己唑醇/介孔SiO_2缓释纳米球的制备及其性能
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摘要
基于St?ber方法,制备出介孔SiO_2纳米球(MSNs)和树枝状介孔SiO_2纳米球(dMSNs),并以己唑醇(He)为模型农药,通过物理吸附方法分别制备了己唑醇/介孔SiO_2复合纳米球(He/MSNs)和己唑醇/树枝状介孔SiO_2复合纳米球(He/dMSNs)。采用透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FT-IR)对制备的介孔纳米球形貌和结构进行表征;利用Brunauer-Emmett-Teller (BET)气体吸附法对介孔二氧化硅纳米球和树枝状介孔二氧化硅纳米球的孔结构进行表征;通过热重分析(TG)、模拟释放实验和抑菌实验对制备的载药复合纳米球载药量、释药性能及药效进行研究。结果表明,MSNs和d MSNs的平均粒径分别为(210±10)和(235±10) nm,比表面积分别为1 092.867和1 289.110 m~2/g,孔容分别为0.690和0.814 cm~3/g,孔径分别为32.144和32.673?。He/MSNs和He/d MSNs载药率分别达到42%和84%,且缓释作用明显。He/MSNs和He/dMSNs(0.1 mg/m L)对可可毛色二孢菌均表现出良好的抑菌性能。
The chemical control is one of the most effective control methods for agriculture and forestry against pests and diseases. However,it also brings many problems such as pesticide residues,environmental pollution and drug resistance during the practical application. The sustained release pesticide has been considered as an effective method to solve the problems. Recently,the nanomaterials have been identified as potential targeted delivery carriers for pesticides.In particular,the mesoporous silica nanoparticles( MSNs) attributes include well defined and tunable pore sizes( 2-50 nm),large pore volumes,high surface areas,chemical stability,resistance to microbial attack,nanostructures that can be tailored,easily modified surface properties,biocompatibility,and aqueous degradability. In addition,MSNs protect loaded guest molecules against environmentally induced enzymatic degradation since no swelling or porosity changes occur in response to external stimuli,such as,pH and temperature. Furthermore,MSNs are excellent pesticide delivery carriers,as their structural properties can be modified to either enhance or slow down release kinetics.Arguably,MSNs offered great promise for the fabrication of stimulus responsive and targeted pesticide delivery scaffolds. In this study,MSNs and dendritic mesoporous SiO_2 nanospheres( dMSNs),fabricated by the St?ber method,were used as carrier materials to prepare hexaconzole/mesoporous SiO_2 composite nanospheres( He/MSNs) and hexaconzole/dendritic mesoporous SiO_2 composite nanospheres( He/dMSNs), respectively. The Transmission electron microscopy( TEM),laser particle size analyzer,fourier transform infrared spectroscopy( FT-IR),thermogravimetric analysis( TG),and nitrogen physisorption were used to analyze the morphology,structure,and the drug contents for the prepared nanospheres. The results showed that the size of the MSNs and dMSNs were( 210±10) nm and( 235±10) nm,respectively. The specific surface areas of the MSNs and dMSNs reached 1 092.867 m~2/g and1 289.110 m~2/g,the pores of volume were 0.690 cm~3/g and 0.814 cm~3/g,the pore diameters were 32.144 ? and32.673 . The drug loadings of the He/MSNs and He/dMSNs were about 42% and 84%,respectively. Both He/MSNs and He/dMSNs showed good sustained release in simulated release experiments by using methanol as the solvent.Furthermore,the hexaconzole loaded nanoshpheres( 0.1 mg/mL) showed good antibacterial properties against Lasiodiplodia theobromae. Therefore,the preparation of pesticide sustainedrelease nanospheres using MSNs and dMSNs as carriers can prolong the action time of the drug,increase the utilization rate of pesticides,declease the frequency of administration,lower the amount of pesticide application and reduce the pollution to environment,and can become an ideal class of pesticide sustainedrelease preparation.
