A Photoactivatable Luminescent Motif through Ring-Flipping Isomerization for Multiple Photopatterning.

Photoactivatable luminescent materials have garnered enormous attention in the field of intelligent responsive materials, yet their design and applications remain challenging due to the limited variety of photoactivatable motifs. In the work described herein, we discovered a new photoactivatable luminescent motif that underwent ring-flipping isomerization under UV irradiation. The emission of this motif exhibited a rapid transformation from dark yellow to bright green, accompanied by a significant enhancement of quantum yield from 1.9% to 34.2%. Experimental and theoretical studies revealed that the effective intramolecular motion (EIM) was crucial to the distinct luminescence performance between two isomers. In addition, polymers containing this motif were achieved through a one-pot alkyne polymerization, exhibiting both photofluorochromic and photo-cross-linking properties. Furthermore, multiple types of photopatterning, including luminescent encryption, fluorescent grayscale imaging, and high-resolution photolithographic patterns, were realized. This work developed a new photoactivatable luminescent motif and demonstrated its potential applications in both small molecules and macromolecules, which will help in the future design of photoactivatable luminescent materials.

Y-Shaped D-A Type Thioxanthone Derivatives: Mechano-Induced Thermally Activated Delayed Fluorescence and High-Contrast Mechano-Responsive Luminescence.

High-contrast mechano-responsive luminescence (MRL) materials with mechano-induced emission enhancement properties are fascinating candidates but few, for applications in rewritable media and recording devices. Here, an interesting design strategy of "Y-shape" donor-acceptor (D-A) type molecules for high-contrast MRL materials was presented, based on substituted diphenylamine donor and planar acceptor. Interestingly, their D-A torsion angles are small in crystals but increased after ground, resulted in planar and twist intramolecular charge transfer (PICT and TICT) states, respectively. Therefore, high-contrast MRL switching between weak blue (450 nm) fluorescence and bright yellow (552 nm) thermally activated delayed fluorescence (TADF) can be achieved for compound TXDO (4,4'-dimethoxydiphenylamine donor), which photoluminescence quantum yield increased from 2.8 % to 54.7 % after ground. Most importantly, the two independent D-A conjugation dihedral angles are actually independent in the "Y-shape" molecules. Especially for compound TXDT (4,4'-di-tert-butyldiphenylamine donor), its crystal exhibited both PICT and TICT processes inside, resulted from the different dihedral angles of 11.8° and 35.5°, respectively. The TXDT crystal thus showed dual-peak emission, including both TICT fluorescence and PICT room-temperature phosphorescence. Therefore, this strategy of "Y-shape" D-A type molecules provide a new approach to design advanced luminescent materials with mechano-induced TADF feature, for high-contrast MRL and single-component white luminescence.

Unveiling the intrinsic role of water in the catalytic cycle of formaldehyde oxidation: a comprehensive study integrating density functional theory and microkinetic analysis.

Previous research is predominantly in consensus on the reaction mechanism between formaldehyde (HCHO) and oxygen (O2) over catalysts. However, water vapor (H2O) always remains present during the reaction, and the intrinsic role of H2O in the oxidation of HCHO still needs to be fully understood. In this study, a single-atom catalyst, Al-doped C2N substrate, Al1/C2N, can be adopted as an example to investigate the relationship and interaction among O2, H2O, and HCHO. Density functional theory (DFT) calculations and microkinetic simulations were carried out to interpret the enhancement mechanism of H2O on HCHO oxidation over Al1/C2N. The outcome demonstrates that H2O directly breaks down a surface hydroxyl group on Al1/C2N, considerably lowering the energy required to form crucial intermediates, thus promoting oxidation. Without H2O, Al1/C2N cannot effectively oxidize HCHO at ambient temperature. During oxidation, H2O takes the major catalytic responsibility, delaying the entrance of O2 into the reaction, which is not only the product but also the crucial reactant to initiate catalysis, thereby sustaining the catalytic cycle. Moreover, this study predicts the catalytic behavior at various temperatures and presents feasible recommendations for regulating the reaction rates. The oxidation mechanism of HCHO is explained at the molecular level in this study, emphasizing the intrinsic role of water on Al1/C2N, which fills in the relevant studies for HCHO oxidation on two-dimensional carbon materials.

