Expression profiles and characterization of microRNAs responding to chitin in Arthrobotrys oligospora.

Extracellular proteases, such as chitinases secreted by Arthrobotrys oligospora (A. oligospora), play a crucial role in the process of nematode infection. However, post-transcriptional regulation of gene expression involving microRNAs (miRNAs) in A. oligospora remains scarcely described. Hereto, transcriptome sequencing was carried out to analyze the expression profiles of chitin-responsive miRNAs in A. oligospora. Based on the RNA-seq data, the differential expression of miRNAs (DEmiRNAs) in response to chitin was screened, identified and characterized in A. oligospora. Meanwhile, the potential target genes were predicted by the online tools miRanda and Targetscan, respectively. Furthermore, the interaction of DEmiRNA with it's target gene was validated by a dual-luciferase reporter assay system. Among 85 novel miRNAs identified, 25 miRNAs displayed significant differences in expression in A. oligospora in response to chitin. Gene Ontology (GO) analysis showed that the potential genes targeted by DEmiRNAs were enriched in the biological processes such as bio-degradation, extracellular components and cell cycle. KEGG analysis revealed that the target genes were mainly involved in Hippo, carbon and riboflavin metabolic pathway. Outstandingly, chitinase AOL_s00004g379, which is involved in the hydrolysis metabolic pathway of chitin, was confirmed to be a target gene of differential miR_70. These findings suggest that chitin-responsive miRNAs are involved in the regulation of cell proliferation, predator hyphae growth and chitinase expression through the mechanisms of post-transcriptional regulation, which provides a new perspective to the molecular mechanisms underlying miRNAs-mediated control of gene expression in A. oligospora.

Correction: Synthesis and properties of siloxane modified perylene bisimide discotic liquid crystals.

Correction for 'Synthesis and properties of siloxane modified perylene bisimide discotic liquid crystals' by Tingjie Zhang et al., Soft Matter, 2013, 9, 10739-10745, https://doi.org/10.1039/C3SM52054D.

Multichromophore Molecular Design for Thermally Activated Delayed-Fluorescence Emitters with Near-Unity Photoluminescence Quantum Yields.

Three multichromophore thermally activated delayed fluorescence (TADF) molecules, p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN, were synthesized and characterized. These molecules were designed by connecting the TADF moiety 4,5-di(9H-carbazol-9-yl)phthalonitrile (2CzPN) to different positions of a central benzene ring scaffold. Three highly soluble emitters all exhibited near-quantitative photoluminescence quantum yields (ΦPL) in toluene. High ΦPLs were also achieved in doped films, 59 and 70% for p-di2CzPN and m-di2CzPN in 10 wt % DPEPO doped film, respectively, and 54% for 1,3,5-tri2CzPN in 20 wt % doped CBP films. The rate constant of reverse intersystem crossing (kRISC) for p-di2CzPN and m-di2CzPN in DPEPO films reached 1.1 × 105 and 0.7 × 105 s-1, respectively, and kRISC for 1,3,5-tri2CzPN in the CBP film reached 1.7 × 105 s-1. A solution-processed organic light-emitting diode based on 1,3,5-tri2CzPN exhibited a sky-blue emission with CIE coordinates of (0.22, 0.44) and achieved a maximum external quantum efficiency of 7.1%.

Managing Locally Excited and Charge-Transfer Triplet States to Facilitate Up-Conversion in Red TADF Emitters That Are Available for Both Vacuum- and Solution-Processes.

Developing red thermally activated delayed fluorescence (TADF) emitters for high-performance OLEDs is still facing great challenge. Herein, three red TADF emitters, pDBBPZ-DPXZ, pDTBPZ-DPXZ, and oDTBPZ-DPXZ, are designed and synthesized with same donor-acceptor (D-A) backbone with different peripheral groups attaching on the A moieties. Their lowest triplet states change from locally excited to charge transfer character leading to significantly enhance reverse intersystem crossing process. In particular, oDTBPZ-DPXZ exhibits efficient TADF feature and exciton utilization. It not only achieves an external quantum efficiency (EQE) of 20.1 % in red vacuum-processed OLED, but also realize a high EQE of 18.5 % in a solution-processed OLED, which is among the best results in solution-processed red TADF OLEDs. This work provides an effective strategy for designing red TADF molecules by managing energy level alignments to facilitate the up-conversion process and thus enhance exciton harvesting.

