交联聚氨基壳聚糖螯合树脂的制备及吸附性能研究

以壳聚糖为原料合成了交联聚氨基球状螯合树脂,并考察了其对Hg(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)的吸附性能及影响因素。结果表明,对高浓度金属离子(约0.01mol/L)吸附量的大小为Hg(Ⅱ)>Pb(Ⅱ)>Zn(Ⅱ),对Zn(Ⅱ)几乎不吸附;而在低浓度时(约20ug/ml)树脂对三种离子均具有较高的吸附率(>55%)。     

天然高分子吸附剂研究 Ⅰ．乙二醇双缩水甘油醚交联壳聚糖的制备及其对Cu（Ⅱ）、Ni（Ⅱ）的吸附性能

报道了乙二醇双缩水甘油醚改性壳聚糖的制备及其对Ｃｕ（Ⅱ）、Ｎｉ（Ⅱ）的吸附性能，同时考察了ｐＨ值、时间、温度等因素对吸附的影响．结果表明，改性后的壳聚糖具有不流失，易再生，在Ｃｕ（Ⅱ）、Ｎｉ（Ⅱ）共存时能选择吸附Ｃｕ（Ⅱ）的特点．     

壳聚糖衍生物对Zn(Ⅱ)的吸附动力学及机理研究

利用吸附体系研究了Zn(Ⅱ)与壳聚糖衍生物的吸附行为。评价了Zn(Ⅱ)在壳聚糖衍生物上的吸附能力。探讨了壳聚糖衍生物对Zn(Ⅱ)的吸附动力学行为,动力学实验数据与二级动力学模型相吻合,表明化学吸附过程为速率控制步骤。通过红外光谱和X射线光电子能谱,研究了壳聚糖衍生物与Zn2 的配位机理。结果表明,配合物中Zn2 与α-酮戊二酸缩壳聚糖中羧基氧原子和氨基氮原子配位,与羟胺α-酮戊二酸缩壳聚糖配位的配位原子为—NH—中的氮原子、羟肟酸中的氧原子及羰基中的氧原子。     

壳聚糖银(Ⅰ)配合物的合成及吸附动力学

研究了壳聚糖对Ag(Ⅰ )离子的吸附动力学 ,并对吸附条件进行优化 ,得到了较为理想的产物。用紫外光谱、红外光谱、元素分析及核磁共振对配合物的结构和组成进行了表征。结果表明 ,壳聚糖与Ag(Ⅰ )离子配位生成配合物Ag(CTS) 2 NO3 ;其吸附行为符合Freundich吸附等温式 ,此反应是一级反应 ,反应的活化能为 2 1 92kJ·mol-1,3 0℃时速率常数为 0 0 41 0h-1。     

铜(Ⅱ)-腺嘌呤的配位吸附波

本文对铜（Ⅱ）－腺嘌呤配位吸附波的极谱行为进行了研究。结果表明，当腺嘌呤浓度大于铜的浓度时，极谱波呈现为两电子还原配位吸附不可逆波。测定了配合物的组成及条件生成常数，对电极反应机制也进行了探讨。     

壳聚糖希夫碱金属[Cu(Ⅱ),Mn(Ⅱ)]配合物的合成及其抑菌活性

壳聚糖的氨基与水杨醛发生反应制得壳聚糖希夫碱配体(L);L与铜盐或锰盐发生配位反应制得壳聚糖希夫碱金属[Cu(Ⅱ)和Mn(Ⅱ)]配合物(1和2),其结构经UV,IR,TGA和荧光光谱表征.L的酚亚胺的N原子和酚羟基的O原子同时参与配位.抑菌活性测试结果表明,1和2对大肠杆菌,金黄色葡萄球菌,沙门氏菌和枯草杆菌的抑菌活性较配体和金属盐均有明显提高.     

硫脲壳聚糖Co(Ⅱ)配合物的制备、抑茵活性及与血清白蛋白的作用

合成了硫脲壳聚糖Co(Ⅱ)配合物,运用红外光谱、紫外光谱和差热热重分析对配合物进行了表征,研究了其对大肠杆菌和金黄色葡萄球菌的抑菌性能及与血清白蛋白(BSA)的相互作用.结果表明,硫脲壳聚糖能与Co(Ⅱ)发生配位反应而生成硫脲壳聚糖-Co(Ⅱ)配合物,该配合物的抑菌性能较壳聚糖和硫脲壳聚 糖有显著提高,并能有规律地猝灭...     

