本文選題：骨修復(fù) + 形狀記憶聚氨酯　； 參考：《西北農(nóng)林科技大學(xué)》2012年碩士論文

【摘要】：隨著組織工程學(xué)的興起，以生物醫(yī)用材料來制作骨移植替代物，，是目前治療大面積骨組織損傷的研究熱點。采用普通骨移植材料進行手術(shù)時，會在骨修復(fù)部位形成應(yīng)力遮擋，并且植入的人工骨通常與缺損骨的兩端因為接觸不緊密而造成骨不連。形狀記憶聚氨酯（Shape memory polyurethane, SMPU）是一類新型功能高分子材料，將SMPU應(yīng)用于骨組織修復(fù)時，可以同時解決骨不連和應(yīng)力遮擋的難題。靜電紡絲可以制備具有極大比表面積、高孔隙率和相互連通的網(wǎng)狀結(jié)構(gòu)的材料，這些特點使得電紡纖維膜可以在一定程度上仿生物細胞外基質(zhì)的結(jié)構(gòu)與功能，為細胞提供生長、增殖以及分化的理想微環(huán)境。采用該方法時，需要確保電紡溶液具有一定的可紡性，同時制得的初始纖維材料具有在溫和環(huán)境下進一步交聯(lián)的潛能。由于有上述條件限制，目前關(guān)于形貌穩(wěn)定、可逆，具有微納米纖維結(jié)構(gòu)SMPU材料的制備及其對細胞生長行為研究的報道還很少。 本研究克服靜電紡絲技術(shù)的難點，成功制得了具有微納米纖維結(jié)構(gòu)的SMPU電紡薄膜。首先，表征了SMPU電紡薄膜的形狀記憶性以及微形貌的穩(wěn)定性；然后對比了同尺寸SMPU電紡薄膜和本體薄膜響應(yīng)回復(fù)性能的差異。最后，將成骨細胞與兩種材料復(fù)合培養(yǎng)，考察了成骨細胞在兩種薄膜上生長行為的差異。研究取得了如下結(jié)果： 1.以聚己內(nèi)酯（PCL）、4,4'-二苯基甲烷二異氰酸酯（MDI）、γ-氨丙基三乙氧基硅烷（APS）為原料，利用溶液聚合法得到的預(yù)聚體-ASPU的結(jié)構(gòu)進行分析，推斷出其可能分子結(jié)構(gòu)；SEM結(jié)果顯示，SMPU本體薄膜表面致密，無孔洞；手動拉伸測試和DMA測定均表明，SMPU本體薄膜具有較好的形狀記憶性，其Rf和Rr均接近于100%。通過DSC分析了材料的熱學(xué)性能，發(fā)現(xiàn)嵌段共聚物的形成影響了SMPU本體薄膜可逆相PCL的結(jié)晶。 2.通過采取特殊的步驟1和2，利用靜電紡絲的方法，成功制得了形狀記憶性良好的SMPU電紡薄膜。SEM結(jié)果表明：SMPU電紡薄膜表面具有微納米纖維形貌，且該形貌經(jīng)過連續(xù)三次的“拉伸-回復(fù)”過程仍可穩(wěn)定保持；同尺寸兩種薄膜響應(yīng)回復(fù)情況結(jié)果表明：SMPU電紡薄膜較先響應(yīng)回復(fù)，且響應(yīng)回復(fù)時間短，響應(yīng)的優(yōu)勢至少可以保持三次循環(huán)。通過兩種薄膜DSC分析，推斷出SMPU電紡薄膜較SMPU本體薄膜響應(yīng)回復(fù)的優(yōu)勢主要與其微納米結(jié)構(gòu)有關(guān)。SMPU電紡薄膜具有微納米纖維堆積的無紡布結(jié)構(gòu)，比表面積大，孔隙率高，使得其熱傳遞較SMPU本體薄膜快，可先達到其相變溫度，最終表現(xiàn)出較早、較快的響應(yīng)回復(fù)趨勢。 3.分別將成骨細胞與SMPU電紡薄膜和本體薄膜復(fù)合培養(yǎng)，考察了成骨細胞在兩種薄膜上黏附情況、鋪展以及增殖活力的不同。結(jié)果表明：經(jīng)DiI細胞膜紅色染料標記后的成骨細胞形態(tài)良好，標記率達100%，是一種研究細胞在支架材料上生長規(guī)律的簡單、有效、及時的觀測手段；成骨細胞在SMPU電紡薄膜表面的黏附、鋪展以及增殖活力都優(yōu)于SMPU本體薄膜。說明具有三維網(wǎng)絡(luò)結(jié)構(gòu)的SMPU電紡薄膜較本體薄膜更利于成骨細胞早期的生長，其生物相容性前景更好。 本研究采用靜電紡絲方法克服了靜電紡絲技術(shù)中的難點，成功制得了形貌穩(wěn)定的具有微納米纖維結(jié)構(gòu)的SMPU電紡薄膜，其較SMPU本體薄膜在響應(yīng)回復(fù)以及成骨細胞早期生長方面都具有一定的優(yōu)勢。這就為下一步利用SMPU進行骨修復(fù)的研制提供理論基礎(chǔ)及前期準備。同時，也為開發(fā)其他形狀記憶材料治療骨組織缺損的研究奠定基礎(chǔ)。
[Abstract]:With the rise of tissue engineering, the use of biomedical materials to make bone graft substitutes is a hot spot in the treatment of large area bone tissue injury. Bone nonunion. Shape memory polyurethane (SMPU) is a new type of functional polymer material. The application of SMPU to bone tissue repair can solve the problem of bone nonunion and stress shielding at the same time. Electrospun fibers can prepare materials with large surface area, high porosity and interconnected network structure. The electrospun fiber membrane can mimic the structure and function of the extracellular matrix to a certain extent and provide the ideal microenvironment for cell growth, proliferation and differentiation. In this method, the spinnability of the electrospun solution must be ensured, and the initial fiber material has the potential to further cross linking in a mild environment. Because of the above conditions, there are few reports on the preparation of SMPU materials with micro nanofiber structure and the study of cell growth behavior.
In order to overcome the difficulty of the electrospinning technology, the SMPU electrospun film with micronanofiber structure was successfully prepared. First, the shape memory of the SMPU electrospun film and the stability of the micromorphology were characterized. Then, the differences in the response of the same size SMPU electrospun film and the bulk film were compared. Finally, the osteoblasts and the two species were formed. The growth behavior of osteoblasts on two kinds of films was investigated.
