A Fluorescent Chemosensor for Sodium Based on Photoinduced Electron Transfer

He, Hong; Mortellaro, Mark A.; Leiner, Marc J. P.; Young, Susanne T.; Fraatz, Robert J.; Tusa, James K.

doi:10.1021/ac0205107

Cited by 188 publications

(96 citation statements)

References 19 publications

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“…This issue takes on added significance given the growing body of sensors and other optical devices which employ 4-amino-1,8-naphthalimide (or closely related) fluorophores. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] Hence, compounds 1-3 and 4-6 were synthesized and tested by steady-state electronic absorption and emission spectroscopy. …”

Section: Introductionmentioning

confidence: 99%

The pH-dependent fluorescence of pyridylmethyl-4-amino-1,8-naphthalimides

Silva¹,

Goligher²,

Gunaratne³

et al. 2003

Arkivoc

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Regioselective photoinduced electron transfer (PET) has been previously observed in aminoalkyl-4-amino-1,8-naphthalimide 'fluorophore-spacer-receptor' systems. PET from the amine to the fluorophore was only observed when the electron entered the fluorophore in the region of its 4-NH group. This has received two related but distinct explanations. The first is a directing effect of the molecular-scale electric field of internal charge transfer (ICT) excited state of the fluorophore. The second is a peculiarity of 4-amino-1,8-naphthalimides in possessing a node at the imide nitrogen in its frontier orbitals. The six isomeric pyridylmethyl-4-amino-1,8-naphthalimides 1-3 and 4-6 are configured as 'fluorophore-spacer-receptor' systems in order to test the relative importance of these two explanations. The two regioisomeric sets are designed such that PET is thermodynamically feasible when they are protonated, which should lead to fluorescence quenching by protons. In practice, the proton-induced fluorescence quenching is moderate and more clearly observed in the set 1-3. This evidence points to the PET-accelerating effect of the molecular-scale electric field being mitigated by the presence of the node at the imide nitrogen in the frontier orbitals. Compound 4 also shows this proton-induced fluorescence quenching effect but to a still smaller extent. In this instance, the PET is hampered by the electric field alone. Compounds 5 and 6 show an excited state intramolecular proton transfer (ESIPT) involving water-mediated hydrogen-bonded rings, which dominates over any residual PET to produce proton-induced fluorescence enhancement. Again, the effect is moderate. The two mechanisms of PET regioselectivity can now be understood to operate additively in the aminoalkyl-4-amino-1,8-naphthalimides and subtractively in the protonated pyridylmethyl-4-amino-1,8-naphthalimides.

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Section: Introductionmentioning

confidence: 99%

The pH-dependent fluorescence of pyridylmethyl-4-amino-1,8-naphthalimides

Silva¹,

Goligher²,

Gunaratne³

et al. 2003

Arkivoc

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“…5,12,13 They absorb around 450 nm and emit in the green, with λ max ~ 550 nm and a high fluorescence quantum yield. Moreover, they are easily synthesized in bulk quantities as well as being well suited for incorporation into polymeric matrixes and onto solid-surfaces.…”

Section: Introductionmentioning

confidence: 99%

“…Such hydrogels are easily handled and, when the composition is chosen judiciously, do not require that the sensor be covalently bonded to the polymeric matrix. 5,14,15 Compounds 1 and 2 are examples of our general design. In this paper we give account of our recent results on the synthesis of, as well as the solution and the soft-matter luminescent properties, of 1 and 2 as a function of pH.…”

Section: Introductionmentioning

confidence: 99%

Towards the development of controllable and reversible ‘on-off’ luminescence switching in soft-matter; synthesis and spectroscopic investigation of 1,8-naphthalimide-based PET (photoinduced electron transfer) chemosensors for pH in water-permeable hydrogels

Gunnlaugsson¹,

McCoy²,

Phelan³

et al. 2003

Arkivoc

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The synthesis of the pH PET sensors 1 and 2 is described. These molecules display 'on-off' switching in their fluorescence as a function of pH in aqueous solution. From the luminescent changes pK a values of 8.4(±0.1) and 6.3(±0.1) were determined respectively. These compounds were incorporated into poly[methylmethacrylate-co-2-(hydroxyethylmethacrylate)]-based hydrogels and the luminescent properties of the resulting polymeric films were investigated using confocal laser-scanning microscopy. Both sensors showed substantial luminescent switching in the soft-matter, where the emission was 'switched off' after treating the hydrogels with alkaline solution and 'switched on' under acidic conditions.

