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    2024年, 第54卷, 第12期 刊出日期:2024-12-22 上一期    下一期
    基础研究
    支链扩展表面活性剂与两性和阳离子表面活性剂复配性能
    Performance of branched-chain extended surfactant mixed with zwitterionic or cationic surfactant
    曾小丁, 郑延成, 张国庆, 曾令迟, 穆健
    2024 (12):  1405-1413.  doi: 10.3969/j.issn.2097-2806.2024.12.001
    摘要 ( 2157 )   HTML ( 14 )   PDF(6684KB) ( 67 )  

    以2-己基-1-癸醇为主要原料制备了嵌段聚醚磺酸盐类扩展型表面活性剂(IC16P6E6S),评价了IC16P6E6S的溶解性和表面性能,并分别与阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)和两性表面活性剂羧基甜菜碱(HAB)进行复配,探讨了混合比对流体力学直径以及界面性能的影响,测试了二元体系的乳化性能、吸附性能以及岩心驱油效果。结果表明,IC16P6E6S在蒸馏水中的临界胶束浓度(cmc)为0.1 mmol/L,γcmc为28.53 mN/m。IC16P6E6S与HAB、CTAB有较强的协同作用,能有效降低界面张力。n(IC16P6E6S) ∶n(HAB)=1∶1和n(IC16P6E6S) ∶n(CTAB)=1∶3混合体系分别在1%~7% NaCl和3%~7% NaCl盐度范围内将界面张力保持在超低(10-3 mN/m数量级)和低界面张力(10-2 mN/m数量级)范围。随着盐度的增加,复配表面活性剂体系形成的乳液经历从Winsor Ⅰ到Winsor Ⅲ再到Winsor Ⅱ的相转变过程,IC16P6E6S/HAB复配体系较IC16P6E6S/CTAB混合体系能够产生更多的中相乳液,乳液体系更稳定,油增溶量高达43 mL/g,同时具有较好的抗吸附性能;与水驱相比,其降压率可达到25.00%,采收率提高11.75%,说明IC16P6E6S/HAB复配体系更有利于低渗透储层的降压增注。

    2-Hexyl-1-decanol was used as the main material to prepare a block-polyether sulfonate extended surfactant (IC16P6E6S). The solubility and surface active properties of IC16P6E6S were evaluated, and then the IC16P6E6S was mixed with a cationic surfactant hexadecyl trimethyl ammonium bromide (CTAB) and a zwitterionic betaine surfactant (HAB), respectively. The effects of mixing ratios of IC16P6E6S∶HAB and IC16P6E6S∶CTAB on the hydrodynamic diameter and interfacial properties were discussed. The emulsification, adsorption and laboratory core displacement experiments of the binary system were tested. The results showed that the critical micelle concentration (cmc) of IC16P6E6S in distilled water was 0.1 mmol/L and the surface tension at cmc (γcmc) was 28.53 mN/m. IC16P6E6S showed strong synergistic effects with HAB and CTAB, and the mixed systems could effectively reduce the interfacial tension compared with single surfactants. The mixed systems with n (IC16P6E6S) ∶n (HAB) of 1∶1 and n (IC16P6E6S) ∶n(CTAB) of 1∶3 could maintain ultra-low interfacial tension (in the order of magnitude of 10-3 mN/m) in the salinity range of 1%-7% NaCl and low interfacial tension (in the order of magnitude of 10-2 mN/m) in the salinity range of 3%-7% NaCl, respectively. With the increase of salinity, the emulsion formed by the mixed surfactant system underwent the phase transition process from Winsor Ⅰ to Winsor Ⅲ and then to Winsor Ⅱ. The emulsion of mixed IC16P6E6S/HAB system had more middle-phase emulsion volume than that of the mixed IC16P6E6S/CTAB system, and the former emulsion system was more stable. The mixed IC16P6E6S/HAB system also had good solubilization effect, and the amount of oil solubilization was up to 43 mL/g. Meanwhile, it had good adsorption resistance. Compared with water flooding, the depressurization rate could reach 25.00% and the recovery could be enhanced by 11.75%, indicating that the IC16P6E6S/HAB system was more conducive to the depressurization and injection enhancement for low-permeability reservoirs.

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    科技讲座
    天然生物质材料的制备、性质与应用(Ⅻ)——多功能酸性植物杂多糖:果胶
    Preparation, properties and applications of natural biomass materials (Ⅻ) Multifunctional acidic heteropolysaccharide: pectin
    刘雅迪, 郭凯越, 高阿秀, 周业杰, 范金石
    2024 (12):  1414-1422.  doi: 10.3969/j.issn.2097-2806.2024.12.002
    摘要 ( 1384 )   HTML ( 17 )   PDF(8209KB) ( 40 )  

    果胶是一种组成和结构复杂的天然植物亲水性胶体,广泛存在于高等植物的细胞中。因果胶具有良好的水溶性、稳定性、胶凝性、乳化性等性质以及安全无毒、生物相容性良好、可生物降解的天然属性和降低胆固醇、抗肿瘤、抗氧化、降血糖等多种生理活性,且利用其分子结构中的羟基、羧基、糖苷键等活性官能团进行物理、化学、酶处理及复合改性后能显著改善其理化性质、增强其功效性能,使得果胶及其改性产物在食品、医药等领域得到广泛应用,并在日用化工、功能材料、可降解生物质材料等领域展现出巨大的应用潜力。本文浅述了果胶的来源、结构和典型理化性质与功能特性,并较为系统地介绍了果胶的提取方法、分离纯化技术和改性手段,同时概述了果胶及其改性产物的应用情况,并提及了果胶及其改性产物当前所面临的主要问题以及将来的研发方向和发展前景。

