Light-Responsive Shape- and Color-Changing Block Copolymer Particles with Fast Switching Speed.

Polymer particles capable of dynamic shape changes in response to light have received substantial attention in the development of intelligent multifunctional materials. In this study, we develop a light-responsive block copolymer (BCP) particle system that exhibits fast and reversible shape and color transitions. The key molecular design is the integration of spiropyran photoacid (SPPA) molecules into the BCP particle system, which enables fast and dynamic transformations of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) particles in response to light. The SPPA photoisomerization, induced by 420 nm light irradiation, lowers the pH of the aqueous surroundings from 5.5 to 3.3. The protonated P4VP block substantially increases in domain size from 14 to 39 nm, resulting in significant elongation of the BCP particles (i.e., an increase in the aspect ratio (AR) of the particles from 1.8 to 3.4). Moreover, SPPA adsorbed onto the P4VP surface induces significant changes in the luminescent properties of the BCP particles via photoisomerization of SPPA. Notably, the BCP particles undergo fast, dynamic shape and color transitions within a period of 10 min, maintaining high reversibility over multiple light exposures. Functional dyes are selectively incorporated into different domains of the light-responsive BCP particles to achieve different ranges of color responses. Thus, this study showcases a light-responsive hydrogel display capable of reversible and multicolor photopatterning.

Rutaecarpine ameliorates imiquimod-induced psoriasis-like dermatitis in mice associated with alterations in the gut microbiota.

Psoriasis is accepted as a chronic, inflammatory, immune-mediated skin disease triggered by complex environmental and genetic factors. For a long time, disease recurrence, drug rejection, and high treatment costs have remained enormous challenges and burdens to patients and clinicians. Natural products with effective immunomodulatory and anti-inflammatory activities from medicinal plants have the potential to combat psoriasis and complications. Herein, an imiquimod (IMQ)-induced psoriasis-like dermatitis model is established in mice. The model mice are treated with 1% rutaecarpine (RUT) (external use) or the oral administration of RUT at different concentrations. Furthermore, high-throughput 16S rRNA gene sequencing is applied to analyze the changes in the diversity and composition of the gut microbiota. Based on the observation of mouse dorsal skin changes, RUT can protect against inflammation to improve psoriasis-like skin damage in mice. Additionally, RUT could suppress the expression levels of proinflammatory cytokines (IL-23, IL-17A, IL-22, IL-6, and IFN-α) within skin tissue samples. Concerning gut microbiota, we find obvious variations within the composition of gut microflora between IMQ-induced psoriasis mice and RUT-treated psoriasis mice. RUT effectively mediates the recovery of gut microbiota in mice induced by IMQ application. Psoriasis is linked to the production of several inflammatory cytokines and gut microbiome alterations. This research shows that RUT might restore gut microbiota homeostasis, reduce inflammatory cytokine production, and ameliorate psoriasis symptoms. In conclusion, the gut microbiota might be a therapeutic target or biomarker for psoriasis that aids in clinical diagnosis and therapy.

Nanosheet Particles with Defect-Free Block Copolymer Structures Driven by Emulsions Containing Crystallizable Surfactants.

Highly anisotropic-shaped particles with well-ordered internal nanostructures have received significant attention due to their unique shape-dependent photonic, rheological, and electronic properties and packing structures. In this work, nanosheet particles with cylindrical block copolymer (BCP) arrays are achieved by utilizing collapsed emulsions as a scaffold for BCP self-assembly. Highly elongated structures with large surface areas are formed by employing crystallizable surfactants that significantly reduce the interfacial tension of BCP emulsions. Subsequently, the stabilized elongated emulsion structures lead to the formation of BCP nanosheets. Specifically, when polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and 1-octadecanol (C18-OH) are co-assembled within an emulsion, C18-OH penetrates the surfactant layer at the emulsion interface, lowering the interfacial tension (i.e., below 1 mN m-1 ) and causing emulsion deformation. In addition, C18-OH crystallization allows for kinetic arrest of the collapsed emulsion shape during solvent evaporation. Consequently, PS-b-PDMS BCPs self-assemble into defect-free structures within nanosheet particles, exhibiting an exceptionally high aspect ratio of over 50. The particle formation mechanism is further investigated by controlling the alkyl chain length of the fatty alcohol. Finally, the coating behavior of nanosheet particles is investigated, revealing that the deposition pattern on a substrate is strongly influenced by the particle's shape anisotropy, thus highlighting their potential for advanced coating applications.

