铅模板交联壳聚糖聚合物的表征及吸附选择性研究

以Pb2+为模板分子,以壳聚糖(CTS)为功能单体合成了CTS-Pb2+复合物、CTS-Pb2+交联聚合物及Pb2+交联CTS分子印迹聚合物(MIP)。采用红外光谱仪、热重分析仪、扫描电镜、X衍射仪等仪器对CTS、CTS-Pb2+复合物、CTS-Pb2+交联聚合物和MIP的表面形貌和结构进行了表征。结果表明,CTS吸附Pb2+是以—NH2为吸附点;CTS吸附Pb2+后,结晶度下降、热稳定性变差;利用分子印迹技术得到的MIP呈具有一定孔径分布的多孔结构,这有利于Pb2+的吸附和洗脱,也为Pb2+的扩散或洗脱提供了良好的通道;MIP在实际水样处理中体现出较高的Pb2+吸附选择性,它在处理含Pb2+废水方面可能具有较好的应用前景。     

表面印迹聚合物吸附复杂基质中的土霉素

为了研究表面分子印迹聚合物对基质复杂的环境样品中的土霉素的吸附分离效果,以应用最为广泛的土霉素(OTC)为研究对象,利用甲基丙烯酸和甲基丙烯酸甲酯为双功能单体、在二氧化硅基质上制备了表面分子印迹聚合物,并对其吸附鸡粪中的四环素类抗生素进行了研究。以聚合物的吸附容量和印迹因子为考核指标,对两种单体的投加比例和二氧化硅的用量进行了优化,确定其合成最佳条件:二氧化硅用量为15 mmol、单体总量一定时各物质的摩尔比为OTC∶MAA∶MMA∶EGDMA=0.08∶2.0∶2.0∶8.0。在此条件下合成的表面印迹聚合物对鸡粪基质中的OTC的最大吸附量可达到9.67 mg/g,印迹因子4.69,可见该表面印迹聚合物对复杂环境样品中的OTC也有良好的吸附性能和识别性能。     

硅胶表面分子印迹聚合物对DEHP的选择性吸附

采用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对硅胶进行改性,并以改性硅胶为载体、邻苯二甲酸二(2-乙基)己酯(DEHP)为模板分子、甲基丙烯酸(MAA)为功能单体,采用表面接枝聚合法合成DEHP-硅胶表面分子印迹聚合物,考察了物料比、反应温度、反应时间对聚合物性能的影响,确定了最佳制备条件。采用傅里叶变换红外光谱、扫描电镜对印迹聚合物进行表征,并对其吸附性能进行了研究。结果表明,最佳制备条件为:模板分子、功能单体、交联剂的摩尔比为1∶4∶12、反应温度60℃、反应时间24 h。红外光谱显示印迹聚合物成功接枝到硅胶表面,扫描电镜分析表明,印迹聚合物表面粗糙,出现了对模板分子DEHP产生选择性识别的孔穴。与DBP、DEP、DMP和DNOP相比,印迹聚合物对DEHP的吸附具有高选择性,吸附DEHP的最适pH为7,吸附平衡时间100 min。吸附等温线可用Langmuir和Freundlich模型描述,饱和吸附量为7.262 mg·g~(-1)。吸附速率可用准二级吸附动力学模型描述。     

砷离子印迹聚合物的制备及性能评价

利用表面印迹技术,以α-甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂在偶氮二异丁腈的引发下发生交联反应生成砷离子印迹聚合物。采用电镜扫描与傅里叶红外光谱对印迹聚合物进行形貌与结构的表征;采用静态吸附法对印迹聚合物吸附过程的pH影响、吸附等温模型和吸附动力学进行研究;同时还研究了在竞争离子存在的情况下砷离子印迹聚合物的选择吸附性能。在25℃、pH=6时,印迹聚合物的吸附量约为非印迹聚合物的1.5倍,对砷离子的吸附过程基本吻合Langmuir吸附等温模型;在动力学研究中发现,吸附过程更为符合准二级动力学方程;在竞争离子存在的情况下,砷离子印迹聚合物有着良好的选择吸附性。     

活性艳橙K-7R分子印迹聚合物微球的制备及结合特性研究

以微米级聚苯乙烯微球为种球,活性艳橙K-7R为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用单步溶胀聚合法在水相中制得了分子印迹聚合物微球(MIPs),并用平衡吸附实验研究了其吸附性能。通过Scatchard分析,结果表明,MIPs在识别K-7R过程中存在两类结合位点,高亲和力结合位点的平衡离解常数Kd1=14.855μmol/L,最大结合量Qmax1=1.282μmol/g;低亲和力结合位点的平衡离解常数Kd2=70.939μmol/L,最大结合量Qmax2=3.930μmol/g。该MIPs对K-7R有较高的亲和性和选择性。     

