Investigations on the adsorbents for uremic middle molecular toxins (Ⅱ)——Influences of crosslinking agent chain length on the adsorption capacities of crosslinked chitosan adsorbents

Chitosan resins, which clinically served as adsorbents in hemoperfusion therapy, were prepared with reversed-phase suspension methodology using three differently structured crosslinking agents, methanal, glyoxal and glutaraldehyde. And the glyoxal and glutaraldehyde crosslinked chitosan resins were reduced with NaBH4 afterwards. By analyzing the results from FTIR and SEM, it was found that the reduction treatment to the adsorbents efficiently improved the chemical stability of these chitosan resins, and the shifts in crosslinking agents exerted influences over the morphologies of the adsorbents obviously. After being put to use in the adsorption tests upon some model uremic middle molecular toxins and BSA in vitro, all three adsorbents demonstrated a fairly realistic adsorption capability to the model toxins but little to BSA. And the adsorption process reached the equilibrium in a clinically qualified short time. But the adsorption capacities of these adsorbents to the model toxins were quite different. It     

Preparation of a Cyclomaltoheptaose(β-cyclodextrin) Cross-linked Chitosan Derivative via Glyoxal or Glutaraldehyde

Chitosan has been regarded as a multifunctional polymer applicable to various purpos-es1. The potential of the material in medical applications, particularly in drug-delivery formu-lations has been demonstrated2, 3. Recently, a crosslinked chitosan with various crosslink-ing agents was prepared as adsorbents4-7. A -cyclodextrin (?CD) has been subjected to numerous studies, particular in terms of its complexing ability with a variety of components8, 9. The complexing ability of -CD has b…     

尿毒症中分子毒物吸附剂的研究(Ⅰ)——戊二醛交联壳聚糖吸附剂

长期以来 ,血液净化疗法一直是临床上处理各种血液中毒的基本手段[1～ 3] .对尿毒症患者 ,目前普遍采用的治疗措施是对其进行定期的血液或腹膜透析 [1] 缓解病情 ;然而单纯血液透析疗法难以清除患者体内的中分子毒物 ,以致血液透析的患者体内 ,中分子毒物的积累会达到很高的程度 .因此 ,通过研制高效的中分子吸附剂 ,以血液灌流的方式清除中分子毒物 ,对于控制和治疗尿毒症具有重要意义 .据文献报道 ,体内蓄积的中分子毒物中肽类物质占了一定的比例[4～ 9] ,患者的许多顽固临床症状与这些毒物的体内蓄积密切相关 [1,10 ] .本课题组的研究结…     

ADSORPTION SELECTIVITY FOR Cu^2＋,Ni^2＋,Co^2＋IONS USING CROSSLINKING CHITOSAN RESINS IMPRINTED BY METAL IONS

Metal ion-imprintedly crosslinked chitosan resin 1 and resin 2 were prepared by the use of Cu^2+ and Ni^2+ as template ions and glutaraldehyde as crosslinking agent,respectively,Through investigation on the adsorption capacties and binding constants for Cu^2+,Ni^2+ and Co^2+ ions on chitosan resins,resin 1 and resin 2 exhibit the adsorption selectivity for the mixture solution of 1L1 Cu^2+ and Ni^2+ ions.The adsorption selectivity of metal ion-imprinted resins for their template ions in much higher than that of uncrosslinked chitosan resin.     

基于壳聚糖及其衍生物的金属离子吸附剂的研究进展

综述了近年来以壳聚糖和壳聚糖衍生物为原料的金属离子吸附剂的研究进展．重点介绍了壳聚糖及其衍生物的交联和功能化反应，以及交联后的树脂对多种金属离子的吸附情况．常用的交联剂包括戊二醛、甲醛及环氧氟丙烷，(聚)乙二醇双缩水甘油醚等，壳聚糖树脂的功能化主要包括向其中引入冠醚、羧甲基等功能团，其中羧甲基化是最常用最有效的方法．另外，还介绍了金属离子模板壳聚糖树脂以及基于壳聚糖衍生物的蛇笼树脂的合成。     

ADSORPTION SELECTIVITY FOR Cu~(2 ),Ni~(2 ),Co~(2 )IONS USING CROSSLINKING CHITOSAN RESINS IMPRINTED BY METAL IONS

1introductionChitosan,adeacetylatedderivativeofchitin,isnatUralpolysaccharideswithfreeaminogroups.Itcanactasanexcellentadsorbenttoadsorbnotonlyvariousorganiccompoundsincludingpolychlorinatedbiphenyls,proteinsandnucleicacids,butalsometalions[1~sl.ChitosanhasbeenwidelyemployedasaneffectivecoagulatingagentinactivatedsludgeplantSandfoodprocessingfactories,andalsoinpreparation,concentTationandpurificationofmetalionsinhydrometallurgy.Chitosanbehavesasanaturalchelatingpolymer.Chitosanundergoeschela…     

