Journal of Fluorescence

, Volume 26, Issue 1, pp 363–369 | Cite as

Two Sensitive Fluorescent BOPIM Probes with Tunable TICT Character for Low-Level Water Detection in Organic Solvents

  • Ping Shen
  • Min Li
  • Chunlin Liu
  • Wei Yang
  • Sen Liu
  • Changying Yang


Two novel Boron-fluorine derivatives bearing dimethylamino moieties, BOPIM-1 and BOPIM-2, were proposed as sensitive fluorescent sensors for low-level water quantification in organic solvents. Two BOPIMs exhibit typical phenomenon for an emission from a twisted intra-molecular charge transfer (TICT) state, the emission red shift and intensity weakening with solvent polarity. Introduction of trace amount of water to solvent resulted in fluorescent quenching, accompanied by the red shift of the emission, which was attributed to the formation of TICT excitation of BOPIMs by hydrolysis. A quantification method to detect water content was developed, described by a linear equation \( \lg \frac{I}{I_0} \) vs. lg φ w in the range of φ w (volume fraction of water) 0.001~0.01, 0.01~0.1, respectively. The experiment results of determination of water in real 1, 4-dioxane (Diox) samples proved that this method can be used in practical application.


BOPIMs Twisted intra-molecular charge transfer (TICT) Fluorescent sensor Water determination Solvent 



We are grateful for the financial support from National Natural Science Foundation of China (21473101).

Supplementary material

10895_2015_1722_MOESM1_ESM.doc (298 kb)
Fig. S1 (DOC 297 kb)
10895_2015_1722_MOESM2_ESM.doc (182 kb)
Fig. S2 (DOC 182 kb)
10895_2015_1722_MOESM3_ESM.doc (985 kb)
Fig. S3 (DOC 985 kb)
10895_2015_1722_MOESM4_ESM.doc (116 kb)
Fig. S4 (DOC 116 kb)
10895_2015_1722_MOESM5_ESM.doc (33 kb)
Fig. S5 (DOC 33 kb)
10895_2015_1722_MOESM6_ESM.doc (32 kb)
Fig. S6 (DOC 32 kb)
10895_2015_1722_MOESM7_ESM.doc (33 kb)
Fig. S7 (DOC 33 kb)
10895_2015_1722_MOESM8_ESM.doc (26 kb)
Fig. S8 (DOC 26 kb)


