Characterization of lysine acetylation in the peripheral subunit-binding domain of the E2 subunit of the pyruvate dehydrogenase-2-oxoglutarate dehydrogenase hybrid complex from Corynebacterium glutamicum.

In Corynebacterium glutamicum, pyruvate dehydrogenase (PDH) and 2-oxoglutarate dehydrogenase (ODH) form a unique hybrid complex in which CgE1p and CgE1o are associated with the CgE2-CgE3 subcomplex. We analyzed the role of a lysine acetylation site in the peripheral subunit-binding domain of CgE2 in PDH and ODH functions. Acetylation-mimic substitution at Lys391 of CgE2 severely reduced the interaction of CgE2 with CgE1p and CgE3, but not with CgE1o, indicating the critical role of this residue in the assembly of CgE1p and CgE3 into the complex. It also suggested that Lys391 acetylation inhibited the binding of CgE1p and CgE3 to CgE2, thereby affecting PDH and ODH activities. Interestingly, the CgE2-K391R variant strain showed increased l-glutamate production and reduced pyruvate accumulation. Kinetic analysis suggested that the increased affinity of the K391R variant toward pyruvate might be advantageous for l-glutamate production.

Effect of lysine succinylation on the regulation of 2-oxoglutarate dehydrogenase inhibitor, OdhI, involved in glutamate production in Corynebacterium glutamicum.

In Corynebacterium glutamicum, the activity of the 2-oxoglutarate dehydrogenase (ODH) complex is negatively regulated by the unphosphorylated form of OdhI protein, which is critical for L-glutamate overproduction. We examined the potential impact of protein acylation at lysine (K)-132 of OdhI in C. glutamicum ATCC13032. The K132E succinylation-mimic mutation reduced the ability of OdhI to bind OdhA, the catalytic subunit of the ODH complex, which reduced the inhibition of ODH activity. In vitro succinylation of OdhI protein also reduced the ability to inhibit ODH, and the K132R mutation blocked the effect. These results suggest that succinylation at K132 may attenuate the OdhI function. Consistent with these results, the C. glutamicum mutant strain with OdhI-K132E showed decreased L-glutamate production. Our results indicated that not only phosphorylation but also succinylation of OdhI protein may regulate L-glutamate production in C. glutamicum.

Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy.

Molecular orientation in amorphous organic semiconducting thin-film devices is an important issue affecting device performance. However, to date it has not been possible to analyze the "distribution" of the orientations. Although solid-state NMR (ssNMR) spectroscopy can provide information on the "distribution" of molecular orientations, the technique is limited because of the small amount of sample in the device and the low sensitivity of ssNMR. Here, we report the first application of dynamic nuclear polarization enhanced ssNMR (DNP-ssNMR) spectroscopy for the orientational analysis of amorphous phenyldi(pyren-1-yl)phosphine oxide (POPy2 ). The 31 P DNP-ssNMR spectra exhibited a sufficient signal-to-noise ratio to quantify the distribution of molecular orientations in amorphous films: the P=O axis of the vacuum-deposited and drop-cast POPy2 shows anisotropic and isotropic distribution, respectively. The different molecular orientations reflect the molecular origin of the different charge transport behaviors.

Triarylboron-Based Fluorescent Organic Light-Emitting Diodes with External Quantum Efficiencies Exceeding 20 .

Triarylboron compounds have attracted much attention, and found wide use as functional materials because of their electron-accepting properties arising from the vacant p orbitals on the boron atoms. In this study, we design and synthesize new donor-acceptor triarylboron emitters that show thermally activated delayed fluorescence. These emitters display sky-blue to green emission and high photoluminescence quantum yields of 87-100 % in host matrices. Organic light-emitting diodes using these emitting molecules as dopants exhibit high external quantum efficiencies of 14.0-22.8 %, which originate from efficient up-conversion from triplet to singlet states and subsequent efficient radiative decay from singlet to ground states.

Thermally Activated Delayed Fluorescent Materials Combining Intra- and Intermolecular Charge Transfers.

