A surface ion-imprinted mesoporous sorbent for separation and determination of Pb(II) ion by flame atomic absorption spectrometry

A surface-imprinted mesoporous sorbent for Pb(II) ion was synthesized by the post-synthesis method. The material was characterized by transmission electron microscopy and nitrogen adsorption-desorption isotherms. The adsorption by the material was studied by batch experiments with respect to effects of pH value, contact time, kinetics, and adsorption isotherms. Both the pseudo-second-order kinetic model and the Langmuir model fit the experimental data well. Compared to other imprints for Pb(II), to the traditional sorbents and to the non-imprinted polymer, the new sorbent displays fast kinetics and higher selectivity. Pb(II) ion can be desorbed from the imprint with 2 M hydrochloric acid with high efficiency. The sorbent was applied to the selective separation and determination of Pb(II) in water and sediment samples with satisfactory results.

A surface-imprinted polymer for removing dibenzothiophene from gasoline

A surface-imprinted polymer for the adsorption of dibenzothiophene (DBT) was obtained from DBT (the template), titanium dioxide (the support), methacrylic acid (the functional monomer), ethylene glycol dimethacrylate (the cross-linker), 2,2´-azobisisobutyronitrile (the initiator) and toluene (the porogen). The material was characterized by Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller model and Scanning electron microscopy. Batch adsorption experiments were performed to study the adsorption of the material in terms of adsorption kinetics, isotherms, and thermodynamic parameters. The adsorption follows pseudo-second-order kinetics, the Freundlich adsorption equation fits the experimental data well, and there is strong evidence for multiple layer adsorption. The negative values of the Gibbs free energy (ΔG₀) range from -6.04 kJ?mol^-1 to -7.69 kJ?mol^-1 between 298 and 318 K, which reveals that the adsorption is endothermic. The material can selectively recognize DBT over similar compounds present in gasoline (such as benzothiophene and 4-methyldibenzothiphene).     

Preparation of molecularly imprinted polymer by surface imprinting technique and its performance for adsorption of dibenzothiophene

The novel surface imprinted polymer composites (MIP/K(2)Ti(4)O(9)) were prepared using dibenzothiophene (DBT) as the template, 4-vinylpyridine as the functional monomer and potassium tetratitanate whisker (K(2)Ti(4)O(9)) as the carrier. The synthetic product was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Parameters influencing DBT adsorption such as contact time, temperature and DBT initial concentration were investigated. The adsorption kinetics were evaluated with the pseudo-first-order and pseudo-second-order models, and the adsorption isotherms were fitted by Langmuir and Freundlich models. Selectivity experiments showed that MIP/K(2)Ti(4)O(9) exhibited excellent recognition capacity and binding affinity to DBT compared with the comparative substrates. MIP/K(2)Ti(4)O(9) could also be easily regenerated and reused ten times with only about 20% loss of adsorption capacity.     

Desulfurization of Gasoline using Molecularly Imprinted Chitosan as Selective Adsorbents

For desulfurization of gasoline, novel chitosan-based molecularly imprinted polymer (MIP) was prepared by cross-linking chitosan with epichlorohydrin in the presence of dibenzothiophene (DBT) as the template. The influence of cross-linking ratio on the specific adsorption was evaluated. The effects of the types and the amounts of porogen on selectivity of the chitosan MIP were also examined. Results showed that MIP has a higher recognition property to DBT. The maximum rebinding capacities of the MIP reached 22.69 mg g⁻¹ in the model solution. The adsorption behaviors of the MIP including adsorption kinetics, isotherms, and thermodynamic parameters were investigated and the experimental data agreed well with the Langmuir model. The dynamical adsorption behaved in first-order kinetics. Negative values for the Gibbs free energy showed that the adsorptions were spontaneous processes. The MIP was further used to selectively adsorb organosulfur from gasoline.     

