Dönüs Tuncel

Conjugated polymer nanoparticles

Conjugated polymer nanoparticles are highly versatile nano-structured materials that can potentially find applications in various areas such as optoelectronics, photonics, bio-imaging, bio-sensing and nanomedicine. Their straightforward synthesis in desired sizes and properties, biocompatibility and non-toxicity make these materials highly attractive for the aforementioned applications. This feature article reviews the recent developments in the synthesis, characterization, properties and application of these exciting nanostructured materials.

Molecular switch based on a cucurbit[6]uril containing bistable [3]rotaxane.

A bistable CB6-based [3]rotaxane with two recognition sites has been prepared very efficiently in a high yield synthesis through CB6 catalyzed 1,3-dipolar cycloaddition; this rotaxane behaves as a reversible molecular switch and exhibits conformational changes caused by the movement of rings under base, acid and heat stimuli from one location to the other.

pH-Triggered dethreading-rethreading and switching of cucurbit[6]uril on bistable [3]pseudorotaxanes and [3]rotaxanes.

A series of water-soluble [3]rotaxanes-(n+2) and [3]pseudorotaxanes-(n+2) with short (propyl, n=1) and long (dodecyl, n=10) aliphatic spacers have been prepared in high yields by a 1,3-dipolar cycloaddition reaction catalyzed by cucurbit[6]uril (CB6). The pH-triggered dethreading and rethreading of CB6 on these pseudorotaxanes was monitored by 1H NMR spectroscopy. A previously reported [3]rotaxane-12 that is known to behave as a bistable molecular switch has two recognition sites for CB6, that is, the diaminotriazole moieties and the dodecyl spacer. By changing the pH of the system, it is possible to observe more than one state in the shuttling process. At low pH values both CB6 units are located on the diaminotriazole moieties owing to an ion-dipole interaction, whereas at high pH values both of the CB6 units are located on the hydrophobic dodecyl spacer. Surprisingly, the CB6 units shuttle back to their initial state very slowly after reprotonation of the axle. Even after eighteen days at room temperature, only about 50 % of the CB6 units had relocated back onto the diaminotriazole moieties. The rate constants for the shuttling processes were measured as a function of temperature over the range from 313 to 333 K and the activation parameters (enthalpy, entropy, and free energy) were calculated by using the Eyring equation. The results indicate that this [3]rotaxane behaves as a kinetically controlled molecular switch. The switching properties of [3]rotaxane-3 have also been studied. However, even under extreme pH conditions this rotaxane has not shown any switching action, which confirms that the propyl spacer is too short to accommodate CB6 units.

Sequence-specific self-sorting of the binding sites of a ditopic guest by cucurbituril homologues and subsequent formation of a hetero[4]pseudorotaxane.

The selectivity and recognition behavior of cucurbit[n]uril (CB[n]) homologues (n=6,7,8) towards a ditopic guest containing two distinct binding sites is explored. CB6, CB7, and CB8 recognize and self-sort the binding sites according to their size, shape, and chemical nature. In the presence of both CB6 and CB8 a hetero[4]pseudorotaxane is formed.

Red Emitting, Cucurbituril-Capped, pH-Responsive Conjugated Oligomer-Based Nanoparticles for Drug Delivery and Cellular Imaging

Here we report the synthesis of nanoparticles based on a conjugated oligomer which is synthesized through Heck-coupling of divinylfluorene and dibromobenzothiodiazole monomers. These water dispersible nanoparticles emit in the region of red tailing to the near-infrared region of the spectrum with high fluorescent quantum yield and brightness. The nanoparticles were found to be stable in water for a prolonged time without forming any aggregates and could carry camptothecin, an anticancer drug with high loading efficiency. MTT cell viability studies performed with breast cancer cell lines showed that half-maximal inhibitory concentration (IC50) values of nanoparticles for MCF7 and MDA-MB-231 were 44.7 μM and 24.8 μM, respectively. In order to further decrease the cytotoxicity and increase the stability of nanoparticles, amine groups were disguised by capping with cucurbit[7]uril (CB7). Drug release studies showed that drugs were released at low pH (at 5.0) faster than physiological pH (7.4) confirming the pH-responsive nature of the nanoparticles. On the other hand, CB7-capped drug-loaded nanoparticles regulated the release rate by providing slower release at pH 7.4 than the nanoparticles in the absence of CB7s. IC50 values for camptothecin in the presence of nanoparticles with or without CB7 were significantly reduced in MCF7 and MDA-MB-231 cells.

