Synthesis of an aggregation-induced emission (AIE) dye with pH-sensitivity based on tetraphenylethylene-pyridine for fluorescent nanoparticles and its applications in bioimaging and in vitro anti-tumor effect.

In this contribution, a novel AIE monomers 2-(4-styrylphenyl)- 1,2-diphenylvinyl)styryl)pyridine (SDVPY) with smart fluorescent pH-sensitivity basing on tetraphenylethylene-pyridine were successfully synthesized for the first time, subsequently, a series of amphiphilic copolymers PEG-PY were achieved by reversible addition-fragmentation chain transfer (RAFT) polymerization of SDVPY and poly(ethylene glycol) methacrylate (PEGMA), which would self-assemble in water solution to form core-shell nanoparticles (PEG-PY FONs) with about 150 nm diameter. The PEG-PY FONs showed obvious fluorescence response to Fe3+, HCO3- and CO32- ions in aqueous solution owing to their smart pH-sensitivity and AIE characteristics, and their maximum emission wavelength could reversibly change from 525 nm to 624 nm. The as-prepared PEG-PY FONs showed also prospective application in cells imaging with the variable fluorescence for different pH cells micro-environment. When PEG-PY copolymers self-assembled with the anti-tumor drug paclitaxel (PTX), the obtained PY-PTX FONs could effectively deliver and release PTX with pH-sensitivity, and could be easily internalized by A549 cells and located at the cytoplasm with high cytotoxicity, which was further confirmed by the Calcein-AM/PI staining of dead and alive A549 cells. Moreover, the flow cytometry results indicated that the PY-PTX FONs could obviously induce the apoptosis of A549 cells, which further showed the great potential of PY-PTX FONs in the application of tumors therapy.

Liquid Crystalline Nanoparticles via Polymerization-Induced Self-Assembly: Morphology Evolution and Function Regulation.

Liquid crystalline nanoparticles (LC NPs) are a kind of polymer NPs with LC mesogens, which can form special anisotropic morphologies due to the influence of LC ordering. Owing to the stimuli-responsiveness of the LC blocks, LC NPs show abundant morphology evolution behaviors in response to external regulation. LC NPs have great application potential in nano-devices, drug delivery, special fibers and other fields. Polymerization-induced self-assembly (PISA) method can synthesize LC NPs at high solid content, reducing the harsh demand for reaction solvent of the LC polymers, being a better choice for large-scale production. In this review, we introduced recent research progress of PISA-LC NPs by dividing them into several parts according to the LC mesogen, and discussed the improvement of experimental conditions and the potential application of these polymers.

Automatically Predicting Material Properties with Microscopic Images: Polymer Miscibility as an Example.

Many material properties are manifested in the morphological appearance and characterized using microscopic images, such as scanning electron microscopy (SEM). Polymer miscibility is a key physical quantity of polymer materials and is commonly and intuitively judged using SEM images. However, human observation and judgment of the images is time-consuming, labor-intensive, and hard to be quantified. Computer image recognition with machine learning methods can make up for the defects of artificial judging, giving accurate and quantitative judgment. We achieve automatic miscibility recognition utilizing a convolutional neural network and transfer learning methods, and the model obtains up to 94% accuracy. We also put forward a quantitative criterion for polymer miscibility with this model. The proposed method can be widely applied to the quantitative characterization of the microstructure and properties of various materials.

Colloidal crystals of monodisperse fluoro-nanoparticles by aqueous polymerization-induced self-assembly.

Here, we prepared monodisperse fluorinated nanospheres with the diameter regulated from 100 to 200 nm and PDI of the diameter lower than 0.05 via polymerization-induced self-assembly (PISA). Mono/multilayered 2D and large-scale ordered 3D lattices were formed by solvent evaporation-induced colloidal self-assembly. This work shows the promising application of PISA in colloidal self-assembly.

A Versatile Theranostic Nanoplatform with Aggregation-Induced Emission Properties: Fluorescence Monitoring, Cellular Organelle Targeting, and Image-Guided Photodynamic Therapy.