Oligosiloxane functionalized with pendant (1,3-bis(9-carbazolyl)benzene) (mCP) for solution-processed organic electronics.

A new oligosiloxane derivative (ODCzMSi) functionalized with the well-known 1,3-bis(9-carbazolyl)benzene (mCP) pendant moiety, directly linked to the silicon atom of the oligosiloxane backbone, has been synthesized and characterized. Compared to mCP, the attachment of the oligosiloxane chain significantly improves the thermal and morphological stabilities with a high decomposition temperature (Td =540 °C) and glass transition temperature (Tg =142 °C). The silicon-oxygen linkage of ODCzMSi disrupts the backbone conjugation and maintains a high triplet energy level (ET =3.0 eV). A phosphorescent organic light-emitting diode (PhOLED) using iridium bis(4,6-difluorophenyl)pyridinato-N,C(2) picolinate (FIrpic) as the emitter and ODCzMSi as the host shows a relatively low turn-on voltage of 5.0 V for solution-processed PhOLEDs, maximum external quantum efficiency of 9.2 %, and maximum current efficiency of 17.7 cd A(-1) . The overall performance of this device is competitive with the best reported solution-processed blue PhOLEDs. Memory devices using ODCzMSi as an active layer exhibit non-volatile write-once read-many-times (WORM) characteristics with high stability in retention time up to 10(4)  s and a low switch on voltage. This switching behaviour is explained by different stable conformations of ODCzMSi with high or low conductivity states which are obtained under the action of electric field through a π-π stacking alignment of the pendant aromatic groups. These results with both PhOLEDs and memory devices demonstrate that this oligosiloxane-mCP hybrid structure is promising and versatile for high performance solution-processed optoelectronic applications.

A temperature sensor with a wide spectral range based on a dual-emissive TADF dendrimer system.

Dual emission from thermally activated delayed fluorescence (TADF) emitters is often difficult to observe, especially in solution, limited by Kasha's rule. Two TADF dendrimers containing N-doped polycyclic aromatic hydrocarbons as acceptors are designed and synthesized. Compound 2GCzBPN, having a strongly twisted geometry, exhibits TADF, while 2GCzBPPZ, possessing a less twisted geometry, shows dual emission associated with the monomer and aggregate that is TADF. The demonstration reveals that 2GCzBPPZ can serve as a temperature sensor with excellent temperature sensitivity and remarkably wide emission color response in solution. By embedding 2GCzBPPZ in paraffin we demonstrate a spatial-temperature sensor that shows a noticeable emission shift from yellow to green and ultimately to blue as the temperature increases from 20 to 200 °C. We finally demonstrate the utility of these TADF dendrimers in solution-processed organic light-emitting diodes.

The Combination of a Donor-Acceptor TADF and a MR-TADF Emitting Core Results in Outstanding Electroluminescence Performance.

Here the utility and potential of an emitter design are demonstrated, consisting of a narrowband-emitting multiresonant thermally activated delayed fluorescent (MR-TADF) core that is decorated with a suitably higher energy donor-acceptor TADF moiety. Not only does this D-A TADF group offer additional channels for triplet exciton harvesting and confers faster reverse intersystem crossing (RISC) kinetics but it also acts as a steric shield, insulating the emissive MR-TADF core from aggregation-caused quenching. Two emitters, DtCzBN-CNBT1 and DtCzBN-CNBT2, demonstrate enhanced photophysical properties leading to outstanding performance of the organic light-emitting diodes (OLEDs). DtCzBN-CNBT2, containing a D-A TADF moiety, has a faster kRISC (1.1 × 105 s-1) and higher photoluminescence quantum yield (ΦPL: 97%) compared to DtCzBN-CNBT1 (0.2 × 105 s-1, ΦPL: 90%), which contains a D-A moiety that itself is not TADF. The sensitizer-free OLEDs with DtCzBN-CNBT2 achieve a record-high maximum external quantum efficiency (EQEmax) of 40.2% and showed milder efficiency roll-off (EQE1000 of 20.7%) compared to the DtCzBN-CNBT1-based devices (EQEmax of 37.1% and EQE1000 of 11.9%).

