A General Molecular Structural Design for Highly Efficient Photopyroptosis that can be Activated within 10 s Irradiation.

Photopyroptosis is an emerging research branch of photodynamic therapy (PDT), whereas there remains a lack of molecular structural principles to fabricate photosensitizers for triggering a highly efficient pyroptosis. Herein, a general and rational structural design principle to implement this hypothesis, is proposed. The principle relies on the clamping of cationic moieties (e.g., pyridinium, imidazolium) onto one photosensitive core to facilitate a considerable mitochondrial targeting (both of the inner and the outer membranes) of the molecules, thus maximizing the photogenerated reactive oxygen species (ROS) at the specific site to trigger the gasdermin E-mediated pyroptosis. Through this design, the pyroptotic trigger can be achieved in a minimum of 10 s of irradiation with a substantially low light dosage (0.4 J cm⁻2), compared to relevant work reported (up to 60 J cm⁻2). Moreover, immunotherapy with high tumor inhibition efficiency is realized by applying the synthetic molecules alone. This structural paradigm is valuable for deepening the understanding of PDT (especially the mitochondrial-targeted PDT) from the perspective of pyroptosis, toward the future development of the state-of-the-art form of PDT.

In situ synergistic reduced graphene oxide-boron carbon nitride nanosheet heterostructures for high-performance fabric-based supercapacitors.

We develop a new type of heterostructure nanocomposite made of reduced graphene oxide-boron carbon nitride nanosheets (rGO-BCN) by B-C covalent bonds. The rGO-BCN nanocomposite delivers a large specific surface and excellent electrochemical properties, and is then constructed into flexible fabric-based high-performance supercapacitor electrodes based on the microfluidic electrospinning technology.

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.

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.

Engineering Tunable Ratiometric Dual Emission in Single Emitter-based Amorphous Systems.

Molecular emitters with multi-emissive properties are in high demand in numerous fields, while these properties basically depend on specific molecular conformation and packing. For amorphous systems, special molecular arrangement is unnecessary, but it remains challenging to achieve such luminescent behaviors. Herein, we present a general strategy that takes advantage of molecular rigidity and S1 -T1 energy gap balance for emitter design, which enables fluorescence-phosphorescence dual-emission properties in various solid forms, whether crystalline or amorphous. Subsequently, the amorphism of the emitters based polymethyl methacrylate films endowed an in situ regulation of the dual-emissive characteristics. With the ratiometric regulation of phosphorescence by external stimuli and stable fluorescence as internal reference, highly controllable luminescent color tuning (yellow to blue including white emission) was achieved. There properties together with a persistent luminous behavior is of benefit for an irreplaceable set of optical information combination, featuring an ultrahigh-security anti-counterfeiting ability. Our research introduces a concept of eliminating the crystal-form and molecular-conformational dependence of complex luminescent properties through emitter molecular design. This has profound implications for the development of functional materials.

Tailored Drug Delivery Platforms: Stimulus-Responsive Core-Shell Structured Nanocarriers.

Core-shell structured nanocarriers have come into the scientific spotlight in recent years due to their intriguing properties and wide applications in materials chemistry, biology, and biomedicine. Tailored core-shell structures to achieve desired performance have emerged as a research frontier in the development of smart drug delivery system. However, systematic reviews on the design and loading/release mechanisms of stimulus-responsive core-shell structured nanocarriers are uncommon. This review starts with the categories of core-shell structured nanocarriers with different means of drug payload, and then highlights the controlled release mechanism realized through stimulus-response processes triggered under different environments. Finally, some multifaceted perspectives on the design of core-shell structured materials as drug carriers are addressed. This work aims to provide new enlightenments and prospects in the drug delivery field for further developing advanced and smart nanocarriers.

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.

Highly Efficient Room-Temperature Light-Induced Synthesis of Polymer Dots: A Programming Control Paradigm of Polymer Nanostructurization from Single-Component Precursor.

