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WO2018036025A1 - 一种基于木聚糖的双网络纳米复合水凝胶及其制备与应用 - Google Patents

一种基于木聚糖的双网络纳米复合水凝胶及其制备与应用 Download PDF

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WO2018036025A1
WO2018036025A1 PCT/CN2016/109906 CN2016109906W WO2018036025A1 WO 2018036025 A1 WO2018036025 A1 WO 2018036025A1 CN 2016109906 W CN2016109906 W CN 2016109906W WO 2018036025 A1 WO2018036025 A1 WO 2018036025A1
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xylan
hydrogel
nanocomposite hydrogel
water
based double
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French (fr)
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任俊莉
孔维庆
孙润仓
黄丹阳
许桂彬
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to US16/317,838 priority patent/US11365293B2/en
Publication of WO2018036025A1 publication Critical patent/WO2018036025A1/zh
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Definitions

  • the invention belongs to the technical field of composite materials, and particularly relates to a xylan-based double network nano composite hydrogel and preparation and application thereof.
  • Hydrogel is a polymer network system that absorbs a large amount of water without dissolving and maintaining a certain shape. Hydrogels have been widely used and studied in drug controlled release, biomedical and tissue engineering. However, some of the traditional chemically crosslinked hydrogels have relatively weak mechanical properties, which greatly limits the deeper and wider application of hydrogels. Especially in biomedicine and tissue engineering, the requirements for the mechanical properties of hydrogels are gradually emerging.
  • the dual-network hydrogel consists of two separate cross-linking networks that improve the mechanical properties of the hydrogel by introducing a new cross-linking network.
  • most double-network hydrogels have the disadvantages of serious environmental pollution, poor biocompatibility and poor degradability. How to prepare a high-strength, biocompatible double-network composite hydrogel has become a challenge.
  • Xylan has good biocompatibility, reproducibility and special physical and chemical properties, can inhibit cell mutation, has detoxification, anti-inflammatory, anti-cancer effects, etc., and has a good application prospect in the field of medicine. So far, xylan has not been used as a raw material, GO is used as a reinforcing filler, acrylamide is used as a monomer graft polymerization network, and graphene oxide (GO) and Ca 2+ crosslinked network form another network.
  • the primary object of the present invention is to provide a method for preparing a xylan-based dual network nanocomposite hydrogel.
  • Another object of the present invention is to provide a xylan-based dual network nanocomposite hydrogel prepared by the above method.
  • a further object of the present invention is to provide the use of the above xylan-based dual network nanocomposite hydrogel.
  • the composite hydrogel is used in the field of biomedicine, especially in tissue engineering, drug sustained release, cell culture scaffold, and cartilage tissue.
  • a preparation method of a xylan-based double network nano composite hydrogel comprises the following steps:
  • the reactive monomer is one or more of acrylamide (AM), polyacrylamide, acrylic acid, N-isoacrylamide, butyl acrylate, preferably acrylamide;
  • the mass ratio of Ca 2+ in the water-soluble calcium salt in the step (3) to GO in the GO aqueous dispersion is (10 to 240) mg: (20 to 60) mg, and the reaction monomer and xylan The mass ratio is (1 to 6) g: (0.5 to 1.5) g, and the mass ratio of GO to xylan in the GO aqueous dispersion is (20 to 60) mg: (0.5 to 1.5) g.
  • the water-soluble calcium salt in the step (3) is CaCl 2 or calcium nitrate.
  • the drying reaction condition in the step (4) is to dry the reaction at 50 to 80 ° C for 2 to 6 hours.
  • the heating and stirring conditions in the step (2) are stirred at 75 to 95 ° C for 0.5 h to 1.5 h, and the wood is gathered.
  • the concentration of the sugar solution is 0.05g/mL to 0.2g/mL;
  • the ultrasonic dispersion temperature in the step (1) is 20 ° C to 40 ° C; the dispersion time is 2 h to 6 h, the ultrasonic power is 100 W to 300 W, and the frequency is 25 kHz to 80 kHz.
  • the concentration of the GO aqueous dispersion in the step (1) is from 0.4 mg/mL to 6 mg/mL.