Poly(dimethylsiloxane)-block-PM6 Polymer Donors for High-Performance and Mechanically Robust Polymer Solar Cells.

High power conversion efficiency (PCE) and stretchability are the dual requirements for the wearable application of polymer solar cells (PSCs). However, most efficient photoactive films are mechanically brittle. In this work, highly efficient (PCE = 18%) and mechanically robust (crack-onset strain (COS) = 18%) PSCs are acheived by designing block copolymer (BCP) donors, PM6-b-PDMSx (x = 5k, 12k, and 19k). In these BCP donors, stretchable poly(dimethylsiloxane) (PDMS) blocks are covalently linked with the PM6 blocks to effectively increase the stretchability. The stretchability of the BCP donors increases with a longer PDMS block, and PM6-b-PDMS19k :L8-BO PSC exhibits a high PCE (18%) and 9-times higher COS value (18%) compared to that (COS = 2%) of the PM6:L8-BO-based PSC. However, the PM6:L8-BO:PDMS12k ternary blend shows inferior PCE (5%) and COS (1%) due to the macrophase separation between PDMS and active components. In the intrinsically stretchable PSC, the PM6-b-PDMS19k :L8-BO blend exhibits significantly greater mechanical stability PCE80% ((80% of the initial PCE) at 36% strain) than those of the PM6:L8-BO blend (PCE80% at 12% strain) and the PM6:L8-BO:PDMS ternary blend (PCE80% at 4% strain). This study suggests an effective design strategy of BCP PD to achieve stretchable and efficient PSCs.

Polymer Acceptors with Flexible Spacers Afford Efficient and Mechanically Robust All-Polymer Solar Cells.

High efficiency and mechanical robustness are both crucial for the practical applications of all-polymer solar cells (all-PSCs) in stretchable and wearable electronics. In this regard, a series of new polymer acceptors (PA s) is reported by incorporating a flexible conjugation-break spacer (FCBS) to achieve highly efficient and mechanically robust all-PSCs. Incorporation of FCBS affords the effective modulation of the crystallinity and pre-aggregation of the PA s, and achieves the optimal blend morphology with polymer donor (PD ), increasing both the photovoltaic and mechanical properties of all-PSCs. In particular, an all-PSC based on PYTS-0.3 PA incorporated with 30% FCBS and PBDB-T PD demonstrates a high power conversion efficiency (PCE) of 14.68% and excellent mechanical stretchability with a crack onset strain (COS) of 21.64% and toughness of 3.86 MJ m-3 , which is significantly superior to those of devices with the PA without the FCBS (PYTS-0.0, PCE = 13.01%, and toughness = 2.70 MJ m-3 ). To date, this COS is the highest value reported for PSCs with PCEs of over 8% without any insulating additives. These results reveal that the introduction of FCBS into the conjugated backbone is a highly feasible strategy to simultaneously improve the PCE and stretchability of PSCs.

Structure-Controlled Preparation of Multicompartment Micelles with Tunable Emission through Hydrodynamics-Dependent Self-Assembly in Microfluidic Chips.

Multicompartment micelles (MCMs) attracted much attention since they have subdivided domains that could be employed to encapsulate and transport diverse compounds simultaneously. Usually, preparation of MCMs relied on precise synthesis of block copolymers (BCPs) and elegant control of assembly kinetics, making it difficult to successively produce MCMs. Herein, we report a facile yet effective method for preparing MCMs by adjusting the hydrodynamics in microfluidic channels. It was found that well-defined MCMs were formed through hydrodynamics-dependent secondary assembly in microfluidic chips. By adjusting the flow diffusion process by varying the flow rate ratio and total flow rate, both the internal structure and size of MCMs could be effectively changed. A product diagram of micellar morphologies associated to the initial polymer concentration and flow rate ratio of water/BCPs solution was constructed. More interestingly, quantum dots (QDs) could be selectively loaded into different domains of the MCMs. Consequently, the Förster resonance energy transfer among QDs could be effectively suppressed. Thus, the emission spectrum of MCMs/QDs hybrid particles could be easily tuned by changing the ratio of QDs, showing great potential application in photonics and sensors.

