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2022年, 第52卷, 第6期　刊出日期：2022-06-22 上一期    下一期

基础研究

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羟乙基纤维素和γ-聚谷氨酸混合体系的流变行为及协同机理 Rheological behavior and synergistic mechanism of the mixed system of hydroxyethyl cellulose and γ-polyglutamic acid 陈晗俊,庄洁,吴旭,沈兴亮,张婉萍,张倩洁 2022 (6):  577-584.  doi: 10.3969/j.issn.1001-1803.2022.06.001 摘要 ( 331 )   HTML ( 312 )   PDF(1433KB) ( 443 )   通过考察羟乙基纤维素（HEC）和γ-聚谷氨酸（γ-PGA）混合体系的表观黏度、流动曲线、黏弹性、黏温曲线等流变学性质,系统研究了该混合体系的流变行为,同时表征了羟乙基纤维素和γ-聚谷氨酸混合体系的微观结构。实验结果表明,固定HEC和γ-PGA总质量分数为1.2%的条件下,HEC和γ-PGA以不同的质量比混合后都有协同增黏的效果,HEC和γ-PGA质量比为2∶1时的协同增黏效果最明显。单一HEC体系、单一γ-PGA体系和HEC/γ-PGA混合体系均为剪切变稀的流体,其流动曲线可用Cross本构方程进行拟合,相关相关系数（R）均大于0.999。对比单一的HEC和γ-PGA体系,HEC/γ-PGA混合体系的线性黏弹区范围增加,即HEC/γ-PGA混合体系整体抗应变能力增强。在频率扫描中,HEC和γ-PGA混合后弹性模量（G'）和黏性模量（G''）的交点向低频方向移动,说明混合体系比单一体系的弹性更加显著。同时,随着温度的升高,单一HEC和γ-PGA体系、HEC/γ-PGA混合体系的表观黏度都呈现不同程度下降,它们的黏温曲线都可以用Arrhenius方程较好地拟合,相关系数都大于0.996。且HEC/γ-PGA混合体系在温度低于45 ℃时混合体系以弹性特征为主,混合体系在温度高于45 ℃时黏性特征占主体。此外,通过微观结构观察可以发现HEC和γ-PGA混合后高分子聚合物的物理缠结和三维网络结构的加强。 The rheological properties of the mixed system of hydroxyethyl cellulose （HEC） and γ-polyglutamic acid （γ-PGA） were systematically studied by investigating the apparent viscosity, flow curves, viscoelasticity, viscosity-temperature curves and other rheological properties. The microstructure of the mixed system of HEC and γ-PGA was also characterized. The experimental results showed that HEC and γ-PGA had synergistic effect of increasing viscosity at different mass ratios when the total mass fraction of HEC and γ-PGA was 1.2%, in which the synergistic effect of increasing viscosity was most obvious when the mass ratio of HEC/γ-PGA was 2∶1. Single HEC system, single γ-PGA system and mixed HEC/γ-PGA system were all shear thinning fluids, and their flow curves could be well fitted by Cross equation, and the correlation coefficients （R） were all greater than 0.999. Compared with the single systems of HEC and γ-PGA, the range of linear viscoelastic region of the mixed HEC/γ-PGA system increased, i.e., the overall strain resistance of the mixed HEC/γ-PGA system was enhanced. In frequency scanning, the intersection of elastic modulus （G'） and viscous modulus （G''） of HEC and γ-PGA mixtures moved to the low frequency direction, indicating that the mixed system was more elastic than the single system. Meanwhile, with the increase of temperature, the apparent viscosities of single HEC, single γ-PGA and mixed HEC/γ-PGA systems were decreased to varying extent. The viscosity-temperature curves of these systems could be well fitted by the Arrhenius equation, and the correlation coefficients were greater than 0.996. For the mixed HEC/γ-PGA system, the elastic feature was dominant when the temperature was lower than 45 ℃, while the viscous feature was dominant when the temperature was higher than 45 ℃. In addition, the physical entanglement and three-dimensional network structure were strengthened after mixing HEC and γ-PGA, as shown in microstructure observation. 数据和表 | 参考文献 | 相关文章 | 计量指标

科技讲座

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天然生物质材料的制备、性质与应用（Ⅵ）——可直可支的植物储能多糖：淀粉 Preparation, properties and applications of natural biomass materials （Ⅵ） Straight or branched energy storage polysaccharide from plants: starch 王长运,郝旸,樊建茹,唐文俊,徐桂云,范金石 2022 (6):  585-593.  doi: 10.3969/j.issn.1001-1803.2022.06.002 摘要 ( 298 )   HTML ( 28 )   PDF(1415KB) ( 364 )   淀粉是自然界中的植物储能多糖,由两种分子结构的高分子——直链淀粉和支链淀粉组成,具有天然无毒、可再生、来源广泛、可生物降解等特点,已广泛应用于食品、医药、造纸、化妆品等不同行业领域。但天然原淀粉自身的结构特点和性质也在一定程度上限制了其开发和应用,物理、化学和生物技术改性可赋予淀粉更丰富的分子结构和更多样的功能性质,能极大地提高其应用性能、拓展其应用范围。本文阐述了淀粉的结构、来源以及理化性质、生产方法、改性手段和近期的应用进展情况,并展望了淀粉未来的研究开发方向。 Starch is the plant energy storage polysaccharide in nature, usually occurring as granules. A starch from a specific plant source is unique among starches, i.e., starch granules from the various plant sources differ in appearance, particle size distribution, fine structure of the constituent polymer molecules and physical properties. Granular starch is generally composed of two types of molecules, amylose and amylopectin. Amylose is a predominantly linear （1,4）-α-D-glucan, although some amylose molecules are slightly branched. Amylopectin has a branch-on-branch structure consisting of mostly short chains of （1,4）-linked α-D-glucopyranosyl units linked to other short, linear chains via α-（1,6） branch points. The amylopectin fraction is composed of much larger molecules than those of amylose. Different molecular structures and size, amylose/amylopectin ratios, and granular architectures give each type of starch its unique properties. Due to the special characteristics of native non-toxicity, renewability, broad sources and biodegradability, starch has been widely used in food, medicine, papermaking industry, cosmetics, etc. Furthermore, after physical, chemical and biological modification, starch can be endowed with more diverse molecular structure and more abundant functional properties, which may greatly improve its applied properties and extend its application fields. Herein, the structure, source, physical and chemical properties, typical production methods, main modification methods and recent application advance of starch are introduced, and the research trend and development prospect of starch in the future are also pointed out. 数据和表 | 参考文献 | 相关文章 | 计量指标