Grafting of molecularly imprinted polymer to porous polyethylene filtration membranes by plasma polymerization

An application of plasma-induced grafting of polyethylene membranes with a thin layer of molecularly imprinted polymer (MIP) was presented. High-density polyethylene (HDPE) membranes, “Vyon,” were used as a substrate for plasma grafting modification. The herbicide atrazine, one of the most popular targets of the molecular imprinting, was chosen as a template. The parameters of the plasma treatment were optimized in order to achieve a good balance between polymerization and ablation processes. Modified HDPE membranes were characterized, and the presence of the grafted polymeric layer was confirmed based on the observed weight gain, pore size measurements, and infrared spectrometry. Since there was no significant change in the porosity of the modified membranes, it was assumed that only a thin layer of the polymer was introduced on the surface. The experiments on the re-binding of the template atrazine to the membranes modified with MIP and blank polymers were performed. HDPE membranes which were grafted with polymer using continuous plasma polymerization demonstrated the best result which was expressed in an imprinted factor equal to 3, suggesting that molecular imprinting was successfully achieved.

Transferrin recognition based on a protein imprinted material prepared by hierarchical imprinting technique

A novel kind of transferrin imprinted polymer particles was synthesized by a hierarchical strategy. First, transferrin was immobilized on silica beads by non-covalent absorption. Then, a pre-polymerization mixture, composed of 1,4-bis(acryloyl)piperazine, methacrylamide, methacrylic acid, ammonium sulfate and polyoxyethylene sorbitan monolaurate, was irrigated into the pores of silica particles, and polymerized at 25 °C. Finally, the silica matrix was etched with ammonium hydrogen fluoride, not only to remove the template protein, but also to expose protein recognition sites on the surface of the imprinted polymer. The binding capacity of the transferrin-imprinted particles is 6.3 mg of protein per gram of material, and the time required to reach adsorption equilibrium was less than 10 min. The imprinting factor of transferrin is ca. 3.3 in the presence of ribonuclease B, cytochrome c and β-lactoglobulin. The results indicate that these imprinted polymer particles can recognize transferrin with good selectivity, high binding capacity and fast mass transfer. They may be applied as an artificial antibody to remove the high abundance proteins in plasma.

Adsorption properties of <Emphasis Type="Italic">Pseudomonas monteilii</Emphasis> for removal of uranium from aqueous solution

The Pseudomonas monteilii. YL-1 was cultured from deep sea sediment to remove uranium from aqueous solution. Different influence factors on uranium adsorption efficiency were investigated. The kinetic model of Pseudomonas monteilii could be described by the pseudo-second-order kinetic model, and the Freundlich isotherm model could fit the experiment data well, indicating that the adsorption was multilayer adsorption. The adsorption was spontaneous and endothermic reaction by thermodynamic analysis. The functional groups of Pseudomonas monteilii such as hydroxy, carboxyl, amino and amide may act with UO₂²⁺ by chemisorption or strong complexation in the process of uranium adsorption.     

Development of a novel molecularly imprinted polymer for the retention of 4,6-dimethyldibenzothiophene

Several molecularly imprinted polymers (MIPs) for the retention of 4,6-dimethyldibenzothiophene (4,6-DMDBT) were prepared. The first was a polymer prepared non-covalently with methacrylic acid and ethylene glycol dimethacrylate polymerized in the presence of 4,6-DMDBT. After extraction of 4,6-DMDBT, the selectivity of the imprinted polymer was evaluated by HPLC and compared to a non-imprinted control polymer prepared without 4,6-DMDBT. The imprinted polymer retained 4,6-DMDBT slightly longer than the control polymer. The second polymer was prepared using nickel (II)-methacryloylhistidinedihydrate monomer which was combined with 4,6-DMDBT, and polymerized with ethylene glycol dimethacrylate. This is a novel use of this monomer for retention of sulfur-containing organic compounds. Selectivity for 4,6-DMDBT was much greater in this polymer compared to the first, and retention in acetonitrile was more than three times greater on the imprinted polymer compared to a control polymer. Results indicate the potential use of this novel MIP for the removal of organosulfur compounds from fuel.

