Abstract
A boronic acid-based anthracene fluorescent probe was functionalised with an acrylamide unit to incorporate into a hydrogel system for monosaccharide detection. In solution, the fluorescent probe displayed a strong fluorescence turn-on response upon exposure to fructose, and an expected trend in apparent binding constants, as judged by a fluorescence response where d–fructose > d–galactose > d–mannose > d–glucose. The hydrogel incorporating the boronic acid monomer demonstrated the ability to detect monosaccharides by fluorescence with the same overall trend as the monomer in solution with the addition of d–fructose resulting in a 10-fold enhancement (⩽ 0.25 mol/L).

References
Levine R. Monosaccharides in health and disease. Annual Review of Nutrition, 1986, 6(1): 211–224
Mergenthaler P, Lindauer U, Dienel G A, Meisel A. Sugar for the brain: The role of glucose in physiological and pathological brain function. Trends in Neurosciences, 2013, 36(10): 587–597
Pickup J C, Hussain F, Evans N D, Rolinski O J, Birch D J S. Fluorescence-based glucose sensors. Biosensors & Bioelectronics, 2005, 20(12): 2555–2565
Wu X, Li Z, Chen X X, Fossey J S, James T D, Jiang Y B. Selective sensing of saccharides using simple boronic acids and their aggregates. Chemical Society Reviews, 2013, 42(20): 8032–8048
Lorand J P, Edwards J O. Polyol complex and structure of the benzene boronate ion. Journal of Organic Chemistry, 1959, 24(6): 769–774
Sun X, James T D. Glucose sensing in supramolecular chemistry. Chemical Reviews, 2015, 115(15): 8001–8037
Huang Y J, Ouyang W J, Wu X, Li Z, Fossey J S, James T D, Jiang Y B. Glucose sensing via aggregation and the use of “knock-out” binding to improve selectivity. Journal of the American Chemical Society, 2013, 135(5): 1700–1703
Cao H S, Heagy M D. Fluorescent chemosensors for carbohydrates: A decade’s worth of bright spies for saccharides in review. Journal of Fluorescence, 2004, 14(5): 569–584
James T D, Sandanayake K, Shinkai S. Novel photoinduced electron-transfer sensor for saccharides based on the interaction of boronic acid and amine. Journal of the Chemical Society. Chemical Communications, 1994, 0(4): 477–478
Zhang X T, Liu G J, Ning Z W, Xing G W. Boronic acid-based chemical sensors for saccharides. Carbohydrate Research, 2017, 452: 129–148
James T D, Sandanayake K R A S, Shinkai S. A glucose-selective molecular fluorescence sensor. Angewvandte Chemie International Edition, 1994, 33: 2207–2209
James T D, Sandanayake K R A S, Iguchi R, Shinkai S. Novel saccharide-photoinduced electron transfer sensors based on the interaction of boronic acid and amine. Journal of the American Chemical Society, 1995, 117(35): 8982–8987
Franzen S, Ni W, Wang B. Study of the mechanism of electron-transfer quenching by boron-nitrogen adducts in fluorescent sensors. Journal of Physical Chemistry B, 2003, 107(47): 12942–12948
Ni W, Kaur G, Springsteen G, Wang B, Franzen S. Regulating the fluorescence intensity of an anthracene boronic acid system: A B-N bond or a hydrolysis mechanism? Bioorganic Chemistry, 2004, 32(6): 571–581
Chapin B M, Metola P, Vankayala S L, Woodcock H L, Mooibroek T J, Lynch V M, Larkin J D, Anslyn E V. Disaggregation is a mechanism for emission turn-on of ortho-aminomethylphenylboronic acid-based saccharide sensors. Journal of the American Chemical Society, 2017, 139(15): 5568–5578
Sun X, James T D, Anslyn E V. Arresting “loose bolt” internal conversion from -B(OH)2 groups is the mechanism for emission turn-on in ortho-aminomethylphenylboronic acid-based saccharide sensors. Journal of the American Chemical Society, 2018, 140(6): 2348–2354
Zhao L, Huang Q W, Liu Y, Wang Q, Wang L Y, Xiao S S, Bi F, Ding J X. Boronic acid as glucose-sensitive agent regulates drug delivery for diabetes treatment. Materials, 2017, 10(2): 170
Guan Y, Zhang Y J. Boronic acid-containing hydrogels: Synthesis and their applications. Chemical Society Reviews, 2013, 42(20): 8106–8121
Ahmed E M. Hydrogel: Preparation, characterization, and applications: A review. Journal of Advanced Research, 2015, 6(2): 105–121
Li Y Y, Zhou S Q. A simple method to fabricate fluorescent glucose sensor based on dye-complexed microgels. Sensors and Actuators. B, Chemical, 2013, 177: 792–799
Matsumoto A, Tanaka M, Matsumoto H, Ochi K, Moro-oka Y, Kuwata H, Yamada H, Shirakawa I, Miyazawa T, Ishii H. Synthetic “smart gel” provides glucose-responsive insulin delivery in diabetic mice. Science Advances, 2017, 3, eaaq0723