Crosslinked chitosan nanofiber mats fabricated by one-step electrospinning and ion-imprinting methods for metal ions adsorption

The Pb(Ⅱ)ion-imprinting electrospun crosslinked chitosan nanofiber mats were fabricated by one-step electrospinning and ion-imprinting methods and their application as adsorbents for metal ions was also investigated.The resulting chitosan nanofiber mats were characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS)and thermal gravimetric analysis(TGA).The Pb(Ⅱ)ion-imprinting electrospun crosslinked chitosan nanofiber mats were used as adsorbents for the removal of Pb(Ⅱ)ions from aqueous or acid solutions.The effects of p H values,contact time,content of crosslinker(glutaraldehyde)on Pb(Ⅱ)ions adsorption were studied.The results indicated that the Pb(Ⅱ)ion-imprinting electrospun crosslinked chitosan nanofiber mats had the highest adsorption capacity of 110.0 mg/g at p H 7.The kinetic study demonstrated that the adsorption of Pb(Ⅱ)ions followed the pseudo-second-order model.The equilibrium isotherm data showed that the Langmuir model was the most suitable for predicting the adsorption isotherm of the studied system.The Pb(Ⅱ)ion-imprinting electrospun crosslinked chitosan nanofiber mats had good adsorption selectivity,which illustrates the equilibrium adsorption capacity in the order of Pb(Ⅱ)Cu(Ⅱ)Zn(Ⅱ)Cd(Ⅱ)Ni(Ⅱ).The Pb(Ⅱ)ion-imprinting electrospun crosslinked chitosan nanofiber mats were stable and had good reuse ability.     

不同交联剂含量对戊二醛交联壳聚糖膜结构与性 能影响的研究

仔细研究壳聚糖膜的结晶度、溶胀度及其对二价铜离子的吸附量与交联剂戊二醛含量(特别是在戊二醛含量较低时)的关系。结果发现膜的结晶度、溶胀度以及对铜离子的吸附量均在戊二醛摩尔分数为0.25%时达到极大值。结晶度的增大可归结于轻度交联能使壳聚糖分子链在成膜时排列更为有序;而溶胀度和对铜离子吸附量的增加则可认为是交联能使壳聚糖中原先被氢键作用所束缚的氨基获得了自由。     

Effect of Crosslinking Agent on Neem (Azadirachta Indica A. Juss.) Seed Oil (NSO) Encapsulated Microcapsules of κ -Carrageenan and Chitosan Polyelectrolyte Complex

Microencapsulation of neem (Azadirachta Indica A. Juss.) seed oil (NSO) was carried out by polyelectrolyte complexation of κ -carrageenan and chitosan. The microcapsules were crosslinked by using three different crosslinking agents - glutaraldehyde, genipin and tannic acid. The lowest and highest water uptake capacities were exhibited by glutaraldehyde and tannic acid crosslinked matrices, respectively. The release behavior of NSO from encapsulated crosslinked microcapsules followed the order: tannic acid > genipin > glutaraldehyde. Polyelectrolyte complex formation and its interaction with crosslinker was studied. Crosslinking improved thermal stability without affecting crystallinity. Roughness appeared on microcapsule's surface indicated interaction between microcapsules and crosslinker.     

Synthesis and metal binding behavior of hydroxamic acid resins from poly(ethyl acrylate) crosslinked with divinylbenzene and hydrophilic crosslinking agent

Porous poly(hydroxamic acid) chelating resin was prepared by the reaction with poly(ethyl acrylate) crosslinked with divinylbenzene and hydrophilic crosslinking agent, and hydroxylamine. The hydrophilic crosslinking agents and diluent used in this article were ethylene glycol dimethacrylate or butanediol dimethacrylate, and 2,2,4-trimethyl pentane, respectively. The characterization of this type chelating resin was carried out by IR spectroscopy, density measurement, and scanning electron microscopy. Various metal binding properties such as extraction, kinetics, and selectivity were investigated with atomic absorption spectrometer and inductively coupled plasma spectrometer. Poly(hydroxamic acid) resins crosslinked with mixed crosslinking agents showed better metal extraction properties and faster adsorption rate than those crosslinked with divinylbenzene alone. And alkali treatment enhances the binding rate for metal ions because of the formation of other chelating ligands or micropores. © 1995 John Wiley & Sons, Inc.     

