羟基螺吡喃探针可视化检测果酸类化妆品的pH值

引用本文: 扈洪志, 周自强, 夏凌, 李攻科, 肖小华. 羟基螺吡喃探针可视化检测果酸类化妆品的pH值[J]. 分析化学, 2023, 51(1): 34-41. doi: 10.19756/j.issn.0253-3820.221198 shu

Citation: HU Hong-Zhi, ZHOU Zi-Qiang, XIA Ling, LI Gong-Ke, XIAO Xiao-Hua. Visual Detection of pH Value of Fruit Acid Cosmetics Based on Hydroxyl Spiropyran Probe[J]. Chinese Journal of Analytical Chemistry, 2023, 51(1): 34-41. doi: 10.19756/j.issn.0253-3820.221198 shu

羟基螺吡喃探针可视化检测果酸类化妆品的pH值

中山大学化学学院, 广州 510006

通讯作者: 李攻科,E-mail:cesgkl@mail.sysu.edu.cn; 肖小华,E-mail:xiaoxhua@mail.sysu.edu.cn

基金项目:
国家自然科学基金面上项目(Nos.21976213,21874159,22076223)和国家自然科学基金重点项目(No.22134007)资助。

摘要: 基于螺吡喃酸致变色性质制备了一种用于可视化检测果酸类化妆品pH值的探针。通常,螺吡喃分子的水溶性较差,未经修饰的螺吡喃难以应用于含水体系的测定。本研究通过在螺吡喃上修饰羟基基团调控探针的pK_a值从而改善其水溶性,拓宽其使用范围,并基于此制备了对H⁺具有识别能力的探针。采用核磁共振氢谱(¹H NMR)、核磁共振碳谱(¹³C NMR)、红外光谱(IR spectra)和高分辨质谱(HRMS)对研制的多羟基螺吡喃(SP-OH)探针进行了表征,考察了探针浓度、含水量及其它阳离子对吸光度的影响。紫外-可见(UV-Vis)吸收光谱显示,H⁺浓度(pH值)与探针在420和560nm处的吸光度的比值呈线性关系,标准曲线方程为A_420nm/A_560nm=-55.66pH+276.83(R²=0.996),线性范围为pH3.0~5.0。通过¹H NMR、分子轨道能级计算验证了探针在酸性溶液下自发地快速转化为有色的开环体。采用SP-OH探针对果酸类化妆品的pH值进行测定,在pH3.0~5.0范围内,本方法可在5min内完成对样品pH值的测定,测定结果与商品化pH计测得结果一致,相对误差为2.4%。

关键词:

English

Visual Detection of pH Value of Fruit Acid Cosmetics Based on Hydroxyl Spiropyran Probe

School of Chemistry, Sun Yat-sen University, Guangzhou 510006, China

Corresponding author: LI Gong-Ke, ; XIAO Xiao-Hua,

Received Date: 23 April 2022
Revised Date: 20 August 2022
Fund Project:
Supported by the National Natural Science Foundation of China (Nos.21976213, 21874159, 22076223) and the State Key Program of the National Natural Science Foundation of China (No.22134007).

Abstract: Based on the acid-induced discoloration of the spiropyran, a visual detection probe was synthesized for pH detection in fruit acid cosmetics. Generally, the spiropyran shows poor water solubility, and it is difficult to apply the unmodified spiropyran to determination of aqueous system. So in this work, by modifying hydroxyl groups, the pK_a value of spiropyran probe was controlled and the water solubility was improved, which broadened the scope of its application. The as-synthesized colorimetric hydrogen ion probe of polyhydroxy spiropyran (SP-OH) was characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR, infrared (IR) spectra and high resolution mass spectra. The influences of probe concentration, water content and other cations on absorbance were investigated, ultraviolet-visible (UV-Vis) spectroscopy results showed that there was a linear relationship between the hydrogen ion concentration and the ratio of absorbance at 420 nm and 560 nm, the standard equation was A_{420 nm}/A_{560 nm}=-55.66pH+276.83 (R²=0.996), and the linear range was 3.0-5.0. The probe could quickly and spontaneously transform into colored ring-open form in acidic solution, which was verified by ¹H NMR and molecular orbital energy level calculation. The pH value of fruit acid cosmetics was determined by the SP-OH probe. In the range of pH 3.0-5.0, the pH value of the samples could be detected by SP-OH probe within 5 min. The measured results were consistent with those of pH meter, and the relative error was 2.4%.

