新型甲醛吸附剂的制备及性能表征

在过氧化苯甲酰引发作用下,将聚酰胺进行处理得到表面改性的接枝种子微粒与模板分子甲醛、功能单体丙烯酸甲酯、交联剂EGDMA等进行聚合反应,制备甲醛分子印迹聚合物。利用红外光谱对分子印迹聚合物进行表征,利用静态和动态平衡吸附法研究印迹聚合物的吸附特征,并与活性炭进行比较。结果表明:与活性炭相比,该印迹化合物吸附量更高,为26.3 mg/g,且可再生重复使用。     

球形印迹交联壳聚糖聚合物的制备及其对尿素的吸附性能研究

采用乳液聚合法制备了球形尿素-壳聚糖分子印迹聚合物。通过正交试验优化了印迹聚合物的制备条件:在乙酸体积分数为2%,戊二醛用量为1 mL,转速为900 r/min,模板分子用量为3 g的条件下制备的印迹聚合物对尿素的吸附量为7.16 mg/g,非印迹聚合物对尿素的吸附量为3.84 mg/g。聚合物的红外图谱研究表明,戊二醛参与了交联反应且模板分子尿素被印迹在聚合物上,聚合物经洗脱后模板分子被基本除去。分子印迹聚合物表面具有均一选择性的吸附位点,最大表观吸附量为9.69 mg/g。     

等离子体引发制备亚甲基蓝印迹聚合物及其吸附性能研究

利用辉光放电等离子体代替传统化学引发剂,以亚甲基蓝为模板分子,丙烯酰胺为单体,N,N-亚甲基双丙烯酰胺作交联剂,采用沉淀聚合法制得分子印迹聚合物,用红外光谱和扫描电镜对其进行了表征。吸附实验表明印迹聚合物在20min达到吸附平衡,印迹聚合物对模板分子吸附量随浓度增加而增加,等离子体引发制备的印迹聚合物吸附量大于化学引发剂制得的印迹聚合物。扫描电镜结果表明等离子体引发制得的分子印迹聚合物颗粒粒径小、表面粗燥、孔穴多、比表面积大。采用等离子体引发制得的分子印迹聚合物对模板分子的吸附常数和最大吸附量分别为0.1528 L/mg和33.62 mg/g。     

Fe-MIL-101@白藜芦醇印迹复合材料的合成及其吸附性能

以MIL-101(Fe)为基质，通过表面接枝白藜芦醇印迹聚合物获得一种对白藜芦醇具有高选择吸附能力的新型印迹复合材料。利用红外光谱仪、扫描电镜以及X射线衍射仪对印迹材料的表面功能基团、颗粒形状及骨架结构进行表征。研究了该印迹复合材料的吸附动力学、热力学及选择性。结果表明，复合印迹材料的印迹效率达4.577,其对模板的选择因子高达3.695,对白藜芦醇也具有较高吸附能力，吸附量为24.9 mg/g。Scatchard分析显示印迹材料表面主要有两类吸附位点。另外，该印迹材料可重复使用，吸附性能变化不大。以Fe-MIL-101@白藜芦醇印迹复合材料为吸附剂，固相萃取虎杖粗提物中的白藜芦醇时，能够较好地分离和富集目标物。     

结晶紫印迹材料的制备及其在鲤鱼样品分析中的应用

以硅胶为基质,结晶紫为模板分子,甲基丙烯酸(MAA)为功能单位,N,N-亚甲基丙烯酰胺(MBA)为交联剂,硅胶为载体,采用表面修饰分子印迹法,制备对结晶紫具有特定亲和选择性的分子印迹聚合物。应用红外光谱对印迹聚合物进行表征,通过静态吸附实验优化实验条件,对聚合物的吸附行为进行分析,采用平衡结合实验评价了分子印迹聚合物的吸附性能。结果表明,采用表面修饰分子印迹法所制备的印迹聚合物对结晶紫表现出较好的特异吸附,对模板分子最大吸附量值为22. 04 mg/g。     

