We present the synthesis and characterization of a series of encapsulated diketopyrrolopyrrole red-emitting conjugated polymers. The novel materials display extremely high fluorescence quantum yields in both solution (>70%) and thin film (>20%). Both the absorption and emission spectra show clearer, more defined features compared to their naked counterparts demonstrating the suppression of inter and intramolecular aggregation. We find that the encapsulation results in decreased energetic disorder and a dramatic increase in backbone colinearity as evidenced by scanning tunnelling microscopy. This study paves the way for diketopyrrolopyrrole to be used in emissive solid state applications and demonstrates a novel method to reduce structural disorder in conjugated polymers.
This paper introduces a novel bacterial identification assay based on thermal wave analysis through surface-imprinted polymers (SIPs). Aluminum chips are coated with SIPs, serving as synthetic cell receptors that have been combined previously with the heat-transfer method (HTM) for the selective detection of bacteria. In this work, the concept of bacterial identification is extended toward the detection of nine different bacterial species. In addition, a novel sensing approach, thermal wave transport analysis (TWTA), is introduced, which analyzes the propagation of a thermal wave through a functional interface. The results presented here demonstrate that bacterial rebinding to the SIP layer resulted in a measurable phase shift in the propagated wave, which is most pronounced at a frequency of 0.03 Hz. In this way, the sensor is able to selectively distinguish between the different bacterial species used in this study. Furthermore, a dose–response curve was constructed to determine a limit of detection of 1 × 104 CFU mL–1, indicating that TWTA is advantageous over HTM in terms of sensitivity and response time. Additionally, the limit of selectivity of the sensor was tested in a mixed bacterial solution, containing the target species in the presence of a 99-fold excess of competitor species. Finally, a first application for the sensor in terms of infection diagnosis is presented, revealing that the platform is able to detect bacteria in clinically relevant concentrations as low as 3 × 104 CFU mL–1 in spiked urine samples.
Molecularly imprinted polymers (MIPs), synthetic polymeric receptors, have been combined successfully with thermal transducers for the detection of small molecules in recent years. However, up until now they have been combined with planar electrodes which limits their use for in vivo applications. In this work, a new biosensor platform is developed by roll-coating MIP particles onto thermocouples, functionalized with polylactic acid (PLLA). As a first proof-of-principle, MIPs for the neurotransmitter dopamine were incorporated into PLLA-coated thermocouples. The response of the synthetic receptor layer to an increasing concentration of dopamine in buffer was analyzed using a homemade heat-transfer setup. Binding of the template to the MIP layer blocks the heat transport through the thermocouple, leading to less heat loss to the environment and an overall higher temperature in the measuring chamber. The measured temperature increase is correlated to the neurotransmitter concentration, which enables measurement of dopamine levels in the micromolar regime. To demonstrate the general applicability of the proposed biosensor platform, thermocouples were functionalized with similar MIPs for cortisol and serotonin, indicating a similar response and limit-of-detection. As the platform does not require planar electrodes, it can easily be integrated in, e.g., a catheter. In this way, it is an excellent fit for the current niche in the market of therapeutics and diagnostics. Moreover, the use of a biocompatible and disposable PLLA-layer further illustrates its potential for in vivo diagnostics.
Conjugated polymers with intense solid-state emission are vital for the development of next-generation optoelectronic devices. In particular, it remains extremely challenging to construct π-conjugated systems which emit in the red region of the electromagnetic spectrum and also retain their optical properties and intense photoluminescence in the solid state. In this article we report the synthesis and characterization of three novel diketopyrrolopyrrole-based conjugated polymers, with systematic variation of the covalent encapsulation density. Through control of the distance and density of encapsulation, our red-emitting polymers demonstrate that aggregation caused quenching can be mostly eliminated, culminating in the most efficient solid-state photoluminescence from red conjugated polymers to date.
Intermolecular interactions play a fundamental role on the performance of conjugated materials in organic electronic devices, as they heavily influence their optoelectronic properties. Synthetic control over the solid state properties of organic optoelectronic materials is crucial to access real life applications. Perylene diimides (PDIs) are one of the most highly studied classes of organic fluorescent dyes. In the solid state, π–π stacking suppresses their emission, limiting their use in a variety of applications. Here, we report the synthesis of a novel PDI dye that is encapsulated by four alkylene straps. X-ray crystallography indicates that intermolecular π–π stacking is completely suppressed in the crystalline state. This is further validated by the photophysical properties of the dye in both solution and solid state and supported by theoretical calculations. However, we find that the introduction of the encapsulating “arms” results in the creation of charge-transfer states which modify the excited state properties. This article demonstrates that molecular encapsulation can be used as a powerful tool to tune intermolecular interactions and thereby gain an extra level of control over the solid state properties of organic optoelectronic materials.
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