  1. 1.
    Liang YY (1990) Automation of Karl Fischer water titration by flow injection sampling. Anal Chem 62:2504–2506CrossRefGoogle Scholar
  2. 2.
    Ohira SI, Goto K, Toda K, Dasgupta PK (2012) A capacitance sensor for water: trace moisture measurement in gases and organic solvents. Anal Chem 848891–8897Google Scholar
  3. 3.
    MacLeod SK (1991) Moisture determination using Karl Fischer titrations. Anal Chem 63:557A–566AGoogle Scholar
  4. 4.
    Margolis SA (1997) Sources of systematic bias in the measurement of water by the coulometric and volumetric Karl Fischer methods. Anal Chem 69:4864–4871PubMedCrossRefGoogle Scholar
  5. 5.
    Langhals H (1990) A simple, quick, and precise procedure for the determination of water in qrganic solvents. Anal Lett 23:2243–2258CrossRefGoogle Scholar
  6. 6.
    Garrigues S, Gallignani M, dela Guardia M (1993) Flow-injection determination of water in organic solvents by near-infrared spectrometry. Anal Chim Acta 281:259–264CrossRefGoogle Scholar
  7. 7.
    Sun H, Wang B, DiMagno SG (2008) A method for detecting water in organic solvents. Org Lett 10:4413–4416PubMedPubMedCentralCrossRefGoogle Scholar
  8. 8.
    Pinheiro C, Lima JC, Parola AJ (2006) Using hydrogen bonding-specific interactions to detect water in aprotic solvents at concentrations below 50 ppm. Sensors Actuators B 114:978–983CrossRefGoogle Scholar
  9. 9.
    Niu HY, Huang DW, Niu CG (2014) Time-gated fluorescence sensor for trace water content determination in organic solvents based on covalently immobilized europium ternary complex. Sensors Actuators B Chem 192:812–817CrossRefGoogle Scholar
  10. 10.
    Kłucińska K, Jurczakowski R, Maksymiuk K, Michalska A (2015) Ultrasensitive 4-methylumbelliferone fluorimetric determination of water contents in aprotic solvents. Talanta 132:392–397PubMedCrossRefGoogle Scholar
  11. 11.
    Yang X, Niu CG, Shang ZJ, Shen GLYRQ (2001) Optical-fiber sensor for determining water content in organic solvents. Sensors Actuators B Chem 75:43–47CrossRefGoogle Scholar
  12. 12.
    Ooyama Y, Matsugasako A, Oka K, Nagano T, Sumomogi M, Komaguchi K, Imae I, Harima Y (2011) Fluorescence PET (photo-induced electron transfer) sensors for water based onanthracene—boronic acid ester. Chem Commun 47:4448–4450CrossRefGoogle Scholar
  13. 13.
    Ooyama Y, Uenaka K, Matsugasako A, Harima Y, Ohshita J (2013) Molecular design and synthesis of fluorescence PET (photo-induced electron transfer) sensors for detection of water in organic solvents. RSC Adv 3:23255–23263CrossRefGoogle Scholar
  14. 14.
    Ooyama Y, Matsugasako A, Hagiwara Y, Ohshita J, Harima Y (2012) Highly sensitive fluorescence PET (photo-induced electron transfer) sensor for water based on anthracene–bisboronic acid ester. RSC Adv 2:7666–7668CrossRefGoogle Scholar
  15. 15.
    Sun Y, Liang X, Wei S, Fan J, Yang XH (2012) Fluorescent turn-on detection and assay of water based on 4-(2-dimethylaminoethyloxy)-N-octadecyl-1,8-naphthalimide with aggregation-induced emission enhancement. Spectrochim Acta A Mol Biomol Spectrosc 97:352–358PubMedCrossRefGoogle Scholar
  16. 16.
    Bangal PR, Panja S, Chakravorti S (2001) Excited state photodynamics of 4-N, N-dimethylamino cinnamaldehyde: a solvent dependent competition of TICT and intermolecular hydrogen bonding. J Photochem Photobiol A Chem 139:5–16CrossRefGoogle Scholar
  17. 17.
    Ghosh R, Palit DK (2013) Dynamics of solvent controlled excited state intramolecular proton transfer coupled charge transfer reactions. Photochem Photobiol Sci 12:987–995PubMedCrossRefGoogle Scholar
  18. 18.
    Ding L, Zhang ZY, Li X, Su JH (2013) Highly sensitive determination of low-level water content in organic solvents using novel solvatochromic dyes based on thioxanthone. Chem Commun 49:7319–7321CrossRefGoogle Scholar
  19. 19.
    Wang S, Xiao SZ, Chen XH, Zhang RH, Cao Q, Zou K (2013) Crystalline solid responsive to mechanical and acidic stimuli: Boron-fluorine derivative with TICT characteristic. Dyes Pigments 99:543–547CrossRefGoogle Scholar
  20. 20.
    Shen P, Xiao SZ, Zhan XQ, Zhang W, Chang KD, Yang CY (2013) A new pH fluorescent molecular switch by modulation of twisted intramolecular charge transfer with protonation. J Phys Org Chem 26:26858–26862CrossRefGoogle Scholar
  21. 21.
    Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su SJ, Windus TL, Dupuis M, Montgomery JA (1993) General atomic and molecular electronic structure system. J Comput Chem 14:1347–1363CrossRefGoogle Scholar
  22. 22.
    Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789CrossRefGoogle Scholar
  23. 23.
    Grabowski ZR, Rotkiewicz K (2003) Structural changes accompanying intramolecular electron transfer: focus on twisted intramolecular charge-transfer states and structures. Chem Rev 103:3899–4031PubMedCrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Ping Shen
    • 1
  • Min Li
    • 1
  • Chunlin Liu
    • 1
  • Wei Yang
    • 1
  • Sen Liu
    • 1
  • Changying Yang
    • 1
  1. 1.College of Biology and Pharmaceutical ScienceThree Gorges UniversityYichangPeople’s Republic of China

Personalised recommendations