纤维素山梨酸酯膜的制备及其抗菌性能研究
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摘要
以木浆纤维素为原材料、山梨酸为抗菌剂、二环己基碳二亚胺为脱水缩合剂,通过一步原位反应和相转化成膜技术制得抗菌纤维素山梨酸酯膜.采用傅里叶红外光谱(FTIR)、X-射线光电子能谱(XPS)、固体核磁分析(NMR)、 X-射线衍射光谱(XRD)、热重分析(TG-DTG)、示差扫描量热分析(DSC)等对其结构和性能进行表征. FTIR和XPS的测试结果表明通过酯化反应成功制得纤维素山梨酸酯膜.但是酯化反应过程会导致纤维素的晶胞类型和晶体结构发生改变. TG和DSC的研究结果显示,山梨酰基的引入一定程度上降低或破坏了纤维素分子内及分子间的氢键作用,使得改性后的纤维素山梨酸酯膜的热稳定性略有降低.动态接触抗菌测试结果表明,纤维素山梨酸酯对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌作用,对大肠杆菌和金黄色葡萄球菌的抑菌率分别达到90.4%～100%和99.2%～100%,特别地,对金黄色葡萄球菌的抑菌效果优于对大肠杆菌的抑菌效果.
Cellulose has attracted considerable attention due to its unique advantages such as abundant availability,renewability,non-pollution,and biocompatibility.However,β-glucose units in cellulose backbone are vulnerable to erosion and degradation by aquatic microorganisms.The antibacterial modification of cellulose was proposed by covalently introducing sorbic acid through esterification process.Antibacterial cellulose sorbate films were prepared by one-step in situ reaction and immersion precipitation phase inversion process with wood-pulp cellulose as raw material,sorbic acid as antibacterial agent,and N,N'-dicyclohexylcarbodiimide(DCC) as dehydrating agent to improve its antibacterial performance.Among them,the molar ratio of hydroxyl in cellulose to sorbic acid was 1:2,the reaction temperature was 80 °C and the reaction time was 4,6,8,10 and 12 h,respectively.The casting solutions were casted with casting knife of 250 μm thickness.And then antibacterial cellulose sorbate films were obtained after solvents evaporation and immersion precipitation process.The structure and performances of the obtained cellulose sorbate films were characterized by various methods such as Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),thermogravimetric analysis(TG-DTG) and differential scanning calorimetry analysis(DSC).The new characteristic peak of ester group(1715 cm-1) in FTIR spectra indicated that cellulose sorbate films were successfully prepared by esterification reaction.XPS and 13C-NMR analysis results also showed the synthesis of cellulose sorbate.However,the crystal type and structure of cellulose had changed during esterification process.The results of TG and DSC showed that the effect of intra-and inter-molecular hydrogen bonds in cellulose were reduced or destroyed by the introduction of sorbic-acyl,leading to slightly lower thermal stability of the cellulose sorbate films.The dynamic contact antibacterial test results indicated that cellulose sorbate films had inhibitory effect on E.coli and S.aureus and possessed higher inhibition rate against S.aureus(99.2%-100%) than that of E.coli(90.4%-100%) due to different cell wall structures of E.coli and S.aureus.Therefore,the synthesized cellulose sorbate may have some potential applications in packing,environmental coatings,as well as some functional materials.