硫脲壳聚糖Co(Ⅱ)配合物的制备、抑茵活性及与血清白蛋白的作用

合成了硫脲壳聚糖Co(Ⅱ)配合物,运用红外光谱、紫外光谱和差热热重分析对配合物进行了表征,研究了其对大肠杆菌和金黄色葡萄球菌的抑菌性能及与血清白蛋白(BSA)的相互作用.结果表明,硫脲壳聚糖能与Co(Ⅱ)发生配位反应而生成硫脲壳聚糖-Co(Ⅱ)配合物,该配合物的抑菌性能较壳聚糖和硫脲壳聚 糖有显著提高,并能有规律地猝灭BSA的内源荧光.     

完全脱乙酰化壳聚糖与Zn(Ⅱ)的配位作用

在均相反应条件下 ,完全脱乙酰化的壳聚糖与ZnSO4 进行配位反应 .用元素分析、IR、固体13 C NMR、UV vis、TGA和X 衍射等表征方法研究了Zn(Ⅱ )与壳聚糖所形成配位聚合物的组成和结构 .在pH =7时 ,一个Zn(Ⅱ )与二个壳聚糖重复单元中的氨基和仲羟基进行了配位     

磁场强化苯甲醛希夫碱吸附Cu(Ⅱ)

研究了磁场作用下,壳聚糖与苯甲醛的合成产物苯甲醛希夫碱(SB-1)对Cu(Ⅱ)的吸附特性,讨论了磁场强度、磁场处理时间、Cu(Ⅱ)溶液的酸度等因素对吸附结果的影响。结果表明,400kA/m的磁场处理前后,壳聚糖和希夫碱对Cu(Ⅱ)的吸附率分别最少增加了4.86%和2.37%,吸附量分别最少增加了0.1459mg/L和0.07111mg/L,而达到吸附饱和的时间均缩短了40%。用经典的等温方程对壳聚糖和希夫碱对Cu(Ⅱ)的吸附平衡数据进行拟合,结果表明,吸附行为与Langmuir和Freundlich两种吸附等温方程式均有较好的相关性。本研究揭示了适当的磁场处理可强化壳聚糖及苯甲醛希夫碱对Cu(Ⅱ)的吸附。     

Copper Adsorption on Chitosan-Derived Schiff Bases

The adsorption of Cu(II) ions onto the chitosan derived Schiff bases obtained from the condensation of chitosan with salicyaldehyde (polymer I), 2,4-dihydroxybenzaldehyde (polymer II) and with 4-(diethylamino) salicyaldehyde (polymer III) in aqueous solutions was investigated. Batch adsorption experiments were carried out as a function of contact time, pH, and polymer mass. The amount of metal-ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS) and the highest Cu(II) ions uptake was achieved at pH 7.0 and by using sodium perchlorate as an ionic strength adjuster for polymers I, II, and III. The isothermal behavior and the kinetics of adsorption of Cu(II) ions on these polymers with respect to the initial mass of the polymer and temperature were also investigated; adsorption isothermal equilibrium data could be clearly explained by the Langmuir equation. The experimental data of the adsorption equilibrium from Cu(II) solution correlates well with the Langmuir isotherm equation.     

表面印迹纳米磁性壳聚糖的制备及对Cu(Ⅱ)的吸附研究

将壳聚糖与自制的纳米四氧化三铁反应,加入一定量的铜盐使其与壳聚糖络合,再用环氧氯丙烷交联,用酸洗脱铜离子,得到表面印迹的纳米磁性壳聚糖.考察了阴离子、交联剂浓度对铜印迹效果的影响.用振动磁力仪及透射电镜对样品的性质进行表征.研究了表面印迹的纳米磁性壳聚糖对Cu2 的吸附性能.研究结果显示,用硝酸铜印迹制备的表面印迹纳米磁性壳聚糖吸附剂平均粒径为25nm,饱和磁化强度为98.56emu/g,壳聚糖含量为18.7%.吸附剂吸附容量大,吸附速度快.在Cu2 初始浓度为3.91mmol/L,pH为5时,15min即达到吸附平衡,以壳聚糖计Cu2 的饱和吸附量为4.07mmol/g,比纯壳聚糖粉高2倍.在含Zn2 或Cd2 、Pb2 的二元体系溶液中,离子印迹吸附剂对Cu2 具有明显的选择吸附性,而未印迹的纯壳聚糖粉几乎没有选择性.吸附剂易回收,重复使用性好,重复使用4次后,吸附量约保留最初饱和吸附量的98%.     