树脂填充聚醚砜纤维吸附剂对牛血清蛋白吸附性能的研究

重点研究树脂填充聚醚砜(PES)纤维吸附剂与模型蛋白质牛血清蛋白(BSA)之间的吸附与脱附行为.结果表明,蛋白质BSA在树脂填充PES纤维吸附剂中的平衡吸附过程较好地符合朗格缪尔吸附模型,树脂Lewatit CNP80ws填充PES吸附剂的最大吸附容量约为139mg BSA/g吸附剂.表面具有开孔结构的树脂填充PES纤维吸附剂的吸附速率较快,在不同结构纤维吸附剂中BSA的扩散系数在1·82×10-14~8·7×10-14m2/s范围内变化.另外,考察了BSA溶液的pH与洗脱剂等因素对吸附剂吸附与脱附性能的影响,研究结果对蛋白质的实际分离纯化具有重要的参考价值.     

尿毒症中分子毒物吸附剂的研究(Ⅲ)——酸性氨基酸修饰交联壳聚糖

以球状壳聚糖为载体,酸性氨基酸为配体,合成了尿毒症中分子毒物吸附剂,并测试了其血液相容性.为了研究吸附剂对尿毒症患者体内多肽蓄积物的吸附性能,选取分子量不同的6种多肽作为体内蓄积多肽的模拟物进行吸附实验.研究表明,吸附剂对多肽模拟物产生一定的吸附作用.在此基础上又对尿毒症患者血清超滤液进行了吸附实验,结果显示,吸附剂对血清中分子级分的清除率为10.3%.     

交联聚苯乙烯型多孔吸附剂的中孔性质研究

采用77K温度下的氮气吸附方法,测定了经悬浮聚合制备的不同交联度的交联聚苯乙烯多孔吸附剂的吸附/脱附等温线.根据BET吸附模型计算了比表面,由吸附量计算了总的孔体积,由孔体积和比表面计算出平均孔径,并依据脱附等温线采用BJH方法计算孔径分布.结果表明,交联度对交联聚苯乙烯多孔吸附剂的孔结构均具有显著影响.随着交联聚苯乙烯多孔吸附剂的交联度升高,其孔径变小,比表面增大,而且低交联度吸附剂的中孔接近圆柱形,高交联吸附剂的中孔形状接近“墨水瓶”形.显然,交联度对孔性质的影响与孔结构在交联聚苯乙烯多孔吸附剂制备和后处理过程中的稳定性密切相关.交联度低时,初期形成的小孔不能保持稳定,在后续聚合及后处理过程中合并为大孔,结果造成低交联吸附剂大孔径、低比表面的现象.通过对孔径分布的研究,揭示了不同吸附剂在中孔范围内的孔特征,并对其形成机制进行了分析.     

几种吸附树脂对五氯酚钠吸附性能的研究

研究了几种树脂对五氯酚钠的吸附能力,其中戊二醛交联的壳聚糖树脂不仅有较好的吸附效果,动态吸附容量为187.5mg/g干树脂,而且易洗脱,洗脱率高达90%以上。     

Crosslinking of chitosan fibers with dialdehydes: Proposal of a new reaction mechanism

A highly deacetylated chitosan from shrimp with a degree of deacetylation of 95.28 ± 3.03% was prepared and spun into a monofilament fiber using a solution of 4% (w/v) chitosan in 4% (v/v) aqueous acetic acid. Samples of the spun fibers were immersed in aqueous solutions containing glutaraldehyde and glyoxal, and subsequently washed and dried. When the concentration of crosslinking agent was varied at room temperature over a constant time of 1 h, dry mechanical properties improved up to a point after which increasing concentrations resulted in degradation. Immersion time was also varied between 1 and 60 min at 25.8°C, and temperature was varied between 25.8 and 70.0°C, at fixed concentrations of both glyoxal and glutaraldehyde. It was demonstrated that mechanical improvements might be rendered at higher temperatures over lesser times. However, it was also shown that at higher temperatures, fiber mechanical properties would begin to diminish. Chitosan films were subjected to similar treatments in aqueous crosslinking solutions. Fourier transform infrared data (FTIR) on the films suggest that some interaction is occurring between the glutaraldehyde or glyoxal and the amine group on the chitosan backbone. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1079–1094, 1999     