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“…[5][6][7][8] Important picosecond laser studies on fluorescent PET sensors/switches have demonstrated the transient existence of radical ion species, [9][10][11] and thus designers can proceed with confidence. As a result of their modular fluorophore-spacer-receptor construction, fluorescent PET systems are very amenable to modification in terms of the format, as well as in terms of the detailed functionalities.…”

mentioning

confidence: 99%

Modification of Fluorescent Photoinduced Electron Transfer (PET) Sensors/Switches To Produce Molecular Photo‐Ionic Triode Action

Huxley¹,

Schroeder²,

Gunaratne³

et al. 2014

Angewandte Chemie

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The fluorophore-spacer 1 -receptor 1 -spacer 2 -receptor 2 system (where receptor 2 alone is photoredox-inactive) shows ionically tunable proton-induced fluorescence off-on switching, which is reminiscent of thermionic triode behavior. This also represents a new extension to modular switch systems based on photoinduced electron transfer (PET) towards the emulation of analogue electronic devices.Fluorescent photoinduced electron transfer (PET) sensors/ switches [1][2][3][4] are a well-established application of molecular devices, to the point of real-life deployment worldwide in blood electrolyte diagnostics. [5][6][7][8] Important picosecond laser studies on fluorescent PET sensors/switches have demonstrated the transient existence of radical ion species, [9][10][11] and thus designers can proceed with confidence. As a result of their modular fluorophore-spacer-receptor construction, fluorescent PET systems are very amenable to modification in terms of the format, as well as in terms of the detailed functionalities. The latter approach has yielded many individual examples of sensors and switches based on fluorescence which target important analytes. [12][13][14][15] On the other hand, the former approach has the potential to set up new areas of endeavor and application, which is exploited here.The controllable quenching of molecular fluorescence [1,2] can be exploited to build switchable systems which emulate familiar electronic devices. Some of these molecular systems have unique applications which are inconvenient for their electronic counterparts, such as wireless operation in micrometric spaces. [16] The first molecular logic gate [17][18][19][20][21][22][23] 1 (an advanced molecular switch [24] ) was a fluorophore-spacer 1 -receptor 1 -spacer 2 -receptor 2 system, [25,26] where two photoinduced electron transfer (PET) [4, 27] channels arising from the two receptors were controlled by binding H + and Na + ions, respectively, and thus the fluorescence output corresponded to photo-ionic AND logic. Strong fluorescence emerges only when all PET processes are suppressed (Figure 1 a). [4] Related, but distinct, fluorophore-spacer 1 -receptor 1 -spacer 2 -receptor 2 systems, [28] where both receptors respond to H + ions, for example, 2, give rise to fluorescent off-on-off action, which can correspond to ternary logic behavior. [22] We now demonstrate aspects of molecular photo-ionic triode action for the first time by structurally mutating the fluorophore-spacer 1 -receptor 1 -spacer 2 -receptor 2 system 1 into a novel format exemplified by 3, where the convenient photoredox capability of receptor 2 is removed from 1 (Figure 1 b). Nearly 20 distinct formats of luminescent PET switching systems, each possessing its own defining features and applications, are known. [26] Fluorescence off-on switching is, therefore, controlled within 3 by selective ion binding of receptor 1 . This switching profile is influenced by the orthogonally selective ion binding of receptor 2 , which is forced into a secondary role...

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A Fluorescent Chemosensor for Sodium Based on Photoinduced Electron Transfer

Cited by 188 publications

References 19 publications

The pH-dependent fluorescence of pyridylmethyl-4-amino-1,8-naphthalimides

The pH-dependent fluorescence of pyridylmethyl-4-amino-1,8-naphthalimides

Towards the development of controllable and reversible ‘on-off’ luminescence switching in soft-matter; synthesis and spectroscopic investigation of 1,8-naphthalimide-based PET (photoinduced electron transfer) chemosensors for pH in water-permeable hydrogels

Modification of Fluorescent Photoinduced Electron Transfer (PET) Sensors/Switches To Produce Molecular Photo‐Ionic Triode Action

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