Zn2+配位双模板印迹聚合物的制备表征及同时萃取升麻中的阿魏酸和咖啡酸

以Zn²⁺-阿魏酸-咖啡酸配合物为模板制备了双分子印迹聚合物,优化了制备条件,用傅里叶红外光谱和扫描电镜对分子印迹聚合物进行结构表征,测试了分子印迹聚合物的吸附特性,探讨了分子印迹聚合物固相萃取应用效能并对萃取条件进行了优化.结果表明,当预反应混合液中金属离子、模板总量(阿魏酸-咖啡酸摩尔比为2:3)、功能单体及交联剂用量比为1:1:3:30(摩尔比)时,所得印迹聚合物对两种模板(阿魏酸和咖啡酸)均具有最好的吸附性能,吸附量分别达51.12mg/g和70.26mg/g.吸附动力学测试表明吸附3h,分子印迹聚合物可达到吸附平衡.用分子印迹聚合物进行固相萃取时,优化的淋洗过程为1.00mL H₂O、1.00mL甲醇-H₂O (3/7,体积比)及1.00mL甲醇-H₂O-ACN (4/4/2,体积比),洗脱溶剂为2.00mL甲醇.在优化条件下,分子印迹聚合物可同时选择富集升麻初提液中的阿魏酸和咖啡酸,二者回收率分别为92.67%和95.42%,而且产品中杂质少于用硅胶萃取所得产品.     

白杨素分子印迹聚合物的制备及其性能评价

以白杨素为模板分子,硅胶为载体,丙烯酰胺为功能单体,采用表面印迹法制备白杨素分子印迹聚合物。并通过红外光谱测定,吸附实验等对印迹聚合物进行表征及性能评价。静态吸附实验表明,印迹聚合物对模板分子的吸附量远远高于非印迹聚合物;印迹聚合物及非印迹聚合物对白杨素、氯霉素、甲砜霉素的选择吸附表明,所制备的分子印迹聚合物对白杨素有特异性吸附效果。     

罗丹明B分子印迹聚合物的制备及分子识别性能研究

以三苯甲烷类碱性染料罗丹明B为模板分子,丙烯酰胺为功能分子,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,采用表面修饰分子印迹法,制备对罗丹明B具有特定亲和选择性的分子印迹聚合物。应用红外光谱对印迹聚合物进行表征,通过静态吸附实验对聚合物的吸附动力学进行分析,采用平衡结合实验评价了分子印迹聚合物的吸附性能。结果表明,采用表面修饰分子印迹法所制备的印迹聚合物对罗丹明B表现出较好的特异吸附,对模板分子最大吸附量值为96μmol/g。     

SAA表面分子印迹材料的制备及吸附性能

将丙烯酸与分散剂、表面活性剂充分混合,加入聚酰胺颗粒、交联剂,致孔剂、模板分子丹参素(SAA),在引发剂过氧化苯甲酰的作用下发生聚合反应,制得SAA分子印迹聚合物。用红外光谱对该聚合物的特征结构进行表征。采用静态、动态平衡吸附法研究SAA印迹聚合物的吸附性能,吸附量最大为9.7 mg/g,优化吸附工艺参数分别为:浓度为1.6 mg/m L、吸附温度为20℃、时间为40 min。     

糠醛分子印迹聚合物的制备及吸附性能研究

以糠醛为模板分子,采用本体聚合法制备了对糠醛具有高特异吸附性的糠醛分子印迹聚合物。利用扫描电镜和红外光谱对聚合物进行表征分析,并利用动态吸附、静态吸附和选择性吸附实验考察糠醛印迹聚合物的吸附性能。结果表明,所制备的糠醛分子印迹聚合物对糠醛呈现出较好的特异性吸附能力,有望作为固相萃取材料应用于食品中糠醛残留的分离、富集和检测。     

Preparation and evaluation of a molecularly imprinted polymer for tolazoline

A uniformly sized molecularly imprinted polymer for the peripheral vasodilator drug tolazoline (T‐MIP) was prepared, and a nonimprinted polymer (NIP) was also synthesized in the same way but in the absence of the template. The T‐MIP was prepared with methylacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker by a multistep swelling and polymerization method. These imprinted materials were characterized by scanning electron microscopy, nitrogen adsorption, and static adsorption experiments. Binding studies were also performed to evaluate the uptake of T‐MIP and NIP with the results that T‐MIP had a significantly higher binding capacity for tolazoline (T) than did NIP. The maximum static adsorption capacities of T‐MIP and NIP for T were 78.9 and 38.8 μmol/g, respectively. The T‐MIPs and NIPs were used as stationary phases of solid‐phase extraction (SPE), and a relative selectivity coefficient (k′) value of 5.21 was obtained, which showed that the T‐MIP sorbent had higher selectivity than the NIP sorbent. The method was applied to the determination of T in urine samples. The prepared polymer sorbent showed promise for SPE for gas chromatography determination of T in urine samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

红霉素分子印迹聚合物纳米微球的制备及其吸附特性

以红霉素为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了粒径均一的红霉素纳米分子印迹聚合物微球,优化了分子印迹聚合物的合成条件,确定了模板分子与功能单体的最佳摩尔比为1:3,对其进行了表征. 结果表明,所制聚合物对红霉素的实际最大吸附量可达202.12 mg/g,吸附约200 min达到平衡,对红霉素具有良好的选择性吸附能力.     

