Anisotropic Polymer Nanoparticles with Tunable Emission Wavelengths by Intersegmental Chain Packing

Perez, Julian D. Ruiz; Mecking, Stefan

doi:10.1002/anie.201701000

Cited by 17 publications

(21 citation statements)

References 28 publications

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“…3,79 They combine desirable processability features with the unique optoelectronic properties of conjugated polymers 79 and the possibility of emission wavelength tuning by covalent incorporation of dyes or by employment of comonomers. 8,[80][81][82][83] Furthermore, colloidal dispersions of CPNs provide attractive building blocks for the formation of films by deposition onto solid substrates. 84 Application fields for such uniform coverage over large areas are for instance photovoltaic devices 85 or OLEDs.…”

Section: Conjugated Polymer Nanoparticlesmentioning

confidence: 99%

“…[148][149][150] Starting from the occasional observation of non-spherical CPNs in different protocols of heterophase polymerization, 80,151 a protocol for the synthesis of anisotropic poly(9,9´-dioctylfluorene) nanoparticles via heterophase Suzuki-Miyaura polycondensation was evolved by Ruiz Perez et al (Figure 1.6). 8 The reaction parameters were examined and optimized for the Pd-catalyzed polymerization of AA/BB-type monomers to develop suitable conditions yielding well-defined ellipsoidal particles (length ≈ 140 nm) with high aspect ratio (ar = 3.6) and narrow size and shape distribution. In order to red-shift the blue-colored fluorescence of the particles, the covalent incorporation of fluorescent dyes during polymerization was successfully demonstrated.…”

Section: Anisotropic Polymer Nanoparticlesmentioning

confidence: 99%

“…By spectroscopic monitoring, a preliminary mechanism of particle formation was elaborated, showing an important contribution of chain conformation and intermolecular polymer packing. 8 Several individual steps (namely chain growth, orientation, particle formation and diffusion of the organic phase) were suggested to occur in a concerted fashion. Although the detailed origin and formation of particle anisotropy remained elusive, a strong correlation between internal polymer chains arrangement and external particle dimension were considered.…”

Section: Anisotropic Polymer Nanoparticlesmentioning

confidence: 99%

“…[5][6][7] Recently, a protocol for the formation of ellipsoidal poly(9,9´-dioctylfluorene) nanoparticles by heterophase Suzuki-Miyaura polycondensation was established by Ruiz Perez et al, enabling the direct synthesis of anisotropic CPNs. 8 The intersegmental packing of polymer chains typically plays a crucial role in the mechanism of particle formation; however, the origin of anisotropy remained elusive to date.…”

Section: General Introductionmentioning

confidence: 99%

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Origin of the Anisotropy and Structure of Ellipsoidal Poly(fluorene) Nanoparticles

Sickinger

Mecking

2021

Macromolecules

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An erster Stelle gilt mein Dank Prof. Dr. Stefan Mecking für die Aufnahme in die Arbeitsgruppe und die hervorragende Betreuung dieser Arbeit. Er vertraute mir ein extrem vielseitiges, interessantes und herausforderndes Thema an und zeigte stets Interesse an meiner Forschung. Für seine jahrelange Unterstützung, viele hilfreichen Gespräche und die mir gewährten Freiheiten möchte ich mich herzlich bedanken. Weiterhin danke ich Prof. Dr. Malte Drescher für die Übernahme der Zweitbetreuung und des Zweitgutachtens genauso wie für die gute Zusammenarbeit im Rahmen des Kooperationsprojektes. Für die Übernahme des Prüfungsvorsitzes möchte ich Prof. Dr. Helmut Cölfen ganz herzlich danken. Ein besonders großer Dank gilt Dr. Julian Ruiz Perez für die umfangreiche und geduldige Einführung in die Thematik der Polyfluoren-Nanopartikel, einschließlich zahlreicher Synthese-und Analytikmethoden.