开发与应用

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脱氢枞氧基聚氧乙烯缩水甘油醚接枝羟乙基壳聚糖制备及其表面活性 Preparation and surface-active properties of dehydroabietyl polyoxyethylene glycidyl ether grafted hydroxyethyl chitosan 黄旭娟,王婷,丁正青,杨欣欣,蔡照胜,商士斌 2022 (6):  594-600.  doi: 10.3969/j.issn.1001-1803.2022.06.003 摘要 ( 196 )   HTML ( 20 )   PDF(1339KB) ( 164 )   脱氢枞醇聚氧乙烯（5）醚（DA（EO） 5H）在BF3·乙醚催化下与环氧氯丙烷缩合后,再在NaOH存在下使生成的缩合产物进行分子内脱氯化氢,得到脱氢枞氧基聚氧乙烯（5）缩水甘油醚（DA（EO） 5GE）;然后通过DA（EO） 5GE与水溶性羟乙基壳聚糖（HECTS）间的亲核加成反应,得到以氢化菲环为主要亲油基、HECTS为主要亲水基和聚氧乙烯链为辅助亲水亲油结构的高分子表面活性剂DA（EO） 5GE接枝HECTS（DA（EO） 5GE-g-HECTS）。用FT-IR、1H NMR和UV-Vis表征了接枝产物结构,元素分析法测定了其接枝度（DG）,表面张力法和乳液稳定时间法分别研究了产物的表面活性和乳化能力。结果表明：利用不同原料比,可以制备得到具有不同接枝度的DA（EO） 5GE-g-HECTS。当DA（EO） 5GE-g-HECTS的DG从12.98 %增加至31.73%时,其临界胶束浓度（cmc）从0.378 g/L降至0.249 g/L,对液体石蜡-水乳液的乳化能力呈现先增强后减弱的趋势;以1.0 g/L的DA（EO） 5GE-g-HECTS4（DG为28.33%）水溶液与等体积液体石蜡形成的乳液,其稳定时间为565 s,优于TX-10为稳定剂时的165 s。 Dehydroabietol polyoxyethylene（5） ether （DA（EO）5H） was condensated with epichlorohydrin in the presence of boron fluoride diethyl etherate firstly. Then, dehydroabietyl polyoxyethylene glycidyl ether （DA（EO） 5GE） was obtained through dehydrochlorination of the condensation product in the presence of NaOH. Finally, DA（EO） 5GE grafted hydroxyethyl chitosan （DA（EO） 5GE-g-HECTS）, a polymeric surfactant with hydrogenate phenanthrene ring as main lipophilic group, sugar chain of hydroxyethyl chitosan （HECTS） as main hydrophilic group, and polyoxyethylene chain as assist lipophilic-hydrophilic structure, was prepared through the grafting modification of DA（EO） 5GE to water-soluble HECTS. The structure of the grafted product was characterized by Fourier transform infrared （FT-IR）, 1H nuclear magnetic resonance 1H NMR and UV-Vis spectrophotometry. The grafting degree （DG） of products were characterized using elemental analysis, and their surface-active activities and emulsifying capacity were investigated using surface tension method and emulsion stabilization time method, respectively. The result show that the DA （EO） 5GE-g-HECTS with different DG can be prepared by using different raw material ratio. When the DG of DA（EO） 5GE-g-HECTS increases from 12.98% to 31.73%, the critical micelle concentration （cmc） decreases from 0.378 g/L to 0.249 g/L. The emulsions are prepared by blending 50% （φ/%） liquid paraffin and 50% （φ/%） DA（EO） 5GE-g-HECTS aqueous suspensions. The emulsifying capacity of DA（EO） 5GE-g-HECTS increases at first and then decreases with the increasing DG. When the DA（EO）5GE-g-HECTS4 （its DG is 28.33% and the mass concentration is 1.0 g/L） is utilized as emulsifier, the stability time of emulsion composed of liquid paraffin and water is 565 s. It is better than the TX-10 emulsifier which is 165 s at the same condition. 数据和表 | 参考文献 | 相关文章 | 计量指标

