A solution-processed n-type conducting polymer with ultrahigh conductivity.

Conducting polymers (CPs) with high conductivity and solution processability have made great advances since the pioneering work on doped polyacetylene1-3, thus creating the new field of 'organic synthetic metals,4. Various high-performance CPs have been realized, which enable the applications of several organic electronic devices5,6. Nevertheless, most CPs exhibit hole-dominant (p-type) transport behaviour7,8, whereas the development of n-type analogues lags far behind and only a few exhibit metallic state, typically limited by low doping efficiency and ambient instability. Here we present a facilely synthesized highly conductive n-type polymer poly(benzodifurandione) (PBFDO). The reaction combines oxidative polymerization and in situ reductive n-doping, greatly increasing the doping efficiency, and a doping level of almost 0.9 charges per repeating unit can be achieved. The resultant polymer exhibits a breakthrough conductivity of more than 2,000 S cm-1 with excellent stability and an unexpected solution processability without extra side chains or surfactants. Furthermore, detailed investigations on PBFDO show coherent charge-transport properties and existence of metallic state. The benchmark performances in electrochemical transistors and thermoelectric generators are further demonstrated, thus paving the way for application of the n-type CPs in organic electronics.

Extremely Stable Perylene Bisimide-Bridged Regioisomeric Diradicals and Their Redox Properties.

Excellent stability is an essential premise for organic diradicals to be used in organic electronic and spintronic devices. We have attached two tris(2,4,6-trichlorophenyl)methyl (TTM) radical building blocks to the two sides of perylene bisimide (PBI) bridges and obtained two regioisomeric diradicals (1,6-TTM-PBI and 1,7-TTM-PBI). Both of the isomers show super stability rather than the monomeric TTM under ambient conditions, due to the increased conjugation and the electron-withdrawing effects of the PBI bridges. The diradicals show distinct and reversible multistep redox processes, and a spectro-electrochemistry investigation revealed the generation of organic mixed-valence (MV) species during reduction processes. The two diradicals have singlet ground states, very small singlet-triplet energy gaps (ΔES-T ) and a pure open-shell character (with diradical character y0 =0.966 for 1,6-TTM-PBI and 0.967 for 1,7-TTM-PBI). This work opens a window to developing very stable diradicals and offers the opportunity of their further application in optical, electronic and magnetic devices.

A theoretical study on π-stacking and ferromagnetism of the perylene diimide radical anion dimer and tetramer.

Ferromagnetism is rare in pure organic materials. Recently, the perylene diimide radical anion (PDI-) salt prepared through solvothermal reduction by hydrazine hydrate has shown room-temperature ferromagnetism in our work [Jiang et al., Adv. Mater., 2022, 34, 2108103]. Based on this, herein we conduct a theoretical study based on density functional theory (DFT) to reveal the stacked geometries between two NH4PDI monomers for low-spin (LS) and high-spin (HS) states and their magnetic exchange interactions (JAB) using Yamaguchi's approximate spin projection. It is observed that the pancake-bonded dimer of NH4PDI is the most stable pimer compared to others on both LS and HS potential energy surfaces. A transition of magnetic properties from strong antiferromagnetic (-1333.9 cm-1) to moderate ferromagnetic (67.0 cm-1) appears after increasing the interplanar distance between monomers and their relative rotation angle to access the HS state. According to energy decomposition analysis, the enhanced hydrogen bond formation and decrease of Pauli repulsion is able to counteract the decrease of attraction induced by electron correlation after accessing the HS state. Stacking patterns of exchange-coupled chain consisting of the NH4PDI tetramer are obtained for the HS state after geometry optimization of the structure constructed by two most stable HS pimers. The exchange interactions (51.8 cm-1, 381.2 cm-1 and 53.2 cm-1) between adjacent NH4PDI monomers are ferromagnetic in the HS state, which is in accordance with the experimentally observed room-temperature ferromagnetism.

Correction: lncRNA PSMB8-AS1 promotes colorectal cancer progression through sponging miR-1299 to upregulate ADAMTS5.

This corrects the article DOI: 10.4149/neo_2022_220111N42.

