Synthesis of Copolymers by Living Carbanionic Alternating Copolymerization.

The synthesis and characterization of copolymers from styrene and 1,3-pentadiene (two isomers) are reported. Styrene/1,3-pentadiene (1:1) copolymerization with carbanion initiator yield living, well-defined, alternating (r1 = 0.037, r2 = 0.056), and highly stereoregular copolymers with 90%-100% trans-1,4 units, designed Mn s and low ÐM s (1.07-1.17). The first-order kinetic resolution and NMR spectra demonstrate that the copolymers obtained possess strictly alternating structure containing both 1,4- and 4,1-enchaiments. Also a series of copolymers with varying degrees of alternation are synthesized from para-alkyl substituted styrene derivatives and 1,3-pentadiene. The degree of alternation is strongly dependent on the polarity of solvent, reaction temperature, type of trans-cis isomer of 1,3-pentadiene and para-substituted group in styrene. The macro zwitterion forms (SPC) through the distribution of electronic charges from the donor (1,3-pentadiene) to the acceptor (styrenes) are proposed to interpret the carbanion alternating copolymerization mechanism. Owing to the versatility of the carbanion-initiating reaction, the present alternating strategy based on 1,3-pentadiene (especially cis isomer) can serve as a powerful tool for precise control of polymer chain microstructure, architecture, and functionalities in one-pot polymerization.

Fabrication of a Micro-Needle Array Electrode by Thermal Drawing for Bio-Signals Monitoring.

A novel micro-needle array electrode (MAE) fabricated by thermal drawing and coated with Ti/Au film was proposed for bio-signals monitoring. A simple and effective setup was employed to form glassy-state poly (lactic-co-glycolic acid) (PLGA) into a micro-needle array (MA) by the thermal drawing method. The MA was composed of 6 × 6 micro-needles with an average height of about 500 µm. Electrode-skin interface impedance (EII) was recorded as the insertion force was applied on the MAE. The insertion process of the MAE was also simulated by the finite element method. Results showed that MAE could insert into skin with a relatively low compression force and maintain stable contact impedance between the MAE and skin. Bio-signals, including electromyography (EMG), electrocardiography (ECG), and electroencephalograph (EEG) were also collected. Test results showed that the MAE could record EMG, ECG, and EEG signals with good fidelity in shape and amplitude in comparison with the commercial Ag/AgCl electrodes, which proves that MAE is an alternative electrode for bio-signals monitoring.

Tat/HA2 Peptides Conjugated AuNR@pNIPAAm as a Photosensitizer Carrier for Near Infrared Triggered Photodynamic Therapy.

To achieve an efficiency of intracellular photosensitizers (PSs) delivery and efficacy of photodynamic therapy, we have developed a novel class of PS formulation for encapsulating sulfonated aluminum phthalocyanine (AlPcS4) by taking advantage of the membrane-disruptive peptides Tat/HA2 and the photothermally triggered delivery system using AuNR@pNIPAAm. The coordinated effects of cell penetrating peptide Tat and fusogenic peptide HA2 could enhance the efficient cellular internalization and endo/lysosome escape of PSs delivery systems. Singlet oxygen generation was inhibited due to the reaction between loaded AlPcS4 and Au nanorods, which indicated that the AlPcS4-loaded, AuNR@pNIPAAm delivery system might be nonphototoxic in the circulatory system. However, this PSs-loaded nanosystem became highly phototoxic as it underwent the near-infrared irradiation by using the combined lights of 808 and 680 nm. Upon irradiation, the Tat/HA2 conjugated AuNR@pNIPAAm-Pc elicited an active photodynamic response against the cancer cells, leading to effective cells killing via mitochondria-associated apoptotic pathway. This study also demonstrated improved PDT therapeutic efficacy after intravenous administration of Tat/HA2-AuNR@pNIPAAm-Pc and the subsequent lights irradiations in tumor-bearing mice. We describe here a strategy for enhanced photodynamic eradication of solid tumors by endo/lysosomal escape and highlight the great promise of peptide-based nanocarriers used for cancer therapy.