A fluorene-bridged double carbonyl/amine multiresonant thermally activated delayed fluorescence emitter for efficient green OLEDs.

Herein, we report a fluorene-bridged double carbonyl/amine-based MR TADF emitter DDiKTa-F, formed by locking the conformation of the previously reported compound DDiKTa. Using this strategy, DDiKTa-F exhibited narrower, brighter, and red-shifted emission. The OLEDs with DDiKTa-F emitted at 493 nm and showed an EQEmax of 15.3% with an efficiency roll-off of 35% at 100 cd m-2.

Synthesis and properties of siloxane modified perylene bisimide discotic liquid crystals.

A series of symmetric and asymmetric 1,6,7,12-tetrachloroperylene bisimides (PBICls) were synthesized and modified by siloxane substituents at the imide nitrogen atom. Siloxane substitutions do not apparently affect the electronic properties of PBICIs as demonstrated by CV experiments. They display both thermotropic and lyotropic liquid crystalline behaviors. The effect of different siloxane substituents on their liquid crystal structures was investigated in detail. Small angle X-ray scattering indicates that PBICls adopt hexagonal columnar packing in thermotropic liquid crystals. In addition, PBICls exhibit good optical properties, good solubility and film-forming ability. Thus the oriented films of PBICl liquid crystals could be easily fabricated by mechanical shear, which show anisotropic properties in UV-vis absorption spectra.

Synthesis of dibenzothiophene-containing ladder polysilsesquioxane as a blue phosphorescent host material.

A ladder polysilsesquioxanes with side chain of dibenzothiophene groups (BS-LPSQ) was successfully synthesized. The ladder structure of BS-LPSQ was characterized by MALDI-TOF MS, XRD, and (1)H NMR spectroscopy. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), atomic force microscopy (AFM), and spectroscopic analyses revealed that the BS-LPSQ has good film-forming ability, high thermal and morphological stability, and good miscibility to the dopant iridium bis(4,6-difluorophenyl)pyridinato-N,C(2)-picolinate (FIrpic), high triplet energy, and a wide bandgap. In addition, compared with the ringed polysiloxane BS-PSQ phosphorescent host material reported previously, the ladder structure of BS-LPSQ has not only a higher thermal resistance, but also could prevent molecular aggregation and effectively avoid quenching of fluorescence. Thus, the BS-LPSQ may be used as a better host for the blue-light-emitting iridium complex FIrpic. The performance of the electrophosphorescent device, based on the ladder BS-LPSQ as the active layer, is superior to that of ringed BS-PSQ and any other polyhedral oligomeric silsesquioxane (POSS)-based or polymer host materials.

Thermally Activated Delayed Fluorescent Dendrimers that Underpin High-Efficiency Host-Free Solution-Processed Organic Light-Emitting Diodes.

