Collective fluorescence switching of counterion-assembled dyes in polymer nanoparticles

Reisch, Andreas; Didier, Pascal; Richert, Ludovic; Oncul, Sule; Arntz, Youri; Mély, Yves; Klymchenko, Andrey S.

doi:10.1038/ncomms5089

Cited by 173 publications

(352 citation statements)

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“…Moreover, these organic fluorescent nanomaterials are potentially biodegradable in contrast to QDs, making them particularly attractive for biomedical imaging applications. 1, 2 Several organic systems have already been developed: conjugated polymer NPs, 6, 7 dyedoped polymer NPs [8][9][10][11][12][13][14] and dye-based NPs.…”

Section: Introductionmentioning

confidence: 99%

Fluorinated counterion-enhanced emission of rhodamine aggregates: ultrabright nanoparticles for bioimaging and light-harvesting

et al. 2015

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The key to ultrabright fluorescent nanomaterials is the control of dye emission in the aggregated state. Here, lipophilic rhodamine B derivatives are assembled into nanoparticles (NPs) using tetraphenylborate counterions with varied fluorination levels that should tune the short-range dye ordering. Counterion fluorination is found to drastically enhance the emission characteristics of these NPs. Highly fluorinated counterions produce 10-20 nm NPs containing >300 rhodamine dyes with a fluorescence quantum yield of 40-60% and a remarkably narrow emission band (34 nm), whereas, for other counterions, aggregation caused quenching with a weak broad-band emission is observed. NPs with the most fluorinated counterion (48 fluorines) are ∼40-fold brighter than quantum dots (QD585 at 532 nm excitation) in single-molecule microscopy, showing improved photostability and suppressed blinking. Due to exciton diffusion, revealed by fluorescence anisotropy, these NPs are efficient FRET donors to single cyanine-5 acceptors with a light-harvesting antenna effect reaching 200. Finally, NPs with the most fluorinated counterion are rather stable after entry into living cells, in contrast to their less fluorinated analogue. Thus, the present work shows the crucial role of counterion fluorination in achieving high fluorescence brightness and photostability, narrow-band emission, efficient energy transfer and high intracellular stability of nanomaterials for light harvesting and bioimaging applications.

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Section: Introductionmentioning

confidence: 99%

Fluorinated counterion-enhanced emission of rhodamine aggregates: ultrabright nanoparticles for bioimaging and light-harvesting

et al. 2015

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“…It was shown that brightly fl uorescent nanoparticles can be made of subjective to self-quenching aggregation cationic rhodamine dye by mixing this dye with hydrophobic anion tetraphenyl borate. Within these particles the fl uorophores exchanged their excitedstate energies and demonstrated collective blinking effect (Reisch et al 2014 ). In this regard, there are the publications describing achieving the effect opposite to aggregation-induced quenching -the aggregation-induced emission (Hu et al 2014 ).…”

Section: Fluorescent Nanoparticles Made Of Organic Dyes and Aggregatimentioning

confidence: 99%

Nanoscale Fluorescence Emitters

Demchenko

2015

Introduction to Fluorescence Sensing

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This chapter provides comparative analysis of properties of different nanoscale materials to absorb and emit visual and near-IR light with the focus on their applications in sensing and imaging technologies. Nowadays we observe that in these applications the novel nanoscale fl uorescent materials appear in strong competition with traditional organic dyes. They demonstrate diverse photophysical behavior and allow obtaining diverse information when they are incorporated into sensor composites or form the images in biological systems. Among these nanoscale emitters are the structures formed of organic dyes or by these dyes incorporated into different types of polymers with the resulting dramatically increased brightness. Collective excitonic effects appear when the aromatic units are coupled in conjugated polymers. Nanoscale structures formed of inorganic carbon in the form of nanodiamonds, graphene and graphene oxide pieces and the so-called carbon dots joined quite recently the family of fl uorophores. Semiconductor quantum dots present a range of bright emitters covering whole visible and near-IR spectral range. Finally, the up-converting nanocrystals make possible visible emission with near-IR excitation. Here we overview the most important features of these nanoscale materials. The following Chap. 6 will be focused on functional nanocomposites that allow extending the useful properties of these basic components.

