Preparation and Property Analysis of Carboxymethyl Nanocellulose Stabilized Low Oil Phase Pickering Emulsion Gels
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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。
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关键词:
- 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.-
Key words:
- carboxymethyl nanocellulose (CMCN) /
- Pickering emulsion gels /
- low oil phase /
- rheology /
- stability
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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 θo/w 47.65±0.75a 61.30±0.30b 66.25±1.25b 57.10±6.90ab 63.45±7.35b 65.05±0.25b 65.85±0.75b 59.70±3.60ab 注:同一行上标字母不同表示差异有统计学意义(P<0.05)。 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 -
[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, 2015FU 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