首页分享壳聚糖微花对原花青素吸附机理的研究

壳聚糖微花对原花青素吸附机理的研究

来源：花匠小妙招时间：2025-07-28 22:51

摘要: 为了了解壳聚糖微花（chitosan microflower，CSMF）对原花青素（Procyanidins，PC）的吸附机理，以CSMF为吸附剂对不同吸附条件下的PC溶液进行吸附，并结合扫描电镜（SEM）、傅里叶红外（FTIR）、X-射线衍射（XRD）等对载药颗粒进行表征，并通过吸附动力学、吸附等温线和吸附热力学等方面对CSMF吸附PC的机理进行系统研究。结果表明，载药颗粒的FTIR图谱在1456 cm-1处有产生一个新的特征峰，表明PC已成功负载到CSMF上。SEM和XRD分析结果表明负载后并不会改变CSMF的形貌和结晶度。吸附动力学表明，CSMF对PC的吸附符合准二级动力学模型，吸附速率受颗粒扩散和边界层扩散相互作用的影响。吸附等温线表明，Freundlich吸附等温线模型能更准确地反映了整个吸附过程，说明CSMF对PC的吸附过程是一种表面能不均匀性多层吸附。最后，吸附热力学表明，CSMF对PC的吸附是一个自发的熵减的物理吸附过程。

Abstract: In order to understand the adsorption mechanism of chitosan microflower (CSMF) on procyanidins (PC), CSMF was used as an adsorbent to adsorb PC solutions under different adsorption conditions. The drug-loaded particles were characterized by scanning electron microscopy (SEM), Fourier infrared (FTIR), X-ray diffraction (XRD), etc. Through adsorption kinetics, adsorption isotherm, and adsorption thermodynamics, the mechanism of CSMF adsorption PC was systematically studied. The results showed that the FTIR pattern of the drug-loaded particles produced a new characteristic peak at 1456 cm−1, indicating that the PC was successfully loaded onto the CSMF. The results of SEM and XRD analysis showed that the morphology and crystallinity of CSMF did not change after loading. The adsorption kinetics showed that the adsorption of PC by CSMF conformed to the pseudo-second-order kinetic model, and the adsorption rate was affected by the interaction between particle diffusion and boundary layer diffusion. The adsorption isotherm showed that the Freundlich adsorption isotherm model could more accurately reflect the entire adsorption process, indicating that the adsorption process of CSMF to PC was multilayer adsorption with surface energy inhomogeneity. Finally, adsorption thermodynamics showed that the adsorption of PC by CSMF was a spontaneous physical adsorption process with reduced entropy.

图 1 CSMF（a）和PC-CSMF（b）的电镜图

Figure 1. SEM image of CSMF (a) and PC-CSMF (b)

图 2 CSMF、PC和PC-CSMF的FTIR图谱

Figure 2. Fourier transform infrared spectroscopic spectra of CSMF, PC and PC-CSMF

图 3 CS、CSMF和PC-CSMF的XRD图

Figure 3. X-ray diffractogram of CS, CSMF, and PC-CSMF

图 4 CSMF和PC-CSMF的TGA-DTG图

注：a和b为CSMF的TG-DTG曲线；c和d为PC-CSMF的TG-DTG曲线。

Figure 4. TGA-DTG diagram of CSMF and PC-CSMF

图 5 吸附量随时间的变化

Figure 5. Change of adsorption amount with time

图 6 颗粒扩散动力学曲线

Figure 6. Kinetic curves for particle diffusion

图 7 不同温度下吸附量随浓度的变化

Figure 7. Variation of adsorption capacity with concentration at different temperatures

表 1 CSMF对PC的吸附动力学参数

Table 1 Kinetics parameters for PC adsorption onto the CSMF

动力学模型动力学方程回归方程R2 PFO$mathrm{ln}({mathrm{q} }_{mathrm{e} }-{mathrm{q} }_{mathrm{t} })=mathrm{ln}{mathrm{q} }_{mathrm{e} }-{mathrm{k} }_{1}mathrm{t}$$ mathrm{y}=3.0767-0.0075mathrm{x} $0.9519PSO$dfrac{mathrm{t} }{ {mathrm{q} }_{mathrm{t} } }=dfrac{mathrm{t} }{ {mathrm{q} }_{mathrm{e} } }+dfrac{1}{ {mathrm{k} }_{2}{mathrm{q} }_{mathrm{e} }^{2} }$$ mathrm{y}=0.0286mathrm{x}+1.3553 $0.9998IPD$ {mathrm{q}}_{mathrm{t}}={mathrm{k}}_{mathrm{d}}times {mathrm{t}}^{1/2}+mathrm{C} $$ mathrm{y}=0.8564mathrm{x}+14.05 $0.8498