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离子液体催化氯乙酸甲酯合成氯乙酸-2-庚酯的研究 Study on the synthesis of 2-heptyl chloroacetate from methyl chloroacetate by using ionic liquid as a catalyst 王萌斐,杜连智,许江辉,白东蕊,张炎,晁建平 2022 (6):  601-605.  doi: 10.3969/j.issn.1001-1803.2022.06.004 摘要 ( 205 )   HTML ( 15 )   PDF(1254KB) ( 264 )   探索了离子液体催化氯乙酸甲酯和2-庚醇的酯交换反应,制备了1-甲基-3-（丙基-3-磺酸基）咪唑对甲苯磺酸盐[MIM-PS][PTSA]、1-甲基-3-（丙基-3-磺酸基）咪唑硫酸氢盐[MIM-PS][HSO4]、1-丁基-3-甲基咪唑硫酸氢盐[BMIM]HSO4、N-甲基咪唑磷酸盐[HMIM]H2PO4四种离子液体催化剂并用于酯交换反应,通过考察产品氯乙酸-2-庚酯收率,筛选出最佳催化剂[MIM-PS][PTSA]。并用[MIM-PS][PTSA]考察了反应温度、反应时间、催化剂添加量、催化剂循环使用对合成产品收率的影响。结果表明：将氯乙酸甲酯和2-庚醇在100 ℃下,添加5% [MIM-PS][PTSA]催化剂,反应6 h,合成氯乙酸-2-庚酯,收率可达76.3%,离子液体重复使用3次,氯乙酸-2-庚酯收率仍大于初次收率的95%。本实验用离子液体做溶剂或催化剂,反应条件稳定,可循环利用、对环境友好,且产品收率高,为工艺放大提供实验条件参考。 2-Heptyl chloroacetate is an important intermediate for synthesizing new pesticides and herbicides. Conventional esterification reactions often use traditional strong acids, which is harmful to equipment and shows low product yield. Using ionic liquids as solvents or catalysts can make the reaction conditions stable, recyclable and environment-friendly, and lead to high product yield. Herein, the transesterification reaction between methyl chloroacetate and 2-heptanol was studied. Four ionic liquid catalysts were synthesized, including 1-methyl-3-（propyl-3-sulfonic acid） imidazole p-toluenesulfonic acid salt [MIM-PS][PTSA], 1-butyl-3-methylimidazole hydrosulfate [BMIM] HSO4, 1-methyl-3-（propyl-3-sulfonic acid） imidazole hydrosulfate [MIM-PS][HSO4] and N-methylimidazole phosphoric acid salt [HMIM] H2PO4. These four ionic liquid catalysts were used in a transesterification reaction. According to the product yield of the transesterification reaction, the optimal catalyst [MIM-PS] [PTSA] was screened. The effects of ester-alcohol ratio, reaction temperature, reaction time, catalyst dosage and catalyst cycle were investigated in the presence of [MIM-PS][PTSA]. The results showed that, for the reaction between methyl chloroacetate and 2-heptanol, 5% [MIM-PS][PTSA] catalyst was added, the reaction temperature was 100 ℃, and the reaction time was 6 h, indicative of a yield of 76.3%. When the ionic liquid was reused for three times, the yield of 2-heptyl chloroacetate was still greater than the 95% of the initial yield. When the catalyst was more than 5% or the temperature was too high, by-products such as 2-heptene or 2-heptyl ether might be formed. When the reaction time was too long, the product might undergo substitution reaction to form corresponding ether compounds. In this work, ionic liquids were used as solvents or catalysts, and the reaction conditions were stable, recyclable and environment-friendly, and the product yield was high, which could provide reference for the conditions of process amplification. 数据和表 | 参考文献 | 相关文章 | 计量指标

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磷石膏对黄壤磷吸附性能及吸附动力学分析 Analysis of phosphorus adsorption performance and adsorption kinetics of phosphogypsum in loess soil 宣超,胡昌荣,易芸,刘飞,曹建新,潘红艳 2022 (6):  606-612.  doi: 10.3969/j.issn.1001-1803.2022.06.005 摘要 ( 157 )   HTML ( 20 )   PDF(1367KB) ( 138 )   研究了磷石膏（PG）对黄壤磷吸附能力的影响,并探讨其影响机制。以贵州省黄壤为研究对象,探索不同掺量的PG在不同培养时间等条件下对黄壤磷吸附性质的影响,并通过吸附动力学实验和数据模型拟合分析了PG对黄壤磷吸附动力学行为的影响。结果表明：PG掺量对黄壤磷吸附量影响显著（P<0.05）。磷吸附量随PG掺量增加呈先增加后降低趋势,掺量为0.5 g/100 g土时达最高值,与原土相比,磷吸附量提高2.80%,pH由3.77升至4.00,无定型氧化铁（Feo）含量上升2.33%;PG掺量分别为0.5 g/100 g土和1.0 g/100 g土的混合土样磷吸附动力学过程符合准一级方程,之后,随掺量增加混合土样磷吸附动力学过程符合准二级方程;磷石膏对黄壤磷吸附能力的影响在前7天最为显著,且磷石膏中Na2SO4、NaH2PO4和CaSO4对黄壤磷吸附能力起促进作用,NaF对黄壤磷吸附能力起抑制作用。 The effects of PG on the phosphorus adsorption capacity of loess soil and the influence mechanism therein were investigated to provide some scientific basis for the resource utilization of phosphogypsum （PG） in agriculture. The effects of different PG dosages on the phosphorus adsorption properties and the adsorption kinetics were analyzed in loess soil with different incubation time. The results showed that the dosage of PG had a significant effect on the adsorption of phosphorus in loess soil （P<0.05）. The phosphorus adsorption capacity was increased first, and then decreased with the increase of PG addition and reached the highest value at 0.5 g PG/100 g soil. Compared with the original soil, the phosphorus adsorption capacity and the content of amorphous iron oxide （Feo） were increased by 2.80% and 2.33%, respectively, and the pH was increased from 3.77 to 4.00. Moreover, the phosphorus adsorption kinetic process of the mixed soil samples fitted the pseudo-first-order kinetic models with PG content of 0.5 g/100 g soil and 1.0 g/100 g soil, and then fitted the pseudo-second-order kinetic models with the increase of PG content. However, the effect of PG on the phosphorus adsorption capacity of loess soil was most significant in the first 7 days. Na2SO4, NaH2PO4 and CaSO4 released from PG promoted the phosphorus adsorption capacity, while NaF inhibited the phosphorus adsorption capacity of loess soil. The present study shows that the phosphorus adsorption capacity of loess soil can be adjusted by PG dosage. 数据和表 | 参考文献 | 相关文章 | 计量指标

