羧甲基纳米纤维素稳定的低油相Pickering乳液凝胶的制备及性质分析

崔颂; 张月; 刘超然; 王一凡; 代蕾

doi:10.13386/j.issn1002-0306.2022070180

羧甲基纳米纤维素稳定的低油相Pickering乳液凝胶的制备及性质分析

doi: 10.13386/j.issn1002-0306.2022070180

青岛农业大学食品科学与工程学院，山东青岛 266109

基金项目: 山东省自然科学基金（ZR2020QC218）；青年人才托举工程（YESS20210248）。

详细信息

作者简介:
崔颂（1999−），女，硕士研究生，研究方向：食品科学与工程，E-mail：cuisong2521@163.com

通讯作者:
代蕾（1988−），女，博士，教授，研究方向：食品科学，E-mail：dailei508@163.com

中图分类号: TS201.7
计量
- 文章访问数: 18
- HTML全文浏览量: 22
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2022-07-19
- 刊出日期: 2023-05-15

Preparation and Property Analysis of Carboxymethyl Nanocellulose Stabilized Low Oil Phase Pickering Emulsion Gels

College of Food Science and Engineering, Qingdao Agricultural University, Qingdao 266109, China

摘要

摘要: 结合pH对羧甲基纳米纤维素（CMCN）的ζ-电位、接触角的影响，本文以CMCN溶液为连续相，玉米油为分散相构建低油相（20%）Pickering乳液凝胶，研究了CMCN稳定的Pickering乳液凝胶的类型、微观结构、流变学特性和不同条件下的稳定性。结果表明：从pH2到pH9，CMCN的ζ-电位从−2 mV减小到−67 mV，其中在pH4时ζ-电位绝对值相对较大且具有最接近90°的接触角，因此pH4时的CMCN更适合稳定低油相Pickering乳液凝胶。荧光显微镜和流变学结果分别证明CMCN稳定的Pickering乳液凝胶为O/W型，且在低油浓度下形成了类弹性结构（G'>G''），为假塑性流体。低油相Pickering乳液凝胶贮藏120 d后仍可保持稳定。在1.3%以上浓度85 ℃加热和pH4以上CMCN稳定的乳液凝胶无分层现象且液滴尺寸变化较小证明其具有优异的pH和热稳定性。本研究制备的低油相Pickering乳液凝胶为绿色新型食品的开发提供了一种新思路，有望解决高油乳液凝胶不利于身体健康的问题。
- 羧甲基纳米纤维素（CMCN） /
- Pickering乳液凝胶 /
- 低油 /
- 流变学 /
- 稳定性
Abstract: Combined with the effect of pH on the ζ-potential and contact angle of carboxymethyl nanocellulose (CMCN), low oil phase (20%) Pickering emulsion gels were constructed with CMCN solution as the continuous phase and corn oil as the dispersant phase. The types, microstructure, rheological properties, and stability of CMCN-stabilized Pickering emulsion gels under different conditions were studied, respectively. The results showed that the ζ-potential of CMCN decreased from −2 mV to −67 mV when pH2 to pH9, the absolute value of the ζ-potential was relatively large at pH4 and the contact angle was closest to 90°. Therefore, CMCN at pH4 was more suitable for stabilizing low-oil phase Pickering emulsion gels. Fluorescence microscopy and rheological results showed that the CMCN-stabilized Pickering emulsion gels were O/W type, and the elastic structure (G'>G'') was formed at low oil concentration, which was pseudoplastic fluid. The low oil phase Pickering emulsion gels remained stable after 120 days of storage. The emulsion gels stabilized by CMCN at a concentration above 1.3% at 85 ℃ and above pH4 had no delamination and small droplet size change, which proved that the emulsion gels had excellent pH and thermal stability. The low oil phase Pickering emulsion gels prepared in this study would provide a new idea for the development of new green food, which was expected to solve the problem that high oil emulsion gels were not conducive to health.
- carboxymethyl nanocellulose (CMCN) /
- Pickering emulsion gels /
- low oil phase /
- rheology /
- stability

HTML全文

图 1 CMCN的TEM图

Figure 1. TEM image of CMCN

下载: 全尺寸图片幻灯片

图 2 不同pH的CMCN的ζ-电位

注：不同字母表示差异显著，P<0.05；图5、图7同。

Figure 2. ζ-Potential of CMCN at different pH

下载: 全尺寸图片幻灯片

图 3 不同pH的CMCN的接触角

Figure 3. Contact angle of CMCN with different pH

下载: 全尺寸图片幻灯片

图 4 CMCN稳定Pickering乳液凝胶的荧光显微镜图像

Figure 4. Fluorescence microscope image of CMCN stabilized Pickering emulsion gels