An Effective Strategy of Combining Surface Passivation and Secondary Grain Growth for Highly Efficient and Stable Perovskite Solar Cells.

Interfacial engineering methods have been developed to solve defect issues of perovskite solar cells (PSCs). However, traditional surface passivation has limited effects on eliminating defect-forming residuals, while secondary grain growth (SGG) is restricted by limited choices of additives and intrinsic properties of perovskites. Here, a pincer strategy of taking advantages of surface passivation and SGG is proposed to modify both exterior and interior of CH3 NH3 PbI3 (MAPbI3 ) perovskite, by employing cyanoacetate-containing donor-acceptor compounds (CA-D-A) including 2-cyano-3-(3,4,5-trimethoxyphenyl)acrylic acid (CA), methanaminium 2-cyano-3-(3,4,5-trimethoxyphenyl)acrylate (CAMA), and aminomethaniminium (Z)-2-cyano-3-(3,4,5-trimethoxyphenyl)acrylate (CAFA). In comparison to untreated perovskite, CA-D-A treated perovskites present better crystallinity because of SGG, lower trap densities due to the synergistic effect of surface passivation and SGG, and tuned energy levels induced by CA-D-A. Accordingly, the CA-D-A treated MAPbI3 -based PSCs exhibit higher open-circuit voltage and fill factor than the control PSC without any treatment, leading to improved power conversion efficiency (PCE) and enhanced device stability, especially the CAMA treated PSCs with an average PCE promoted from 17.77 (control PSCs) to 18.71%, and importantly an excellent PCE of 19.71% through further optimization. This work provides an effective strategy for developing highly efficient and stable PSCs with the assistance of both surface passivation and SGG.

Single-Atom Fe Catalyst Outperforms Its Homogeneous Counterpart for Activating Peroxymonosulfate to Achieve Effective Degradation of Organic Contaminants.

Recently, reactive iron species (RFeS) have shown great potential for the selective degradation of emerging organic contaminants (EOCs). However, the rapid generation of RFeS for the selective and efficient degradation of EOCs over a wide pH range is still challenging. Herein, we constructed FeN4 structures on a carbon nanotube (CNT) to obtain single-atom catalysts (FeSA-N-CNT) to generate RFeS in the presence of peroxymonosulfate (PMS). The obtained FeSA-N-CNT/PMS system exhibited outstanding and selective reactivity for oxidizing EOCs over a wide pH range (3.0-9.0). Several lines of evidences suggested that RFeS existing as an FeN4═O intermediate was the predominant oxidant, while SO4·- and HO· were the secondary oxidants. Density functional theory calculation results revealed that a CNT played a key role in optimizing the distribution of bonding and antibonding states in the Fe 3d orbital, resulting in the outstanding ability of FeSA-N-CNT for PMS chemical adsorption and activation. Moreover, CNT could significantly enhance the reactivity of the FeN4═O intermediate by increasing the overlap of electrons of the Fe 3d orbital, O 2p orbital, and bisphenol A near the Fermi level. The results of this study can advance the understanding of RFeS generation in a heterogeneous system over a wide pH range and the application of RFeS in real practice.

Activating Versatile Mechanoluminescence in Organic Host-Guest Crystals by Controlling Exciton Transfer.

Mechanoluminescence (ML) materials are attracting increasing interest owing to promising applications in various areas. However, to date, it remains a major challenge to develop a precise and universal route to achieving organic ML materials. Herein, we show that ML can be easily realized in organic piezophotonic host-guest crystals, under conditions in which neither the host nor the guest is ML-active. The experimental and theoretical results reveal that excitons of the host generated by piezoelectricity can be harvested effectively by the guest for light emission, owing to the restraint of intersystem crossing process. Moreover, different host-guest crystals are constructed, wherein the emission color, intensity, color purity, and emission duration of ML can be manipulated. This work deepens our understanding of organic ML generation in piezophotonic host-guest crystals and provides an inspiring principle to design more organic ML materials.

