[논문]과분지 폴리글리세롤(HPG) 강화를 통해 기계적 물성이 향상된 새로운 천연 고분자 기반 자성 하이드로젤의 제조

장은혜; 장지수; 권세현; 박정현; 정유정; 정성욱

doi:10.7464/ksct.2023.29.1.10

과분지 폴리글리세롤(HPG) 강화를 통해 기계적 물성이 향상된 새로운 천연 고분자 기반 자성 하이드로젤의 제조
Preparation of Novel Natural Polymer-based Magnetic Hydrogels Reinforced with Hyperbranched Polyglycerol (HPG) Responsible for Enhanced Mechanical Properties 원문보기

청정기술 = Clean technology, v.29 no.1, 2023년, pp.10 - 21

장은혜 (부산대학교 응용화학공학부) , 장지수 (부산대학교 화공생명.환경공학부 화공생명공학전공) , 권세현 (부산대학교 화공생명.환경공학부 화공생명공학전공) , 박정현 (부산대학교 화공생명.환경공학부 화공생명공학전공) , 정유정 (부산대학교 응용화학공학부) , 정성욱 (부산대학교 응용화학공학부)

초록
AI-Helper

천연 고분자 이중 네트워크를 기반으로 하는 하이드로젤은 뛰어난 생체 적합성, 낮은 세포 독성, 높은 함수율을 가져 다양한 의학 분야 재료로서 우수한 성능을 가지며 생체 조직 내 표적 약물 전달 시스템에의 응용에도 많은 주목을 받고 있지만 상대적으로 약한 기계적 물성에 의한 한계를 가진다. 본 연구에서는 천연 고분자 산화 알지네이트(alginate di-aldehyde, ADA)와 젤라틴(gelatin)이 형성하는 이중 네트워크 기반의 하이드로젤을 합성하였으며 하이드로젤 내부의 기능기와 수소 결합을 할 수 있는 다량의 수산기(-OH) 기능기를 가지는 과분지 고분자(hyperbranched polyglycerol, HPG)를 0~25%의 범위로 조절하여 첨가하여 최종적으로 기계적 물성이 향상된 천연 고분자 기반 하이드로젤을 합성하였다. 또한, 자철석 나노 입자(Fe₃O₄ nanoparticles (NPs))를 하이드로젤 내부에 in-situ 방법으로 합성하여 자성이 부여된 천연고분자 하이드로젤의 제조 및 특성 분석을 진행하였다. 결과적으로 Fe₃O₄ NPs를 도입한 15% HPG 함량의 하이드로젤은 3.8 emu g^-1의 포화자화 값을 가지는 초상자성을 보였고, 변형률 67.4%에서 최대 압축 강도 1.1 MPa으로 높은 기계적 물성을 가졌다. 향상된 기계적 물성을 가지는 천연 고분자 기반의 초상자성 하이드로젤은 약물 전달 시스템 및 생체 재료에 매우 중요한 잠재적 용도가 있을 것으로 사료된다.

Abstract ▼ AI-Helper

Hydrogels that are made of natural polymer-based double networks have excellent biocompatibility, low cytotoxicity, and high water content, assuring that the material has the properties required for a variety of biomedical applications. However, hydrogels also have limitations due to their relatively weak mechanical properties. In this study, hydrogels based on an alginate di-aldehyde (ADA) and gelatin (Gel) double network that is reinforced with additional hydrogen bonds formed between the hydroxyl (-OH) groups of the hyperbranched polymer (HPG) and the functional groups present inside of the hydrogels were successfully synthesized. The enhanced mechanical properties of these synthesized hydrogels were evaluated by varying the amount of HPG added during the hydrogel synthesis from 0 to 25%. In addition, magnetite nanoparticles (Fe3O4 NPs) were synthesized within the hydrogels and the structures and the magnetic properties of the hydrogels were also characterized. The hydrogels that contained 15% HPG and Fe3O4 NPs exhibited superparamagnetic behaviors with a saturation magnetization value of 3.8 emu g-1. These particular hydrogels also had strengthened mechanical properties with a maximum compressive stress of 1.1 MPa at a strain of 67.4%. Magnetic hydrogels made with natural polymer-based double networks provide improved mechanical properties and have a significant potential for drug delivery and biomaterial application.

주제어

표/그림 (8)

그림 Figure 1. Scheme of preparing novel natural polymer-based magnetic hydrogels reinforced with hyperbranched polyglycerol (HPG). (A) Preparation of HPG. (B) Gelatin (Gel). (C) ADA-borax complex. (D) Organization of natural polymer-based hydrogels reinforced with HPG followed by in-situ formation of Fe₃O₄ NPs.
그림 Figure 2. (A) ¹H-NMR and (B) ¹³C-NMR spectra of the synthesized HPG showing the assignments of characteristic functional groups of HPG.
그림 Figure 3. (A) ¹H NMR spectrum of Alg and ADA with the assignments of characteristic hemiacetallic protons of oxidized structure of ADA. (B) FT-IR spectra of the synthesized hydrogels with the assignments of characteristic IR bands corresponding to the amide bonds of shiff base formed between the aldehyde groups of ADA and amine groups of Gel.
그림 Figure 4. Optical micrographs of cylindrical hydrogels: (A) ADA/Gel, (B) ADA/Gel/HPG, and (C) ADA/Gel/HPG/Fe₃O₄ NPs. Crosssectional scanning electron microscopy (SEM) images of porous hydrogels: (D) ADA/Gel with an average 3.9 μm size of micropores. (E) ADA/Gel/HPG with an average 4.9 μm size of micropores. (F) ADA/Gel/HPG/Fe₃O₄ NPs with an average 5.2 μm size of micropores. Inset plots show histograms of measured pore size. (G) XRD patterns of the hydrogels showing the characteristic peaks of Fe3O4 NPs overlayed by peak broadening due to the sub-10 nm size of Fe₃O₄ NPs and the surrounding matrix of hydrogels. (H) Cross-sectional transmission electron microscopy (TEM) image of an average 10.7 nm diameter Fe₃O₄ NPs embedded within the hydrogels. Inset plot shows a histogram of measured Fe₃O₄ NP diameter.
표 Table 1. Analysis of TGA measurements of ADA/Gel/HPG-15% and ADA/Gel/HPG-15%/Fe₃O₄ NPs hydrogels
그림 Figure 5. (A) TGA graphs of ADA/Gel/HPG and ADA/Gel/HPG/Fe₃O₄ NPs hydrogels showing the thermal stability. (B) Field-dependent magnetization (M-H) curve of ADA/Gel/HPG/Fe₃O₄ NPs hydrogel. Inset image shows remnant magnetization (Mr) and coervice field (Hc) values of ADA/Gel/HPG/Fe₃O₄ NPs hydrogels.
그림 Figure 6. (A) Strain and stress curves of the hydrogels as a function of HPG content (0 ~ 25%). (B) Strain and stress curves of the swollen hydrogels of 15 and 20% HPG content with and without embedded Fe3O4 NPs within the hydrogels.
표 Table 2. Maximum compressive strength, strain, and Young's modulus of ADA/Gel/HPG hydrogels as a function of HPG contents

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