    Pectin is a kind of natural hydrophilic colloid with complicated composition and structure, which has been abundantly found in the cells of higher plants. Pectin has good water solubility, stability, gelling ability and emulsifying ability, as well as safety and non-toxicity, good biocompatibility, biodegradability, and many excellent biological activities such as lowering cholesterol, anti-tumor, anti-oxidation, and lowering blood sugar. Moreover, both its physicochemical properties and functional performance can be further improved by physical, chemical and enzymatic treatments and compound modification upon the active functional groups, such as hydroxyl groups, carboxyl groups and glycosidic bonds. Therefore, pectin has been widely used in many fields, including food industry and pharmaceutical industry. Furthermore, great application potential has emerged in daily-use chemical industry, functional materials, and biodegradable biological materials. In this review, the source, chemical structure, main physicochemical properties and functional characteristics of pectin were briefly introduced. The extraction methods, separation and purification technologies, and modification methods for pectin were also systematically presented. In addition, the situation of application as well as the current problems for pectin and its modified products were summarized. Finally, some of the directions of future research and development of pectin were pointed out.

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    开发与应用
    氧化型谷胱甘肽凝聚及其在染料去除中的应用
    Coacervation of oxidized glutathione with a cationic surfactant and the application in dye removal
    张月, 刘玉, 赵莉, 王策, 徐宝财
    2024 (12):  1423-1430.  doi: 10.3969/j.issn.2097-2806.2024.12.003
    摘要 ( 1682 )   HTML ( 10 )   PDF(6082KB) ( 38 )  

    在静电和疏水作用的共同驱动下,氧化型谷胱甘肽(GSSG)与阳离子表面活性剂十二烷基二甲基溴化铵(DDAB)混合发生凝聚,利用此凝聚过程可以实现从水中提取染料的目的。文章分析了GSSG-DDAB (摩尔比为1∶4)的凝聚作用随pH值的变化情况。结果发现在酸性和中性条件下,观察到形成了浑浊的液滴悬浮液,而在碱性pH值下发生分相,凝聚相作为上层自动分离出来。我们选用了5种带不同电荷的染料,包括亮黄、酸性红13、甲酚紫、铬蓝SE和4-羟基偶氮苯,染料在酸性条件下加入GSSG-DDAB悬浮液中,然后将pH值调至约10时,染料在凝聚相中富集,从体系中自发分离出来,漂浮在溶液表面,实现对染料的富集和去除,结果均表现出良好的去除效率(均超过85%)。GSSG与DDAB的凝聚作用为处理废水中有机污染物的提取提供了一种简单的方法。

    Coacervation of oxidized glutathione (GSSG) and a cationic surfactant, didodecyldimethylammonium bromide (DDAB), was constructed mainly driven by the electrostatic and hydrophobic interactions. The pH-dependent coacervate of GSSG-DDAB (1∶4, mol/mol) was analyzed. Under acidic and neutral conditions, a turbid suspension of droplets is observed, and alkaline pH results in the phase separation of coacervates as the top phase. The coacervate phase exhibits good performance (extraction efficiency>85%) in extracting several dyes from water, including brilliant yellow, acid red 13, cresyl violet acetate, eriochrom blue SE, and 4-hydroxyazobenzene. The dyes are added into the suspension in acidic conditions. Then, the dyes are enriched and extracted along with the coacervates as the top phase when pH is adjusted to~10. Coacervation of GSSG with DDAB provides a simple approach to extract organic pollutants in wastewater treatment.

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    基于牛血清白蛋白LB膜模板诱导蜂巢状碱式碳酸锌薄膜生长研究
    Study on the growth of honeycomb-like film of basic zinc carbonate induced by bovine serum albumin LB film template
    王海威, 肖文波, 贾秀玲, 肖洋, 杜祖亮
    2024 (12):  1431-1436.  doi: 10.3969/j.issn.2097-2806.2024.12.004
    摘要 ( 46 )   HTML ( 3 )   PDF(5612KB) ( 15 )  

    以牛血清白蛋白(BSA)这种可溶性生物大分子蛋白为模板,在室温下成功制备了多孔蜂巢状碱式碳酸锌薄膜。经过低温退火后得到了具有良好电子迁移率的高比表面积多孔ZnO薄膜。经SEM、TEM、XRD、光致发光光谱和紫外-可见吸收光谱等测量手段,分别对碱式碳酸锌薄膜及其退火后的ZnO薄膜进行表面形貌、结晶性能以及光致发光特性分析。通过对无蛋白质薄膜诱导所得的样品进行比较,判断BSA分子与Zn2+离子之间的络合作用是碱式碳酸锌多孔薄膜合成的首要因素。实验表明该方法制备的ZnO薄膜样品具有高比表面积和在近紫外范围的宽带发光特性。

    Honeycomb-like films of basic zinc carbonate were successfully prepared on FTO (SnO2: F) conductive glass using bovine serum albumin (BSA) as a template at room temperature. After low-temperature annealing, a high-specific-surface-area porous ZnO film with excellent electron mobility was obtained. The surface morphology, crystallization performance, and photoluminescence characteristics of basic zinc carbonate thin films and annealed ZnO thin film were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence spectroscopy (PL) and UV-Visible spectroscopy (UV-vis). By comparing with those samples prepared without any protein, it was determined that the complexation between BSA molecules and Zn2+ ions was the primary factor in the synthesis of porous films of basic zinc carbonate. The experimental results showed that the ZnO thin film samples prepared with this method had high specific surface area and broadband luminescence characteristics in the near ultraviolet range.

