摘要:The chemotactic system of nanomotor is a new kind of nanomaterial that can move along the concentration gradient vector field of chemical substances. Its unique chemotactic movement performance is expected to bring new effects for the efficient and accurate delivery of drugs. However, due to the complex disease microenvironment within the body, constructing a nanomotor chemotactic system that can effectively target disease tissues remains a challenge. Combining the unique advantages of polymer nanomaterials, the author's team has made a series of innovative achievements in developing new strategies to build polymer nanomotor chemotatic systems and developing new methods to assemble them with therapeutic agents. Starting from the construction method of polymer nanomotor chemotactic system, this monograph focuses on the general construction strategy of a kind of polymer nanomotor that can move in the disease microenvironment in vivo, summarizes their assembly strategies with different therapeutic agents and their related mechanisms in the treatment of a variety of major diseases, and prospects the future development direction of this field.
关键词:Nanomotors;Chemotactic systems;Polymer nanomaterials;Treatment of major diseases
摘要:Dielectric elastomer actuators (DEAs), which can produce muscle-like contraction-diastolic deformation under external electrical stimulation, are known as artificial muscle. Due to the advantages of simple structure, fast response speed, large strain output, and high energy density, DEAs have been showing a broad application prospect in the field of soft robotics, prosthetic organs, and braille displays. However, DEAs are susceptible to electrical and mechanical damage during operation, largely limits their long-term and stable service life. Design and preparation of elastomer materials that can endure mechanical and electrical damage is the key to solve the above problem. In this paper, the working principles and material characteristics of DEAs are firstly outlined, then the corresponding optimization methods for improving their actuation performance are introduced. Afterwards, DEAs with various configurations and their working mechanism are issued, showcasing the development of DEAs in biomimetic robots. Next, recent advances in self-healing DEAs containing self-healing dielectric elastomers and self-healing flexible electrodes are summarized. By introducing reversible covalent bonds and noncovalent bonds into polymer chains is a common method to synthesized the self-healing dielectric elastomers. Besides, preparing self-clearing elastomers and adding liquid dielectrics into elastomer matrices can also endow DEAs with self-healing abilities. However, self-cleaning process of dielectric elastomers will lead to the gradual decline of the actuation performance in DEAs and the strict encapsulation is required to avoid liquid leakage in liquid dielectric filled-DEAs. By doping polymers with conductive components, self-clearing compliant electrodes can be obtained by isolating the defects after the device underwent electrical breakdown. However, the mechanical damages such as cracks and scratches on the self-clearing compliant electrodes can hardly be healed. Otherwise, the self-healing compliant electrode with reversible covalent bonds and noncovalent bonds can endure both electrical damage and mechanical damage. At last, the future challenges in DEAs are proposed for promoting their rapid development and application in soft robots.
摘要:Developing adhesive sensor devices for extreme environments necessitates properties like fast preparation, cost-effectiveness, robust environmental adhesion, stability, and superior sensing capabilities, which are in high demand. In this research, ionic liquids with diverse chemical bonds were employed as solvents for copolymerization with lipoic acid (LA) under mild conditions to produce lipoic acid-based ionic gels, leveraging the rapid ring-opening polymerization of LA during heating. The findings indicated that the prepared poly-lipoic acid ionic gels displayed outstanding adhesive strength (120 kPa), rapid self-healing abilities (ca. 10 s), exceptional resistance to extreme environmental conditions (-196 ℃), and remarkable sensing performance (331 ms). The developed poly-lipoic acid ionic gel is easy to prepare, exhibits enduring adhesion at ultra-low temperatures, and holds promise for adhesive sensing applications in extreme environments, introducing a novel design strategy for advancing next-generation adhesive materials.
