Modification of cyclodextrin and use in environmental applications.

Water pollution, which has become a global problem in parallel with environmental pollution, is a problem that needs to be solved urgently, considering the gradual depletion of water resources. The inadequacy of the water treatment methods and the materials used somehow directed the researchers to look for dual character structures such as biocompatible and biodegradable ß-cyclodextrin (ß-CD). ß-CD, which is normally insoluble in water, is used in demanding wastewater applications by being modified with the help of different agents to be water soluble or transformed into polymeric adsorbents as a result of co-polymerization via cross-linkers. In this way, in addition to the host-guest interactions offered by ß-CD, secondary forces arising from these interactions provide advantages in terms of regeneration and reusability. However, the adsorption efficiency and synthesis steps need to be improved. Based on the current studies presented in this review, in which cross-linkers and modification methods are also mentioned, suggestions for novel synthesis methods of new-generation ß-CD-based materials, criticisms, and recent methods of removal of micropollutants such as heavy metals, industrial dyes, harmful biomolecules, and pharmaceutics wastes are mentioned.

Molecularly imprinted polymers in toxicology: a literature survey for the last 5 years.

The science of toxicology dates back almost to the beginning of human history. Toxic chemicals, which are encountered in different forms, are always among the chemicals that should be investigated in criminal field, environmental application, pharmaceutic, and even industry, where many researches have been carried out studies for years. Almost all of not only drugs but also industrial dyes have toxic side and direct effects. Environmental micropollutants accumulate in the tissues of all living things, especially plants, and show short- or long-term toxic symptoms. Chemicals in forensic science can be known by detecting the effect they cause to the body with the similar mechanism. It is clear that the best tracking tool among analysis methods is molecularly printed polymer-based analytical setups. Different polymeric combinations of molecularly imprinted polymers allow further study on detection or extraction using chromatographic and spectroscopic instruments. In particular, methods used in forensic medicine can detect trace amounts of poison or biological residues on the scene. Molecularly imprinted polymers are still in their infancy and have many variables that need to be developed. In this review, we summarized how molecular imprinted polymers and toxicology intersect and what has been done about molecular imprinted polymers in toxicology by looking at the studies conducted in the last 5 years.

Effect of immobilization on the activity of catalase carried by poly(HEMA-GMA) cryogels.

Hydrogen peroxide is converted by catalase to molecular oxygen and water to remove oxidative stress. In this study, catalase immobilization was performed using poly(2-hydroxyethyl methacrylate-glycidyl methacrylate) (poly(HEMA-GMA)) cryogels with different amounts of GMA. Catalase adsorption capacity of 298.7 ±â€¯9.9 mg/g was achieved at the end of 9 h using the poly(HEMA-GMA)-250 cryogel. Kinetic parameters and the inhibitory effects of pesticides such as 4,4'-DDE and 4,4'-DDT on the activity of free and immobilized catalase enzyme were investigated. While the Vmax value of the immobilized enzyme was reduced 4-fold compared to the free enzyme, in the case of the comparison of the KM values, the affinity of the immobilized enzyme was increased by 1.94 times against the substrate. The inhibitory effect of 4,4'-DDT pesticide was found to be higher for the immobilized and free enzyme. NaCl (1 M, pH: 7.0) solution was used for desorption of the adsorbed catalase enzyme. A desorption ratio of 96.45% was achieved. The technique used in this study is promising regarding for the immobilization of catalase enzyme to increase the operational activity. Therefore, poly(HEMA-GMA) cryogels have the potential to be used for immobilization of catalase enzyme in the fields of biology and biochemistry.

Use of nicotinamide decorated polymeric cryogels as heavy metal sweeper.