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    4-己基间苯二酚的美白功效及新作用机理探讨
    Skin brightening benefit of 4-hexylresorcinol in vivo and in vitro and its underlying mechanism
    顾学兰, 张红, 肖雪, 周壮, 瞿珏, 施奕冰
    2024 (12):  1437-1446.  doi: 10.3969/j.issn.2097-2806.2024.12.005
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    文章旨在系统评价4-己基间苯二酚(4-HR)的皮肤美白功效,并探索其新的作用机理。临床测试以祛斑美白化妆品功效原料研究技术指导原则为指南,开展了一项为期8周、安慰剂对照的人体测试研究,结果表明精华露中添加0.4% 4-HR能显著提高皮肤ITA°值,降低皮肤黑色素含量。表面涂抹等量4-HR能明显提高体外重组3D黑素模型的表观亮度,显著减少黑色素含量。基于角质细胞的转录组学分析提示被4-HR影响表达的基因除参与皮肤发育过程、角质化过程,还影响氧化活性调控、细胞自噬功能等。进一步体外研究证明,4-HR能够抑制蓝光诱导的活性氧水平,减轻角质形成细胞的氧化应激反应。在人角质-黑素细胞共培养模型中,4-HR不仅能降低黑素含量,同时还能明显提高细胞自噬标记物LC3表达。加入自噬抑制剂氯喹后,4-HR对黑色素含量的抑制作用也随之显著降低。研究表明,添加0.4% 4-HR的精华露具有良好的美白功效,4-HR可能以减轻氧化应激、调节细胞自噬功能的新作用机理而起到美白作用。

    4-Hexylresorcinol (4-HR), a potent tyrosinase inhibitor, has been used as an even-tone active ingredient for skin care application since 2007. While the skin brightening efficacy of 4-HR in Chinese population has not been thoroughly investigated and its significance in keratinocytes has not been fully raveled. This study aims to evaluate the skin brightening potential of 4-HR in vivo and in vitro and explore its new mechanism of action through transcriptome approach. The skin brightening effect of 0.4% 4-HR in a facial serum was assessed in an 8-week, double-blinded, placebo-controlled, and randomized clinical study in 67 Chinese participants. ITA°, melanin index (MI) and visual grading were measured at baseline and 2, 4 and 8 weeks after use. A pigmented living skin equivalent (pLSE) model constructed from Asian skin cells was utilized to assess the brightening efficacy of 0.4% 4-HR by measuring the model’s brightness (L* value) and melanin content. Then, transcriptomic analysis of 4-HR treated human epidermal keratinocytes was conducted, and the two in vitro models were adopted for hypothesis validation afterwards. In the clinical study, the result shows both 0.4% 4-HR serum and placebo chassis can significantly improve all measures as compared to baseline at the 2, 4, and 8 weeks. Furthermore, 0.4% HR serum demonstrates a better performance in increasing ITA° as early as 2 weeks of application and decreasing MI value than the placebo group at Week 2. In the pLSE model, 0.4% 4-HR with topical application evidently increases L* value by 15.88% and decreases melanin content by 47.61% compared to UVB group. RNA-sequencing analysis implies that 4-HR can regulate multiple biological processes including skin development, keratinocyte differentiation, oxidant activity and autophagy function. In the blue-light challenged human keratinocytes model, 4-HR shows a significant ROS suppression capacity. In the keratinocytes-melanocytes co-culture model, 4-HR prompts autophagy activity and decreases melanin content. Most importantly, the melanin inhibitory activity of 4-HR is compromised after co-treating with Chloroquine, an autophagy inhibitor, suggesting autophagy regulation property of 4-HR may partially contribute to its skin brightening efficacy. Taken together, these data demonstrate skin brightening efficacy of 0.4% 4-HR in vivo and in vitro, in addition to acting as a tyrosinase inhibitor, 4-HR can contribute to skin brightening benefit via enhancing cellular antioxidant capacity and autophagy activation.

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    O/W/Si多重防晒乳液的制备及性能研究
    Study on the preparation and properties of sunscreen O/W/Si multiple emulsion
    张婉萍, 周率, 高子豪, 朱海洋
    2024 (12):  1447-1455.  doi: 10.3969/j.issn.2097-2806.2024.12.006
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    为解决防晒乳液中有机防晒剂带来的油腻感和刺激性风险,文章使用包覆了有机防晒剂的固体脂质纳米粒,通过两步乳化法制备了外油相为硅油,内油相为有机防晒剂的O/W/Si多重防晒乳液;分析了外硅油相体积比、W/O乳化剂用量、无机盐对乳液形成及稳定性的影响,深入研究了不同类型防晒乳液的体外防晒性能、抗水性及防晒剂皮肤渗透性能的不同。结果显示,在实验条件下,含有22.5%的外硅油相、2.5%的乳化剂及0.2%的NaCl所制得的O/W/Si多重防晒乳液稳定性最佳;O/W/Si多重防晒乳液的SPF值和抗水性略高于W/O防晒乳液,但显著高于O/W防晒乳液;对比于W/O防晒乳液,O/W/Si多重防晒乳液中有机防晒剂的体外经皮渗透率降低了约60%,具备更高安全性,展现了在防晒化妆品中的良好应用前景。

    To solve the greasiness and irritation risks brought about by organic sun-screening agents in sunscreen emulsions, in this work, a sunscreen O/W/Si multiple emulsion was prepared by two-step emulsification method, in which the outer oil phase was silicone oil and the inner oil phase was solid lipid nanoparticles coated with organic sun-screening agent. Several influencing factors on the formation and stability of the emulsion were analyzed, including inorganic salts, the volume fraction of outer oil phase (silicone oil), and the dosage of W/O emulsifier. The in vitro sunscreen performance, water resistance and skin permeability of different types of sunscreen emulsions were further studied. The results showed that the sunscreen O/W/Si multiple emulsion containing 22.5% silicone oil, 2.5% emulsifier and 0.2% NaCl had the best stability under the experimental conditions. The SPF value and water resistance of sunscreen O/W/Si multiple emulsion were slightly higher than those of sunscreen W/O emulsion, but significantly higher than those of sunscreen O/W emulsion. Compared with sunscreen W/O emulsion, the in vitro transdermal permeability of organic sun-screening agent in sunscreen O/W/Si multiple emulsion was reduced by approximately 60%, indicative of higher safety and good application prospect in sunscreen cosmetics.