  • the initiator in the step (3) is ammonium persulfate or potassium persulfate; and the mass ratio of the initiator to the reaction monomer is (0.01 to 0.05) g: (1 to 6) g.
  • the crosslinking agent in the step (3) is N,N'-methylenebisacrylamide; and the mass ratio of the crosslinking agent to the reaction monomer is (0.0025 to 0.03) g: (1 to 6) g.
  • the accelerator described in the step (3) is tetramethylethylenediamine or N,N,N',N'-tetramethyleneethylenediamine; the volume-mass ratio of the accelerator to the reactive monomer is ( 10 to 50) uL: (1 to 6) g.
  • a xylan-based dual network nanocomposite hydrogel prepared by the above method.
  • the xylan-based double-network nanocomposite hydrogel has a compressive strength of 0.17 MPa to 2.3 MPa and an elongation of 629% to 3967%.
  • the xylan-based dual network nanocomposite hydrogel is used in the field of biomedicine, especially tissue engineering, drug sustained release, cell culture scaffold, and cartilage tissue.
  • the invention combines a preparation method of a nano-composite hydrogel and a double-network hydrogel to prepare a high-strength hydrogel, using water as a solvent, xylan as a raw material, and a reactive monomer (acrylamide as a single Graft copolymerization to form a layer of network, the introduction of GO as a reinforcing filler, and the introduction of Ca 2+ and GO cross-linking into another layer network, not only improve the mechanical strength of the hydrogel, but also improve the bio-facies of the hydrogel Capacitive and biodegradable;
  • the preparation process of the invention adopts a one-step synthesis method, the operation is simple, the reaction conditions are mild, and the reaction conditions are easy to control;
  • the composite hydrogel obtained by the invention has high mechanical properties, is biodegradable, has good biocompatibility, and can be applied in biomedical fields, such as tissue engineering, drug sustained release, cell culture scaffold and cartilage tissue. Wait.
  • Example 3 is a cyclic compressive stress-strain curve of the GO/Ca 2+ /PAM/XH composite hydrogel of Example 2.
  • a method for preparing a GO/PAM/XH hydrogel material comprising the steps of:
  • the GO/PAM/XH composite hydrogel obtained in this comparative example had a maximum compressive strength of 0.17 MPa and an elongation of 629% when the compression set reached 95%.
  • a method for preparing a xylan-based dual network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH hydrogel) material comprising the following steps:
  • step (3) The mixed solution in step (3) is placed in an oven and reacted at 60 ° C for 4 h to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) ).
  • the composite hydrogel performance test curve is shown in Figures 1 and 2.
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break and break when the compression set reached 95%, and recovered rapidly after compression.
  • the compressive strength of the hydrogel was 0.184 MPa, and the elongation was 0.184 MPa.
  • the rate is 775%.
  • a method for preparing a xylan-based dual network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) material comprising the following steps:
  • step (1) 111 mg of CaCl 2 , 4 g of monomeric acrylamide, xylan solution is added to the GO water dispersion of step (1), and uniformly stirred and dispersed under ice bath; 0.03 g of initiator ammonium persulfate is added, 0.01 g cross-linking agent N, N'-methylenebisacrylamide and 50 uL of promoter tetramethylethylenediamine, stirred uniformly to obtain a mixed solution;
  • step (3) The mixed solution in step (3) is placed in an oven and reacted at 60 ° C for 4 h to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) ).
  • the composite hydrogel performance test curves are shown in Figures 1, 2 and 3.
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break and break when the compression set reached 95%, and recovered rapidly after compression.
  • the compressive strength of the hydrogel was 1.84 MPa, and the elongation was 1.84 MPa.
  • the rate is 1918%.
  • a method for preparing a xylan-based nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) material of the embodiment comprises the following steps:
  • step (3) The mixed solution in step (3) is placed in an oven and reacted at 60 ° C for 4 h to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) ).
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break and break when the compression set reached 95%, and it recovered rapidly after compression.
  • the compressive strength of the hydrogel was 1.1 MPa, and the elongation was 1.1 MPa.