Removal of benzoic acid from industrial wastewater using metal organic frameworks: equilibrium,kinetic and thermodynamic study

In this work, the adsorption of benzoic acid (BA) over metal organic framework of chromium-benzenedicarboxylates (MIL-101) is reported for the first time. The influences of pH, contact time, initial concentration, and temperature of BA solution on the adsorption behavior were investigated. The Langmuir adsorption isotherm was adequate to represent the experimental data (R² > 0.99) and the adsorption kinetics was well-represented by a pseudo-second order kinetic model (R² > 0.96). The zeta potential of MIL-101 decreased with increasing pH confirming the importance of electrostatic interactions between MIL-101 and BA as well as the importance of the large pore volume (1.32 m³/g) and large surface area (2390 m²/g) of MIL-101 for adsorption interaction. The thermodynamics analysis indicated negative free energy, enthalpy, and entropy changes suggesting that the adsorption of BA on MIL-101 is spontaneous and exothermic. The adsorption capacity of BA adsorption over MIL-101 was compared with those for other conventional adsorbents. The maximum capacities of BA uptake on MIL-101, activate carbon, and multiwall carbon nanotubes were 769.2, 406.5, and 341.2 mg/g, respectively, suggesting the superiority of MIL-101 as an adsorbent. Adsorption of real wastewaters containing other organic compounds in addition to BA confirmed the versatility of MIL-101 as a suitable adsorbent in wastewater treatment compared with conventional adsorbents.     

分子印迹聚合物微球对亚甲基蓝的去除特性研究

以亚甲基蓝为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯（EGDMA）为交联剂,偶氮二异丁腈（AIBN）为引发剂．采用沉淀聚合法制备了亚甲基蓝分子印迹聚合物微球（MIP）。用扫描电镜表征了MIP的形貌,结果显示制备的MIP的粒径为1～3μm,粒径较为均匀。考察了MIP对亚甲基蓝的吸附性能,结果表明其吸附动力学过程可以用假二级吸附速率方程来描述,MIP对亚甲基蓝的最大吸附量为27．1mg／g,吸附效果较好,可以用于染料废水中亚甲基蓝的分离富集。     

Hierarchically structural polyacrylonitrile/MIL-101(Cr) nanofibrous membranes with super adsorption performance for indoxyl sulfate

Excess protein-bound uremic toxins (such as indoxyl sulfate [IS]) in the blood could aggravate chronic kidney disease and also predispose to serious cardiovascular disease. In this study, we constructed a novel IS adsorbent polyacrylonitrile/MIL-101(Cr) (PAN-M) nanofibrous membrane with high adsorption capacity and ultra-fast sorption rate for IS. The porous metal–organic framework MIL-101(Cr) were embedded in PAN nanofibers by electrospinning as an adsorbent for easy recovery. It was found that MIL-101(Cr) had a strong electrostatic effect on the SO₃⁻ of IS and could reach the adsorption equilibrium within 5 min. Notably, MIL-101(Cr) showed an extremely high adsorption capacity (~170 mg/g) for IS. The MIL-101(Cr) loading of prepared PAN-M nanofibrous membrane was optimized at 60 wt% and the optimal PAN-M60 exhibited an appreciable IS adsorption capacity (103 mg/g). The removal of IS was enhanced from 35.4% to 62.5% during hemodialysis by using PAN-M60 as adsorbent immersed in dialysate. This efficient adsorption performance can greatly reduce the consumption of dialysate and may shorten the hemodialysis time. This work would provide a fresh perspective on the development of MOF-based adsorbents to improve hemodialysis therapies.     

