An aluminium-based fluorinated counterion for enhanced encapsulation and emission of dyes in biodegradable polymer nanoparticles

Andreiuk, Bohdan; Reisch, Andreas; Pivovarenko, Vasyl G.; Klymchenko, Andrey S.

doi:10.1039/c7qm00248c

Cited by 19 publications

(37 citation statements)

References 56 publications

(68 reference statements)

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“…We expect that the non‐encapsulated dye desorbs from the surface of NPs due to contact with cell membranes and then gets dissolved in lipids of membranes, generating high fluorescence signal all over the cells. The observed significantly higher fluorescence intensity in this case is due to much higher efficiency of contact‐mediated dye transfer from all NPs outside and inside the cells comparing to endocytosis of NPs, in agreement with our previous work . The intermediate case was observed for NPs containing B(CF 3 ) 4 , F5‐3PB‐OH and B 21 H 18 , where both continuous fluorescence from the leaked dye and dotted fluorescence from NPs were observed.…”

Section: Resultssupporting

confidence: 90%

“…However, the larger dye cyanine 5 delivered higher quantum yields in couple with F12‐TPB, which is larger than F5‐TPB, which shows that critical size of counterion should be reached also for cyanines. It was also shown that fluorination of counterion plays an important role to prevent ACQ in pure dye salts of R18 and some cyanines . In this work, we found the first example of non‐fluorinated counterion (B 21 H 18 ) that prevents well ACQ in dye‐loaded NPs.…”

Section: Resultsmentioning

confidence: 58%

“…We could speculate that the size of the counterion should not be significantly smaller than the size of the dye. Previously, we showed that both F5‐TPB and F12‐TPB are efficient against ACQ in cyanine 3 dye . However, the larger dye cyanine 5 delivered higher quantum yields in couple with F12‐TPB, which is larger than F5‐TPB, which shows that critical size of counterion should be reached also for cyanines.…”

Section: Resultsmentioning

confidence: 89%

“…This approach was proven to be compatible with other cationic dyes, such as cyanines, leading to the development of a method for long‐term rainbow cell barcoding . Moreover, F5‐TPB counterion can be replaced with another fluorinated tetraphenylborate and a fluorinated aliphatic aluminate . Finally, the counterion‐based approach was recently applied to create an unprecedented giant light‐harvesting nanoantenna that allowed detection of single molecules in ambient light conditions, and amplified detection of nucleic acids …”

Section: Introductionmentioning

confidence: 99%

“…[18] Moreover,F 5-TPB counterion can be replaced with another fluorinated tetraphenylborate [18] and af luorinated aliphatic aluminate. [19] Finally,t he counterion-based approach was recently applied to create an unprecedented giant lightharvesting nanoantenna that allowed detection of single molecules in ambientl ight conditions, [20] and amplifiedd etection of nucleic acids. [21] These bulky hydrophobic counterions belong to the class of weakly coordinating anions, characterizedb yh igh charge delocalization,l arge size, absence of basic sites, presenting mainly fluorine or hydrogen at their anions urface.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Fighting Aggregation‐Caused Quenching and Leakage of Dyes in Fluorescent Polymer Nanoparticles: Universal Role of Counterion