  • the rate is 1100%.
  • the preparation method of the carboxymethyl xylan-based nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) material of the embodiment comprises the following steps:
  • step (3) The mixed solution in the step (3) is placed in an oven and reacted at 80 ° C for 6 hours to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel). ).
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break and break when the compression set reached 95%, and it recovered rapidly after compression.
  • the compressive strength of the hydrogel was 2.3 MPa, and the elongation was 2.3 MPa.
  • the rate is 3310%.
  • a method for preparing a xylan-based nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) material comprising the following steps:
  • step (3) The mixed solution in the step (3) is placed in an oven and reacted at 80 ° C for 6 hours to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel). ).
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break or break when the compression set reached 95%, and recovered rapidly after compression.
  • the compressive strength of the hydrogel was 1.63 MPa, and the elongation was 1.63 MPa.
  • the rate is 3976%.
  • a method for preparing a xylan-based dual network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) material comprising the following steps:
  • step (1) (3) adding 55.5 mg of CaCl 2 , 4 g of monomeric acrylamide, xylan solution to the GO water dispersion of step (1), stirring and dispersing uniformly under ice bath conditions; adding 0.03 g of initiator ammonium persulfate, 0.01 g of a crosslinking agent N, N'-methylenebisacrylamide and 50 uL of a promoter tetramethylethylenediamine, and uniformly stirred to obtain a mixed solution;
  • step (3) The mixed solution in step (3) is placed in an oven and reacted at 60 ° C for 4 h to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) ).
  • the composite hydrogel performance test curve is shown in Figures 1 and 2.
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break and break when the compression set reached 95%, and it recovered rapidly after compression.
  • the compressive strength of the hydrogel was 0.757 MPa, and the elongation was 0.757 MPa.
  • the rate is 942%.
  • a method for preparing a xylan-based dual network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) material comprising the following steps:
  • step (1) (3) adding 222 mg of CaCl 2 , 4 g of monomeric acrylamide, xylan solution to the GO water dispersion of step (1), stirring and dispersing uniformly under ice bath conditions; adding 0.03 g of initiator ammonium persulfate, 0.01 g cross-linking agent N, N'-methylenebisacrylamide and 50 uL of promoter tetramethylethylenediamine, stirred uniformly to obtain a mixed solution;
  • step (3) The mixed solution in step (3) is placed in an oven and reacted at 60 ° C for 4 h to obtain a xylan-based double network nanocomposite hydrogel (GO/Ca 2+ /PAM/XH composite hydrogel) ).
  • the composite hydrogel performance test curve is shown in Figures 1 and 2.
  • the GO/Ca 2+ /PAM/XH composite hydrogel obtained in this example did not break and break when the compression set reached 95%, and it recovered rapidly after compression.
  • the compressive strength of the hydrogel was 0.175 MPa, and the elongation was 0.175 MPa.
  • the rate is 630%.
  • 1 and 2 are compression stress-strain curves and tensile stress-strain curves of hydrogels of different Ca 2+ /GO (Comparative Example 1, Examples 1, 2, 6, and 7), respectively. It can be seen that the content of Ca 2+ has a great influence on the mechanical strength of the GO/PAM/XH composite hydrogel.
  • the amount of GO is 20 mg
  • the amount of the crosslinking agent is 0.01 g
  • the maximum compressive strength is 0.17 MPa and the maximum elongation is 629% when the compression shape becomes 95%.
  • XH and AM graft copolymerization cross-linking networks and Ca 2+ and GO cross-linking network segments can be connected by covalent bonds.
  • This allows the GO/Ca 2+ /PAM/XH hydrogel to exhibit excellent mechanical properties as well as high elasticity and toughness.
  • the ratio of Ca 2+ /GO was increased from 2 to 4
  • the compressive strength of the hydrogel decreased from 1.84 MPa to 0.37 MPa and the elongation decreased from 1918% to 942% when the compression shape became 95%.
  • FIG. 3 is a cyclic compressive stress-strain curve of the GO/Ca 2+ /PAM/XH composite hydrogel of Example 2.
