The genome-the source of life and platform of evolution-is continuously exposed to harmful factors, both extra- and intra-cellular. Their activity causes different types of DNA damage, with approximately 80 different types of lesions having been identified so far. In this paper, the influence of a clustered DNA damage site containing imidazolone (Iz) or oxazolone (Oz) and 7,8-dihydro-8-oxo-2\'-deoxyguanosine (OXOdG) on the charge transfer through the double helix as well as their electronic properties were investigated. To this end, the structures of oligo-Iz, d[A1Iz2A3OXOG4A5]*d[T5C4T3C2T1], and oligo-Oz, d[A1Oz2A3OXOG4A5]*d[T5C4T3C2T1], were optimized at the M06-2X/6-D95**//M06-2X/sto-3G level of theory in the aqueous phase using the ONIOM methodology; all the discussed energies were obtained at the M06-2X/6-31++G** level of theory. The non-equilibrated and equilibrated solvent-solute interactions were taken into consideration. The following results were found: (A) In all the discussed cases, OXOdG showed a higher predisposition to radical cation formation, and B) the excess electron migration toward Iz and Oz was preferred. However, in the case of oligo-Oz, the electron transfer from Oz2 to complementary C4 was noted during vertical to adiabatic anion relaxation, while for oligo-Iz, it was settled exclusively on the Iz2 moiety. The above was reflected in the charge transfer rate constant, vertical/adiabatic ionization potential, and electron affinity energy values, as well as the charge and spin distribution. It can be postulated that imidazolone moiety formation within the CDL ds-oligo structure and its conversion to oxazolone can significantly influence the charge migration process, depending on the C2 carbon hybridization sp2 or sp3. The above can confuse the single DNA damage recognition and removal processes, cause an increase in mutagenesis, and harm the effectiveness of anticancer therapy.

We demonstrate the importance of addressing the Γ vertex and thus going beyond the GW approximation for achieving the energy levels of liquid water in many-body perturbation theory. In particular, we consider an effective vertex function in both the polarizability and the self-energy, which does not produce any computational overhead compared with the GW approximation. We yield the band gap, the ionization potential, and the electron affinity in good agreement with experiment and with a hybrid functional description. The achieved electronic structure and dielectric screening further lead to a good description of the optical absorption spectrum, as obtained through the solution of the Bethe-Salpeter equation. In particular, the experimental peak position of the exciton is accurately reproduced.

In the present study, we have investigated factors affecting the accuracy of computational chemistry calculation of redox potentials, namely the gas-phase ionization energy (IE) and electron affinity (EA), and the continuum solvation effect. In general, double-hybrid density functional theory methods yield IEs and EAs that are on average within ~0.1 eV of our high-level W3X-L benchmark, with the best performing method being DSD-BLYP/ma-def2-QZVPP. For lower-cost methods, the average errors are ~0.2-0.3 eV, with ωB97X-3c being the most accurate (~0.15 eV). For the solvation component, essentially all methods have an average error of ~0.3 eV, which shows the limitation of the continuum solvation model. Curiously, the directly calculated redox potentials show errors of ~0.3 eV for all methods. These errors are notably smaller than what can be expected from error propagation with the two components (IE and EA, and solvation effect). Such a discrepancy can be attributed to the cancellation of errors, with the lowest-cost GFN2-xTB method benefiting the most, and the most accurate ωB97X-3c method benefiting the least. For organometallic species, the redox potentials show large deviations exceeding ~0.5 eV even for DSD-BLYP. The large errors are attributed to those for the gas-phase IEs and EAs, which represents a major barrier to the accurate calculation of redox potentials for such systems.

It is a huge challenge to explore how charge traps affect the electric breakdown of polymer-based dielectric composites. In this paper, alkane and aromatic molecules with different substituents are investigated according to DFT theoretical method. The combination of strong electron-withdrawing groups and aromatic rings can establish high electron affinity molecules. 4\'-Nitro-4-dimethylaminoazobenzene (NAABZ) with a vertical electron affinity of 1.39 eV and a dipole moment of 10.15 D is introduced into polystyrene (PSt) to analyze the influence of charge traps on electric properties. Marcus charge transfer theory is applied to calculate the charge transfer rate between PSt and NAABZ. The nature of charge traps is elaborated from a dynamic perspective. The enhanced breakdown mechanism of polymers-based composites stems from the constraint of carrier mobility caused by the change in transfer rate. But the electrophile nature of high electron affinity filler can decrease the potential barriers at the metal-polymer interface. Simultaneously, the relationship between the electron affinity of fillers and the breakdown strength of polymer-based composites is nonlinear because of the presence of the inversion region. Based on the deep understanding of the molecular trap, this work provides the theoretical calculation for the design and development of high-performance polymer dielectrics.

