Fluorescence-based monitoring of the pressure-induced aggregation microenvironment evolution for an AIEgen under multiple excitation channels.

The development of organic solid-state luminescent materials, especially those sensitive to aggregation microenvironment, is critical for their applications in devices such as pressure-sensitive elements, sensors, and photoelectric devices. However, it still faces certain challenges and a deep understanding of the corresponding internal mechanisms is required. Here, we put forward an unconventional strategy to explore the pressure-induced evolution of the aggregation microenvironment, involving changes in molecular conformation, stacking mode, and intermolecular interaction, by monitoring the emission under multiple excitation channels based on a luminogen with aggregation-induced emission characteristics of di(p-methoxylphenyl)dibenzofulvene. Under three excitation wavelengths, the distinct emission behaviors have been interestingly observed to reveal the pressure-induced structural evolution, well consistent with the results from ultraviolet-visible absorption, high-pressure angle-dispersive X-ray diffraction, and infrared studies, which have rarely been reported before. This finding provides important insights into the design of organic solid luminescent materials and greatly promotes the development of stimulus-responsive luminescent materials.

AIE-Active Photosensitizers: Manipulation of Reactive Oxygen Species Generation and Applications in Photodynamic Therapy.

Photodynamic therapy (PDT) is a non-invasive approach for tumor elimination that is attracting more and more attention due to the advantages of minimal side effects and high precision. In typical PDT, reactive oxygen species (ROS) generated from photosensitizers play the pivotal role, determining the efficiency of PDT. However, applications of traditional PDT were usually limited by the aggregation-caused quenching (ACQ) effect of the photosensitizers employed. Fortunately, photosensitizers with aggregation-induced emission (AIE-active photosensitizers) have been developed with biocompatibility, effective ROS generation, and superior absorption, bringing about great interest for applications in oncotherapy. In this review, we review the development of AIE-active photosensitizers and describe molecule and aggregation strategies for manipulating photosensitization. For the molecule strategy, we describe the approaches utilized for tuning ROS generation by attaching heavy atoms, constructing a donor-acceptor effect, introducing ionization, and modifying with activatable moieties. The aggregation strategy to boost ROS generation is reviewed for the first time, including consideration of the aggregation of photosensitizers, polymerization, and aggregation microenvironment manipulation. Moreover, based on AIE-active photosensitizers, the cutting-edge applications of PDT with NIR irradiated therapy, activatable therapy, hypoxic therapy, and synergistic treatment are also outlined.

Janus-Structural AIE Nanofiber with White Light Emission and Stimuli-Response.

White-light emitting elastomers (WLEEs) based on stimuli-responsive aggregation-induced emission (AIE) and regulated Förster resonance energy transfer (FRET) have aroused increasing attention due to the demands for wearable optoelectronic devices. Herein, the blue and orange AIEgens with different environmental sensitivities are synthesized and then encapsulated on both sides of nanofibers via side-by-side electrospinning aiming to achieve the Janus WLEEs. After regulating the blue-orange AIEgens ratio, efficient and stable white light emission with a CIE coordinate of about (0.33, 0.31) is achieved at a blue-orange AIEgens mass ratio of 3:1. Besides, the Janus nanofibers (Janus-NFs) also present super stretchability with elongation at the break over 150% and tensile strength close to 7 MPa. The sensitivity of fluorescence for Janus-NFs to its stretching deformation is used to visualize the evolution of the microstructure of nanofibers during stretching. Moreover, the Janus-NFs are also sensitive to HCl and NH3 , of which the fluorescence color would change under HCl and NH3 fuming above 2 and 57 ppm in air, respectively. The promising applications of the white light Janus-NFs in smart fabrics, warning sensors, and anti-counterfeiting packaging are demonstrated. This finding provides an efficient strategy for achieving wearable WLEEs with multiple functionalities, promoting the development of wearable devices.

Diradical-Featured Organic Small-Molecule Photothermal Material with High-Spin State in Dimers for Ultra-Broadband Solar Energy Harvesting.