The chemical control is one of the most effective control methods for agriculture and forestry against pests and diseases. However,it also brings many problems such as pesticide residues,environmental pollution and drug resistance during the practical application. The sustained release pesticide has been considered as an effective method to solve the problems. Recently,the nanomaterials have been identified as potential targeted delivery carriers for pesticides.In particular,the mesoporous silica nanoparticles( MSNs) attributes include well defined and tunable pore sizes( 2-50 nm),large pore volumes,high surface areas,chemical stability,resistance to microbial attack,nanostructures that can be tailored,easily modified surface properties,biocompatibility,and aqueous degradability. In addition,MSNs protect loaded guest molecules against environmentally induced enzymatic degradation since no swelling or porosity changes occur in response to external stimuli,such as,pH and temperature. Furthermore,MSNs are excellent pesticide delivery carriers,as their structural properties can be modified to either enhance or slow down release kinetics.Arguably,MSNs offered great promise for the fabrication of stimulus responsive and targeted pesticide delivery scaffolds. In this study,MSNs and dendritic mesoporous SiO_2 nanospheres( dMSNs),fabricated by the St?ber method,were used as carrier materials to prepare hexaconzole/mesoporous SiO_2 composite nanospheres( He/MSNs) and hexaconzole/dendritic mesoporous SiO_2 composite nanospheres( He/dMSNs), respectively. The Transmission electron microscopy( TEM),laser particle size analyzer,fourier transform infrared spectroscopy( FT-IR),thermogravimetric analysis( TG),and nitrogen physisorption were used to analyze the morphology,structure,and the drug contents for the prepared nanospheres. The results showed that the size of the MSNs and dMSNs were( 210±10) nm and( 235±10) nm,respectively. The specific surface areas of the MSNs and dMSNs reached 1 092.867 m~2/g and1 289.110 m~2/g,the pores of volume were 0.690 cm~3/g and 0.814 cm~3/g,the pore diameters were 32.144 ? and32.673 . The drug loadings of the He/MSNs and He/dMSNs were about 42% and 84%,respectively. Both He/MSNs and He/dMSNs showed good sustained release in simulated release experiments by using methanol as the solvent.Furthermore,the hexaconzole loaded nanoshpheres( 0.1 mg/mL) showed good antibacterial properties against Lasiodiplodia theobromae. Therefore,the preparation of pesticide sustainedrelease nanospheres using MSNs and dMSNs as carriers can prolong the action time of the drug,increase the utilization rate of pesticides,declease the frequency of administration,lower the amount of pesticide application and reduce the pollution to environment,and can become an ideal class of pesticide sustainedrelease preparation.
引文
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[10]赵文生,孙彦红,赵万明.改性沸石和膨润土对氟离子吸附性能研究[J].工业水处理,2016,36(2):82-85.DOI:10.11894/1005-829x.2016.36(2).082.ZHAO W S,SUN Y H,ZHAO W M.Study on the adsorption capacity of modified zeolite and bentonite for fluoride ions[J].Industrial Water Treatment,2016,36(2):82-85.
[11]SUN Z,LI H,CUI G,et al.Multifunctional magnetic core-shell dendritic mesoporous silicananospheres decorated with tiny Ag nanoparticles as a highly active heterogeneous catalyst[J].Applied SurfaceScience,2016(360):252-262.DOI:10.1016/j.apsusc.2015.11.013.
[12]穆静娟,焦加国,葛新成,等.植物病原真菌广谱拮抗菌M29的筛选、鉴定及其抑菌机制[J].南京农业大学学报,2017,40(1):84-92.DOI:10.7685/jnau.201604007.MU J J,JIAO J G,GE X C,et al.Isolation and identification of a plant pathogenic fungi and broad-spectrum antagonistic bacterium Bacillus subtilis M29 and its antibiotic mechanism[J].Journal of Nanjing Agricultural University,2017(1):84-92.
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[14]CHAUHAN N,DILBAGHI N,GOPAL M,et al.Development of chitosan nanocapsules for the controlled release of hexaconazole[J].International Journal of Biological Macromolecules,2017,97:616-624.DOI:10.1016/j.ijbiomac.2016.12.059.
[15]BOVEN G,OOSTERLING M L C M,CHAIIA G,et al.Grafting kinetics of poly(methyl methacrylate)on microparticulate silica[J].Polymer,1990,31(12):2377-2383.DOI:10.1016/0032-3861(90)90327-U.
[16]郑林萍,许光宇,石莹莹,等.介孔二氧化硅复合纳米球的制备及药物控释应用[J].河南科技大学学报(自然科学版),2017,38(2):99-104.DOI:10.15926/j.cnki.issn1672-6871.2017.02.019.ZHEN L P,XU G Y,SHI Y Y,et al.Preparation of mesoporous silica composite microspheres and its application to drug controlled release[J].Journal of Henan University of Science&Technology(Natural Science),2017,38(2):99-104.
[17]GAO Y,KAZIEM A E,ZHANG Y,et al.A hollow mesoporous silica and poly(diacetone acrylamide)composite with sustainedrelease and adhesion properties[J].Microporous&Mesoporous Materials,2017,255.DOI:10.1016/j.micromeso.2017.07.025.
[2]TSUJI K.Microencapsulation of pesticides and their improved handling safety[J].Journal of Microencapsulation,2001,18(2):137-147.DOI:10.1080/026520401750063856.
[3]杨淑珍.农药缓释剂研究进展[J].山西农业科学,2012,40(2):186-188.DOI:10.3969/j.issn.1002-2481.2012.02.26.YANG S Z.Research progress about pesticide release[J].Shanxi Agricultural Sciences,2012,40(2):186-188.
