Preparation and photo-thermal controlled release properties of nanodiamond/yeast-chitosan composite microspheres
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摘要: 开发高性能功能性光热凝胶并建立药物控释模型对农药智能输送材料的开发具有重要意义。以酵母-壳聚糖水凝胶(YS-CS)为基体,引入光热材料纳米金刚石(DND),通过碱凝胶法合成了纳米金刚石/酵母-壳聚糖(DND/YS-CS)交联网络结构复合凝胶微球,研究了复合微球的微观结构、力学性能和光热转换性能;以吲哚丁酸(IBA)为模型药物,探讨DND/YS-CS对IBA的负载性能和控释性能,揭示复合微球对IBA的光热控释机制。结果表明:复合微球具有良好的力学性能,在分别超声和离心1 h后,DND含量为2.0 mg/mL复合微球保水能力分别达到70.5%和74%;复合微球具有良好的光热转换能力,一个太阳光强度下,最高温度可达37.6℃;DND含量为1.2 mg/mL复合微球对IBA的吸附量最高,可达到41.73 μg/mg;微球在光下药物释放模式符合Korsmeyer-Peppas模型,在光下具有明显的刺激响应行为,药物释放呈现“开-关”模式。通过控制光的照射强度控制药物释放,在农业领域有广阔的应用前景。Abstract: It is important to develop high-performance functional photo-thermal materials and establish controlled drug release models for the development of intelligent transportation materials for pesticides. Herein, nanodiamond (DND) was employed to prepare novel nanodiamond/yeast-chitosan (DND/YS-CS) composite hydrogel microspheres which had a cross-linked network structure through alkali gelation method. The microstructure, mechanical resistance and photo-thermal conversion performance of the composites were investigated. Moreover, indole-3-butyric acid (IBA) was used as a model to discuss the loading and controlled drug release and reveal the photo-thermal controlled release mechanism of IBA by DND/YS-CS. The results show that the composite microspheres has good mechanical properties, and the water retention capacity of the composite microspheres with DND content of 2.0 mg/mL reached 70.5% and 74% after ultrasonication and centrifugation for 1 h, respec-tively. The maximum temperature of the composites can reach to 37.6℃ under one sunlight intensity, proving that the composites possess excellent photothermal conversion ability. The maximum adsorption of IBA is 41.73 μg/mg when the composites have a DND concentration of 1.2 mg/mL. Finally, the controled drug release pattern of the composites is in accordance with the Korsmeyer-Peppas model, which exhibits an obvious stimulus response behavior and an "on-off" pattern of drug release under light.
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Key words:
- nanodiamond /
- chitosan /
- composite hydrogel microsphere /
- photo-thermal properties /
- drug release
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图 3 DND (a)、CS (b) 和YS (d) 的照片;(c) DND的TEM图像;(e) 溶胀平衡的复合材料(湿)和干燥后的复合材料(干)照片;CS ((f), (g))、DND/YS-CS ((h), (i)) 的SEM图像;YS-CS (j)、DND/YS-CS (k) 的截面及相应的元素分布图
Figure 3. Photographs of DND (a), CS (b) and YS (d); (c) TEM image of DND; (e) Photograph of dissolution equilibrium composite (wet) and dried composite (dry); SEM images of CS ((f), (g)), DND/YS-CS ((h), (i)); Cross sections and the corresponding elemental distributions of YS-CS (j), DND/YS-CS (k)
图 5 (a) DND、YS-CS和DND/YS-CS的紫外可见漫反射光谱图;(b)纯水和1.2 mg/mL DND溶液的温度变化图;100 mW/cm2下不同DND含量DND/YS-CS复合微球的红外热成像图(c)及相应的温度随时间变化图(d)
Figure 5. (a) UV-vis diffuse reflectance spectra of DND, YS-CS and DND/YS-CS; (b) Temperature variation of pure water and 1.2 mg/mL DND solution; Infrared thermal imaging (c) of DND/YS-CS microspheres with different contents of DND under irradiation 100 mW/cm2 and the corresponding temperature variation (d)
图 7 (a) 不同DND含量DND/YS-CS复合微球在光下的IBA释放及其相对应的模型:(b) 一级模型;(c) Korsmeyer-Peppas模型;(d) Higuchi模型
Figure 7. (a) IBA release from DND/YS-CS composite microspheres with different contents of DND under light and their corresponding models: (b) Primary model; (c) Korsmeyer-Peppas model; (d) Higuchi model
