Extended Triangulenium Ions: Syntheses and Characterization of Benzo-Bridged Dioxa- and Diazatriangulenium Dyes

Rosenberg, Martin; Santella, Marco; Bogh, Sidsel Ammitzbøll; Muñoz, Alberto Viñas; Andersen, Helene O B; Hammerich, Ole; Bora, Ilkay; Lincke, Kasper; Laursen, Bo W.

doi:10.1021/acs.joc.8b02978

Cited by 22 publications

(33 citation statements)

References 67 publications

(161 reference statements)

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“…[20] However,i ts uffers from low water solubility, which reduces its brightnessa nd FLTina queous solutions. The chromophore is closely structurally related to other reported cationic triangulenium fluorophores such as:A DOTA + , [21] DMQA + , [22] CDATA + [23] and BDATA + [24] dyes (Figure 1), but also to other much studied cationic dyes including helicenes, [25] acridines [26] and rhodamines. [27] Thus, we expect the here derived guidelines to be generally applicable to al arge range of cationic fluorescent dyes.…”

Section: Introductionsupporting

confidence: 56%

What is Best Strategy for Water Soluble Fluorescence Dyes?—A Case Study Using Long Fluorescence Lifetime DAOTA Dyes**

Bisballe

Laursen

2020

Chemistry A European J

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The lipophilic natureo fo rganic dyes complicates their effectiveness in aqueous solutions. In this work we investigate threed ifferent strategies for achieving water-solubility of the diazaoxatriangulenium (DAOTA +)c hromophore: hydrophilic counter ions, aromatic sulfonationo ft he chromophore, and attachment of charged side chains. The long fluorescence lifetime(FLT, t f = 20 ns) of DAOTA + makes it a sensitive probet oa nalyze solvation and aggregation effects. Direct sulfonation of the chromophore was found to increase solubility drastically,b ut at the cost of greatly re-ducedq uantum yields (QYs) due to enhanced non-radiative deactivation processes. The introduction of either cationic (4) or zwitterionic side chains (5), however,b rings the FLT (t f = 18 ns) and QY (f f = 0.56) of the dye to the same level as the parent chromophorei na cetonitrile. Time-resolved fluorescence spectroscopya lso reveals ah igh resistance to aggregation and non-specific binding in ah igh loading of bovines erum albumin (BSA). The results clearly show that addition of charged flexibles ide chains is preferable to directs ulfonation of the chromophore core.

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Section: Introductionsupporting

confidence: 56%

What is Best Strategy for Water Soluble Fluorescence Dyes?—A Case Study Using Long Fluorescence Lifetime DAOTA Dyes**

Bisballe

Laursen

2020

Chemistry A European J

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“…Although DAOTA‐M2 has already demonstrated its use as an optical probe to study G4 DNA, some of its properties, such as its brightness, could be improved. The triangulenium core structure easily lends itself to synthetic modifications [36–40] . Therefore, we set out to explore whether alternative triangulenium cores may have attractive properties as G4s probes such as greater discrimination of lifetimes for G4 over other topologies, increased brightness or different binding selectivity.…”

Section: Introductionmentioning

confidence: 99%

Assessing The Key Photophysical Properties of Triangulenium Dyes for DNA Binding by Alteration of the Fluorescent Core

Lewis

Bisballe

Santella

et al. 2020

Chemistry A European J

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Four‐stranded G‐quadruplex (G4) DNA is a non‐canonical DNA topology that has been proposed to form in cells and play key roles in how the genome is read and used by the cellular machinery. Previously, a fluorescent triangulenium probe (DAOTA‐M2) was used to visualise G4s in cellulo, thanks to its distinct fluorescence lifetimes when bound to different DNA topologies. Herein, the library of available triangulenium probes is expanded to explore how modifications to the fluorescent core of the molecule affect its photophysical characteristics, interaction with DNA and cellular localisation. The benzo‐bridged and isopropyl‐bridged diazatriangulenium dyes, BDATA‐M2 and CDATA‐M2 respectively, featuring ethyl‐morpholino substituents, were synthesised and characterised. The interactions of these molecules with different DNA topologies were studied to determine their binding affinity, fluorescence enhancement and fluorescence lifetime response. Finally, the cellular uptake and localisation of these optical probes were investigated. Whilst structural modifications to the triangulenium core only slightly alter the binding affinity to DNA, BDATA‐M2 and CDATA‐M2 cannot distinguish between DNA topologies through their fluorescence lifetime. It is argued theoretically and experimentally that this is due to reduced effectiveness of photoinduced electron transfer (PET) quenching. This work presents valuable new evidence into the critical role of PET quenching when using the fluorescence lifetime of triangulenium dyes to discriminate G4 DNA from duplex DNA, highlighting the importance of fine tuning redox and spectral properties when developing new triangulenium‐based G4 probes.

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“…[14][15] Shifting the absorption and emission further to the red side of the spectrum is highly attractive for imaging applications and have been successfully achieved by replacing one of the oxygen bridges by saturated or unsaturated carbon bridges, yielding dyes with emission between 580 nm and 652 nm. [16][17] However, in all cases these modifications come at the price of enhanced non-radiative deactivation rates resulting in somewhat reduced quantum yields (30-60%) and lifetimes (12-18 ns).…”

Section: Introductionmentioning

confidence: 99%

Utilizing Selective Chlorination to Synthesize New Triangulenium Dyes with Redshifted Absorption and Emission

Jd¹,

Bisballe²,

Kacenauskaite³

et al. 2020

Preprint

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Access to functionalization of a new site in the triangulenium core structure has been achieved at an early stageby chlorination with N-chlorosuccinimide (NCS), giving rise to two new triangulenium dyes (1 and 2). By introducing the chlorine functionalities in the acridinium precursor, positions complementary to those previously accessed by electrophilic aromatic substitution of the dyes are functionalized. The chlorination is highly selective giving only one regioisomer for both mono- and dichlorination. For the monochlorinated acridinium compound a highly selective ring-closing reaction was discovered generating only a single regioisomer of the cationic [4]helicene product. This discovery aspired further investigations into the mechanism of [4]helicene formation and to the first isolation of the previously proposed intermediate of the two-step SNAr reaction key to all aza bridged triangulenium and helicenium synthesis. The fully ring closed mono- and di-chlorinated triangulenium dyes 1 and 2 show a redshift in absorption and emission relative to the non-chlorinated analogues, while still maintaining relative high quantum yields of 36% and 41 %, and long fluorescence lifetimes of 15 ns and 16 ns, respectively.

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Extended Triangulenium Ions: Syntheses and Characterization of Benzo-Bridged Dioxa- and Diazatriangulenium Dyes

Cited by 22 publications

References 67 publications

What is Best Strategy for Water Soluble Fluorescence Dyes?—A Case Study Using Long Fluorescence Lifetime DAOTA Dyes**

What is Best Strategy for Water Soluble Fluorescence Dyes?—A Case Study Using Long Fluorescence Lifetime DAOTA Dyes**

Assessing The Key Photophysical Properties of Triangulenium Dyes for DNA Binding by Alteration of the Fluorescent Core

Utilizing Selective Chlorination to Synthesize New Triangulenium Dyes with Redshifted Absorption and Emission

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