Construction of Carbon Dots@LiCl-polyacrylamide with Humidity-Induced Ultralong Room-Temperature Phosphorescence to Fluorescence and Rigid-to-Flexible Transition Behavior.

The continuous advancement of luminescent materials has placed increasingly stringent requirements on dynamic color-tunable ultralong room-temperature phosphorescence (URTP) materials that can respond to external stimuli. Nevertheless, endowing URTP materials with stimuli-response-induced dynamic color tuning is a challenging task. This study introduces a carbon dots (CDs)@LiCl-polyacrylamide (PAM) polymer system that switches from URTP to fluorescence under humidity stimuli, accompanied by a transition from rigidity to flexibility. The obtained rigid CDs@LiCl-PAM exhibits ultralong green phosphorescence with a lifetime of 560 ms in the initial state. After absorbing moisture, it becomes flexible and its phosphorescence switches off. Moreover, the emission of the CDs@LiCl-PAM film depends on the excitation wavelength. This property can potentially used in multicolored luminescence applications and displays. Moreover, multicolor luminescent patterns can be constructed in situ using the water-absorption ability of the obtained thin film and the Förster resonance energy-transfer strategy. The proposed strategy is expected to promote the interdisciplinary development of intelligent information encryption, anti-counterfeiting, and smart flexible display materials.

Synthesis, Self-assembly, and Fluorescence Application of Bottlebrush Polyfluorene-g-Polycaprolactone with Conjugated Backbone and Crystalline Brushes.

A series of bottlebrush copolymers with conjugated backbone and crystalline branch chains, polyfluorene-g-polycaprolactone (PF-g-PCL), are synthesized by combining Suzuki cross-coupling polymerization and cationic ring-opening polymerization. The PF-g-PCLs are prepared to self-assembled in solution and thin film. Due to the J-type aggregation of the polyfluorene main chains, the self-assembly spherical micelles have been observed. Meanwhile, in film, they exhibited self-assembly ringed spherulites because of the PF microregions in the bottlebrush copolymer. As a result of the interruption of PCL side chains, the aggregation tendency of PF main chains is weakened. And both the polymer solution and solid can overcome the aggregation-caused quenching to provide more pronounced fluorescence. Especially, owing to the good processability of the PF-g-PCL, as a fluorescent ink for different substrates, they can easily be prepared as high-brightness fluorescent films that are invisible under ambient light.

Engineering topochemical polymerizations using block copolymer templates.

With the aim to achieve rapid and efficient topochemical polymerizations in the solid state, via solution-based processing of thin films, we report the integration of a diphenyldiacetylene monomer and a poly(styrene-b-acrylic acid) block copolymer template for the generation of supramolecular architectural photopolymerizable materials. This strategy takes advantage of non-covalent interactions to template a topochemical photopolymerization that yields a polydiphenyldiacetylene (PDPDA) derivative. In thin films, it was found that hierarchical self-assembly of the diacetylene monomers by microphase segregation of the block copolymer template enhances the topochemical photopolymerization, which is complete within a 20 s exposure to UV light. Moreover, UV-active cross-linkable groups were incorporated within the block copolymer template to create micropatterns of PDPDA by photolithography, in the same step as the polymerization reaction. The materials design and processing may find potential uses in the microfabrication of sensors and other important areas that benefit from solution-based processing of flexible conjugated materials.

Versatile Bioactive Glass/Zeolitic Imidazolate Framework-8-Based Skin Scaffolds toward High-Performance Wound Healing.