A novel thermally activated delayed fluorescent (TADF) compound, 9-(3-((4,6-diphenyl-1,3,5-triazin-2-yl)oxy)phenyl)-3,6-diphenyl-9 H-carbazole (PhCz- o-Trz), with a donor-σ-acceptor (D-σ-A) motif is developed. A flexible small space σ-junction is adopted to partly suppress the intramolecular charge transfer (intra-CT) while inversely enhancing the intermolecular charge transfer (inter-CT) between D/A moieties, realizing the coexistence of both intra-CT and inter-CT in an amorphous aggregate. The coexistence of dual CTs increases the complexity of the singlet and triplet state mixing, enhancing the triplet-to-singlet spin-flip transition and thereby the TADF emission. Additionally, PhCz- o-Trz is evaluated not only as an emitter but also as a sensitizing host for fluorescent and phosphorescent dopants, all exhibiting high efficiencies with alleviated efficiency roll-offs. These results shed light on the development of new TADF materials with dual CTs and may further deepen our understanding about TADF mechanisms.

Parameter-Free Multiscale Simulation Realising Quantitative Prediction of Hole and Electron Mobilities in Organic Amorphous System with Multiple Frontier Orbitals.

In amorphous organic semiconducting systems, hole and electron transfer has been considered to occur based on the overlap of highest occupied molecular orbitals (HOMOs) and that of lowest unoccupied molecular orbitals (LUMOs) between two adjacent molecules, respectively. Other molecular orbitals (MOs), HOMO-1, HOMO-2, … and LUMO+1, LUMO+2, …, have been neglected in charge transport calculations. However, these MOs could potentially contribute to charge transport. In this study, our multiscale simulations show that carriers are effectively transported not only via HOMOs or LUMOs but also via other MOs when the MOs are close in energy. Because these multiple MOs are active in charge transports, here we call them multiple frontier orbitals. Molecules with multiple frontier orbitals are found to possess high carrier mobility. The findings in this study provide guidelines to aid design of materials with excellent charge transport properties.

Adamantyl Substitution Strategy for Realizing Solution-Processable Thermally Stable Deep-Blue Thermally Activated Delayed Fluorescence Materials.

Highly efficient solution-processable emitters, especially deep-blue emitters, are greatly desired to develop low-cost and low-energy-consumption organic light-emitting diodes (OLEDs). A recently developed class of potentially metal-free emitters, thermally activated delayed fluorescence (TADF) materials, are promising candidates, but solution-processable TADF materials with efficient blue emissions are not well investigated. In this study, first the requirements for the design of efficient deep-blue TADF materials are clarified, on the basis of which, adamantyl-substituted TADF molecules are developed. The substitution not only endows high solubility and excellent thermal stability but also has a critical impact on the molecular orbitals, by pushing up the lowest unoccupied molecular orbital energy and triplet energy of the molecules. In the application to OLEDs, an external quantum efficiency (EQE) of 22.1% with blue emission having Commission Internationale de l'Eclairage (CIE) coordinates of (0.15, 0.19) is realized. A much deeper blue emission with CIE (0.15, 0.13) is also achieved, with an EQE of 11.2%. These efficiencies are the best yet among solution-processed TADF OLEDs of CIE y < 0.20 and y < 0.15, as far as known. This work demonstrates the validity of adamantyl substitution and paves a pathway for straightforward realization of solution-processable efficient deep-blue TADF emitters.

Effects of Structural and Energetic Disorders on Charge Transports in Crystal and Amorphous Organic Layers.

Understanding charge transports in organic films is important for both fundamental science and practical applications. Here, contributions of off-diagonal (structural) and diagonal (energetic) disorders to charge transports were clarified using molecular-based multiscale simulation. These disorders, important for understanding charge transport in organic systems, are investigated by comparing crystal and amorphous aggregates of N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPD). Although NPD has been used as a hole transport material, it also exhibits comparable electron mobility experimentally. The experimental mobility and its electric field dependence in amorphous layers were reasonably reproduced by the multiscale simulation, confirming the electron transport properties of NPD. We assumed that the structural disorder would lower mobilities; however, the mobilities were found to be independent of the degree of structural disorder. Energetic disorder markedly lowered charge mobility instead. Charge migration in crystals was dominated by maximum electronic coupling pairs, whereas small electronic coupling pairs significantly contributed to charge transport in amorphous aggregate.

Blue organic light-emitting diodes realizing external quantum efficiency over 25% using thermally activated delayed fluorescence emitters.