Generalized Multifunctional Coating Strategies Based on Polyphenol-Amine-Inspired Chemistry and Layer-by-Layer Deposition for Blood Contact Catheters.

Blood-contacting catheters play a pivotal role in contemporary medical treatments, particularly in the management of cardiovascular diseases. However, these catheters exhibit inappropriate wettability and lack antimicrobial characteristics, which often lead to catheter-related infections and thrombosis. Therefore, there is an urgent need for blood contact catheters with antimicrobial and anticoagulant properties. In this study, we employed tannic acid (TA) and 3-aminopropyltriethoxysilane (APTES) to create a stable hydrophilic coating under mild conditions. Heparin (Hep) and poly(lysine) (PL) were then modified on the TA-APTES coating surface using the layer-by-layer (LBL) technique to create a superhydrophilic TA/APTES/(LBL)4 coating on silicone rubber (SR) catheters. Leveraging the superhydrophilic nature of this coating, it can be effectively applied to blood-contacting catheters to impart antibacterial, antiprotein adsorption, and anticoagulant properties. Due to Hep's anticoagulant attributes, the activated partial thromboplastin time and thrombin time tests conducted on SR/TA-APTES/(LBL)4 catheters revealed remarkable extensions of 276 and 103%, respectively, when compared to uncoated commercial SR catheters. Furthermore, the synergistic interaction between PL and TA serves to enhance the resistance of SR/TA-APTES/(LBL)4 catheters against bacterial adherence, reducing it by up to 99.9% compared to uncoated commercial SR catheters. Remarkably, the SR/TA-APTES/(LBL)4 catheter exhibits good biocompatibility with human umbilical vein endothelial cells in culture, positioning it as a promising solution to address the current challenges associated with blood-contact catheters.

The effects of Micro/Nano-plastics exposure on plants and their toxic mechanisms: A review from multi-omics perspectives.

In recent years, plastic pollution has become a global environmental problem, posing a potential threat to agricultural ecosystems and human health, and may further exacerbate global food security problems. Studies have revealed that exposure to micro/nano-plastics (MPs/NPs) might cause various aspects of physiological toxicities, including plant biomass reduction, intracellular oxidative stress burst, photosynthesis inhibition, water and nutrient absorption reduction, cellular and genotoxicity, seed germination retardation, and that the effects were closely related to MP/NP properties (type, particle size, functional groups), exposure concentration, exposure duration and plant characteristics (species, tissue, growth stage). Based on a brief review of the physiological toxicity of MPs/NPs to plant growth, this paper comprehensively reviews the potential molecular mechanism of MPs/NPs on plant growth from perspectives of multi-omics, including transcriptome, metabolome, proteome and microbiome, thus to reveal the role of MPs/NPs in plant transcriptional regulation, metabolic pathway reprogramming, protein translational and post-translational modification, as well as rhizosphere microbial remodeling at multiple levels. Meanwhile, this paper also provides prospects for future research, and clarifies the future research directions and the technologies adopted.

Broadband terahertz polarizers with ideal performance based on aligned carbon nanotube stacks.

We demonstrate a terahertz polarizer built with stacks of aligned single-walled carbon nanotubes (SWCNTs) exhibiting ideal broadband terahertz properties: 99.9% degree of polarization and extinction ratios of 10(-3) (or 30 dB) from ~0.4 to 2.2 THz. Compared to structurally tuned and fragile wire-grid systems, the performance in these polarizers is driven by the inherent anistropic absorption of SWCNTs that enables a physically robust structure. Supported by a scalable dry contact-transfer approach, these SWCNT-based polarizers are ideal for emerging terahertz applications.

Polystyrene and low-density polyethylene pellets are less effective in arsenic adsorption than uncontaminated river sediment.