摘要:To address the need for an integrated antibacterial and anti-inflammatory approach in treating bacterial infections, this study developed a novel triblock poly-β-amino ester (Dai-encapsulating poly-β-amino ester, D-PAE) incorporating daidzein into the polymer backbone. Daidzein is a bioactive compound with known antibacterial and anti-inflammatory properties. The D-PAE nanoparticles utilize a unique mechanism where the tertiary amine segments of the polymer undergo protonation in the acidic microenvironment of bacterial infection sites, resulting in a positive charge. This enhances the nanoparticles' interaction with the negatively charged bacterial membranes, facilitating targeted drug delivery. Additionally, bacterial lipases, which are overexpressed at infection sites, hydrolyze the ester bonds in the polymer backbone, triggering the controlled release of daidzein.Once released, daidzein exerts its antibacterial effects by inhibiting bacterial growth and biofilm formation, while also reducing inflammation by modulating the immune response. This dual action helps to address both the bacterial infection and the inflammatory damage associated with it. In vitro and in vivo studies demonstrated that D-PAE nanoparticles exhibit superior bioactivity and biocompatibility compared to the free drug. The nanoparticles are more efficient in delivering daidzein directly to the infection site, offering prolonged therapeutic effects with reduced toxicity to healthy tissues.This study offers an innovative approach to overcoming the limitations of conventional polymeric prodrugs. By incorporating daidzein into a polymeric matrix, D-PAE nanoparticles provide a more effective and targeted solution for bacterial infections, addressing both the bacterial presence and the associated inflammation. The results highlight the potential for this strategy to be expanded to other therapeutic applications, offering a valuable reference for future designs in drug delivery systems. These findings open new avenues for the development of advanced prodrug systems that combine multiple therapeutic actions for improved patient outcomes.
摘要:Colorectal cancer peritoneal metastases stand as a prevalent form of advanced-stage metastasis. Currently, cytoreductive surgery combined with hyperthermic intraperitoneal chemotherapy (CRS-HIPEC) is the sole clinically effective treatment available. Nevertheless, the efficacy and safety of HIPEC are severely hampered by its intense toxic side effects and the activation of heat shock protein 90 (HSP90) within tumor cells. To enhance the therapeutic efficiency and safety of CRS-HIPEC, this study ingeniously designed and developed a novel redox-responsive chitosan-based delivery system (CsB) for the delivery of the reactive oxygen species (ROS)-responsive prodrug gambogenic acid (GB). This nanoprodrug capitalizes on the elevated levels of glutathione (GSH) and ROS in the tumor microenvironment to achieve targeted drug release. Moreover, by incorporating β-lapachone, a substrate of NAD(P)H: quinone oxidoreductase-1 (NQO-1), the system substantially boosts intracellular ROS levels. As a result, it accelerates the conversion of GB into its active form, gambogenic acid (GA). GA exerts its therapeutic effects through multiple mechanisms. It inhibits HSP90 expression, promotes apoptosis, reduces drug resistance, and suppresses tumor angiogenesis. These combined actions comprehensively improve the efficacy and safety of intraperitoneal hyperthermic therapy. This study presents a novel strategy for the precision treatment of colorectal cancer peritoneal metastases and furnishes a solid theoretical and experimental foundation for future clinical applications.
关键词:Colorectal cancer peritoneal metastases;Hyperthermic intraperitoneal chemotherapy;Dual-responsive chitosan-based delivery system;Heat shock protein 90 inhibition;Synergistic anti-tumor therapy
摘要:Porous oil-containing polyimide (PI) is widely used in high-precision fields such as aerospace due to its excellent mechanical properties and wear resistance. However, the plastic slip behavior of molecular chains during operation severely impacts the service life of porous bearings. To address this challenge, this study proposes a novel strategy of pre-fluorination followed by re-sintering. In this study, polyimide particles within porous PI are crosslinked through direct fluorination, forming a certain degree of chemical covalent bonding. The influence of different fluorination degrees on the pore structure of PI sheets during sintering, as well as the friction behaviors of the final products, were investigated. Results demonstrated that the pre-fluorination-re-sintering strategy achieved covalent cross-linking on the surface of porous PI particles, effectively restricting the plastic slip of molecular chains and inhibiting the formation of large pores and non-uniform pore sizes caused by particle agglomeration. Consequently, the friction and wear behavior of porous oil-containing PIs were significantly improved. Compared to the untreated PI samples, the friction coefficients and wear-resistant properties of the pre-fluorinated-re-sintered samples could be further optimized. This study provides a new idea for addressing the problem of solid-phase agglomeration and pore size regulation in porous polyimide. It also offers a novel strategy for limiting the plastic slip behavior of PI molecular chains in the future studies.