下载: 全尺寸图片幻灯片

图 5 不同浓度的CMCN稳定的Pickering乳液凝胶的液滴尺寸和ζ-电位

注：A为液滴尺寸测量值；B为ζ-电位测量值。

Figure 5. Droplet size and ζ-potential of the Pickering emulsion gels stabilized with different concentrations of CMCN

下载: 全尺寸图片幻灯片

图 6 不同浓度的CMCN稳定Pickering乳液凝胶的流变学特性

注：A为黏度扫描；B为频率扫描。

Figure 6. Rheological properties of CMCN stabilized Pickering emulsion gels with different concentrations

下载: 全尺寸图片幻灯片

图 7 不同pH CMCN稳定的Pickering乳液凝胶的液滴尺寸图及外观

Figure 7. Droplet size and appearance of Pickering emulsion gels stabilized with different pH CMCN

下载: 全尺寸图片幻灯片

图 8 不同浓度CMCN的稳定的Pickering乳液凝胶的外观图及液滴尺寸

注：A为新鲜制备的Pickering乳液凝胶；B为室温下放置120 d后的Pickering乳液凝胶；C为Pickering乳液凝胶的液滴尺寸测量结果；不同小写字母为初乳差异显著（P<0.05）；不同大写字母为贮藏120 d后差异显著（P<0.05）。

Figure 8. Appearance and droplet size of Pickering emulsion gels stabilized with different concentrations of CMCN

下载: 全尺寸图片幻灯片

图 9 Pickering乳液凝胶的热稳定性

注：A为不同加热温度；B为加热不同浓度。字母不同的值差异有统计学意义（P<0.05），不同大小写字母代表不同样品。

Figure 9. Thermal stability of Pickering emulsion gels

下载: 全尺寸图片幻灯片

表 1 不同pH的CMCN的接触角

Table 1. Contact angle of CMCN at different pH values

pH	pH2	pH3	pH4	pH5	pH6	pH7	pH8	pH9
θ_o/w	47.65±0.75^a	61.30±0.30^b	66.25±1.25^b	57.10±6.90^ab	63.45±7.35^b	65.05±0.25^b	65.85±0.75^b	59.70±3.60^ab
注：同一行上标字母不同表示差异有统计学意义（P<0.05）。

下载: 导出CSV

表 2 不同CMCN浓度的Pickering乳液凝胶的流变学参数

Table 2. Rheological parameters of Pickering emulsion gels with different CMCN concentrations

CMCN浓度	1.0%	1.1%	1.2%	1.3%	1.4%
K	17.44948	23.73159	33.88483	34.65759	53.44787
n	0.30829	0.24731	0.23365	0.2105	0.18148
R²	0.99934	0.99951	0.99935	0.99918	0.99914

下载: 导出CSV

参考文献(32)