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棉织物洗涤中染料转移抑制的影响因素研究 Study on the influencing factors of dye transfer inhibition in cotton fabric washing 孟明珠,张真真,梁帅童,张红娟,王际平 2022 (6):  613-619.  doi: 10.3969/j.issn.1001-1803.2022.06.006 摘要 ( 215 )   HTML ( 26 )   PDF(1158KB) ( 176 )   研究了水硬度、用水量、洗涤温度和染料转移抑制剂（Dye transfer inhibitor,DTI）对直接蓝6的转移抑制影响。实验结果显示水硬度越小,用水量越大,温度越高,染料转移抑制效果越好。洗涤体系中Ca2+和Mg2+的存在不仅降低了纤维表面的Zeta电位,还降低了染料与纤维之间的静电排斥力,染料不易脱落。水量越大,染料质量浓度越低,洗涤体系中的初始动压增大,织物内的染料较快流过,减少在织物上的沉积。高温下染料分子解吸速率大于染色速率,20 min的洗涤时间足以使染料从纤维上脱落。在0.3 g/L质量浓度范围内DTI中仅有聚乙烯吡咯烷酮和它的交联聚合物对染料有明显的抑制作用。聚合物因具有许多亲水基团,易与染料结合。而吡啶-n-氧化物和月桂基甜菜碱属于小分子表面活性剂。 Dye transfer in household washing has always been a problem that disturbs people. Herein, the influences of four factors including water hardness, water amount, washing temperature and Dye transfer inhibitor （DTI） on the transfer inhibition of Direct Blue 6 on cotton fabrics were studied. The response surface method （RSM） models of the 4 factors were built. All the RSM models show that water hardness is the most significant negative factor. Based on the DLVO theory, due to the presence of Ca2+ and Mg2+, the increase of water hardness can not only reduce the zeta potential of the fabric surface, but also cause the decrease of electrostatic repulsion between Direct Blue 6 and the fabric, and thus the dye won’t go off the fabric easily, that is, the dye is more likely to be adsorbed on the surface of the fabric. The increase of water amount can enhance the dye transfer inhibition effect. When the water amount increases, the initial mass concentration of dye is decreased, and the initial dynamic pressure of washing is increased, so that the dye flows through the fabric rapidly and the deposition on the fabric is reduced. The washing temperature also has a positive effect. When the washing temperature increases, the movement speed of dye molecules is increased, and the desorption rate is greater than the dyeing rate, so the dye molecules can shed from the fiber. Within the mass concentration range of 0.3 g/L DTI, only polyvinylpyrrolidone （PVP） and its cross-linked polymer have obvious inhibition effects on dye. Polymers have many hydrophilic groups and are easy to bind with direct dyes. However, pyridine-n-oxide （PNO） and lauryl betaine are small-molecule surfactants. Their structural differences make the RSM model show that polymers have better effects. The results of quantum chemical calculation also prove that the interactions between polymers and Direct Blue 6 are greater than the interactions between PNO and Direct Blue 6 or between lauryl betaine and Direct Blue 6. In addition, there is interplay between different washing factors. This work provides necessary basic information for the optimization of washing process for cotton fabrics and the modification of DTI. 数据和表 | 参考文献 | 相关文章 | 计量指标

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甘草次酸对金黄地鼠皮脂腺斑影响的实验研究 Experimental study on the effect of glycyrrhetinic acid on sebaceous gland of golden hamsters 何益飞,鲁旺旺,马诗经,刘冠廷,王梦萍,杜志云 2022 (6):  620-625.  doi: 10.3969/j.issn.1001-1803.2022.06.007 摘要 ( 242 )   HTML ( 20 )   PDF(1042KB) ( 182 )   以甘草次酸为活性成分,通过3T3-L1脂肪前体细胞模型测试不同质量浓度的甘草次酸对3T3-L1增殖及分泌甘油三酯（Triglyceride,TG）成分的影响,进一步采用金黄地鼠动物模型实验测定不同剂量的甘草次酸对金黄地鼠皮脂腺斑影响,并初步分析其可能的作用机制。结果显示,在25~100 μg/mL质量浓度范围内不抑制3T3-L1细胞增殖,在质量浓度为50~100 μg/mL时具有显著抑制3T3-L1细胞分泌TG（P<0.01）并呈浓度依赖性。给予金黄地鼠药物30 d后,与空白对照组、基质组（50%丙二醇水溶液）相比,甘草次酸在设定质量浓度下显著降低金黄地鼠腹部双侧皮脂腺斑面积,减少皮脂腺厚度及数量,抑制皮脂腺生长进而减少皮脂腺分泌皮脂中的甘油三酯成分,甘草次酸在100 μg/mL质量浓度下主要通过显著调控皮脂腺组织中SREBP-1C（P<0.001）,TG（P<0.01）,K6（P<0.01）,K16（P<0.01）,IL-6（P<0.05）指标的表达,即抑制皮脂腺组织中SREBP蛋白活性,抑制皮脂合成及分泌TG成分的含量,进一步降低角质形成细胞中角蛋白K6及K16表达,发挥调控皮脂腺生长及皮脂中甘油三酯成分分泌的作用。 This experiment preliminarily confirmed that glycyrtinic acid at the mass concentration of 50-100 μg/mL could significantly inhibit the secretion of triglyceride by 3T3-L1 cells （P<0.01） in a mass concentration-dependent manner. 3T3-L1 cells, as preadipocytes, continue to increase adipocyte proliferation and triglyceride accumulation under exogenous stimulation. They differentiate into mature adipocytes and form adipose tissue. Glycyrrhetinic acid can inhibit the proliferation of preadipocytes and reduce the accumulation of triglycerides, indicating that glycyrrhetinic acid has the effect of inhibiting lipid synthesis and metabolism at the cellular level. Further, through the golden hamsters model, it is confirmed that glycyrrhetic acid at the set mass concentration significantly reduces the area of bilateral sebaceous gland on the abdomen of golden hamsters, reduces the thickness and number of sebaceous glands, inhibites the growth of sebaceous glands and thus reduces the abnormal excessive secretion of sebaceous glands. At the mass concentration of 100 μg/mL, glycyrrhetinic acid significantly regulates the expression of SrebP-1C （P<0.001）, TG （P<0.01）, K6 （P<0.01）, K16 （P<0.01） and IL-6 （P<0.05） in sebaceous glands. It inhibits the SREBP protein activity in sebaceous gland tissue, inhibits sebum synthesis and secretion of triglyceride composition content, and further reduces the cutin formation and keratin K6, K16 expression in cells, which play a role in regulating sebaceous gland growth and oil secretion. Abnormal sebum secretion from sebaceous glands can induce skin health problems such as acne, skin barrier dysfunction and specific dermatitis. Through the above experimental studies, it has been preliminarily confirmed that the single use of glycyrrhetinic acid can effectively inhibit the growth of sebaceous gland spots in golden hamsters and reduce sebum secretion and inflammatory reaction. These results suggest that glycyrrhetinic acid may play a role in regulating oily skin, inhibiting acne, improving skin barrier function and specific dermatitis, and can be used as an active ingredient in skin surgery drugs and functional daily cosmetics that relieve acne and skin inflammation. 数据和表 | 参考文献 | 相关文章 | 计量指标

