RESUMO
The stereoregular nonconjugated pendant electroactive polymer (NCPEP) poly((N-carbazolylethylthio) propyl methacrylate) (PCzETPMA) has recently shown charge carrier mobilities that are on par with conjugated polymers. Here, we increased the complexity of the architecture for this NCPEP by introducing a polystyrene (PS) block via an anionic, living polymerization yielding a family of PS-b-PCzETPMA block copolymers as the first examples of NCPEP-block-copolymers with controlled stereoregularity of the NCPEP-blocks. Through this methodology we were able to control the molar masses, PS to PCzETPMA block ratios, and tacticities of the PCzETPMA-blocks. We found all three parameters to significantly impact the hole mobilities (µh) of the resulting copolymers, which increased with higher molar masses, longer PCzETPMA-blocks, and higher isotacticity of the PCzETPMA-block, giving the best µh of 2.33 × 10-5 cm2/V·s after annealing at 150 °C for the highest molar mass copolymer with a dominant isotactic PCzETPMA-block. This work is the first reported synthesis of a block copolymer bearing a NCPEP-block with a controlled tacticity and demonstrates that such complex polymer architectures can be realized with NCPEPs while maintaining control over their stereoregularity and without significantly suppressing the hole mobility in the resulting copolymers.
RESUMO
Here, brand new ternary hybrid solar cells comprising perovskite nanocrystals (NCs) with a complementary absorption profile of the organic host matrix are reported. In particular, NH2CH[double bond, length as m-dash]NH2PbI3 (FAPbI3) perovskite NCs are implemented in bulk heterojunction organic solar cells based on the pDPP5T-2 electron donating polymer and a [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) acceptor at various loading amounts and the fabricated hybrid photovoltaics are thoroughly studied by employing different optoelectrical characterization methods. Current-voltage measurements and photoinduced charge carrier extraction by linear increasing voltage (photo-CELIV) reveal improved charge generation and charge transport properties upon incorporation of perovskite NCs into the photo-active layer of the hybrid solar cell. The power conversion efficiency (PCE) of the hybrid solar cell comprising 5% perovskite NCs is 10% enhanced compared to the organic reference, mainly due to the enlarged light harvesting and increased short circuit current density (Jsc). However, results suggest that introducing a higher amount of perovskite content induces bimolecular and trap-assisted recombination in the ternary devices. We perform a comprehensive transient absorption study of the charge transfer/transport mechanisms by employing femto-second pump-probe transient absorption spectroscopy (fs-TAS). fs-TAS measurements demonstrate a slower charge carrier recombination rate due to the introduction of perovskite NCs into the photoactive layer. Results reveal that DPP injects electrons from the singlet excited state into the perovskite NCs, which causes the desired cascading charge carrier transfer. In ternary blends, a small amount of FAPbI3 NCs provides an additional pathway in favor of the charge-separated state via the NCs, which, despite accelerating the depopulation of DPP's singlet excited state slightly slows down the charge-separation process between DPP and PC61BM. Interestingly, the loss processes are slowed down; an effect that is more important and, hence, explains the improved solar cell efficiency.
RESUMO
Low-bandgap near-infrared polymers are usually synthesized using the common donor-acceptor (D-A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D-A1 -D-A2 low bandgap semiconducting polymers is reported for the first time. Correlation between the chemical structure of single-component polymer films and their optoelectronic properties has been achieved in terms of absorption maxima, optical bandgap, ionization potential, and electron affinity. Preliminary organic photovoltaic results based on blends of the D-A1 -D-A2 polymers as the electron donor mixed with the fullerene derivative [6,6]-phenyl-C71 -butyric acid methyl ester demonstrate power conversion efficiencies close to 4% with short-circuit current densities (J sc ) of around 11 mA cm-2 , high fill factors up to 0.70, and high open-circuit voltages (V oc s) of 0.70 V. All the devices are fabricated in an inverted architecture with the photoactive layer processed in air with doctor blade technique, showing the compatibility with roll-to-roll large-scale manufacturing processes.
Assuntos
Fontes de Energia Elétrica , Polímeros/química , Energia Solar , Estrutura Molecular , Polímeros/síntese químicaRESUMO
1. Macrolides belong to the polyketide class of natural products. These products are a group of drugs (typically antibiotics) which their activity stems from the presence of a macrolide ring. Antibiotic macrolides are used to treat infections caused by Gram-positive bacteria and Haemophilus influenzae infections such as respiratory tract and soft-tissue infections. Macrolides, mainly erythromycin and clarithromycin, rarely show QT prolongation, as their infamous adverse reaction which can lead to torsades de pointes. Electrophysiological studies showed that macrolides prolonging the QT interval inhibit the rapid component of the delayed rectifier K(+) current (IKr) through the block of potassium channels encoded by the human ether-a-go-go-related gene (HERG). Other studies suggest that increased ROS generation alters the kinetics of hERG K(+) conductance. 2. In our study, rat cardiomyocytes were isolated with collagen perfusion technique. Finally, mitochondria isolated from cardiomyocytes were exposed to erythromycin, azithromycin and clarithromycin for their probable toxicity effects. 3. Our results demonstrated that macrolides induced reactive oxygen species formation, mitochondrial membrane permeabilization and mitochondrial swelling and finally cytochrome c release in cardiomyocyte mitochondria. 4. These findings suggested that the toxicity of heart mitochondria is a starting point for cardiotoxic effects of macrolides including QT prolongation, torsades de pointes and arrhythmia.