New insights into the water-solubilisation of fluorophores by post-synthetic “click” and Sonogashira reactions

Massif, Cédrik; Dautrey, Sébastien; Haefelé, Alexandre; Ziessel, Raymond; Renard, Pierre; Romieu, Anthony

doi:10.1039/c2ob25428j

Cited by 26 publications

(16 citation statements)

References 52 publications

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“…In particular, they prevent aggregation and self-quenching of the dye residues, reduce the unspecific binding, and increase the fluorescence quantum yields. [3][4][5][6] Next we tested whether the photophysical properties of the selected dyes in biological samples fit to the parameters of the two-color STED microscope, which we planned to use. [1l] Therefore, the cells were labeled with a single fluorophore and imaged using the twocolor STED setup ( Figure S3 in the Supporting Information).…”

Section: Single-and Two-color Sted Nanoscopymentioning

confidence: 99%

“…Thus, a click reaction between an azide‐derivatized dye 2 d with primary phosphate residues and an alkyne reagent, already bearing an amino‐reactive moiety, was applied to avoid undesired activation of the phosphate groups. Quite recently, certain click and Sonogashira reactions broadened the scope of post‐synthetic dye modifications 5b. We report a synthesis that bypassed the selectivity problem and led to a phosphorylated “amphiphilic” dye 3 d (Figure 1) in the form of an NHS ester.…”

Section: Introductionmentioning

confidence: 99%

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Polar Red‐Emitting Rhodamine Dyes with Reactive Groups: Synthesis, Photophysical Properties, and Two‐Color STED Nanoscopy Applications

Kolmakov

Wurm

Meineke

et al. 2013

Chemistry A European J

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The synthesis, reactivity, and photophysical properties of new rhodamines with intense red fluorescence, two polar residues (hydroxyls, primary phosphates, or sulfonic acid groups), and improved hydrolytic stability of the amino‐reactive sites (NHS esters or mixed N‐succinimidyl carbonates) are reported. All fluorophores contain an N‐alkyl‐1,2‐dihydro‐2,2,4‐trimethylquinoline fragment, and most of them bear a fully substituted tetrafluoro phenyl ring with a secondary carboxamide group. The absorption and emission maxima in water are in the range of 635–639 and 655–659 nm, respectively. A vastly simplified approach to red‐emitting rhodamines with two phosphate groups that are compatible with diverse functional linkers was developed. As an example, a phosphorylated dye with an azide residue was prepared and was used in a click reaction with a strained alkyne bearing an N‐hydroxysuccinimid (NHS) ester group. This method bypasses the undesired activation of phosphate groups, and gives an amphiphilic amino‐reactive dye, the solubility and distribution of which between aqueous and organic phases can be controlled by varying the pH. The presence of two hydroxyl groups and a phenyl ring with two carboxyl residues in the dyes with another substitution pattern is sufficient for providing the hydrophilic properties. Selective formation of a mono‐N‐hydroxysuccinimidyl ester from 5‐carboxy isomer of this rhodamine is reported. The fluorescence quantum yields varied from 58 to 92 % for free fluorophores, and amounted to 18–64 % for antibody conjugates in aqueous buffers. The brightness and photostability of these fluorophores facilitated two‐color stimulated emission depletion (STED) fluorescence nanoscopy of biological samples with high contrast and minimal background. Selecting a pair of fluorophores with absorption/emission bands at 579/609 and 635/655 nm enabled two‐color channels with low cross‐talk and negligible background at approximately 40 nm resolution.

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Section: Single-and Two-color Sted Nanoscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polar Red‐Emitting Rhodamine Dyes with Reactive Groups: Synthesis, Photophysical Properties, and Two‐Color STED Nanoscopy Applications

Kolmakov

Wurm

Meineke

et al. 2013

Chemistry A European J

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“…The linker can be introduced through well-known couplings like amidation and the click-reaction, which many commercially available dyes are already set up for. [30][31][32] This strategy, however, seems to work best for dyes that already contain hydrophilic elements.…”

Section: Introductionmentioning

confidence: 99%

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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“…Especially problematic is the case of NIR-emitting BODIPYs since these chromophores tend to have larger aromatic structures and are thus more hydrophobic. [7,31] Several strategies have been reported to improve the water solubility of BODIPY dyes [8] such as the introduction of ionizable functional groups -carboxylate, sulfonate [18,32,33] or ammonium [33,34] groups -or the functionalization with carbohydrates, [35,36] dendrimers, [37,38] poly(ethylene glycol) (PEG) chains [18,21,24,39] or combinations thereof. [40,41] PEG functionalization can be even employed for NIR-emitting BODIPYs.…”

Section: Introductionmentioning

confidence: 99%

On the Aggregation Behaviour and Spectroscopic Properties of Alkylated and Annelated Boron‐Dipyrromethene (BODIPY) Dyes in Aqueous Solution

et al. 2019

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The tendency of boron‐dipyrromethene (BODIPY) dyes to associate in water is well known, and usually a cause for inferior fluorescence properties. Synthetic efforts to chemically improve BODIPYs’ water solubility and minimize this problem have been numerous in the past. However, a deeper understanding of the phenomena responsible for fluorescence quenching is still required. Commonly, the spectroscopic behaviour in aqueous media has been attributed to aggregate or excimer formation, with such works often centring on a single BODIPY family. Herein, we provide an integrating discussion including very diverse types of BODIPY dyes. Our studies revealed that even subtle structural changes can distinctly affect the association behaviour of the fluorophores in water, involving different photophysical processes. The palette of behaviour found ranges from unperturbed emission, to the formation of H or J aggregates and excimers, to the involvement of tightly bound, pre‐formed excimers. These results are a first step to a more generalized understanding of spectroscopic properties vs. structure, facilitating future molecular design of BODIPYs, especially as probes for biological applications.

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New insights into the water-solubilisation of fluorophores by post-synthetic “click” and Sonogashira reactions

Cited by 26 publications

References 52 publications

Polar Red‐Emitting Rhodamine Dyes with Reactive Groups: Synthesis, Photophysical Properties, and Two‐Color STED Nanoscopy Applications

Polar Red‐Emitting Rhodamine Dyes with Reactive Groups: Synthesis, Photophysical Properties, and Two‐Color STED Nanoscopy Applications

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

On the Aggregation Behaviour and Spectroscopic Properties of Alkylated and Annelated Boron‐Dipyrromethene (BODIPY) Dyes in Aqueous Solution

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