  • Ca 2+ /GO 2 mg
  • the amount of GO 20 mg
  • the amount of cross-linking agent 0.01 g
  • the compression shape is changed to 70%
  • the hydrogel is not broken and broken, and the elasticity is maintained, and after releasing the pressure, the water
  • the gel quickly returns to its original shape.
  • the hydrogel showed almost no plastic deformation and a decrease in compressive strength.
  • This high-strength hydrogel is expected to be used in biomedical applications such as tissue engineering, drug delivery, cell culture scaffolds, and cartilage tissue.

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Abstract

本发明属于复合材料技术领域，公开了一种基于木聚糖的双网络纳米复合水凝胶及其制备与应用。所述方法为(1)将氧化石墨粉末加入去离子水中，超声分散，得到GO水分散液；(2)将木聚糖加入去离子水中，加热搅拌，得到木聚糖溶液；(3)将水溶性钙盐，反应单体和木聚糖溶液加入到GO水分散液中，冰浴条件下，搅拌分散均匀，加入引发剂、交联剂和促进剂，搅拌混合均匀，得到混合溶液；(4)将步骤(3)的混合溶液进行烘干反应，得到基于木聚糖的双网络纳米复合水凝胶。本发明所得复合水凝胶有较高机械性能，同时可生物降解、具有良好的生物相容性，应用在生物医学领域，如组织工程、药物缓释、细胞培养支架以及软骨组织等方面。

Description

一种基于木聚糖的双网络纳米复合水凝胶及其制备与应用 技术领域
本发明属于复合材料技术领域，具体涉及一种基于木聚糖的双网络纳米复合水凝胶及其制备与应用。
背景技术
水凝胶(Hydrogel)是一种能吸收大量的水而不溶解，并保持一定的形状的高分子网络体系。水凝胶在药物缓控释，生物医学以及组织工程等方面得到了广泛的应用和研究。然而，传统的一些化学交联结构水凝胶机械性能相对较弱，大大限制了水凝胶更深更广的应用。尤其在生物医学以及组织工程等方面，对于水凝胶机械性能的要求也逐步显现。
近年来，大量的研究工作致力于改善水凝胶的机械性能。聚合物复合水凝胶和双网络水凝胶一直以来被认为是有效提高凝胶机械性能的常用途径。聚合物复合水凝胶，即在水凝胶的聚合物网络结构中引入增强有机/无机填料，例如，蒙脱土，纳米纤维素，碳纳米管等从而提高水凝胶的机械性能。GO/PAM纳米复合水凝胶已有相关报道(R.Liu,S.Liang,X.-Z.Tang,D.Yan,X.Li and Z.Z.Yu,J.Mater.Chem 2012,22,14160–14167；N.Zhang,R.Li,L.Zhang,H.Chen,W.Wang,Y.Liu,T.Wu,X.Wang,W.Wang and Y.Li,Soft Matter 2011,7,7231–7239；H.Wei,L.Han,Y.Tang,J.Ren,Z.Zhao and L.Jia,J.Mater.Chem.B 2015,3,1646–1654)，但是机械强度的增强有限，压缩强度一般是在1MPa以下，仍然有很大的提升空间。双网络水凝胶，是由两个独立的交联网络构成的，通过引入新的交联网络来提高水凝胶的机械性能。但是大部分双网络水凝胶存在环境污染严重、生物相容性和降解性差等缺点。如何制备出高强度、生物相容性好的双网络的复合水凝胶成为了一种挑战。
木聚糖具有良好的生物相容性、可再生性并且具有特殊的理化性能，能对细胞突变产生抑制，具有解毒、消炎、抗癌等作用，在医药领域具有良好的应 用前景。到目前为止，还未见以木聚糖为原料，以GO为增强填料，以丙烯酰胺为单体接枝聚合网络以及氧化石墨烯(GO)与Ca2+交联网络形成另一网络的双网络的纳米复合水凝胶的相关报道。
发明内容
为了克服现有技术的缺点和不足，本发明的首要目的在于提供一种基于木聚糖的双网络纳米复合水凝胶的制备方法。
本发明的另一目的在于提供由上述方法制备得到的基于木聚糖的双网络纳米复合水凝胶。
本发明的再一目的在于提供上述基于木聚糖的双网络纳米复合水凝胶的应用。所述复合水凝胶在生物医学领域，特别是组织工程、药物缓释、细胞培养支架以及软骨组织等方面的应用。
本发明目的通过以下技术方案实现：
一种基于木聚糖的双网络纳米复合水凝胶的制备方法，包括以下步骤：
(1)将氧化石墨粉末(GO)加入去离子水中，超声分散，得到GO水分散液；
(2)将木聚糖(XH)加入去离子水中，加热搅拌，得到木聚糖溶液；