Organic materials with radical characteristics are gaining increasing attention, due to their potential implications in highly efficient utilization of solar energy. Manipulating intermolecular interactions is crucial for tuning radical properties, as well as regulating their absorption bands, and thus improving the photothermal conversion efficiency. Herein, a diradical-featured organic small-molecule croconium derivative, CR-DPA-T, is reported for highly efficient utilization of solar energy. Upon aggregation, CR-DPA-T exists in dimer form, stabilized by the strong intermolecular π-π interactions, and exhibits a rarely reported high-spin state. Benefiting from the synergic effects of radical characteristics and strong intermolecular π-π interactions, CR-DPA-T powder absorbs broadly from 300 to 2000 nm. In-depth investigations with transient absorption analysis reveal that the strong intermolecular π-π interactions can promote nonradiative relaxation by accelerating internal conversion and facilitating intermolecular charge transfer (ICT) between dimeric molecules to open up faster internal conversion pathways. Remarkably, CR-DPA-T powder demonstrates a high photothermal efficiency of 79.5% under 808 nm laser irradiation. By employing CR-DPA-T as a solar harvester, a CR-DPA-T-loaded flexible self-healing poly(dimethylsiloxane) (H-PDMS) film, named as H-PDMS/CR-DPA-T self-healing film, is fabricated and employed for solar-thermal applications. These findings provide a feasible guideline for developing highly efficient diradical-featured organic photothermal materials.

Photoactivatable Biomedical Materials Based on Luminogens with Aggregation-Induced Emission (AIE) Characteristics.

Fluorescence probes with aggregation-induced emission (AIE) property are fascinating and vital in biological fields due to their bright fluorescence in the solid state. In contrast, traditional AIE materials are obscured by the off-target effects and lack of spatial and temporal control. Photoactivatable materials with AIE characteristics, whose physicochemical behaviors can be remotely activated by light, provide great potential in biochemical information acquisition with high spatial and temporal resolution. By using AIE-featured photoactivatable fluorescence probes, accurate analysis of the targets of interest is possible. For example, where, when, and to what extent a process is started or stopped by manipulating the non-invasive light accurately. Thus, many researchers are enthusiastic about developing AIE-featured photoactivatable materials and mainly focus on developing novel molecules by rational molecular structure design, and exploring advanced applications by appropriate molecular functionalization. In this review, the recent achievements of photoactivatable materials with AIE characteristics from the aspects involving inherent mechanism of photoactivity, molecular design strategy, and the corresponding applications in biological fields, are summarized. The biological applications are highlighted and discussed, including photoactivatable bioimaging, diagnosis, and photo-controlled therapy. Finally, the challenges and prospects of the AIE-featured photoactivatable materials are also outlined and discussed.

Core-Shell Fluorescent Polymeric Particles with Tunable White Light Emission Based on Aggregation Microenvironment Manipulation.

White-light emitting polymers (WLEPs) based on aggregation microenvironment-sensitive aggregation-induced emission (AIE) and Förster resonance energy transfer (FRET) have aroused great interest in lighting and optoelectronic devices. Herein, we developed a novel strategy to construct WLEP particles via a stepwise self-stabilized precipitation polymerization of two emission-complementary AIEgens under core-shell engineering, where the AIE characteristics and FRET process of core-shell fluorescent polymeric particles (CS-FPPs) could be modulated by altering aggregation microenvironment under swelling and shrinking of polymers, facilitating the tunable white light emission of CS-FPPs. Furthermore, such tuning could be fast realized in the solid state, thus demonstrating the potential in anti-counterfeiting. This work proved the significance of aggregation microenvironment on emission of luminogens, guiding the development of high-efficiency emission-tunable materials.

Biradical-Featured Stable Organic-Small-Molecule Photothermal Materials for Highly Efficient Solar-Driven Water Evaporation.