Cryogels are synthetic polymers used in adsorption experiments in recent years. Because of their macropores, they provide an excellent advantage as an adsorbent in continuous and batch adsorption processes. In this study, nicotinamide (NAA) decorated poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA), cryogels were synthesized. Heavy metal adsorption was carried out in wastewater obtained from six different sources in Çorum, Turkey. This study has a novelty regarding the application, i.e., it is the first time to use a polymeric adsorbent for the removal of 15 different heavy metal at the same time without any competition (despite the fact that there is a competition between the metals, the only thing is the removal regarding the purpose the study) as a heavy metal sweeper. Inductively coupled plasma-mass spectrometer (ICP-MS) was used for the determination of the initial amount of heavy metal in the wastewater samples. Adsorption studies were performed using poly(HEMA-GMA) and NAA-decorated poly(HEMA-GMA) cryogel to see the effect of NAA decoration. Higher adsorption capacity was achieved using NAA decorated poly(HEMA-GMA) cryogel. The total heavy metal amount adsorbed from six different sources was about 686 and 387 mg for poly(HEMA-GMA)-NAA and poly(HEMA-GMA) cryogels, respectively. The highest heavy metal adsorption value was obtained in the wastewater from source 2, and Zn (II) was the heavy metal adsorbed most for both cryogel. Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermal, surface area, elemental, and computerized microtomography (µCT) analyses were used for the characterization of cryogels.

Solvent effect on endosulfan adsorption onto polymeric arginine-methacrylate cryogels.

Endosulfan is a persistent insecticide that is still used in some countries even though it is life-threatening and banned in the agricultural struggle. The solubility of pesticides in water is negligible. It is known that pesticides with better solubility in organic solvents have different solubility when the dielectric constants of these solvents are taken into account. The polymeric structure of arginine was modified with methacrylate to be a functional monomer, and it was immobilized on a solid support, poly(HEMA), and finally, poly(2-hydroxyethyl methacrylate-arginine methacrylate) was obtained and used as an effective adsorbent. The effect of organic solvents on endosulfan adsorption was investigated for the first time in the literature. Endosulfan was removed from alcohol media by using this polymeric structure synthesized by exploiting alcoho-phobic interaction in this work. Nuclear magnetic resonance (NMR), elemental analysis, and Fourier transform infrared spectroscopy (FTIR) methods were used for the structural characterization and therefore to prove successful synthesis of cryogels. Morphological characteristics were also investigated by scanning electron microscopy (SEM), an N2 adsorption method, and swelling test. Adsorption experiments were carried out against varying interaction time and concentration parameters in the batch system. Since the alcohol used as a solvent has a pH value close to the ionic strength of drinking water, no change was made in the pH of the solution. Endosulfan molecules dissolved in solvents such as toluene, dichloromethane, acetone, and chloroform were removed using poly(HEMA-ArMA) cryogels to determine the solvent effect on the adsorption of endosulfan. As expected, the removal of endosulfan from the solvent toluene provided the best result. Although the adsorption in toluene is almost 9.5 times higher than that in ethanol, the use of toluene in the adsorption process due to its chemical structure is not feasible. Thus, experiments were carried out in ethanol.

Synthesis and characterization of Ag+-decorated poly(glycidyl methacrylate) microparticle design for the adsorption of nucleic acids.

In this study, we report on the adsorption of RNA and DNA molecules by exploiting the high binding affinity of these nucleic acids to Ag+ ions anchored on magnetic poly(glycidyl methacrylate) (PGMA) microparticles. PGMA microparticles were synthesized and modified with nicotinamide which enabled to anchor Ag+ ions on the surface. The successful preparation of PGMA was confirmed by the presence of characteristic FTIR peaks. The ESR results showed that the incorporation of FeNi salt to the polymeric structure provided a magnetic property to the microparticles. The amount of nicotinamide and Ag+ ions used to modify the surface of the particles were found to be 1.79 wt% and 52.6 mg Ag/g microparticle, respectively. The high affinity of nucleic acids to Ag+ ions were exploited for the adsorption studies. At the optimum working conditions, the adsorption capacity of microparticles was found to be 40.1 and 11.48 mg nucleic acid/g microparticle for RNA and DNA, respectively. Our study indicated that the use of novel Ag+-decorated magnetic PGMA particles can be successfully employed as adsorbents for fast, easy, and cost-friendly adsorption of nucleic acids with high purity as well as high in quantity.