Mt, M∞—Cumulative amount of drug released at time t and equilibrium, respectively (μg/mL)
表 1 不同动力学模型相对应的参数
Table 1. Parameters corresponding to different dynamics models
Sample/
(mg·mL−1)Primary model Korsmeyer-Peppas model Higuchi model K R2 K R2 n K R2 0 0.0353 0.8326 2.5592 0.9454 0.4677 11.129 0.9436 0.4 0.0600 0.7889 40.1852 0.9474 0.5580 11.490 0.9135 0.8 0.0623 0.8045 25.0882 0.9491 0.5346 13.146 0.9278 1.2 0.0654 0.7799 46.9132 0.9258 0.5241 14.143 0.8676 2.0 0.0625 0.7647 46.0717 0.9297 0.5347 13.173 0.8880 Notes: K—Release kinetic constant; n—Diffusional exponent characteristic to describe the release mechanism; R2—Coefficient of association. -
[1] ZHAO M, ZHOU H, CHEN L, et al. Carboxymethyl chitosan grafted trisiloxane surfactant nanoparticles with pH sensitivity for sustained release of pesticide[J]. Carbohydrate Polymers,2020,243:116433. doi: 10.1016/j.carbpol.2020.116433 [2] MICHALIK R, WANDZIK I. A mini-review on chitosan-based hydrogels with potential for sustainable agricultural applications[J]. Polymers, 2020, 12(10): 2425. [3] VAKILI M, RAFATULLAH M, SALAMATINIA B, et al. Application of chitosan and its derivatives as adsorbents for dye removal from water and wastewater: A review[J]. Carbohydrate Polymers,2014,113:115-130. doi: 10.1016/j.carbpol.2014.07.007 [4] QU B, LUO Y C. Chitosan-based hydrogel beads: Preparations, modifications and applications in food and agriculture sectors-A review[J]. International Journal of Biologi-cal Macromolecules,2020,152:437-448. doi: 10.1016/j.ijbiomac.2020.02.240 [5] LZA B, YW B, ZL A, et al. Characteristics of equilibrium, kinetics studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic chitosan microspheres[J]. Journal of Hazardous Materials,2009,161(2-3):995-1002. doi: 10.1016/j.jhazmat.2008.04.078 [6] MONVISADE P, SIRIPHANNON P. Chitosan intercalated montmorillonite: Preparation, characterization and cationic dye adsorption[J]. Applied Clay Science,2009,42(3-4):427-431. doi: 10.1016/j.clay.2008.04.013 [7] FENG D, BAI B, WANG H, et al. Enhanced mechanical stability and sensitive swelling performance of chitosan/yeast hybrid hydrogel beads[J]. New Journal of Chemistry,2016,40(4):3350-3362. doi: 10.1039/C5NJ02404H [8] OMIDI S, PIRHAYATI M, KAKANEJADIFARD A. Co-delivery of doxorubicin and curcumin by a pH-sensitive, injectable, and in situ hydrogel composed of chitosan, graphene, and cellulose nanowhisker[J]. Carbohydrte Polymers,2020,231:115745. doi: 10.1016/j.carbpol.2019.115745 [9] WANG Y, LIU S, YU W. Functionalized graphene oxide-reinforced chitosan hydrogel as biomimetic dressing for wound healing[J]. Macromol Biosci,2021,21(4):e2000432. doi: 10.1002/mabi.202000432 [10] ZHANG L, BAI B, HU N, et al. Efficient 3D-interfacial solar steam generation enabled by photothermal nanodiamonds paint-coat with optimized heat management[J]. Applied Thermal Engineering,2020,171:115059. doi: 10.1016/j.applthermaleng.2020.115059 [11] MEI M, BAI B, ZHENG D, et al. Novel fabrication of a yeast biochar-based photothermal-responsive platform for controlled imidacloprid release[J]. RSC Advances,2021,11(32):19395-19405. doi: 10.1039/D1RA02143E [12] ŌSAWA E. Monodisperse single nanodiamond particulates[J]. Pure and Applied Chemistry,2008,80(7):1365-1379. doi: 10.1351/pac200880071365 [13] ZHENG D, BAI B, XU X, et al. Fabrication of detonation nanodiamond@sodium alginate hydrogel beads and their performance in sunlight-triggered water release[J]. RSC Advances,2019,9(48):27961-27972. doi: 