Exploration of new electron-withdrawing building blocks plays a key role in the development of n-type organic semiconductors. Herein, a strong electron-withdrawing building block, dipyridyl-fused quinoxalineimide (DPQI), was successfully designed and synthesized. Single-crystal structure reveals that DPQI molecule possesses a completely planar backbone, which is beneficial for charge transport. For comparison, dibenzo-fused quinoxalineimide (DBQI) was also synthesized. The frontier molecular orbital (FMO) energy levels downshift with the incorporation of nitrogen atoms onto the π-conjugated backbone of quinoxalineimide. Two acceptor-acceptor (or all-acceptor) polymers P(BTI-DBQI) and P(BTI-DPQI) based on DBQI and DPQI were synthesized, respectively. Two polymers exhibit deep lowest-unoccupied molecular orbital (LUMO) levels (~-3.5 eV). Additionally, P(BTI-DPQI) exhibits unipolar n-type charge transport with μe of 1.4×10-4  cm2  V-1  s-1 in the organic field-effect transistors (OFET), which render them highly attractive for developing n-type semiconductors device. This work demonstrates that DPQI is a promising building block for constructing n-type polymer semiconductors.

The role of hypoxic tumour cells in resistance to radiotherapy, and in suppression of immune response, continues to endorse tumour hypoxia as a bona fide, yet largely untapped, drug target. Radiotherapy innovations such as stereotactic body radiotherapy herald new opportunities for classical oxygen-mimetic radiosensitisers. Only nimorazole is used clinically as a radiosensitiser, and there is a dearth of new radiosensitisers in development. In this report, we augment previous work to present new nitroimidazole alkylsulfonamides and we document their cytotoxicity and ability to radiosensitise anoxic tumour cells in vitro. We compare radiosensitisation with etanidazole and earlier nitroimidazole sulfonamide analogues and we identify 2-nitroimidazole and 5-nitroimidazole analogues with marked tumour radiosensitisation in ex vivo assays of surviving clonogens and with in vivo tumour growth inhibition.

Polyhedral molecules are appealing for their eye-catching architecture and distinctive chemistry. Perfluorination of such, often greatly strained, compounds is a momentous challenge. It drastically changes the electron distribution, structure and properties. Notably, small high-symmetry perfluoropolyhedranes feature a centrally located, star-shaped low-energy unoccupied molecular orbital that can host an extra electron within the polyhedral frame, thus producing a radical anion, without loss of symmetry. This predicted electron-hosting capacity was definitively established for perfluorocubane, the first perfluorinated Platonic polyhedrane to be isolated pure. Hosting atoms, molecules, or ions in such \"cage\" structures is, however, all but forthright, if not illusionary, offering no easy access to supramolecular constructs. While adamantane and cubane have fostered numerous applications in materials science, medicine, and biology, specific uses for their perfluorinated counterparts remain to be established. Some aspects of highly fluorinated carbon allotropes, such as fullerenes and graphite, are briefly mentioned for context.

We have proposed a new method for the exploration of organic functional molecules, using an exhaustive molecular generator combined without combinatorial explosion and electronic state predicted by machine learning and adapted for developing n-type organic semiconductor molecules for field-effect transistors. Our method first enumerates skeletal structures as much as possible and next generates fused ring structures using substitution operations for atomic nodes and bond edges. We have succeeded in generating more than 4.8 million molecules. We calculated the electron affinity (EA) of about 51 thousand molecules with DFT calculation and trained the graph neural networks to estimate EA values of generated molecules. Finally, we obtained the 727 thousand molecules as candidates that satisfy EA values over 3 eV. The number of these possible candidate molecules is far beyond what we have been able to propose based on our knowledge and experience in synthetic chemistry, indicating a wide diversity of organic molecules.

Understanding the hole-injection mechanism and improving the hole-injection property are of pivotal importance in the future development of organic optoelectronic devices. Electron-acceptor molecules with high electron affinity (EA) are widely used in electronic applications, such as hole injection and p-doping. Although p-doping has generally been studied in terms of matching the ionization energy (IE) of organic semiconductors with the EA of acceptor molecules, little is known about the effect of the EA of acceptor molecules on the hole-injection property. In this work, the hole-injection mechanism in devices is completely clarified, and a strategy to optimize the hole-injection property of the acceptor molecule is developed. Efficient and stable hole injection is found to be possible even into materials with IEs as high as 5.8 eV by controlling the charged state of an acceptor molecule with an EA of about 5.0 eV. This excellent hole-injection property enables direct hole injection into an emitting layer, realizing a pure blue organic light-emitting diode with an extraordinarily low turn-on voltage of 2.67 V, a power efficiency of 29 lm W-1 , an external quantum efficiency of 28% and a Commission Internationale de l\'Eclairage y coordinate of less than 0.10.

Covalent organic frameworks have recently shown high potential for photocatalytic hydrogen production. However, their structure-property-activity relationship has not been sufficiently explored to identify a research direction for structural design. Herein, we report the design and synthesis of four benzotrithiophene (BTT)-based covalent organic frameworks (COFs) with different conjugations of building units, and their photocatalytic activity for hydrogen production. All four BTT-COFs had slipped parallel stacking patterns with high crystallinity and specific surface areas. The change in the degree of conjugation was found to rationally tune the rate of photocatalytic hydrogen evolution. Based on the experimental and calculation results, the tunable photocatalytic performance could be mainly attributed to the electron affinity and charge trapping of the electron accepting units. This study provides important insights for designing covalent organic frameworks for efficient photocatalysts.