The adsorption process of inorganic arsenic (As) plays an important role in its mobility, bioavailability, and toxicity in the river environment. In this work, the adsorption of dissolved arsenite (As(III)) and arsenate (As(V)) by microplastics (MPs) pellets (polystyrene (PS) and low-density polyethylene (LDPE)), river sediment, and their mixture were investigated to assess the adsorption affinities and mechanism. The adsorption kinetics showed slow and mild rising zones from the natural behavior of the chemical adsorption. The results indicated that both MP characteristics and water properties played a significant role in the adsorption behavior of inorganic As species. The As adsorption equilibrium was modeled well by both Langmuir and Freundlich isotherms and partly fitted with the Sips model suggesting that both mono-layer and multi-layer adsorption occurred during adsorption The spontaneous adsorption process for both As(III) and As(V) was evidenced by the adsorption thermodynamics. The maximum adsorption capacities of As(III) and As(V) reached 143.3 mg/kg and 109.8 mg/kg on PS in deionized water, which were higher than those on sediment-PS mixture (119.3 mg/kg, 99.2 mg/kg), which were all lower than on sediment alone (263.3 mg/kg, 398.7 mg/kg). The Fourier transform infrared spectroscopy analysis identified that As(III) and As(V) interaction with sediment surface functional groups was the main adsorption mechanism from surface complexation and coordination. Two functional groups of polystyrene (-NH2, -OH) were mainly involved in the adsorption of inorganic As species on PS, while -COO- and -OH functional groups contributed to the adsorption mechanism of inorganic As species on LDPE. The findings provide valuable insight on the adsorption behavior and mechanisms of As(III) and As(V) in river systems in the presence of MPs particles. Both PS and LDPE were shown to be less effective than river sediment in the adsorption of As species from water, which provides a different perspective in understanding the scale of MPs impact in pollutant transport in the aquatic environment.

Poly(aspartic acid)-based self-healing hydrogel with precise antibacterial ability for rapid infected-wound repairing.

The development of wound dressings with antibacterial activities and simultaneous pro-healing functions are always urgent in treating bacterial wound infection. Herein, a novel multifunctional self-healing hydrogel was designed and prepared by crosslinking quaternary ammonium/boronic acid modified poly(aspartic acid) and poly (vinyl alcohol) polymers with targeted peptide MP196- conjugated polydopamine. The formation of this hydrogel not only improves the biocompatibility of quaternary poly(aspartic acid), but also enhances antibacterial efficacy by pH-triggering dissociation under the low pH bacterial microenvironment. Moreover, precise photothermal treatment can be achieved. In vitro study suggested high synergistic antibacterial efficiency(∼100 %) under near-infrared light, significantly higher than a single antibacterial strategy (66.0-82.6 %). In vivo study suggested infected wounds treated with the hydrogel showed an optimal healing rate(92.0 %) after 7 days. The survival rate of the bacteria in the epidermal tissues was reduced to 2.3 %. Besides, the suitable self-healing property of this hydrogel facilitated its application in the diversity of wound shapes. Thus, the novel poly(aspartic acid) hydrogel might be a promising candidate for precise therapy of bacteria-infected wounds.

Photo-Fenton self-cleaning carbon fibers membrane supported with Zr-MOF@Fe2O3 for effective phosphate removal from algae-rich water.

Adsorbents featuring abundant binding sites and high affinity to phosphate have been used to resolve water eutrophication. However, most of the developed adsorbents were focused on improving the adsorption ability of phosphate but ignored the effect of biofouling on the adsorption process especially used in the eutrophic water body. Herein, a novel MOF-supported carbon fibers (CFs) membrane with high regeneration and antifouling capability, was prepared by in-situ synthesis of well-dispersed MOF on CFs membrane, to remove phosphate from algae-rich water. The hybrid UiO-66-(OH)2@Fe2O3@CFs membrane exhibits a maximum adsorption capacity of 333.3 mg g-1 (pH 7.0) and excellent selectivity for phosphate sorption over coexisting ions. Moreover, the Fe2O3 nanoparticles anchored on the surface of UiO-66-(OH)2 through 'phenol-Fe(III)' reaction can endow the membrane with the robust photo-Fenton catalytic activity, which improves long-term reusability even under algae-rich condition. After 4 times photo-Fenton regenerations, the regeneration efficiency of the membrane could remain 92.2%, higher than that of hydraulic cleaning (52.6%). Moreover, the growth of C. pyrenoidosa was significantly reduced by 45.8% within 20 days via metabolism inhibition due to membrane-induced P-deficient conditions. Hence, the developed UiO-66-(OH)2@Fe2O3@CFs membrane holds significant prospects for large-scale application in phosphate sequestration of eutrophic water bodies.