Catalytically self-threading polyrotaxanes

A mainchain polyrotaxane is formed in which polymerisation and rotaxane formation occur simultaneously, due to the presence of the catalytically-active self-threading macrocycle cucurbituril.

Facile synthesis of cross-linked patchy fluorescent conjugated polymer nanoparticles by click reactions

Here, we report a novel method to synthesize multifunctional nanoparticles that can be used in biological studies, such as in cell imaging and as a carrier for biomolecules/drugs. The nanoparticles were prepared either viaCu-catalyzed or cucurbit[6]uril (CB6)-catalyzed click reactions between azide groups containing hydrophobic blue, green and yellow emitting fluorene-based conjugated polymers and a hydrophilic diaminodialkyne containing cross-linker. Through the click reaction, not only does the cross-linking confer stability, but it also introduces functional groups, such as triazoles and amines, to the nanoparticles. Moreover, CB6 not only acted as a catalyst to facilitate the copper-free click reaction, but it also allowed us to obtain nanoparticles containing rotaxanes in which the triazole units were encapsulated by CB6 units. TEM images of the nanoparticles also showed that they display very interesting morphologies. Incorporation of hydrophilic functional groups to the hydrophobic conjugated polymers resulted in a distinct phase separation, producing Janus-like or patchy particles.

pH-Responsive polypseudorotaxane synthesized through cucurbit[6]uril catalyzed 1,3-dipolar cycloaddition

A pH-responsive polypseudorotaxane has been synthesized via cucurbit[6]uril (CB6)-catalyzed 1,3-dipolar cycloaddition using diazide and dialkyne monomers, which contain a long aliphatic-spacer. The polypseudorotaxane was characterized by spectroscopic techniques (1H, 13C NMR and FT-IR) and matrix assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF MS). The experimental results reveal that this polypseudorotaxane behaves as a pH-driven polymeric switch. Thus, when amine groups are protonated at an appropriate pH, CB6s are located on the triazole rings due to ion–dipole interaction, whereas at high pH they move onto the hydrophobic aliphatic spacer rather than slipping off the polypseudorotaxane.

Quantum efficiency enhancement in film by making nanoparticles of polyfluorene

We report on conjugated polymer nanoparticles of polyfluorene that were formed to exhibit higher fluorescence quantum efficiency in film (68%) and reduce undesired emission peak wavelength shifts in film (by 20 nm), compared to the solid-state polymer thin film made directly out of the same polymer solution without forming nanoparticles. Using the facile reprecipitation method, solutions of poly[9,9-dihexyl-9H-fluorene] in THF were added at different volume ratios to obtain different size distributions of nanoparticle dispersions in water. This allowed us to control the sizedependent optical emission of our polyfluorene nanoparticles. Such organic nanoparticles hold great promise for use as efficient emitters in optoelectronic device applications.

White emitting polyfluorene functionalized with azide hybridized on near-UV light emitting diode for high color rendering index

We develop and demonstrate high-quality white light generation that relies on the use of a single-type simple conjugated polymer of polyfluorene functionalized with azide groups (PFA) integrated on a near-UV LED platform. The high-quality white emission from the polyfluorene is achieved by using the azide functionalization to facilitate cross-linking intentionally when cast into solid-state form. Hybridized on n-UV InGaN/GaN LED at 378 nm, the PFA emitters collectively generate a very broad down-converting photoluminescence at longer wavelengths across the entirety of the visible spectrum, yielding high color rendering indices up to 91.