[1]	WEI Y, TONG Z, DAI L, et al. Novel colloidal particles and natural small molecular surfactants co-stabilized Pickering emulsions with hierarchical interfacial structure: Enhanced stability and controllable lipolysis[J]. Journal of Colloid and Interface Science,2020,563:291−307. doi: 10.1016/j.jcis.2019.12.085
[2]	SUN G G, LIU X K, MCClEMENTS D J, et al. Chitin nanofibers improve the stability and functional performance of Pickering emulsions formed from colloidal zein[J]. Journal of Colloid and Interface Science,2021,589:388−400. doi: 10.1016/j.jcis.2021.01.017
[3]	CHANG S Q, CHEN X, LIU S W, et al. Novel gel-like Pickering emulsions stabilized solely by hydrophobic starch nanocrystals[J]. International Journal of Biological Macromolecules,2020,152:703−708. doi: 10.1016/j.ijbiomac.2020.02.175
[4]	URIBE-WANDURRAGA Z N, MARTINEZ-SANCHEZ I, SAVALL C, et al. Microalgae fortification of low-fat oil-in-water food emulsions: An evaluation of the physicochemical and rheological properties[J]. Journal of Food Science and Technology,2021,58(10):3701−3711. doi: 10.1007/s13197-020-04828-1
[5]	ALLAFCHIAN A, HOSSEINI H, GHOREISHI S M. Electrospinning of PVA-carboxymethyl cellulose nanofibers for flufenamic acid drug delivery[J]. International Journal of Biological Macromolecules,2020,163:1780−1786. doi: 10.1016/j.ijbiomac.2020.09.129
[6]	ZHOU Z L, XIA K, LIU T, et al. Preparation of carboxymethyl cellulose nanofibers and their application in warp size of textile[J]. International Journal of Biological Macromolecules,2022,207:40−47. doi: 10.1016/j.ijbiomac.2022.03.003
[7]	WEI J, ZHOU Y, LV Y Y, et al. Carboxymethyl cellulose nanofibrils with a treelike matrix: Preparation and behavior of Pickering emulsions stabilization[J]. ACS Sustainable Chemistry & Engineering,2019,7(15):12887−12896.
[8]	LIU Q, CHANG X, SHAN Y, et al. Fabrication and characterization of Pickering emulsion gels stabilized by zein/pullulan complex colloidal particles[J]. Journal of the Science of Food and Agriculture,2021,101(9):3630−3643. doi: 10.1002/jsfa.10992
[9]	LI X M, XIE Q T, ZHU J, et al. Chitosan hydrochloride/carboxymethyl starch complex nanogels as novel Pickering stabilizers: Physical stability and rheological properties[J]. Food Hydrocolloids,2019,93:215−225. doi: 10.1016/j.foodhyd.2019.02.021
[10]	SUN Y, TANG W T, PU C F, et al. Improved stability of liposome-stabilized emulsions as a co-encapsulation delivery system for vitamin B₂, vitamin E and β-carotene[J]. Food & Function,2022,13:2966.
[11]	HAN J, CHEN F L, GAO C C, et al. Environmental stability and curcumin release properties of Pickering emulsion stabilized by chitosan/gum arabic nanoparticles[J]. International Journal of Biological Macromolecules,2020,157:202−211. doi: 10.1016/j.ijbiomac.2020.04.177
[12]	PEI Y Q, WAN J W, YOU M, et al. Impact of whey protein complexation with phytic acid on its emulsification and stabilization properties[J]. Food Hydrocolloids,2019,87:90−96. doi: 10.1016/j.foodhyd.2018.07.034
[13]	NIU F G, LI M Y, HUANG Q, et al. The characteristic and dispersion stability of nanocellulose produced by mixed acid hydrolysis and ultrasonic assistance[J]. Carbohydrate Polymers,2017,165:197−204. doi: 10.1016/j.carbpol.2017.02.048
[14]	MIKULCOVA V, BORDES R, ANTONIN M, et al. Pickering oil-in-water emulsions stabilized by carboxylated cellulose nanocrystals-effect of the pH[J]. Food Hydrocolloids,2018,80:60−67. doi: 10.1016/j.foodhyd.2018.01.034
[15]	MICHAEL ESKIN N A, NI Y, DUAN H, et al. The application of cellulose nanocrystals in Pickering emulsion as the particle stabilizer[J]. Science and Technology of Cereals, Oils and Foods,2021,29(3):39−46.
[16]	焦博, 石爱民, 刘红芝, 等. 基于食品级固体颗粒稳定的Pickering乳液研究进展[J]. 食品科学,2018,39(5):296−303. [JIAO B, SHI A M, LIU H Z, et al. A review on food-grade particle stabilized Pickering emulsion[J]. Food Science,2018,39(5):296−303.