Boosting the Quantum Efficiency of Ultralong Organic Phosphorescence up to 52 % via Intramolecular Halogen Bonding.

Ultralong organic phosphorescence (UOP) has attracted increasing attention due to its potential applications in optoelectronics, bioelectronics, and security protection. However, achieving UOP with high quantum efficiency (QE) over 20 % is still full of challenges due to intersystem crossing (ISC) and fast non-radiative transitions in organic molecules. Here, we present a novel strategy to enhance the QE of UOP materials by modulating intramolecular halogen bonding via structural isomerism. The QE of CzS2Br reaches up to 52.10 %, which is the highest afterglow efficiency reported so far. The crucial reason for the extraordinary QE is intramolecular halogen bonding, which can not only effectively enhance ISC by promoting spin-orbit coupling, but also greatly confine motions of excited molecules to restrict non-radiative pathways. This work provides a reasonable strategy to develop highly efficient UOP materials for practical applications.

Selective Expression of Chromophores in a Single Molecule: Soft Organic Crystals Exhibiting Full-Colour Tunability and Dynamic Triplet-Exciton Behaviours.

Soft luminescent materials are attractive for optoelectronic applications, however, switching dominant chromophores for property enrichment remains a challenge. Herein, we report the first case of a soft organic molecule (DOS) featuring selective expression of chromophores. In response to various external stimuli, different chromophores of DOS can take turns working through conformation changes, exhibiting full-colour emissions peaking from 469 nm to 583 nm from ten individual single crystals. Dynamic triplet-exciton behaviours including thermally activated delayed fluorescence (TADF), room-temperature phosphorescence (RTP), mechanoluminescence (ML), and distinct mechano-responsive luminescence (MRL) can all be realized. This novel designed DOS molecule provides a multifunctional platform for detection of volatile organic compounds (VOCs), multicolour dynamic displays, sensing, anticounterfeiting, and hopefully many others.

Boosting Fenton-Like Reactions via Single Atom Fe Catalysis.

The maximization of the numbers of exposed active sites in supported metal catalysts is important to achieve high reaction activity. In this work, a simple strategy for anchoring single atom Fe on SBA-15 to expose utmost Fe active sites was proposed. Iron salts were introduced into the as-made SBA-15 containing the template and calcined for simultaneous decomposition of the iron precursor and the template, resulting in single atom Fe sites in the nanopores of SBA-15 catalysts (SAFe-SBA). X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and extended X-ray absorption fine structure (EXAFS) imply the presence of single atom Fe sites. Furthermore, EXAFS analysis suggests the structure of one Fe center with four O atoms, and density functional theory calculations (DFT) simulate this structure. The catalytic performances of SAFe-SBA were evaluated in Fenton-like catalytic oxidation of p-hydroxybenzoic acid (HBA) and phenol. It was found that the single atom SAFe-SBA catalysts displayed superior catalytic activity to aggregated iron sites (AGFe-SBA) in both HBA and phenol degradation, demonstrating the advantage of SAFe-SBA in catalysis.

Alkyl Chain Introduction: In†Situ Solar-Renewable Colorful Organic Mechanoluminescence Materials.

Mechanoluminescence (ML) materials are environmentally friendly and emit light by utilizing mechanical energy. This has been utilized in light sources, displays, bioimaging, and advanced sensors. Organic ML materials are strongly limited to application by in situ unrepeatable ML. Now, in situ solar-renewable organic ML materials can be formed by introducing a soft alkyl chain into an ML unit. For the first time, the ML from these polycrystalline thin films can be iteratively produced by simply recrystallizing the fractured crystal in situ after a contactless exposure to sunlight within a short time (≤60 s). Additionally, their ML color and lifetime can be also easily tuned by doping with organic luminescent dyes. Therefore, large-area sandwich-type organic ML devices can be fabricated, which can be repeatedly used in a colorful piezo-display, visual handwriting monitor, and sensitive optical sensor, showing a lowest pressure threshold for ML of about 5 kPa.

Research Advances in Neuroblast Migration in Traumatic Brain Injury.

