Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (05): 116-124.doi: 10.13475/j.fzxb.20240700101

• Fiber Materials • Previous Articles     Next Articles

Preparation and degradation performance of silk fibroin/chitosan/gelatin embolic microspheres

LI Pengfei1, LUO Yixin1, ZHANG Zifan1, LU Ning1, CHEN Biling1, XU Jianmei1,2()   

  1. 1. College of Textile and Clothing Engineering, Soochow University, Suzhou, Jiangsu 215021, China
    2. Jiangsu Engineering Research Center of Textile Dyeing and Printing for Energy Conservation, Discharge Reduction and Cleaner Production, Soochow University, Suzhou, Jiangsu 215127, China
  • Received:2024-07-01 Revised:2025-02-08 Online:2025-05-15 Published:2025-06-18
  • Contact: XU Jianmei E-mail:xujianmei@suda.edu.cn

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Abstract:

Objective Embolic microspheres with varying degradation rates are better suited for personalized treatment protocols, considering different tumor types, stages, and treatment approaches. In order to achieve controlled degradation in embolic microspheres, the distinct degradation properties of silk fibroin, chitosan, and gelatin were utilized to design and fabricate microspheres with precise degradation profiles and rates.
Method Embolic microspheres were prepared using a two-step emulsification method. The extreme vertex method in material mixing design was employed to obtain silk fibroin/chitosan/gelatin (SF/CS/GEL) microspheres with varying component ratios. Regression equations were established, and mixed contour maps were drawn to reflect the specific degradation mass residual rate of the microsphere components in the presence of different enzymes after 21 d.
Results The photos of embolic microspheres from three orthogonal experiments were utilized to assess the roundness and adhesion levels, and the results were subjected to analysis of variance so as to determine the optimal process conditions. SEM images showed that the SF/CS microspheres had a porous surface while retaining a generally spherical shape. The SF/CS/GEL microspheres exhibited improved roundness, with smoother surfaces and smaller pore sizes as the gelatin content increased. Infrared spectroscopy analysis demonstrated that the silk fibroin structure transformed from random coiling to β-pleated sheets during microsphere formation. The aldehyde groups of glutaraldehyde reacted with amino groups on silk fibroin, chitosan, and gelatin, forming Schiff bases, with significant hydrogen bonding interactions observed between the three matrix materials. Thermogravimetric analysis indicated that the thermal stability of SF/CS and SF/CS/GEL microspheres significantly surpassed that of the individual materials, suggesting structural changes due to crosslinking agents during microsphere formation. Regression analysis was performed on the mass residual rate of the microspheres after 21 d of degradation in relation to the proportions of silk fibroin, chitosan, and gelatin, resulting in a fitted regression equation. The mixed contour map of mass residual rates was adopted to analyze the trends in the mass residual rates of microspheres after 21 d of degradation, correlating with varying component proportions.
Conclusion Optimal preparation conditions were determined through orthogonal experiments with varying ratios of silk fibroin and chitosan, resulting in spherical, round, and well-dispersed microspheres. The regression equations for degradation rates of various formulations across three enzyme systems exhibited significant goodness of fit, enabling the prediction and design of degradation performance for embolic microspheres with different ratios. This approach offers a method and theoretical foundation for achieving controlled degradation of embolic microspheres.

Key words: embolic material, embolic microsphere, silk fibroin, chitosan, gelatin, degradation performance

CLC Number: 

  • TS101.4

Fig.1

Preparation process of SF/CS embolic microspheres"

Tab.1

Orthogonal experiment factor values"

SF与CS
质量比		 水平 A
油水比		 B
乳化剂体积
分数/%		 C
戊二醛体积
分数/%
9:1 1 3:2 0.92 4.0
2 7:4 0.96 4.4
3 2:1 1.00 4.8
7:3 1 3:2 0.92 3.6
2 7:4 0.96 3.8
3 2:1 1.00 4.0
5:5 1 3:2 0.92 2.4
2 7:4 0.96 3.0
3 2:1 1.00 3.6

Fig.2

Schematic diagram of experimental points for extreme vertex method"

Tab.2

Mass fraction of each component material"

水平
数		 SF质量
分数(x1)/
%		 CS质量
分数(x2)/
%		 GEL质量
分数(x3)/
%		 微球
命名
1 50.00 50.00 0 MS1
2 61.25 16.25 22.50 MS2
3 54.75 37.75 7.50 MS3
4 63.00 7.00 30.00 MS4
5 90.00 10.00 0 MS5
6 35.00 35.00 30.00 MS6
7 47.25 30.25 22.50 MS7
8 74.75 17.75 7.50 MS8
9 59.50 25.50 15.00 MS9

Fig.3

Photos of microspheres prepared under different conditions"

Fig.4

SEM images of SF/CS and SF/CS/GEL microspheres (550-750 μm)"

Fig.5

SEM images of SF/CS and SF/CS/GEL microspheres(200-400 μm)"

Fig.6

Infrared spectra of SF, CS, GEL and microspheres with different components"

Fig.7

Thermogravimetric analysis of SF, CS, GEL, SF/CS and SF/CS/GEL microspheres. (a) TG curves; (b) DTG curves"

Tab.3

Degradation mass residual rate of microspheres with different components"

微球尺
寸规格/μm		 试验号 21 d时的降解质量残留率/%
蛋白酶ⅩⅣ组 溶菌酶组 2种酶联用组
550~750 1 92.47±1.14 68.93±3.07 65.33±3.21
2 74.53±3.01 79.47±2.76 69.93±2.61
3 88.20±8.55 73.67±7.29 73.40±2.23
4 76.27±3.53 80.20±3.83 67.67±1.03
5 84.93±11.72 95.47±0.64 86.67±5.74
6 85.40±9.01 62.47±6.70 60.33±7.40
7 89.73±0.31 69.47±3.70 67.13±2.16
8 84.00±4.06 85.87±8.04 79.60±1.25
9 82.00±4.13 76.47±4.15 74.07±2.70
200~400 1 90.07±0.58 66.40±1.74 62.87±7.33
2 76.87±2.10 76.20±11.81 68.53±1.53
3 85.60±3.27 72.13±6.90 70.73±3.61
4 69.40±8.66 79.53±2.73 65.33±1.45
5 81.30±6.20 94.40±2.75 85.47±4.61
6 80.30±4.44 59.67±3.40 58.67±3.69
7 83.20±0.92 67.47±1.20 65.80±1.25
8 81.07±1.67 84.47±2.50 78.80±7.63
9 80.87±6.09 76.27±3.70 71.87±4.41

Fig.8

Mixed contour maps of degradation mass residual rate of microspheres with different component ratioes in presence of different enzymes after 21 d. (a) Protease X IV; (b) Lysozyme; (c) Protease X IV+ lysozyme"

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