Interaction of crosslinked polyethylenimine with a homologous series of methyl orange derivatives in aqueous solution

Polyethylenimine (PEI) was crosslinked with dichloroethane, glyoxal, or glutaraldehyde and polymers of various degrees of crosslinkage were made. The insoluble polymers obtained were examined for their ability to bind methyl orange and its homologs, methyl, ethyl, propyl, and butyl orange at 5, 15, 25, and 35°C, respectively, in an aqueous solution. PEI crosslinked with glutaraldehyde showed markedly increased binding affinity toward these cosolutes compared with the polymers crosslinked with dichloroethane or glyoxal. The extent of the binding increased with an increase in the degree of crosslinkage. These results suggest that the enhancement of the binding by the crosslinking is due mainly to a dual effect, introduction of hydrophobic moieties and proximity of neighboring polymer chains. The first binding constants and the thermodynamic parameters that accompanied the binding were calculated. The thermodynamic data show that the binding process is athermal and is stabilized entirely by the entropy term. Water-soluble PEI exhibited stronger cooperative interactions than the crosslinked polymer because the mobilities of the chains of the former are greater than those of the latter.     

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

The present investigation describes a novel method for preparing spherical chitosan particles based on crosslinking with epichlorohydrin.Certain amount of pre-crosslinking agent was added to form chitosan gels by traditional inverse phase suspension polymerization.Then the gels were crosslinked by epichlorohydrin at basic condition to obtain chitosan beads.The effects of reaction conditions,such as crosslinking time,the amount of crosslinking agent and the NaOH concentration,on the physical properties of the chitosan beads were investigated.The beads were found to have more amino groups in the polymer chains than the beads crosslinked by glutaraldehyde.The capacity for copper ions in as high as 40mg/g,The beads have good mechanical strength and can be reused.     

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

1. INTRODUCTION Chitosan is the deacetylated chitin which is one of the most abundant natural polymers produced from crab, lobster and shrimp shells or fungal fermentation processes [1]. It is a family of deacetylated β1→4 D-glucosamine polymers. Chitosan has properties including bioactivity, biocompatibility and biodegradability, so it is potentially more useful than cellulose for developing advanced of attention not only as an unutilized biomass resource but also as a novel type of sp…     

交联黄原酸壳聚糖对铅离子的吸附研究

以壳聚糖为原料,通过交联和黄原酸化反应制备出交联黄原酸壳聚糖,采用FT-IR和XRD表征了其结构,并探讨壳聚糖及交联黄原酸壳聚糖对Pb2+的吸附性能。研究了初始溶液pH值、温度以及吸附时间等因素对Pb2+吸附量的影响。结果表明,在Pb2+起始浓度0.01 M,起始溶液pH=5,室温25℃吸附2h条件下,壳聚糖和交联黄原酸壳聚糖对铅离子的吸附量分别为126.8 mg/g和238.9 mg/g,交联黄原酸壳聚糖吸附能力为壳聚糖的1.89倍。     

Ice-templated porous polymer/UiO-66 monolith for Congo Red adsorptive removal

Chitosan/MOF composite porous monolith used in water remediation as adsorbent can realize high-efficient removal of pollutant in water and facile recycling from water. However, dissolution of chitosan (without crosslinking) in acidic aqueous solution will cause breakage of composite monolith. Herein, we report a chitosan/UiO-66 monolith prepared by ice-templating method. Specially, a pre-crosslinking treatment (by glutaraldehyde) is employed before the monolith formation, which obviously boosts its stability in aqueous solution. The composite monolith is evaluated by SEM, N₂ adsorption, XRD, and batch adsorption tests for Congo Red (CR). The results show that the composite monolith possesses a typical ice-templating structure with hierarchical (mirco- / meso- and macro-) pores. UiO-66 particles are embedded on the surface of chitosan matrix, and the crystal structure of UiO-66 is not changed obviously by the crosslinking and freezing process. The composite monolith exhibits high adsorption efficiency (90% of CR was removed from its aqueous solution in 60 min) and the maximum adsorption capacity of 246.21 mg/g (derived from Langmuir model) can be reached. After adsorption, the monolith is collected by a facile procedure and recovered using ethanol for evaluating its reusability. After 4 cycles, the CR removal efficiency of the composite monolith still remains ~90% of the initial efficiency. This work demonstrates that the simple crosslinking procedure before monolith formation can ensure the intact shape of the chitosan/MOF monolith during adsorption.