Designing a novel biomaterial for wound healing is based on biocompatibility and excellent mechanical strength. In this study, bioactive glass (BG) and zeolitic imidazolate framework-8 (ZIF-8) have been incorporated into poly(ε-caprolactone)/poly(vinyl alcohol) (PCL/PVA) composite skin scaffolds via microfluidic electrospinning. Interestingly, the addition of ZIF-8 further strengthens the BG stability and demonstrates better antibacterial effects. Utilizing the slow release of Zn, Ca, and Si ions, it also significantly promotes growth factor expression and skin regeneration. In addition, it is further demonstrated by in vitro and in vivo studies that the prepared composite skin scaffolds possess excellent biocompatibility, antibacterial capabilities, and mechanical properties. The prepared BG/ZIF-8-loaded scaffold possesses high tensile strength (26 MPa) and excellent antibacterial properties (achieves 89.64 and 78.8% inhibition of E. coli and S. aureus, respectively), and cell viability increased by 51.2%. More importantly, the wound shrinkage of the BG/ZIF-8-loaded scaffold is better than that of an unloaded scaffold, and the shrinkage rates of PCL/PVA@BG/ZIF-8(1 wt %) group is 95% with 2.2 mm granulation growth thickness within 12 days. Thus, the composite skin scaffold loaded with BG/ZIF-8 prepared by microfluidic electrospinning provides a new perspective for accelerating wound healing and is a potential novel therapeutic strategy for efficient wound healing.

Edible Long-Afterglow Photoluminescent Materials for Bioimaging.

Confining luminophores into modified hydrophilic matrices or polymers is a straightforward and widely used approach for afterglow bioimaging. However, the afterglow quantum yield and lifetime of the related material remain unsatisfactory, severely limiting the using effect especially for deep-tissue time-resolved imaging. This fact largely stems from the dilemma between material biocompatibility and the quenching effect of water environment. Herein an in situ metathesis promoted doping strategy is presented, namely, mixing ≈10-3 weight ratio of organic-emitter multicarboxylates with inorganic salt reactants, followed by metathesis reactions to prepare a series of hydrophilic but water-insoluble organic-inorganic doping afterglow materials. This strategy leads to the formation of edible long-afterglow photoluminescent materials with superior biocompatibility and excellent bioimaging effect. The phosphorescence quantum yield of the materials can reach dozens of percent (the highest case: 66.24%), together with the photoluminescent lifetime lasting for coupes of seconds. Specifically, a long-afterglow barium meal formed by coronene salt emitter and BaSO4 matrix is applied into animal experiments by gavage, and bright stomach afterglow imaging is observed by instruments or mobile phone after ceasing the photoexcitation with deep tissue penetration. This strategy allows a flexible dosage of the materials during bioimaging, facilitating the development of real-time probing and theranostic technology.

Biodegradable zwitterionic polymer-cloaked defective metal-organic frameworks for ferroptosis-inducing cancer therapy.

Ferroptosis inhibits tumor growth by iron-dependently accumulating lipid peroxides (LPO) to a lethal extent, which can result from iron overload and glutathione peroxidase 4 (GPX4) inactivation. In this study, we developed biodegradable zwitterionic polymer-cloaked atorvastatin (ATV)-loaded ferric metal-organic frameworks (Fe-MOFs) for cancer treatment. Fe-MOFs served as nanoplatforms to co-deliver ferrous ions and ATV to cancer cells; the zwitterionic polymer membrane extended the circulation time of the nanoparticles and increased their accumulation at tumor sites. In cancer cells, the structure of the Fe-MOFs collapsed in the presence of glutathione (GSH), leading to the depletion of GSH and the release of ATV and Fe2+. The released ATV decreased mevalonate biosynthesis and GSH, resulting in GPX4 attenuation. A large number of reactive oxygen species were generated by the Fe2+-triggered Fenton reaction. This synergistic effect ultimately contributed to a lethal accumulation of LPO, causing cancer cell death. The findings both in vitro and in vivo suggested that this ferroptosis-inducing nanoplatform exhibited enhanced anticancer efficacy and preferable biocompatibility, which could provide a feasible strategy for anticancer therapy.

A Paper-Based Fluorescent Sensor for Rapid Early Screening of Oral Squamous Cell Carcinoma.

