Novel Sensors for the Detection of Biologically Important Species

  • Meng Li

Student thesis: Doctoral ThesisPhD


The ability to monitor the presence of analytes is of great importance both in industrial applications and physiological systems. Since the crucial recognition events of chemistry, biology, and materials science occur in a much smaller world, it is very difficult to gather this kind of information. Therefore much effort has been devoted to the detection of chosen molecules selectively and signalling this presence. This thesis highlighted the uniqueness and utility of both fluorescent sensor and electrochemical sensor to investigate biologically important species.The determination of copper(II) ion is very crucial to both environment and human health. To utilise the fluorescent sensors for recognition has plenty of advantages, such as high sensitivity, “on-off” switch ability and submillisecond temporal resolution. Naphthalimide based probes has always been the key point of the chemosensors due to its excellent photophysical properties. Therefore, the aim of the project is to investigate boronic acid receptor linked to the naphthalimide fluorophore for copper(II) detection. And the utility of boronic acid as binding site is one of the rare examples of fluorescent chemosensors for Cu2+ detection.Neutral molecules such as glutathione (GSH) play a crucial role in maintaining appropriate redox homeostasis in biological systems. We creatively use the chromophore of dicyanomethylene-4H-pyran(DCM) for the design of probe, due to its emission located at the red or near infra-red (NIR) region, which is particularly suitable for application in biological samples. GSH, the most abundant cellular thiol, is of great importance in cellular defence against toxins and free radicals. Therefore we developed a colorimetric and NIR fluorescence turn-on thiol probe containing DCM as the fluorophore and DNBS as the fluorescence quencher and recognition moiety. The interaction of ferrocene-boronic acid with fructose is investigated in aqueous 0.1 M phosphate buffer at pH 7, 8, and 9. Two voltammetric methods, (i) based on a dual-plate generator-collector micro-trench electrode (steady state) and (ii) based on square-wave voltammetry (transient), are applied and compared in terms of mechanistic resolution. A combination of experimental data is employed to obtain new insights into the binding rates and the cumulative binding constants for both the reduced ferrocene-boronic acid (pH dependent and weakly binding) and for the oxidised ferrocene-boronic acid (pH independent and strongly binding).Finally, a redox-activated fluorescence switch based on a ferrocene - fluorophore - boronic ester conjugate was investigated. The development of multifunctional systems that can integrate individual basic logic gates into combinational circuits has drawn much attention to smart materials. A novel electrochemically and fluorescence active boronic ester sensor molecule has been developed containing ferrocence and naphthalimide as the redox and fluorophore units. The solid state electrochemical characterisation of the compound was investigated in aqueous media and it indicates a direct interaction with fluoride anions. The fluorescence can also be modulated through photoinduced electron transfer (PET) by a redox process. An OFF-ON fluorescence response occurs when the ferrocene is oxidised by Fe3+. While in the presence of F-, the fluorescence enhancement was offset. Therefore, the combinations of iron (Fe3+ ) ions, sodium L-ascorbate, and fluoride (F-) ions can be used to produce a molecular system displaying INHIBIT logic gate, due to indirect fluorescence quenching.
Date of Award29 Jun 2015
Original languageEnglish
Awarding Institution
  • University of Bath
SupervisorTony James (Supervisor)


  • fluorescent sensor
  • electrochemical snesor

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