Removal of DDE by exploiting the alcoho-phobic interactions.

DDE (1,1-bis-(4-chlorophenyl)-2,2-dichloroethene), which is a commonly used pesticides in agriculture, has harmful effects on human health. Therefore, the removal of this substance from the drinking water and the soil is essential. Since DDT (1,1″-(2,2,2-Trichloroethane-1,1-diyl) bis(4-chlorobenzene)) is derivation of DDE, the presence of DDT can be monitored by the detection of DDE present in the environment. Herein, we report on the development of aspartic acid-incorporated poly(2-hydroxyethyl methacrylate-L-aspartic acid) [poly(HEMA-MAsp)] cryogel for the removal of DDE from aqueous solutions for the first time in the literature. The synthesized cryogels were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), an N2 adsorption method, elemental analysis, and swelling test. The separation experiments were carried out via a batch system to get the optimum adsorption conditions including pH, interaction time, initial DDE concentration, and temperature. The desorption and the reusability results revealed that there was no significant decrease in the DDE adsorption capacity of the cryogels after five adsorption-desorption cycles. The maximum DDE adsorption capacity of poly(HEMA-MAsp) cryogels was found to be 31.51 mg DDE/g polymer for 50 mg DDE/L solution.

Affinity purification lipase from wheat germ: comparison of hydrophobic and metal chelation effect.

Cryogels are used quite a lot nowadays for adsorption studies as synthetic adsorbents. In this study, lipase enzyme (obtained from Candida cylindracea) adsorption capacity of poly(2-hydroxyethyl methacrylate-N-methacryloyl-L-tryptophan), poly(HEMA-MATrp), and Cu(II) ions immobilized poly(HEMA-MATrp), poly(HEMA-MATrp)-Cu(II), cryogel membranes were synthesized to determine and compare the adsorption behavior of lipase enzyme. In this regard, the effect of pH, interaction time, lipase initial concentration, temperature and ionic strength on the adsorption capacity of these membranes was investigated. Maximum lipase enzyme adsorption capacities of poly(HEMA-MATrp) and poly(HEMA-MATrp)-Cu(II) cryogel membranes were determined as 166.4 mg/g and 196.4 mg/g, respectively.

Efficient polymeric material for separation of human hemoglobin.

In this study, negatively charged acrylic acid was used as a functional ligand to synthesise net-poly(2-hydroxyethyl methacrylate-co-acrylic acid) microparticles for the removal of hemoglobin having a positively charged Fe2+ ion in the core, as an alternative to conventional techniques to achieve a cost effective high-capacity purification. The characterization of microparticles was performed via Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, the Brunauer - Emmett - Teller surface area analysis, and swelling test methods. Optimum adsorption conditions such as pH, initial hemoglobin concentration, temperature, and interaction time were studied batch wise. The highest adsorption capacity of microparticles was observed at pH 7.4 as 1276.4 mg hemoglobin/g polymer. The reusability of microparticles was also promising with ∼5% decrease in the adsorption capacity at the end of the five adsorption-desorption cycles.

PolyAdenine cryogels for fast and effective RNA purification.

Cryogels are used effectively for many diverse applications in a variety of fields. The isolation or purification of RNA, one of the potential utilizations for cryogels, is crucial due to their vital roles such as encoding, decoding, transcription and translation, and gene expression. RNA principally exists within every living thing, but their tendency to denaturation easily is still the most challenging issue. Herein, we aimed to develop adenine incorporated polymeric cryogels as an alternative sorbent for cost-friendly and fast RNA purification with high capacity. For this goal, we synthesized the polymerizable derivative of adenine called as adenine methacrylate (AdeM) through the substitution reaction between adenine and methacryloyl chloride. Then, 2-hydroxyethyl methacrylate (HEMA)-based cryogels were prepared in a partially frozen aqueous medium by copolymerization of monomers, AdeM, and HEMA. The cryogels were characterized by using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), surface area measurements, thermogravimetric analysis (TGA), and swelling tests. RNA adsorption experiments were performed via batch system while varying different conditions including pH, initial RNA concentration, temperature, and interaction time. We achieved high RNA adsorption capacity of cryogels, with the swelling ratio around 510%, as 11.86mg/g. The cryogels might be reused at least five times without significant decrease in adsorption capacity.