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers.

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end-on polymers over centimeter-sized areas have a subnanometer-uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch-to-batch consistency for micro-sized organic materials and electronics.

Sulfone-Embedded Heterocyclic Narrowband Emitters with Strengthened Molecular Rigidity and Suppressed High-Frequency Vibronic Coupling.

Sulfone-embedded heterocyclics are of great interest in organic light-emitting diodes (OLEDs), however, exploring highly efficient narrowband emitters based on sulfone-embedded heterocyclics remains challenging. Herein, five emitters with different sulfur valence state and molecular rigidity, namely tP, tCPD, 2tCPD, tPD and tPT, are thoroughly analysed. With restricted twisting of flexible peripheral phenyl by strengthening molecular rigidity, molecular emission spectra can be enormously narrowed. Further, introducing the sulfone group with bending vibration in low-frequency region that suppresses high-frequency vibration, sharp narrow full-widths at half-maximum of 28 and 25 nm are achieved for 2tCPD and tPD, respectively. Maximum external quantum efficiencies of 22.0 % and 27.1 % are successfully realized for 2tCPD- and tPD-based OLED devices. These results offer a novel design strategy for constructing narrowband emitters by introducing sulfone group into a rigid molecular framework.

Electrocleavage Synthesis of Solution-Processed, Imine-Linked, and Crystalline Covalent Organic Framework Thin Films.

Developing a general, facile, and direct strategy for synthesizing thin films of covalent organic frameworks (COFs) is a major challenge in this field. Herein, we report an unprecedented electrocleavage synthesis strategy to produce imine-linked COF films directly on electrodes from electrolyte solutions at room temperature. This strategy enables the cathodic exfoliation of the COF powders to nanosheets by electrochemical reduction and protonation, followed by nanosheets migrating to the anode and reproducing the COF structures by anodic oxidation. Our method is adaptable with most imine-linked COFs by virtue of the low redox potential of the imine bonds, whereas the COF films possess high crystallinity and hierarchical porosity. We highlight these COF films as a superb platform for promoting mass transfer by demonstrating their extraordinarily rapid iodine adsorption with record-high rate constants.

Upregulated IncRNA WTAPP1 in Triple Negative Breast Cancer Predicts Survival.

The migration and angiogenesis of endothelial progenitor cells require the involvement of WTAPP1. Cell migration and angiogenesis are critical for cancer development, we therefore speculated that WTAPP1 may participate in cancer biology. This study aimed to explore the role of WTAPP1 in triple-negative breast cancer (TNBC). A total of 68 patients (females, 38 to 67 years old, mean age 52.1 ± 5.9 years old) were enrolled in this study. The effects of over-expression of WTAPP1 and miR-34a on EEF2K were evaluated by reverse transcription quantitative polymerase chain reaction (RT-qPCR) and Western blot. Transient cell transfections were performed to explore the interactions between genes. Cell proliferation assay was used to analyze cell proliferation. Transwell assays were performed to detect cell invasive and migration. Flow cytometry was used to evaluate apoptosis. WTAPP1 was upregulated in tumor tissues of TNBC patients and high expression levels of WTAPP1 in tumor tissues predicted poor survival. In contrast, miR-34a was downregulated in TNBC. Correlation analysis showed that WTAPP1 and miR-34a were negatively correlated with each other. In cancer cells, overexpression of WTAPP1 resulted in downregulation of miR-34a. Remarkably, overexpression of WTAPP1 increased the expression levels of EEF2K, a target of miR-34a. Overexpression of WTAPP1 and EEF2K increased proliferation, invasion and migration of TNBC cells, while overexpression of miR-34a showed different results. In addition, overexpression of miR-34a enhanced the effects of overexpression of WTAPP1 and EEF2K on apoptosis. WTAPP1 may promote TNBC cell proliferation by downregulating miR-34a.

lncRNA PSMB8-AS1 promotes colorectal cancer progression through sponging miR-1299 to upregulate ADAMTS5.