With recent progress in photothermal materials, organic small molecules featured with flexibility, diverse structures, and tunable properties exhibit unique advantages but have been rarely applied in solar-driven water evaporation owing to limited sunlight absorption resulting in low solar-thermal conversion. Herein, a stable croconium derivative, named CR-TPE-T, is designed to exhibit the unique biradical property and strong π-π stacking in the solid state, which facilitate not only a broad absorption spectrum from 300 to 1600 nm for effective sunlight harvesting, but also highly efficient photothermal conversion by boosting nonradiative decay. The photothermal efficiency is evaluated to be 72.7% under 808 nm laser irradiation. Based on this, an interfacial-heating evaporation system based on CR-TPE-T is established successfully, using which a high solar-energy-to-vapor efficiency of 87.2% and water evaporation rate of 1.272 kg m-2 h-1 under 1 sun irradiation are obtained, thus making an important step toward the application of organic-small-molecule photothermal materials in solar energy utilization.

Fluorescence Self-Reporting Precipitation Polymerization Based on Aggregation-Induced Emission for Constructing Optical Nanoagents.

Precipitation polymerization is becoming increasingly popular in energy, environment and biomedicine. However, its proficient utilization highly relies on the mechanistic understanding of polymerization process. Now, a fluorescence self-reporting method based on aggregation-induced emission (AIE) is used to shed light on the mechanism of precipitation polymerization. The nucleation and growth processes during the copolymerization of a vinyl-modified AIEgen, styrene, and maleic anhydride can be sensitively monitored in real time. The phase-separation and dynamic hardening processes can be clearly discerned by tracking fluorescence changes. Moreover, polymeric fluorescent particles (PFPs) with uniform and tunable sizes can be obtained in a self-stabilized manner. These PFPs exhibit biolabeling and photosensitizing abilities and are used as superior optical nanoagents for photo-controllable immunotherapy, indicative of their great potential in biomedical applications.

Self-Healable, Stretchable, Transparent Triboelectric Nanogenerators as Soft Power Sources.

Despite the rapid advancements of soft electronics, developing compatible energy devices will be the next challenge for their viable applications. Here, we report an energy-harnessing triboelectric nanogenerator (TENG) as a soft electrical power source, which is simultaneously self-healable, stretchable, and transparent. The nanogenerator features a thin-film configuration with buckled Ag nanowires/poly(3,4-ethylenedioxythiophene) composite electrode sandwiched in room-temperature self-healable poly(dimethylsiloxane) (PDMS) elastomers. Dynamic imine bonds are introduced in PDMS networks for repairing mechanical damages (94% efficiency), while the mechanical recovery of the elastomer is imparted to the buckled electrode for electrical healing. By adjusting the buckling wavelength of the electrode, the stretchability and transparency of the soft TENG can be tuned. A TENG (∼50% stretchabitliy, ∼73% transmittance) can recover the electricity genearation (100% healing efficiency) even after accidental cutting. Finally, the conversion of biomechanical energies into electricity (∼100 V, 327 mW/m2) is demonstrated by a skin-like soft TENG. Considering all these merits, this work suggests a potentially promising approach for next-generation soft power sources.

Triboelectric-Nanogenerator-Based Soft Energy-Harvesting Skin Enabled by Toughly Bonded Elastomer/Hydrogel Hybrids.

A major challenge accompanying the booming next-generation soft electronics is providing correspondingly soft and sustainable power sources for driving such devices. Here, we report stretchable triboelectric nanogenerators (TENG) with dual working modes based on the soft hydrogel-elastomer hybrid as energy skins for harvesting biomechanical energies. The tough interfacial bonding between the hydrophilic hydrogel and hydrophobic elastomer, achieved by the interface modification, ensures the stable mechanical and electrical performances of the TENGs. Furthermore, the dehydration of this toughly bonded hydrogel-elastomer hybrid is significantly inhibited (the average dehydration decreases by over 73%). With PDMS as the electrification layer and hydrogel as the electrode, a stretchable, transparent (90% transmittance), and ultrathin (380 µm) single-electrode TENG was fabricated to conformally attach on human skin and deform as the body moves. The two-electrode mode TENG is capable of harvesting energy from arbitrary human motions (press, stretch, bend, and twist) to drive the self-powered electronics. This work provides a feasible technology to design soft power sources, which could potentially solve the energy issues of soft electronics.