[17]	程杰, 王彤, 黄云艳, 等. 磁性纤维素微晶稳定O/W型Pickering乳液特性分析[J]. 食品科学,2022,43(2):48−54. [CHENG J, WANG T, HUANG Y Y, et al. Characteristics of magnetic cellulose microcrystalline-stabilized O/W Pickering emulsion[J]. Food Science,2022,43(2):48−54. doi: 10.7506/spkx1002-6630-20201202-031
[18]	牛云蔚, 高雨辰, 毛铖挺, 等. Pickering乳液的形成、微观结构表征及其在香料香精包埋中的研究进展[J]. 食品与发酵工业,2023,49(1):321−329. [NIU Y W, GAO Y C, MAO C T, et al. A review on formation, microstructure characterization of Pickering emulsion and its encapsulation in flavor and fragrance[J]. Food and Fermentation Industries,2023,49(1):321−329.
[19]	刘智敏, 尚成新. 羧甲基纤维素稳定的丙烯酸酯乳液的工业研究[J]. 化学工程师,2018,276(9):1−4. [LIU Z M, SHANG C X. Research on the preparation of acrylate emulsion with carboxymethyl cellulose as stabilizer[J]. Chemical Engineer,2018,276(9):1−4.
[20]	付伟. 细菌纤维素纳米纤维稳定Pickering乳液的研究[D]. 天津: 天津科技大学, 2015 FU W. Study on Pickering emulsions stabilized by bacterial cellulose nanofiber[D]. Tianjin: Tianjin University of Science and Technology, 2015.
[21]	BORTNOWSKA G, BALEJKO J, TOKARCZYK G, et al. Effects of pregelatinized waxy maize starch on the physicochemical properties and stability of model low-fat oil-in-water food emulsions[J]. Food Hydrocolloids,2014,36:229−237. doi: 10.1016/j.foodhyd.2013.09.012
[22]	牛付阁, 韩备竞, 寇梦璇, 等. 纳米纤维素颗粒稳定的Pickering乳液的性能研究[J]. 中国食品学报,2020,20(6):166−172. [NIU F G, HAN B J, KOU M X, et al. Studies on characterization of Pickering emulsions stabilized with nanocellulose particles[J]. Journal of Chinese Institute of Food Science and Technology,2020,20(6):166−172. doi: 10.16429/j.1009-7848.2020.06.020
[23]	汤淼, 陈敏智, 周晓燕. 纤维素基Pickering乳液研究进展[J]. 纤维素科学与技术,2021,29(2):36−47. [TANG M, CHEN M Z, ZHOU X Y. Progress in cellulose-based Pickering emulsions[J]. Journal of Cellulose Science and Technology,2021,29(2):36−47. doi: 10.16561/j.cnki.xws.2021.02.04
[24]	易辉永, 王世彬, 李帅帅, 等. 纤维素纳米晶杂化压裂液的流变性能[J]. 油田化学,2021,38(2):230−234. [YI H Y, WANG S B, LI S S, et al. Rheological properties of nano hybrid cellulose fracturing fluid[J]. Oilfield Chemistry,2021,38(2):230−234. doi: 10.19346/j.cnki.1000-4092.2021.02.007
[25]	LI S N, ZHANG B, TAN C P, et al. Octenylsuccinate quinoa starch granule-stabilized Pickering emulsion gels: Preparation, microstructure and gelling mechanism[J]. Food Hydrocolloids,2019,91:40−47. doi: 10.1016/j.foodhyd.2019.01.001
[26]	许馨予, 杨鹄隽, 贾斌, 等. 大豆分离蛋白-高酯柑橘果胶-没食子酸复合Pickering乳液制备及其稳定性分析[J]. 食品科学,2022,43(24):42−51. [XU X Y, YANG H J, JIA B, et al. Preparation and stability analysis of soy protein isolate-high methoxyl citrus pectin-gallic acid Pickering emulsion[J]. Food Science,2022,43(24):42−51.
[27]	ZHU F. Starch based Pickering emulsions: Fabrication, properties, and applications[J]. Trends in Food Science & Technology,2019,85:129−137.
[28]	XIAO J, LI Y Q, HUANG Q R. Recent advances on food-grade particles stabilized Pickering emulsions: Fabrication, characterization and research trends[J]. Trends in Food Science & Technology,2016,55:48−60.
[29]	DE FARIA J T, DE OLIVEIRA E B, MINMIN V P R, et al. Emulsifying properties of β-lactoglobulin and quillaja bark saponin mixtures: Effects of number of homogenization passes, pH, and NaCl concentration[J]. International Journal of Food Properties,2016,20(7):1643−1654.
[30]	CAI Y J, HUANG L H, TAO X, et al. Carboxymethyl cellulose/okara protein influencing microstructure, rheological properties and stability of O/W emulsions[J]. Journal of the Science of Food and Agriculture,2021,101(9):3685−3692. doi: 10.1002/jsfa.10998
[31]	WEI Y, ZHAN X Y, DAI L, et al. Formation mechanism and environmental stability of whey protein isolate-zein core-shell complex nanoparticles using the pH-shifting method[J]. LWT-Food Science and Technology,2021,139:110605. doi: 10.1016/j.lwt.2020.110605
[32]	LIU G, WANG Q, HU Z Z, et al. Maillard-reacted whey protein isolates and epigallocatechin gallate complex enhance the thermal stability of the Pickering emulsion delivery of curcumin[J]. Journal of Agricultutal and Food Chemistry,2019,67:5212−5220. doi: 10.1021/acs.jafc.9b00950