Adsorption behavior of Fe(II) and Fe(III) ions on thiourea cross-linked chitosan with Fe(III) as template

A new type of thiourea cross-linked chitosan with Fe(III) as template (TCCTS template) was synthesized. The adsorption of Fe(II) and Fe(III) on this TCCTS template was studied. The factors affecting adsorption such as pH and contact time were considered. The results showed that the optimum pH value for adsorption was pH = 5.0 and the adsorption equilibrium time was about 60 min. The adsorption isotherms and kinetics were investigated, and the equilibrium data agreed very well with the Langmuir model and the pseudo second-order model could describe adsorption process better than the pseudo first-order model. Results also showed that TCCTS template was a favourable adsorbent for Fe(II) and Fe(III) in aqueous solution.     

Cu(II)-脱乙酰壳聚糖配位聚合物的配位数

IR,ESR和XPS的测试结果表明,脱乙酰壳聚糖(简记CS)膜在铜氨水溶液浸渍过程中Cu(II)既与CS发生配位反应形成Cu(II)-CS配位聚合物,也产生吸附作用。ESR谱示出CuCl~2.2H~2O与Cu(II)-CS膜中的Cu(II)均含有一个单电子,可以利用XPS的Shake-up效应研究Cu(II)-CS配位聚合物的配位数,所得结果为4。又以同样的方法研究Cu(II)-聚乙烯醇(简记PVA)配位聚合物的配位数,发现Cu(II)是以低自旋状态的dsp^2杂化空轨道与PVA的羟基氧配位,其配位数也是4,这与资料所报道的一致,从而间接地验证了此方法研究Cu(II)-CS配位聚合物配位数的可靠性。     

Cu(Ⅱ)脱乙酰壳聚精配位聚合物的配位数

IR,ESR和XPS的测试结果表明,脱乙酰壳聚糖(简记CS)膜在铜氨水溶液浸渍过程中Cu(Ⅱ)既与CS发生配位反应形成Cu(Ⅱ)-CS配位聚合物,也产生吸附作用.ESR谱示出CuCl_2·2H_2O与Cu(Ⅱ)-CS膜中的Cu(Ⅱ)均含有一个单电子,可以利用XPS的Shake-up效应研究Cu(Ⅱ)-CS配位聚合物的配位数,所得结果为4.又以同样的方法研究Cu(Ⅱ)-聚乙烯醇(简记PVA)配位聚合物的配位数,发现Cu(Ⅱ)是以低自旋状态的dsp~2杂化空轨道与PVA的羟基氧配位,其配位数也是4,这与资料所报道的一致,从而间接地验证了此方法研究Cu(Ⅱ)-CS配位聚合物配位数的可靠性.     

Supramolecular sequential assembly of polymer thin films based on dimeric, dendrimeric, and polymeric Schiff-base ligands and metal ions

New metal-Schiff-base coordination polymer films were prepared using multiple sequential adsorption of metal ions and salen-based ligand molecules. As the ligands, bis-bidentate 5,5'-methylene-bis(N-methylsalicylidenamine) (MBSA), tetra-bidentate N,N',N' ',N' '-tetrasalicylidene-polyamidoamine (TSPA), and multi-bidentate poly(N-salicylidenevinylamine) (PSVA) were used. The metal ions were Cu(II), Zn(II), Fe(II), Fe(III), and Ce(IV). The resulting films are deeply colored due to the formation of coordinative bonds between the metal ions and the salen groups. Our study indicates that film formation becomes progressively easier, if the number of salen groups per ligand molecule increases. While Cu(II), Ni(II), Fe, and Ce(IV) are well suited for complex formation, Zn(II) is less suited. Possible structures of the polymers are discussed. Cyclic voltammetric studies of the films are also presented.     