Various types of sensors play an irreplaceable role in the detection of biomarkers, but their high cost and complicated operation make it difficult to benefit ordinary people. Herein, we develop a low-cost, double-layered, paper-based fluorescent sensor (CP/HQ) structurally consisting of the upper reaction layer loaded with two oxidases (lactate oxidase and choline oxidase) and the bottom fluorescent layer that physically associates with the porphine-grafted composite fluorescent polymer colloids (PF-PDMTP/HQ). Based on the dramatic and rapid fluorescence decrease of porphine induced by the oxidation between saliva and oxidases and subsequent fluorescence resonance energy transfer from oxidized hydroquinone, the resultant fluorescent paper sensor enables us to achieve visual detection of OSCC, which was further recognized by smartphone scanning as the grayscale variation. It was found that the linear sensing range of grayscale value are 10-200 µM for lactic acid and 10-100 µM for choline, with LODs of 5.7 and 8.9 µM, respectively. More importantly, the sensor can achieve a powerful detection capability comparable to that of high-performance liquid chromatography (HPLC) in clinical settings with simple operation, demonstrating its great application potential. Our proposed sensor not only improves the accuracy of OSCC diagnosis but also provides a valuable attempt for the device modification of polymer-sensing systems and the development of non-invasive and easy-to-operate disease screening methods.

In Situ Regulation of Microphase Separation-Recognized Circularly Polarized Luminescence via Photoexcitation-Induced Molecular Aggregation.

Circularly polarized luminescence (CPL) has attracted great interest owing to its extensive optical information and chiral structural dependence. However, rationally regulating solid-phase CPL signals remains difficult because of the close packing of molecules in solid-state materials and the lack of structural visualization. In this work, we proposed a microphase-separation-recognized CPL regulation strategy via coassembly of a hexathiobenzene-based luminophore and chiral block copolymer (cBCP) with in situ photocontrollability. As a consequence to the continuous increase in the luminophore-to-cBCP ratio, the CPL signal of the supramolecular system exhibited an increasing trend until a critical point. Then, further increasing the ratio stretched the helical pitch of cBCP, which led to CPL reduction. With the photoexcitation-induced molecular aggregation of the luminophore, which was implemented using in situ photoirradiation, the helical pitch was retracted along with the restoration of the CPL signal. These processes were fully recognized and monitored by the microphase-separated nanomorphological change of the coassembled system, which indicated that such a structural contrast could be an effective method for rationally regulating the supramolecular chiropticity of solid-state materials.

Polystyrene microplastics increase Pb bioaccumulation and health damage in the Chinese mitten crab Eriocheir sinensis.

Microplastics may be potential vectors for environmental contaminants such as heavy metals in the aquatic ecosystem due to their highly hydrophobic surfaces and fugacity property. To investigate the combined effects of microplastics with Pb, we exposed juvenile Chinese mitten crabs Eriocheir sinensis to different Pb concentrations (0, 5 and 50 µg/L) combined with microplastics (0 and 400 µg/L) for 21 days to determine the Pb bioaccumulation, oxidative stress, lipid anabolism, and histopathology of hepatopancreas. In general, the results showed that compared to single Pb exposure, the combination of MPs and Pb significantly increased the bioaccumulation of Pb, activities/content of antioxidant biomarkers and lipid metabolism enzymes, and liver injury parameters in crabs, indicating MPs are potential vector of heavy metals and co-exposure exerts more severe effects on crabs. This study provides the insights into the oxidative defense and preliminary lipid anabolism of economic crustaceans in response to combined stress of Pb and MPs.

Chirality Transfer in Coassembled Organogels Enabling Wide-Range Naked-Eye Enantiodifferentiation.