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    美藤果发酵多肽对液晶乳液结构的影响
    Effect of fermented polypeptide of Sacha Inchi (Plukenetia volubilis L.) on the structure of liquid crystal emulsion
    刘晓纯, 罗婷婷, 戴洁, 陈来成, 何秋星
    2024 (12):  1456-1464.  doi: 10.3969/j.issn.2097-2806.2024.12.007
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    为研究美藤果多肽对液晶乳液的作用机制,通过制备以美藤果发酵多肽作为活性成分的水包油液晶乳液,采用偏光显微镜、粒度仪、热重-差热同步测定系统、流变仪等对液晶乳液在不同发酵产物浓度下的微观结构、粒径、稳定性、热力学特性和流变特性进行观察。结果表明:美藤果发酵多肽液晶乳液的平均粒径为(25.7±2.8) μm,液晶结构完整、乳液稳定性好,1%的美藤果多肽添加量的乳液其结合水含量占比、液晶含量均较3%,5%的美藤果多肽添加量的乳液多;通过流变学显示,液晶乳液黏度随剪切速率变化曲线展现剪切变稀现象,属于非牛顿流体;1%添加量的液晶乳液其滞后面积、储能模量、损耗模量均大于空白乳液、3%,5%液晶乳液,表明其触变性大,抗剪切能力强,1%添加量的液晶乳液中多肽的亲水性氨基酸残基与水相结合,其疏水性氨基酸残基进入油相,在油水界面形成一层黏弹膜,使得液晶乳液具有更稳定的三维网络结构。

    In order to study the action mechanism of Sacha Inchi polypeptide in liquid crystal emulsion, oil-in-water liquid crystal emulsions with Sacha Inchi fermented polypeptide as the active component were prepared. The microstructures, particle sizes, stabilities, thermodynamic properties, and rheological properties of liquid crystal emulsions with different concentrations of the fermentation products were observed by Polarizing microscope, Particle size meter, Thermogravimetric differential thermal synchronous measurement system, and Rheometer, respectively. The results showed that the average particle size of fermented peptide liquid crystal emulsion was (25.7±2.8) μm, and the liquid crystal structure was complete and stable. The content of bound water and liquid crystal in the emulsion with 1% Sacha Inchi polypeptide were higher than those in the blank emulsion and the emulsions with 3% and 5% Sacha Inchi polypeptide. Rheological results indicated that the viscosity of liquid crystal emulsion with the change curve of shear rate registered the shear thinning phenomenon, which belongs to non-Newtonian fluid. The hysteresis area, energy storage modulus, and loss modulus of the 1% additive amount of liquid crystal emulsion were larger than those of the blank emulsion and the emulsions with 3% and 5% Sacha Inchi polypeptide, indicating greater thixotropy and stronger shear resistance. The hydrophilic amino acid residues of the peptide in the 1% additive amount of the emulsion were combined with the water phase, while the hydrophobic amino acid residues of the peptide entered the oil phase, which formed a viscoelastic film at the oil-water interface, so that the liquid crystal emulsion had a more stable gel network structure.

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    Ce-TiO2-RGO催化剂的制备及在印染废水处理中的应用研究
    Preparation of Ce-TiO2-RGO catalyst and its application in the treatment of printing and dyeing wastewater
    朱宝, 潘艳
    2024 (12):  1465-1472.  doi: 10.3969/j.issn.2097-2806.2024.12.008
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    以溶胶-凝胶法和超声复合法制备了Ce-TiO2-RGO复合光催化剂,研究了Ce掺杂质量分数对光催化剂降解纺织印染废水性能的影响。通过XRD、SEM、TEM、UV-vis、PL对复合光催化剂进行了表征。研究结果表明:Ce-TiO2颗粒均匀吸附在GO表面,Ce-TiO2的粒径约25~110 nm。Ce的掺杂后使TiO2-RGO复合光催化剂的吸收带边发生了红移,禁带宽度减小。随着Ce掺杂质量分数的增大,Ce-TiO2-RGO复合光催化剂的PL强度先降低后轻微增大,6% Ce-TiO2-RGO复合光催化剂在410和470 nm的发射峰强度最低。以纺织印染废水为降解对象,在180 min时,6% Ce-TiO2-RGO对COD的去除率达到最大值82.21%,降解后COD值为88.95 mg/L,符合废水排放标准。在180 min时,6% Ce-TiO2-RGO对纺织印染废水的降解率达到了最大值99.21%。Ce-TiO2-RGO复合光催化剂在染色纺织废水的处理方面表现出巨大的应用潜力。

    Ce-TiO2-RGO composite photocatalyst was prepared by sol-gel method and ultrasonic treatment. The effect of Ce doping mass fraction on the degradation of textile printing and dyeing wastewater was studied. The catalysts were characterized by XRD, SEM, TEM, UV-vis and PL. The results showed that, Ce-TiO2 particles uniformly adsorbed on the GO surface, and the particle diameter of Ce-TiO2 was approximately 25-110 nm. After Ce doping, the absorption band edge of TiO2-RGO composite photocatalyst was redshifted and the band gap was reduced. With the increase of Ce doping mass fraction, the PL intensity of Ce-TiO2-RGO composite photocatalyst first decreased and then slightly increased, and the emission peak intensity of 6% Ce-TiO2-RGO composite photocatalyst was the lowest at 410 nm and 470 nm. Taking textile printing and dyeing wastewater as the research object of degradation, the COD removal rate of 6% Ce-TiO2-RGO reached the maximum of 82.21% at 180 min, and the COD value after degradation was 88.95 mg/L which was in line with the wastewater discharge standard. On the other hand, at 180 min, the degradation rate for textile printing and dyeing wastewater by 6% Ce-TiO2-RGO also reached the maximum (99.21%). Therefore, the Ce-TiO2-RGO composite photocatalyst showed great application potential in the treatment of textile dyeing wastewater.

