chemical standards of prohibited or restricted ingredients in hair dyes could be maintained in solution for 48 hours at most. Thus, it is difficult to conduct analysis on a large number of samples. In order to maintain the chemical stability of standards, benzyl bromide, a nucleophilic substitution reagent with a simple structure and high reactivity, was used to introduce benzyl groups to seven aniline-type hair dye molecules (i.e. 2-nitro-p-phenylenediamine, 4-nitro-o-phenylenediamine, p-aminophenol, 4-amino-m-cresol, 2-amino-3-hydroxypyridine, 2,3-hydroxypyridine), to obtain derivatives with stable chemical properties and improve the accuracy and sensitivity of the analytical results. The results show that the derivatives of 7 hair dyes are stable within 10 days. This project provides a new idea for the analysis of chemical labile components, which are banned or restricted in chemical products.

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