Enantiodifferentiation is crucial in organic chemistry, pharmacochemistry, material chemistry, and life science. However, it remains tremendously challenging to achieve a broad enantioselectivity to different types of chiral substrates via a single-material design. Here, we report a coassembled organogel strategy with chirality transfer to make an enantioselective generality possible. This coassembly contains two components: a chiral rigid molecular linker and an achiral block copolymer. Different from routine helically packed chiral self-assemblies, chirality transfer from the linker to the copolymer directed the coassembly to form a phase-segregated twisted nanofiber, in cooperation with H-bonding and microphase segregation. An organogel was accordingly formed by the further cross-linking in ethanol, where the rigid chiral linker served as the scaffold. On this basis, the system becomes highly sensitive, enabling a naked-eye sensing toward the single enantiomer of a diverse series of chiral species (including axial, point, planar, and polymeric chirality) via gel-to-micelle transformation, due to the asymmetric interaction hampering the chirality transfer in the coassembly and destroying the hierarchical structure. Such a strategy, based on a significant amplification of the stereoselective interactions, facilitates a simple and straightforward way to distinguish a broad optical activity independent of devices.

Photoinduced charge transfer within polyaniline-encapsulated quantum dots decorated on graphene.

A new method to enhance the stability of quantum dots (QDs) in aqueous solution by encapsulating them with conducting polymer polyaniline was reported. The polyaniline-encapsulated QDs were then decorated onto graphene through π-π interactions between graphene and conjugated polymer shell of QDs, forming stable polyaniline/QD/graphene hybrid. A testing electronic device was fabricated using the hybrid in order to investigate the photoinduced charge transfer between graphene and encapsulated QDs within the hybrid. The charge transfer mechanism was explored through cyclic voltammetry and spectroscopic studies. The hybrid shows a clear response to the laser irradiation, presenting a great advantage for further applications in optoelectronic devices.

Engineering a hollow nanocontainer platform with multifunctional molecular machines for tumor-targeted therapy in vitro and in vivo.

In order to selectively target malignant cells and eliminate severe side effects of conventional chemotherapy, biocompatible and redox-responsive hollow nanocontainers with tumor specificity were fabricated. The mechanized nanocontainers were achieved by anchoring mechanically interlocked molecules, i.e., [2]rotaxanes, onto the orifices of hollow mesoporous silica nanoparticles via disulfide bonds as intermediate linkers for intracellular glutathione-triggered drug release. The [2]rotaxane employed was mainly composed of U.S. Food and Drug Administration approved tetraethylene glycol chains, α-cyclodextrin, and folic acid. In this study, folate groups on the mechanized hollow nanocontainers act as both the tumor-targeting agents and stoppers of the [2]rotaxanes. Detailed investigations showed that anticancer drug doxorubicin loaded mechanized nanocontainers could selectively induce the apoptosis and death of tumor cells. The drug-loaded nanocontainers enhanced the targeting capability to tumor tissues in vitro and inhibited the tumor growth with minimal side effects in vivo. The present controlled and targeted drug delivery system paves the way for developing the next generation of nanotherapeutics toward efficient cancer treatment.

Luminescent color conversion on cyanostilbene-functionalized quantum dots via in-situ photo-tuning.

Photo-responsive CdSe quantum dots functionalized with the cyanostilbene unit are synthesized. The as-prepared quantum dot hybrid reveals a photo-tunable dual fluorescent characteristic. White light emission can be generated in situ from the hybrid through photoirradiation to adjust the relative intensities of the two complementary emissions. Luminescent color conversion through yellow, white, and blue can be realized by varying the photoirradiation time.

Photolockable ratiometric viscosity sensitivity of cyclodextrin polypseudorotaxane with light-active rotor graft.

A prototype, based on light-active fluorescent rotor grafted to beta-cyclodextrin, shows a good solvent viscosity-sensitive behavior due to the environment-dependent nonradiative decay. With the reversible photoisomerization of the cyanostilbene unit, the viscosity sensitivity of the molecular rotor could be locked and activated, and the two switchable states can be distinguished by fluorescent signals. This cyclodextrin derivative was threaded to form a novel polypseudorotaxane. Such supramolecular assembly displays a lockable ratiometric fluorescent viscosity sensitivity with two emission channels: one aroused by fluorophore's intramolecular excimer without influenced by viscosity is used to gauge the concentration of the compound, while the other corresponding to the monomer's rotor fluorescence acts as a viscosity-sensitive signal and it can be shut off by UV irradiation.