Neuroblasts were first derived from the adult mammalian brains in the 1990s by Reynolds et al. Since then, persistent neurogenesis in the subgranular zone (SGZ) of the hippocampus and subventricular zone (SVZ) has gradually been recognized. To date, reviews on neuroblast migration have largely investigated glial cells and molecular signaling mechanisms, while the relationship between vasculature and cell migration remains a mystery. Thus, this paper underlines the partial biological features of neuroblast migration and unravels the significance and mechanisms of the vasculature in the process to further clarify theoretically the neural repair mechanism after brain injury. Neuroblast migration presents three modes according to the characteristics of cells that act as scaffolds during the migration process: gliophilic migration, neurophilic migration, and vasophilic migration. Many signaling molecules, including brain-derived neurotrophic factor (BDNF), stromal cell-derived factor 1 (SDF-1), vascular endothelial growth factor (VEGF), and angiopoietin-1 (Ang-1), affect vasophilic migration, synergistically regulating the migration of neuroblasts to target areas along blood vessels. However, the precise role of blood vessels in the migration of neuroblasts needs to be further explored. The in-depth study of neuroblast migration will most probably provide theoretical basis and breakthrough for the clinical treatment of brain injury diseases.

Dynamic Measurements of Cerebral Blood Flow Responses to Cortical Spreading Depolarization in the Murine Endovascular Perforation Subarachnoid Hemorrhage Model.

Delayed cerebral ischemia (DCI) is the most severe complication after subarachnoid hemorrhage (SAH), and cortical spreading depolarization (CSD) is believed to play a vital role in it. However, the dynamic changes in cerebral blood flow (CBF) in response to CSD in typical SAH models have not been well investigated. Here, SAH was established in mice with endovascular perforation. Subsequently, the spontaneous CBF dropped instantly and then returned to baseline rapidly. After KCl application to the cortex, subsequent hypoperfusion waves occurred across the groups, while a lower average perfusion level was found in the SAH groups (days 1-7). Moreover, in the SAH groups, the number of CSD decreased within day 7, and the duration and spreading velocity of the CSD increased within day 3 and day 14, respectively. Next, we continuously monitored the local field potential (LFP) in the prefrontal cortex. The results showed that the decrease in the percentage of gamma oscillations lasted throughout the whole process in the SAH group. In the chronic phase after SAH, we found that the mice still had cognitive deficits but experienced no obvious tissue damage. In summary, SAH negatively affects the CBF responses to CSD and the spontaneous LFP activity and causes long-term cognitive deficits in mice. Based on these findings, in the specific phase after SAH, DCI is induced or exacerbated more easily by potential causers of CSD in clinical practice (edema, erythrocytolysis, inflammation), which may lead to neurological deterioration.

A dish-like molecular architecture for dynamic ultralong room-temperature phosphorescence through reversible guest accommodation.

Developing dynamic organic ultralong room-temperature phosphorescent (URTP) materials is of practical importance in various applications but remains a challenge due to the difficulty in manipulating aggregate structures. Herein, we report a dish-like molecular architecture via a bottom-up way, featuring guest-responsive dynamic URTP. Through controlling local fragment motions in the molecular architecture, fascinating dynamic URTP performances can be achieved in response to reversible accommodation of various guests, including solvents, alkyl bromides and even carbon dioxide. Large-scale regulations of phosphorescence lifetime (100-fold) and intensity (10-fold) can be realized, presenting a maximum phosphorescence efficiency and lifetime of 78.8% and 483.1 ms, respectively. Moreover, such a dish-like molecular architecture is employed for temperature-dependent multiple information encryption and visual identification of linear alkyl bromides. This work can not only deepen our understanding to construct multifunctional organic aggregates, but also facilitate the design of high-performance dynamic URTP materials and enrich their practical applications.

Oily sludge derived carbons as peroxymonosulfate activators for removing aqueous organic pollutants: Performances and the key role of carbonyl groups in electron-transfer mechanism.