Polyethyleneimine assisted-two-step polymerization to develop surface imprinted cryogels for lysozyme purification.

Surface imprinting strategy is one of the promising approaches to synthesize plastic antibodies while overcoming the problems in the protein imprinting research. In this study, we focused our attentions on developing two-step polymerization to imprint on the bare surface employing polyethyleneimine (PEI) assisted-coordination of template molecules, lysozyme. For this aim, we firstly synthesized poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA) cryogels as a bare structure. Then, we immobilized PEI onto the cryogels through the addition reaction between GMA and PEI molecules. After that, we determined the amount of free amine (NH2) groups of PEI molecules, subsequently immobilized methacrylate functionalities onto the half of them and another half was used to chelate Cu(II) ions as a mediator between template, lysozyme and PEI groups. After the characterization of the materials developed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and the micro-computed tomography (µCT), we optimized the lysozyme adsorption conditions from aqueous solution. Before performing lysozyme purification from chicken egg white, we evaluated the effects of pH, interaction time, the initial lysozyme concentration, temperature and ionic strength on the lysozyme adsorption. Moreover, the selectivity of surface imprinted cryogels was examined against cytochrome c and bovine serum albumin (BSA) as the competitors. Finally, the mathematical modeling, which was applied to describe the adsorption process, showed that the experimental data is very well-fitted to the Langmuir adsorption isotherm.

PolyGuanine methacrylate cryogels for ribonucleic acid purification.

The isolation and purification of ribonucleic acid have attracted attention recently for the understanding of the functions in detail because of the necessity for the treatment of genetic diseases. In this study, guanine-incorporated polymeric cryogels were developed to obtain highly purified ribonucleic acid. The satisfactory purification performance was achieved with the guanine-incorporated poly (2-hydroxyethyl methacrylate-guanine methacrylate) cryogels. The most crucial advantages to use guanine as a functional monomer are to obtain a real natural interaction between guanine on the polymeric material and cytosine on the ribonucleic acid. Moreover, using cryogel with a highly porous structure and high swelling ratio provide advantages of getting more water within the structure to get more analyte to interact. The characterization of cryogels has proved the success of the synthesis and the perfect natural interaction to be taken place between the ligand (guanine methacrylate) and the cytosine in the ribonucleic acid molecules. Although the pores within the structure of cryogels are small, they provide efficient and fast adsorption. The chromatographic separation performance was investigated for different conditions (pH, temperature etc.). The desorption ratio and reusability were also analyzed at the end of the five adsorption-desorption cycles with no significant changes.

Fe(II)-Co(II) Double Salt Incorporated Magnetic Hydrophobic Microparticles for Invertase Adsorption.

Invertase (ß-fructofuranoside fructohydrolase, EC 3.2.1.26) is an enzyme widely used in the food industry. Its main function is the formation of glucose and fructose through hydrolysis of sucrose. For the separation and purification of this commercially important enzyme from aqueous solutions, magnetic poly(2-hydroxyethyl methacrylate-N-methacryloyl-L-tryptophan), m-poly(HEMA-MATrp) microparticles were developed. Magnetic properties of microparticles are provided using ferromagnetic Fe(II)-Co(II) double salt. Characterization studies of magnetic microparticles were conducted via vibrating sample magnetometer (VSM), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) analysis. Specific surface area of magnetic microparticles is 6.75 m(2)/g. Because of all experiments performed in this study, the adsorption capability of magnetic microparticles was optimized by variation of different conditions (pH, interaction time, initial invertase concentration, temperature, and ionic strength) and maximum adsorption capacity was determined as 992.64 mg invertase/g magnetic microparticles.