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    AgBr/C3N5复合材料可见光去除无机废水中氨氮
    Removal of ammonia nitrogen from inorganic wastewater by AgBr/C3N5 heterojunction under visible light irradiation
    朱炳生
    2024 (12):  1473-1480.  doi: 10.3969/j.issn.2097-2806.2024.12.009
    摘要 ( 37 )   HTML ( 3 )   PDF(5696KB) ( 12 )  

    通过原位沉淀法将AgBr原位沉淀到富氮氮化碳(C3N5)表面,制备了AgBr/C3N5复合材料,通过X射线衍射(XRD)、傅里叶红外光谱(FTIR)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-vis DRS)和光致发光光谱(PL)等技术手段对复合材料的物相晶型、化学组成、元素组成、光谱吸收和光电子-空穴分离进行了表征分析。AgBr和C3N5异质结的构建使得光谱响应范围拓宽,实现了光电子-空穴的高效分离,提升了光催化性能。使用NH4Cl溶液模拟无机氨氮废水研究复合材料的光催化性能,复合材料投加量为0.10 g,NH4Cl溶液初始质量浓度100 mg/L,初始pH=10.0,模拟可见光照射60 min复合材料对氨氮的去除率达到了90.27%,循环使用5次后氨氮的去除率仅仅降低了0.12%,复合材料表现出良好的光催化性能和稳定性。Z-scheme机理有效保留了光电子和空穴的还原和氧化活性,将O2和H2O分别还原和氧化为超氧自由基(·O2-)和羟基自由基(·OH)等活性基团,实现了无机氨氮的高效去除。

    AgBr/C3N5 composite was prepared by in-situ precipitation of AgBr on the surface of nitrogen-rich carbon nitride (C3N5). The crystal phase, chemical composition, elemental composition, spectral absorption and photoelectron-hole separation of the composite were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS) and photoluminescence spectroscopy (PL). The construction of AgBr and C3N5 heterojunction could broaden the spectral response range, realize the efficient separation of photoelectrons and holes, and thus improve the photocatalytic performance. The photocatalytic performance of the composite material was studied by simulating inorganic ammonia nitrogen wastewater with NH4Cl solution. The dosage of the composite material was 0.10 g, the initial mass concentration of NH4Cl solution was 100 mg/L, and the initial pH was 10.0. The removal rate of ammonia nitrogen by the composite material reached 90.27% after 60 min of simulated visible light irradiation. After 5 cycles, the removal rate of ammonia nitrogen only declined by 0.12%. The composite material showed good photocatalytic performance and stability. The Z-scheme mechanism effectively retained the reduction and oxidation activities of photoelectrons and holes, which could change O2 and H2O to active groups such as superoxide radicals (·O2-) and hydroxyl radicals (·OH), respectively, achieving efficient removal of inorganic ammonia nitrogen.

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    聚(N-乙烯基吡咯烷酮-co-甲基丙烯酸)对烫/漂发质的修复
    Study on the repairing effect of poly (N-vinylpyrrolidone-co-methacrylic acid) on permed or bleached damaged hair
    张云, 王欢, 杨玉云, 于思涵, 曹玉华
    2024 (12):  1481-1488.  doi: 10.3969/j.issn.2097-2806.2024.12.010
    摘要 ( 57 )   HTML ( 2 )   PDF(6335KB) ( 16 )  

    研究了无规共聚物聚(N-乙烯基吡咯烷酮-co-甲基丙烯酸)(P(NVP-co-MAA)对烫发及漂发发质的修护效果。分别对烫/漂发质修护前后发样的梳理性及抗拉伸性能进行了测试,测试了聚合物质量分数及浸泡时间对梳理性及抗拉伸性能的影响,并对受损发质的修护机理进行了探究。结果表明:分别使用0.3%及0.5%的聚合物溶液浸泡2 h后的烫发及漂发发样相较于未处理发样的断裂强度分别提升15.55%及18.12%。通过对修护前后发样的红外光谱分析及尿素氢键破坏实验证实,聚合物对受损发样抗拉伸强度的提升主要依靠氢键的形成。聚合物修护后,烫发发样的干梳及湿梳摩擦系数降低了30.73%与28.55%,漂发发样干梳及湿梳摩擦系数分别降低28.55%与24.83%。通过扫描电子显微镜对修护前后的烫/漂发样进行观察,发现聚合物能有效抚平毛鳞片,并填充于翘起的毛鳞片之间。