The development of high-performance solution-processed organic light-emitting diodes (OLEDs) remains a challenge. An effective solution, highlighted in this work, is to use highly efficient thermally activated delayed fluorescence (TADF) dendrimers as emitters. Here, the design, synthesis, density functional theory (DFT) modeling, and photophysics of three triazine-based dendrimers, tBuCz2pTRZ, tBuCz2mTRZ, and tBuCz2m2pTRZ, is reported, which resolve the conflicting requirements of achieving simultaneously a small ΔEST and a large oscillator strength by incorporating both meta- and para-connected donor dendrons about a central triazine acceptor. The solution-processed OLED containing a host-free emitting layer exhibits an excellent maximum external quantum efficiency (EQEmax ) of 28.7%, a current efficiency of 98.8 cd A-1 , and a power efficiency of 91.3 lm W-1 . The device emits with an electroluminescence maximum, λEL , of 540 nm and Commission International de l'Éclairage (CIE) color coordinates of (0.37, 0.57). This represents the most efficient host-free solution-processed OLED reported to date. Further optimization directed at improving the charge balance within the device results in an emissive layer containing 30 wt% OXD-7, which leads to an OLED with the similar EQEmax of 28.4% but showing a significantly improved efficiency rolloff where the EQE remains high at 22.7% at a luminance of 500 cd m-2 .

Regiochemistry of Donor Dendrons Controls the Performance of Thermally Activated Delayed Fluorescence Dendrimer Emitters for High Efficiency Solution-Processed Organic Light-Emitting Diodes.

The potential of dendrimers exhibiting thermally activated delayed fluorescence (TADF) as emitters in solution-processed organic light-emitting diodes (OLEDs) has to date not yet been realized. This in part is due to a poor understanding of the structure-property relationship in dendrimers where reports of detailed photophysical characterization and mechanism studies are lacking. In this report, using absorption and solvatochromic photoluminescence studies in solution, the origin and character of the lowest excited electronic states in dendrimers with multiple dendritic electron-donating moieties connected to a central electron-withdrawing core via a para- or a meta-phenylene bridge is probed. Characterization of host-free OLEDs reveals the superiority of meta-linked dendrimers as compared to the already reported para-analogue. Comparative temperature-dependent time-resolved solid-state photoluminescence measurements and quantum chemical studies explore the effect of the substitution mode on the TADF properties and the reverse intersystem crossing (RISC) mechanism, respectively. For TADF dendrimers with similarly small ∆EST , it is observed that RISC can be enhanced by the regiochemistry of the donor dendrons due to control of the reorganization energies, which is a heretofore unexploited strategy that is distinct from the involvement of intermediate triplet states through a nonadiabatic (vibronic) coupling with the lowest singlet charge transfer state.

Nonconjugated Triptycene-Spaced Donor-Acceptor-Type Emitters Showing Thermally Activated Delayed Fluorescence via Both Intra- and Intermolecular Charge-Transfer Transitions.

Thermally activated delayed fluorescence (TADF) emitters have aroused considerable attention, particularly for their great potential in organic light-emitting diodes (OLEDs). In typical TADF molecules, intramolecular charge transfer (CT) between electron-donor (D) and electron-acceptor (A) moieties is the dominant transition. Actually, CT transitions can possibly occur between different molecules as well. Herein, we used a nonconjugated triptycene (TPE) moiety to space D and A moieties and developed two novel emitters tBuDMAC-TPE-TRZ and tBuDMAC-TPE-TTR to explore the roles of intra- and intermolecular CT transitions. Along with weak intramolecular CT transitions, intermolecular CT transitions are dominant for tBuDMAC-TPE-TRZ and tBuDMAC-TPE-TTR neat films. Particularly, tBuDMAC-TPE-TRZ showed a high maximum external quantum efficiency of 10.0% in a nondoped solution-processed OLED, which was evidently higher than that of a corresponding 10 wt % tBuDMAC-TPE-TRZ-doped OLED with 4,4',4″-tris(carbazol-9-yl)triphenylamine (TCTA) as the host matrix. The results prove that intermolecular CT transitions indeed participate in the CT transition process in these systems and they are helpful to enhance the electroluminescence performance of emitting systems with weak intramolecular CT transitions.

Thermally Activated Delayed Fluorescence Carbonyl Derivatives for Organic Light-Emitting Diodes with Extremely Narrow Full Width at Half-Maximum.