关键词:Porous polyimide;friction and wear;direct fluorination;Crosslinking
摘要:In this study, the drying process of poly(vinyl alcohol) (PVA) aqueous solution under the coupled effects of wind field, temperature field, and concentration field was investigated using COMSOL software. A simplified multi-physics coupling model for flow, heat, and mass transfer was developed by integrating Fick's law, the free volume theory, and the Flory-Huggins theory. The mass transfer coefficient, initially calculated using boundary layer theory, was subsequently refined based on experimental data obtained from drying and weighing PVA aqueous solutions at varying air speeds (1.5-2.5 m/s). The findings reveal that the pressure at the interface between the film and the air undergoes minimal changes. This is attributed to the high Peclet number (Pe) calculated for hot air drying, indicating that the diffusion process of the PVA aqueous solution during the rapid drying phase is predominantly governed by convection. Furthermore, the modified mass transfer coefficient reaches its peak at an intermediate wind speed of 2.0 m/s, suggesting a nonmonotonic relationship between the mass transfer coefficient and wind speed. Through a combination of experimental methods and numerical simulations, this study elucidates the mechanism by which wind speed influences the drying rate of polymer solutions. The insights gained provide a valuable foundation for optimizing the operational conditions for the drying and film formation of PVA aqueous solutions in engineering applications.
摘要:Cycloaddition of carbon dioxide (CO2) and epoxides can boast 100% atomic economy, and it is considered an up-and-coming method for CO2 utilization. However, the need for harsh reaction conditions presents a significant challenge. This study addresses this issue by successfully preparing the cellulose-supported ionic liquid as a porous catalyst (PPCIL) via the reaction of allyl cellulose ether (AHP-cellulose) and vinyl imidazolium bromide ([VPIM]Br). The catalytic activity of PPCIL was thoroughly investigated. It was found that end epoxides with small-sized substituents such as epichlorohydrin, epibromohydrin, and propylene oxide, can be completely converted to corresponding carbonates over PPCIL at 80 ℃ and 0.1 MPa. When the temperature rose to 100 ℃, PPCIL also revealed good catalytic activity towards end epoxides with larger size such as allyl glycidyl ether and styrene oxide. PPCIL can effectively activate the CO2 and epoxy substrates, and potential reaction mechanisms were proposed. Notably, PPCIL demonstrated high catalytic activity even after being recycled for five times, maintaining a yield of 88.5% and a selectivity of 98%. In summary, this study offers an effective strategy for heterogenizing ionic liquids for catalytic activation CO2 to cyclic carbonates under mild conditions.