    The repairing effect of poly (N-vinylpyrrolidone-co-methacrylic acid) on permed or bleached damaged hair was studied. The combing and tensile strength of permed and bleached hair before and after treatment with the copolymer solution were tested, and the effects of the mass fraction of copolymer solution and immerseing time on the combing and tensile strength for permed or bleached damaged hair were investigated. The repair mechanism of permed or bleached damaged hair was also explored. The results show that when the immersing time is 3 hours, the tensile strength of the permed hair increases with the mass fraction of the copolymer solution within 0%-0.3%, but no obvious change is observed when the mass fraction is over 0.3%. Therefore, the optimal mass fraction of the copolymer solution for repairing the permed hair is 0.3%. Similarly, the optimal mass fraction of the copolymer solution for repairing the bleached hair is 0.5%. Furthermore, the effects of immersing time on the tensile strength of the damaged hair fibers were compared between the permed and bleached hair before and after treatment with the copolymer solution. Coincidentally, the optimal immersion time for permed or bleached damaged hair is both 2 hours. The tensile strength of the permed and bleached hair soaked in 0.3% and 0.5% copolymer solutions for 2 hours increases by 15.55% and 18.12%, respectively, compared to untreated hair. Through infrared spectroscopy analysis, it is found that the amide II band in hair fibers shifted to the blue after repair, with the wave number shift of 11.12 and 11.09 cm-1, which confirm the formation of hydrogen bonds in the hair samples. Additionally, the urea hydrogen bond disruption experiment demonstrates that urea does not disrupt the hydrogen bonds in untreated hair fibers, but prevents the formation of new hydrogen bonds in damaged hair fibers. It further validates that the improvement of the tensile strength of the copolymer treated damaged hair fibers is mainly due to the formation of hydrogen bonds. After treatment with the copolymer, the dry and wet combing friction decrease by 30.73% and 28.55% for the permed hair, and decrease by 28.55% and 24.83% for the bleached hairs, respectively. The scanning electron microscope shows that the copolymer can flatten the cuticle and fill the space between the raised cuticles.

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    专论与综述
    阿魏酸在化妆品中的应用研究进展
    Research progress on the application of ferulic acid in cosmetics
    邓诗雨, 金建明, 吴华
    2024 (12):  1489-1496.  doi: 10.3969/j.issn.2097-2806.2024.12.011
    摘要 ( 2039 )   HTML ( 8 )   PDF(7103KB) ( 57 )  

    阿魏酸是广泛存在于植物中的酚类化合物,其主要来源是从植物中提取,另外也可以通过生物合成法和化学合成法得到。而生物合成阿魏酸是最有前景的工业生产方法。在化妆品应用中,阿魏酸具有多种生物活性。阿魏酸常作为美白功效成分,其通过竞争性抑制酪氨酸酶的活性以减少黑色素的生成。阿魏酸也可以作为抗氧化剂,它能消除细胞自由基、抑制ROS的产生、参与多种细胞信号通路和调节抗氧化酶活性而发挥抗氧化作用。阿魏酸也具有很好的防晒功效,通过吸收紫外线,抑制UVB诱导的基质金属蛋白酶MMP-2和MMP-9活性来减少紫外辐射造成的皮肤伤害;阿魏酸也对人表皮角质形成细胞和成纤维细胞具有保护作用。阿魏酸还能有效延缓衰老,主要通过降低胶原酶和透明质酸酶活性来抑制透明质酸的降解,诱导前胶原和透明质酸的合成而发挥功效。阿魏酸对特应性皮炎和银屑病等皮肤炎症性疾病的有一定的治疗作用,其通过抑制多种炎症因子和细胞信号通路发挥抗炎作用。阿魏酸也具有广谱的抗菌效果,其作用机制是破坏细菌和真菌细胞膜,导致细胞质膜渗漏,最终导致细胞死亡。另外,阿魏酸还能促进皮肤伤口愈合和再生。但阿魏酸相对比较差的稳定性限制了其在化妆品中的应用。

    Ferulic acid is a phenolic compound widely exists in plants. Currently ferulic acid on the market is mainly extracted from plants, but it can also be obtained via biosynthesis or chemical synthesis. The biosynthesis method has a great potential for future production of ferulic acid. Ferulic acid is frequently used as a whitening ingredient in cosmetics, since it reduces melanin production by competitively inhibiting tyrosinase activity. It also has strong antioxidant activity, including elimination of free radicals, inhibition of ROS production, and regulation of various signaling pathways and the activity of antioxidant enzymes. The anti-UV activity of ferulic acid makes it applicable in sunscreen cosmetics. It can absorb UV rays and inhibit UVB-induced matrix metalloproteinase MMP-2 and MMP-9 activities to attenuate the damage caused by UV radiation. Ferulic acid is also reported to display protective effects on human keratinocytes and human skin fibroblasts. In addition, it is found to have effective anti-aging effect, mainly through inhibiting the degradation of hyaluronic acid by reducing the activities of collagenase and hyaluronidase, and inducing the biosynthesis of pre-collagen and hyaluronic acid. Ferulic acid shows potential for the treatment of atopic dermatitis, psoriasis and other inflammatory diseases of the skin. Its anti-inflammatory effect results from the inhibition of multiple inflammatory factors and signaling pathways. Ferulic acid displays broad-spectrum antibacterial effect, by damaging the cell membranes of bacteria and fungi which leads to membrane leakage and cell death. Furthermore, ferulic acid can also promote skin healing and regeneration. However, the instability of ferulic acid limits its applications in cosmetics.

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    硫酸化糖胺聚糖护肤功效研究进展
    Research progress on the skincare efficacy of sulfated glycosaminoglycans
    张彦位, 许忠良, 杜曦, 李振, 田志鹏
    2024 (12):  1497-1503.  doi: 10.3969/j.issn.2097-2806.2024.12.012
    摘要 ( 59 )   HTML ( 3 )   PDF(5966KB) ( 36 )  

    随着消费者科学护肤意识的不断提高,以皮肤问题为导向的功效护肤和精准护肤方式成为化妆品重要的发展趋势。糖胺聚糖是由重复双糖单元组成的长链、线性多糖,在皮肤中进行高水平内源表达,普遍存在于皮肤细胞内、细胞表面和细胞外基质中,具有复杂的生物结构和多效生物活性。除透明质酸外,硫酸化的肝素、硫酸乙酰肝素、硫酸皮肤素和硫酸软骨素在抗皱、紧致、舒缓和改善微血管循环方面发挥着重要作用,但目前还未在化妆品领域得到广泛的应用。文章综述了硫酸化糖胺聚糖的护肤作用机理,展示了硫酸化糖胺聚糖作为功效成分在化妆品领域的应用潜力。