5,6-Difluorobenzothiazole-Based Conjugated Polymers with Large Band Gaps and Deep Highest Occupied Molecular Orbital Levels.

A 5,6-difluorobenzothiazole-based dibromo monomer was successfully synthesized, from which new fluorinated conjugated polymers PF-ffBTz and PFN-ffBTz were prepared via copolymerizations with two fluorene-based diboronic ester monomers. Twisted fluorene-ffBTz backbones enable PF-ffBTz and PFN-ffBTz with large band gaps up to 3.10 eV and deep-lying highest occupied molecular orbital levels down to -6.2 eV. The chemical structures of PF-ffBTz and PFN-ffBTz impart some new functionalities of fluorinated conjugated polymers. PF-ffBTz can show deep blue electroluminescent emission, with high external quantum efficiency of 3.71%. PFN-ffBTz, with amino-functionalized side chains on the fluorene unit, can serve as an efficient cathode interlayer in inverted polymer solar cells (PSCs), showing better photovoltaic performances if compared with a ZnO interlayer. In addition, it is found that using an optical filter to cut off the short wavelength section (≤380 nm) of incident light can significantly elevate photostability of PSCs under continuous illumination.

Hierarchically porous carbon/red phosphorus composite for high-capacity sodium-ion battery anode.

Red phosphorus has received remarkable attention as a promising anode material for sodium ion batteries (NIBs) due to its high theoretical capacity. However, its practical application has been impeded by its intrinsic low electronic conductivity and large volume variations during sodiation/desodiation process. Here, we design a composite to confine nanosized red phosphorus into the hierarchically porous carbon (HPC) walls by a vaporization-condensation strategy. The mass loading of P in the HPC/P composite is optimized to deliver a reversible specific capacity of 2,202 mAh/gp based on the mass of red P (836 mAh/gcomposite based on the total composite mass), a high capacity retention over 77% after 100 cycles, and excellent rate performance of 929 mAh/gp at 2 C. The hierarchical porous carbon serves as the conductive networks, downsize the red phosphorus to nanoscale, and provide free space to accommodate the large volume expansions. The suppressed mechanical failure of the red phosphorus also enhances the stability of solid-electrolyte interface (SEI) layer, which is confirmed by the microscopy and impedance spectroscopy after the cycling tests. Our studies provide a feasible approach for potentially viable high-capacity NIB anode.

Self-powered electrochromic devices with tunable infrared intensity.

Triboelectric nanogenerator (TENG) is an efficient way to convert ambient mechanical energy into electricity to power up portable electronics. In this work, a flexible infrared electrochromical device (IR-ECD) with stable performances was assembled with a TENG for building self-powered infrared detector with tunable intensity. As driven by TENG, the electrochromic device could be operated in the mid-IR region due to the reversible electrochromic reactions. An average infrared reflectance contrast of 46% was achieved in 8-14 µm regions and as well a clear thermal image change can be observed. This work indicates that the TENG-driven infrared electrochromical device has potential for use in self-powered camouflage and thermal control.

Knowledge Domain and Emerging Trends in Organic Photovoltaic Technology: A Scientometric Review Based on CiteSpace Analysis.

To study the rapid growth of research on organic photovoltaic (OPV) technology, development trends in the relevant research are analyzed based on CiteSpace software of text mining and visualization in scientific literature. By this analytical method, the outputs and cooperation of authors, the hot research topics, the vital references and the development trend of OPV are identified and visualized. Different from the traditional review articles by the experts on OPV, this work provides a new method of visualizing information about the development of the OPV technology research over the past decade quantitatively.

A molecular pathology method for sequential fluorescence in situ hybridization for multi-gene analysis at the single-cell level.