Clinical Significance of Inflammatory Factors, Osteocalcin, and Matrix Metalloproteinase-8 in Gingival Crevicular Fluid in Drug Treatment of Severe Periodontitis.

Whether gingival crevicular fluid (GCF) indexes in patients with severe periodontitis affect the efficacy of drug treatment was a new direction of recent research. At present, there were few studies on the effects of inflammatory indicators, BGP, and MMP-8 levels in GCF on the efficacy of drug treatment in such patients. So the purpose of this study was to observe the changes in osteocalcin (BGP), matrix metalloproteinase-8 (MMP-8), and inflammatory indexes levels in GCF of patients with severe periodontitis. The correlation between the above indexes and the effect of drug treatment in the patients was analyzed, in order to provide guidance for improving the clinical curative effect of severe periodontitis. A retrospective analysis was conducted to collect the baseline data of patients with severe periodontitis who were treated with Minocycline Hydrochloride Ointment in our hospital. The inflammatory indicators, BGP, and MMP-8 levels in GCF were analyzed before drug treatment, and the treatment effect on the patients was counted. Logistic regression was used to analyze the correlation between BGP, MMP-8, and inflammatory indicators levels in GCF and the drug treatment effect on the patients. After statistical analysis, we found that the response rate was 69% and the inefficiency was 31%. There were no significant differences in C-reactive protein (CRP) and tumor necrosis factor-α (TNF-α) levels between the inefficacy group and efficacy group (P > 0.05). Compared with the efficacy group, the levels of interleukin-6 (IL-6), interleukin-1ß (IL-1ß), interleukin-8 (IL-8), BGP, and MMP-8 were increased in the inefficacy group. High levels of IL-6, IL-1ß, IL-8, BGP, and MMP-8 were associated with ineffective drug treatment in patients with severe periodontitis (all OR >1 and P < 0.05). Levels of IL-6, IL-1ß, IL-8, BGP, and MMP-8 predicted that the AUCs of drug treatment failure in patients with severe periodontitis were all greater than 0.7, which were 1.398, 1.458, 1.244, 1.012, and 1.012, respectively. From this, we can conclude that increased levels of BGP, MMP-8, and inflammatory indicators such as IL-6, IL-1ß, and IL-8 in GCF would increase the risk of ineffective drug treatment in patients with severe periodontitis. The clinical treatment plan could be adjusted according to the levels of the above indicators in GCF to improve the effectiveness of drug treatment in patients.

Impact of the surrounding environment on antibiotic resistance genes carried by microplastics in mangroves.

The pollution of antibiotic resistance genes (ARGs) carried by microplastics (MPs) is a growing concern. Mangroves are located at the intersection of land and sea and are seriously affected by MP pollution. However, few studies have systematic research evaluating the transmission risk of ARGs carried by MPs in mangroves. We conducted in situ experiments by burying five different MPs (polypropylene, high-density polyethylene, polystyrene, polyethylene glycol terephthalate, and polycaprolactone particles) in mangroves with different surrounding environments. A total of 10 genes in the MPs of mangroves were detected using quantitative real-time polymerase chain reactions, including eight ARGs and two mobile genetic elements (MGEs). The abundance of ARGs in Guanhai park mangroves in living areas (GH) was higher than that of Gaoqiao mangroves in protected areas (GQ) and Beiyue dike mangroves in aquaculture pond areas (BY). Pathogenic bacteria, such as Acinetobacter, Bacillus, and Vibrio were found on the MP surfaces of the mangroves. The number of ARGs carried by multiple drug-resistant bacteria in the GH mangroves was greater than that in the GQ and BY mangroves. Moreover, the ARGs carried by MPs in GH mangroves had the highest potential transmission risk by horizontal gene transfer. Sociometric and environmental factors were the main drivers shaping the distribution characteristics of ARGs and MGEs. Polypropylene and high-density polyethylene particles are preferred substrates for obtaining diffuse ARGs. This study investigated the drivers of ARGs in the MPs of mangroves and provided essential guidance on the use and handling of plastics.

