掺杂钙银介孔氧化硅凝胶抗菌止血材料的研究

doi:10.3724/SP.J.1077.2012.00513

摘要/Abstract

摘要：

以十六烷基三甲基溴化铵(CTAB)为模板, 用溶胶-凝胶法合成了掺杂钙银介孔氧化硅凝胶(m-SCA)抗菌止血材料. 结果表明: m-SCA具有介孔结构, 比表面积为416 m²/g, 孔径在2 nm左右. 高比表面积的m-SCA具有很好的凝血功能, 能明显缩短血液的凝血酶原时间(PT)和部分凝血活酶时间(APTT). 含少量银的m-SCA对其凝血性能没有明显影响, 而m-SCA中的钙能促进凝血. 含银0.02wt%的m-SCA无细胞毒性, 对大肠杆菌有明显的抑制作用. 动物试验表明: m-SCA具有很好的止血性能, 能阻止兔耳伤口的流血并缩短其流血时间. m-SCA是一种有很好应用前景的抗菌止血材料.

关键词: 掺杂银, 掺杂钙, 氧化硅凝胶, 止血材料, 抗菌, 生物相容性

Abstract:

An antibacterial hemostatic material of mesoporous silicon oxide gel doped with Ca and Ag (m-SCA) gel was fabricated by using cetyltrimethylammonium bromide(CTAB) as templates and Sol-Gel process. The results showed that m-SCA with mesoporous structure had the surface area of 416 m²/g and pore size of around 2 nm. The m-SCA with high surface area and good clotting function could significantly shorten the prothrombin time (PT) and activated partial thromboplastin time (APTT). The m-SCA containing a small quantity of Ag had no obvious effects on its clotting properties while Ca in m-SCA could promote clotting. The m-SCA doped 0.02wt% Ag without cytotoxicity had good antibacterial properties against E.coli. Animal experimental results showed that the m-SCA could control hemorrhage and shorten the bleeding time of rabbit ear wound, showing good hemostatic properties. It suggestes that the m-SCA is a good hemostatic material with antibacterial properties.

Key words: Ag-doped, Ca-doped, mesoporous silicon oxide gel, hemostatic materials, antibacterial, biocompatibility

中图分类号:

R318

陈于, 李文锐, 徐灿, 苏佳灿, 李明, 刘昌胜. 掺杂钙银介孔氧化硅凝胶抗菌止血材料的研究[J]. 无机材料学报, 2012, 27(5): 513-518.

CHEN Yu, LI Wen-Rui, XU Can, SU Jia-Can, LI Ming, LIU Chang-Sheng. Study on Hemostatic Materials of Mesoporous Silicon Dioxide Doped Ca and Ag with Antibacterial Properties[J]. Journal of Inorganic Materials, 2012, 27(5): 513-518.

图/表 9

图1 掺杂钙银(a, b)和不掺杂钙银(c, d)的介孔氧化硅凝胶的微观形貌

Fig. 1 Micro-morphologies of mesoporous silicon dioxide gel doped with Ca and Ag (a,b) and without Ca and Ag(c,d)

图2 掺杂钙银(5wt% Ca, 0.02wt% Ag)介孔氧化硅凝胶的(a)N2吸附-脱附曲线和(b)孔径分布

Fig. 2 Nitrogen adsorption-desorption isoterms (a) and pore size distribution (b) of m-SCA (5wt% Ca, 0.02wt% Ag)

图3 掺杂钙银介孔氧化硅凝胶的吸水性能

Fig. 3 Water adsorption properties of m-SCA (m-SA and SD as controls)

图4 掺杂钙银介孔氧化硅在磷酸缓冲溶液中随时间而释放钙和银离子的情况

Fig. 4 m-SCA release Ca and Ag ions into PBS with time

图5 掺杂钙银介孔氧化硅的凝血性能(PT和APTT)

Fig.5 Clotting time (PT and APTT) of m-SCA(m-SA and SD as controls)

图6 钙含量对掺杂钙银介孔氧化硅凝胶的凝血性能(PT和APTT)的影响

Fig. 6 Effects of Ca content on clotting time (PT and APTT) of m-SCA

图7 银含量对掺杂钙银介孔氧化硅抗菌性能的影响: 大肠杆菌培养(a)1 h和(b)12 h

Fig. 7 Effects of Ag ontetent on antibacterial properties of m-SCA against E.coli incubation for 1h (a) and (b) 12 h