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驴油提升皮肤屏障功能及潜在作用机制研究 The effect of donkey oil on the improvement of skin barrier function and its potential mechanism 樊雨梅,帖航,赵海晴,苏宁,廖峰 2022 (6):  626-631.  doi: 10.3969/j.issn.1001-1803.2022.06.008 摘要 ( 503 )   HTML ( 23 )   PDF(1153KB) ( 181 )   探讨驴油提升皮肤屏障功能的作用及其可能的作用机制。将十二烷基硫酸钠作用于体外重组三维表皮模型（EpiKutis）构建皮肤屏障损伤模型,采用四唑盐比色法（MTT）检测组织活力,利用酶联免疫吸附检测方法（ELISA）检测IL-1α的水平,考察驴油对人3D皮肤屏障损伤模型的屏障指数和IL-1α水平的影响。采用转录组高通量测序（RNA-seq）技术揭示驴油对皮肤生理的机制,并揭示驴油提升皮肤屏障功能的可能机制。结果表明,驴油可显著提升人3D皮肤屏障损伤模型的屏障指数和降低IL-1α水平,效果与地塞米松类似。驴油作用于人3D皮肤模型后,筛选出1 649个差异表达基因,其中619个基因上调,1 030个基因下调。基因本体论（Gene Ontology,GO）功能富集分析表明差异表达基因与表皮发育、表皮细胞分化及皮肤发育有关;京都基因与基因组百科全书（kyoto encyclopedia of genes and genomes,KEGG）通路富集分析结果表明差异基因参与TGF-β信号通路、IL-17信号通路、HIF-1信号通路、细胞因子-细胞因子受体相互作用、NF-κB信号通路等重要生物学通路,其中与驴油提升皮肤屏障功能有关的通路可能是TGF-β信号通路、HIF-1信号通路和NF-κB信号通路。 The aim of the study was to explore the effect of donkey oil in enhancing the skin barrier function and its possible mechanism. Sodium lauryl sulfate was applied to the three-dimensional epidermal model （EpiKutis） to construct the skin barrier damage model, the tissue activity was detected by the MTT method and the level of IL-1α by the ELISA method. It was used to study the effect of the donkey oil on the barrier index and IL-1α level of the SLS-induced EpiKutis. RNA-seq technology was used to explain the physiological mechanism of donkey oil on the skin, and to reveal the possible mechanism of donkey oil to enhance the skin barrier function. The results show that donkey oil can significantly increase the barrier index of the SLS- EpiKutis model and reduce the level of IL-1α, and the effect is similar to that of dexamethasone. After the donkey oil acting on the EpiKutis model, 1 649 differentially expressed genes are screened, of which 619 genes are up-regulated and 1 030 genes are down-regulated. GO functional enrichment analysis shows that differentially expressed genes are related to epidermal development, epidermal cell differentiation and skin development. KEGG pathway enrichment analysis results show that differential genes are involved in TGF-β signaling pathway, IL-17 signaling pathway, HIF-1 signaling pathway, and cell factor-cytokine receptor interaction, NF-κB signaling pathway and other important biological pathways. The pathways related to donkey oil enhancing the skin barrier function may be TGF-β signaling pathway, HIF-1 signaling pathway and NF-κB signaling pathway. 数据和表 | 参考文献 | 相关文章 | 计量指标

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烟酰胺与茶多酚复配对抑制PIG1细胞黑色素的影响 Effects of nicotinamide mixed with tea polyphenols on inhibiting melanin in PIG1 cells 方婷欢,蒋晴,唐礼荣 2022 (6):  632-637.  doi: 10.3969/j.issn.1001-1803.2022.06.009 摘要 ( 615 )   HTML ( 47 )   PDF(1292KB) ( 238 )   研究了烟酰胺及其与茶多酚复配组分对黑色素生物合成及转运机制的作用,以促黑素细胞激素（α-MSH）诱导黑色素高表达的正常人皮肤黑色素细胞（PIG1细胞）为研究模型,通过NaOH裂解比色法测定PIG1细胞黑色素含量,多巴氧化比色法测定PIG1细胞内酪氨酸酶活性,免疫印迹法（Western blot）检测PIG1细胞内调节黑色素生物合成及转运关键受体酪氨酸酶相关蛋白1（TRP-1）、酪氨酸酶相关蛋白2（TRP-2）、黑皮质素受体1（MC1R）及Rab27a蛋白表达情况。结果表明,当2 g/L烟酰胺+0.5 g/L茶多酚、3 g/L烟酰胺+0.3 g/L茶多酚、3 g/L烟酰胺+0.5 g/L茶多酚复配组合时,对α-MSH诱导黑色素高表达的PIG1细胞中黑色素含量、细胞内酪氨酸酶活性、TRP-1、TRP-2、MC1R及Rab27a蛋白均存在极显著的抑制作用,并强于5 g/L烟酰胺,而当烟酰胺质量浓度为2 g/L时仅对细胞内酪氨酸酶活性存在抑制作用,即复配组合具有更显著的抑制PIG1细胞中黑色素生物合成及转移的作用。 The aim was to study and compare the effects of nicotinamide and its complexes with tea polyphenols on melanin biosynthesis and transport mechanism. Taking human skin melanocytes PIG1 cell line with high melanin expression induced by melanocyte-stimulating hormone （α-MSH） as the model, the effects of nicotinamide and its complexes matching with tea polyphenols on melanin content, intracellular tyrosinase activity and the key receptors in melanin biosynthesis and transport pathway were determined via western blot and colorimetric method with NaOH and L-DOPA. The results show that 2 g/L nicotinamide+0.5 g/L tea polyphenols, 3 g/L nicotinamide+0.3 mg/L tea polyphenols, 3 g/L nicotinamide+0.5 g/L tea polyphenols complexes show significantly inhibitory effects on melanin content, intracellular tyrosinase activity, the expression of tyrosinase-related protein-1 （TRP-1）, tyrosinase-related protein-2 （TRP-2）, melanocyte melanin cortisol receptor （MC1R） and human epidermal melanocyte transport-related proteins （Rab27a） protein in α-MSH-induced high melanin expression human PIG1 cell lines, which are stronger than that of 5 g/L nicotinamide. While 2 g/L nicotinamide only has the effects of suppressing intracellular tyrosinase activity. The combination of nicotinamide and tea polyphenols had more obvious effect to suppress the melanin biosynthesis and transport pathway in PIG1 cell lines. 数据和表 | 参考文献 | 相关文章 | 计量指标