Synergistic co-removal of zinc(II) and cefazolin by a Fe/amine-modified chitosan composite

A novel Fe/amine modified chitosan composite (Fe/N-CS) was facilely synthesized and showed great potential in the efficient co-removal of heavy metal ions and antibiotics from wastewater.     

Synergistic co-removal of zinc(II) and cefazolin by a Fe/amine-modified chitosan composite

A novel Fe/amine modified chitosan composite (Fe/N-CS) was facilely synthesized and showed higher affinity to both Zn(II) and cefazolin (CEF) than its precursors. Synergistic co-adsorption of them by Fe/N-CS was observed in varied conditions. The adsorption amount maximally increased by 100.1% for Zn and 68.2% for CEF in bi-solute systems. The initial adsorption rate of Zn(II) also improved with CEF. The increasing temperature facilitated coadsorption. The results of the preloading tests, FTIR/XPS characterizations and DFT calculations suggested that (1) both polyamines and Fe sites participated in the adsorption of Zn(II) and CEF, (2) Zn(II) could serve as a new efficient site for CEF, forming [amine-Zn-CEF]/[FeOH-Zn-CEF] ternary complexes, and (3) the co-presence of CEF shielded the electrostatic repulsion between protonated amines and Zn(II), contributing to the enhancement of Zn(II) adsorption. Further, the ion strength exerted positive and negative influences on the adsorption of Zn(II) and CEF, respectively. Additionally, CEF and Zn(II) were successively recovered by 0.1 mol/L NaOH followed by 2 mmol/L HCl. Fe/N-CS could be stably reused five times. The findings imply that Fe/N-CS is promising for the highly efficient co-removal of concurrent heavy metals and antibiotics.     

Preparation and adsorption properties of monodisperse chitosan-bound Fe3O4 magnetic nanoparticles for removal of Cu(II) ions

Monodisperse chitosan-bound Fe(3)O(4) nanoparticles were developed as a novel magnetic nano-adsorbent for the removal of heavy metal ions. Chitosan was first carboxymethylated and then covalently bound on the surface of Fe(3)O(4) nanoparticles via carbodiimide activation. Transmission electron microscopy micrographs showed that the chitosan-bound Fe(3)O(4) nanoparticles were monodisperse and had a mean diameter of 13.5 nm. X-ray diffraction patterns indicated that the magnetic nanoparticles were pure Fe(3)O(4) with a spinel structure, and the binding of chitosan did not result in a phase change. The binding of chitosan was also demonstrated by the measurement of zeta potential, and the weight percentage of chitosan bound to Fe(3)O(4) nanoparticles was estimated to be about 4.92 wt%. The chitosan-bound Fe(3)O(4) nanoparticles were shown to be quite efficient for the removal of Cu(II) ions at pH>2. In particular, the adsorption rate was so fast that the equilibrium was achieved within 1 min due to the absence of internal diffusion resistance. The adsorption data obeyed the Langmuir equation with a maximum adsorption capacity of 21.5 mg g(-1) and a Langmuir adsorption equilibrium constant of 0.0165 L mg(-1). The pH and temperature effects revealed that the adsorption capacity increased significantly with increasing pH at pH 2-5, and the adsorption process was exothermic in nature with an enthalpy change of -6.14 kJ mol(-1) at 300-330 K.     

8-羟基喹啉化学修饰壳聚糖亚铁配合物的合成及结构表征

为了利用高分子壳聚糖的生物特性降低药物的毒副作用,寻找理想的高分子药物载体,增加药物的生物特性,本文以高分子壳聚糖为载体,以8-羟基喹啉对其进行共价修饰,合成了喹啉类抗疟杀菌药的高分子药物前体,为增加其活性,与亚铁配位,合成了壳聚糖-8-羟基喹啉-亚铁配合物,用元素分析、TG-DTA分析、IR光谱、UV光谱和荧光光谱等研究了配合物的性质,并优化了配合物合成条件.结果表明,CTS-HQ对Fe2+离子的吸附等温线符合Langmuir吸附等温线方程,在室温下,pH=4时吸附8h的饱和吸附量Qmax=86.96mg/g,K=1.474J/mg.