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Section: Conjugated Polymer Nanoparticlesmentioning

confidence: 99%

Section: Anisotropic Polymer Nanoparticlesmentioning

confidence: 99%

Section: Anisotropic Polymer Nanoparticlesmentioning

confidence: 99%

Section: General Introductionmentioning

confidence: 99%

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Origin of the Anisotropy and Structure of Ellipsoidal Poly(fluorene) Nanoparticles

Sickinger

Mecking

2021

Macromolecules

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“…Alternative chemical strategies include polymer modification with different core units/side substituents, or the controlled synthesis of oligomeric species differing on the number of repetitive monomers (and therefore conjugation length) . Only very recently the synthesis of nanoparticles with tunable optical properties has been partially achieved through the synthesis of polymer dots with packing‐dependent emission . Therefore, there is a need to find novel approaches for the simultaneous spectral tuning and nanostructuration of semiconductive polymers.…”

mentioning

confidence: 99%

Sonochemical Synthesis of Optically Tuneable Conjugated Polymer Nanoparticles

Bellacanzone

Roscini

Delgado

et al. 2018

Part & Part Syst Charact

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the development of novel and simple methodologies for the obtaining of semiconductive nanoparticles with fine-tuned optical (especially emission) properties, [9] due to its implicit technological relevance and the applications that can be derived from there. So far, spectral emission tuning of bulk semiconductive polymers has raised lots of interest and has been reported through encapsulation and confinement in nano porous silica NPs, [10] systematic variation of solvent and polymer concentration [11] or after postfabrication annealing/cooling or pressure/mechanical cycles. [12][13][14] Alternative chemical strategies include polymer modification with different core units [15] / side substituents, [16] or the controlled synthesis of oligomeric species differing on the number of repetitive monomers (and therefore conjugation length). [17] Only very recently the synthesis of nanoparticles with tunable optical properties has been partially achieved through the synthesis of poly mer dots with packing-dependent emission. [5,18] Therefore, there is a need to find novel approaches for the simultaneous spectral tuning and nanostructuration of semiconductive polymers.Sonication in chloroform/water mixtures can be an excellent technique to achieve this target. First, emulsification induced by ultrasonic radiation is a process broadly used for the formation of nanoparticles. Second, sonication of chloroform/water mixture is known to generate reactive species (Scheme S1, Supporting Information) such as chlorine radicals (·Cl, ·CHCl 2 , ·CCl 3 ) [19] and hypochlorous acid (HOCl), [20] which can be used to systematically cleave conjugated species, and therefore to modify the final optical properties. Indeed, chlorine radicals obtained by different means such as daylight, [21] γ-radiations [22] or thermal treatment, [23,24] have already been shown to tune the properties of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) upon polymer fragmentation, [21][22][23][24] whereas HOCl acts as strong oxidative species cleaving linear conjugated systems. [25][26][27] Conjugated polymer scission and chain shortening caused by oxidative species (i.e., H 2 O 2 ) has been previously exploited to confer biodegradability to fluorescent CPNs suitable for bioimaging, [28] but no controlled tuning of the emission properties has been reported. Therefore, herein we hypothesize that sonication of the semiconductive polymer of the polymer. Here, starting from poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], this objective is achieved with the one-pot synthesis of oligomers with tunable conjugation length and their nanostructuration, employing a miniemulsion method. Ultrasound irradiation of heterogeneous mixtures leads to the formation of hypochlorous acid that disrupts the electronic conjugation through polymer chain cleavage. Moreover, control over the degree of the electronic conjugation of the oligomers, and therefore of the optical properties, is achieved simply by varying the polymer concentration of the initial so...

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Formation of Polymeric Nanocubes by Self‐Assembly and Crystallization of Dithiolane‐Containing Triblock Copolymers

et al. 2017

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Template-free fabrication of non-spherical polymeric nanoparticles is desirable for various applications,b ut has had limited success owing to thermodynamic favorability of sphere formation. Herein we present as imple way to prepare cubic nanoparticles of blockcopolymers by self-assembly from aqueous solutions at room temperature.Nanocubes with edges of 40-200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing ac entral poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks.T hese polymers self-assemble into 28 AE 5nmmicelles in water.Upon drying, micelle aggregation and ak inetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol-or photo-induced crosslinking was developed. The ability to solubilizeamodel hydrophobic drug, curcumin, was also explored.

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Anisotropic Polymer Nanoparticles with Tunable Emission Wavelengths by Intersegmental Chain Packing

Cited by 17 publications

References 28 publications

Origin of the Anisotropy and Structure of Ellipsoidal Poly(fluorene) Nanoparticles

Origin of the Anisotropy and Structure of Ellipsoidal Poly(fluorene) Nanoparticles

Sonochemical Synthesis of Optically Tuneable Conjugated Polymer Nanoparticles

Formation of Polymeric Nanocubes by Self‐Assembly and Crystallization of Dithiolane‐Containing Triblock Copolymers

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