分子印迹型TiO_2的制备及其对邻苯二甲酸二(2-乙基)己酯的光催化性能

以邻苯二甲酸二(2-乙基)己酯为模板分子、甲基丙烯酸为功能单体和乙二醇二甲基丙烯酸酯为交联剂,在TiO_2表面合成DEHP分子印迹聚合物,制备了分子印迹型TiO_2(MIP-TiO_2),优化了制备工艺条件。利用傅里叶红外光谱(FIIR)和X-射线衍射(XRD)对MIP-TiO_2进行表征,并考察了MIP-TiO_2对DEHP的光催化降解性能。结果表明,MIP-TiO_2的最佳制备工艺条件为模板分子、单体、交联剂和TiO_2的摩尔比为1∶4∶10∶1.875,反应温度为60℃;聚合时间为18 h。MIPTiO_2仍保持了和TiO_2一样的锐钛矿型结构,对DEHP的光催化效果明显高于TiO_2,对浓度为5 mg·L~(-1)的DEHP的光催化降解效率可达88.15%。     

Fe_3O_4@PEG@SiO_2人工抗体的制备及其对噻吩磺隆的吸附性能

以FeCl_2·4H_2O和FeCl_3·6H_2O为原料采用共沉淀法制备Fe_3O_4磁性纳米粒子,在其表面修饰聚乙二醇2000(PEG-2000),在所得的修饰了PEG-2000的Fe_3O_4磁性纳米粒子溶液中加入模板分子噻吩磺隆、交联剂正硅酸乙酯和催化剂氨水,水解后制得印迹了噻吩磺隆的Fe_3O_4@PEG@SiO2人工抗体。用体积比为1:4的乙酸和丙酮溶液为洗脱剂,洗脱位于SiO_2壳层中的印迹分子,形成具有与印迹分子结构、大小和功能基团互补的特异性识别位点空穴。制备的Fe_3O_4@PEG@SiO_2人工抗体对目标分析物噻吩磺隆分子选择性识别和吸附,对噻吩磺隆的最大饱和结合量为41.28 mg·g~(-1),前30 min内,其吸附速率为0.45 mg·(min·g)~(-1),分别是非印迹方法的5.34倍和3.46倍。     

菌丝体表面分子印迹壳聚糖吸附剂对Cr3+的吸附性能研究

菌丝体表面分子印迹吸附剂所保留的印迹对过渡金属离子有着良好的吸附作用,以Cr3 作为吸附离子,系统研究了该吸附剂的吸附特性和影响因素.结果表明:吸附剂对Cr3 的饱和吸附容量可达60 mg/g;其吸附行为满足Langmuir方程式.初始浓度为200 mg/L时,最佳吸附pH在3～4,吸附容量可达到50 mg/g左右,离子强度对吸附没有影响,用0.5 mol/L硝酸或硫酸解吸Cr3 ,解吸率在90%以上.     

高分子量高纯度阳离子聚丙烯酰胺的合成

以丙烯酰胺与丙烯酰氧乙基三甲基氯化铵为单体,在复合引发剂的作用下,选择水溶液共聚法合成高分子量与高纯度阳离子型聚丙烯酰胺(CPAM)。实验表明,有机偶氮引发剂A用量0.5‰、氧化还原引发剂用量0.45‰、还原剂与氧化剂摩尔比2∶1、反应体系pH为4与反应时间5 h条件下,CPAM分子量为1 042万,且溶解性好。通过对聚合物残单含量影响因素添加剂用量、反应时间的研究,结果表明,添加剂EDTA和增溶剂D对残留AM含量影响小,而苯甲酸钠对聚合物残留AM的含量影响显著;延长反应时间至7 h,残单含量可降低至0.27%,CPAM的纯度高。通过与国内外3种同类型产品进行对比,结果表明,自制产品的分子量明显高于其他产品,且残单含量比国内产品降低了50%～75%。     

多孔水凝胶P(HEA/AMPS)对水溶液中 Fe(Ⅲ) 的吸附

以2-丙烯酸羟乙酯(HEA)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体合成了聚合物水凝胶(PHEA/AMPS),采用水凝胶对水溶液中Fe(Ⅲ)的吸附行为进行了研究。实验主要考察了聚合物组分、溶液pH、初始Fe(Ⅲ)浓度和吸附时间对水凝胶吸附作用的影响,并通过FT-IR和XPS分析了吸附前后水凝胶的变化。结果表明,当单体摩尔比AMPS∶HEA=1∶1,pH=2时,水凝胶对Fe(Ⅲ)的吸附容量最大。水凝胶对水溶液中Fe(Ⅲ)的吸附容量随着溶液中初始Fe3+浓度的增加而增加,但当初始Fe3+的浓度达到1 g/L时,吸附容量基本达到饱和。吸附等温线符合Langmuir等温线方程,吸附动力学符合准二级模型。FI-IR和XPS的分析表明,水凝胶的磺酸基和酰胺基是吸附Fe3+的有效功能性基团,吸附机理为螯合和离子交换。     

Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q_max) of 324.8 mg/g and a dissociation constant (K_d) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.     