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“…The area of organic NPs for bioimaging develops very rapidly. Here, one should mention conjugated polymer NPs, [4] dye-loaded polymer NPs, [5] DNA nanostructures, [6] and dye-based NPs, [7] including those exploiting aggregation induced emission. [5b, 8] However, obtaining bright and stable fluorescent NPs of 5-10 nm hydrodynamic diameter remains a challenge.…”

Section: Introductionmentioning

confidence: 99%

Protein‐Sized Bright Fluorogenic Nanoparticles Based on Cross‐Linked Calixarene Micelles with Cyanine Corona

et al. 2016

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The key challenge in the field of fluorescent nanoparticles (NPs) for biological applications is to achieve superior brightness for sizes equivalent to single proteins (3-7 nm). We propose a concept of shell-cross-linked fluorescent micelles, where PEGylated cyanine 3 and 5 bis-azides form a covalently attached "corona" on micelles of amphiphilic calixarene bearing four alkyne groups. The obtained monodisperse NPs of 7 nm size increase their fluorescence quantum yield as a function of viscosity reaching 15% in glycerol. In the on-state they are ~2-fold brighter than quantum dots (QD-585), being the smallest PEGylated organic NPs of this high brightness. FRET between cyanine 3 and 5 cross-linkers at the surface of NPs suggests their integrity in physiological media, organic solvents and living cells, where they rapidly internalize showing excellent imaging contrast. Calixarene micelles with cyanine corona constitute a new platform for development of protein-sized ultrabright fluorescent NPs.* andrey.klymchenko@unistra.fr. Presently, we propose a concept of protein-sized fluorescent NPs based on calixarene micelles that are shell-cross-linked by fluorescent bi-functional dyes via Cu-catalysed "click" chemistry. In one recent report, a surfactant bearing three acetylene groups was polymerized using non-fluorescent cross-linker, while the non-reacted alkynes were further modified with fluorescent mono-functional dyes. Europe PMC Funders Group[15] In our strategy, we designed fluorescent cross-linkers to enable both micelle cross-linking and introduction of the fluorescent units. To this end, we selected cyanine 3 and 5 dyes, because of their excellent optical properties [16] and symmetric structure ( Figure 1). They were modified with two azide groups for crosslinking of the micelle and two hydrophilic PEG(8) chains to create its biocompatible shell. We call this design "cyanine corona", similarly to well-known protein corona that modifies the surfaces of a variety of NPs. (Figure 1). They are the first protein-sized NPs combining fluorogenic response to viscosity with superior brightness compared to quantum dots (QD-585).The calixarene amphiphile CX8TP at 150 μM concentration in aqueous solution (75 mM sodium sulfate) forms micelles of 5 nm according to dynamic light scattering (DLS) ( Figure S1). These micelles were further reacted with 2 eq of the cross-linkers Cy3L or Cy5L in the presence of copper catalyst for 24h at 30 °C. Then these reaction mixtures were dialyzed and their pick absorbance was compared to that before the dialysis. We found that after the reaction only a fraction (≤50%) of the cross-linkers was removed, whereas the control samples without added Cu-catalyst lost nearly all cross-linkers after the dialysis ( Figure 1A). These results provide an evidence for the successful cross-linking of micellar NPs with Cy3L and Cy5L. The absorption data suggested the cross-linking yields of 59 and 49% for Cy3L and Cy5L dyes, respectively. Moreover, the IR spectrum of the cross-linked micelles (CX/C...

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Collective fluorescence switching of counterion-assembled dyes in polymer nanoparticles

Cited by 173 publications

References 58 publications

Fluorinated counterion-enhanced emission of rhodamine aggregates: ultrabright nanoparticles for bioimaging and light-harvesting

Fluorinated counterion-enhanced emission of rhodamine aggregates: ultrabright nanoparticles for bioimaging and light-harvesting

Nanoscale Fluorescence Emitters

Protein‐Sized Bright Fluorogenic Nanoparticles Based on Cross‐Linked Calixarene Micelles with Cyanine Corona

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