Two novel thermally activated delayed fluorescence (TADF) emitters, 3-phenylquinolino[3,2,1- de]acridine-5,9-dione (3-PhQAD) and 7-phenylquinolino[3,2,1- de]acridine-5,9-dione (7-PhQAD), were designed and synthesized based on a rigid quinolino[3,2,1- de]acridine-5,9-dione (QAD) framework. With the effective superimposed resonance effect from electron-deficient carbonyls and electron-rich nitrogen atom, both emitters realize significant TADF characteristics with small Δ ESTs of 0.18 and 0.19 eV, respectively. And, molecular relaxations were dramatically suppressed for both emitters because of their conjugated structure. In the devices, 3-PhQAD realizes superior performance with a maximum external quantum efficiency (EQE) of 19.1% and a narrow full width at half-maximum (FWHM) of 44 nm, whereas a maximum EQE of 18.7% and an extremely narrow FWHM of 34 nm are realized for 7-PhQAD. These superior results reveal that apart from nitrogen and boron-aromatic systems, QAD framework can also act as a TADF matrix with effective resonance effect, and QAD derivatives are ideal candidates to develop TADF emitters with narrow FWHMs for practical applications.

Thermally Activated Delayed Fluorescence Pendant Copolymers with Electron- and Hole-Transporting Spacers.

To study the effect of hole- and electron-transporting spacers in copolymers on the thermally activated delayed fluorescence (TADF) properties and device efficiency of copolymers, two series of copolymers PCzPT-x and POPT-x have been designed and synthesized successfully. In these copolymers, 2-(10H-phenothiazin-10-yl)dibenzothiophene-S,S-dioxide units give green-yellow TADF, while hole-transporting 9-(4-vinylphenyl)-9H-carbazole units or electron-transporting diphenyl(4-vinylphenyl)phosphine oxide act as spacers or hosts. Their thermal, electrochemical, photophysical, and electroluminescent properties and theoretical calculations are systematically investigated to illustrate the relationships between molecular structures and photophysical properties. By optimizing the upconversion and radiative decay rate and managing the energy transfer, a green-yellow device based on POPT-25 achieves a maximum external quantum efficiency of 5.2%, a current efficiency of 16.8 cd/A, and a power efficiency of 7.8 lm/W with CIE coordinates of (0.36, 0.50). Moreover, an external quantum efficiency of 3.5% at the practical luminescence of 100 cd/m2 is obtained.

Multi-3,3'-Bicarbazole-Substituted Arylsilane Host Materials with Balanced Charge Transport for Highly Efficient Solution-Processed Blue Phosphorescent Organic Light-Emitting Diodes.

A series of 3,3'-bicarbazole (mCP)-functionalized tetraphenylsilane derivatives (SimCPx), including bis(3,5-di(9H-carbazol-9-yl)phenyl)diphenylsilane (SimCP2), tris(3,5-di(9H-carbazol-9-yl)phenyl)methylsilane (SimCP3-CH3), tris(3,5-di(9H-carbazol-9-yl)phenyl)phenylsilane (SimCP3-Ph), and tetrakis(3,5-di(9H-carbazol-9-yl)phenyl)silane (SimCP4), serving as bipolar blue hosts for bis[2-(4,6-difluorophenyl)pyridyl-N,C2']iridium(III) (FIrpic), have been synthesized by incorporating different ratios of mCP subunits into a central silicon atom. All of the SimCPx derivatives have wide bandgaps and high triplet energies because of the indirect linkage by silicon between each mCP subunit. The good solubility and high thermal and morphological stability of SimCPx are beneficial for forming amorphous and homogeneous films through solution processing. Density functional theory simulations manifest the better bipolar characteristics for SimCPx using three and four mCP units rather than the represented bipolar host SimCP2. As a result, SimCP4 presents the best electron-transporting ability for charge balance. Consequently, the lowest driving voltage of 4.8 eV, and the favorable maximum efficiencies of 14.2% for external quantum efficiency (28.4 cd A(-1), 13.5 lm W(-1)), are achieved by solution-processed, SimCP4-based blue phosphorescent organic light-emitting diodes as the highest performance among SimCPx, in which 32% improved device efficiencies compared to that of SimCP2 are obtained. It is inspiring to develop efficient bipolar hosts for blue phosphors by just incorporating monopolar carbazole into arylsilanes in two steps.

