Understanding chemical degradation at the interface between different layers in an organic photovoltaic device (OPV) is crucial to improving the long‐term stability of OPVs. Herein, molecular‐level insights are provided into the impact of different metal top electrodes on the interfacial morphology and stability of photoactive layers in PM6:Y6 bulk‐heterojunction (BHJ) OPVs. OPVs with an aluminum (Al) top electrode exhibit inferior stability compared to silver (Ag) electrode devices upon thermal annealing, whereby thermal stress induces the diffusion of both Al and Ag atoms to the PM6:Y6 BHJ layer. The diffused Al atoms cause surface recombination at the interface between the photoactive layer and an interlayer. Specifically, X‐ray photoelectron spectroscopy suggests the different local chemical environments of PM6 and Y6 moieties in PM6:Y6/Al‐contact devices. These results are corroborated by solid‐state nuclear magnetic resonance and electron paramagnetic resonance spectroscopy measurements, indicating the formation of ionic and organo‐metallic‐like species at the sub‐layers of the PM6:Y6 BHJ morphology, which are estimated to be less than 5 wt% of the PM6:Y6/Al blend. By comparison, the Ag atoms do not adversely affect PM6:Y6 BHJ morphology and the associated device physics. The investigation of reactive electrode‐BHJ interfaces by multiscale characterization techniques and device physics is expected to provide guidance to future interfacial engineering strategies to develop stable and efficient OPVs.
The series of unnatural base pairs (UBPs) developed by the Romesberg lab, which pair via hydrophobic and packing interactions have been replicated, transcribed, and translated inside of a living organism. However, as to why these UBPs exhibit variable fidelity and efficiency when used in different contexts is not clear. In an effort to gain some insights, we investigated the thermal stability and pairing selectivity of the (d)NaM‐(d)TPT3 UBP in 11nt duplexes via UV spectroscopy and the effects on helical structure via CD spectroscopy. We observed that while the duplexes containing a UBP are less stable than fully natural duplexes, they are generally more stable than duplexes containing natural mispairs. This work provides the first insights connecting the thermal stability of the (d)NaM‐(d)TPT3 UBP to the molecular mechanisms for varying replication fidelity in different sequence contexts in DNA, asymmetrical transcription fidelity, and codon:anticodon interactions and can assist in future UBP development.
more » « less- PAR ID:
- 10307689
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- Volume:
- 27
- Issue:
- 56
- ISSN:
- 0947-6539
- Page Range / eLocation ID:
- p. 13991-13997
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Inosine is an important RNA modification, furthermore RNA oxidation has gained interest due, in part, to its potential role in the development/progression of disease as well as on its impact on RNA structure and function. In this report we established the base pairing abilities of purine nucleobases G, I, A, as well as their corresponding, 8‐oxo‐7,8‐dihydropurine (common products of oxidation at the C8‐position of purines), and 8‐bromopurine (as probes to explore conformational changes), derivatives, namely 8‐oxoG, 8‐oxoI, 8‐oxoA, 8‐BrG, and 8‐BrI. Dodecamers of RNA were obtained using standard phosphoramidite chemistry via solid‐phase synthesis, and used as models to establish the impact that each of these nucleobases have on the thermal stability of duplexes, when base pairing to canonical and noncanonical nucleobases. Thermal stabilities were obtained from thermal denaturation transition (
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