石墨烯诱导水凝胶成核的高强韧人造蛛丝

天然蜘蛛丝是由β-sheet交联的蛛丝蛋白溶剂流入S-型导管后经牵引拉伸形成,它显示了高强度与高韧性的完美结合。其优异的力学性质主要源于它的多级结构：交联、线性排列的纳米组装体以及核壳结构。受此启发,我们合成了一种交联的水凝胶,通过牵引拉丝的方法,制备了交联的、含有取向排列的纳米组装体结构以及核壳结构的凝胶纤维,并通过少量引入二维纳米材料—氧化石墨烯(0.01%),进一步调控纳米组装体的取向和尺寸,实现了蜘蛛丝般优异的力学性能(断裂强度560 MPa,断裂韧性200 MJ·m^–3,缓冲能94%)。这种纤维可以用于高速下落物体的能量耗散和降低冲击力。     

可交联且可生物降解的高分子膜

高分子膜在生物医用、电子器件、食品包装,以及气体分离等领域有着广泛的应用。实际应用中往往通过交联提高其稳定性、强度等性能。然而,传统的交联高分子膜材料在温和环境下难以降解。针对这一挑战,本文分别基于聚(α-(肉桂酰氧基甲基)-1, 2, 3-三唑)己内酯(PCTCL₁₃₃)及其与己内酯(CL)的无规共聚物P(CL₁₅₆-stat-CTCL₂₈),通过溶液浇铸法制备了两种可交联且可生物降解的高分子膜。由于肉桂酸酯侧链阻止了PCL主链的结晶,因此PCTCL₁₃₃均聚物可形成透明膜,而P(CL₁₅₆-stat-CL₂₈)无规共聚物则形成半透明膜。该高分子膜可进一步在紫外光照射下交联,而所形成的交联膜结构可以在酸催化下充分降解。理论上,这两种膜材料均可完全降解为分子量小于300 g∙mol⁻¹的产物。而通过调节聚合物中己内酯的重量百分数以及膜的交联度,可以有效调节其降解速率、透明度等性能。在此基础上,我们进一步通过分子动力学模拟探究了溶液浇铸过程中高分子的不同初始浓度对膜材料杨氏模量的影响。结果表明,随着初始浓度上升,由于分子链间的缠结程度升高,最终制备的膜材料具有更高的模量。因此,该可交联、可降解,且降解性能可调的高分子膜在生物医用领域具有一定的应用前景,并可拓展到其他领域以实现更为广泛的应用。     

光交联固化的聚合物囊泡用于降温触发的药物释放

The stability of nanocarriers in physiological environments is of importance for biomedical applications. Among the existing crosslinking approaches for enhancing the structural integrity and stability, photocrosslinking has been considered to be an ideal crosslinking chemistry, as it is non-toxic and cost-effective, and does not require an additional crosslinker or generate by-products. Meanwhile, most current temperature-responsive nanocarriers are designed and synthesized for drug release by increasing temperature. However, heating may induce cell damage during triggered drug release. Therefore, lowering temperature-triggered nanocarriers need to be developed for drug delivery and safe drug release during therapeutic hypothermia. In this study, we prepared an amphiphilic block copolymer, poly(ethylene oxide)-block-poly[N-isopropyl acrylamide-stat-7-(2-methacryloyloxyethoxy)-4-methylcoumarin]-block-poly(acrylic acid) [PEO₄₃-b-P(NIPAM₇₁-stat-CMA₈)-b-PAA₁₃], by reversible addition fragmentation chain transfer (RAFT) polymerization. Successful synthesis of the polymer was verified by proton nuclear magnetic resonance (¹H NMR) and size exclusion chromatography (SEC). The copolymers self-assembled into vesicles in aqueous solution, with the P(NIPAM-stat-CMA) block forming an inhomogeneous membrane and the PEO chains and PAA chains forming mixed coronas. The cavity of this vesicle could be utilized to load hydrophilic drugs. The CMA groups could undergo photocrosslinking and enhance the stability of vesicles in biological applications, and the PNIPAM moiety endowed the vesicle with temperature-responsive properties. Upon decreasing the temperature, the vesicles swelled and released the loaded drugs. The size distribution and morphology of the vesicles were characterized by dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) experiments. After staining with phosphotungstic acid, the hollow morphology of the vesicles with a phase-separated inhomogeneous membrane was observed by TEM and SEM. The DLS results showed that the hydrodynamic diameter of the vesicles was 208 nm and the polydispersity was 0.075. The size of the vesicles observed by TEM was between 180 and 200 nm, which was in accordance with that measured by DLS. To verify the drug loading capacity and controlled release ability of the vesicle, a water-soluble antibiotic was encapsulated in the vesicles. The experimental results showed that the drug loading content was 10.4% relative to the vesicles and the drug loading efficiency was approximately 32.7%. For vesicles containing the same amount of antibiotics, the release rate at 25 ℃ was 35% higher than that at 37 ℃ after 12 h in aqueous solution. Overall, this photocrosslinked vesicle with temperature-responsive properties facilitates lowering temperature-triggered drug release during therapeutic hypothermia.     