Photosensitizers (PSs) play a key role in the photodynamic therapy (PDT) of tumors. However, commonly used PSs are prone to intrinsic fluorescence aggregation-caused quenching and photobleaching; this drawback severely limits the clinical application of PDT, necessitating new phototheranostic agents. Herein, a multifunctional theranostic nanoplatform (named TTCBTA NP) is designed and constructed to achieve fluorescence monitoring, lysosome-specific targeting, and image-guided PDT. TTCBTA with a twisted conformation and D-A structure is encapsulated in amphiphilic Pluronic F127 to form nanoparticles (NPs) in ultrapure water. The NPs exhibit biocompatibility, high stability, strong near-infrared emission, and desirable reactive oxygen species (ROSs) production capacity. The TTCBTA NPs also show high-efficiency photo-damage, negligible dark toxicity, excellent fluorescent tracing, and high accumulation in lysosome for tumor cells. Furthermore, TTCBTA NPs are used to obtain fluorescence images with good resolution of MCF-7 tumors in xenografted BALB/c nude mice. Crucially, TTCBTA NPs present a strong tumor ablation ability and image-guided PDT effect by generating abundant ROSs upon laser irradiation. These results demonstrate that the TTCBTA NP theranostic nanoplatform may enable highly efficient near-infrared fluorescence image-guided PDT.

Super solvent of cellulose with extra high solubility for tunable cellulose structure with versatile application.

Low-temperature two-step concentrated H2SO4 was discovered to be a solvent with high cellulose solubility [>300 g/L (17 wt%)], fast cellulose dissolution, high regeneration yield (>0.92 g/g), and cellulose being mouldable during regeneration. The superior performance was enabled by the much better compatibility of cellulose with lower concentrated H2SO4 at low temperature, compared with that of high concentrated H2SO4. The regenerated cellulose was characterized by mostly unchanged composition and highly tunable degree of polymerization (DP). The H2SO4 starting content, cotton fibre temperature, dissolution temperature, regeneration temperature, regeneration bath and storage time were factors determining the DP of regenerated cellulose, which could be equivalent to 4-90 % of the original cotton. These advantages of the solvent enabled versatile application in fabrication of extra strong cellulose hydrogels, manufacture of strong cellulose fibres, preparation of various homogenous composites which would be prepared with much more difficulty by using other solvents, and facile manufacture of cellooligosaccharides.

In situ generation and evolution of polymer toroids by liquid crystallization-assisted seeded dispersion polymerization.

An effective method is presented for preparing high solid content azobenzene-containing triblock copolymer toroidal assemblies by liquid crystallization-assisted seeded dispersion polymerization. Vesicles are prepared via polymerization-induced self-assembly (PISA), and used as seeds for further chain extension. By introducing smectic liquid crystalline (LC) ordering into the core-forming block, toroids are formed in situ during the polymerization. The morphological transformation from toroids to barrels is observed under ultraviolet irradiation due to the photo-isomerization of the azobenzene mesogens. This strategy expands the scope of tunable anisotropic morphologies for potential functional nanomaterials based on a LC copolymer by seeded dispersion polymerization.

Stimuli-Responsive Pickering Emulsions Regulated via Polymerization-Induced Self-Assembly Nanoparticles.

With the development of reversible deactivated radical polymerization techniques, polymerization-induced self-assembly (PISA) is emerging as a facile method to prepare block copolymer nanoparticles in situ with high concentrations, providing wide potential applications in different fields, including nanomedicine, coatings, nanomanufacture, and Pickering emulsions. Polymeric emulsifiers synthesized by PISA have many advantages comparing with conventional nanoparticle emulsifiers. The morphologies, size, and amphiphilicity can be readily regulated via the synthetic process, post-modification, and external stimuli. By introducing stimulus responsiveness into PISA nanoparticles, Pickering emulsions stabilized with these nanoparticles can be endowed with "smart" behaviors. The emulsions can be regulated in reversible emulsification and demulsification. In this review, the authors focus on recent progress on Pickering emulsions stabilized by PISA nanoparticles with stimuli-responsiveness. The factors affecting the stability of emulsions during emulsification and demulsification are discussed in details. Furthermore, some viewpoints for preparing stimuli-responsive emulsions and their applications in antibacterial agents, diphase reaction platforms, and multi-emulsions are discussed as well. Finally, the future developments and applications of stimuli-responsive Pickering emulsions stabilized by PISA nanoparticles are highlighted.