(3)将水溶性钙盐，反应单体和木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀，加入引发剂、交联剂和促进剂，搅拌混合均匀，得到混合溶液；所述反应单体为丙烯酰胺(AM)、聚丙烯酰胺，丙烯酸，N-异丙烯酰胺、丙烯酸丁酯中的一种以上，优选为丙烯酰胺；
(4)将步骤(3)的混合溶液进行烘干反应，得到基于木聚糖的双网络纳米复合水凝胶。
步骤(3)中所述水溶性钙盐中Ca2+与GO水分散液中GO的质量比为(10～240)mg:(20～60)mg，所述反应单体与木聚糖的质量比为(1～6)g：(0.5～1.5)g，所述GO水分散液中GO与木聚糖的质量比为(20～60)mg:(0.5～1.5)g。
步骤(3)中所述水溶性钙盐为CaCl2或硝酸钙。
步骤(4)中所述烘干反应的条件为在50～80℃烘干反应2～6h。
步骤(2)中所述加热搅拌的条件为于75～95℃下搅拌0.5h～1.5h，所述木聚 糖溶液的浓度为0.05g/mL～0.2g/mL；
步骤(1)中所述超声分散的温度为20℃～40℃；分散时间为2h～6h，超声的功率为100W～300W，频率为25kHz～80kHz。
步骤(1)中所述GO水分散液的浓度为0.4mg/mL～6mg/mL。
步骤(3)中所述引发剂为过硫酸铵或过硫酸钾；所述引发剂与反应单体的质量比为(0.01～0.05)g：(1～6)g。
步骤(3)中所述交联剂为N,N’-亚甲基双丙烯酰胺；所述交联剂与反应单体的质量比为(0.0025～0.03)g：(1～6)g。
步骤(3)中所述的促进剂为四甲基乙二胺或N,N,N’,N’-四亚甲基乙二胺；所述促进剂与反应单体的体积质量比为(10～50)uL：(1～6)g。
一种基于木聚糖的双网络纳米复合水凝胶，通过以上方法制备得到。
所述基于木聚糖的双网络纳米复合水凝胶的压缩强度为0.17MPa～2.3MPa,伸长率为629％～3967％。
所述基于木聚糖的双网络纳米复合水凝胶在生物医学领域，特别是组织工程、药物缓释、细胞培养支架以及软骨组织等方面的应用。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)本发明结合纳米复合水凝胶和双网络水凝胶的制备方法来制备高强度的水凝胶，以水做溶剂，以木聚糖为原料，以反应单体(丙烯酰胺为单体)接枝共聚形成一层网络，引入GO为增强填料，同时引入Ca2+与GO交联成另一层网络，不仅提高了水凝胶的机械强度，还改善了水凝胶的生物相容性和生物降解性；
(2)本发明的制备工艺采用一步合成法，操作简单，反应条件温和，反应条件易控制；
(3)本发明所得复合水凝胶有较高机械性能，同时可生物降解、具有良好的生物相容性，可应用在生物医学领域，如组织工程、药物缓释、细胞培养支架以及软骨组织等。
附图说明
图1为不同Ca2+含量的水凝胶(对比实施例1(1：Ca2+/GO＝0)、实施例1 (2：Ca2+/GO＝0.5)、实施例2(4：Ca2+/GO＝2)、实施例6(3：Ca2+/GO＝1)和实施例7(5：Ca2+/GO＝4))的压缩应力-应变曲线图；
图2为不同Ca2+含量的水凝胶(对比实施例1(1：Ca2+/GO＝0)、实施例1(2：Ca2+/GO＝0.5)、实施例2(4：Ca2+/GO＝2)、实施例6(3：Ca2+/GO＝1)和实施例7(5：Ca2+/GO＝4))的拉伸应力-应变曲线图；
图3为实施例2中GO/Ca2+/PAM/XH复合水凝胶的循环压缩应力应变曲线。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
对比例1
一种GO/PAM/XH水凝胶材料的制备方法，包括以下步骤：
(1)将20mg氧化石墨粉末(GO)加入10mL去离子水中，20℃下超声(100W，25kHz)分散4h，得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液；
(3)将4g单体丙烯酰胺(AM)，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.01g引发剂过硫酸铵，0.008g交联剂N,N’-亚甲基双丙烯酰胺和40uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，50℃下反应2h，得到复合水凝胶即GO/PAM/XH水凝胶材料。所述复合水凝胶性能测试曲线如图1和2所示。
本对比例所得GO/PAM/XH复合水凝胶在压缩形变达到95％时，最大压缩强度为0.17MPa，伸长率为629％。
实施例1
一种基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH水凝胶)材料的制备方法，包括以下步骤：
(1)将20mg氧化石墨粉末(GO)加入10mL去离子水中，20℃下超声 (100W，40kHz)分散4h，得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液；