Rapid preparation of molecularly imprinted polymer by frontal polymerization

Frontal polymerization was successfully applied, for the first time, to obtain molecularly imprinted polymers (MIPs). The method provides a solvent-free polymerization mode, and the reaction can be completed in 30 min. By this approach, MIPs were synthesized using a mixture of levofloxacin (template), methacrylic acid, and divinylbenzene. The effect of template concentration and the amount of comonomer on the imprinting effect of the resulting MIPs was investigated. The textural and morphological parameters of the MIP particles were also characterized by mercury intrusion porosimetry, nitrogen adsorption isotherms, and scanning electron microscopy, providing evidence concerning median pore diameter, pore volumes, and pore size distributions. The levofloxacin-imprinted polymer formed in frontal polymerization mode showed high selectivity, with an imprinting factor of 5.78. The results suggest that frontal polymerization provides an alternative means to prepare MIPs that are difficult to synthesize and may open up new perspectives in the field of MIPs.

Magnetic nanoparticles with an imprinted polymer coating for the selective extraction of uranyl ions

We have synthesized ferromagnetic nanoparticles with an imprinted polymer coating that is capable of adsorbing and extracting uranyl ions. The adsorbent was characterized using infrared spectroscopy, elemental analysis, X-ray powder diffraction analysis, and scanning electron microscopy. The effects of sample pH, sample volume, weight of the adsorbent, contact time and of other ions have been investigated in the batch extraction mode. The performance of the material was compared to that of particles coated with a non-imprinted polymer. The adsorbent containing the imprinted coating displays higher sorption capacity and better selectivity to uranyl ions. The method was successfully applied to the determination of uranyl ions in water samples.

Surface molecular imprinting for chemiluminescence detection of the organophosphate pesticide chlorpyrifos

We report on a surface molecular imprinting strategy for synthesizing core-shell particles whose shell is imprinted with chlorpyrifos (CPF). The particles were prepared by copolymerization of the methacryloyl groups on the surface of silica particles modified with 3-methacryloxypropyl trimethoxysilane a functional monomer and a cross-linking agent. The imprinted particles exhibit larger binding capacity, faster binding kinetics, and higher recognition selectivity for CPF. Combined with highly sensitive chemiluminescence assay, the method was applied to the determination of CPF with a detection limit of 0.92?nM which is about 2 orders of magnitude lower than that by conventional CL method. The method also displays repeatability for more than 200 times.

Extraction of tributyltin by magnetic molecularly imprinted polymers

We have prepared core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT). The use of particles strongly improves the imprinting effect and leads to fast adsorption kinetics and high adsorption capacities. The functional monomer acrylamide was grafted to the surface of Fe₃O₄ nanospheres in two steps, and MIP layers were then formed on the surface by creating a MIP layer on the surface consisting of poly(ethyleneglycol dimethacrylate) with a TBT template. The particles were characterized in terms of morphological, magnetic, adsorption, and recognition properties. We then have developed a method for the extraction of TBT from spiked mussel (Mytilidae), and its determination by liquid chromatography-tandem mass spectrometry. The method has a limit of detection of 1.0 ng?g^?1 (n?=?5) of TBT, with a linear response between 5.0 and 1,000 ng?g^?1. The proposed method was successfully applied to the determination of trace TBT in marine food samples with recoveries in the range of 78.3–95.6 %.