Multi-gene detection at the single-cell level is desirable to enable more precise genotyping of heterogeneous hematology and oncology samples. This study aimed to establish a single-cell multi-gene fluorescence in situ hybridization (FISH) method for use in molecular pathology analyses. Five fluorochromes were used to label different FISH gene probes, and 5 genes were detected using a five-color FISH protocol. After the first hybridization, the previous FISH probe set was stripped, and a second set of five-color FISH probes was used for rehybridization. After each hybridization, the fluorescence signals were recorded in 6 fluorescence filter channels that included DAPI, Spectrum Green™, Cy3™ v1, Texas Red, Cy5, and PF-415. A digital automatic relocation procedure was used to ensure that exactly the same microscopic field was studied in each stripping and hybridization cycle. By using this sequential stripping and rehybridization strategy, up to 20 genes can be detected within a single nucleus. In conclusion, a practical molecular pathology method was developed for analyzing multiple genes at the single-cell level.

Large-Area All-Textile Pressure Sensors for Monitoring Human Motion and Physiological Signals.

Wearable pressure sensors, which can perceive and respond to environmental stimuli, are essential components of smart textiles. Here, large-area all-textile-based pressure-sensor arrays are successfully realized on common fabric substrates. The textile sensor unit achieves high sensitivity (14.4 kPa-1 ), low detection limit (2 Pa), fast response (≈24 ms), low power consumption (<6 µW), and mechanical stability under harsh deformations. Thanks to these merits, the textile sensor is demonstrated to be able to recognize finger movement, hand gestures, acoustic vibrations, and real-time pulse wave. Furthermore, large-area sensor arrays are successfully fabricated on one textile substrate to spatially map tactile stimuli and can be directly incorporated into a fabric garment for stylish designs without sacrifice of comfort, suggesting great potential in smart textiles or wearable electronics.

Ultrastretchable, transparent triboelectric nanogenerator as electronic skin for biomechanical energy harvesting and tactile sensing.

Rapid advancements in stretchable and multifunctional electronics impose the challenge on corresponding power devices that they should have comparable stretchability and functionality. We report a soft skin-like triboelectric nanogenerator (STENG) that enables both biomechanical energy harvesting and tactile sensing by hybridizing elastomer and ionic hydrogel as the electrification layer and electrode, respectively. For the first time, ultrahigh stretchability (uniaxial strain, 1160%) and transparency (average transmittance, 96.2% for visible light) are achieved simultaneously for an energy-harvesting device. The soft TENG is capable of outputting alternative electricity with an instantaneous peak power density of 35 mW m-2 and driving wearable electronics (for example, an electronic watch) with energy converted from human motions, whereas the STENG is pressure-sensitive, enabling its application as artificial electronic skin for touch/pressure perception. Our work provides new opportunities for multifunctional power sources and potential applications in soft/wearable electronics.

Pressure-Induced Polymerization of Acetylene: Structure-Directed Stereoselectivity and a Possible Route to Graphane.

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.

[Growth kinetics and phenol degradation of highly efficient phenol-degrading Ochrobactrum sp. CH10].

The strain Ochrobactrum sp. CH10 was a highly efficient phenol degrading bacterial strain isolated from soil in a constructed wetland in Yuan Dynasty Capital City Wall Relics in Beijing. Growth and biodegradation were investigated in details with phenol as the sole carbon and energy source. The best growth and most efficient phenol biodegradation occurred when the strain was cultured in medium containing 400 mg x L(-1) phenol at initial pH of 7.0 and 30 degrees C, with 5% inoculation volume. The phenol degradation rate was around 100% , 92.3 and 82.2% with an initial concentration of 400, 900 and 1 000 mg x L(-1) phenol in 24, 44 and 48 h, respectively. Phenol degradation kinetic studies indicated that the strain followed Haldane's model, and the parameters were: upsilon(max) (maximum specific rate) = 0.126 h(-1), K(s) (half-saturation constant) = 23.53 mg x L(-1) and K(I) (inhibition constant) = 806.1 mg x L(-1). The phenol-limited growth kinetics of CH10 by Andrews's model also followed a similar trend to that of phenol degradation. Among all the strains belonging to Ochrobactrum genus, this strain is the most efficient at present. The strain has a good application potential for the phenolic wastewater treatment.