(3)将27.75mg CaCl2，4g单体丙烯酰胺和木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.01g引发剂过硫酸铵，0.01g交联剂N,N’-亚甲基双丙烯酰胺和50uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，60℃下反应4h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。所述复合水凝胶性能测试曲线如图1和2所示。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为0.184MPa，伸长率为775％。
实施例2
一种基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)材料的制备方法，包括以下步骤：
1)将20mg氧化石墨粉末(GO)加入10mL去离子水中，30℃下超声(200W，40kHz)分散4h，得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液；
(3)将111mg CaCl2,4g单体丙烯酰胺，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.03g引发剂过硫酸铵，0.01g交联剂N,N’-亚甲基双丙烯酰胺和50uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，60℃下反应4h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。所述复合水凝胶性能测试曲线如图1、2和3所示。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没 有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为1.84MPa,伸长率为1918％。
实施例3
本实施例的一种基于木聚糖的纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)材料的制备方法，包括以下步骤：
1)将4mg氧化石墨粉末(GO)加入10mL去离子水中，30℃下超声(200W，40kHz)分散2h得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液；
(3)将22.2mg CaCl2,4g单体丙烯酰胺，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.03g引发剂过硫酸铵，0.01g交联剂N,N’-亚甲基双丙烯酰胺和20uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，60℃下反应4h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为1.1MPa,伸长率为1100％。
实施例4
本实施例的一种基于羧甲基木聚糖的纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)材料的制备方法，包括以下步骤：
1)将60mg氧化石墨粉末(GO)加入10mL去离子水中，40℃下超声(300W，80kHz)分散6h得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液。
(3)将166.5mg CaCl2,4g单体丙烯酰胺，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.05g引发剂过硫酸铵，0.01g交联剂N,N’-亚甲基双丙烯酰胺和50uL促进剂四甲基乙二胺，搅拌均匀， 得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，80℃下反应6h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为2.3MPa,伸长率为3310％。
实施例5
一种基于木聚糖的纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)材料的制备方法，包括以下步骤：
1)将60mg氧化石墨粉末(GO)加入10mL去离子水中，30℃下超声(300W，80kHz)分散6h得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液；
(3)将166.5mg CaCl2,4g单体丙烯酰胺，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.05g引发剂过硫酸铵，0.005g交联剂N,N’-亚甲基双丙烯酰胺和50uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，80℃下反应6h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为1.63MPa,伸长率为3976％。