Cellulose has attracted considerable attention due to its unique advantages such as abundant availability,renewability,non-pollution,and biocompatibility.However,β-glucose units in cellulose backbone are vulnerable to erosion and degradation by aquatic microorganisms.The antibacterial modification of cellulose was proposed by covalently introducing sorbic acid through esterification process.Antibacterial cellulose sorbate films were prepared by one-step in situ reaction and immersion precipitation phase inversion process with wood-pulp cellulose as raw material,sorbic acid as antibacterial agent,and N,N'-dicyclohexylcarbodiimide(DCC) as dehydrating agent to improve its antibacterial performance.Among them,the molar ratio of hydroxyl in cellulose to sorbic acid was 1:2,the reaction temperature was 80 °C and the reaction time was 4,6,8,10 and 12 h,respectively.The casting solutions were casted with casting knife of 250 μm thickness.And then antibacterial cellulose sorbate films were obtained after solvents evaporation and immersion precipitation process.The structure and performances of the obtained cellulose sorbate films were characterized by various methods such as Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),thermogravimetric analysis(TG-DTG) and differential scanning calorimetry analysis(DSC).The new characteristic peak of ester group(1715 cm-1) in FTIR spectra indicated that cellulose sorbate films were successfully prepared by esterification reaction.XPS and 13C-NMR analysis results also showed the synthesis of cellulose sorbate.However,the crystal type and structure of cellulose had changed during esterification process.The results of TG and DSC showed that the effect of intra-and inter-molecular hydrogen bonds in cellulose were reduced or destroyed by the introduction of sorbic-acyl,leading to slightly lower thermal stability of the cellulose sorbate films.The dynamic contact antibacterial test results indicated that cellulose sorbate films had inhibitory effect on E.coli and S.aureus and possessed higher inhibition rate against S.aureus(99.2%-100%) than that of E.coli(90.4%-100%) due to different cell wall structures of E.coli and S.aureus.Therefore,the synthesized cellulose sorbate may have some potential applications in packing,environmental coatings,as well as some functional materials.
引文
1Sheridan C.Nat Biotechnol,2013,31(10):870-873
2Eichhorn S J,Young R J,Davies G R.Biomacromolecules,2005,6(1):507-513
3Klemm D,Heublein B,Fink H,Bohn A.Angew Chem Int Ed,2005,44(22):3358-3393
4Tizzotti M,Charlot A,Fleury E,Stenzel M,Bernard J.Macromol Rapid Commun,2010,31(20):1751-1772
5Wu R L,Wang X L,Wang Y Z,Bian X C,Li F.Ind Eng Chem Res,2009,48(15):7132-7136
6Yang Q,Fukuzumi H,Saito T,lsogai A,Zhang L.Biomacromolecules,2011,12(7):2766-2771
7Campos C A,Gerschenson L N,Flores S K.Food Bioprocess Technol,2011,4(6):849-875
8Muenduen P,Nirun J.Carbohyd Polym,2008,74(3):482-488
9Cruz-Romero M C,Murphy T,Morris M,Cummins E,Kerry J P.Food Control,2013,34(2):393-397