Polymer dots (PDs) have raised considerable research interest due to their advantages of designable nanostructures, high biocompatibility, versatile photoluminescent properties, and recyclability as nanophase. However, there remains a lack of in situ, real-time, and noncontact methods for synthesizing PDs. Here we report a rational strategy to synthesize PDs through a well-designed single-component precursor (an asymmetrical donor-acceptor-donor' molecular structure) by photoirradiation at ambient temperature. In contrast to thermal processes that normally lack atomic economy, our method is mild and successive, based on an aggregation-promoted sulfonimidization triggered by photoinduced delocalized intrinsic radical cations for polymerization, followed by photooxidation for termination with structural shaping to form PDs. This synthetic approach excludes any external additives, rendering a conversion rate of the precursor exceeding 99%. The prepared PDs, as a single entity, can realize the integration of nanocore luminescence and precursor-transferred luminescence, showing 41.5% of the total absolute luminescence quantum efficiency, which is higher than most reported PD cases. Based on these photoluminescent properties, together with the superior biocompatibility, a unique membrane microenvironmental biodetection could be exemplified. This strategy with programming control of the single precursor can serve as a significant step toward polymer nanomanufacturing with remote control, high-efficiency, precision, and real-time operability.

An invertible, invariant crystal representation for inverse design of solid-state materials using generative deep learning.

The past decade has witnessed rapid progress in deep learning for molecular design, owing to the availability of invertible and invariant representations for molecules such as simplified molecular-input line-entry system (SMILES), which has powered cheminformatics since the late 1980s. However, the design of elemental components and their structural arrangement in solid-state materials to achieve certain desired properties is still a long-standing challenge in physics, chemistry and biology. This is primarily due to, unlike molecular inverse design, the lack of an invertible crystal representation that satisfies translational, rotational, and permutational invariances. To address this issue, we have developed a simplified line-input crystal-encoding system (SLICES), which is a string-based crystal representation that satisfies both invertibility and invariances. The reconstruction routine of SLICES successfully reconstructed 94.95% of over 40,000 structurally and chemically diverse crystal structures, showcasing an unprecedented invertibility. Furthermore, by only encoding compositional and topological data, SLICES guarantees invariances. We demonstrate the application of SLICES in the inverse design of direct narrow-gap semiconductors for optoelectronic applications. As a string-based, invertible, and invariant crystal representation, SLICES shows promise as a useful tool for in silico materials discovery.

Advances in photothermal regulation strategies: from efficient solar heating to daytime passive cooling.

Photothermal regulation concerning solar harvesting and repelling has recently attracted significant interest due to the fast-growing research focus in the areas of solar heating for evaporation, photocatalysis, motion, and electricity generation, as well as passive cooling for cooling textiles and smart buildings. The parallel development of photothermal regulation strategies through both material and system designs has further improved the overall solar utilization efficiency for heating/cooling. In this review, we will review the latest progress in photothermal regulation, including solar heating and passive cooling, and their manipulating strategies. The underlying mechanisms and criteria of highly efficient photothermal regulation in terms of optical absorption/reflection, thermal conversion, transfer, and emission properties corresponding to the extensive catalog of nanostructured materials are discussed. The rational material and structural designs with spectral selectivity for improving the photothermal regulation performance are then highlighted. We finally present the recent significant developments of applications of photothermal regulation in clean energy and environmental areas and give a brief perspective on the current challenges and future development of controlled solar energy utilization.

Multifunctional Self-Assembled Ionic Liquid Modified Rigid and Flexible Substrates for Efficient Simple-Structured Perovskite Solar Cells.

The advancement of electron transport layer (ETL)-free perovskite solar cells (PSCs) is crucial for the commercialization of PSCs. At present, the slow electron extraction and significant carrier recombination, related to the energy-level alignment at the FTO/perovskite interface, restrict the performance of ETL-free PSCs. The facile modification of bottom electrodes is pivotal for tackling these issues and stimulating the photovoltaic potential of perovskite. Herein, a cost-competitive and neoteric 1-hydroxyethyl-3-methylimidazolium chloride, [HOEtMIM]Cl, ionic liquid is employed to modify the surface of rigid and flexible electrodes, and thus enable an energetically well-aligned interface with perovskite layer via the electric dipole effects. The resulting barrier-free FTO/perovskite contact can tremendously ameliorate the electron extraction and collection, with mitigated nonradiative interfacial carrier recombination loss. Additionally, the lone pair on the nitrogen of the imidazole group passivates the surface defects of perovskite layers, and the chloride anion plays a role in the crystallinity improvement of perovskite. Leveraged by the [HOEtMIM]Cl modification, the resulting ETL-free rigid and flexible devices deliver an outstanding power conversion efficiency of 19.60 % and 15.57 %, along with the ameliorated hysteresis and long-term tenability. This finding highlights the drastic potential of the engineered [HOEtMIM]Cl in manufacturing stable and high-performance ETL-free PSCs for their scaled-up production.

Maternal protein deficiency alters primary cilia length in renal tubular and impairs kidney development in fetal rat.

