熔融缩聚合成聚乳酸-聚乙二醇共聚物及其性能研究

采用羧基封端乳酸预聚物与聚乙二醇熔融缩聚合成了聚乳酸-聚乙二醇共聚物,并用GPC、FTIR、1H-NMR等方法表征了预聚物与共聚物,结果表明,预聚物的羧基封端率高于95%,预聚物的相对分子质量可由投料比(物质的量比)控制.热分析结果表明,共聚物中聚乳酸链段呈无规分布,而聚乙二醇链段能够形成结晶微区.力学性能测试结果表明,共聚物的断裂伸长率达371%,有望在聚乳酸韧性改性方面得到应用.     

以聚苯乙烯磺酸钠接枝聚乙二醇为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

以苯乙烯磺酸钠(SSNa)和烯丙基聚乙二醇(APEG)为原料,制备了不同结构的聚苯乙烯磺酸钠接枝聚乙二醇(P(SS-APEG))共聚物,并以此为模板制备了聚3,4-二氧乙烯噻吩∶聚(苯乙烯磺酸钠-烯丙基聚乙二醇)(PEDOT∶P(SS-APEG))水分散体;研究了聚乙二醇(PEG)链段长度对PEDOT∶P(SS-APEG)结构与性能的影响。结果表明,通过自由基共聚,成功制备了聚苯乙烯磺酸钠接枝聚乙二醇(P(SS-APEG))共聚物。以P(SS-APEG)为模板时,EDOT的聚合速率加快,分散体粒径随APEG相对分子质量的增加而增大,水分散体表面张力减小。PEDOT薄膜的方块电阻明显降低,且APEG的相对分子质量越小,薄膜的方块电阻越低,导电性越好。当APEG的相对分子质量为700,n(SSNa)∶n(APEG)=32∶1,m(EDOT)∶m(P(SS-APEG))=1∶3时,PEDOT∶P(SS-APEG)薄膜的方块电阻较PEDOT∶PSS(m(EDOT)∶m(PSS)=1∶3)薄膜下降了3倍。     

Tunable Assembly of Gold Nanoparticles on Nanopatterned Poly(ethylene glycol) Brushes

The organization of metallic nanoparticles (NPs) into ordered arrays on nanopatterned surfaces is an enabling process to fabricate devices and study the properties of the particles. Tailoring the interaction between NPs and nanopatterns is a necessity to gain a high level of control in this process. Here, nanopatterned poly(ethylene glycol) (PEG) brushes are presented as a platform for the organization of Au NPs on surfaces. The binding of citrate‐stabilized Au NPs to the PEG brushes depends on the size of the particles and molecular weight of the brushes: the density of NPs immobilized on the nanopatterns of PEG brushes increases with decreasing the diameter of the particles and increasing the chain length of the brushes. The key aspect of the process is to pattern PEG brushes with high resolution and chemical contrast to provide controllable and specific interaction between Au NPs and nanopatterns at a single particle resolution. The modulation of the number (0–4) of Au NPs (e.g., 30 nm) per patterned feature with a high level of accuracy and the generation of patterned heterostructures that consist of two different sizes (e.g., 40 and 20 nm) of particles constitute two examples showing the capabilities of the presented platform.     

不同相对分子质量聚乙二醇增塑聚乳酸共混物的制备与性能

文中探究不同相对分子质量聚乙二醇(PEG)对聚乳酸(PLA)增塑改性的影响。采用转矩流变仪、万能试验机、差示扫描量热分析、动态力学、热重分析、旋转流变仪等测试表征方法对共混材料的增塑效果、力学性能、热行为、流变行为进行分析。实验结果表明,PEG可有效增塑PLA,PEG相对分子质量越低增塑效果越好,可以使PLA的塑化时间从250 s降低到128 s;加入PEG后,共混物的拉伸强度下降,断裂伸长率提高,PEG相对分子质量越低,拉伸强度下降越明显;PEG的加入使PLA的T_g和T_(cc)降低20℃左右,而T_m有所提高,其中低相对分子质量PEG可以更好地促进PLA结晶,但是随着PEG的加入共混体系的热分解温度降低,相对分子质量越低,热分解温度降低越明显;流变实验表明共混体系的复数黏度(η*)、储能模量(G')及损耗模量(G')的变化随PEG相对分子质量的减小下降越明显。     