1. with polyhexyl ester (PCL), 4,4'- two phenyl methane diisocyanate (MDI), gamma amyl triethoxy silane (APS) as raw material, the structure of prepolymer -ASPU obtained by solution polymerization was analyzed and its possible molecular structure was deduced. The results of SEM showed that the surface of SMPU was compact and non porous; both manual tensile test and DMA determination were used. It is shown that the SMPU film has better shape memory, and its Rf and Rr are close to the thermal properties of 100%. through DSC, and the formation of block copolymers affects the crystallization of the reversible phase PCL in the SMPU bulk film.
2. by taking special steps 1 and 2, the SMPU electrospinning film with good shape memory was successfully prepared by electrostatic spinning method. The results showed that the surface of the SMPU electrospun film had the morphology of the micro nanofiber, and the morphology was still stable after three consecutive "tensile recovery" processes, and the response responses of the two kinds of thin films in the same size were recovered. The results show that the SMPU electrospun film is responsive to the response first, and the response time is short, and the advantage of the response can be kept at least three times. Through the analysis of two kinds of thin film DSC, it is concluded that the advantage of SMPU electrospun film in response to the response of the SMPU film is mainly related to the micronano structure of the.SMPU electrospun film with micro nanofiber accumulation. The non-woven fabric with large specific surface area and high porosity makes the heat transfer faster than the SMPU film. The phase transition temperature can be reached first, and the response trend is earlier and faster.
3. the osteoblasts were cultured with the SMPU electrospun film and the bulk film respectively. The adhesion of osteoblasts on the two kinds of films, spreading and proliferating activity were investigated. The results showed that the form of osteoblasts marked by the red dye of the DiI cell membrane was good and the labeling rate reached 100%. It was a kind of cell growth on the scaffold material. The regularities are simple, effective and timely observation. The adhesion, spreading and proliferation of osteoblasts on the surface of SMPU electrospun film are better than that of SMPU. It shows that the SMPU electrospun film with three-dimensional network structure is more beneficial to the early growth of osteoblast than that of the bulk film, and its biocompatibility is better.
In this study, the electrospun method was used to overcome the difficulties in the electrospinning technology. The SMPU electrospun film with a micro nanofiber structure with stable morphology has been successfully prepared. It has a certain advantage over the response recovery and early growth of osteoblasts compared with the SMPU bulk film. This is the next step of using SMPU for bone repair. It provides a theoretical basis and preliminary preparation, and lays the foundation for the development of other shape memory materials in the treatment of bone tissue defects.
【學(xué)位授予單位】：西北農(nóng)林科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2012
【分類號】：R318.08

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