Improving the performance of blue organic light-emitting diodes (OLEDs) is needed for full-colour flat-panel displays and solid-state lighting sources. The use of thermally activated delayed fluorescence (TADF) is a promising approach to efficient blue electroluminescence. However, the difficulty of developing efficient blue TADF emitters lies in finding a molecular structure that simultaneously incorporates (i) a small energy difference between the lowest excited singlet state (S1) and the lowest triplet state (T1), ΔE ST, (ii) a large oscillator strength, f, between S1 and the ground state (S0), and (iii) S1 energy sufficiently high for blue emission. In this study, we develop TADF emitters named CCX-I and CCX-II satisfying the above requirements. They show blue photoluminescence and high triplet-to-singlet up-conversion yield. In addition, their transition dipole moments are horizontally oriented, resulting in further increase of their electroluminescence efficiency. Using CCX-II as an emitting dopant, we achieve a blue OLED showing a high external quantum efficiency of 25.9%, which is one of the highest EQEs in blue OLEDs reported previously.

Detailed analysis of charge transport in amorphous organic thin layer by multiscale simulation without any adjustable parameters.

Hopping-type charge transport in an amorphous thin layer composed of organic molecules is simulated by the combined use of molecular dynamics, quantum chemical, and Monte Carlo calculations. By explicitly considering the molecular structure and the disordered intermolecular packing, we reasonably reproduce the experimental hole and electron mobilities and their applied electric field dependence (Poole-Frenkel behaviour) without using any adjustable parameters. We find that the distribution of the density-of-states originating from the amorphous nature has a significant impact on both the mobilities and Poole-Frenkel behaviour. Detailed analysis is also provided to reveal the molecular-level origin of the charge transport, including the origin of Poole-Frenkel behaviour.

Altered acetylation and succinylation profiles in Corynebacterium glutamicum in response to conditions inducing glutamate overproduction.

The bacterium Corynebacterium glutamicum is utilized during industrial fermentation to produce amino acids such as L-glutamate. During L-glutamate fermentation, C. glutamicum changes the flux of central carbon metabolism to favor L-glutamate production, but the molecular mechanisms that explain these flux changes remain largely unknown. Here, we found that the profiles of two major lysine acyl modifications were significantly altered upon glutamate overproduction in C. glutamicum; acetylation decreased, whereas succinylation increased. A label-free semi-quantitative proteomic analysis identified 604 acetylated proteins with 1328 unique acetylation sites and 288 succinylated proteins with 651 unique succinylation sites. Acetylation and succinylation targeted enzymes in central carbon metabolic pathways that are directly related to glutamate production, including the 2-oxoglutarate dehydrogenase complex (ODHC), a key enzyme regulating glutamate overproduction. Structural mapping revealed that several critical lysine residues in the ODHC components were susceptible to acetylation and succinylation. Furthermore, induction of glutamate production was associated with changes in the extent of acetylation and succinylation of lysine, suggesting that these modifications may affect the activity of enzymes involved in glutamate production. Deletion of phosphotransacetylase decreased the extent of protein acetylation in nonproducing condition, suggesting that acetyl phosphate-dependent acetylation is active in C. glutamicum. However, no effect was observed on the profiles of acetylation and succinylation in glutamate-producing condition upon disruption of acetyl phosphate metabolism or deacetylase homologs. It was considered likely that the reduced acetylation in glutamate-producing condition may reflect metabolic states where the flux through acid-producing pathways is very low, and substrates for acetylation do not accumulate in the cell. Succinylation would occur more easily than acetylation in such conditions where the substrates for both acetylation and succinylation are limited. This is the first study investigating the acetylome and succinylome of C. glutamicum, and it provides new insight into the roles of acyl modifications in C. glutamicum biology.

Purely organic electroluminescent material realizing 100% conversion from electricity to light.

Efficient organic light-emitting diodes have been developed using emitters containing rare metals, such as platinum and iridium complexes. However, there is an urgent need to develop emitters composed of more abundant materials. Here we show a thermally activated delayed fluorescence material for organic light-emitting diodes, which realizes both approximately 100% photoluminescence quantum yield and approximately 100% up-conversion of the triplet to singlet excited state. The material contains electron-donating diphenylaminocarbazole and electron-accepting triphenyltriazine moieties. The typical trade-off between effective emission and triplet-to-singlet up-conversion is overcome by fine-tuning the highest occupied molecular orbital and lowest unoccupied molecular orbital distributions. The nearly zero singlet-triplet energy gap, smaller than the thermal energy at room temperature, results in an organic light-emitting diode with external quantum efficiency of 29.6%. An external quantum efficiency of 41.5% is obtained when using an out-coupling sheet. The external quantum efficiency is 30.7% even at a high luminance of 3,000 cd m(-2).