聚(ε-己内酯)-多肽共聚物胶束增强抗生素的抗菌活性

Bacterial infection is a major threat to human health, and can cause several diseases including gastroenteritis, influenza, tetanus, and tuberculosis. As conventional antibiotic treatment may cause various undesirable effects such as stomach disorder and bacterial resistance, it is necessary to improve the antibacterial efficiency of antibiotics. Here, we synthesized a peptide-based copolymer, poly(ε-caprolactone)-block-poly(glutamic acid)-block-poly(lysine-stat-phenylalanine)[PCL₃₄-b-PGA₃₀-b-P(Lys₁₆-stat-Phe₁₂)] by ring-opening polymerization (ROP) of ε-caprolactone and amino acid N-carboxyanhydride (NCA). Successful synthesis of the copolymer was verified by proton nuclear magnetic resonance and size exclusion chromatography. This copolymer can self-assemble into negatively charged micelles (-26.7 mV) under alkaline conditions by solvent switch method. The micelle structure was confirmed by transmission electron microscopy and dynamic light scattering, and revealed to have a diameter of ~42 nm. Antibiotics were loaded into micelles during the self-assembly process, and cell viability assay was conducted to evaluate its cytotoxicity with and without tobramycin. No obvious cytotoxicity was observed for both micelles when the concentration was lower than 300 μg·mL^-1. The antibiotic-loaded micelles demonstrated very low minimum inhibitory concentrations (MICs) against both Gram-negative Escherichia coli (E. coli) (7.8 μg·mL^-1) and Gram-positive Staphylococcus aureus (S. aureus) (18.2 μg·mL^-1), while the MICs of free tobramycin were 3.9 and 1.0 μg·mL^-1, respectively. The drug-loading content and efficiency of the micelles were 5.2% and 24.3%, respectively. Therefore, the MICs of the loaded tobramycin against E. coli and S. aureus were 0.4 and 0.9 μg·mL^-1, respectively, suggesting that the micelle could enhance the antibacterial activity of antibiotics. Tobramycin-loaded micelles demonstrated a sustained release characteristic, with 85% of the antibiotics released after 8 h. In bacteria-induced acidic microenvironment, the coil conformation of PGA blocks transforms and PGA blocks shrink toward the micelle core. Concomitantly, the carboxyl side chains are protonated in an acidic environment, increasing the hydrophobicity of this micelle. Antibiotics will be captured when reaching the outer core to slow down the releasing process. Furthermore, the poly(lysine-stat-phenylalanine) [P(Lys-stat-Phe)] coronas with broad spectrum intrinsic antibacterial activity can penetrate the bacterial cell membrane, leading to leakage of the cellular contents of the bacteria and ultimately their death. Due to the sustained release property of micelle and the intrinsic activity of the antibacterial peptide segments, this micelle can greatly enhance the antibacterial activity of antibiotics. Overall, this antibiotic-loaded micelle provides a novel approach for significantly reducing the antibiotics dosage and avoiding the associated health risks.     

高锂离子电导的有机-无机复合电解质的渗流结构设计

固态聚合物电解质被认为是解决传统液态锂金属电池安全隐患和循环性能的关键材料,但仍然存在离子电导率低,界面兼容性差等问题。近年来,基于无机填料与聚合物电解质的高锂离子电导的有机-无机复合电解质备受关注。根据渗流理论,有机-无机界面被认为是复合电解质离子电导率改善的主要原因。因此,设计与优化有机-无机渗流界面对提高复合电解质离子电导率具有重要意义。本文从渗流结构的设计出发,综述了不同维度结构的无机填料用于高锂离子电导的有机-无机复合电解质的研究进展,并对比分析了不同渗流结构的优缺点。基于上述评述,展望了有机-无机复合电解质的未来发展趋势和方向。     

Anode Catalytic Dependency Behavior on Ionomer Content in Direct CO Polymer Electrolyte Membrane Fuel Cell

In this work, the effect of Nafion ionomer content on the structure and catalytic performance of direct CO polymer electrolyte membrane fuel cell(CO-PEMFC) by using Rh-N-C single-atom catalyst as the anode catalyst layers was studied. The ionic plaque and roughness of the anode catalyst layers increase with the increase of Nafion ionomer content. Furthermore, the contact angle measurement results show that the hydrophilicity of the anode catalyst layers also increases with the increase of Nafion ionomer content. However, when the Nafion ionomer content is too low, the binding between microporous layers, catalyst layers and membrane cannot meet the requirement for either electric conductivity or mass transfer. While Nafion ionomer content increased above 30%, the content of water in anode is difficult to control. Therefore, it was found that AN 30(30% Nafion ionomer content of anode) is the best level to effectively extend the three-phase boundary and improve CO-PEMFCs performance.     