    With the improvement of consumers’ scientific skin care consciousness, skin problems-oriented efficacy skin care and precise skin care methods have become the future development trend. Glycosaminoglycans are long, linear polysaccharides comprised of repeated disaccharide units, which are highly expressed endogenously in the skin. They are commonly present in skin cells, cell surface and extracellular matrix, with pleiotropic biological function. In addition to hyaluronic acid, the sulfated glycosaminoglycans heparin, heparan sulfate, dermatan sulfate and chondroitin sulfate play an important role in anti-wrinkle, firming, soothing, and improving microvascular circulation, but are still in the research and development stage in cosmetics. This paper summarizes the skincare mechanism of sulfated glycosaminoglycans, and demonstrates the potential of sulfated glycosaminoglycans as functional raw materials in cosmetics.

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    基于毛囊生长周期机制评估防脱化妆品功效的研究进展
    A review of methods for evaluating effectiveness of cosmetic products and ingredients based on mechanisms of the human hair growth cycle
    张嘉琪, 万可宁, Ranjit Kaur Bhogal, 浦铭铭, 顾佳音, 盘瑶
    2024 (12):  1504-1514.  doi: 10.3969/j.issn.2097-2806.2024.12.013
    摘要 ( 140 )   HTML ( 7 )   PDF(9295KB) ( 74 )  

    近年来,受到脱发困扰的人群数量持续增加并向年轻化发展,消费者对防脱发产品的多样化需求日渐增多,国内外对防脱发功效原料和产品的研发越来越重视。然而,针对防脱发化妆品功效评估和功效成分的测试方法尚无统一标准,因此亟待建立完善的评价体系用于衡量防脱发化妆品功效。本文从毛发的基本结构和毛囊的生长周期出发,梳理了调控毛囊周期的相关信号分子、信号通路和反馈机制,为防脱发活性成分的作用机理和功效验证,以及防脱发产品的功效评估的相关方法和技术提供了基本理解,并基于正常毛发周期的变化提出了减少和延缓脱发的方法以及相应的化妆品策略。本文旨在基于毛囊生长周期机制为防脱发功效原料和产品的功效评估提供建议,从而为未来防脱发功效原料和产品研发提供参考标准。

    With the increasing incidence of hair loss and especially among younger population in recent years, the demand for diversified products on anti-hair loss solutions is growing and the market of cosmetic products expanding accordingly. Worldwide attention is being paid to the research and development of anti-hair loss actives, while there is no unified standard for the efficacy evaluation and testing methods of anti-hair loss cosmetics. Therefore, it is critical to establish standardized methodology for assessing the effectiveness of anti-hair loss actives and their cosmetic products. In this review, an overview of the human hair follicle structure, the hair follicle cycle, and the biological pathways and signaling mechanisms involved in hair growth are summarized. This provides the fundamental understanding of human hair growth for reviewing anti-hair loss actives and cosmetic hair loss products, and respective methods and techniques applied for evaluating their efficacy. Additionally, changes in the normal hair cycle, and corresponding cosmetic strategies to slow down and reduce hair loss have been provided. This review aims to provide recommendations for evaluating the effectiveness of anti-hair loss actives on the mechanisms involved in the hair follicle growth cycle, and so provide criteria for new technology development and scientific research for cosmetic products.

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    分析与检测
    高效液相色谱法同时测定牙膏中27种防腐剂
    Simultaneous determination of 27 preservatives in toothpaste by high-performance liquid chromatography
    吴志珊, 王彦超, 姜成君, 龙雨晨, 殷帅, 尹伟成
    2024 (12):  1515-1523.  doi: 10.3969/j.issn.2097-2806.2024.12.014
    摘要 ( 56 )   HTML ( 5 )   PDF(4865KB) ( 28 )  

    为了准确高效地检测牙膏中防腐剂的添加量,建立了牙膏中27种防腐剂含量同时检测的高效液相色谱方法。采用50%甲醇水溶液处理牙膏样品,经超声提取后,过滤,以乙腈、磷酸水溶液为流动相,在以C18色谱柱为分析柱,柱温30 ℃,进样量为10 μL,流速为1 mL/min的色谱条件下,以液相色谱分离,二极管阵列检测器进行检测。分析结果表明,在该实验条件下27种防腐剂各组分分离度良好,其质量浓度在线性范围内与峰面积呈良好线性关系,相关系数(R2)均大于0.999 5,该方法可用于牙膏中27种防腐剂的检测。

    A method of high-performance liquid chromatography (HPLC) was established for simultaneous determination of 27 preservatives in toothpaste. Toothpaste samples were extracted with 50% aqueous methanol solution, ultrasonicated and then filtered. The target compounds were separated on a C18 column (250 mm×4.6 μm, 5 μm) with the mobile phase consisting of acetonitrile and aqueous phosphoric acid solution, the column temperature was 30 ℃, the sample volume was 10 μL, the flow rate was 1 mL/min, and diode array detector was used. Under the optimal experimental conditions, good linear relationship was obtained and the correlation coefficient (R2) was greater than 0.999 5. This method was accurate and sensitive, which was suitable for the qualitative and quantitative analysis of 27 preservatives in toothpaste.