Prevalence and Genetic Analysis of ß-Thalassemia in the Dali Bai Autonomous Prefecture of the Yunnan Province, China.

Background: ß-Thalassemia is the most common monogenetic hemolytic hemoglobin-associated disease in the south of China; the distribution of genetic mutations associated with this condition varies according to geographic regions. This study investigated the prevalence and distribution of ß-thalassemia-associated mutations across different ethnic groups in the Dali Bai Autonomous Prefecture of the Yunnan Province, China. Methods: This cross-sectional study included 4723 participants (15-45 years old) who volunteered for thalassaemia screening from the Dali Bai Autonomous Prefecture from May 2017 to October 2020. Cellulose acetate membrane electrophoresis was used to screen for ß-thalassemia carriers. Genotypic analyses was performed using polymerase chain reaction-based reverse dot blotting and DNA sequencing. Results: The overall prevalence of ß-thalassemia in the study population was 2.01%. The genotypic analyses showed the presence of four types of mutations in the ß-globin gene: CD26 (GAG→AAG), CD56 (GGC→GAC), IVS-II-81 (C→T), and CD121 (GAA→CAA). In contrast to previous studies from other regions of Yunnan Province, our results showed that the prevalence of CD26 mutations was significantly higher than that of the other mutations. Conclusion: Our data suggests that the Dali Autonomous Prefecture is an area with a high prevalence of ß-thalassemia. Moreover, CD26 was the only ß-thalassemia mutation that we have detected. Moreover, the vast majority of the ß-thalassemia mutations observed were CD26.

In Situ Visualization of Reversible Diels-Alder Reactions with Self-Reporting Aggregation-Induced Emission Luminogens.

The dynamic reversible Diels-Alder (DA) reactions play essential roles in both academic and applied fields. Currently, in situ visualization and direct monitoring of the formation and cleavage of covalent bonds in DA reactions are hampered by finite compatibility and expensive precise instruments, especially limited in solid reactions. We herein report a fluorescence system capable of in situ visualization by naked eyes and monitoring DA/retro-DA reactions. With the fluorescence quenching effect, the synthesized TPEMI could work as an innovative self-indicator for both DA termination and retro-DA occurrence. The fluorescence increases during DA reactions, and the mechanism is investigated to establish qualitative and quantitative relations. Besides rapid screening of reaction conditions and monitoring of DA exchange processes, the TPEMI fluorescence system can visualize heterogeneous and solid-state reactions with the AIE character. The TPEMI platform is expected to offer novel insights into reversible DA processes and dynamic covalent chemistry.

In situ observation of heterogeneous catalytic organic reactions via aggregation-induced emission luminogens.

Herein, we demonstrated for the first time that customized aggregation-induced emission luminogens can be utilized to directly visualize heterogeneous catalytic organic reactions, which further enables catalyst screening. We used the retro-Diels-Alder reaction as a model reaction for illustration, and identified montmorillonite K10 as the best catalyst in our catalyst screening.

Polymeric nanostructures based on azobenzene and their biomedical applications: synthesis, self-assembly and stimuli-responsiveness.

Amphiphilic polymers can self-assemble to form nanoparticles with different structures under suitable conditions. Polymer nanoparticles functionalized with aromatic azo groups are endowed with photo-responsive properties. In recent years, a variety of photoresponsive polymers and nanoparticles have been developed based on azobenzene, using different molecular design strategies and synthetic routes. This article reviews the progress of this rapidly developing research field, focusing on the structure, synthesis, assembly and response of photo-responsive polymer assemblies. According to the molecular structure, photo-responsive polymers can be divided into linear polymers containing azobenzene in a side chain, linear polymers containing azobenzene in the main chain, linear polymers containing azobenzene in an end group, branched polymers containing azobenzene and supramolecular polymers containing azobenzene. These systems have broad biomedical application prospects in the field of drug delivery and imaging applications.

Recent advances in electrospinning supramolecular systems.