四臂星形聚乙二醇-苯甲酸雌二醇大分子前药的合成与表征

采用哌啶氧化物自由基氧化法将四臂星形聚乙二醇(s PEG,Mn=4400)的端羟基氧化为端羧基,合成得到了一种端羧基四臂星形聚乙二醇(s PEG-CA),并将其对苯甲酸雌二醇(EB)的17位羟基进行酯化修饰,得到四臂星形聚乙二醇-苯甲酸雌二醇大分子前药(s PEG-EB),用红外光谱和核磁共振确认了各步合成产物的结构。研究结果表明,与EB原药相比,s PEG-EB在水中的有效溶解度提高了约1630倍。s PEG-EB在p H 7.2的模拟体液中的释药试验表明,其在0~2 d内具有良好的零级释药特征,2 d时的累积释药率达到61%,5 d时的累积释药率则可达96.5%,说明s PEG-CA适合作为注射用EB的大分子前药载体。     

磺化聚芳醚酮酮砜离子交换膜的制备与性能

采用直接缩聚的方法,通过调整磺化单体(3,3′-二磺酸钠基-4,4′-二氯二苯砜)和非磺化单体(1,4′-二(4′-氟苯甲酰)苯)的比例与双酚单体(2,2′-二(4-羟基苯基)丙烷)共聚合成了系列具有不同磺化度(0.2～1.2)的磺化聚芳醚酮酮砜共聚物。通过红外分析(FT-IR),差示扫描量热分析(DSC),热重分析(TGA)对其结构和性能进行了表征,研究表明,随着磺化度的增加,Na+离子的扩散系数从0.96×10-11S2/m增加到1.25×10-10S2/m,并通过透射电镜(TEM)对其进行了微观结构研究,从结构上解释了膜的物理性能,初步建立了结构与性能之间的关系。     

Shining Light on Poly(ethylene glycol): From Polymer Modification to 3D Laser Printing of Water Erasable Microstructures

The implementation of stimuli-responsive bonds into 3D network assemblies is a key concept to design adaptive materials that can reshape and degrade. Here, a straightforward but unique photoresist is introduced for the tailored fabrication of poly(ethylene glycol) (PEG) materials that can be readily erased by water, even without the need for acidic or basic additives. Specifically, a new class of photoresist is developed that operates through the backbone crosslinking of PEG when irradiated in the presence of a bivalent triazolinedione. Hence, macroscopic gels are obtained upon visible light-emitting diode irradiation (λ > 515 nm) that are stable in organic media but rapidly degrade upon the addition of water. Photoinduced curing is also applicable to multiphoton laser lithography (λ > 700 nm), hence providing access to 3D printed microstructures that vanish when immersed in water at 37 °C. Materials with varying crosslinking densities are accessed by adapting the applied laser writing power, thereby allowing for tunable hydrolytic erasing timescales. A new platform technology is thus presented that enables the crosslinking and 3D laser printing of PEG-based materials, which can be cleaved and erased in water, and additionally holds potential for the facile modification and backbone degradation of polyether-containing materials in general.     

聚乙二醇刷型聚合物在聚砜膜上的光化接枝

对在聚砜薄膜上接枝的聚乙二醇的形貌做了大量研究,探讨了在透明平整的无孔聚砜薄膜上接枝刷型聚乙二醇的条件。首先制作出了透明且光滑平整的无孔聚砜薄膜,然后以对叠氮苯甲酸为光敏剂,在λ=365 nm紫外光的辐照下,用二步法将聚乙二醇接枝在聚砜膜表面,通过X射线-光电子能谱分析、原子力学显微镜及椭圆偏振仪等测试手段,对接枝前后聚砜膜表面形貌进行了表征,证明接枝的聚乙二醇层呈刷状。     

利用衰减全反射红外光谱检测聚合物薄膜中各组分的扩散系数

利用ATR-FTIR法分析聚乙二醇组分在聚乙二醇/聚乙烯共混物薄膜中的组成和结构,建立了以峰面积比为测试基准的扩散方程,描述了聚乙二醇组分在聚乙烯基体中的迁移扩散行为,计算了140℃退火处理时,不同分子量的聚乙二醇组分在聚乙烯基体中的扩散系数.     