Key words:

1. [1]
  PROKSCH E. J. Dermatol., 2018, 45(9):1044-1052.PROKSCH E. J. Dermatol., 2018, 45(9):1044-1052.
2. [2]
  ALI S M, YOSIPOVITCH G. Acta Derm.-Venereol., 2013, 93(3):261-267.ALI S M, YOSIPOVITCH G. Acta Derm.-Venereol., 2013, 93(3):261-267.
3. [3]
  National Medical Products Administration. Technical Specification for Safety of Cosmetics, 2015 Edition. Beijing:Standards Press of China, 2015. 国家食品药品监督管理总局. 化妆品安全技术规范. 2015版. 北京:中国标准出版社, 2015.
4. [4]
  HESSE S J A, RUIJTER G J G, DIJKEMA C, VISSER J. J. Biotechnol., 2000, 77(1):5-15.HESSE S J A, RUIJTER G J G, DIJKEMA C, VISSER J. J. Biotechnol., 2000, 77(1):5-15.
5. [5]
  NING L, LI X, YANG D, MIAO P, YE Z, LI G. Anal. Chem., 2014, 86(16):8042-8047.NING L, LI X, YANG D, MIAO P, YE Z, LI G. Anal. Chem., 2014, 86(16):8042-8047.
6. [6]
  MANI G K, MIVAKODA K, SAITO A, YASODA Y, KAIJIWARA K, KIMURA M, TSUCHIYA K. ACS Appl. Mater. Interfaces, 2017, 9(26):21651-21659.MANI G K, MIVAKODA K, SAITO A, YASODA Y, KAIJIWARA K, KIMURA M, TSUCHIYA K. ACS Appl. Mater. Interfaces, 2017, 9(26):21651-21659.
7. [7]
  SERRAPEDE M, PESCE G L, BALL R J, DENUAULT G. Anal. Chem., 2014, 86(12):5758-5765.SERRAPEDE M, PESCE G L, BALL R J, DENUAULT G. Anal. Chem., 2014, 86(12):5758-5765.
8. [8]
  YANG T, MA J, ZHEN S J, HUANG C Z. ACS Appl. Mater. Interfaces, 2016, 8(23):14802-14811.YANG T, MA J, ZHEN S J, HUANG C Z. ACS Appl. Mater. Interfaces, 2016, 8(23):14802-14811.
9. [9]
  ZHENG X S, HU P, CUI Y, ZONG C, FENG J M, WANG X, REN B. Anal. Chem., 2014, 86(24):12250-12257.ZHENG X S, HU P, CUI Y, ZONG C, FENG J M, WANG X, REN B. Anal. Chem., 2014, 86(24):12250-12257.
10. [10]
  GUHLKE M, HEINER Z, KNEIPP J. Phys. Chem. Chem. Phys., 2015, 17(39):26093-26100.GUHLKE M, HEINER Z, KNEIPP J. Phys. Chem. Chem. Phys., 2015, 17(39):26093-26100.
11. [11]
  WEI H, SHI N, ZHANG J, WAN X. Chem. Commun., 2014, 50(66):9333-9335.WEI H, SHI N, ZHANG J, WAN X. Chem. Commun., 2014, 50(66):9333-9335.
12. [12]
  AHMAD N A, YOOK H L, SALAM F. Sensors, 2019, 19(21):4813.AHMAD N A, YOOK H L, SALAM F. Sensors, 2019, 19(21):4813.
13. [13]
  LEE W, LEE D, KIM J Y. Mater. Chem. Front., 2018, 2(2):291-295.LEE W, LEE D, KIM J Y. Mater. Chem. Front., 2018, 2(2):291-295.
14. [14]
  MIAO X, ZHU Z, JIA H. Sens. Actuators, B, 2020, 320:128435.MIAO X, ZHU Z, JIA H. Sens. Actuators, B, 2020, 320:128435.
15. [15]
  YAN Z, ZHANG X, BAO C. Sens. Actuators, B, 2018, 262:869-875.YAN Z, ZHANG X, BAO C. Sens. Actuators, B, 2018, 262:869-875.
16. [16]
  YAN Ping-Yao, LI Zai-Jun. Chin. J. Anal. Chem., 2018, 46(5):670-677. 严平摇, 李在均. 分析化学, 2018, 46(5):670-677.
17. [17]
  KIM H J, HEO C H, KIM H M. J. Am. Chem. Soc., 2013, 135(47):17969-17977.KIM H J, HEO C H, KIM H M. J. Am. Chem. Soc., 2013, 135(47):17969-17977.
18. [18]
  ZHANG Yuan, ZHAI Jiang-Li, LI Fan-Lin, GUO Ping, YAN Xin. Chin. J. Anal. Chem., 2020, 48(8):1041-1049. 张源, 翟江丽, 李繁麟, 郭平, 闫昕. 分析化学, 2020, 48(8):1041-1049.
19. [19]
  WAN S, ZHENG Y, SHEN J. ACS Appl. Mater. Interfaces, 2014, 6(22):19515-19519.WAN S, ZHENG Y, SHEN J. ACS Appl. Mater. Interfaces, 2014, 6(22):19515-19519.
20. [20]