介孔碳CMK-3对苯酚的吸附动力学和热力学研究

研究了介孔碳CMK-3对苯酚的吸附性能, 与传统商用活性碳(CAC)进行了比较, 结果表明, CMK-3比CAC的吸附量大、吸附速率快、达到平衡时间短, 是一种较好的吸附剂. 同时探讨了介孔碳CMK-3对苯酚的吸附热力学和动力学特征. CMK-3对苯酚的吸附行为可用Langmuir和Freundlich等温式进行描述, 相关性都较好, 但更符合Freundlich经验公式. 分别采用模拟一阶反应和二阶反应模型考察了吸附动力学, 并计算了这些动力学模型的速率常数. 模拟二级反应模型和实验数据之间有较好的相关性. 分别计算了热力学参数ΔG0, ΔS0和ΔH0, 结果表明, CMK-3对苯酚的吸附过程是吸热和自发的.     

Activated carbon from bamboo waste modified with iron and its application in the study of the adsorption of arsenite and arsenate

Activated carbon obtained from bamboo waste was synthesised and modified with iron (BAC-Fe) and used for the removal of arsenic from aqueous solutions. Two different adsorption models were used for analysing the data. The adsorption capacities were determined for BAC-arsenite, BAC-Fe-arsenite, BAC-arsenate and BAC-Fe-arsenate, with a qmax (μg g^?1) of 14.89, 19.19, 22.32 and 27.32 respectively. Adsorption capacity varied as a function of pH and modifications to the sorbent. Adsorption isotherms from an aqueous solution of arsenite and arsenates on activated carbons were determined. These adsorption isotherms were consistent with the Langmuir and Freundlich adsorption models. Adsorption kinetics followed a pseudo-first order rate equation, as did the kinetics for BAC-Fe-arsenite and BAC-Fe-arsenate adsorption.      

Sol–gel derived ion imprinted thiocyanato-functionalized silica gel as selective adsorbent of cadmium(II)

A Cd(II)-imprinted thiocyanato-functionalized silica gel adsorbent with high adsorption capacity was prepared by surface imprinting technique combined with sol–gel process for the selective adsorption of Cd(II) ion in aqueous solution, and was characterized by Fourier-transform infrared spectroscopy, nitrogen gas sorption and thermogravimetric analysis. The influences of different conditions (such as the pH of solutions, the contact time and the initial concentrations of Cd(II) ions) on the adsorption capacity of Cd(II) were investigated. The optimum pH of adsorption was in the range of 4–8.5. The adsorption equilibrium could be reached in 20 min. The relatively selectivity coefficients of the imprinted silica were higher than those of the non-imprinted adsorbents. Ho’s pseudo-second-order model well described the kinetics of the adsorption reaction. The adsorption process of metals followed Redlich–Peterson isotherm model, and the experimental value of maximum adsorption capacity for Cd(II) was 72.8 mg·g^?1. The positive value of ΔH ^o suggested endothermic nature of Cd(II) adsorption on the imprinted silica adsorbent. Increase in entropy of adsorption reaction was shown by the positive value of ΔS ^o and the negative value of ΔG ^o indicating that the adsorption was spontaneous in nature.     

A molecularly imprinted polymer for solid phase extraction of allantoin

We describe a molecularly imprinted polymer (MIP) for the solid-phase extraction of the skin protectant allantoin. The MIP was deposited on the surface of monodisperse silica microspheres possessing acroyl groups on the surface (MH-SiO₂). The resulting MIP microspheres (MH-SiO₂@MIP) showed a 3.4-fold higher adsorption capacity and a 1.9-fold better selectivity for allantoin than the respective non-imprinted polymer (MH-SiO₂@NIP). The monolayer adsorption capacities of the MH-SiO₂@MIP and the MH-SiO₂@NIP were calculated with the help of the Langmuir model and found to be 6.8 and 1.9 mg?g^?1, respectively. Adsorption kinetics fit a pseudo-second order rate mechanism, with an initial adsorption rate of 1.44 for the MH-SiO₂@MIP, and of 0.07 mg?g^?1?min^?1 for the MH-SiO₂@NIP. The material can be regenerated, and its adsorption capacity for allantoin remains stable for at least five regeneration cycles. It was successfully used as a sorbent for the selective solid-phase extraction of allantoin from Rhizoma dioscoreae.