实施例6
一种基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)材料的制备方法，包括以下步骤：
1)将20mg氧化石墨粉末(GO)加入10mL去离子水中，30℃下超声(200W，40kHz)分散4h，得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成 均匀的木聚糖溶液；
(3)将55.5mg CaCl2,4g单体丙烯酰胺，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.03g引发剂过硫酸铵，0.01g交联剂N,N’-亚甲基双丙烯酰胺和50uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，60℃下反应4h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。所述复合水凝胶性能测试曲线如图1和2所示。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为0.757MPa,伸长率为942％。
实施例7
一种基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)材料的制备方法，包括以下步骤：
1)将20mg氧化石墨粉末(GO)加入10mL去离子水中，30℃下超声(200W，40kHz)分散4h，得到GO水分散液；
(2)称取1g木聚糖，溶解于10mL的去离子水中，85℃下搅拌1h，形成均匀的木聚糖溶液；
(3)将222mg CaCl2,4g单体丙烯酰胺，木聚糖溶液加入到步骤(1)的GO水分散液中，冰浴条件下，搅拌分散均匀；加入0.03g引发剂过硫酸铵，0.01g交联剂N,N’-亚甲基双丙烯酰胺和50uL促进剂四甲基乙二胺，搅拌均匀，得到混合溶液；
(4)将步骤(3)中的混合溶液放入烘箱中，60℃下反应4h，得到基于木聚糖的双网络纳米复合水凝胶(GO/Ca2+/PAM/XH复合水凝胶)。所述复合水凝胶性能测试曲线如图1和2所示。
本实施例所得GO/Ca2+/PAM/XH复合水凝胶在压缩形变达到95％时，也没有发生断裂和破碎，压缩后能迅速恢复，水凝胶的压缩强度为0.175MPa,伸长率为630％。
图1和图2分别为不同Ca2+/GO的水凝胶(对比实施例1、实施例1、2、6、和7)的压缩应力应变曲线和拉伸应力应变曲线。可以看出，Ca2+的含量对GO/PAM/XH复合水凝胶的机械强度有较大的影响。当GO用量为20mg，交联剂用量为0.01g，不加Ca2+时，在压缩形变为95％时，最大压缩强度为0.17MPa，最大伸长率为629％。然而，将少量Ca2+(Ca2+/GO＝0.5～2)引入GO/PAM/XH水凝胶网络形成第二网络后，水凝胶的机械强度明显提高。当Ca2+/GO的比值由0.5增加到2时，在压缩形变为95％时，水凝胶也没有发生断裂和破碎，水凝胶的压缩强度由0.184MPa增加到1.84MPa，伸长率由775％增加到1918％，即当Ca2+的添加量是GO的2倍时，压缩强度提高到原来的10倍，伸长率提高到原来的近3倍。这是因为Ca2+与GO交联形成了另一层网络结构，XH与AM接枝共聚交联网络以及Ca2+与GO交联的两种网络链段之间可通过共价键相连接，使得GO/Ca2+/PAM/XH水凝胶显示了优异的机械性能以及很高的弹性和韧性。然而继续增加Ca2+的添加量(Ca2+/GO＝3～4)，水凝胶的压缩强度和伸长率都逐渐降低。当Ca2+/GO的比值由2增加到4时，在压缩形变为95％时，水凝胶的压缩强度由1.84MPa降低至0.37MPa，伸长率由1918％降低至942％。这是因为GO一方面作为新的化学交联点，另一方面与Ca2+结合形成另一网络，继续增加Ca2+的含量，使得化学交联点相对减少，导致了机械性能一定程度上的下降。由上可知，Ca2+与GO网络引入能有效提高水凝胶的机械强度，当Ca2+/GO＝2时，机械强度最好。
图3为实施例2中的GO/Ca2+/PAM/XH复合水凝胶的循环压缩应力应变曲线。当Ca2+/GO为2，GO用量为20mg，交联剂用量为0.01g，压缩形变为70％，水凝胶没有发生断裂和破碎，而且保持了很好的弹性，释放压力后，水凝胶能迅速恢复到原来的形状。循环压缩100次后，水凝胶几乎没有出现塑性变形和压缩强度的降低。这种高强度的水凝胶有望应用于生物医学领域，如组织工程、药物缓释、细胞培养支架以及软骨组织等。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于包括以下步骤：
    (1)将氧化石墨粉末加入去离子水中，超声分散，得到GO水分散液；
    (2)将木聚糖加入去离子水中，加热搅拌，得到木聚糖溶液；
