聚电解质基的韧性双网络水凝胶纤维

在聚电解质网络中引入氢键作用或共价键作用,分别形成物理-物理交联双网络和物理-化学交联双网络水凝胶纤维,纤维表面经水分蒸发形成类蜘蛛丝样的核-壳纤维结构。这种聚电解质基的水凝胶纤维展现了114.5MPa的高断裂强度、41.73MJ/m~3的高韧性、90%的高阻尼以及湿度响应的超收缩行为。     

基于糖基化反应及自组装法制备大豆分离蛋白-可溶性大豆多糖核壳结构纳米凝胶

结合大分子拥挤环境下的糖基化反应与自组装两步法,制备了安全而新型的具有核壳结构的纳米凝胶.首先,通过水相体系中的Maillard反应使亲水性大豆多糖(SSPS)共价连接到大豆分离蛋白(SPI)上形成两亲性嵌段共聚物;然后,在疏水聚集及静电吸引作用力的驱动下诱导接枝共聚物自组装形成SPI-SSPS纳米凝胶.原子力显微镜与透射电子显微镜分析表明,SPI-SSPS纳米凝胶为分布均匀、具有核壳结构的球形粒子,以亲水性的SPI为壳,以交联的SSPS为核;利用圆二色光谱法与荧光光谱法表征了SPI-SSPS纳米凝胶的结构,结果表明,SPI-SSPS纳米凝胶中蛋白的三级结构发生改变,疏水基团暴露于蛋白表面使纳米凝胶内部形成疏水微区,有利于荷载疏水性药物;稳定性实验结果表明,所制备的SPI-SSPS纳米凝胶具有环境稳定性,在一定的pH值与生理离子强度范围内粒子基本不变,于4℃能稳定储藏120 d以上.因此,SPI-SSPS纳米凝胶在生物医药领域具有广阔的应用前景.     

可控核/壳结构聚合物电纺纤维的制备与应用

核/壳结构纳米纤维是一种兼具核层与壳层优异性能的功能化复合纤维, 通常具有优于核层和壳层自身的性能, 如可控的机械强度和较好的热传导系数等。其特殊的结构极大地提高了纤维的使用价值, 拓宽了纤维的应用领域, 因此, 核/壳结构纳米纤维成为纤维领域的研究热点之一。静电纺丝技术因其简单有效的特点, 近些年来在众多纳米纤维制备技术中一直备受关注, 制备结构和形貌可控的核/壳结构纤维的方法对于指导其在实际中的应用尤为重要。本文系统介绍了以静电纺丝技术制备核/壳结构纳米纤维的方法, 主要包括单喷头相分离法、同轴静电纺丝法、乳液静电纺丝法以及模板法, 重点讨论了影响核/壳结构的主要因素以及核/壳结构对纤维性能的影响。综述了近几年来国内外关于可控核/壳结构电纺纤维制备的研究新进展及其在药物缓释体系、组织工程支架、多功能敷料、污水处理材料、疏水性材料等领域的潜在应用价值。     

刀豆球蛋白A诱导的葡聚糖纳米凝胶高层级自组装

基于葡聚糖这类结构明确的水溶性多糖,以接枝聚合诱导自组装法(GISA)制备得到具有交联结构的葡聚糖纳米凝胶。在此基础上,利用刀豆球蛋白A(Con A)与葡聚糖中葡萄糖单元之间的特异性识别作用,诱导葡聚糖纳米凝胶的高层级自组装,从而制备尺度可控的Con A-葡聚糖纳米凝胶高层级自组装体。通过透射电镜、红外光谱、核磁共振光谱、等温滴定量热法等手段对高层级自组装体的粒径、结构和形貌进行表征,探讨了其高层级自组装的机理。此外,还探究了Con A以及Con A-葡聚糖纳米凝胶高层级自组装体对人肺癌细胞A549的细胞毒性。结果表明:该自组装体的尺寸同葡聚糖与Con A的质量比直接相关;游离的Con A对A549细胞具有抑制作用,且Con A在参与高层级自组装的过程中生物活性保持不变。     

三维交联石墨烯纳米纤维的合成及储锂性能

以氧化石墨烯为原料, 高温下自组装得到高结晶的三维交联石墨烯纳米纤维. 扫描电子显微镜和透射电子显微镜观测结果表明, 三维石墨烯纳米纤维为实心结构, 直径小于100 nm, 石墨烯片层有序排列卷曲, 具有较高的结晶度. 电化学性能研究结果表明, 该纳米纤维作为锂离子电池负极材料时, 展现出较高的首次库仑效率(72.4%)与储锂容量(0.1C倍率下容量为692.7 mA·h/g)、 良好的倍率性能(20C倍率下容量为373.3 mA·h/g)及优异的循环稳定性(1000次循环后容量保持率为84.1%).     