Long non-coding RNAs (lncRNAs) have been reported to be vital participants in tumor progression. Recently, lncRNA PSMB8-AS1 has been uncovered to facilitate pancreatic cancer progression by regulating miR-382-3p/STAT1/PD-L1 network. Nonetheless, the role of PSMB8-AS1 and its underlying mechanism have not been well-explored in colorectal cancer (CRC). The expression of RNAs or proteins was detected via qRT-PCR or western blot assays. Functional assays were involved in evaluating the effects of PSMB8-AS1/miR-1299/ADAMTS5 on the malignant behaviors of CRC cells. The molecular mechanism of PSMB8-AS1 was explored via mechanism analyses in CRC cells. Based on experimental results, PSMB8-AS1 expression was notably higher in CRC cell lines than in normal cells. The downregulation of PSMB8-AS1 repressed cell viability, proliferation, migration, invasion, and epithelial-mesenchymal transition (EMT) of CRC while promoting cell apoptosis. It was also revealed that PSMB8-AS1 could sponge miR-1299 to upregulate ADAMTS5 in CRC cells. In rescue assays, we further discovered that miR-1299 inhibition or ADAMTS5 overexpression abrogated the suppressive influence of PSMB8-AS1 deficiency on CRC cell growth. In addition, PSMB8-AS1 was validated to induce M2 polarization. In conclusion, PSMB8-AS1 sponges miR-1299 to increase PSMB8-AS1 expression, thus promoting CRC cell growth.

Recent progress in hot exciton materials for organic light-emitting diodes.

According to Kasha's rule, high-lying excited states usually have little effect on fluorescence. However, in some molecular systems, the high-lying excited states partly or even mainly contribute to the photophysical properties, especially in the process of harvesting triplet excitons in organic electroluminescent devices. In the current review, we focus on a type of organic light-emitting diode (OLED) materials called "hot exciton" materials, which can effectively harness the non-radiative triplet excitons via reverse intersystem crossing (RISC) from high-lying triplet states to singlet states (Tn→ Sm; n≥ 2, m≥ 1). Since Ma and Yang proposed the hot exciton mechanism for OLED material design in 2012, there have been many reports aiming at the design and synthesis of novel hot exciton luminogens. Herein, we present a comprehensive review of the recent progress in hot exciton materials. The developments of the hot exciton mechanism are reviewed, the fundamental principles regarding molecular design are discussed, and representative reported hot exciton luminogens are summarized and analyzed, along with their structure-property relationships and OLED applications.

Multicolour Fluorescence Based on Excitation-Dependent Electron Transfer Processes in o-Carborane Dyads.

Organic materials with excitation wavelength-dependent (Ex-de) emission are highly attractive for anticounterfeiting, optoelectronics and bioassay applications; however, the realization of Ex-de fluorescence, independent of aggregation states, remains a challenge. We herein report a photoinduced electron transfer (PeT) strategy to design Ex-de fluorescence materials by manipulating the relaxation pathways of multiple excited states. As expected, the o-carborane dyad presents a clear Ex-de fluorescence colour in the aggregated states, resulting from the tunable relative intensity of the dual-fluorescence spectra. Taking TP[1]B as an example, the amorphous powders emitted bright blue-violet, white and yellow colours under 390 nm, 365 nm and 254 nm UV illumination, respectively. Importantly, multicolour, flexible and transparent films as well as an anticounterfeiting application using this o-carborane dyad are demonstrated.

Electrochemical Deposition of a Single-Crystalline Nanorod Polycyclic Aromatic Hydrocarbon Film with Efficient Charge and Exciton Transport.

Electrochemical deposition has emerged as an efficient technique for preparing conjugated polymer films on electrodes. However, this method encounters difficulties in synthesizing crystalline products and controlling their orientation on electrodes. Here we report electrochemical film deposition of a large polycyclic aromatic hydrocarbon. The film is composed of single-crystalline nanorods, in which the molecules adopt a cofacial stacking arrangement along the π-π direction. Film thickness and crystal size can be controlled by electrochemical conditions such as scan rate and electrolyte species, while the choice of anode material determines crystal orientation. The film supports exceptionally efficient migration of both free carriers and excitons: the free carrier mobility reaches over 30 cm2 V-1 s-1 , whereas the excitons are delocalized with a low binding energy of 118.5 meV and a remarkable exciton diffusion length of 45 nm.