A fully integrated graphene-polymer field-effect transistor biosensing device for on-site detection of glucose in human urine

Convenient and rapid self-measurement of the glucose level in the body is of great significance for diabetics to know their health conditions in time. In view of this, a polymer functionalized graphene field-effect transistor (P-GFET) portable biosensing device is demonstrated for glucose monitoring. The polymer is synthesized by acrylamide/3-acrylamidophenylboronic acid (AAPBA)/N, N-dimethylaminopropyl acrylamide. In the presence of glucose, the P-GFET shows Dirac point shifts and current changes as a result of the covalent bond between glucose and AAPBA in the synthesized polymer on graphene. The sensitivity of this P-GFET sensor can increase while the density of AAPBA in polymer increases. The used sensor could regain the detection capability after hydrochloric acid treatment due to the reversible reaction between polymer and glucose. In addition, the chemisorption interaction between polymer and glucose, which is stronger than physisorption interaction with other objects in urine, has been supported by the density functional theory study. The P-GFET shows high sensitivity of 822 μA1cm^?21mM^?1 with a limit of detection of 1.9 μM during human urine glucose monitoring. The sensor holds a detection range of 0.04–10 mM and good reusability over 20 times. With the customized portable real-time measurement capability in urine, our P-GFET sensor can offer advantages over current glucose detection methods.     

Depolymerization using sonochemical reactors: A critical review

Ultrasonic irradiation has been proposed as a novel approach for degradation of polymer compounds, especially considering the fact that the reduction in the molecular weight (also the intrinsic viscosity) is simply by splitting the most susceptible chemical bond without causing any changes in the chemical nature. An overview of the application of ultrasound for the polymer degradation has been presented in this work, discussing the mechanism of degradation, kinetic modeling, effect of operating parameters and the type of reactors generally used for depolymerization. The effect of important operating parameters such as initial polymer concentration, presence of functional groups in the polymer chain, reaction volume, initial molecular weight, temperature, operating frequency, power dissipation and use of process intensifying additives have been discussed also giving guidelines about selection of the optimum parameters. It has been observed that the low concentrations and higher power dissipation (till an optimum) are favorable resulting in higher extents of degradation. Typically low frequency is recommended but for the case of water soluble polymers, higher frequencies would also give similar results due to the dominant action of chemical effects of cavitation. It has been demonstrated that the alkyl group substituent also affects the degradation rate of polymer. An overview of degradation using combined approach based on ultrasound and additives with comparison with individual approach has also been presented. It has been observed that the main contributing factor for the synergy of the combined approach is the selection of optimum loading of additives. Overall, it has been observed that efficient polymer degradation can be achieved using combined process based on the use of ultrasound.     

聚合物太赫兹光纤布喇格光栅

研究了一种基于聚合物太赫兹光纤的太赫兹光纤布喇格光栅.通过二氧化碳激光器或紫外激光器点对点加工聚合物太赫兹光纤,实现聚合物太赫兹光纤直径的周期性调制,从而实现太赫兹光纤布喇格光栅的周期性折射率调制.基于有限元方法和光纤布喇格光栅相关理论,考虑反射峰波长、反射率、带宽、光纤长度、光纤直径和光纤直径形状变化程度等因素,研究了太赫兹光纤布喇格光栅的特性.理论模拟表明,反射峰波长和光栅周期存在与传统光学波段光纤布喇格光栅不同的非线性关系.     

Synthesis and characterization of a novel polymer electrolyte based on acrylonitrile/N-[4-(aminosulfonyl)phenyl]acrylamide copolymers

<正>Acrylonitrile/N-[4-(aminosulfonyl)phenyl]acrylamide(AN/ASPAA) copolymers were synthesized and used as a host of lithium ion conducting electrolytes.The composition,molecular weight and molecular weight distribution of AN/ASPAA copolymers were determined,and the influence of copolymer composition on the glass temperature of AN/ASPAA copolymers and the ion conductivity of electrolytes were investigated.The molecular weights of AN/ASPAA copolymers were lower than those of AN and ASPAA homopolymers due to the cross-termination reaction.The glass temperatures of AN/ASPAA copolymers increased as the molar fraction of ASPAA units in copolymers increased.The lithium ion conductivities of the polymer electrolytes increased initially as the molar fraction of ASPAA units in copolymers increased,and a maximum conductivity was achieved when the molar fraction of ASPAA in the copolymer was 16.8%.