[4]缪昌文,冉千平,洪锦祥,等.聚羧酸系高性能减水剂的研究现状及发展趋势[J].中国材料进展,2009,28(11):36-45.MIAO C W,RAN Q P,HONG J X,et al.Present situation and developmental trends of polycarboxylate-type superplasticizers[J].Materials China,2009,28(11):36-45.
[5]KAZUHIRO Y,ETSUO S,MASAKI D,et al.Role of steric hindrance in the performance of superplasticizers for concrete[J].Journal of the American Ceramic Society,1997,80(10):2667-2671.DOI:10.1111/j.1151-2916.1997.tb03169.x.
[6]LIU X,WANG Z,ZHU J,et al.Synthesis,characterization and performance of a polycarboxylate superplasticizer with amide structure[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014(448):119-129.DOI:10.1016/j.colsurfa.2014.02.022.
[7]马莉,吴光耀,陈君,等.二氧化硅负载磷钨酸催化罗汉柏木烯的异构反应[J].林业工程学报,2017,2(6):60-66.DOI:10.13360/j.issn.2096-1359.2017.06.011.MA L,WU G Y,CHEN J,et al.Silica-supported phosphotungstic acids catalyze isomerization reaction of thujopsene[J].Journal of Forestry Engineering,2017,2(6):60-66.
[8]BARRETO A S,AQUINO A,SILVA S C S,et al.A novel application of mesoporous silica material for extraction of pesticides[J].Materials Letters,2011,65(9):1357-1359.DOI:10.1016/j.matlet.2011.01.082.
[9]JU C,XU J,WU X,et al.Effects of hexaconazole application on soil microbes community and nitrogen transformations in paddy soils[J].Science of the Total Environment,2017,609:655-663.DOI:10.1016/j.scitotenv.2017.07.146.
[10]赵文生,孙彦红,赵万明.改性沸石和膨润土对氟离子吸附性能研究[J].工业水处理,2016,36(2):82-85.DOI:10.11894/1005-829x.2016.36(2).082.ZHAO W S,SUN Y H,ZHAO W M.Study on the adsorption capacity of modified zeolite and bentonite for fluoride ions[J].Industrial Water Treatment,2016,36(2):82-85.
[11]SUN Z,LI H,CUI G,et al.Multifunctional magnetic core-shell dendritic mesoporous silicananospheres decorated with tiny Ag nanoparticles as a highly active heterogeneous catalyst[J].Applied SurfaceScience,2016(360):252-262.DOI:10.1016/j.apsusc.2015.11.013.
[12]穆静娟,焦加国,葛新成,等.植物病原真菌广谱拮抗菌M29的筛选、鉴定及其抑菌机制[J].南京农业大学学报,2017,40(1):84-92.DOI:10.7685/jnau.201604007.MU J J,JIAO J G,GE X C,et al.Isolation and identification of a plant pathogenic fungi and broad-spectrum antagonistic bacterium Bacillus subtilis M29 and its antibiotic mechanism[J].Journal of Nanjing Agricultural University,2017(1):84-92.
[13]SHE X D,CHEN L J,VELLEMAN L,et al.Fabrication of high specificity hollow mesoporous silica nanoparticles assisted by Eudragit for targeted drug delivery[J].Journal of Colloid&Interface Science,2015,445:151-160.DOI:10.1016/j.jcis.2014.12.053.
[14]CHAUHAN N,DILBAGHI N,GOPAL M,et al.Development of chitosan nanocapsules for the controlled release of hexaconazole[J].International Journal of Biological Macromolecules,2017,97:616-624.DOI:10.1016/j.ijbiomac.2016.12.059.
[15]BOVEN G,OOSTERLING M L C M,CHAIIA G,et al.Grafting kinetics of poly(methyl methacrylate)on microparticulate silica[J].Polymer,1990,31(12):2377-2383.DOI:10.1016/0032-3861(90)90327-U.
[16]郑林萍,许光宇,石莹莹,等.介孔二氧化硅复合纳米球的制备及药物控释应用[J].河南科技大学学报(自然科学版),2017,38(2):99-104.DOI:10.15926/j.cnki.issn1672-6871.2017.02.019.ZHEN L P,XU G Y,SHI Y Y,et al.Preparation of mesoporous silica composite microspheres and its application to drug controlled release[J].Journal of Henan University of Science&Technology(Natural Science),2017,38(2):99-104.
[17]GAO Y,KAZIEM A E,ZHANG Y,et al.A hollow mesoporous silica and poly(diacetone acrylamide)composite with sustainedrelease and adhesion properties[J].Microporous&Mesoporous Materials,2017,255.DOI:10.1016/j.micromeso.2017.07.025.