Identifying the "true" repeat unit of a copolymer using time-resolved electron paramagnetic resonance spectroscopy: a case study involving PNDIT2, NDI-T2 and T-NDI-T

Semiconducting polymers promise to revolutionise the way electronic devices can be built and deployed for a vast array of applications ranging from light-energy conversion to sensors to thermoelectric generators. Conjugated push-pull copolymers consisting of alternating donor and acceptor moieties are at the heart of these applications, due to the large tunability of their electronic structure. Hence, knowing the repeat unit and thus the chromophore of these materials is essential for a detailed understanding of the structure--function relationship of conjugated polymers used in organic electronics applications. Therefore, spectroscopic tools providing the necessary molecular resolution that allows to discriminate between different building blocks and to decide which one actually resembles the electronic structure of the polymer are of utmost importance. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is both, perfectly suited for this task and clearly superior to optical spectroscopy, particularly when supported by quantum-chemical calculations. This is due to its molecular resolution and unique capability of using light-induced triplet states to probe the electronic structure as well as the impact of the local environment. Here, we demonstrate the power of this approach for the polymer PNDIT2 (poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)}) revealing NDI-T2 unambiguously as the "true" repeat unit of the polymer, representing the chromophore. The alternative building block T-NDI-T has a markedly different electronic structure. These results are of high importance for the rational design of conjugated polymers for organic electronics applications.

Dipolar pathways in dipolar EPR spectroscopy

Dipolar electron paramagnetic resonance (EPR) experiments such as double electron--electron resonance (DEER) measure distributions of nanometer-scale distances between unpaired electrons, which provide valuable information for structural characterization of proteins and...

Electron paramagnetic resonance in organic binder aging in dispersely reinforced substructures

Purpose: To study the intensity of binder aging in organo-mineral mixtures using electron paramagnetic resonance. The aging intensity of the organic binder is provided by its concentration in paramagnetic centers, since asphaltenes are almost one hundred percent of paramagnet concentration and indicate to the aging intensity of the petroleum dispersion system.Approach: Dispersed reinforcement of substructures with chemical fibers made of spent sorbents containing a controlled amount of absorbed oil products allows to partially solve the problem of crack formation and fracture of road pavements designed in accordance with the regulatory documents.Research implications: The service life of substructure made of dispersely reinforced organo-mineral mixtures reduces owing to organic binder aging, which begins at the stage of preparation of organo-mineral mixtures and continues during the substructure operation. Organic binder ageing results in the formation of solvation layers on the surface of mineral materials that become more viscous and brittle.Findings: The substructure dispersed reinforcement with chemical fibers made of spent sorbents containing a controlled amount of absorbed oil products decreases the concentration of paramagnetic centers. This indicates to a decrease in the asphaltene concentration, thereby reducing the aging intensity of the oil dispersion system.

Contribution of Biological and EPR Dosimetry to the Medical Management Support of Acute Radiation Health Effects

In this review, we discuss the value of biological dosimetry and electron paramagnetic resonance (EPR) spectroscopy in the medical management support of acute radiation syndrome (ARS). Medical management of an ionizing radiation scenario requires significant information. For optimal medical aid, this information has to be rapidly (< 3 days) delivered to the health-care provider. Clinical symptoms may initially enable physicians to predict ARS and initiate respective medical treatment. However, in most cases at least further verification through knowledge on radiation exposure details is necessary. This can be assessed by retrospective dosimetry techniques, if it is not directly registered by personal dosimeters. The characteristics and potential of biological dosimetry and electron paramagnetic resonance (EPR) dosimetry using human-derived specimen are presented here. Both methods are discussed in a clinical perspective regarding ARS diagnostics. The presented techniques can be used in parallel to increase screening capacity in the case of mass casualties, as both can detect the critical dose of 2 Gy (whole body single dose), where hospitalization will be considered. Hereby, biological dosimetry based on the analysis of molecular biomarkers, especially gene expression analysis, but also in vivo EPR represent very promising screening tools for rapid triage dosimetry in early-phase diagnostics. Both methods enable high sample throughput and potential for point-of-care diagnosis. In cases of higher exposure or in small-scale radiological incidents, the techniques can be used complementarily to understand important details of the exposure. Hereby, biological dosimetry can be employed to estimate the whole body dose, while EPR dosimetry on nails, bone or teeth can be used to determine partial body doses. A comprehensive assessment will support optimization of further medical treatment. Ultimately, multipath approaches are always recommended. By tapping the full potential of all diagnostic and dosimetric methods, effective treatment of patients can be supported upon exposure to radiation.