    (3)将水溶性钙盐，反应单体和木聚糖溶液加入到GO水分散液中，冰浴条件下，搅拌分散均匀，加入引发剂、交联剂和促进剂，搅拌混合均匀，得到混合溶液；所述反应单体为丙烯酰胺、聚丙烯酰胺，丙烯酸，N-异丙烯酰胺、丙烯酸丁酯中的一种以上；
    (4)将步骤(3)的混合溶液进行烘干反应，得到基于木聚糖的双网络纳米复合水凝胶。
  2. 根据权利要求1所述基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于：步骤(3)中所述水溶性钙盐中Ca2+与GO水分散液中氧化石墨粉末的质量比为(10～240)mg:(20～60)mg，所述反应单体与木聚糖的质量比为(1～6)g：(0.5～1.5)g，所述GO水分散液中氧化石墨粉末与木聚糖的质量比为(20～60)mg:(0.5～1.5)g。
  3. 根据权利要求1所述基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于：步骤(3)中所述水溶性钙盐为CaCl2或硝酸钙；所述引发剂为过硫酸铵或过硫酸钾；所述交联剂为N,N’-亚甲基双丙烯酰胺；所述的促进剂为四甲基乙二胺或N,N,N’,N’-四亚甲基乙二胺。
  4. 根据权利要求1所述基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于：步骤(4)中所述烘干反应的条件为在50～80℃烘干反应2～6h；步骤(2)中所述加热搅拌的条件为于75～95℃下搅拌0.5h～1.5h。
  5. 根据权利要求1所述基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于：步骤(1)中所述GO水分散液的浓度为0.4mg/mL～6mg/mL；步骤(2)中所述木聚糖溶液的浓度为0.05g/mL～0.2g/mL。
  6. 根据权利要求1所述基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于：步骤(3)中所述引发剂与反应单体的质量比为(0.01～0.05)g：(1～6) g；步骤(3)中所述交联剂与反应单体的质量比为(0.0025～0.03)g：(1～6)g；步骤(3)中所述促进剂与反应单体的体积质量比为(10～50)uL：(1～6)g。
  7. 根据权利要求1所述基于木聚糖的双网络纳米复合水凝胶的制备方法，其特征在于：步骤(1)中所述超声分散的温度为20℃～40℃，分散时间为2h～6h；超声的功率为100W～300W，频率为25kHz～80kHz。
  8. 一种由权利要求1～7任一项所述制备方法制备得到的基于木聚糖的双网络纳米复合水凝胶。
  9. 根据权利要求8所述基于木聚糖的双网络纳米复合水凝胶在生物医学领域中应用。
  10. 根据权利要求9所述的应用，其特征在于：所述基于木聚糖的双网络纳米复合水凝胶在组织工程、药物缓释、细胞培养支架以及软骨组织方面的应用。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012127119A2 (en) * 2011-03-22 2012-09-27 Teknologian Tutkimuskeskus Vtt A method for making specific products from polysaccharide molecule
CN105461859A (zh) * 2015-12-29 2016-04-06 华南理工大学 一种基于羧甲基木聚糖的纳米复合水凝胶及制备与应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435951B (zh) * 2013-09-09 2016-04-27 江南大学 一种纳米复合高分子双网络水凝胶及其制备方法
US20160251470A1 (en) * 2013-10-14 2016-09-01 The University Of Akron Zwitterionic polysaccharide polymers having antifouling, antimicrobial and optical transparency properties
CN104262540B (zh) * 2014-09-19 2016-10-05 华南理工大学 一种温度和pH双重响应木聚糖基水凝胶及其制法与应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012127119A2 (en) * 2011-03-22 2012-09-27 Teknologian Tutkimuskeskus Vtt A method for making specific products from polysaccharide molecule
CN105461859A (zh) * 2015-12-29 2016-04-06 华南理工大学 一种基于羧甲基木聚糖的纳米复合水凝胶及制备与应用

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