In Situ Detecting Thermal Stability of Solid Electrolyte Interphase (SEI)

Solid electrolyte interphase (SEI) plays an important role in regulating the interfacial ion transfer and safety of Lithium-ion batteries (LIBs). It is unstable and readily decomposed releasing much heat and gases and thus triggering thermal runaway. Herein, in situ heating X-ray photoelectron spectroscopy is applied to uncover the inherent thermal decomposition process of the SEI. The evolution of the composition, nanostructure, and the released gases are further probed by cryogenic transmission electron microscopy, and gas chromatography. The results show that the organic components of SEI are readily decomposed even at room temperature, releasing some flammable gases (e.g., H₂, CO, C₂H₄, etc.). The residual SEI after heat treatment is rich in inorganic components (e.g., Li₂O, LiF, and Li₂CO₃), provides a nanostructure model for a beneficial SEI with enhanced stability. This work deepens the understanding of SEI intrinsic thermal stability, reveals its underlying relationship with the thermal runaway of LIBs, and enlightens to enhance the safety of LIBs by achieving inorganics-rich SEI.     

透明质酸/胶原蛋白/聚乙二醇复合水凝胶的研究

针对透明质酸、胶原蛋白水凝胶力学性能差的问题,采用两步交联法将透明质酸、胶原蛋白与聚乙二醇双丙烯酸酯制备成一种兼具生物相容性和高强度的复合水凝胶。研究制备了具有相同胶原蛋白和聚乙二醇双丙烯酸酯质量分数,不同透明质酸质量分数的水凝胶,从微观结构和力学强度调控了复合水凝胶的理化性能,并用L-赖氨酸对复合凝胶进行改性。SEM结果表明,三元复合水凝胶具有蜂窝状的内部结构,孔径范围在80~180μm,赖氨酸浓度达40 mmol/L时,水凝胶的压缩模量达414 k Pa,是改性前模量的19倍。细胞毒性和体内植入实验表明该水凝胶浸提环境对细胞生长无明显抑制作用,产生较低的免疫排斥反应,有望用于软骨等组织的修复。     

梳状水性聚氨酯固态聚合物电解质的制备及性能

以异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇(N220)、三羟甲基丙烷聚乙二醇单甲醚(N120)为主要原料并通过改变N120的质量分数合成一系列梳状非离子水性聚氨酯(NPU),再添加LiClO4制备不同的固态聚合物电解质(SPE)。傅里叶变换红外光谱研究锂离子与醚氧基(C-O-C)作用结果表明,当N120质量分数为25%时,锂离子与C-O-C络合数量达到最大;交流阻抗测试结果显示,聚合物电解质离子电导率此时达到最大值,为3.08×10~(-6)S/cm,温度与离子电导率关系基本符合Arrhenius方程。热学和力学测试结果显示,随着N120含量增加,SPE的玻璃化转变温度降低,耐热性增加,拉伸强度降低,而断裂生长率增加,当N120质量分数为10%时,拉伸强度达到最大值,为10.58 MPa。     

聚丙烯接枝聚乙二醇改性聚丙烯微孔膜

以聚丙烯接枝聚乙二醇(PP-g-PEG)对聚丙烯共混改性,通过单向拉伸工艺制备亲水性聚丙烯微孔膜。使用压汞仪、扫描电镜、Gurley值和水蒸气透过率表征微孔膜的孔结构和透过性能,研究PP-g-PEG含量、PEG接枝率及链长对微孔膜孔结构、水蒸汽透过率及锂电池性能的影响。结果表明,对于接枝率为0.78%的PP-g-PEG,随着添加剂PP-g-PEG含量增加,微孔膜孔隙率和微孔尺寸下降,反映孔道结构的曲挠度及喉孔比上升;微孔膜孔结构与亲水性的综合作用导致水蒸气透过率在PP-g-PEG含量为2.5%时达到最大值。PP-g-PEG含量为2.5%和5.0%的微孔膜组装的锂电池具有较低的电荷转移电阻和较高的充放电比容量,电池性能优于未改性微孔膜组装的电池。提高PEG接枝率使得改性微孔膜孔结构有所变差,但是水蒸气透过率提高,组装电池的性能也更好。长PEG侧链PP-g-PEG对微孔膜孔结构的破坏程度大于短PEG侧链PP-g-PEG,导致组装电池的性能变差。     

