SUMMARYNon-homologous end joining (NHEJ) is the major model proposed for Agrobacterium T-DNA integration into the plant genome. In animal cells, several proteins, including KU70, KU80, ARTEMIS, DNA-PKcs, DNA ligase IV (LIG4), Ataxia telangiectasia mutated (ATM), and ATM-and Rad3-related (ATR), play an important role in 'classical' (c)NHEJ. Other proteins, including histone H1 (HON1), XRCC1, and PARP1, participate in a 'backup' (b)NHEJ process. We examined transient and stable transformation frequencies of Arabidopsis thaliana roots mutant for numerous NHEJ and other related genes. Mutants of KU70, KU80, and the plant-specific DNA LIGASE VI (LIG6) showed increased stable transformation susceptibility. However, these mutants showed transient transformation susceptibility similar to that of wild-type plants, suggesting enhanced T-DNA integration in these mutants. These results were confirmed using a promoter-trap transformation vector that requires T-DNA integration into the plant genome to activate a promoterless gusA (uidA) gene, by virus-induced gene silencing (VIGS) of Nicotiana benthamiana NHEJ genes, and by biochemical assays for T-DNA integration. No alteration in transient or stable transformation frequencies was detected with atm, atr, lig4, xrcc1, or parp1 mutants. However, mutation of parp1 caused high levels of T-DNA integration and transgene methylation. A double mutant (ku80/parp1), knocking out components of both NHEJ pathways, did not show any decrease in stable transformation or T-DNA integration. Thus, T-DNA integration does not require known NHEJ proteins, suggesting an alternative route for integration.

A novel chiral nanographene (i.e. EP9H) with a pentadecabenzo[9]helicene core fragment has been synthesized and fully characterized. Single‐crystal X‐ray diffraction unambiguously confirms the helical structure. The fluorescence emission of EP9H is located in the near infrared region (λem=684 nm) with a medium quantum yield (0.10) for helicene derivatives. Cyclic voltammetry reveals its seven quasi‐reversible redox states from −2 to +5. Furthermore, enantiopure EP9H displays distinct CD signals in a broad spectral range from 300 to 700 nm. Notably, compared to the reported small organic molecules, EP9H displays an outstanding |glum| value of 4.50×10−2 and BCPL as 304 M−1 cm−1.

Substituent effects play critical roles in both modulating reaction chemistry and supramolecular self-assembly processes. Using substituted terephthalate dianions (p-phthalic acid dianions; PTADAs), the effect of varying the type, number, and position of the substituents was explored in terms of their ability to regulate the inherent anion complexation features of a tetracationic macrocycle, cyclo[2]­(2,6-di­(1H-imidazol-1-yl)­pyridine)­[2]­(1,4-dimethylenebenzene) (referred to as the Texas-sized molecular box; 1 4+), in the form of its tetrakis-PF6 – salt in DMSO. Several of the tested substituents, including 2-OH, 2,5-di­(OH), 2,5-di­(NH2), 2,5-di­(Me), 2,5-di­(Cl), 2,5-di­(Br), and 2,5-di­(I), were found to promote pseudorotaxane formation in contrast to what was seen for the parent PTADA system. Other derivatives of PTADA, including those with 2,3-di­(OH), 2,6-di­(OH), 2,5-di­(OMe), 2,3,5,6-tetra­(Cl), and 2,3,5,6-tetra­(F) substituents, led only to so-called outside binding, where the anion interacts with 1 4+ on the outside of the macrocyclic cavity. The differing binding modes produced by the choice of PTADA derivative were found to regulate further supramolecular self-assembly when the reaction components included additional metal cations (M). Depending on the specific choice of PTADA derivatives and metal cations (M = Co2+, Ni2+, Zn2+, Cd2+, Gd3+, Nd3+, Eu3+, Sm3+, Tb3+), constructs involving one-dimensional polyrotaxanes, outside-type rotaxanated supramolecular organic frameworks (RSOFs), or two-dimensional metal–organic rotaxane frameworks (MORFs) could be stabilized. The presence and nature of the substituent were found to dictate which specific higher order self-assembled structure was obtained using a given cation. In the specific case of the 2,5-di­(OH), 2,5-di­(Cl), and 2,5-di­(Br) PTADA derivatives and Eu3+, so-called MORFs with distinct fluorescence emission properties could be produced. The present work serves to illustrate how small changes in guest substitution patterns may be used to control structure well beyond the first interaction sphere.

Carbon-rich macrocycles and carbon nanoribbons are considered as the combination of carbon rich molecular materials and supramolecular macrocycle hosts. They can act as unique optical material candidate choices with free...

A novel chiral nanographene (i.e. EP9H) with a pentadecabenzo[9]helicene core fragment has been synthesized and fully characterized. Single‐crystal X‐ray diffraction unambiguously confirms the helical structure. The fluorescence emission of EP9H is located in the near infrared region (λem=684 nm) with a medium quantum yield (0.10) for helicene derivatives. Cyclic voltammetry reveals its seven quasi‐reversible redox states from −2 to +5. Furthermore, enantiopure EP9H displays distinct CD signals in a broad spectral range from 300 to 700 nm. Notably, compared to the reported small organic molecules, EP9H displays an outstanding |glum| value of 4.50×10−2 and BCPL as 304 M−1 cm−1.