图8 掺杂钙银介孔氧化硅浸提液对L929细胞增殖的影响

Fig. 8 Effects of m-SCA extracts on L929 cell proliferation(m-SC and SD as controls)

图9 掺杂钙银介孔氧化硅覆盖伤口后, 耳部伤口的流血时间

Fig. 9 Bleeding time of ear wound after being applied by m-SCA(m-SC and SD as controls)

参考文献 19

[1]	Bjorsesa K, Holst J. Various local hemostatic agents with different modes of action; an in vivo comparative randomized vascular surgical experimental study. Eur. J. Vasc. Endovasc. , 2007, 33(3): 363-370.
[2]	Sohn V Y, Eckert M J, Martin M J, et al. Efficacy of three topical hemostatic agents applied by medics in a lethal groin injury model. J. Surg. Res. , 2009, 154(2): 258-261.
[3]	Humphreys M R, Castle E P,Andrews P E, et al. Microporous polysaccharide hemospheres for management of laparoscopic trocar injury to the spleen. Am. J. Sur., 2008, 195(1): 99-103.
[4]	Khalid AL-Qahtani. Initial experience with hemostatic fibrin glue as adjuvant during drainless parotidectomy. Saudi. Med. J. , 2011, 23(2): 67-71.
[5]	Hoffmann N E, Siddiqui S A, Agarwal S, et al. Choice of hemostatic agent influences adhesion formation in a rat cell adhesion model. J. Sur. Res., 2009, 155(1): 77-81.
[6]	Ong S Y, Wu J, Moochhala S M, et al. Development of a chitosan- based wound dressing with improved hemostatic and antimicrobial properties. Biomaterials, 2008, 29(32): 4323-4332.
[7]	Emily Blocha, Trang Phanb, Denis Bertinb, et al. Direct synthesis of mesoporous silica presenting large and tunable pores using BAB triblock copolymers: influence of each copolymer block on the porous structure. Micropor. Mesopor. Mat., 2007, 112(1/2/3): 612-620.
[8]	Dai Chenglong, Liu Changsheng, Wei Jie, et al. Molecular imprinted macroporous chitosan coated mesoporous silica xerogels for hemorrhage control. Biomaterials, 2010, 31(30):7620-7630.
[9]	LI Xiao-Sheng, LIU Chang-Sheng, YUAN Yuan, et al. Preparation and hemostatic properties of mesoporous silica-based xerogels. Journal of Inorganic Materials, 2008, 23(2): 327-331.
[10]	余承忠, 严晓霞, 赵东元. 新型的介孔分子筛止血材料及其制备方法. 中国发明专利, ZL200510026838. 9, 2006.02.01.
[11]	Hobday C D, Milam M R, Milam R A, et al. Postoperative small bowel obstruction associated with use of hemostatic agents. J. Minim. Invas. Gyn. , 2009, 16(2): 224-226.
[12]	Simon Silver. Bacterial silver resistance: molecular biology and uses and misuses of silver compounds. FEMS Microbiol. Rev., 2003, 27(2/3):341-353.
[13]	Percival S L, Bowler P G, Russell D. Bacterial resistance to silver in wound care. J. Hospl. Infect. , 2005, 60(1):1-7.
[14]	Dai Chenglong, Yuan Yuan, Liu Changsheng, et al. Degradable, antibacterial silver exchanged mesoporous silica spheres for hemorrhage control. Biomaterials, 2009, 30(29): 5364-5375.
[15]	Wei Jie, Chen Fangping, Shin Jung-Woog, et al. Preparation and chara- cte------rization of bioactive mesoporous wollastonit-polycaprolactone composite scaffold. Biomaterials, 2009, 30(6): 1080-1088.
[16]	Parveen Kumar, Vadim V Guliants. Periodic mesoporous organic-inorganic hybrid materials: applications in membrane separations and adsorption. Micropor. Mesopor. Mat., 2010, 132(1/2): 1-14.
[17]	Emily W Y Tam, Glenn Rosenbluth, Elizabeth E Rogers. Cerebellar hemorrhage on magnetic resonance imaging in preterm newborns associated with abnormal neurologic outcome. The Journal of Pediatrics, 2011, 158(2): 245-250.
[18]	Ostomel T A, Shi Q, Stoimenov P K, et al. Metal oxide surface charge mediated hemostasis. Langmuir, 2007, 23(22): 11233-11238.
[19]	Tuthill D D, Bayer V, Gallagher A M, et al. Assessment of topical hemostats in a renal hemorrhage model in heparinized rats. J. Surg. Res., 2001, 95(2): 126-132.