Solution-Processed Blue/Deep Blue and White Phosphorescent Organic Light-Emitting Diodes (PhOLEDs) Hosted by a Polysiloxane Derivative with Pendant mCP (1,3-bis(9-carbazolyl)benzene).

The synthesis and characterization is reported of an efficient polysiloxane derivative containing the 1,3-bis(9-carbazolyl)benzene (mCP) moiety as a pendant unit on the polysiloxane backbone. In comparison with mCP, the mCP-polysiloxane hybrid (PmCPSi) has significantly improved thermal and morphological stabilities with a high decomposition temperature (Td = 523 °C) and glass transition temperature (Tg = 194 °C). The silicon-oxygen linkage of PmCPSi prevents intermolecular π-stacking and ensures a high triplet energy level (ET = 3.0 eV). Using PmCPSi as a host, blue phosphorescent organic light emitting devices (PhOLEDs) effectively confine triplet excitons, with efficient energy transfer to the guest emitter and a relatively low turn-on voltage of 5.8 V. A maximum external quantum efficiency of 9.24% and maximum current efficiency of 18.93 cd/A are obtained. These values are higher than for directly analogous poly(vinylcarbazole) (PVK) based devices (6.76%, 12.29 cd/A). Good color stability over a range of operating voltages is observed. A two-component "warm-white" device with a maximum current efficiency of 10.4 cd/A is obtained using a blend of blue and orange phosphorescent emitters as dopants in PmCPSi host. These results demonstrate that well-designed polysiloxane derivatives are highly efficient hosts suitable for low-cost solution-processed PhOLEDs.

Thermo-sensitive graphene oxide-polymer nanoparticle hybrids: synthesis, characterization, biocompatibility and drug delivery.

We report the covalent interaction mediated assembly of thermo-sensitive polymer nanoparticles (PNPs) on functionalized graphene oxide (GO) nanosheets to create novel GO-PNP hybrids for drug delivery. To this end, thermo-sensitive PNPs with an average diameter of about 50 ± 12 nm were first synthesized with the free radical polymerization reaction, and GO nanosheets were noncovalently modified with a bifunctional linker to provide reactive sites for the binding of PNPs. Finally, GO-PNP hybrids were successfully synthesized by the covalent interaction mediated assembly of PNPs on GO nanosheets. Multi-characterization techniques were utilized to identify the formation of PNPs, the modification of GO nanosheets, and the formation of GO-PNP hybrids. Cell culture experiment with the mouse osteoblast-like MC3T3-E1 cells indicates that the synthesized GO-PNP hybrids have satisfactory biocompatibility. The loading efficiency of drug molecules (Adriamycin, ADR) with GO-PNP (∼87%) is close to that with GO (∼91%), but significantly higher than that with PNPs (∼46%). The release efficiency of GO-PNP hybrids with the highest surface coverage of PNPs (∼85 PNPs per µm2) is about 22%, which is very close to that of PNPs (∼25%) and significantly higher than that of GO (∼11%). Our study indicates that this thermo-sensitive GO-PNP hybrid, when considering the drug loading and release comprehensively, has better performance than both PNPs and GO and thus can be used as a novel nanocarrier for temperature-controllable drug release. The GO-PNP hybrids with and without ADR were applied to kill cancer cells in vitro and the result shows that the GO-PNP hybrid with ADR has an obvious effect on killing cancer cells, and its performance is obviously better than both GO and PNPs. It is expected that this new hybrid material based on GO and PNPs will have great potential for in vivo applications such as to kill target cancer cells by modifying with specific antibodies.