核-壳结构微球的制备进展

综述了近年来核-壳结构微球制备方面的研究进展,介绍了高分子胶束交联、模板逐层组装、模板微球表面原位引发聚合、动态溶胀法、种子聚合法以及溶胶-凝胶法等主要制备方法,并对各种方法所涉及的核-壳微球形成机理进行了必要阐述.     

原位聚合法制备具有温敏PNIPAM壳的核-壳结构聚合物纳米微球的研究

结合大分子自组装和原位自由基聚合方法,采用油溶性引发剂偶氮二异丁腈(AIBN),在聚(ε-已内酯)(PCL)纳米粒子表面引发聚合单体N-异丙基丙烯酰胺(NIPAM)和交联剂亚甲基双(丙烯酰胺)(MBA),制备得到了核-壳结构的PCL/PNIPAM聚合物纳米微球.系统研究了单体和交联剂用量、壳层目标交联度、初始PCL/DMF溶液的浓度及引发剂AIBN含量4个反应参数对核-壳结构PCL/PNIPAM纳米微球的PNIPAM壳层得率、微球尺寸、温敏性能及电镜形貌的影响.结果表明,在制备核-壳结构PCL/PNIPAM纳米微球的反应过程中,PCL粒子表面的聚合和水中的聚合二者之间相互竞争.适当增加引发剂AIBN的添加量,有利于制备得到核/壳比例可控的PCL/PNIPAM纳米微球;交联剂MBA较高的反应活性导致形成了非均匀交联的PNIPAM壳层.     

固相合成法制备组氨酸-苯丙二肽分子及其自组装研究

本文以组装性能良好的苯丙氨酸二肽(FF)为母体分子,用组氨酸对其进行化学修饰,通过多肽固相合成法合成了组氨酸-苯丙二肽(HisFF)凝胶因子。合成的HisFF分子通过质谱、核磁氢谱和液相色谱等确定其精确结构和纯度。通过透射电镜和扫描电镜观察HisFF聚集体的形貌结构。HisFF分子在甲苯、氯仿和乙酸乙酯溶剂中形成的凝胶的强度不同,透射电镜实验结果表明纤维强度和聚集形态也影响其凝胶的强度。通过不同组装方法,HisFF可以在多种溶剂中组装成各种各样的纳米结构。例如,HisFF在丙酮、甲醇和乙酸乙酯溶剂中可组装成纳米颗粒、纳米管和螺旋状纳米纤维;HisFF先经六氟异丙醇溶解再通过溶剂稀释后,可得到不同直径的纳米纤维。     

功能性无机-晶态纳米纤维素复合材料的研究进展与展望

纤维素是自然界储藏量最大,可再生且可生物降解的生物高分子。晶态纳米纤维素是天然纤维素复合材料的结构支撑体,其多级孔道结构,手性液晶排列和活性羟基官能团赋予它优异的模板效应。本篇综述回顾了功能性无机-晶态纳米纤维素复合材料的研究进展。概述组装方法,侧重讨论静电纺丝法,细菌纤维素和纤维素气凝胶模板矿化法,凝胶-溶胶法,溶液浇铸法和静电层贴法的组装特点。扼要介绍了晶态纳米纤维素的形貌和晶体结构,提取方法,排列方式,化学修饰和溶剂等。天然复合材料的生物功能与其多级结构和多元组分的协同效应息息相关,文章以木质纤维素的刚性和海参表皮的化学感应性为例,浅谈晶态纳米纤维素微束的螺旋结构和纤维素复合体的多级结构在仿生组装功能性纤维素复合材料中的应用。最后,作者对晶态纳米纤维素在设计组装功能性复合材料领域的未来方向提出了一些设想,藉此综述抛砖引玉。     