10Li S M,Jia N,Ma M G,Zhang Z,Liu Q H,Sun R C.Carbohyd Polym,2011,86(2):441-447
11Daoud W A,Xin J H,Zhang Y H.Surf Sci,2005,599(1):69-75
12Fu F,Li L,Liu L,Cai J,Zhang Y,Zhou J,Zhang L.ACS Appl Mater Interfaces,2015,7(4):2597-2606
13Bao Wenyi(鲍文毅),Xu Chen(徐晨),Song Fei(宋飞),Wangm Xiuli(汪秀丽),Wang Yuzhong(王玉忠).Acta Polymerica Sinica(高分子学报),2015,(1):49-56
14Xu W Z,Gao G Z,Kadla J F.Cellulose,2013,20(3):1187-1199
15Kawabata A,Taylor J A.Carbohyd Polym,2007,67(3):375-389
16Jipa I M,Stoica-Guzun A,Stroescu M.LWT-Food Sci Technol,2012,47(2):400-406
17Dobre L M,Stoica-Guzun A,Stroescu M,Jipa I M,Dobre T,Ferdes M,Ciumpiliac S.Chem Pap,2012,66(2):144-151
18Zhang Mingxin(张明新),Zhu Tianrong(朱天容),Tang Kai(唐开),Hu Siqian(胡思前),Wang Liang(王亮),Yang Ziran(杨自然).Guangzhou Chemical Industry(广州化工),2016,44(14):55-58
19Zheng Y,Song J,Cheng B,Fang X.Fiber Polym,2016,17(1):1-8
20Wu J,Zhang J,Zhang H,He J,Ren Q,Guo M.Biomacromolecules,2004,5(2):266-268
21Heinze T,Liebert T.Prog Polym Sci,2001,26(9):1689-1762
22Dorn S,Pfeifer A,Schlufter K,Heinze T.Polym Bull,2010,64(9):845-854
23Zhang Jingqiang(张景强),Lin Lu(林鹿),He Beihai(何北海),Liu Shijie(刘世界),OuYang Ping-kai(欧阳平凯).Journal of South China University of Technology(华南理工大学学报),2009,37(6):17-21
24Dorris G M,Gray D G.Cell Chem Technol,1978,12:9-23
25Dorris G M,Gray D G.Cell Chem Technol,1978,12:721-734
26Song J L,Liang J,Liu X M,Wendy E K,Juan P H,Orlando J R.Thin Solid Films,2009,517(15):4348-4354
27Cai Jie(蔡杰),Lv Ang(吕昂),Zhou Jinping(周金平),Zhang Lina(张丽娜).Cellulose Science and Materials(纤维素科学与材料).Beijing(北京):Chemical Industry Press(化学工业出版社),2014.82-113
28Zhan Huaiyu(詹怀宇),Li Zhiqiang(李志强),Cai Zaisheng(蔡再生).Fiber Chemistry and Physics(纤维化学与物理).Beijing(北京):Science Press(科学出版社),2005.104-109
29Li Xiqi(李茜琪),Yao Xueliang(姚雪亮),Wang Haifeng(王海风).Materials Review(材料导报),2010,24(s2):72-74
30Agustin M B,Nakatsubo F,Yano H.Carbohyd Polym,2018,192:28-36
31Sinha N,Gupta M K,Goel N,Kumar B.Physica B,2011,406(21):4068-4076
32Kimura M,Hatakeyama T,Nakano J.J Appl Polym Sci,1974,18(10):3069-3076
33Ning Zhengxiang(宁正祥),Tan Longfei(谭龙飞),Zhang Decong(张德聪),Fu Hang(付航),Wang Yijun(王毅军),Gao Jianhua(高建华).Chinese Journal of Applied Chemistry(应用化学),1996,(1):38-42
34Ning Zhengxiang(宁正祥),Gao Jianhua(高建华).Modern Food Science and Technology(现代食品科技),1997,(3):1-4
35Narasimhan B,Judge V,Narang R,Ohlan R,Ohlan S.Bioorg Med Chem Lett,2007,17(21):5836-5845
36Huang Zhiliang(黄志良).Studies on the Synthesis and Anti-microbial Activity of Sorbic Acid Derivatives(山梨酸衍生物的合成与抗菌活性研究).Doctoral Dissertation of South China University of Technology(华南理工大学博士学位论文),2002.
37Stratford M,Anslow P A.Lett Appl Microbiol,1998,27:203-206
38Brul S,Coote P.Int J Food Microbiol,1999,50(1-2):1-17
39Abee T,Krockel L,Hill C.Int J Food Microbiol,1995,28(2):169-185
2Eichhorn S J,Young R J,Davies G R.Biomacromolecules,2005,6(1):507-513
3Klemm D,Heublein B,Fink H,Bohn A.Angew Chem Int Ed,2005,44(22):3358-3393
4Tizzotti M,Charlot A,Fleury E,Stenzel M,Bernard J.Macromol Rapid Commun,2010,31(20):1751-1772
5Wu R L,Wang X L,Wang Y Z,Bian X C,Li F.Ind Eng Chem Res,2009,48(15):7132-7136