Research of fatal car-to-pedestrian precrash scenarios for the testing of the active safety system in China.

Road safety remains a challenge with numerous Vulnerable Road Users (VRUs) suffering from injuries and death every year. Pedestrian protection using active safety systems, such as Automated Emergency Braking (AEB), is an effective measure to combat the situation. Furthermore, the perception of precrash scenarios plays an important role in active safety research. It is essential to understand and define precrash scenarios. This study aimed to apply the obtained typical car-to-pedestrian precrash scenarios from Chinese severely injured pedestrian traffic accidents to develop and test active safety systems. The National Automobile Accident In-Depth Investigation System (NAIS) recorded 467 cases from 2011 to 2018 in China, and 12 items were selected from the NAIS database as description variables for the precrash scenario. The items were divided into four categories: car, pedestrian, road, and environment. Group decision theory was applied to evaluate the importance of each variable in its category. A total of 34 basic scenarios were defined and obtained according to the extracted significant variables. These basic scenarios represented diverse fatal scenarios in China which are crucial for autonomous driving. The frequency distribution of the scenarios demonstrated that the top five scenarios covered 85.3 % of the total. Five scenarios were identified to have the common characteristic of cars going straight. Additionally, 13 detailed scenarios were obtained from the five basic scenarios by using cluster and frequency analyses. In contrast to the New Car Assessment Program (NCAP) test scenarios, weather and lighting conditions were considered in these 13 scenarios, and the driving speed before the crash were mostly distributed in the range of 40-80 km/h (20-60 km/h in the NCAP). Meanwhile, both walking and running were commonly recorded for pedestrians to cross the street from the nearside, compared with records of walking only to cross from the nearside in the NCAP. These results contribute to a reference for test scenarios of pedestrian AEB or Forward Collision Warning (FCW) in China.

Solvent Quality-Mediated Regioselective Modification of Gold Nanorods with Thiol-Terminated Polymers.

Modification of nanorods (NRs) with functional polymer ligands is of great significance to enhance their surface chemistry and prompt their applications in many fields (e.g., photothermal therapy, bioimaging, and catalysis). However, the regioselective modification of AuNRs still remains a great challenge. Herein, we introduce a facile yet versatile strategy to achieve the regioselective modification of AuNRs through a solvent quality-mediated strategy. By employing a poor solvent of the original ligand cetyltrimethylammonium bromide (CTAB) as the medium in the modification, polymer ligands would selectively graft onto the two ends of AuNRs, while polymer ligands would graft onto the entire surface when employing a good solvent. This strategy demonstrates good reproducibility and is applicable to both hydrophilic and hydrophobic polymer ligand modifications. Moreover, by combing our strategy with the preoccupation route, the two ends and sidewall of AuNRs modified by two different polymers form an "ABA"-type building block, which can further self-assemble into well-ordered superstructures. Our finding provides a new opportunity for multifunctionalization of NRs.

Kinetic Control of Length and Morphology of Segmented Polymeric Nanofibers in Microfluidic Chips.

In this work, we report an approach to prepare segmented polymer nanofibers (SPNFs) composed of rodlike subunits by kinetically controlled self-assembly of polystyrene-b-poly(4-vinylpyridine)-based supramolecules in microfluidic chips. The length and morphology of the SPNFs could be effectively adjusted by changing the total flow rate (Vtotal) and the molar ratio (x) of 4-vinylpyridine (4VP) unit to a hydrogen-bonding molecule, 3-n-pentadecyphenol. Moreover, the subunits of SPNFs could transform from short rods to spheres when the interfacial tension between PS core and solvent increased. On the contrary, the SPNFs elongated along the major axis when the interfacial tension decreased. This work not only offers mechanism insights into the hierarchical self-assembly of block copolymer-based supramolecules but also provides a versatile and effective method for kinetically controlling the hierarchical structures of assemblies.