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    化妆品中黄芪提取液的质量控制技术研究
    Research on the quality control technology for the Astragalus membranaceus extraction solution in cosmetics
    汪汝沛, 楚亮, 陈清影, 李文莉, 李春艳, 傅萍
    2024 (12):  1524-1531.  doi: 10.3969/j.issn.2097-2806.2024.12.015
    摘要 ( 71 )   HTML ( 4 )   PDF(6221KB) ( 24 )  

    选取黄芪提取液中指标成分毛蕊异黄酮苷,采用高效液相色谱-二极管阵列检测器法(HPLC-DAD)研究其含量测定方法;采用高效液相色谱-电雾式检测器法(HPLC-CAD),建立黄芪提取液的特征图谱;同时对其重金属含量水平进行测定,建立黄芪提取液的质量控制技术。结果表明,在4~80 μg/mL测定质量浓度范围内毛蕊异黄酮苷峰面积与质量浓度的线性关系良好(r=0.999),相对标准偏差RSD=2.4%,加标回收率在99.2%~102.7%之间。黄芪提取液的特征图谱标定了14个共有峰,指认了其中5个共有峰,相似度在0.485~0.995之间。重金属铅、汞、镉的含量均小于检出限,砷的含量小于2 mg/kg。该方法结合定性与定量评价,操作简便,具有良好重复性及稳定性,能较全面控制黄芪提取液内在质量。可作为黄芪提取液的工艺优化依据和质量控制技术,并对其他以中药材提取液作为原料的化妆品的质量技术研究提供参考。

    Calycosin-7-glucoside, which is the target ingredient of the Astragalus membranaceus extraction solution, was studied by the high-performance liquid chromatography-diode array detector method (HPLC-DAD), and a high-performance liquid chromatography-electrospray ionization detector method (HPLC-CAD) was also established for fingerprint chromatogram analysis. Meanwhile, the heavy metal content was tested to build a quality control standard for Astragalus membranaceus extraction solution. Result shows a good linearity in 4-80 μg/mL mass concentration range with the correlation coefficient r=0.999, RSD=2.4%, and the recovery rate is between 99.2%-102.7%. The fingerprint chromatogram analysis features with 14 specific peaks, including 5 identified components. The similarity is between 0.485 to 0.995. Content of heavy metals such as lead, mercury, and cadmium are below the detection limit, and the content of arsenic is less than 2 mg/kg. This research results can serve as process optimization basis and quality control standards for Astragalus membranaceus extraction solution, and provide reference to quality control and research guideline for other cosmetics using herbal extracts as raw materials.

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    化妆品中13种防腐剂的高效液相色谱分析及质谱确证
    Determination of 13 preservatives in cosmetics by high performance liquid chromatography and verification by mass spectrometry
    邹坡, 徐炜, 李雪艳, 李长于, 陈艳, 陈勤勤
    2024 (12):  1532-1540.  doi: 10.3969/j.issn.2097-2806.2024.12.016
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    建立了同时测定化妆品中13种防腐剂(乙酰丙酸、对羟基苯乙酮、覆盆子酮、对茴香酸、辛酰羟肟酸、羟基乙氧基苯基丁酮、甲基异噻唑啉酮、苯氧乙醇、苯甲酸、4-羟基苯甲酸甲酯、氯苯甘醚、脱氢乙酸、5-溴-5-硝基-1,3-二噁烷)的高效液相色谱分析方法和质谱确证方法。不同基质类型的化妆品样品经甲醇超声提取后,使用Agilent ZORBAX Eclipse XDB-C18 (250 mm×4.6 mm,5 μm)色谱柱进行色谱分离,以0.1%磷酸水溶液和乙腈作为流动相梯度洗脱,流速1.0 mL/min,柱温30 ℃,检测波长为275,230和210 nm。对疑似阳性的样品,进一步采用液相色谱-串联质谱法或气相色谱-质谱法进行确证。结果表明,13种防腐剂组分在各自的质量浓度范围内,线性关系良好(r>0.999 8),检出限为0.4~100.0 mg/kg,定量限为1.2~250.0 mg/kg。在低、中、高3个加标水平下,13种目标组分在3种基质样品中的平均回收率为84.0%~115.4%,相对标准偏差为0.5%~4.8%(n=6)。该方法操作简便、分离效果好、精密度高,适用于化妆品中常见表外防腐剂和准用防腐剂的定性和定量测定。

    A method using high performance liquid chromatography (HPLC) was developed for the simultaneous determination of 13 preservatives (levulinic acid, p-hydroxyacetophenone, raspberry ketone, p-anisic acid, caprylhydroxamic acid, hydroxyethoxyphenyl butanone, methylisothiazolinone, phenoxyethanol, benzoic acid, methylparaben, chlorphenesin, dehydroacetic acid, and 5-bromo-5-nitro-1,3-dioxane) in cosmetics. Different types of samples were ultrasonically extracted by methanol, then the separation of 13 preservatives was carried out on a column of Agilent ZORBAX Eclipse XDB-C18 (250 mm×4.6 mm, 5 μm) by gradient elution at a flow rate of 1.0 mL/min, using 0.1% phosphoric acid solution and acetonitrile as mobile phases. The column temperature was 30 ℃, and the detection was completed by a diode array detector with the wavelengths at 275, 230 and 210 nm. Suspected positive samples were further confirmed by liquid chromatography-tandem mass spectrometry or gas chromatography-mass spectrometry. The linear regression analysis data shows good linearity for 13 preservatives in the respective mass concentration range, with their correlation coefficients (r) greater than 0.999 8. The limits of detection (LODs) and limits of quantitation (LOQs) of the method are in the ranges of 0.4-100.0 mg/kg and 1.2-250.0 mg/kg, respectively. At three spiked levels, the average recoveries for 13 target compounds in three kinds of matrix samples are within 84.0%-115.4%, and the relative standard deviations (RSD) are within 0.5%-4.8% (n = 6). This method is convenient, efficient, and precise, which can be used for qualitative and quantitative analysis of common preservatives in daily cosmetics.

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