表 2 CSMF对PC的吸附等温线方程及参数

Table 2 Adsorption isotherm equation and parameters of PC on CSMF

温度（K）Freundlich吸附模型 Langmuir吸附模型KF（（mg/g）·（L/mg）1/n）1/nR2qm（mg/g）KL（×10−4 L/g）R2 288.150.5250.85820.9953 416.676.19150.8999298.150.32250.92670.9951714.293.31430.688308.150.27450.92860.9945833.332.37320.4307

表 3 CSMF的热力学参数

Table 3 Thermodynamic parameters of CSMF

初始浓度
（mg/L）ΔH
（kJ/mol）ΔG（kJ/mol） ΔS（J/（mol·K））288.15 K298.15 K308.15 K318.15 K288.15 K298.15 K308.15 K318.15 K 200−4.96−2.79−2.67−2.76−2.78 −7.5−7.68−7.14−6.85400−6.11−11.52−11.54−10.87−10.47600−5.42−9.13−9.22−8.63−8.3 [1]

ENOMOTO T, NAGASAKO-AKAZOME Y, KANDA T, et al. Clinical effects of apple polyphenols on persistent allergic rhinitis: A randomized double-blind placebo-controlled parallel arm study[J]. Journal of Investigational Allergology and Clinical Immunology,2006,16(5):283−289.

[2]

GONZALEZ-BARRIO R, NUNEZ-GOMEZ V, CIENFUEGOS-JOVELLANOS E, et al. Improvement of the flavanol profile and the antioxidant capacity of chocolate using a phenolic rich cocoa powder[J]. Foods,2020,9(2):12.

[3]

MAO J T, XUE B Y, SMOAKE J, et al. MicroRNA-19a/b mediates grape seed procyanidin extract-induced anti-neoplastic effects against lung cancer[J]. Journal of Nutritional Biochemistry,2016,34:118−125. doi: 10.1016/j.jnutbio.2016.05.003

[4]

SHARMA S D, MEERAN S M, KATIYAR S K. Proanthocyanidins inhibit in vitro and in vivo growth of human non-small cell lung cancer cells by inhibiting the prostaglandin E-2 and prostaglandin E-2 receptors[J]. Molecular Cancer Therapeutics,2010,9(3):569−580. doi: 10.1158/1535-7163.MCT-09-0638

[5]

ZHU F. Proanthocyanidins in cereals and pseudocereals[J]. Critical Reviews in Food Science and Nutrition,2019,59(10):1521−1533. doi: 10.1080/10408398.2017.1418284

[6]

LU W C, HUANG W T, KUMARAN A, et al. Transformation of proanthocyanidin A2 to its isomers under different physiological pH conditions and common cell culture medium[J]. Journal of Agricultural and Food Chemistry,2011,59(11):6214−6220. doi: 10.1021/jf104973h

[7]

XU Z, WEI L H, GE Z Z, et al. Comparison of the degradation kinetics of A-type and B-type proanthocyanidins dimers as a function of pH and temperature[J]. European Food Research and Technology,2015,240(4):707−717. doi: 10.1007/s00217-014-2375-9

[8]

KHAN M K, AHMAD K, HASSAN S, et al. Effect of novel technologies on polyphenols during food processing[J]. Innovative Food Science & Emerging Technologies,2018,45:361−381.

[9]

LUKIC K, VUKUSIC T, TOMASEVIC M, et al. The impact of high voltage electrical discharge plasma on the chromatic characteristics and phenolic composition of red and white wines[J]. Innovative Food Science & Emerging Technologies,2019,53:70−77.