摘要:Organic porous membrane materials are widely used in many fields, but commonly used materials such as polyethylene and polypropylene have defects such as poor high temperature resistance, oxidation resistance, and chemical corrosion resistance. Polytetrafluoroethylene (PTFE) has excellent chemical corrosion resistance, high and low temperature resistance, and good mechanical properties. Its high-temperature stretching method for preparing microporous membranes is widely used in industry. However, the structural evolution and morphological changes during high-temperature stretching are difficult to explore due to the lack of tracking and characterization techniques. This study takes expanded polytetrafluoroethylene (ePTFE) substrate as the research object, and prepares ePTFE microporous membrane by transverse stretching and then longitudinal stretching. During the transverse stretching process, it was found through testing methods such as scanning electron microscopy (SEM), two-dimensional small angle X-ray scattering (2D-SAXS), and differential scanning calorimetry (DSC) that the microstructure and morphological evolution of ePTFE can be divided into two stages with a strain of 200% as the boundary. The structural changes of fibers, micropores, and other structures in each stage are obvious and related to changes in crystallinity. Longitudinal stretching studies have shown that the longitudinal stretching ratio significantly affects the pore size, porosity, surface roughness, and mechanical properties of ePTFE films, with 6-8 times the longitudinal stretching ratio showing better overall performance in practical applications. This research provides a key basis for a deeper understanding of the tensile deformation mechanism of ePTFE, and has important guiding value for the reasonable selection of longitudinal stretching ratio in actual production, which helps to promote the industrial production optimization of ePTFE microporous membranes.
关键词:Expanded polytetrafluoroethylene;Tensile deformation mechanism;Longitudinal stretch ratio
摘要:Covalent organic framework nanosheets (CONs) are a class of two-dimensional layered materials with exceptional properties. The inherent features of COF materials, such as pre-designable periodic structures, atomic-level precision, tunable functionality, excellent thermal stability, permanent porosity, and ultralow density, endow CONs with significant potential for further development. However, challenges such as low exfoliation efficiency of COF nanosheets and poor size controllability complicate membrane fabrication processes. In this study, a liquid-phase exfoliation method was employed to prepare pyridine-based COF nanosheets (TpBpy-CON) and assemble them into COF membranes (TpBpy-COM). COF powders were exfoliated under mild conditions to obtain size-controllable TpBpy-CON. The resulting COF nanosheets exhibited high aspect ratios, specific surface areas, and porosity. Subsequently, the nanosheets were assembled into COF membranes using vacuum-assisted techniques. The fabricated TpBpy-COM demonstrated a compact membrane surface structure and excellent H2/CO2 gas separation performance.
摘要:To improve the compatibility of hydroxyapatite (HA) and thermoplastic polyurethane (TPU), hexamethylene diisocyanate (HDI) was employed to modify HA by primary and secondary grafting to obtain isocyanate-modified HA (NCO@HA and dNCO@HA). The TPU matrix was synthesized based on polycarbonate diol, isophorone diisocyanate and 1,4-butanediol, and the composites were prepared separately based on three HA and TPU matrix by solution blending method. The HA before and after modification and their composites were characterized by FTIR, XRD, SEM, TGA, contact angle tester and electronic universal tensile machine. The results indicate that the ―NCO group of HDI reacts with the ―OH group on the surface of HA to generate the ―NHCOO― group, the grafted side chains can be encapsulated into layers on the surface of modified HA, and the crystal structure of modified HA does not change significantly. Affected by the interfacial interactions between HA and TPU, the thermal stability of the composites is better than that of pure TPU, the initial thermal degradation temperature is increased by about 30 ℃. The thermal degradation phase changes from two in the pure TPU to one in the composite, and the temperature of the fastest thermal degradation rate increases. HA/TPU has a hydrophilic surface, while modified HA/TPU has a hydrophobic surface, similar to the TPU matrix. The tensile strengths of NCO@HA/TPU and dNCO@HA/TPU is 25.9% and 45.7% higher than that of HA/TPU, and the elongation at break is 21.9% and 45.2% higher than that of HA/TPU, indicating that the enhancement effect of modified HA on the mechanical properties of composites is more obvious, and the modification of fillers is expected to be widely used in PU-based composites.
