牙膏中不同形态氟化物的固体NMR研究

doi:10.3969/j.issn.2097-2806.2023.08.013

摘要/Abstract

摘要：

采用¹⁹F固体核磁共振技术（¹⁹F SS-NMR）对38款含氟牙膏样品中不同形态氟化物进行了分析研究。牙膏样品经少量淀粉混合固化后直接装样采集，采用hahn-echo回波序列，魔角旋转转速12~14 kHz。结果显示，不同摩擦剂与氟化物匹配的稳定性有较大差异，其中摩擦剂水合硅石与氟化物的匹配一般较稳定，氟化物主要以可溶性/游离状态存在于牙膏体系中；部分碳酸钙基质牙膏中，除原料氟化物信号外，还观测到新生成的不可溶性固体氟化钙信号。除摩擦剂的影响外，在一些添加了羟基磷灰石等功效成分的牙膏中，也观测到不可溶性的氟化钙的生成，不可溶性氟化物的生成将降低牙膏中有效氟的含量。对牙膏这种半固体样品，¹⁹F SS-NMR具有前处理操作简便、专属性强、灵敏度高等特点，可对含氟牙膏中氟化物进行形态分析，为牙膏配方研发、质量提升提供技术支持。

关键词: 牙膏, 氟化物

Abstract:

Different forms of fluoride in 38 fluoride toothpaste samples were determined by ¹⁹F solid-state nuclear magnetic resonance （¹⁹F SS-NMR）. The results show that the matching stability of different friction agents and fluoride is quite different. The soluble and free types are the main forms of fluoride in hydrated silica toothpaste, but newly generated insoluble solid calcium fluoride signal is observed in some calcium carbonate-based toothpastes. In addition to the influence of friction agents, in some toothpastes with functional ingredients such as hydroxyapatite, the formation of insoluble calcium fluoride is also observed. The formation of insoluble fluoride will reduce the amount of available fluoride in toothpaste. ¹⁹F SS-NMR has the characteristics of simple pretreatment, strong specificity and high sensitivity. It can quickly analyze the morphology of fluoride in fluoride toothpaste, and provide technical support for toothpaste formulation development and quality improvement.

Key words: toothpaste, fluoride

中图分类号:

TQ658

周雷,曹东霞,李家宏,苏哪锋,李文辉. 牙膏中不同形态氟化物的固体NMR研究[J]. 日用化学工业（中英文）, 2023, 53(8): 963-967.

Zhou Lei,Cao Dongxia,Li Jiahong,Su Nafeng,Li Wenhui. Study of different forms of fluoride in toothpaste by solid state NMR[J]. China Surfactant Detergent & Cosmetics, 2023, 53(8): 963-967.

图/表 11

图1

图2

表1

表2

图3

图4

图5

图6

图7

图8

图9

参考文献 15

[1]	Li Mingyu, Liu Zheng, Zhu Cailian. Fluoride concentration in fluoride toothpaste[J]. Oral Care Industry, 2002, 3: 39-40.
[2]	Huang Dingming, Zhou Xuedong. Research progress on the anti-caries effect of fluoridated toothpaste[J]. Journal of Modern Stomatology, 1999, 13 (4) : 298-299.
[3]	National Technical Committee 492 on Oral Cavity Nursing Materials of Standardization Administration of China. Toothpaste: GB/T 8372—2017[S]. Beijing: China Light Industry Press, 2017.
[4]	Wang Xiaoling, Cheng Zhuoyue, Ge Yao, et al. Investigation on the stability of fluoride content in fluoride toothpaste sold in Beijing[J]. Chinese Journal of Public Health, 2005, 21 (10) : 1258.
[5]	Du Baoshan, Qi Huixin, Wang Qin, et al. The relationship between effective F and total F in fluoride toothpaste for anti-caries[J]. Journal of Beijing Normal University (Natural Science), 1993, 29 (1) : 113-116.
[6]	Deng Quanfu, Tang Weiyue, Zhang Huan, et al. Theoretical exploration of soluble fluoride retention in calcium carbonate-based toothpaste[J]. Oral Care Industry, 2020, 30 (4) : 16-18.
[7]	Huang Qianjun, Liu Jianguo, Li Lanqing, et al. Influence of particle size of natural calcium carbonate abrasive on properties of fluoride toothpaste[J]. Oral Care Industry, 2021, 31 (3) : 30-33.
[8]	Meng Yu. Influence of toothpaste raw materials on toothpaste quality[J]. Toothpaste Industry, 2001 (4) : 36-38.
[9]	Ni Chengzhu, Jiang Xinhua, Li Gang, et al. Research advance on the instrumental analysis methods of fluoride[J]. Chinese Journal of Chromatography, 2016, 34 (10) : 942-945. doi: 10.3724/SP.J.1123.2016.05035
[10]	Jiao Yang, Duan Xiaohong. Recent research progress in the detection of fluoride ion[J]. Pharmaceutical Biotechnology, 2014, 21 (2) : 180-184.
[11]	Hu Guoyuan, Yu Guilan, Yang Yang, et al. Detection of soluble fluoride and free fluoride in toothpaste[J]. Chinese Journal of Health Laboratory Technology, 2005 (3) : 341-345.
[12]	Chen Jinling, Cao Dongxia, Kuang Boyang. Determination of soluble fluoride in toothpaste by ion chromatography[J]. Chemical Analysis and Meterage, 2014, 23 (1) : 60-62.
[13]	Huang Jing, Liu Wenjia, Liang Xuesong, et al. Determination of total fluoride in toothpaste by HS-GC[J]. Oral Care Industry, 2021, 31 (5) : 24-26.
[14]	Chou Zhenwu, Liu Yaling, Ye Ruhan, et al. Analysis of inorganic fluorine-containing compounds in surface treating agents by ¹⁹F NMR[J]. Chinese Journal of Analysis Laboratory, 2013, 32 (12) : 70-73.
[15]	Liu Yang, Yuan Song, Zhao Zhuang, et al. Application of ¹⁹F qNMR in the assay of fluorine-containing preparation[J]. Chinese Journal of Pharmaceutical Analysis, 2018, 38 (9) : 1507-1510.

种类	固体NMR化学位移（峰型）	液体NMR化学位移（峰型）^[1]
氟化钠	-223（s，br）	-122.6（s）
单氟磷酸钠	-73.6＆-76.1（d，br）	-73.0＆-74.9（d）

检测样品	氟化物和摩擦剂配方	样品数量
1	氟化钠和水合硅石	23
2	单氟磷酸钠和水合硅石	11
3	单氟磷酸钠和碳酸钙	4