Electrospinning is one of the simple, versatile, and convenient techniques for producing nanofibers that have found numerous applications in the fields of biomedical engineering, surface materials, and catalysis. Despite the great achievements, the electrospinning compounds are still limited to the utilization of polymers with high molar mass which are regarded as an indispensable element for the production of nanofibers. It is found that electrospinning chemicals based on supramolecular systems can avoid the use of high molecular weight polymers, and it is emerging as a powerful route to generate fibers in the nano-scale size. The presence of strong intermolecular interactions that function as chain entanglements allows for the formation of nanofibers during the process of electrospinning. This article provides recent impressive developments concerning nanofiber preparation made by the combination of electrospinning and supramolecular chemistry, which enables easy access to tailor-made nanofibers. Electrospinning supramolecular systems consisting of phospholipids, surfactants, crown ether derivatives as well as cyclodextrins will be highlighted in this review. Moreover, we will pay particular attention to the functionalities of electrospun nanofibers obtained from supramolecular systems.

Host-guest complexation modulated aqueous polymerization-induced self-assembly for monodisperse hierarchical nanoflowers.

This work presents a one-step synthesis of monodisperse nanoflowers by aqueous polymerization-induced self-assembly (PISA), modulated by host-guest interactions. Owing to the low monomer swelling of nanoparticles restricted by host-guest complexation, hierarchical surficial micellar structures were generated at the outer surface of the vesicles, forming fractal nanoflowers with a diameter polydispersity as low as 1.01. Our method allows the straightforward synthesis of monodisperse hierarchical nanoparticles for a wide range of applications.

Gas-Responsive Self-Assemblies for Mimicking the Alveoli.

In human body, alveoli are the primary sites for gas exchange which are formed by the dilation and protrusion of bronchioles at the end of the lung, and the rapid gas-exchanging process in the alveoli ensures normal life activities. Based on the unique structures and functions of alveoli, it is necessary to study the regulation mechanism of its formation, respiration, and apoptosis. Herein, a class of reversible addition-fragmentation chain transfer (RAFT)-derived amphiphilic triblock copolymers, PEO-b-P(DEAEMA-co-FMA)-b-PS is designed and synthesized. Due to the amphiphilic and gas-responsive segments, these triblock copolymers can self-assemble in aqueous solution and undergo the morphological transition from nanotubes to vesicles under gas stimulation; meanwhile, in the cycles of CO2 /O2 stimulation, these vesicles can further realize the volume expansion and contraction, eventually rupture. The gas-driven morphological transformations of these aggregates successfully imitate the formation, respiration, and apoptosis of alveoli, and provide an essential basis for revealing the life phenomena.

Multidimensional Information Encryption and Storage: When the Input Is Light.

The issue of information security is closely related to every aspect of daily life. For pursuing a higher level of security, much effort has been continuously invested in the development of information security technologies based on encryption and storage. Current approaches using single-dimension information can be easily cracked and imitated due to the lack of sufficient security. Multidimensional information encryption and storage are an effective way to increase the security level and can protect it from counterfeiting and illegal decryption. Since light has rich dimensions (wavelength, duration, phase, polarization, depth, and power) and synergy between different dimensions, light as the input is one of the promising candidates for improving the level of information security. In this review, based on six different dimensional features of the input light, we mainly summarize the implementation methods of multidimensional information encryption and storage including material preparation and response mechanisms. In addition, the challenges and future prospects of these information security systems are discussed.

Multifunctional Organic Fluorescent Probe with Aggregation-Induced Emission Characteristics: Ultrafast Tumor Monitoring, Two-Photon Imaging, and Image-Guide Photodynamic Therapy.