Removal of carbamazepine and clofibric acid from water using double templates–molecularly imprinted polymers

A novel double templates–molecularly imprinted polymer (MIP) was prepared by precipitation polymerization using carbamazepine (CBZ) and clofibric acid (CA) as the double templates molecular and 2-vinylpyridine as functional monomer. The equilibrium data of MIP was well described by the Freundlich isotherm model. Two kinetic models were adopted to describe the experimental data, and the pseudo second-order model well-described adsorption of CBZ and CA on the MIP. Adsorption experimental results showed that the MIP had good selectivity and adsorption capacity for CBZ and CA in the presence of competitive compounds compared with non-imprinted polymer, commercial powdered activated carbon, and C18 adsorbents. The feasibility of removing CBZ and CA from water by the MIP was demonstrated using tap water, lake water, and river water.     

Synthesis, properties and application research of atrazine Fe3O4@SiO2 magnetic molecularly imprinted polymer

Introduction

Magnetic Fe₃O₄ nanoparticles were prepared by coprecipitation and then were coated with SiO₂ on the surface.

Materials and methods

Fe₃O₄@SiO₂ composite microspheres were modified by KH570. Using molecular imprinting technology, atrazine magnetic molecularly imprinted polymer was prepared by using atrazine as template molecule, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linkers. The morphology, composition and magnetic properties of magnetic nanoparticles were characterized. The recognition selectivity of polymer was studied for template molecule and simulation by UV spectrophotometry. The adsorption properties and selectivity ability were analyzed by Scatchard analysis.

Results

Scatchard linear regression analysis indicated that there are two binding sites of the target molecules. The magnetic molecularly imprinted polymer has been applied to the analysis of atrazine in real samples.

Conclusion

The results show that: the recovery rates and the relative standard deviation were 94.0??98.7% and 2.1??4.0% in corn, the recovery rates and the relative standard deviation were 88.7??93.5% and 2.8??7.2% in water.     

Molecularly imprinted polymer for analysis of trace atrazine herbicide in water

A molecularly imprinted polymer (MIP) for atrazine was synthesized by non-covalent method. The binding capacity of MIP was 1.00 mg g^{? 1} polymer. The selectivity and recovery were investigated with various pesticides which are mostly, found in the environment, for both similar and different chemical structure of atrazine. The competitive recognition between atrazine and structurally similar compounds was evaluated and it was found that the system provided highest recovery and selectivity for atrazine while low recovery and selectivity were obtained for the other compounds. The highest recovery was obtained from MIP compared with non-imprinted polymer (NIP), a commercial C₁₈ and a granular activated carbon (GAC) sorbent. The method provided high recoveries ranged from 94 to 99% at two spiked levels with relative standard deviations less than 2%. The lower detection limit of the method was 80 ng L^{? 1}. This method was successfully applied for analysis of environmental water samples.     

Selective removal of 2,4-dichlorophenol from contaminated water using non-covalent imprinted microspheres

A molecularly imprinted polymer (MIP) for selective removal of 2,4-dichlorophenol (2,4-DCP) in water was prepared as microspheres by the reverse microemulsion polymerization method based on the non-covalent interactions between 2,4-DCP, oleic acid, and divinylbenzene in acetonitrile. Microspheres have been characterized by Fourier transform infrared spectrometer (FTIR) and energy dispersive X-ray spectrometer (EDS) studies with evidence of 2,4-DCP linkage in polymer particles and scanning electron microscopy (SEM) to study their morphological properties. The proper adsorption and selective recognition ability of the MIP were studied by an equilibrium-adsorption method. The MIP showed outstanding affinity towards 2,4-DCP in aqueous solution and the optimum pH value for binding has been found around the neutral range. The molecular recognition of 2,4-DCP was analyzed in detail by using molecular modeling software. In addition, by investigating the variation in the adsorption ability of the MIP, it clearly showed excellent reproducibility.     

Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent

Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon.     

Removal of cyanotoxins from surface water resources using reusable molecularly imprinted polymer adsorbents

Introduction

Microcystins (MCs; cyclic heptapeptides) are produced by freshwater cyanobacteria and cause public health concern in potable water supplies. There are more than 60 types of MCs identified to date, of which MC-LR is the most common found worldwide. For MC-LR, the WHO has established a threshold value of 1???g?L^?1 for drinking water. The present MCs removal methods such as coagulation, flocculation, adsorption, and filtration showed low efficiency for removing dissolved MC fraction from surface waters to the stipulated limit prescribed by WHO based on MC health impacts. The search for cost-effective and efficient removal method is still warranted for remediation of dissolved MC-LR-contaminated water resources.