Introduction: Intrauterine malnutrition impairs embryo kidney development and leads to kidney disease and hypertension in adulthood, yet the underlying mechanism remains unclear. Methods: With a maternal protein restriction (MPR) rat model, we investigated the critical ciliogenesis factors and ß-catenin pathway in FGR fetal kidneys and analyzed the impact of aberrant primary cilia on renal tubular epithelium. Results: The data showed decreased nephron number and renal tubular dysgenesis in FGR fetus. FGR fetus showed deregulated expression of ciliogenesis factors including upregulation of IFT88 and downregulation of DYNLT1, accompanied with cilia elongation in renal tubular epithelial cells. Wnt7b, the key ligand for Wnt/ß-catenin signaling, was downregulated and nuclear translocation of ß-catenin was decreased. The proapoptotic protein was upregulated. In vitro study with HK-2 cells showed that overexpression of IFT88 lengthened the cilia, inhibited ß-catenin signaling. Besides, IFT88 overexpression suppressed cell proliferation, activated autophagy, and induced cell apoptosis. Inhibition of autophagy partly restored the cilia length and cell viability. Likewise, knockdown of DYNLT1 led to cilia elongation, suppressed cell proliferation, and promoted apoptosis in HK-2 cell. However, the cilia elongation induced by DYNLT1 knockdown was not autophagy-dependent, but associated with reactive oxygen species (ROS) accumulation. Discussion: We elucidated that intrauterine protein malnutrition led to deregulation of ciliogenesis factors and cilia elongation in renal tubular epithelial, inhibited ß-catenin signaling, and induced cell apoptosis and ultimately, compromised kidney development.

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.

Subvacuum environment-enhanced cell migration promotes wound healing without increasing hypertrophic scars caused by excessive cell proliferation.

Cell migration and proliferation are conducive to wound healing; however, regulating cell proliferation remains challenging, and excessive proliferation is an important cause of scar hyperplasia. Here, we aimed to explore how a subvacuum environment promotes wound epithelisation without affecting scar hyperplasia. Human immortalized keratinocyte cells and human skin fibroblasts were cultured under subvacuum conditions (1/10 atmospheric pressure), and changes in cell proliferation and migration, target protein content, calcium influx, and cytoskeleton and membrane fluidity were observed. Mechanical calcium (Ca2+ ) channel blockers were used to prevent Ca2+ influx for reverse validation. A rat wound model was used to elucidate the mechanism of the subvacuum dressing in promoting healing. The subvacuum environment was observed to promote cell migration without affecting cell proliferation; intracellular Ca2+ concentrations and PI3K, p-PI3K, AKT1, p-AKT 1 levels increased significantly. The cytoskeleton was depolymerized, pseudopodia were reduced or absent, and membrane fluidity increased. The use of Ca2+ channel blockers weakened or eliminated these changes. Animal experiments confirmed these phenomena and demonstrated that subvacuum dressings can effectively promote wound epithelisation. Our study demonstrates that the use of subvacuum dressings can enhance cell migration without affecting cell proliferation, promote wound healing, and decrease the probability of scar hyperplasia.

A Single Carbon-Dot System Enabling Multiple Stimuli Activated Room-Temperature Phosphorescence.

Room-temperature phosphorescent carbon dots (RTPCDs) have attracted considerable interests due to their unique nanoluminescent characteristic with time resolution. However, it is still a formidable challenge to construct multiple stimuli-activated RTP behaviors on CDs. Since the address of this issue facilitates complex and high-regulatable phosphorescent applications, we here develop a novel strategy to achieve a multiple stimuli responsive phosphorescent activation on a single carbon-dot system (S-CDs), using persulfurated aromatic carboxylic acid as the precursor. The introduction of aromatic carbonyl groups and multiple S atoms can promote the intersystem crossing process to generate RTP characteristic of the produced CDs. Meanwhile, by introducing these functional surface groups into S-CDs, the RTP property can be activated by light, acid, and thermal stimuli in solution or in film state. In this way, multistimuli responsive and tunable RTP characteristics are realized in the single carbon-dot system. Based on this set of RTP properties, S-CDs is applied to photocontrolled imaging in living cells, anticounterfeit label, and multilevel information encryption. Our work will benefit the development of multifunctional nanomaterials together with extending their application scope.

Photoexcitation-Induced Assembly: A Bottom-Up Physical Strategy for Driving Molecular Motion and Phase Evolution.