专论与综述

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欧盟RAPEX系统通报情况分析及对我国化妆品原料管理的启示 Information bulletin analysis of EU RAPEX system and enlightenment to cosmetic ingredient management in China 黄湘鹭,卢家灿,邢书霞,孙磊 2022 (6):  638-644.  doi: 10.3969/j.issn.1001-1803.2022.06.010 摘要 ( 248 )   HTML ( 17 )   PDF(972KB) ( 192 )   分析欧盟非食品类消费产品快速预警系统（RAPEX系统）通报的化妆品情况,对具有化学风险的产品进行重点分析,为制定与完善中国化妆品原料管理措施提供参考。汇总2005年至2021年欧盟RAPEX系统通报的化妆品情况,对违规情况进行归类分析。2005年2月至2021年5月,REPEX系统共通报具有化学风险的化妆品364件,涉及违规物质92种,需要引起重视的物质包括美白剂、防腐剂、致敏性香精香料、染发剂、着色剂、重金属和药物成分。建议针对氢醌、甲基氯异噻唑啉酮和甲基异噻唑啉酮与氯化镁及硝酸镁的混合物、汞,加强相关产品上市后监管力度;加强或明确曲酸、致敏性香精香料、比马前列素等原料管理要求;加大防腐剂和染发剂规范使用的培训力度,对于甲基氯异噻唑啉酮和甲基异噻唑啉酮与氯化镁及硝酸镁的混合物和甲基异噻唑啉酮等行业使用较多且易发生违规行为的原料,制定相应原料技术标准;针对重金属原料（如镍、锆、锑、铬、钴等）开展风险监测,必要时制定管理措施;建议在新原料注册备案中予以关注着色剂CI 45161、CI 45174和溶剂黄172;参考欧盟灵活通报和处置机制,对具有安全风险的原料及时采取控制措施。 The aim was to analyze the cosmetic information bulletin of EU RAPEX, focusing on the analysis of products with chemical risks, and to provide reference for cosmetic ingredient management. The data from EU RAPEX system in 2005-2021 were summarized. The violations of the products were analyzed. According to the illegal substance, product type, country of origin and reason of violation, the notified results were analyzed statistically. Comparative analysis was made on the management of the notified substances according to the relevant information in European Union and China cosmetics ingredient management. At the same time, according to the whitening agent, preservative, flavor and fragrance, hair colorant, colorant, heavy metal, drug composition and other different categories of in-depth interpretation, its enlightenment was explored to the management of cosmetics raw materials in China. From February 2005 to May 2017, the REPEX system notifies 364 cosmetic products with chemical risk, involving 92 substances with violations. The most frequently reported violation is the addition of hydroquinone for skin-lightening products. Perfume is the most frequently reported product type. The main reason for violation is not as requiring to mark allergenic flavor fragrance. The most frequently reported country of origin is China, mainly because China does not have formulated management requirements for allergenic flavor fragrances, which leads to the labeling of flavor fragrances in China’s exported cosmetics does not meet the relevant requirements of the EU. The most frequently reported reasons for product violations are the detection or illegal addition of banned ingredients. Substances that need attention include whitening agents, preservatives, allergenic fragrances, hair colorants, colorants, heavy metal and pharmaceutical ingredients. Stronger post-marketing regulation of the related products is recommended for hydroquinone, Kathon and mercury. Strengthening or clarifying the requirements for raw material management such as kojic acid, allergenic flavor fragrances, and bimatoprost are needed. Increased training in the regulated use of preservatives and hair dyes should be implemented to establish technical standards for ingredients used in industries such as carbamazone and methylisothiazolinone that are more expensive and prone to violations. Risk monitoring is carried out for heavy metal starting materials （e.g., nickel, zirconium, antimony, chromium, cobalt, etc.）, and management measures are in place if necessary. Special attention should be paid to colorants CI 45161, CI 45174 and solvent yellow 172 in the new cosmetic ingredient registration filing work. With reference to the EU flexible notification and disposal mechanism, timely control measures should be taken on cosmetic ingredients with safety risks. 数据和表 | 参考文献 | 相关文章 | 计量指标

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代谢工程改造酵母生产香料的研究进展 Research progress in yeast metabolic engineering to produce natural product flavors 张永涛,赵净沙,蒋雁冰,赵丹,王昌涛,李萌 2022 (6):  645-655.  doi: 10.3969/j.issn.1001-1803.2022.06.011 摘要 ( 333 )   HTML ( 16 )   PDF(1185KB) ( 242 )   天然产物香料作为食品、药品和日用化学品的添加成分,市场需求高,有着较高的开发利用价值。从动植物中提取香料产物存在来源少、含量低和分离困难等缺点,化学合成香料又存在着安全隐患和污染问题,很难满足市场需求。因此,研究与开发生产天然产物香料的微生物来补充或代替原有的传统提取和化学合成方法具有重要的理论意义和潜在的应用价值。酵母菌作为代谢工程菌株的一类,细胞内具有更好表达异源蛋白的细胞结构和翻译后修饰机制。文章总结了有关对酵母菌进行代谢改造生产萜类、芳香族类及脂肪族类香料化合物的具体实例和研究进展,包括所涉及的宿主菌株、关键酶、代谢途径、改造策略以及发酵条件优化等,并在最后讨论了酵母代谢工程改造生产天然产物香料目前所面临的问题和未来的发展方向。 Natural product flavors, as additives for food, medicine and daily chemicals, have high market demand and have high development and utilization value. The extraction of fragrance products from animals and plants has the disadvantages of few sources, low content and difficulty in separation. Chemically synthesized fragrances also have potential safety hazards and pollution problems, and it is difficult to meet market demand. Therefore, the research and development of microorganisms that produce natural product fragrances to supplement or replace the original traditional extraction and chemical synthesis methods has important theoretical significance and potential application value. This article mainly summarizes the specific examples and research progress related to the metabolic modification of yeasts to produce terpenoids, aromatics and aliphatic fragrance compounds, including the host strains involved, key enzymes, metabolic pathways, modification strategies, and optimization of fermentation conditions. Yeasts, as a class of metabolically engineered strains, have a cell structure and a post-translational modification mechanism for expressing heterologous proteins that other microorganisms do not possess. Therefore, compared with other microorganisms, yeast can better express heterologous proteins and has greater potential as a chassis cell for the production of natural products. This article systematically summarizes the specific examples and research progress of yeast metabolic transformation to produce terpenoids, aromatics and aliphatic spices. It is found that the competition pathway and negative feedback regulation of the target product metabolism pathway, the tolerance of the chassis cells to the target product, the supply of the target product precursor compound and the difference in the selection of the substrate by the enzyme in the synthesis pathway are the biggest problems that limit the output of the product. Furthermore, relevant suggestions and prospects are put forward for the bottleneck problems faced by the use of metabolic engineering to transform microorganisms to synthesize natural product fragrance products, aiming to provide a reference for constructing chassis yeast cells for efficient production of fragrance products. 数据和表 | 参考文献 | 相关文章 | 计量指标