Materials and methods

Molecularly imprinted polymer (MIP) adsorbent has been prepared using non-covalent imprinting approach. Using MC-LR as a template, itaconic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linking monomer, a MIP has been synthesized. Computer simulations were used to design effective binding sites for MC-LR binding in aqueous solutions. Batch binding adsorption assay was followed to determine binding capacity of MIP under the influence of environmental parameters such as total dissolved solids and pH.

Results and discussion

The adsorptive removal of MC-LR from lake water has been investigated using MIPs. The MIP showed excellent adsorption potential toward MC-LR in aqueous solutions with a binding capacity of 3.64???g?mg^?1 which is about 60% and 70% more than the commercially used powdered activated carbon (PAC) and resin XAD, respectively. Environmental parameters such as total organic carbon (represented as chemical oxygen demand (COD)) and total dissolved solids (TDS) showed no significant interference up to 300?mg?L^?1 for MC-LR removal from lake water samples. It was found that the binding sites on PAC and XAD have more affinity toward COD and TDS than the MC-LR. Further, the adsorption capacity of the MIP was evaluated rigorously by its repeated contact with fresh lake water, and it was found that the adsorption capacity of the MIP did not change even after seven adsorption/desorption cycles. The contaminated water of MC-LR (1.0???g?L^?1) of 3,640?L could be treated by 1?g of MIP with an estimated cost of US $1.5.

Conclusions

The adsorption capacity of the MIP is 40% more than commercially used PAC and resins and also the polymer showed reusable potential which is one of the important criteria in selection of cyanotoxins remediation methods.     

Evaluation of pectin binding of heavy metal ions in aqueous solutions

Evaluation of adsorption performance of several industrially manufactured pectins towards some toxic heavy metals was carried out. Adsorption isotherms for divalent cations in simulant aqueous solutions were measured and corresponding distribution coefficients were calculated. The following selectivity sequences we found for pectins: Pb2+ > Cu2+ > Co2+ > Ni2+ > Zn2+ > Cd2+. It was shown that a beet pectin exhibits a high affinity for Pb2+ and Cu2+ ions, an apple pectin for Co2+ ion and a citrus pectin for Ni2+ ion. The binding properties of all pectins towards Zn2+ and Cd2+ ions are extremely poor. The quantitative data on adsorption performance of pectins suggest their applicability as food additives or remedies for efficient removal of Pb2+, Cu2+, Co2+, and Ni2+ ions from different biological systems, including human and animal organisms.     

壳聚糖双冠醚的合成及其对金属离子的吸附性能研究

将二苯并16－冠－5氯代乙酸酯冠醚分别接枝到西佛碱型壳聚糖冠醚CT－15C和CT－18C上,制备了1,4－壳聚糖双冠醚CT－15CAC和CT－18CAC,经元素分析、FT－IR红外光谱分析和X－射线粉末衍射分析表征了结构。研究了CT－15CAC和CT－18CAC对Pd^2 、Ag^ 、Pt^4 、Au^3 、Cu^2 、Hg^2 的静态吸附性能,并与CT－15C和CT－18C进行了比较。结果表明,这4种吸附剂对贵金属离子如Au^3 、Ag^ 、Pt^4 、Pd^2 都具有较好的吸附性能,并能在Cu^2 和Hg^2 共存的条件下选择吸附Pd^2 ,而且壳聚糖双冠醚CT－15CAC和CT－18CAC比壳聚糖单冠醚CT－15C和CT－18C具有更好的选择性。     

Adsorption of Cu and Mn on covalently cross-linked alginate gel beads

The covalently cross-linked alginate gel beads were prepared by the reactions of Ca(2+)-doped alginate gel beads, which were formed by spraying a viscous alginate solution into a calcium chloride solution, with cyanogen bromide and following 1,6-diaminohexane. The cross-linking of alginate matrix decreased the mean bead diameter by about 30% and made the beads durable in some extent under alkaline conditions. The adsorption of metal ions on the covalently cross-linked alginate gel beads was rapid and reached at equilibrium within 30 min at 25 degrees C. Adsorption isotherms of Cu(II), Mn(II), and Ca2+ on the beads possessed a stepwise shape, which was firstly determined by Rorrer et al. [Ind. Eng. Chem. Res. 32 (1993) 2170] for cross-linked chitosan gel beads and explained by a pore-blockage mechanism. Higher selectivity was determined against Cu(II) over Mn(II) and Ca2+, especially at a low concentration region. These metal adsorption profiles for the covalently cross-linked alginate gel beads was almost the same as those for the un-cross-linked beads, indicating that the cross-linking reactions were performed without interfering the adsorption characteristics of alginate gel beads.