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柞蠶絲素的溶解再生及其絲蛋白復合材料的結(jié)構(gòu)與性能研究

發(fā)布時間:2018-05-28 05:49

  本文選題:柞蠶絲素 + 家蠶絲素; 參考:《武漢紡織大學》2017年碩士論文


【摘要】:柞蠶絲素蛋白(ASF)具有優(yōu)異的生物相容性和緩慢的降解能力,而且攜帶哺乳動物細胞的整合素受體RGD三肽序列,在生物材料領域的應用方面擁有廣泛的潛力。然而,一方面,柞蠶絲素溶解比較困難,再生的ASF材料力學性能較差,其溶解、再生以及材料的力學有待進一步的提高。另一方面,通過將ASF與不同材料的共混,能夠調(diào)控其結(jié)構(gòu)與性能,拓展其作為生物材料的應用。本文首先研究了在硝酸鈣體系下,不同溶解條件對ASF的分子量和絲素膜力學性能的影響,從而獲得高分子量的ASF,以增強ASF材料的力學性能。研究發(fā)現(xiàn),柞蠶絲素纖維的溶解與其溶解的溫度和時間密切相關。溫度過低,溶解的能力有限,低于90℃時柞蠶絲素纖維難以溶解;溫度越高,溶解時間越長,對柞蠶絲素的破壞越大,所得再生絲素蛋白分子量也越小。進一步,以不同溶解方法獲得的ASF制備絲素膜,研究了溶解條件對絲素膜力學性能的影響。結(jié)果發(fā)現(xiàn),溫度為90℃下溶解4 h時,絲素膜的力學性能最佳,干態(tài)和濕態(tài)下的平均斷裂強度分別為28.1±2.4 MPa,2.2±0.3 MPa。在本文中,柞蠶絲素纖維的最佳溶解條件為90℃下溶解4 h。其次,研究了柞蠶絲素蛋白/家蠶絲素蛋白(BSF)共混絲素蛋白溶液的凝膠化行為。研究結(jié)果發(fā)現(xiàn)ASF凝膠快,5%濃度的ASF在37℃下,33 min左右就能完全凝膠化。但是,ASF水凝膠力學性能差,在濃度低于5%時均無法形成凝膠,而且凝膠在凍干后易碎,難以保持完整形態(tài)。家蠶絲素蛋白凝膠十分緩慢,5%濃度的BSF在37℃下,要7天左右才能完全凝膠化。凝膠動力學測試表明,ASF/BSF共混溶液的凝膠化速率可以通過調(diào)節(jié)共混比例來進行調(diào)控。隨著ASF的含量逐漸增加,凝膠速率逐漸加快,而隨著BSF含量的增加,其凝膠的力學性能增加。再次,研究了ASF/BSF共混膜的結(jié)構(gòu)和性能。研究結(jié)果表明,不同比例ASF/BSF共混膜結(jié)構(gòu)主要以無規(guī)卷曲為主,并存在少量β-折疊結(jié)構(gòu),經(jīng)乙醇處理后,β-折疊為主要分子構(gòu)象。在力學性能上,ASF/BSF共混膜的斷裂強度和斷裂伸長性能隨著BSF含量的增加而增加。進一步,研究了ASF膜、BSF膜以及共混膜的酶降解行為。研究發(fā)現(xiàn),ASF膜在PBS溶液中溶失更大,酶降解速率更快。在降解21天后,ASF膜的降解剩余率僅為46.4%,而BSF膜降解剩余率為77.0%,50ASF/50BSF的降解剩余率為62.3%。通過調(diào)節(jié)ASF和BSF的共混比,能夠調(diào)節(jié)共混絲素膜的降解速率。本文的研究結(jié)果表明,通過改變ASF和BSF的共混比,可以在一定范圍內(nèi)調(diào)控絲素蛋白膜的力學性能和降解速率。最后,初步研究了氧化石墨烯(GO)對ASF/BSF共混膜的結(jié)構(gòu)與性能的影響。結(jié)果發(fā)現(xiàn),GO的加入對共混膜的分子構(gòu)象沒有明顯的影響。但是,GO含量而過高和過低都會造成共混膜強度下降,會明顯降低其強力和斷裂伸長,這可能與GO對共混膜內(nèi)絲素蛋白分子間作用力和結(jié)晶結(jié)構(gòu)的影響以及氧化石墨烯與柞蠶絲素可能存在相分離有關,其作用機理有待今后的進一步研究。通過本文的研究發(fā)現(xiàn),溶解條件對ASF的分子量具有重要影響,通過優(yōu)化溶解條件可以提高ASF的分子量,提高材料的力學性能。同時,通過調(diào)節(jié)ASF和BSF的共混比例,可以有效調(diào)節(jié)絲素蛋白的凝膠化速率以及絲素膜的降解速率和力學性能,從而為調(diào)控絲素蛋白生物材料的性能提供了新的思路和途徑。而GO的加入對ASF/BSF共混膜的分子構(gòu)象沒有明顯的影響,但GO的含量對共混膜力學性能具有明顯影響。
[Abstract]:Tussah silk fibroin (ASF) has excellent biocompatibility and slow degradation ability, and the integrin receptor RGD three peptide sequence of mammalian cells has a wide potential in the application of biological materials. However, on the one hand, tussah silk fibroin is difficult to dissolve, the mechanical properties of regenerated ASF materials are poor, and then they dissolve. On the other hand, by blending ASF with different materials, the structure and properties of different materials can be adjusted to expand its application as a biomaterial. In this paper, the influence of different dissolving conditions on the molecular weight and the mechanical properties of ASF membrane in the system of calcium nitrate is first studied. It is found that the dissolving of tussah silk fibroin fiber is closely related to the temperature and time of dissolving. It is found that the solubility of tussah fibroin fiber is closely related to the temperature and time of dissolving. The temperature is too low and the ability of dissolving is limited, and the tussah fibroin fiber is difficult to dissolve at 90 C. The higher the temperature, the longer the dissolution time is, the greater the destruction of tussah silk fibroin, the regenerative fibroin protein is obtained. The molecular weight is also smaller. Further, the effect of dissolution conditions on the mechanical properties of silk fibroin film is studied by ASF obtained by different dissolution methods. The results show that the mechanical properties of silk fibroin film are the best when the temperature is 4 h at 90 C, and the average fracture strength under dry and wet state is 