摘要:Polymer-based fibrous filtration materials are widely used, however, the development of high-temperature filtration application using engineering thermoplastics is limited by the difficulty of wet spinning and fiber refinement. In this paper, a nanofibrous membrane was prepared by electrospinning using the high performance engineering polymer polyetherketoneketone (PEKK), which can be dissolved in trifluoroacetic acid. And the regulation laws of the fiber diameter and morphology were investigated, as well as its characteristics for high temperature filtration application. The average diameter of the fiber can be refined to 87 nm, the pore size of the fiber membrane can be reduced to 293 nm, and the tensile strength can reach 7.77 MPa. The fiber membrane shows excellent filtration performance with the filtration efficiency of higher than 99.9% at a thickness of 6 μm. The fiber membrane maintains a good morphological structure, force, thermal properties, and high-temperature air filtration properties at 300 ℃.
关键词:Polyetherketoneketone;Electrospinning;Nanofiber;High temperature filtration
摘要:Polydicyclopentadiene (PDCPD) is flammable, its polymerization process is complicated and the period is long. In this paper, a flame retardant monomer NB-DOPO were designed and synthesized by introducing 9,10-dihydro-9-oxaze-10-phosphoxene-10-oxide (DOPO) into the norbornene. This monomer can be copolymerized with dicyclopentadiene (DCPD) by frontal ring-opening metathesis polymerization (FROMP) to prepare the PDCPD/NB-DOPO copolymers with intrinsic flame retardant properties. The effects of the introduction of NB-DOPO on the FROMP process and the dynamic mechanical properties, thermal stability, mechanical properties as well as the flame-retardant properties of the copolymers were studied. On that basis, the possible flame retardant mechanism of the PDCPD/NB-DOPO copolymer was explored further. The results indicated that NB-DOPO could copolymerize with DCPD randomly, and thus the frontal polymerization velocity of the copolymerization was reduced. According to this, a controllable FROMP was achieved while maintaining a high curing degree of the material. When the content of NB-DOPO was below 10%, the introduction of NB-DOPO with high ring tension promoted the formation of cross-linking points in the system, reduced the molecular weight of cross-linking points (Mc), and enhanced the storage modulus and mechanical properties of the copolymer; When the concentration of NB-DOPO reached 30%, the cross-linking density of PDCPD/NB-DOPO declined, the rigid structures in the NB-DOPO acted as physical cross-linking points, hence the mechanical properties of the material could be kept at a high level accompanied by a markedly enhanced flame retardancy. The limiting oxygen index (LOI) of the material was increased by 38% compared to that of PDCPD, and it exhibited excellent comprehensive performance.
关键词:Polydicyclopentadiene;Frontal ring-opening metathesis polymerization;Intrinsic flame retardant;Random copolymerization;Crosslinking density
摘要:In the present work, the effect of sample thickness and saturation pressure on foaming behavior and foaming window of polystyrene (PS) and poly(methyl methacrylate) (PMMA) was systematically studied. First, the effect of sample thickness and saturation pressure on sorption of CO2 of PS and PMMA was studied; Then, PS and PMMA foams were prepared via a batch foaming process, and the effect of sample thickness and saturation pressure on cell structure and expansion ratio was studied; Last, the upper and the lower limits of the foaming temperature were defined based on the cell structure and the expansion ratio, and hence the foaming temperature window was obtained, and the effect of sample thickness and saturation pressure on foaming temperature window was studied. The results show that the higher the saturation pressure was, and the higher the sorption of CO2 of PS and PMMA was. The sorption of CO2 in PMMA was larger than in PS under the same saturation pressure. Under a lower saturation pressure, PMMA with a larger thickness showed slower sorption of CO2. The sample thickness and saturation pressure significantly affected the cell structure and the expansion ratio. A higher saturation pressure showed a more obvious plasticization effect of CO2. The sample thickness showed a more significant effect on foaming of PMMA. A higher saturation pressure made the upper and the lower foaming temperature limits move to the lower temperature direction. PMMA was more sensitive to the change in thickness and saturation pressure, and had much narrower foaming temperature window than PS did.
关键词:Polystyrene;Poly(methyl methacrylate);Thickness;Saturation pressure;Foaming temperature window