Synthesis of hydrolytically and oxidation‐responsive networks using thiol‐ene “click” chemistry with pentaerythritol tetrakis(3‐mercaptopropionate) and tri/tetra‐acrylates

Abstract

Thiol‐ene click reactions of pentaerythritol tetrakis(3‐mercaptopropionate) with pentaerythritol tetraacrylate and trimethylolpropane triacrylate were used to prepare polymeric degradable networks. The structure and properties of these networks were studied using Fourier‐transform infrared and Raman spectroscopy, thermal gravimetric analysis and scanning electron microscopy. Degradation of these materials was evaluated in different media including phosphate buffer with and without esterase as well as in oxidative environment with hydrogen peroxide. Exposure of the samples to these media results in their degradation. Slow hydrolytic degradation was observed in phosphate buffer and it was not accelerated by the presence of an enzyme. Faster degradation is observed in solutions of hydrogen peroxide. The mechanisms of this degradation are discussed.

Functional Materials for DLP-SLA 3D Printing Using Thiol–Acrylate Chemistry: Resin Design and Postprint Applications

“…The remaining FTIR peaks in the control chip are typical of a cross-linked thiol−acrylate resin, such as the CO stretching (1747 cm −1 ), C−O−C stretching (1163 cm −1 ), alkyl-substituted ether C−O stretching (1033 cm −1 ), a weak C−S stretching (659 cm −1 ), and C−H bending vibrations (1458 cm −1 ). 56 The three grafted polymers present typical vibrations characteristic of these polymers, consistent with surface modification: in the case of the DMAEMA, a peak at 2760 cm −1 is the characteristic stretching of the C−H bonds in −N(CH 3 ) 2 . 57 The chip modified with TFEMA shows a characteristic stretching peak at 748 cm −1 due to the symmetric deformation of the −CF 3 group, 58,59 while strong peaks in the region of 1400−1000 cm −1 represent the C−F stretching and bending vibrations.…”

“…The grafting process consumes free surface thiols, and FTIR analysis before and after modification shows that the disappearance of the characteristic thiol stretching peak is at 2542 cm –1 (Figure , including the inset). The remaining FTIR peaks in the control chip are typical of a cross-linked thiol–acrylate resin, such as the CO stretching (1747 cm –1 ), C–O–C stretching (1163 cm –1 ), alkyl-substituted ether C–O stretching (1033 cm –1 ), a weak C–S stretching (659 cm –1 ), and C–H bending vibrations (1458 cm –1 ) . The three grafted polymers present typical vibrations characteristic of these polymers, consistent with surface modification: in the case of the DMAEMA, a peak at 2760 cm –1 is the characteristic stretching of the C–H bonds in −N­(CH 3 ) 2 .…”

Thiol-Ene “Click Reactions” as a Promising Approach to Polymer Materials

“…Наша группа получила деградируемые гели на основе пентаэритритолтетракис(3-меркаптопропионата) (ПЭМП) с пентаэритритолтетраакрилатом (ПЭТА) и триметилолпропантриакрилатом посредством тиол-ен "клик" реакции [65]. На рисунке 6 приведено предлагаемое нами строение этих гелей.…”

“…Перепечатано из [65] с разрешения John Wiley and Sons Деградация полимеров может быть использована в создании материалов биомедицинского назначения для доставки малых лекарственных молекул [66], а также белковых молекул [67,68]. Гидрогели полиэтиленгликоля (ПЭГ), полученные в результате тиолен "клик" реакций, создают подходящие условия для устойчивой и локализованной доставки биоактивных малых молекул, например, глюкокортикоидов [69].…”