Matsumoto A, Kataoka K, Miyahara Y. New directions in the design of phenylboronate-functionalized polymers for diagnostic and therapeutic applications. Polymer Journal, 2014, 46(8): 483–491
Sanjoh M, Miyahara Y, Kataoka K, Matsumoto A. Phenylboronic acids-based diagnostic and therapeutic applications. Analytical Sciences, 2014, 30(1): 111–117
Sedgwick A C, Chapman R S L, Gardiner J E, Peacock L R, Kim G, Yoon J, Bull S D, James T D. A bodipy based hydroxylamine sensor. Chemical Communications, 2017, 53(75): 10441–10443
Sedgwick A C, Sun X L, Kim G, Yoon J, Bull S D, James T D. Boronate based fluorescence (ESIPT) probe for peroxynitrite. Chemical Communications, 2016, 52(83): 12350–12352
Sun X L, Odyniec M L, Sedgwick A C, Lacina K, Xu S Y, Qiang T T, Bull S D, Marken F, James T D. Reaction-based indicator displacement assay (RIA) for the colorimetric and fluorometric detection of hydrogen peroxide. Organic Chemistry Frontiers: An International Journal of Organic Chemistry, 2017, 4(6): 1058–1062
Sedgwick A C, Han H H, Gardiner J E, Bull S D, He X P, James T D. Long-wavelength fluorescent boronate probes for the detection and intracellular imaging of peroxynitrite. Chemical Communications, 2017, 53(95): 12822–12825
Wu D, Sedgwick A C, Gunnlaugsson T, Akkaya E U, Yoon J, James T D. Fluorescent chemosensors: The past, present and future. Chemical Society Reviews, 2017, 46(23): 7105–7123
Sedgwick A C, Han H H, Gardiner J E, Bull S D, He X P, James T D. The development of a novel AND logic based fluorescence probe for the detection of peroxynitrite and GSH. Chemical Science (Cambridge), 2018, 9(15): 3672–3676
Lampard E V, Sedgwick A C, Sombuttan T, Williams G T, Wannalerse B, Jenkins A T A, Bull S D, James T D. Dye displacement assay for saccharides using benzoxaborole hydrogels. ChemistryOpen, 2018, 7(3): 266–268
Kreisig T, Hoffmann R, Zuchner T. Homogeneous fluorescence-based immunoassay detects antigens within 90 seconds. Analytical Chemistry, 2011, 83(11): 4281–4287
Grabchev I, Qian X H, Xiao Y, Zhang R. Novel heterogeneous PET fluorescent sensors selective for transition metal ions or protons: Polymers regularly labelled with naphthalimide. New Journal of Chemistry, 2002, 26(7): 920–925
Basabe-Desmonts L, Reinhoudt D N, Crego-Calama M. Design of fluorescent materials for chemical sensing. Chemical Society Reviews, 2007, 36(6): 993–1017
Li M, Liu Z J, Wang H C, Sedgwick A C, Gardiner J E, Bull S D, Xiao H N, James T D. Dual-function cellulose composites for fluorescence detection and removal of fluoride. Dyes and Pigments, 2018, 149: 669–675
Hall D G. Boronic acids: Preparation and applications in organic synthesis, medicine and materials. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2005, 1–550
Fossey J S, Brittain W D G. The CASE 2014 symposium: Catalysis and sensing for our environment, Xiamen 7th–9th November 2014. Organic Chemistry Frontiers: An International Journal of Organic Chemistry, 2015, 2(2): 101–105
Payne D T, Fossey J S, Elmes R B P. Catalysis and Sensing for our Environment (CASE2015) and the Supramolecular Chemistry Ireland Meeting (SCI 2015): Dublin and Maynooth, Ireland. 8th–11th July. Supramolecular Chemistry, 2016, 28(11–12): 921–931
Acknowledgements
The University of Bath are thanked for support. ACS thanks the EPSRC for a PhD studentship. TDJ and JSF are grateful for the support of the EPSRC and DTI (DT/F00267X/1). Preliminary results of this project stemmed from another project pump-primed by the University of Bath Enterprise Development Fund (EDF award to investigators including JSF, ATAJ and TDJ). TDJ wishes to thank the Royal Society for a Wolfson Research Merit Award. JSF and WC thanks the Leverhulme Trust for support (F00094BC). JSF thanks the JDRF (2-SRA-2016-267-A-N) for support. Spectroscopy facilities were provided through the Material and Chemical Characterisation Facility (MC2) at the University of Bath. The investigators are grateful to the CASE consortium for providing knowledge transfer and networking opportunities [36,37].
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Xu, S., Sedgwick, A.C., Elfeky, S.A. et al. A boronic acid-based fluorescent hydrogel for monosaccharide detection. Front. Chem. Sci. Eng. 14, 112–116 (2020). https://doi.org/10.1007/s11705-019-1812-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11705-019-1812-5