ZnO纳米管有序阵列与Cu2O纳米晶核壳结构的光电化学性能及全固态纳米结构太阳电池研究简

采用电化学方法在铟锡氧化物(ITO)导电玻璃基底上制备了高度有序的ZnO纳米管阵列,然后在ZnO纳米管阵列上电化学沉积Cu2O纳米晶颗粒,获得了一维有序Cu2O/ZnO核壳式纳米阵列结构,通过控制Cu2O纳米晶的沉积电量得到不同厚度的Cu2O壳层,并对该核壳式纳米阵列的形貌和结构进行了分析. 以Cu2O/ZnO一维核壳式纳米阵列结构为光电极组装全固态纳米结构太阳电池,研究了Cu2O壳层厚度对光电极光吸收性能、光电性能以及组装电池光伏性能的影响,优化了电池中对电极材料的喷金厚度. 结果表明,以Cu2O沉积电量为1.5 C的Cu2O/ZnO为光活性层,以4 mA电流下真空镀金20~25 min的铜基底为对电极组装的简易太阳电池最高可获得0.013%的光电转换效率.     

PVA微晶交联和SA/PAA双网络协效增强增韧SA纤维

为了提高海藻酸钠(SA)纤维的断裂强度和断裂伸长率, 以丙烯酸(AA)为化学交联组分, SA为离子交联组分, 聚乙烯醇(PVA)为微晶交联组分, 采用湿法纺丝和冻融循环方法制备含有PVA微晶交联点和海藻酸钠/聚丙烯酸(SA/PAA)双网络结构的海藻酸钠/聚丙烯酸/聚乙烯醇(SA/PAA/PVA)复合纤维. 通过流变性能、 力学性能、 红外光谱、 X射线衍射仪(XRD)和扫描电子显微镜(SEM)测试研究了交联剂N,N-亚甲基双丙烯酰胺(MBA)含量和PVA微晶交联对SA/PAA/PVA纺丝原液和复合纤维的结构与性能的影响. 结果表明, 当MBA质量分数为0.5%时, 纺丝原液的损耗模量(G″)最小, 可纺性最好, 复合纤维的断裂强度达到2.83 cN/dtex, 断裂伸长率达到9.38%, 比再生SA纤维分别提高了15.98%和38.96%; PVA冷冻之后形成微晶交联点并且PAA和PVA已经复合到体系中; PAA和PVA的加入提高了复合纤维的结晶度; 复合纤维的表面形貌趋于光滑和规整, 纤维断面更加致密.     

Bioinspired and Mechanically Strong Fibers Based on Engineered Non-Spider Chimeric Proteins

Silk-protein-based fibers have attracted considerable interest due to their low weight and extraordinary mechanical properties. Most studies on fibrous proteins focus on the recombinant spidroins, but these fibers exhibit moderate mechanical performance. Thus, the development of alternative structural proteins for the construction of robust fibers is an attractive goal. Herein, we report a class of biological fibers produced using a designed chimeric protein, which consists of the sequences of a cationic elastin-like polypeptide and a squid ring teeth protein. Remarkably, the chimeric protein fibers exhibit a breaking strength up to about 630 MPa and a corresponding toughness as high as about 130 MJ m⁻³, making them superior to many recombinant spider silks and even comparable to some native counterparts. Therefore, this strategy is a novel concept for exploring bioinspired ultrastrong protein materials through the development of new types of structural chimeric proteins.     

吸湿发热型黏胶纤维的性能

通过盐酸肼交联羧甲基化黏胶纤维制得具有吸湿发热功能的黏胶纤维,讨论了纤维在吸湿发热量、断裂强度、热性能及微观结构等方面的特性.结果表明:当纤维中氮的质量分数为2%～4%,回潮率为25%～26%(相对湿度90%)时,纤维吸湿发热效果明显,发热量最高可达7.67J/g;交联使纤维的湿断裂强度明显提高,湿干强度比可提高16....     