The development of multifunctional photosensitizers (PSs) with aggregation-induced emission (AIE) properties plays a critical role in promoting the progress of the photodynamic therapy (PDT). In this work, a multifunctional PS (named DSABBT NPs) with AIE activity has been designed and prepared to carry out ultrafast staining, excellent two-photon bioimaging, and high-efficiency image-guided PDT. Simply, DSABBT with AIE characteristic was synthesized by one-step Schiff reaction of 4-(diethylamino)-salicylaldehyde (DSA) and 4,7-bis(4-aminophenyl)-2,1,3-benzothiadiazole (BBT). Then, DSABBT and DSPE-PEG2000-cRGD generate nanoparticles (NPs) easily in an ultrapure water/tetrahydrofuran mixture through a facile nanoprecipitation at room temperature. We found that DSABBT NPs exhibit bright solid-state fluorescence with large stokes shifts (180 nm) and two-photon absorption cross-section (1700 GM). Importantly, DSABBT NPs exhibited excellent ability of ultrafast staining and two-photon imaging, which can readily label suborganelles by subtly shaking the living cells for 5 s under mild conditions. Moreover, DSABBT NPs displayed high singlet oxygen (1O2) generation capacity and remarkable image-guided PDT efficiency. Therefore, DSABBT NPs can act as the promising candidate for multifunctional PSs, which can destroy cancer cells and block malignant tumor growth via the production of reactive oxygen species upon irradiation conditions. These outcomes provide us with a selectable strategy for developing multifunctional theranostic systems.

Organelle-Specific Photoactivation of DNA Nanosensors for Precise Profiling of Subcellular Enzymatic Activity.

Understanding of the functions of enzymes in diverse cellular processes is important, but the design of sensors with controllable localization for in situ imaging of subcellular levels of enzymatic activity is particularly challenging. We introduce herein a spatiotemporally controlled sensor technology that permits in situ localization and photoactivated imaging of human apurinic/apyrimidinic endonuclease 1 (APE1) within an intracellular organelle of choice (e.g., mitochondria or nucleus). The hybrid sensor platform is constructed by photoactivatable engineering of a DNA-based fluorescent probe and further combination with an upconversion nanoparticle and a specific organelle localization signal. Controlled localization and NIR-light-mediated photoactivation of the sensor "on demand" effectively constrains the imaging signal to the organelle of interest, with improved subcellular resolution. We further demonstrate the application of the nanosensors for the imaging of subcellular APE1 translocation in response to oxidative stress in live cells.

Intrinsic hydroquinone-functionalized aggregation-induced emission core shows redox and pH sensitivity.

Aggregation-induced emission (AIE) fluorophores exhibit strong fluorescence in an aggregated state but emit no or weak fluorescence in dilute solutions. This emerging class of AIE optical materials comprise a variety of functionalities. Here an AIE luminescence core, 1-hydroquinol-1,2,2-triphenylethene (HQTPE), has been designed and synthesized. This AIE core is simple but is fundamentally important to chemistry because of its intrinsic redox and pH activities. The incorporation of hydroquinone (HQ) moiety into a common AIE core tetraphenylethene (TPE) yields HQTPE with unique fluorescent properties like nonlinear self-quenching over most other AIE-active fluorophores (AIEgens) so far reported. There are differences of photochemical properties between HQTPE, 1-benzoquinol-1,2,2-triphenylethene (QTPE, the oxidized counterpart) and its anions. Interestingly, as the solution concentration is increased, AIEgen HQTPE shows stronger fluorescence but QTPE exhibits rapid quenching of fluorescence in a nonlinear fashion, which are in agreement with theoretical studies. The fluorescence of HQTPE is also highly dependent on the pH value of media. We have further explored HQTPE as an ultrasensitive redox probe and efficient deoxidizer, which could lead to potential applications in health care, food security, environmental monitoring, optic and electronic devices.

An Adaptable Cryptosystem Enabled by Synergies of Luminogens with Aggregation-Induced-Emission Character.

The strong emission in the solid state and the feasibility of introducing stimuli responsiveness make aggregation-induced-emission luminogens promising for optical information encryption. Yet, the vast majority of previous reports rely on subtle changes in the molecular conformation or intermolecular interactions, limiting the robustness, multiplicity, capacity, and security of the resulting cryptosystems. Herein, a versatile cryptographic system is presented based on three interconnected and orthogonal covalent transformations concerning a tetraphenylethylene-maleimide conjugate. The cryptosystem is adapted into four configurations with different functionalities by organizing the reactions and molecules in different ways. These variants either balance the accessibility and security of the encrypted information or improve the security and density in data encryption. Significantly, they allow variable decryption from a single encryption and reconstruction of the chemical nature hidden in the fluorescent pattern can only be accessed through given algorithms. These results highlight the importance of multi-component synergies in advancing information encryption systems, which is enabled by the robustness and diversity stemming from the covalent nature of these transformations.