Microplastics accumulation in mangroves increasing the resistance of its colonization Vibrio and Shewanella.

The enrichment of various pollutants in mangrove has attracted widespread attention. Especially, microplastics accumulation in mangrove may provide a more challenging ecological colonization site by enriching pollutants, thus affecting the change of microplastics antibiotic resistance and increasing the risk of antibiotic failure. Herein, the antibiotic-resistant of microplastics and sediment from mangrove were investigated. The results show that isolates are mainly colonized by Vibrio parahemolyticus (V. parahemolyticus), Vibrio alginolyticus (V. alginolyticus), and Shewanella. 100% mangrove microplastics isolates are resistant to chloramphenicol, cefazolin, and tetracycline, especially amoxicillin clavulanate and ampicillin. Meanwhile, the multiple antibiotics resistance (MAR) indexes of V. parahaemolyticus, Shewanella, and V. alginolyticus in mangrove microplastics are 0.72, 0.77, and 0.77, respectively, which are far higher than the MAR index standard (0.2) and that of mangrove sediment isolates. Furthermore, compared with V. parahaemolyticus isolated from the same mangrove microplastics, Shewanella and V. alginolyticus show stronger drug resistance. It should be noted that there is a closely related relationship between the type of microplastics and the antibiotics resistance of isolated bacteria. For the antibiotics sensitivity test of norfloxacin, streptomycin, amoxicillin, and chloramphenicol, V. parahaemolyticus have the lower antibiotics resistance than that of V. alginolyticus isolated from the same mangrove microplastics. However, Vibrio isolated from PE has stronger antibiotics resistance. Results reveal that mangrove may be one of the potential risks for emergence and spread of bacterial antibiotics-resistant and multidrug-resistant, and microplastic biofilms may act as promoters of bacterial antibiotic resistance.

Blocking IbmiR319a Impacts Plant Architecture and Reduces Drought Tolerance in Sweet Potato.

MicroRNA319 (miR319) plays a key role in plant growth, development, and multiple resistance by repressing the expression of targeted TEOSINTE BRANCHED/CYCLOIDEA/PCF (TCP) genes. Two members, IbmiR319a and IbmiR319c, were discovered in the miR319 gene family in sweet potato (Ipomoea batatas [L.] Lam). Here, we focused on the biological function and potential molecular mechanism of the response of IbmiR319a to drought stress in sweet potato. Blocking IbmiR319a in transgenic sweet potato (MIM319) resulted in a slim and tender phenotype and greater sensitivity to drought stress. Microscopic observations revealed that blocking IbmiR319a decreased the cell width and increased the stomatal distribution in the adaxial leaf epidermis, and also increased the intercellular space in the leaf and petiole. We also found that the lignin content was reduced, which led to increased brittleness in MIM319. Quantitative real-time PCR showed that the expression levels of key genes in the lignin biosynthesis pathway were much lower in the MIM319 lines than in the wild type. Ectopic expression of IbmiR319a-targeted genes IbTCP11 and IbTCP17 in Arabidopsis resulted in similar phenotypes to MIM319. We also showed that the expression of IbTCP11 and IbTCP17 was largely induced by drought stress. Transcriptome analysis indicated that cell growth-related pathways, such as plant hormonal signaling, were significantly downregulated with the blocking of IbmiR319a. Taken together, our findings suggest that IbmiR319a affects plant architecture by targeting IbTCP11/17 to control the response to drought stress in sweet potato.

Rapid Surface Display of mRNA Antigens by Bacteria-Derived Outer Membrane Vesicles for a Personalized Tumor Vaccine.