Bioinspired surface modification of poly(2-hydroxyethyl methacrylate) based microbeads via oxidative polymerization of dopamine.

Surface modification of support materials is crucial for improving their selectivities and biocompatibilities in bioaffinity applications. However, conventional modification techniques including chemical or physical conjugations mostly suffer from limitations of their multistep and complicated procedures, surface denaturations, batch-to-batch inconsistencies, and insufficient surface conjugations. In this study, we demonstrate a simple yet effective bioinspired approach for the surface modification of poly(2-hydroxyethyl methacrylate) [PHEMA] based bioaffinity adsorbents through oxidative polymerization of dopamine. The magnetic (mPHEMA) and non-magnetic (PHEMA) polymeric microbeads were fabricated by suspension polymerization technique. Surface modification of obtained microbeads was then carried out by using dopamine molecules under alkaline conditions. The polydopamine (PDOPA) coated microbeads were further employed as a bioaffinity absorbent targeted for immunoglobulin G (IgG) molecules. The effects of pH, temperature, protein concentration and ionic strength on the IgG adsorption process have been investigated. We found that PDOPA coated microbeads display dramatically higher IgG adsorption capacities when compared with their un-modified forms. Adsorption capacities also increased with increasing temperature. Monolayer Langmuir adsorption model can be thought more applicable for these adsorbent systems.

Poly(hydroxyethyl methacrylate) based magnetic nanoparticles for lysozyme purification from chicken egg white.

The purpose of this article is to synthesize poly(hydroxyethyl methacrylate-N-methacryloyl-(L)-tryptophan) [mPHEMATrp] magnetic nanoparticles for lysozyme purification from chicken egg white. mPHEMATrp nanoparticles (38 nm in diameter) were synthesized by surfactant-free emulsion polymerization. Specific surface area of the mPHEMATrp nanoparticles was calculated to be 896 m2/g. Elemental analysis of mPHEMATrp nanoparticles was estimated in the range of 5.7-48.3 µmol MATrp/g. The maximum lysozyme adsorption capacity of the mPHEMATrp nanoparticles was 376.1 mg/g. The mPHEMATrp nanoparticles could be used five times without decreasing the lysozyme adsorption capacity significantly. The results indicate that the mPHEMATrp nanoparticles promise high selectivity for lysozyme purification.

Glutamic acid containing supermacroporous poly(hydroxyethyl methacrylate) cryogel disks for UO22+ removal.

Supermacroporous cryogel with an average pore size of 10-200µm in diameter was prepared by cryopolymerization of N-methacryloyl-(l)-glutamic acid (MAGA) and 2-hydroxyethyl methacrylate (HEMA). The poly(HEMA-MAGA) cryogel was characterized by surface area measurements, FTIR, swelling studies, elemental analysis and SEM. The poly(HEMA-MAGA) cryogel had a specific surface area of 23.2m2/g. The equilibrium swelling ratio of the cryogel is 9.68g H2O/g for poly(HEMA-MAGA) and 8.56g H2O/g cryogel for PHEMA. The poly(HEMA-MAGA) cryogel disks with a pore volume of 71.6% containing 878µmol MAGA/g were used in the removal of UO22+ from aqueous solutions. Adsorption equilibrium of UO22+ was obtained in about 30min. The adsorption of UO22+ ions onto the PHEMA cryogel disks was negligible (0.78mg/g). The MAGA incorporation significantly increased the UO22+ adsorption capacity (92.5mg/g). The adsorption process is found to be a function of pH of the UO22+ solution, with the optimum value being pH 6.0. Adsorption capacity of MAGA contained PHEMA based cryogel disks increased significantly with pH and then reached the maximum at pH 6.0. Consecutive adsorption and elution cycles showed the feasibility of repeated use for poly(HEMA-MAGA) cryogel disks.