6Yang Q,Fukuzumi H,Saito T,lsogai A,Zhang L.Biomacromolecules,2011,12(7):2766-2771
7Campos C A,Gerschenson L N,Flores S K.Food Bioprocess Technol,2011,4(6):849-875
8Muenduen P,Nirun J.Carbohyd Polym,2008,74(3):482-488
9Cruz-Romero M C,Murphy T,Morris M,Cummins E,Kerry J P.Food Control,2013,34(2):393-397
10Li S M,Jia N,Ma M G,Zhang Z,Liu Q H,Sun R C.Carbohyd Polym,2011,86(2):441-447
11Daoud W A,Xin J H,Zhang Y H.Surf Sci,2005,599(1):69-75
12Fu F,Li L,Liu L,Cai J,Zhang Y,Zhou J,Zhang L.ACS Appl Mater Interfaces,2015,7(4):2597-2606
13Bao Wenyi(鲍文毅),Xu Chen(徐晨),Song Fei(宋飞),Wangm Xiuli(汪秀丽),Wang Yuzhong(王玉忠).Acta Polymerica Sinica(高分子学报),2015,(1):49-56
14Xu W Z,Gao G Z,Kadla J F.Cellulose,2013,20(3):1187-1199
15Kawabata A,Taylor J A.Carbohyd Polym,2007,67(3):375-389
16Jipa I M,Stoica-Guzun A,Stroescu M.LWT-Food Sci Technol,2012,47(2):400-406
17Dobre L M,Stoica-Guzun A,Stroescu M,Jipa I M,Dobre T,Ferdes M,Ciumpiliac S.Chem Pap,2012,66(2):144-151
18Zhang Mingxin(张明新),Zhu Tianrong(朱天容),Tang Kai(唐开),Hu Siqian(胡思前),Wang Liang(王亮),Yang Ziran(杨自然).Guangzhou Chemical Industry(广州化工),2016,44(14):55-58
19Zheng Y,Song J,Cheng B,Fang X.Fiber Polym,2016,17(1):1-8
20Wu J,Zhang J,Zhang H,He J,Ren Q,Guo M.Biomacromolecules,2004,5(2):266-268
21Heinze T,Liebert T.Prog Polym Sci,2001,26(9):1689-1762
22Dorn S,Pfeifer A,Schlufter K,Heinze T.Polym Bull,2010,64(9):845-854
23Zhang Jingqiang(张景强),Lin Lu(林鹿),He Beihai(何北海),Liu Shijie(刘世界),OuYang Ping-kai(欧阳平凯).Journal of South China University of Technology(华南理工大学学报),2009,37(6):17-21
24Dorris G M,Gray D G.Cell Chem Technol,1978,12:9-23
25Dorris G M,Gray D G.Cell Chem Technol,1978,12:721-734
26Song J L,Liang J,Liu X M,Wendy E K,Juan P H,Orlando J R.Thin Solid Films,2009,517(15):4348-4354
27Cai Jie(蔡杰),Lv Ang(吕昂),Zhou Jinping(周金平),Zhang Lina(张丽娜).Cellulose Science and Materials(纤维素科学与材料).Beijing(北京):Chemical Industry Press(化学工业出版社),2014.82-113
28Zhan Huaiyu(詹怀宇),Li Zhiqiang(李志强),Cai Zaisheng(蔡再生).Fiber Chemistry and Physics(纤维化学与物理).Beijing(北京):Science Press(科学出版社),2005.104-109
29Li Xiqi(李茜琪),Yao Xueliang(姚雪亮),Wang Haifeng(王海风).Materials Review(材料导报),2010,24(s2):72-74
30Agustin M B,Nakatsubo F,Yano H.Carbohyd Polym,2018,192:28-36
31Sinha N,Gupta M K,Goel N,Kumar B.Physica B,2011,406(21):4068-4076
32Kimura M,Hatakeyama T,Nakano J.J Appl Polym Sci,1974,18(10):3069-3076
33Ning Zhengxiang(宁正祥),Tan Longfei(谭龙飞),Zhang Decong(张德聪),Fu Hang(付航),Wang Yijun(王毅军),Gao Jianhua(高建华).Chinese Journal of Applied Chemistry(应用化学),1996,(1):38-42
34Ning Zhengxiang(宁正祥),Gao Jianhua(高建华).Modern Food Science and Technology(现代食品科技),1997,(3):1-4
35Narasimhan B,Judge V,Narang R,Ohlan R,Ohlan S.Bioorg Med Chem Lett,2007,17(21):5836-5845
36Huang Zhiliang(黄志良).Studies on the Synthesis and Anti-microbial Activity of Sorbic Acid Derivatives(山梨酸衍生物的合成与抗菌活性研究).Doctoral Dissertation of South China University of Technology(华南理工大学博士学位论文),2002.
37Stratford M,Anslow P A.Lett Appl Microbiol,1998,27:203-206
38Brul S,Coote P.Int J Food Microbiol,1999,50(1-2):1-17
39Abee T,Krockel L,Hill C.Int J Food Microbiol,1995,28(2):169-185