Flow-Induced Micellar Morphological Transformation in Microfluidic Chips under Nonequilibrium State: From Aggregates to Spherical Micelles.

Self-assembly of block copolymers (BCPs) in microfluidic chips is a versatile yet effective route to produce micellar aggregates with various controllable sizes and morphologies. In this study, the morphological transformation of the BCP of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) assemblies from irregular aggregates to multicompartment micelles and ultimately to ordered spherical micelles is demonstrated in microfluidic chips. Our experimental and computational simulation results indicate that the transverse diffusion of solvents plays an important role in the morphological transformation of PS-b-P4VP assemblies in the confined flow condition. We find that the mixing time (tmix) between a BCP/tetrahydrofuran (THF) solution and water affects the morphological transformation. Micellar morphologies are intended to transform from aggregates to ordered spherical structures under a relatively long mixing time (tmix). In addition, it is observed that the size of the micelles decreases with the increase of the flow velocity ratio by tuning the hydrodynamic conditions of the flows. Moreover, by adjusting the initial polymer solution concentration, temperature, and weight fraction of the introduced homopolystyrene (hPS), which can affect the viscosity of the BCP solution, the flow diffusion in the microfluidic chip and the resulted micellar structures can also be readily adjusted. The current study provides a new flow-driven method to adjust the micellar ordered structural transformation under the nonequilibrium state.

Polyethylenimine Hybrid Thin-Shell Hollow Mesoporous Silica Nanoparticles as Vaccine Self-Adjuvants for Cancer Immunotherapy.

Conventional adjuvants (e.g., aluminum) are insufficient to trigger cell-mediated immunity, which plays a crucial role in triggering specific immunity against cancer. Therefore, developing appropriate adjuvants for cancer vaccines is a central way to stimulate the antitumor immune response. Hollow mesoporous silica nanoparticles (HMSNs) have been proven to stimulate Th1 antitumor immunity in vivo and promote immunological memory in the formulation of novel cancer vaccines. Yet, immune response rates of existing HMSNs for anticancer immunity still remain low. Here, we demonstrate the generation of polyethylenimine (PEI)-incorporated thin-shell HMSNs (THMSNs) through a facile PEI etching strategy for cancer immunotherapy. Interestingly, incorporation of PEI and thin-shell hollow structures of THMSNs not only improved the antigen-loading efficacy and sustained drug release profiles but also enhanced the phagocytosis efficiency by dendritic cells (DCs), enabled DC maturation and Th1 immunity, and sustained immunological memory, resulting in the enhancement of the adjuvant effect of THMSNs. Moreover, THMSNs vaccines without significant side effects can significantly reduce the potentiality of tumor growth and metastasis in tumor challenge and rechallenge models, respectively. THMSNs are considered to be promising vehicles and excellent adjuvants for the formulation of cancer vaccines for immunotherapy.

Biodegradable Polymer Microparticles with Tunable Shapes and Surface Textures for Enhancement of Dendritic Cell Maturation.

In this report, we present a facile approach to produce biodegradable polymeric microparticles with uniform sizes and controllable morphologies by blending hydrophobic poly(d, l-lactic-co-glycolide) (PLGA) and amphiphilic poly(d, l-lactic acid)-b-poly(ethylene glycol) (PLA-b-PEG) in a microfluidic chip. Microparticles with tentacular, hollow hemispherical, and Janus structures were obtained after complete evaporation of the organic solvent by manipulating the interfacial behavior of emulsion droplets and the phase separation behavior inside the droplets. The number and length of the tentacles on the surface of tentacular microparticles could be tailored by varying the initial concentration and blending ratios of the polymers. The organic solvent played an important role in controlling the morphologies of microparticles. For example, blending PLA16k-b-PEG5k with PLGA100k in dichloromethane resulted in tentacular microparticles, whereas hollow hemispherical microparticles were obtained in trichloromethane. Moreover, these microparticles with controllable shapes and surface textures have significant influence on the immune response of dendritic cells (DCs), showing a morphology-dependent enhancement of DC maturation.