[10]

TIE S S, ZHANG X D, WANG H T, et al. Procyanidins-loaded complex coacervates for improved stability by self-crosslinking and calcium ions chelation[J]. Journal of Agricultural and Food Chemistry,2020,68(10):3163−3170. doi: 10.1021/acs.jafc.0c00242

[11]

LIU C Z, GE S J, YANG J, et al. Adsorption mechanism of polyphenols onto starch nanoparticles and enhanced antioxidant activity under adverse conditions[J]. Journal of Functional Foods,2016,26:632−644. doi: 10.1016/j.jff.2016.08.036

[12]

LIU K, FENG Z Q, SHAN L, et al. Preparation, characterization, and antioxidative activity of Bletilla striata polysaccharide/chitosan microspheres for oligomeric proanthocyanidins[J]. Drying Technology,2017,35(13):1629−1643. doi: 10.1080/07373937.2016.1269123

[13]

RAMPINO A, BORGOGNA M, BLASI P, et al. Chitosan nanoparticles: Preparation, size evolution and stability[J]. International Journal of Pharmaceutics,2013,455(1-2):219−228. doi: 10.1016/j.ijpharm.2013.07.034

[14]

LUO C, WU S Z, LI J, et al. Chitosan/calcium phosphate flower-like microparticles as carriers for drug delivery platform[J]. International Journal of Biological Macromolecules,2020,155:174−183. doi: 10.1016/j.ijbiomac.2020.03.172

[15]

DHAVALE R P, DHAVALE R P, SAHOO S C, et al. Chitosan coated magnetic nanoparticles as carriers of anticancer drug telmisartan: pH-responsive controlled drug release and cytotoxicity studies[J]. Journal of Physics and Chemistry of Solids,2021,148:8.

[16]

SOHAIL R, ABBAS S R. Evaluation of amygdalin-loaded alginate-chitosan nanoparticles as biocompatible drug delivery carriers for anticancerous efficacy[J]. International Journal of Biological Macromolecules,2020,153:36−45. doi: 10.1016/j.ijbiomac.2020.02.191

[17]

LIANG J, LI F, FANG Y, et al. Cytotoxicity and apoptotic effects of tea polyphenol-loaded chitosan nanoparticles on human hepatoma HepG2 cells[J]. Materials Science & Engineering C-Materials for Biological Applications,2014,36:7−13.

[18]

JIANG S W, YU Z Y, HU H L, et al. Adsorption of procyanidins onto chitosan-modified porous rice starch[J]. LWT-Food Science and Technology,2017,84:10−17. doi: 10.1016/j.lwt.2017.05.047

[19]

JI Y, LIN X, YU J C. Preparation and characterization of oxidized starch-chitosan complexes for adsorption of procyanidins[J]. LWT-Food Science and Technology,2020,117:6.

[20] 焦思宇, 姚先超, 史永桂, 等. 壳聚糖微花对原花青素的负载表征及缓释性能[J]. 食品科学,2022,43(14):28−34. [JIAO S Y, YAO X C, SHI Y G, et al. Characterization and sustained release properties of chitosan microflowers loaded with procyanidins[J]. Food Science,2022,43(14):28−34.

JIAO S Y, YAO X C, SHI Y G, et al. Characterization and sustained release properties of chitosan microflowers loaded with procyanidins[J]. Food Science, 2022, 43(14): 28-34.

[21] 王天佑, 毛星星, 张义云, 等. UIO-66-NH2金属-有机骨架材料吸附分离四甲苯异构体[J]. 高校化学工程学报,2022,36(4):488−497. [WANG T Y, MAO X X, ZHANG Y Y, et al. Adsorption and separation of tetramethylbenze isomers by metal-organic frameworks UIO-66-NH2[J]. Journal of Chemical Engineering of Chinese Universities,2022,36(4):488−497.

WANG T Y, MAO X X, ZHANG Y Y, et al. Adsorption and separation of tetramethylbenze isomers by metal-organic frameworks UIO-66-NH2[J]. Journal of Chemical Engineering of Chinese Universities 2022, 36(4): 488-497.

[22]

SINGH S, KUMAR A, GUPTA H. Activated banana peel carbon: a potential adsorbent for rhodamine B decontamination from aqueous system[J]. Applied Water Science,2020,10(8):8.

[23] 陈煜南, 付赵跃, 何欢乐. 改性壳聚糖水凝胶对废水中Cu2+、Cd2+和Pb2+的吸附[J]. 皮革与化工,2022,39(1):24−28. [CHEN Y N, FU Z Y, HE H L. Adsorption of Cu2+, Cd2+ and Pb2+ in wastewater by modified chitosan hydrogel[J]. Leather and Chemicals,2022,39(1):24−28.

CHEN Y N, FU Z Y, HE H L. Adsorption of Cu2+, Cd2+ and Pb2+ in wastewater by modified chitosan hydrogel[J]. Leather and Chemicals, 2022, 39(1): 24-28.