  YUAN W, GAO X, PEI E. Polym. Chem., 2018, 9(26):3651-3661.YUAN W, GAO X, PEI E. Polym. Chem., 2018, 9(26):3651-3661.
21. [21]
  LI J, LI X, JIA J. Dyes Pigm., 2019, 166:433-442.LI J, LI X, JIA J. Dyes Pigm., 2019, 166:433-442.
22. [22]
  WU L, CHEN R J, LUO Z W, WANG P. J. Mater. Sci., 2020, 55(27):12826-12835.WU L, CHEN R J, LUO Z W, WANG P. J. Mater. Sci., 2020, 55(27):12826-12835.
23. [23]
  GENOVESE M E, ABRAHAM S, CAPUYO G, NANNI G, KUMARAN S K, MONTEMAGNO C D, ATHANASSIOU A, FRAGOULI D. ACS Omega, 2018, 3(10):13484-13493.GENOVESE M E, ABRAHAM S, CAPUYO G, NANNI G, KUMARAN S K, MONTEMAGNO C D, ATHANASSIOU A, FRAGOULI D. ACS Omega, 2018, 3(10):13484-13493.
24. [24]
  ZHANG R Q, HU L P, XU Z X, SONG Y X, LI H Q, ZHANG X, GAO X C, WANG M X, XIAN C Y. J. Mol. Struct., 2020, 1204:127481.ZHANG R Q, HU L P, XU Z X, SONG Y X, LI H Q, ZHANG X, GAO X C, WANG M X, XIAN C Y. J. Mol. Struct., 2020, 1204:127481.
25. [25]
  SAKATA T, JACKSON D K, MAO S, MARRIOTT G. J. Org. Chem., 2008, 73(1):227-233.SAKATA T, JACKSON D K, MAO S, MARRIOTT G. J. Org. Chem., 2008, 73(1):227-233.
26. [26]
  BARACHEVSKY V A, VALOVA T M, ATABEKYAN L S, LYUBIMOV A V. High Energy Chem., 2017, 51(6):415-419.BARACHEVSKY V A, VALOVA T M, ATABEKYAN L S, LYUBIMOV A V. High Energy Chem., 2017, 51(6):415-419.
27. [27]
  MIYAGISHI H V, TAMAKI T, MASAI H, TERAO J. Molecules, 2019, 24(7):1301.MIYAGISHI H V, TAMAKI T, MASAI H, TERAO J. Molecules, 2019, 24(7):1301.
28. [28]
  ABDOLLAHI A, ALINEJAD Z, MAHDAVIAN A R. J. Mater. Chem. C, 2017, 5(26):6588-6600.ABDOLLAHI A, ALINEJAD Z, MAHDAVIAN A R. J. Mater. Chem. C, 2017, 5(26):6588-6600.
29. [29]
  TIAN W G, TIAN J T. Dyes Pigm., 2014, 105:66-74.TIAN W G, TIAN J T. Dyes Pigm., 2014, 105:66-74.
30. [30]
  BEYER C, WAGENKNECHT H A. J. Org. Chem., 2010, 75(8):2752-2755.BEYER C, WAGENKNECHT H A. J. Org. Chem., 2010, 75(8):2752-2755.
31. [31]
  GB/T 13531.1-2008. General Methods on Determination of Cosmetics-Determination of pH. National Standards of the People's Republic of China. 化妆品通用检验方法pH值的测定. 中华人民共和国国家标准. GB/T 13531.1-2008.
32. [32]
  HE X J, XU W, XU C C, DING F, CHEN H, SHEN J L. Dyes Pigm., 2020, 180:108497.HE X J, XU W, XU C C, DING F, CHEN H, SHEN J L. Dyes Pigm., 2020, 180:108497.
33. [33]
  YUE Y K, HUO F J, LEE S, YIN C X, YOON J Y, CHAO J B, ZHANG Y B, CHENG F Q. Chem.-Eur. J., 2016, 22(4):1239-1243.YUE Y K, HUO F J, LEE S, YIN C X, YOON J Y, CHAO J B, ZHANG Y B, CHENG F Q. Chem.-Eur. J., 2016, 22(4):1239-1243.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

羟基螺吡喃探针可视化检测果酸类化妆品的pH值

通讯作者: 李攻科,E-mail:cesgkl@mail.sysu.edu.cn; 肖小华,E-mail:xiaoxhua@mail.sysu.edu.cn

English

Visual Detection of pH Value of Fruit Acid Cosmetics Based on Hydroxyl Spiropyran Probe

Corresponding author: LI Gong-Ke, ; XIAO Xiao-Hua,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羟基螺吡喃探针可视化检测果酸类化妆品的pH值

通讯作者: 李攻科,E-mail:cesgkl@mail.sysu.edu.cn; 肖小华,E-mail:xiaoxhua@mail.sysu.edu.cn

English

Visual Detection of pH Value of Fruit Acid Cosmetics Based on Hydroxyl Spiropyran Probe

Corresponding author: LI Gong-Ke, ; XIAO Xiao-Hua,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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