In this work, low-cost carbon-based materials were developed via a facile one-pot pyrolysis of oily sludge (OS) and used as catalysts to activate peroxymonosulfate (PMS) for removing aqueous recalcitrant pollutants. By adjusting the pyrolysis temperature, the optimized OS-derived carbocatalyst manifested good performance for PMS activation to abate diverse organic pollutants in water treatment. Particularly, an average removal rate of 0.87 mol phenol per mol PMS per hour at a catalyst dosage of 0.2 g L-1 is attained by the OS-derived carbocatalyst, higher than many other documented catalysts. A series of experimental evidences consolidated that organic pollutants were oxidized mainly via electron-transfer mechanism albeit the detection of singlet oxygen (1O2) from PMS activation driven by the OS-derived carbocatalyst. Specifically, the proportion of carbonyl groups (CË­O) in the carbocatalyst adopted with selective modification treatments to tailor the surface chemistry was found to be linearly correlated with the catalytic activity and theoretical calculations demonstrated that the reactions between CË­O and PMS to form surface reactive complexes were more energetically favorable compared to 1O2 generation. Herein, this study not only offers a new strategy for reusing OS as value-added persulfate activators but also deepens the fundamental understanding on the nonradical regime.

Insight into the effect of lignocellulosic biomass source on the performance of biochar as persulfate activator for aqueous organic pollutants remediation: Epicarp and mesocarp of citrus peels as examples.

In this work, the cellulose-enriched mesocarp of tangerine peels (TP) and the lignin-enriched epicarp of the peels (e-TPs) were used as examples to unveil the link between the basic components (cellulose, hemicellulose and lignin) in lignocellulosic biomass and catalytic activity of biochar towards peroxymonosulfate (PMS) activation. The TP biochar exhibits sheet-like morphology and high porosity, while the e-TPs biochar shows a bulk morphology. Accordingly, the former outperformed the latter in terms of catalytic degradation of phenol with PMS, attributing to the higher content of cellulose than lignin in the TP precursor, which was further supported by comparing the catalytic activity of biochar prepared from binary mixtures containing different proportions of cellulose and lignin. Nonradical oxidation pathway based on singlet oxygen (1O2) and electron-transfer mechanism was involved in the TP biochar/PMS system and the key role of CO group in biochar for 1O2 generation was computationally demonstrated. Additionally, the unique porous structure and surface chemistry of TP biochar endows it an excellent adsorbent for various organic pollutants. Herein, this work provides an insight into the effect of lignocellulosic biomass source on the catalytic property of biochar, which would be beneficial to screen lignocellulosic biowastes to prepare high-performance biochar for water remediation.

Amphiphilic Polymer-Mediated Aggregation-Induced Emission Nanoparticles for Highly Sensitive Organophosphorus Pesticide Biosensing.

Biosensing applications require signal reporters to be sufficiently stable and biosafe as well as highly efficient. Aggregation-induced emission (AIE) nanoparticles have proven to be capable of cell-imaging and cancer therapy; however, realizing sensitive detection of biomolecules remains a great challenge because of their instability, biotoxicity, and lack of modifiable functional groups. Herein, we report a self-assembling strategy to fabricate AIE nanoparticles (PTDNPs) through the dispersion of amphiphilic polymers (PTDs) in phosphate-buffered saline. The PTDs were prepared through radical copolymerization of N-(1,2,2-triphenylvinyl)-4-acetylaniline and dimethyl diallyl ammonium chloride. We found that the particle size, morphology, functional groups, and fluorescence property of PTDNPs can be fine-tuned. Further, PTDNPs-0.10 were chosen as signal reporters to detect organophosphorus pesticides (OPs) with the aid of gold nanoparticles. Their sensing performance on OPs is superior to that using C-dot/quantum dot/rhodamine B as the signal reporter. This study not only provides new possibilities to fabricate novel AIE nanoparticles with exceptional properties, but also facilitates the AIE nanoparticle's application for target analyte biosensing.

Nondoped Red Fluorophores with Hybridized Local and Charge-Transfer State for High-Performance Fluorescent White Organic Light-Emitting Diodes.