A molecular imprint-coated stirrer bar for selective extraction of caffeine, theobromine and theophylline

We have prepared a novel caffeine imprinted polymer on a stir bar that can be used for selective extraction of caffeine, theobromine and theophylline from beverages. The polymerization time and quantities of reagents (template, cross-linker, porogenic solvent) were optimized. The morphology of the molecularly imprinted polymer-coating was studied by scanning electron microscopy and Fourier transform IR spectroscopy. A rapid and sensitive method was worked out for the extraction of caffeine, theobromine and theophylline from beverages by using the molecularly imprinted stir bar followed by HPLC analysis. The effects of extraction solvent, stirring speed, desorption solvent, adsorption and desorption time were optimized. The method displays a linear response in the 5–150 μg L^?1 caffein concentration range, with a correlation coefficient of >0.9904. The recoveries for three analytes in tea, carbonated and functional beverages were 91–108 %, 90–110 % and 93–109 %, with relative standard deviations ranging from 3.6–5.7 %, 3.5–7.9 % and 3.2–7.9 %, respectively.

Flame photometric determination of cesium ion after its preconcentration with nanoparticles imprinted with the cesium-dibenzo-24-crown-8 complex

We report on the synthesis of cesium ion-imprinted polymer nanoparticles that were prepared by a precipitation polymerization strategy using dibenzo-24-crown-8 ether as a selective crown ether, methacrylic acid as the functional monomer, ethyleneglycol dimethacrylate as the crosslinker, and AIBN as the radical initiator. The prepared sorbents have a diameter of 50–90 nm and display highly selective binding capability for Cs(I) ion, with rapid adsorption and desorption. The maximum adsorption capacity is 50 mg g^?1, and the preconcentration factor is around 100 at pH 9.0. Cesium ion was then determined by flame photometry with a detection limit (3σ) of 0.7 ng mL^?1 and with a standard deviation of 0.9 %.

Removal of heavy metals from industrial wastewaters using amine-functionalized nanoporous carbon as a novel sorbent

Nano-porous carbon (NPC) was synthesized by hydrothermal condensation of fructose and characterized by X-ray powder diffraction and also nitrogen adsorption analysis. It was then modified with amino groups and used as a sorbent for the removal of heavy metal ions. The formation of amino-modified NPC was confirmed by X-ray powder diffraction, infrared spectroscopy, thermogravimetric and elemental analysis. NPC was applied for removal of Pb(II), Cd(II), Ni(II) and Cu(II) ions. The effects of sample pH and the adsorption kinetics were studied, and the adsorption capacity was determined. The sorbent was applied to the removal of heavy metal ions in industrial waste water samples.

Study on the adsorption of DNA on Fe3O4 nanoparticles and on ionic liquid-modified Fe3O4 nanoparticles

We have investigated the adsorption of herring sperm DNA on Fe₃O₄ magnetic nanoparticles (NPs) before and after modification with the ionic liquid 1-hexyl-3-methylimidazolium bromide. Experiments were performed in a batch mode, and the effects of DNA concentration, pH of the sample solution, ionic strength, temperature, and contact time between reagents were optimized. An evaluation of the adsorption isotherm revealed that the Langmuir model better fits the equilibrium data than the Freundlich model. The maximum adsorption capacities of the unmodified and modified NPs, respectively, were found to be 11.8 and 19.8 mg DNA per gram of adsorbent. The adsorption of DNA onto the modified NPs was endothermic, while it was exothermic in the case of the unmodified NPs. The DNA can be desorbed from the modified surfaces of the NPs by using EDTA as the eluent. The NPs were able to adsorb about 90?±?1.5 % of DNA after being recycled for three times. The method is simple, fast, robust, and does not require organic solvents or sophisticated equipment.