Therapeutic mRNA vaccination is an attractive approach to trigger antitumor immunity. However, the mRNA delivery technology for customized tumor vaccine is still limited. In this work, bacteria-derived outer membrane vesicles (OMVs) are employed as an mRNA delivery platform by genetically engineering with surface decoration of RNA binding protein, L7Ae, and lysosomal escape protein, listeriolysin O (OMV-LL). OMV-LL can rapidly adsorb box C/D sequence-labelled mRNA antigens through L7Ae binding (OMV-LL-mRNA) and deliver them into dendritic cells (DCs), following by the cross-presentation via listeriolysin O-mediated endosomal escape. OMV-LL-mRNA significantly inhibits melanoma progression and elicits 37.5% complete regression in a colon cancer model. OMV-LL-mRNA induces a long-term immune memory and protects the mice from tumor challenge after 60 days. In summary, this platform provides a delivery technology distinct from lipid nanoparticles (LNPs) for personalized mRNA tumor vaccination, and with a "Plug-and-Display" strategy that enables its versatile application in mRNA vaccines.

Separation of false-positive microplastics and analysis of microplastics via a two-phase system combined with confocal Raman spectroscopy.

In the field of microplastics research, more accurate standardised methods and analytical techniques still need to be explored. In this study, a new method for the microplastics quantitatively and qualitatively analysis by two-phase (ethyl acetate-water) system combined with confocal Raman spectroscopy was developed. Microplastics can be separated from false-positive microplastics in beach sand and marine sediment, attributing to the hydrophobic-lipophilic interaction (HLI) of the two-phase system. Results show that the recovery rates of complex environment microplastics (polypropylene (PP), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide 66 (PA 66), polycarbonate (PC) and polyethylene (PE)) are higher than 92.98%. Moreover, the new technique can also be used to detect hydrophobic and lipophilic antibiotics, such as sulfamethoxazole (SMX), erythromycin (EM), madimycin (MD), and josamycin (JOS), which adsorbed on microplastics and are extracted based on the dissolving-precipitating mechanism. This innovative research strategy provides a new scope for further detection of marine environment microplastics and toxic compounds adsorbed on its surface.

Surface Design for Antibacterial Materials: From Fundamentals to Advanced Strategies.

Healthcare-acquired infections as well as increasing antimicrobial resistance have become an urgent global challenge, thus smart alternative solutions are needed to tackle bacterial infections. Antibacterial materials in biomedical applications and hospital hygiene have attracted great interest, in particular, the emergence of surface design strategies offer an effective alternative to antibiotics, thereby preventing the possible development of bacterial resistance. In this review, recent progress on advanced surface modifications to prevent bacterial infections are addressed comprehensively, starting with the key factors against bacterial adhesion, followed by varying strategies that can inhibit biofilm formation effectively. Furthermore, "super antibacterial systems" through pre-treatment defense and targeted bactericidal system, are proposed with increasing evidence of clinical potential. Finally, the advantages and future challenges of surface strategies to resist healthcare-associated infections are discussed, with promising prospects of developing novel antimicrobial materials.

Chemotaxis-selective colonization of mangrove rhizosphere microbes on nine different microplastics.

Microplastics pollution poses a new threat to the environment of intertidal zone. The sea forest, mangrove, has been polluted by a large number of plastic debris worldwide. To fill the gaps in knowledge of mangrove rhizosphere microbes connected with the 'plasticsphere', a semi-controlled in situ exposure experiment for nine different types of microplastics were conducted in mangrove ecosystem. A sign of biodegrading was observed on polyethylene, polyamide 6 and polyvinyl chloride microplastics surface after 3 months exposure. We discovered that the metabolic activities of the dominant bacteria on certain microplastics were related to the specific groups on polymers molecule. The selective colonization may be driven by the chemotaxis of bacteria. Specially, microplastics biofilms of polyethylene, polyamide 6, polyvinyl chloride and expanded polystyrene possess distinctive dominant bacteria assemblages which have great significance in ecosystem processes involving carbon cycle or sulfur cycle. Community of mangrove soil microorganism and microplastic biofilm varies as the seasons changes. As a new niche, microplastics has higher inclusivity to bacteria than surrounding soil. Additionally, pathogens for human beings (Vibrio parahaemolyticus and Escherichia-Shigella) were detected both in microplastics and soil. We stress that the interaction between microplastics and rhizosphere microorganisms may affect the growth and health of mangrove plants. Besides, we point out that mangrove rhizosphere microorganism can be an ideal candidate for plastics-degradation.