Shape-Anisotropic Diblock Copolymer Particles with Varied Internal Structures.

Anisotropic polymer particles have promising applications in various fields, whereas their preparation usually suffers from tedious procedures. Here, we introduce a facile strategy to fabricate novel shape-anisotropic particles with varied internal structures via self-assembly of block copolymers (BCPs), with perfluorooctane (PFO) as the liquid template in emulsion droplets. By increasing the volume ratio of PFO to polystyrene- block-poly(4-vinylpyridine) (PS- b-P4VP) or decreasing the initial concentration of the BCPs, the self-assembled polymer particles change from spherical core-shell structures to anisotropic particles. Moreover, the anisotropic shape and internal structure of the polymer particles, including cone-like particles with alternative PS and P4VP lamellas, crescent-shaped particles with cylindrical P4VP domains, and plate-like particles with spherical P4VP domains, can be obtained by changing the block ratio or molecular weight or by adding a hydrogen-bonding agent. Based on the in situ optical microscopy investigation of the morphology evolution of the emulsion droplet, we conclude that both kinetic and thermodynamic factors during emulsion evolution determine the formation of shape-anisotropic polymeric particles with controllable internal structures.

Kinetically Controlled Self-Assembly of Block Copolymers into Segmented Wormlike Micelles in Microfluidic Chips.

Kinetically controlled self-assembly of block copolymers (BCPs) in solution is an efficient route to fabricate complex hierarchical colloids which are of great importance for nanoencapsulation, microreactors, and biomimics. Herein, segmented wormlike micelles (SWMs) with controllable size are generated by the self-assembly of polystyrene- block-poly(4-vinyl pyridine) in microfluidic channel. Different from the assembly of BCPs off-chip at the same solution properties, it is found that the fabricated SWMs are kinetically controlled assemblies with thermodynamic metastable structures, which are formed by the orderly aggregation of preformed spherical micelles because of the fast mixing process in microfluidic channels. Moreover, by manipulating the total flow velocity of water and BCPs solution or their flow velocity ratio, both of the percentages of SWMs among the whole assemblies and their sizes can be effectively tuned. On the basis of electron microscopy and dynamic light scatting investigations, a product diagram of micellar morphologies associated to initial polymer concentration and flow velocity ratio of water/BCPs solution was constructed, which is important for the rational design and fabrication of complex hierarchical BCP colloids.

The 6-item Kessler psychological distress scale to survey serious mental illness among Chinese undergraduates: Psychometric properties and prevalence estimate.

OBJECTIVE: To evaluate the psychometric properties of the 6-item Kessler psychological distress scale (K6) in screening for serious mental illness (SMI) among undergraduates in a major comprehensive university in China. METHOD: The K6 was self-completed by 8289 randomly sampled participants. A group of them (n=222) were re-assessed using K6 and interviewed using the Chinese version of Composite International Diagnostic Interview 3.1 (CIDI-3.1). RESULTS: The test-retest reliability of the K6 scale was 0.79, the Cronbach's alpha was 0.84, and its area under the receiver operating curve (AUC) for diagnosing CIDI-3.1 SMI was 0.85 (95% CI=0.80-0.90). For the optimal cut-off of K6 (12/13), the sensitivity (SEN), specificity (SPE), positive predictive value (PPV), negative predictive value (NPV), and classification accuracy (AC) were 0.83, 0.79, 0.60, 0.93, and 0.80, respectively. The 12-month prevalence of SMI was estimated as 3.97% using this optimal cut-off. Binary logistic regression analysis (including gender, ethnicity, grade, number of siblings and family residency location) showed that only family residency location in rural areas compared to urban areas was significantly associated with more SMI. CONCLUSIONS: This study documented the value of using the K6 for detecting SMI in Chinese undergraduate populations and supported its cross-cultural reliability and validity.