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洁面产品用表面活性剂的分类及应用 Classification and application of surfactants in cleansing products 杨秀芬 2022 (6):  656-663.  doi: 10.3969/j.issn.1001-1803.2022.06.012 摘要 ( 948 )   HTML ( 44 )   PDF(1047KB) ( 631 )   表面活性剂在洁面产品中可起到乳化、发泡、去污、增稠等作用,用量一般为10%~15%,是洁面产品的重要原料,对洁面产品的清洁力、温和性及肤感体验等性能影响至关重要,因而备受关注。为适应洁面产品的发展趋势,表面活性剂的应用也逐步从过去单一化学属性趋向性能多样、绿色环保方向发展。本文将以洁面产品用表面活性剂分类与应用为研究基点,对不同类型表面活性剂的发展现状及其性能应用进行阐释分析,并对其发展进化过程中存在的瓶颈问题及应用挑战进行总结,对未来发展趋势进行展望,以期为洁面产品的高质量发展提供有效参考。 Surfactants can play the roles of emulsification, foaming, detergency and thickening in cleansing products. Their dosages are usually 10%-15%. Surfactants are important raw materials of facial cleaning products, which have important influences on the performance of cleansing products, such as cleanliness, mildness and skin feeling experience. To adapt to the development trend of facial cleaning products, the application of surfactants has gradually changed from single chemical properties to diverse properties and greenness and environmental protection. Herein, based on the classification and application of surfactants for facial cleaning products, the development status, performance and application of different types of surfactants were explained and analyzed. Furthermore, the bottleneck problems and application challenges in the process of their development and evolution were summarized. Finally, the future development trend was prospected. This review might provide effective reference for the high-quality development of cleansing products. 数据和表 | 参考文献 | 相关文章 | 计量指标

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LSPR金属催化醇氧化制备醛类与酯类化合物的研究进展及其在日化领域的应用 Advances of LSPR metal-catalyzed oxidation of alcohols to aldehydes and esters and their application in daily chemical field 王晓宇,高晓星,王瑞义,牛宇岚 2022 (6):  664-671.  doi: 10.3969/j.issn.1001-1803.2022.06.013 摘要 ( 251 )   HTML ( 12 )   PDF(1103KB) ( 143 )   醛类化合物与酯类化合物由于普遍具有杀菌、防腐以及持久香气的特点,广泛被用作日用化学品当中的添加剂使用。而醛类与酯类化合物通过醇的选择性氧化可实现低毒、绿色、无污染的合成路径。其中LSPR金属基催化剂作为醇氧化反应的优良催化剂被广泛使用。本文对LSPR金属催化醇氧化制备醛类与酯类化合物的催化机理及其催化反应的发展趋势以及在日化领域的应用进行综述,其中以Au,Ag,Cu 3种LSPR金属作活性中心,对于醇的氧化反应具有较高的催化活性,且所制备的产物醛与酯均具备选择性高的特点,使其更加有利于二者在日用化学品当中的应用。此外,从此3种金属的LSPR效应出发,对LSPR金属在光照条件下的催化机理以及光催化醇选择性氧化反应的应用进展进行综述,基于LSPR金属表面在光照下可以产生大量热电子的理论,其在醇氧化制备醛与酯的反应中,不仅可以使反应在更加温和的条件下进行,产物的选择性还可得到进一步提升。 Aldehydes and esters have been widely used as additives in daily chemicals due to the characteristics of sterilization, antisepsis and long-lasting aroma. The selective oxidation of alcohols to aldehydes and esters can achieve low-toxic, green and pollution-free synthetic routes. The LSPR metal catalysts are widely used as excellent catalysts for the oxidation of alcohols. Herein, the catalytic mechanism of LSPR metal-catalyzed oxidation of alcohols to aldehydes and esters are summarized, as well as the applications in the field of daily chemicals. The LSPR metals of Au, Ag and Cu are used as the active centers, which display high catalytic activity for the oxidation of alcohols, and the high selectivity to aldehydes and esters can also be obtained. In addition, the catalytic mechanism of LSPR metals under light conditions and the advances of photocatalytic selective oxidation of alcohols are reviewed based on the LSPR effects of the three metals, which can generate a large number of hot electrons on the surface of metals under light conditions. The oxidation of alcohols to aldehydes and esters can be promoted by the hot electrons. Besides, the reaction not only can be carried out under milder conditions, but also be more selective to the aldehydes and esters. In addition, the application of aldehydes and esters in daily chemical field are summarized. It is found that the aldehydes and esters prepared by the oxidation of alcohols as catalyzed by LSPR metals can achieve comparatively practical value in daily chemical field. 数据和表 | 参考文献 | 相关文章 | 计量指标