Andreiuk

Reisch

Bernhardt

et al. 2019

Chemistry An Asian Journal

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134

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Dye‐loaded polymer nanoparticles (NPs) emerge as a powerful tool for bioimaging applications, owing to their exceptional brightness and controlled small size. However, aggregation‐caused quenching (ACQ) and leakage of dyes at high loading remain important challenges of these nanomaterials. The use of bulky hydrophobic counterions has been recently proposed as an effective approach to minimize ACQ and dye leakage, but the role of counterion structure is still poorly understood. Here, a systematic study based on ten counterions, ranging from small hydrophilic perchlorate up to large hydrophobic tetraphenylborate derivatives, reveals how counterion nature can control encapsulation and emission of a cationic dye (rhodamine B octadecyl ester) in NPs prepared by nanoprecipitation of a biodegradable polymer, poly‐lactide‐co‐glycolide (PLGA). We found that increase in counterion hydrophobicity enhances dye encapsulation efficiency and prevents dye adsorption at the particle surface. Cellular imaging studies revealed that ≥95 % encapsulation efficiency, achieved with most hydrophobic counterions (fluorinated tetraphenylborates), is absolutely required because non‐encapsulated dye species at the surface of NPs are the origin of dye leakage and strong fluorescence background in cells. The size of counterions is found to be essential to prevent ACQ, where the largest species, serving as effective spacer between dyes, provide the highest fluorescence quantum yield. Moreover, we found that the most hydrophobic counterions favor dye–dye coupling inside NPs, leading to ON/OFF fluorescence switching of single particles. By contrast, less hydrophobic counterions tend to disperse dyes in the polymer matrix favoring stable emission of NPs. The obtained structure‐property relationships validate the counterion‐based approach as a mature concept to fight ACQ and dye leakage in the development of advanced polymeric nanomaterials with controlled optical properties.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 58%

Section: Resultsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Fighting Aggregation‐Caused Quenching and Leakage of Dyes in Fluorescent Polymer Nanoparticles: Universal Role of Counterion

Andreiuk

Reisch

Bernhardt

et al. 2019

Chemistry An Asian Journal

Self Cite

134

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show abstract

Bulky Hydrophobic Counterions for Suppressing Aggregation‐caused Quenching of Ionic Dyes in Fluorescent Nanoparticles

Aparin¹,

Adarsh²,

Reisch³

et al. 2022

Handbook of Aggregation‐Induced Emission

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Protein‐Sized Dye‐Loaded Polymer Nanoparticles for Free Particle Diffusion in Cytosol

Reisch

Heimburger

Ernst

et al. 2018

Adv Funct Materials

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How small should nanoparticles be in order to travel freely through the cytosol similar to proteins? Answering this question remains a challenge, because the majority of nanoparticles are relatively large and their size cannot be finely tuned to match that of proteins. Here, poly(methyl methacrylate) copolymers with varied fraction and type of charged groups (carboxylate, sulfonate, and trimethylammonium) are developed, yielding nanoparticles with controlled sizes from 50 to 7 nm through nanoprecipitation. Loading these nanoparticles with a rhodamine dye/bulky counterion pair at 10wt% makes them highly fluorescent. After their coating with polyethylene glycol groups for preventing non-specific protein binding and microinjection into living cells, the first systematic study of the size effect on diffusion in the cytosol for solid nanoparticles of the same nature is realized. Single-particle-tracking data provide evidence for distinct particle sieving in the cytosol, suggesting that only nanoparticles below a critical size of 23 nm exhibit free diffusion and spreading. These findings show the size limitations imposed by intracellular crowding and compartmentalization, which is critical for applications of nanomaterials in the cytosol. The proposed concept of polymer design opens the route to organic nanoparticles of ultrasmall sizes and high loading for bioimaging and drug-delivery applications.

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An aluminium-based fluorinated counterion for enhanced encapsulation and emission of dyes in biodegradable polymer nanoparticles

Abstract: An aluminium-based anion allows preparation of ultra-bright fluorescent polymer nanoparticles with nearly quantitative cationic dye encapsulation, minimized self-quenching and no dye leakage in live cells.

Cited by 19 publications

References 56 publications

Fighting Aggregation‐Caused Quenching and Leakage of Dyes in Fluorescent Polymer Nanoparticles: Universal Role of Counterion

Fighting Aggregation‐Caused Quenching and Leakage of Dyes in Fluorescent Polymer Nanoparticles: Universal Role of Counterion

Bulky Hydrophobic Counterions for Suppressing Aggregation‐caused Quenching of Ionic Dyes in Fluorescent Nanoparticles

Protein‐Sized Dye‐Loaded Polymer Nanoparticles for Free Particle Diffusion in Cytosol

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