磁性金属有机框架材料制备及吸附性能研究

利用简单的溶剂热法合成了MIL-101（Fe）/CoFe₂O₄和MIL-101（Fe）/NiFe₂O₄磁性金属有机框架纳米复合材料。通过X射线衍射仪（XRD）、扫描电子显微镜（SEM）、振动磁强计（VSM）、热重分析仪（TGA）和紫外可见分光光度计（UV）等对复合材料的相结构、形貌、磁性能和吸附性能进行了研究。将磁性金属有机框架材料用于吸附污水中罗丹明B（RhB）,研究了罗丹明B初始质量浓度对复合材料吸附能力的影响。结果表明,制备的磁性金属有机框架复合材料的形貌均匀、结晶度高,具有高的饱和磁化强度。复合物具有金属有机框架材料和磁性材料的双重优点。MIL-101（Fe）/CoFe₂O₄对罗丹明B有较高的吸附能力（97.3 mg/g）。热力学研究发现吸附等温方程符合Langmuir模型,吸附动力学研究表明吸附机制与吸附质和吸附剂有关。磁性金属有机框架纳米复合材料作为污水处理剂将具有广阔的应用前景。     

Computer simulation and preparation of molecularly imprinted polymer membranes with chlorogenic acid as template

A computational approach was developed for screening functional monomers for rational design of molecularly imprinted polymer (MIP) membranes. It was based on a comparison of the binding energy of complexes between a template and various functional monomers. According to the results of theoretical calculations, MIP membranes with chlorogenic acid as a template were prepared with a UV irradiation polymerization method, using 4‐vinylpyridine as a functional monomer and N,N′‐methylenebisacrylamide as a crosslinker, with poly(vinylidene fluoride) microfiltration membranes as the support. Membranes covered with a thin layer of imprinted polymer selective to chlorogenic acid were then obtained and tested using the equilibrium‐adsorption method. The high affinity of these synthetic membranes to chlorogenic acid, together with their straightforward and inexpensive preparation, provides a good basis for the development of applications of imprinted polymers in separation processes such as solid‐phase extraction. Copyright © 2011 Society of Chemical Industry     

Adsorption Isotherms,Kinetics, and Desorption of 1,2-Dichloroethane on Chromium-Based Metal Organic Framework MIL-101

Adsorption equilibrium and kinetics of 1,2-dichloroethane on a chromium-based metal-organic framework MIL-101 were studied. Desorption activation energies of 1,2-dichloroethane on the MIL-101 were measured using temperature program desorption (TPD) experiments. Results showed that the adsorption capacity of the MIL-101 for 1,2-dichloroethane is 19 mmol/g at 288 K, being much higher than those of some activated carbon, zeolite, and MWCNTs. The isotherms of 1,2-dichloroethane were well fitted by the Langmuir equation. The isosteric heat and diffusion coefficients of 1,2-dichloroethane adsorption on the MIL-101 were separately within the range of 42.0–61.6 kJ/mol and range of 0.854–2.246 × 10^?10 cm²/s. TPD spectra exhibited two types of adsorption sites on the MIL-101 with desorption activation energy of 48.6 and 87.6 kJ/mol separately. Multiple recycle runs of 1,2-dichloroethane adsorption-desorption at 298 K (10 mbar for adsorption and 0.05 mbar for desorption) showed the 1,2-dichloroethane adsorption on the MIL-101 is highly reversible, and desorption efficiency is up to 98.42%.     

Bovine serum albumin-imprinted polymer gels prepared by graft copolymerization of acrylamide on chitosan

A graft copolymerization of acrylamide with N,N′-methylenebisacrylamide on chitosan in aqueous medium was utilized in the synthesis of molecularly imprinted polymer (MIP) gels using bovine serum albumin (BSA) as a template. The effect of the amount of initiator and the molecular weight and amount of chitosan on BSA rebinding was investigated. It was found that the resultant MIP gels based on chitosan-g-polyacrylamide (CS-g-PAM) showed significantly higher imprinting efficiency than those only consisting of polyacrylamide (PAM), and also better than those composed of chitosan/PAM semi-interpenetrating polymer network (CS/PAM-s-IPN). The batchwise adsorption of BSA and some non-template proteins showed that the CS-g-PAM based MIP gels demonstrated a quite significant template binding capacity different from the non-imprinted polymer (NIP) gels, and an obvious binding specificity for BSA. The adsorption isotherms of BSA on the MIP gels were determined and well fitted by a Langmuir model with a maximum binding capacity of 39.49 mg/g wet gels. The adsorption kinetics was analyzed by a linear driving force mass-transfer model. The MIP gels also showed much better stability in rebinding of the imprint molecules than those based on CS/PAM-s-IPN after three adsorption–regeneration cycles.