Super-tough and rapidly self-recoverable multi-bond network hydrogels facilitated by 2-ureido-4[1H]-pyrimidone dimers

Multi-bond network(MBN) hydrogels contain hierarchical dynamic bonds with different bond association energy as energy dissipation units,enabling super-tough mechanical properties.In this work,we copolymerize a protonated 2-ureido-4[1 H]-pyrimidone(UPy)-contained monomer with acrylic acid in HCl solution.After removing excess HCl,UPy motifs are deprotonated and from dimers,thus generating an UPy-contained MBN hydrogel.The obtained MBN hydrogels(75 wt% watercontent) exhibit super-tough mechanical properties(0.39 MPa to 2.51 MPa tensile strength),with tremendous amount of energy(1.68 MJ/m³ to 11.1 MJ/m³) dissipated by the dissociation of UPy dimers.The introduction of ionic bonds can further improve the mechanical properties.Moreover,owing to their dynamic nature,both UPy dimers and ionic bonds can re-associate after being dissociated,resulting in excellent self-recovery ability(around 90% recovery efficiency within only 1 h).The excellent self-recovery ability mainly originates from the re-association of UPy dimers based on the high dimerization constant of UPy motifs.     

强韧抗溶胀水凝胶的简单构筑及性能

以聚乙烯醇(PVA)和壳聚糖(CS)为原料, 采用循环冻融法制备了前驱体水凝胶(PVA-CS), 并经过浸泡氯化钠溶液和透析后处理构筑了强韧抗溶胀复合水凝胶(PVA-CS-6.16-30). 采用扫描电子显微镜(SEM)、 傅里叶变换红外光谱仪(FTIR)、 X射线衍射分析仪(XRD)、 差示扫描量热分析仪(DSC)及流变仪表征了两种水凝胶的微观结构, 采用拉力机测试了其机械性能. 结果表明: 由于结晶微区、 氢键及链缠结等协同交联作用, PVA-CS-6.16-30具备高效能量耗散机制. 与前驱体PVA-CS相比, PVA-CS-6.16-30的交联密度由7.69×10^?4 mol/cm³增加至9.97×10^?4 mol/cm³, 自由水含量由62.8%降低至52.6%, 网络尺寸由6.11 nm降低至5.21 nm, 凝胶分数由58.6%增加至86.8%, PVA结晶度由14.8%增加至17.2%, 其抗拉强度、 断裂伸长率、 韧性及抗压强度分别为2.9 MPa, 229%, 3.3 MJ/m³和7.6 MPa. 此外, 该复合水凝胶还具有优异的耐溶胀与抗蠕变性能. 在37 ℃的PBS缓冲溶液中浸泡7 d后, 其抗拉和抗压强度分别高达2.8和7.5 MPa, 优于常见水凝胶. 商品化的原料、 简单的构筑方法及优异的综合性能有望推动水凝胶在组织工程和生物医疗领域的应用.     

Water-Resistant and Stretchable Conductive Ionic Hydrogel Fibers Reinforced by Carboxymethyl Cellulose

Conductive ionic hydrogels (CIH) have been widely studied for the development of stretchable electronic devices, such as sensors, electrodes, and actuators. Most of these CIH are made into 3D or 2D shape, while 1D CIH (hydrogel fibers) is often difficult to make because of the low mechanical robustness of common CIH. Herein, we use gel spinning method to prepare a robust CIH fiber with high strength, large stretchability, and good conductivity. The robust CIH fiber is drawn from the composite gel of sodium polyacrylate (PAAS) and sodium carboxymethyl cellulose (CMC). In the composite CIH fiber, the soft PAAS presents good conductivity and stretchability, while the rigid CMC significantly enhances the strength and toughness of the PAAS/CMC fiber. To protect the conductive PAAS/CMC fiber from damage by water, a thin layer of hydrophobic polymethyl acrylate (PMA) or polybutyl acrylate (PBA) is coated on the PAAS/CMC fiber as a water-resistant and insulating cover. The obtained PAAS/CMC-PMA and PAAS/CMC-PBA CIH fibers present high tensile strength (up to 28 MPa), high tensile toughness (up to 43 MJ/m³), and good electrical conductivity (up to 0.35 S/m), which are useful for textile-based stretchable electronic devices.     

