Department of Chemical Engineering, Bucknell University, Lewisburg, Pennsylvania 17837, United States.
J Phys Chem B. 2023 Jun 8;127(22):5055-5061. doi: 10.1021/acs.jpcb.3c00861. Epub 2023 May 26.
Differential scanning calorimetry (DSC) and pulsed field gradient spin echo nuclear magnetic resonance (PFGSE NMR) were used to characterize water in hydrogels of ethoxylated trimethylolpropane tri-3-mercaptopropionate (ETTMP) and poly(ethylene glycol) diacrylate (PEGDA). Freezable and nonfreezable water were quantified using DSC; water diffusion coefficients were measured using PFGSE NMR. No freezable water (free or intermediate) was detected from DSC for hydrogels of 0.68 and greater polymer mass fractions. Water diffusion coefficients, from NMR, decreased with increasing polymer content and were assumed to be weighted averages of free and bound water contributions. Both techniques showed decreasing ratios of bound or nonfreezable water mass per polymer mass with increasing polymer content. Swelling studies were used to quantify the equilibrium water content (EWC) to determine which compositions would swell or deswell when placed in the body. At 30 and 37 °C, fully cured, non-degraded ETTMP/PEGDA hydrogels at polymer mass fractions of 0.25 and 0.375, respectively, were shown to be at EWC.
差示扫描量热法(DSC)和脉冲梯度磁场自旋回波核磁共振(PFGSE NMR)被用于对乙氧基化三羟甲基丙烷三-3-巯基丙酸酯(ETTMP)和聚乙二醇二丙烯酸酯(PEGDA)水凝胶中的水进行特性分析。通过 DSC 对可冻结水和不可冻结水进行定量分析;通过 PFGSE NMR 对水的扩散系数进行测量。在聚合物质量分数为 0.68 及更高的水凝胶中,通过 DSC 没有检测到可冻结水(游离态或中间态)。水的扩散系数随着聚合物含量的增加而降低,被认为是自由水和结合水贡献的加权平均值。这两种技术都表明,随着聚合物含量的增加,结合水或不可冻结水的质量与聚合物质量的比值逐渐减小。溶胀研究用于定量测定平衡水含量(EWC),以确定在体内放置时哪些组成会溶胀或收缩。在 30 和 37°C 下,完全固化、未降解的 ETTMP/PEGDA 水凝胶,其聚合物质量分数分别为 0.25 和 0.375,其 EWC 分别为。