Electrochemical Synthesis, Deposition, and Doping of Polycyclic Aromatic Hydrocarbon Films.

Polycyclic aromatic hydrocarbons (PAHs) are employed as organic semiconductors because their delocalized π-electron systems and strong intermolecular interactions endow them with an exceptional charge-transport ability. However, the deposition of PAHs from solution onto high-quality thin films is often difficult. Here, we report a one-step electrochemical method to synthesize and deposit unsubstituted PAHs, starting from twisted oligophenyl precursors. The cyclodehydrogenated products were analyzed by matrix-assisted laser-desorption time-of-flight mass spectrometry as well as Fourier transform infrared and Raman spectroscopy. With this electrosynthesis and deposition, the PAHs stack into compact and ordered supramolecular structures along the π-π direction to form thin films with controllable thicknesses and doping levels. The direct fabrication of PAH films opens new pathways toward PAH-based optoelectronic devices.

Tailorable Membrane-Penetrating Nanoplatform for Highly Efficient Organelle-Specific Localization.

Given the breadth of currently arising opportunities and concerns associated with nanoparticles for biomedical imaging, various types of nanoparticles have been widely exploited, especially for cellular/subcellular level probing. However, most currently reported nanoparticles either have inefficient delivery into cells or lack specificity for intracellular destinations. The absence of well-defined nanoplatforms remains a critical challenge hindering practical nano-based bio-imaging. Herein, the authors elaborate on a tailorable membrane-penetrating nanoplatform as a carrier with encapsulated actives and decorated surfaces to tackle the above-mentioned issues. The tunable contents in such a versatile nanoplatform offer huge flexibility to reach the expected properties and functions. Aggregation-induced emission luminogen (AIEgen) is applied to achieve sought-after photophysical properties, specific targeting moieties are installed to give high affinity towards different desired organelles, and critical grafting of cell-penetrating cyclic disulfides (CPCDs) to promote cellular uptake efficiency without sacrificing the specificity. Hereafter, to validate its practicability, the tailored nano products are successfully applied to track the dynamic correlation between mitochondria and lysosomes during autophagy. The authors believe that the strategy and described materials can facilitate the development of functional nanomaterials for various life science applications.

Highly sensitive detecting system to precisely evaluate the emission spectra and quantum efficiency of organic crystal light-emitting transistors.

The lack of a reliable and sensitive measure system has strongly hindered the progress of organic single-crystal light-emitting transistors, since their emission spectra and absolute intensity were rather difficult to be measured as a consequence of small area and weak emission, as well as their edge emission feature. Hence, a tailor-made detecting system was set up by combining a semiconductor analyzer and a rotatable microscope coupling with a highly sensitive grating spectrometer. The detecting system solved the important issue of quantitatively characterizing the optoelectronic properties of organic transistors, especially those based on single crystals. With organic lamellar single crystals, we confirmed that the measurement system was reliable and had enough sensitivity to precisely evaluate the performance of light-emitting transistors corresponding to the emission spectra.

Light-Up Lipid Droplets Dynamic Behaviors Using a Red-Emitting Fluorogenic Probe.

Intracellular lipid metabolism occurs in lipid droplets (LDs), which is critical to the survival of cells. Imaging LDs is an intuitive way to understand their physiology in live cells. However, this is limited by the availability of specific probes that can properly visualize LDs in vivo. Here, an LDs-specific red-emitting probe is proposed to address this need, which is not merely with an ultrahigh signal-to-noise (S/N) ratio and a large Stokes shift (up to 214 nm) but also with superior resistance to photobleaching. The probe has been successfully applied to real-time tracking of intracellular LDs behaviors, including fusion, migration, and lipophagy processes. We deem that the proposed probe here offers a new possibility for deeper understanding of LDs-associated behaviors, elucidation of their roles and mechanisms in cellular metabolism, and determination of the transition between adaptive lipid storage and lipotoxicity as well.

CO2 Capture and Separations Using MOFs: Computational and Experimental Studies.