Bionic intelligent soft actuators: high-strength gradient intelligent hydrogels with diverse controllable deformations and movements.

A series of novel nanofibrillated cellulose (NFC) reinforced gradient intelligent hydrogels with high response rate, multiple response patterns and diversified self-driven functions were successfully prepared. Based on the effect of the hydroxide radical of NFC on the addition reaction, and on the dehydration synthesis, the variation of NFC significantly regulated the gradient structure of the intelligent hydrogels. In addition to the infiltration property of graphene oxide (GO), reinforcement of NFC enhanced the crosslinking density and Young's modulus, which built a relationship between material characteristics and near infrared laser response rate. Intelligent hydrogel actuators realized bending deformation, curling deformation, switching movements and obstacle avoidance movements. The hydrogels with high Young's modulus exhibited relatively low self-driven rates and efficiency. The self-driven mechanisms of NFC reinforced gradient intelligent hydrogels were revealed effectively by constructing the mathematical relationship curvature variation, bending degree, deformation displacement, material characteristics and incentive intensity. The investigation showed a new path for the combination of mechanical property, intelligent property and functional property of intelligent hydrogels in a bionic soft robot and health engineering.

Biomimetic Nonuniform, Dual-Stimuli Self-Morphing Enabled by Gradient Four-Dimensional Printing.

Programmable nonuniform deformation is of great significance for self-shape-morphing systems that are commonly seen in biological systems and also has practical applications in drug delivery, biomedical devices and robotics, etc. Here, we present a novel gradient four-dimensional (4D) printing method toward biomimetic nonuniform, dual-stimuli self-morphing. By modeling and printing graded active materials with water swelling properties, we can configure continuously smooth gradients of volume fraction of the active material in bilayer structures. The variation of swelling ratio mismatch between the two layers can be delicately regulated, which results in the programmable nonuniform shape transformation. The shape-shifting results can be predicted by the established mathematical model and computational simulations. Furthermore, we demonstrate dual-stimuli self-morphing structures by printing the graded water-responsive elastomer materials onto a heat-shrinkable shape memory polymer, which could produce different shape changes in response to humidity and different temperatures. This method pioneers a versatile approach to broaden the design space for 4D printing and will be compatible with a wide range of active materials meeting various requirements in diverse potential applications.

A Porous Au@Rh Bimetallic Core-Shell Nanostructure as an H2 O2 -Driven Oxygenerator to Alleviate Tumor Hypoxia for Simultaneous Bimodal Imaging and Enhanced Photodynamic Therapy.

In treatment of hypoxic tumors, oxygen-dependent photodynamic therapy (PDT) is considerably limited. Herein, a new bimetallic and biphasic Rh-based core-shell nanosystem (Au@Rh-ICG-CM) is developed to address tumor hypoxia while achieving high PDT efficacy. Such porous Au@Rh core-shell nanostructures are expected to exhibit catalase-like activity to efficiently catalyze oxygen generation from endogenous hydrogen peroxide in tumors. Coating Au@Rh nanostructures with tumor cell membrane (CM) enables tumor targeting via homologous binding. As a result of the large pores of Rh shells and the trapping ability of CM, the photosensitizer indocyanine green (ICG) is successfully loaded and retained in the cavity of Au@Rh-CM. Au@Rh-ICG-CM shows good biocompatibility, high tumor accumulation, and superior fluorescence and photoacoustic imaging properties. Both in vitro and in vivo results demonstrate that Au@Rh-ICG-CM is able to effectively convert endogenous hydrogen peroxide into oxygen and then elevate the production of tumor-toxic singlet oxygen to significantly enhance PDT. As noted, the mild photothermal effect of Au@Rh-ICG-CM also improves PDT efficacy. By integrating the superiorities of hypoxia regulation function, tumor accumulation capacity, bimodal imaging, and moderate photothermal effect into a single nanosystem, Au@Rh-ICG-CM can readily serve as a promising nanoplatform for enhanced cancer PDT.