分析与检测

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织物洗涤剂除菌性能的测试评价方法 An evaluation method for sterilization performance of fabric detergents 杨洁,姚晨之,严方,王杰,李晓婷 2022 (6):  672-676.  doi: 10.3969/j.issn.1001-1803.2022.06.014 摘要 ( 193 )   HTML ( 14 )   PDF(984KB) ( 150 )   以金黄色葡萄球菌作为试验菌,3 cm×3 cm的JB-00棉布作为染菌载体,8种市售织物洗涤剂作为待测试样,使用无菌硬水将待测试样于广口瓶中稀释至作用浓度后,向每个广口瓶中加入3片染菌载体后置于200 r/min磁力搅拌下洗涤20 min,再换水漂洗2次,每次5 min,以模拟织物实际的洗涤过程,最后通过平板计数法计算不同产品的除菌率。结果表明,试样A,G,H的除菌率在95%以上,试样B的除菌率在80%以上,试样C和E的除菌率在60%以上,试样D的除菌率在30%以上,试样F的除菌率在30%以下。可见,使用该方法对不同试样的除菌性能具有较好的区分度（P<0.05）;使用该方法评价除菌性能的稳定性与试样除菌率的高低有关,对于除菌效果好的试样A,G,H的除菌率的稳定性也较高。因此,该方法可作为织物洗涤剂除菌性能的测试评价方法。 Staphylococcus aureus was used as the test bacteria, and the 3 cm×3 cm JB-00 cotton cloth was used as the carrier. The staining carrier was prepared by inoculating 20 μL of the test bacteria suspension on each piece of cotton cloth by the 5-point method. 8 kinds of commercially available fabric detergents were used as the samples to be tested. Sterile hard water was used as the diluent to dilute the sample to be tested in a wide-mouth bottle to an effective concentration. 3 pieces of staining carrier were added to each wide-mouth bottle and washed for 20 minutes with magnetic stirring at 200 r/min, and then the water was changed and they were rinsed for 2 times and 5 min each time, which simulated the actual washing process of the fabric. Finally, the sterilization rate of different products was calculated by the plate counting method. The results show that the sterilization rate of samples A, G and H is above 95%, the sterilization rate of sample B is above 80%, the sterilization rate of samples C and E is above 60%, the sterilization rate of sample D is above 30%, and the sterilization rate of sample F is below 30%. This method can effectively distinguish the sterilization performance of different samples （P<0.05）; The stability of sterilization performance evaluated by this method is related to the level of the sterilization rate of the sample. For samples A, G and H that have good sterilization effects, the stability of sterilization rate is also high, while for samples D and F that have poor sterilization effects, the stability of sterilization rate is also low. Therefore, this method can be used as an evaluation method for the sterilization performance of fabric detergents. 数据和表 | 参考文献 | 相关文章 | 计量指标

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高效液相色谱-串联质谱法快速测定护肤透明质酸中抗菌药物 Rapid determination of antibacterial agents in skin care hyaluronic acid by high performance liquid chromatography-tandem mass spectrometry 张君芳 2022 (6):  677-682.  doi: 10.3969/j.issn.1001-1803.2022.06.015 摘要 ( 260 )   HTML ( 13 )   PDF(1272KB) ( 289 )   建立护肤透明质酸中抗生素类和硝基咪唑类两大类抗菌药物的高效液相色谱-串联质谱快速测定方法。分别选取两类抗菌药物各10种试剂,通过涡旋振荡、超声提取以及离心处理和过滤后,制备了两类抗菌药物的混合溶液。经色谱柱分离,梯度洗脱下通过正离子模式电喷雾电离,多反应监测模式检测。测定结果表明：两种抗菌药物的溶液样本中,各自含有的10种化合物成分的总离子均在不同时间下发生分离,并产生相应的响应值,呈现较好的线性关联,相关系数分别在0.997和0.996以上。两种抗菌药物的检出限、定量限分别为1.6,6 mg/kg和0.9~201,5~401 mg/kg。该方法准确、高效,适用于护肤透明质酸中抗生素类和硝基咪唑类抗菌药物的快速测定。 The aim was to establish a rapid method for the determination of antibiotics and nitroimidazoles in skin care hyaluronic acid by high performance liquid chromatography tandem mass spectrometry. Ten reagents for each of the two kinds of antibiotics were selected. After vortex oscillation, ultrasonic extraction, centrifugation and filtration, the mixed solution samples of the two kinds of antibiotics were prepared. They were separated by chromatographic column, ionized by electrospray ionization in positive ion mode and detected by multiple reaction monitoring mode under gradient elution. The results show that the total ions of 10 compounds contained in the solution samples of the two antibiotics have separation reactions at different times and produce corresponding response values, showing a good linear correlation. The correlation coefficient results are 0.997 and above 0.996, respectively. The detection limits and quantitative limits of the two antibiotics are 1.6, 6 mg/kg, 0.9-201 mg/kg and 5-401 mg/kg, respectively. The method can accurately and efficiently complete the rapid determination of antibiotics and nitroimidazoles in skin care hyaluronic acid. 数据和表 | 参考文献 | 相关文章 | 计量指标

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微波法制备乳酸碳量子点及荧光猝灭法测定对硝基苯胺 Microwave-assisted preparation of lactic acid carbon quantum dots and determination of p-nitroaniline with fluorescence quenching 魏增云 2022 (6):  683-688.  doi: 10.3969/j.issn.1001-1803.2022.06.016 摘要 ( 160 )   HTML ( 14 )   PDF(1248KB) ( 140 )   以乳酸为碳前驱体,聚乙二醇为表面修饰剂,经一步微波法制备了碳量子点（CDs）,并用透射电子显微镜、荧光及紫外初步考察了该量子点的结构与性质。研究了12种物质分子对量子点荧光猝灭效应,建立了对硝基苯胺猝灭CDs荧光分析新方法,浓度范围在6×10-6~1×10-4 mol/L范围内呈良好线性关系,检出限为8.76×10-6 mol/L。应用于染发膏中对硝基苯胺的检测,3种染发膏中均含有对硝基苯胺,分别为栗棕89.7 mg/g,枣红129.2 mg/g,亚麻44.4 mg/g。 Carbon quantum dots （CDs） were prepared by one-step microwave method using lactic acid as carbon precursor and polyethylene glycol as a surface modifier. The structure and properties of the CDs were investigated by transmission electron microscopy, fluorescence and ultraviolet. The fluorescence quenching effect of 12 kinds of molecules to the quantum dots was studied. A new method for fluorescence analysis of p-nitroaniline quenching CDs is established. The linear relationship is good in the concentration range of 6×10-6-1×10-4 mol/L, and the limit of detection is 8.76×10-6 mol/L. The test for p-nitroaniline in hair dye pastes reveals that p-nitroaniline is contained in the three hair dyeing creams, which are 89.7 mg/g in chestnut brown, 129.2 mg/g in purplish red and 44.4 mg/g in flaxen. 数据和表 | 参考文献 | 相关文章 | 计量指标