10.1039/C9RA03914G [14] FRICK E M, STRADER L C. Roles for IBA-derived auxin in plant development[J]. Journal of Experimental Botany,2018,69(2):169-177. doi: 10.1093/jxb/erx298 [15] ZHENG D, BAI B, HE Y, et al. Synthesis and characterization of dopamine-modified Ca-alginate/poly(N-isopropylacrylamide) microspheres for water retention and multi-responsive controlled release of agrochemicals[J]. International Journal of Biological Macromolecules,2020,160:518-530. doi: 10.1016/j.ijbiomac.2020.05.234 [16] ZHENG D, BAI B, ZHAO H, et al. Stimuli-responsive Ca-alginate-based photothermal system with enhanced foliar adhesion for controlled pesticide release[J]. Colloids Surfaces B: Biointerfaces,2021,207:112004. doi: 10.1016/j.colsurfb.2021.112004 [17] LIU Y, SUI Y, LIU C, et al. A physically crosslinked polydopamine/nanocellulose hydrogel as potential versatile vehicles for drug delivery and wound healing[J]. Carbohydrate Polymers,2018,188:27-36. doi: 10.1016/j.carbpol.2018.01.093 [18] WANG L, LI B, XU F, et al. UV-crosslinkable and thermo-responsive chitosan hybrid hydrogel for NIR-triggered localized on-demand drug delivery[J]. Carbohydrate Polymers,2017,174:904-914. doi: 10.1016/j.carbpol.2017.07.013 [19] SONG R, ZHENG J, LIU Y, et al. A natural cordycepin/chitosan complex hydrogel with outstanding self-healable and wound healing properties[J]. International Journal of Biological Macromolecules,2019,134:91-99. doi: 10.1016/j.ijbiomac.2019.04.195 [20] CHEN X, ZHOU J, ZHANG Y, et al. Polydopamine-modified polyaniline/nanodiamond ternary hybrids with brain fold-like surface for enhanced dual band electromagnetic absorption[J]. ACS Applied Polymer Materials,2019,1(3):405-413. doi: 10.1021/acsapm.8b00127 [21] NIU B, JIA J, WANG H, et al. In vitro and in vivo release of diclofenac sodium-loaded sodium alginate/carboxymethyl chitosan-ZnO hydrogel beads[J]. International Journal of Biological Macromolecules,2019,141:1191-1198. doi: 10.1016/j.ijbiomac.2019.09.059 [22] LIU P, JIANG L, ZHU L, et al. Novel covalently cross-linked attapulgite/poly(acrylic acid-co-acrylamide) hybrid hydrogels by inverse suspension polymerization: Synthesis optimization and evaluation as adsorbents for toxic heavy metals[J]. Industrial & Engineering Chemistry Research,2014,53(11):4277-4285. [23] SIANGSANOH C, UMMARTYOTIN S, SATHIRAKUL K, et al. Fabrication and characterization of triple-responsive composite hydrogel for targeted and controlled drug delivery system[J]. Journal of Molecular Liquids,2018,256:90-99. doi: 10.1016/j.molliq.2018.02.026 [24] REINA G, ORLANDUCCI S, CAIRONE C, et al. Rhodamine/nanodiamond as a system model for drug carrier[J]. Journal of Nanoscience and Nanotechnology,2015,15(2):1022-1029. doi: 10.1166/jnn.2015.9736 [25] NAZLI A B, AÇIKEL Y S. Loading of cancer drug resveratrol to pH-sensitive, smart, alginate-chitosan hydrogels and investigation of controlled release kinetics[J]. Journal of Drug Delivery Science and Technology,2019,53(8):101199. [26] DONG X, WEI C, LIANG J, et al. Thermosensitive hydrogel loaded with chitosan-carbon nanotubes for near infrared light triggered drug delivery[J]. Colloids and Surfaces B: Biointerfaces,2017,154:253-262. doi: 10.1016/j.colsurfb.2017.03.036 [27] WU W, WAN M, FEI Q, et al. PDA@Ti3C2Tx as a novel carrier for pesticide delivery and its application in plant protection: NIR-responsive controlled release and sustained antipest activity[J]. Pest Management Science,2021,77(11):4960-4970. doi: 10.1002/ps.6538