聚乙二醇法在温和条件下制备不同结构的磁性Fe3O4纳米晶

以Fe（acac）3为原料,乙二醇、聚乙二醇1000和聚乙二醇5000为还原剂和溶剂,在温和的溶剂热的条件下制备了不同尺寸的顺磁性Fe3O4纳米颗粒.利用X射线衍射（XRD）、光电子能谱（XPS）、透射电子显微镜（TEM）和磁性测量技术对制备的Fe3O4纳米颗粒的结构、形貌、磁性能进行了表征测试.结果发现,聚乙二醇分子链的长度对Fe3O4纳米颗粒的平均粒径大小、结晶度和饱和磁化强度均有重要影响.以乙二醇、聚乙二醇1000和聚乙二醇5000为还原剂制备的Fe3O4纳米颗粒的尺寸分别为2～3nm、5nm和7～8nm;相应的纳米Fe3O4颗粒饱和磁化强度分别为55.2、61.5和81.3emu/g;同时结晶度也随分子链的增加而增加.随分子链长度的增加,还原剂还原性的逐渐增加是导致Fe3O4纳米颗粒平均粒径大小、结晶度和饱和磁化强度逐渐增大的重要因素.     

Engineering of poly(ethylene glycol) chain-tethered surfaces to obtain high-performance bionanoparticles

Abstract

A poly(ethylene glycol)-b-poly[2-(N,N-dimethylamino)ethyl methacrylate] block copolymer possessing a reactive acetal group at the end of the poly(ethylene glycol) (PEG) chain, that is, acetal-PEG-b-PAMA, was synthesized by a proprietary polymerization technique. Gold nanoparticles (GNPs) were prepared using the thus-synthesized acetal-PEG-b-PAMA block copolymer. The PEG-b-PAMA not only acted as a reducing agent of aurate ions but also attached to the nanoparticle surface. The GNPs obtained had controlled sizes and narrow size distributions. They also showed high dispersion stability owing to the presence of PEG tethering chains on the surface. The same strategy should also be applicable to the fabrication of semiconductor quantum dots and inorganic porous nanoparticles. The preparation of nanoparticles in situ, i.e. in the presence of acetal-PEG-b-PAMA, gave the most densely packed polymer layer on the nanoparticle surface; this was not observed when coating preformed nanoparticles. PEG/polyamine block copolymer was more functional on the metal surface than PEG/polyamine graft copolymer, as confirmed by angle-dependent x-ray photoelectron spectroscopy. We successfully solubilized the C₆₀ fullerene into aqueous media using acetal-PEG-b-PAMA. A C₆₀/acetal-PEG-b-PAMA complex with a size below 5 nm was obtained by dialysis. The preparation and characterization of these materials are described in this review.     

Ocular permeability of pirenzepine hydrochloride enhanced by methoxy poly(ethylene glycol)-poly(D, L-lactide) block copolymer

Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymer was tested as an ocular permeation enhancer for pirenzepine hydrochloride. The block copolymers with the methoxy poly(ethylene glycol) to poly(D,L-lactide) weight ratio of 80/20, 50/50, 40/60 were synthesized by a ring-opening polymerization procedure. In vitro transcorneal experiments demonstrated that the block copolymer 80/20 significantly enhanced the transcorneal permeation of pirenzepine at the mass ratio of 1/1.4 (pirenzepine hydrochloride/copolymer). Interaction between pirenzepine and copolymer was identified by infrared spectroscopy analysis and dialysis experiments. Ocular pharmacokinetics of pirenzepine/copolymer preparation by in vivo instillation experiments confirmed that block copolymer could enhance the ocular penetration of pirenzepine. Ocular chronic toxicity experiments of block copolymer and pirenzepine/copolymer preparation were studied on rabbits, and no significant toxicity in both groups was observed within 9 months. It could conclude that pirenzepine/copolymer preparation is effective and safe in ocular delivery of pirenzepine.