ConspectusIn the field of molecular assembly, photodriven self-assembly is a smart and crucial strategy to regulate the molecular orderliness, multiscale structure, and optoelectronic properties. Traditionally, photodriven self-assembly is based on photochemical processes, through molecular structural change induced by photoreactions. Despite great progress in the photochemical self-assembly, there still exists disadvantages (e.g., the photoconversion rate never reaches 100% with the possible side reactions). Therefore, the photoinduced nanostructure and morphology are often difficult to predict due to insufficient phase transition or defects. In contrast, the physical processes based on photoexcitation are straightforward and can fully utilize photons to avoid the drawbacks of photochemistry. The photoexcitation strategy excludes the change of molecular structure, only utilizing the molecular conformational change from the ground state to excited state. Then, the excited state conformation is employed to drive molecular movement and aggregation, further promoting the synergistic assembly or phase transition of the entire material system. The regulation and exploration of molecular assembly upon photoexcitation can open up a new paradigm to deal with the "bottom-up" behavior and develop unprecedented optoelectronic functional materials.This Account starts with a brief introduction to the problems faced by photocontrolled self-assembly and presents the photoexcitation-induced assembly (PEIA) strategy. Then, we focus on exploring PEIA strategy based on persulfurated arenes as the prototype. The molecular conformational transition of persulfurated arenes from the ground state to the excited state is conducive to the formation of intermolecular interactions, successively driving molecular motion, aggregation, and assembly. Next, we describe our progress in exploring PEIA of persulfurated arenes at the molecular level and then demonstrate that the PEIA of persulfurated arenes can synergistically drive molecular motion and phase transition in various block copolymer systems. Moreover, we provide the potential applications of PEIA in dynamic visual imaging, information encryption, and surface property regulation. Finally, an outlook on further development of PEIA is prospected.

Making multi-twisted luminophores produce persistent room-temperature phosphorescence.

Multi-twisted molecules, especially those with more than four branched rotation axes, have served as superior prototypes in diverse fields like molecular machines, optical materials, sensors, and so forth. However, due to excessive non-radiative relaxation of these molecules, it remains challenging to address their persistent room-temperature phosphorescence (pRTP), which limits their further development. Herein, we develop a host-guest energy-transfer relay strategy to improve the phosphorescence lifetime of multi-twisted luminophores by over thousand-fold to realize pRTP, which can be witnessed by the naked eye after removing the excitation light source. Moreover, we employ photoexcitation-induced molecular rearrangement to further prolong the phosphorescence lifetime, which, to the best of our knowledge, is the first example of photoactivation in ordered host-guest systems. Our systems show superior humidity and oxygen resistance, enabling long-term (at least over 9-12 months) stability of the pRTP properties. By achieving pRTP of multi-twisted luminophores, this work can advance the understanding of molecular photophysical mechanisms and guide the study of more molecular systems that are difficult to achieve pRTP.

Light-triggered Modulation of Supramolecular Chirality.

Dynamically controlling the supramolecular chirality is of great significance in development of functional chiral materials, which is thus essential for the specific function implementation. As an external energy input, light is remote and accurate for modulating chiral assemblies. In non-polarized light control, some photochemically reactive units (e. g., azobenzene, ɑ-cyanostilbene, spiropyran, anthracene) or photo-induced directionally rotating molecular motors were designed to drive chiral transfer or amplification. Besides, photoexcitation induced assembly based physical approach was also explored recently to regulate supramolecular chirality beyond photochemical reactions. In addition, circularly polarized light was applied to induce asymmetric arrangement of organic molecules and asymmetric photochemical synthesis of inorganic metallic nanostructures, in which both wavelength and handedness of circularly polarized light have effects on the induced supramolecular chirality. Although light-triggered chiral assemblies have been widely applied in photoelectric materials, biomedical fields, soft actuator, chiral catalysis and chiral sensing, there is a lack of systematic review on this topic. In this review, we summarized the recent studies and perspectives in the constructions and applications of light-responsive chiral assembled systems, aiming to provide better knowledge for the development of multifunctional chiral nanomaterials.

Highly efficient light-induced self-assembly of gold nanoparticles promoted by photoexcitation-induced aggregatable ligands.

There are numerous ways to achieve light-induced self-assembly of gold nanoparticles, but most of them are through chemical reaction and slow. Ligands that can perform photoexcitation-induced aggregation were synthesized and modified onto gold nanoparticles. The leading functionalized nanoparticles exhibit highly efficient light-induced self-assembly properties and show high-contrast color fading in tens of seconds.