28.1 + 2.4 MPa respectively, and 2.2 + 0.3 MPa. in this paper, tussah The optimum dissolving condition of silk fibroin fiber was 4 h. at 90 C and then 4 h.. The gelation behavior of tussah silk fibroin / silk fibroin (BSF) blend silk fibroin solution was studied. The results showed that the ASF gel was fast and the 5% concentration of ASF could be completely gelatinized at about 33 min at 37 C. However, the mechanical properties of the hydrogel were poor and the concentration was lower than that of the gel. The gel was not formed at 5%, and the gel was fragile after freeze-drying, and it was difficult to maintain a complete form. The gels of silk fibroin protein were very slow, and the 5% concentration of BSF could be completely gelatinization at about 7 days at 37 C. The gel kinetics test showed that the gelation rate of the ASF/BSF blend solution could be regulated by adjusting the blending ratio. With A The content of SF increased gradually and the gel speed increased gradually, and the mechanical properties of the gel increased with the increase of BSF content. Again, the structure and properties of the ASF/BSF blend membranes were studied. The results showed that the structure of ASF/BSF blend membranes was mainly composed of random curling, and there was a small amount of beta folding structure, after ethanol treatment, beta folding. The fracture strength and elongation properties of ASF/BSF blend films increase with the increase of BSF content in mechanical properties. Further, the enzyme degradation behavior of ASF film, BSF film and blend membrane is studied. It is found that the ASF membrane dissolves more greatly in PBS solution and the rate of enzyme degradation is faster. After 21 days degradation, the degradation of ASF film is left. The residual rate is only 46.4%, while the residual rate of BSF film degradation is 77%. The degradation residual rate of 50ASF/50BSF is 62.3%. by adjusting the blending ratio of ASF and BSF. The results of this study show that the mechanical properties and degradation of the silk fibroin membrane can be regulated in a certain range by changing the blending ratio of ASF and BSF. At last, the effect of graphene oxide (GO) on the structure and properties of ASF/BSF blends was preliminarily studied. The results showed that the addition of GO had no obvious effect on the molecular conformation of the blend membrane. However, the content of GO, which was too high and too low, would cause the decrease of the strength of the blend membrane, which would obviously reduce the strength and elongation of the blends, which may be blended with GO. The influence of the intermolecular force and crystalline structure of the membrane and the possible phase separation of graphene oxide and tussah silk fibroin may be related to the further study on the molecular weight of ASF, and the molecular weight of ASF can be improved by optimizing the dissolving conditions. At the same time, by adjusting the blending ratio of ASF and BSF, the gelation rate of silk fibroin and the degradation rate and mechanical properties of silk fibroin membrane can be effectively regulated, which provides a new way of thinking and way to regulate the properties of silk fibroin biomaterials, and the molecular conformation of the ASF/BSF blend membrane has not been added by the addition of GO. Obviously, the content of GO has obvious effect on the mechanical properties of blend film.
【學位授予單位】:武漢紡織大學
【學位級別】:碩士
【學位授予年份】:2017
【分類號】:TB33;R318.08

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