Effect of kappa-carrageenan on the properties of poly(N-vinyl pyrrolidone)/kappa-carrageenan blend hydrogel synthesized by γ-radiation technology

A series of hydrogels in the form of rods were prepared from kappa-carrageenan (KC) and poly (N-vinyl pyrrolidone) (PVP) by gamma radiation with ⁶⁰Co γ source at room temperature. The properties of the prepared hydrogels, such as the gel strength, gel fraction and swelling behavior were investigated. Incorporation of KC into the PVP/water system increased obviously the gel strength and equilibrium degree of swelling (EDS) of PVP hydrogel. The experimental analyses showed that the crosslinking reaction of PVP was quicker than the degradation of KC at a low dose (less than 30 kGy), and the degradation of KC was inhibited in the PVP/KC mixture system. So an interpenetrating polymer network (IPN) hydrogel composed of PVP (a chemical crosslinking network) and KC (a physical crosslinking network) was proposed here. The existence of different classes of water in this IPN system was shown by water melting curves using DCS.     

非冻结水对微球复合水凝胶机械性能的影响

本文旨在用DSC的方法研究水凝胶结合水的能力与韧性的关系。 分别以甲基丙烯酸丁酯(BMA)或甲基丙烯酸六氟丁酯(HFBMA)和烯丙基胺为单体,制备了2种核壳纳米微球(BMA微球和HFBMA微球)。 再以其作为大分子引发剂和交联剂,制备了微球交联复合水凝胶(BMA-H凝胶和HFBMA-H凝胶)。 通过差示扫描量热仪(DSC)、傅里叶变换红外光谱仪(FTIR)和透射电子显微镜(TEM)等技术手段研究凝胶的结构和性能。 结果表明,HFBMA-H凝胶具有更好的机械性能,其拉伸强度和断裂伸长率分别可达280 kPa和3960%,远高于BMA-H凝胶(101 kPa,2700%)。 通过对2种复合凝胶体系内不同状态的水进行分析,发现HFBMA-H凝胶的非冻结水的质量分数明显高于BMA-H凝胶,这种非冻结水的增塑作用对于凝胶机械强度的提升具有重要影响。     

Effect of Draw Ratio on the Morphologies and Properties of BPDA/PMDA/ODA Polyimide Fibers

3,3,4,4-Biphenyltetracarboxylic dianhydride/pyromellitic dianhydride/4,4-oxydianiline（BPDA/PMDA/ODA） polyimide copolymer fibers with different draw ratios were prepared from the imidization of polyacrylic acid（PAA） fibers via a dry-jet wet-spinning process.Their morphologies,microcrystal orientations,thermal stabilities,and mechanical properties were investigated via scanning electron microscopy（SEM）,wide angle X-ray diffraction（WAXD）,thermogravimetric analysis（TGA）,and tensile experiments.In order to acquire fibers with better mechanical performance,we aimed at obtaining the optimal draw ratio.Drawing during thermal imidization resulted in a decreased diameter of fiber from 25.8 μm to 16.9 μm corresponding to draw ratio from 1 to 3.5.WAXD results show that the degree of the orientation of the undrawn sample is 64.1％,whereas that of the drawn sample is up to 82％.The as-spun fiber and those with different draw ratios all exhibit high thermal stabilities,i.e.,the temperature at a mass loss of 5％ can reach as high as 570 ℃.The tensile strengths and tensile modulus of the fibers increase with the draw ratios,and the maximum tensile strength and modulus are 0.90 and 12.61 GPa,respectively.     

勃姆石纤维增强二氧化硅气凝胶的制备及性能

以六水合氯化铝为铝源, 通过水热法制备勃姆石纤维; 以甲基三甲氧基硅烷和正硅酸乙酯为硅源共前驱体, 采用溶胶-凝胶法进而常压干燥制备了勃姆石纤维掺杂的二氧化硅复合气凝胶; 探究了勃姆石纤维的掺杂量对复合气凝胶性能的影响. 当勃姆石纤维的掺杂量(质量分数)为1%时, 气凝胶的机械性能最好, 能够承受17.1%的压缩应变, 最大压缩强度为1.12 MPa, 压缩模量高达2.57 MPa, 复合气凝胶在150 ℃仍然具有较低的导热系数(0.0670 W·m^?1·K^?1). 勃姆石纤维能够一定程度地抑制二氧化硅颗粒在高温下的烧结和相转变, 对二氧化硅气凝胶的耐高温性能有显著的提升作用, 复合气凝胶在1100 ℃高温热处理后, 仍能保持良好的隔热性能和较高的机械强度.