Two red fluorophores (TPABTPA and TPABCHO) with hybridized local and charge-transfer properties were systematically studied. TPABTPA and TPABCHO enabled nondoped organic light-emitting diodes (OLEDs) with excellent external quantum efficiency (EQE) of 11.1% and 5.0%, respectively, attributed to high exciton utilization efficiency of 82% and 46%, respectively. Furthermore, TPABTPA and TPABCHO were utilized as complementary emitters for a sky-blue thermally activated delayed fluorescence material to fabricate two-color fluorescent white OLEDs (WOLEDs) in a fully nondoped emissive-layer configuration. Furthermore, device performance was optimized through a simple device engineering strategy by sandwiching a suitable interlayer between the emitting layers. As a result, the optimized TPABTPA- and TPABCHO-based WOLEDs successfully achieved high EQEs of 23.0% and 8.6%, respectively, along with a low efficiency roll-off and good spectral stability, due to high exciton utilization efficiency of the emitters and importantly efficient suppression of a nonradiative energy-transfer process.

The methylation effect in prolonging the pure organic room temperature phosphorescence lifetime.

Prolonging the phosphorescence lifetime of pure organic phosphorescent materials by a methyl-substitution strategy is described. We present a chemical strategy for improving the phosphorescence lifetime of triplet excitons under ambient conditions by incorporating methyl groups into the chemical structures. This is observed by a long-lived phosphorescence lifetime of up to 0.83 s detected for methylated 9-(4-(mesitylsulfonyl)phenyl)-9H-carbazole (3M), compared to 0.36 s for 9-(4-(phenylsulfonyl)phenyl)-9H-carbazole (0M) without any methyl groups. Additionally, enhanced phosphorescence efficiency can be obtained at an appropriate methylation degree, because of the smaller ΔE ST (singlet and triplet energy gap) and ΔE TT* (normal phosphorescence and long-lived phosphorescence energy gap). A comprehensive investigation on the packing mode in the crystalline state reveals that the methyl groups occupy the free volume and result in a suppression of non-radiative decay, accounting for the enhanced phosphorescence lifetime.

An exceptionally flexible hydrogen-bonded organic framework with large-scale void regulation and adaptive guest accommodation abilities.

Flexible hydrogen-bonded organic frameworks (FHOFs) are quite rare but promising for applications in separation, sensing and host-guest chemistry. They are difficult to stabilize, making their constructions a major challenge. Here, a flexible HOF (named 8PN) with permanent porosity has been successfully constructed. Nine single crystals of 8PN with different pore structures are obtained, achieving a large-scale void regulation from 4.4% to 33.2% of total cell volume. In response to external stimuli, multimode reversible structural transformations of 8PN accompanied by changes in luminescence properties have been realized. Furthermore, a series of high-quality co-crystals containing guests of varying shapes, sizes, aggregation states and even amounts are obtained, showing that 8PN can adapt to different guests by regulating the molecular conformations and assembling forms of its building blocks. The unexpected flexibility of 8PN makes it a promising material for enriching the applications of existing porous materials.

Mechano-induced persistent room-temperature phosphorescence from purely organic molecules.

The persistent room-temperature phosphorescence (RTP) of purely organic materials in the solid state has recently attracted much research interest and found promising, rapid and visual applications by the naked eye, after the removal of the excitation source. However, almost all reported organic persistent RTP processes are induced by using a UV-light irradiation source. In this report, persistent RTP with an emission lifetime as long as 0.15 s which can be induced not only by photoirradiation but also by mechanical action is presented, which merges mechano-induced luminescence and persistent RTP together. It is found that such persistent RTP is produced through intermolecular electronic coupling (IEC) of units with different excited state configurations. Interestingly, there are two different crystals with and without mechano-induced persistent RTP which can be grown from this organic material, as such a new type of mechano-luminescence (ML) is strongly dependent on their intermolecular interactions. Furthermore, the intensity of such mechano-induced persistent RTP can be increased by lowing the temperature as well, similar to that of photo-induced persistent RTP. Notably, these two crystals exhibit a ML enhancement and ML "turn on", respectively, with decreasing temperature. Therefore, such mechano-induced persistent RTP provides an example of new types of organic luminescent materials, which is a missing jigsaw piece of organic luminescence and important for both fundamental research and practical applications of both persistent RTP and ML of organic materials.