This Review focuses on research oriented toward elucidation of the various aspects that determine adsorption of CO2 in metal-organic frameworks and its separation from gas mixtures found in industrial processes. It includes theoretical, experimental, and combined approaches able to characterize the materials, investigate the adsorption/desorption/reaction properties of the adsorbates inside such environments, screen and design new materials, and analyze additional factors such as material regenerability, stability, effects of impurities, and cost among several factors that influence the effectiveness of the separations. CO2 adsorption, separations, and membranes are reviewed followed by an analysis of the effects of stability, impurities, and process operation conditions on practical applications.

Salidroside improved cerebrovascular vasodilation in streptozotocin-induced diabetic rats through restoring the function of BKCa channel in smooth muscle cells.

Vessel disease is a kind of severe complication in diabetic patients. However, few pharmacologic agents can directly recover diabetic vascular function. Salidroside (SAL), a major ingredient from Rhodiola rosea, has been found to have an obvious hypoglycemic effect and a beneficial protection on vascular function in diabetes. However, whether SAL is a suitable treatment for diabetes has not so far been evaluated and the underlying mechanisms remain unknown. The present work aims to (1) investigate the potential effects of SAL on cerebrovascular relaxation in streptozotocin-induced diabetic rats or when exposed to acute hyperglycemia condition and (2) examine whether function of the BKCa channel is involved in SAL treatment for diabetic vascular relaxation. Our results indicate that chronic administration of 100 mg/kg/day SAL not only improves cerebrovascular relaxation but also increases BKCa ß1-subunit expressions at both protein and mRNA levels and enhances BKCa whole-cell and single-channel activities in cerebral VSMCs of diabetic rats. Correspondingly, acute application of 100 µM SAL induces cerebrovascular relaxation by activation of the BKCa channel. Furthermore, SAL activated the BKCa channel mainly through acting on the ß1-subunit in HEK293 cells transfected with hSloα+ß1 constructs. We concluded that SAL improved vasodilation in diabetic rats through restoring the function of the BKCa-ß1 subunit in cerebrovascular smooth muscle cells, which may be the underlying mechanism responsible for the vascular protection of SAL in diabetes.

Restorable piezochromism phenomenon in an AIE molecular crystal: combined synchronous Raman scattering.

Many AIE active molecules have been designed and synthesized, and have been found to possess many interesting characteristics. In recent years, research into AIE crystals has increased, and it has been clearly shown that the piezochromic effect of AIE crystals depends on their structure. While most of the related research has given qualitative results, to quantitatively reveal molecular conditions under different pressure conditions, crystals of an AIE material (2Z,2'Z)-3,3'-(1,4-phenylene)bis(2-(naphthalen-2-yl)acrylonitrile) were investigated by synchronous Raman scattering and fluorescence spectroscopies. The molecular structure of the crystal changed during the process of pressurizing and then depressurizing under hydrostatic pressure, and a 142 nm red-shift value was observed in the emission spectrum of the PBNA crystal. The crystal was transformed into a new phase when the pressure was above 1.03 GPa and returned to the original phase when the pressure was decreased. The unique restorable phase transformation process of the crystal of this AIE active material could be used for erasable optical information storage and stress sensing devices.

E/Z isomerization, solvatachromism and aggregation-induced emission enhancement of donor-acceptor type oligo(p-phenylene vinylene)s.

A donor-acceptor molecule, PICNDSB, with cyclopenta[b]indole as the donor and (1,4-phenylene)bis(3-phenylacrylonitrile) as the acceptor, is designed and synthesized. PICNDSB shows typical aggregation-induced emission characteristics. The photoluminescence quantum yield of PICNDSB in dilute THF was only 0.7% and reaches 51.4% in the solid state. Compared with its analogue CzCNDSB, PICNDSB possesses stronger intramolecular charge transfer properties, as revealed from CV measurements, theoretical calculations, and their fluorescence behaviors. Correspondingly, the relatively more efficient electron-donating terminal group of cyclopenta[b]indole endows the molecule with a much higher two-photon absorption cross section of 1286 GM compared to CzCNDSB (357 GM).