[24]

MUNOZ-LABRADOR A, PRODANOV M, VILLAMIEL M. Effects of high intensity ultrasound on disaggregation of a macromolecular procyanidin-rich fraction from Vitis vinifera L. seed extract and evaluation of its antioxidant activity[J]. Ultrasonics Sonochemistry,2019,50:74−81. doi: 10.1016/j.ultsonch.2018.08.030

[25] 国田, 张娜, 符群, 等. 几种辅助提取方式对蓝莓原花青素浸提效果及抗氧化活性的影响[J]. 北京林业大学学报,2020,42(9):139−148. [GUO T, ZHANG N, FU Q, et al. Effects of several assisted extraction methods on extraction effect and antioxidant activity of proanthocyanins from blueberry[J]. Journal of Beijing Forestry University,2020,42(9):139−148.

GUO T, ZHANG N, FU Q, et al. Effects of several assisted extraction methods on extraction effect and antioxidant activity of proanthocyanins from blueberry[J]. Journal of Beijing Forestry University, 2020, 42(9): 139-148.

[26]

KHOERUNNISA F, NURHAYATI M, DARA F, et al. Physicochemical properties of TPP-crosslinked chitosan nanoparticles as potential antibacterial agents[J]. Fibers and Polymers,2021,22(11):2954−2964. doi: 10.1007/s12221-021-0397-z

[27]

YAZDI F, ANBIA M, SALEHI S. Characterization of functionalized chitosan-clinoptilolite nanocomposites for nitrate removal from aqueous media[J]. International Journal of Biological Macromolecules,2019,130:545−555. doi: 10.1016/j.ijbiomac.2019.02.127

[28] 阮湘梅, 杨子明, 李普旺, 等. 水杨酸/季鏻盐双改性壳聚糖抗菌保鲜剂的制备及表征[J]. 现代食品科技,2022,38(6):145−151,115. [RUAN X M, YANG Z M, LI P W, et al. Preparation and characterization of salicylic acid/quaternary phosphonium salt-modified chitosan as an antibacterial preservative[J]. Modern Food Science and Technology,2022,38(6):145−151,115. doi: 10.13982/j.mfst.1673-9078.2022.6.1299

RUAN X M, YANG Z M, LI P W, et al. Preparation and characterization of salicylic acid/quaternary phosphonium salt-modified chitosan as an antibacterial preservative[J]. Modern Food Science and Technology, 2022, 38(6): 145-151, 115. doi: 10.13982/j.mfst.1673-9078.2022.6.1299

[29]

VASILIU S, BUNIA I, RACOVITA S, et al. Adsorption of cefotaxime sodium salt on polymer coated ion exchange resin microparticles: Kinetics, equilibrium and thermodynamic studies[J]. Carbohydrate Polymers,2011,85(2):376−387. doi: 10.1016/j.carbpol.2011.02.039

[30]

LORENC-GRABOWSKA E, GRYGLEWICZ G. Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons[J]. Journal of Colloid and Interface Science,2005,284(2):416−423. doi: 10.1016/j.jcis.2004.10.031

[31] 王伟涛, 陈香李, 杨百勤. 固体在液相中吸附热力学参数计算介绍[J]. 大学化学,2021,36(2):233−240. [WANG W T, CHEN X L, YANG B Q. Calculation of adsorption thermodynamics parameters for adsorption on the solid-liquid interface[J]. Univ Chem,2021,36(2):233−240.

WANG W T, CHEN X L, YANG B Q. Calculation of adsorption thermodynamics parameters for adsorption on the solid-liquid interface[J]. Univ Chem, 2021, 36(2): 233-240.

[32]

FENG-MIN S, HONG-GUANG G, SHI J, et al. Adsorption kinetics and thermodynamics of Ni (II) by Pisha sandstone[J]. Journal of Nanoparticle Research,2020,22(7):179. doi: 10.1007/s11051-020-04894-8

[33]

AHMAD M A, ALROZI R. Removal of malachite green dye from aqueous solution using rambutan peel-based activated carbon: Equilibrium, kinetic and thermodynamic studies[J]. Chemical Engineering Journal,2011,171(2):510−516. doi: 10.1016/j.cej.2011.04.018

[34]

WU J G, XIA A Q, CHEN C Y, et al. Adsorption thermodynamics and dynamics of three typical dyes onto bio-adsorbent spent substrate of Pleurotus eryngii[J]. International Journal of Environmental Research and Public Health,2019,16(5):11.

[35]

WU Y H, SU M H, CHEN J W, et al. Superior adsorption of methyl orange by h-MoS2 microspheres: Isotherm, kinetics, and thermodynamic studies[J]. Dyes and Pigments,2019,170:8.