Metal ion coordination interactions for biomolecule recognition: a review

Molecular imprinting is an effective method to create selective binding sites in polymeric matrices for biomolecule recognition. This review gives recent improvements of the design and preparation of selective binding sites via metal coordination interactions in molecularly imprinted polymers MIPs and focuses on particularly metal coordination bonds between biomolecules such as amino acids, peptides, proteins and templated polymers. The discussion will evaluate key parameters for molecular imprinting in the perspective of metal coordination

Bio-liquefaction/solubilization of low-rank Turkish lignites and characterization of the products

The effect of some white-rot fungi on the bio-liquefaction/solubilization of two low-rank Turkish coals and the chemical composition of the liquid products and the microbial mechanisms of coal conversion were investigated. Turkish Elbistan and Beypazari lignites were used in this study. The white-rot fungi received from various laboratories used in the bio-liquefaction/solubilization of the lignites were Pleurotus sajor-caju, Pleurotus sapidus, Pleurotus florida, Pleurotus ostreatus, Phanerochaete chrysosporium, and Coriolus versicolor. FT-IR spectra of raw and treated coal samples were measured, and bio-liquefied/solubilized coal samples were investigated by FT-IR and LC-MS techniques. The Coriolus versicolor fungus was determined to be most effective in bio-liquefying/solubilizing nitric acid-treated Elbistan lignite. In contrast, raw and nitric acid-treated Beypazari lignite seemed to be unaffected by the action of any kind of white-rot fungi. The liquid chromatogram of the water-soluble bio-liquefied/solubilized product contained four major peaks. Corresponding mass spectra of each peak indicated the presence of very complicated structures

Performance of dye-affinity beads for aluminium removal in magnetically stabilized fluidized bed

BACKGROUND: Aluminum has recently been recognized as a causative agent in dialysis encephalopathy, osteodystrophy, and microcytic anemia occurring in patients with chronic renal failure who undergo long-term hemodialysis. Only a small amount of Al(III) in dialysis solutions may give rise to these disorders. METHODS: Magnetic poly(2-hydroxyethyl methacrylate) (mPHEMA) beads in the size range of 80–120 μm were produced by free radical co-polymerization of HEMA and ethylene dimethacrylate (EDMA) in the presence of magnetite particles (Fe(3)O(4)). Then, metal complexing ligand alizarin yellow was covalently attached onto mPHEMA beads. Alizarin yellow loading was 208 μmol/g. These beads were used for the removal of Al(III) ions from tap and dialysis water in a magnetically stabilized fluidized bed. RESULTS: Al(III) adsorption capacity of the beads decreased with an increase in the flow-rate. The maximum Al(III) adsorption was observed at pH 5.0. Comparison of batch and magnetically stabilized fluidized bed (MSFB) maximum capacities determined using Langmuir isotherms showed that dynamic capacity (17.5 mg/g) was somewhat higher than the batch capacity (11.8 mg/g). The dissociation constants for Al(III) were determined using the Langmuir isotherm equation to be 27.3 mM (MSFB) and 6.7 mM (batch system), indicating medium affinity, which was typical for pseudospecific affinity ligands. Al(III) ions could be repeatedly adsorbed and desorbed with these beads without noticeable loss in their Al(III) adsorption capacity. CONCLUSIONS: Adsorption of Al(III) demonstrate the affinity of magnetic dye-affinity beads. The MSFB experiments allowed us to conclude that this inexpensive sorbent system may be an important alternative to the existing adsorbents in the removal of aluminium

Inspirations of biomimetic affinity ligands: a review

Affinity chromatography is a well-known method dependent on molecular recognition and is used to purify biomolecules by mimicking the specific interactions between the biomolecules and their substrates. Enzyme substrates, cofactors, antigens, and inhibitors are generally utilized as bioligands in affinity chromatography. However, their cost, instability, and leakage problems are the main drawbacks of these bioligands. Biomimetic affinity ligands can recognize their target molecules with high selectivity. Their cost-effectiveness and chemical and biological stabilities make these antibody analogs favorable candidates for affinity chromatography applications. Biomimetics applies to nature and aims to develop nanodevices, processes, and nanomaterials. Today, biomimetics provides a design approach to the biomimetic affinity ligands with the aid of computational methods, rational design, and other approaches to meet the requirements of the bioligands and improve the downstream process. This review highlighted the recent trends in designing biomimetic affinity ligands and summarized their binding interactions with the target molecules with computational approaches

Molecularly imprinted surface plasmon resonance (SPR) sensor for uric acid determination

The main objective of this study was to prepare a surface plasmon resonance (SPR) sensor for uric acid (UA) detection by using molecularly imprinted nanoparticles as a molecular recognition element. For imprinting, metal ion mediated preorganization was performed to interact between template molecules (UA) and functional monomer by using Fe3+ ions. UA-imprinted poly (hydroxyethyl methacrylate methacryloyl-l-cysteine methyl ester)-Fe3+ [poly(HEMA-MAC)-Fe3+] nanoparticles were synthesized by emulsion polymerization in the presence of MAC-Fe3+-UA pre-polymerization complex. The characterization of UA-imprinted poly(HEMA-MAC)-Fe3+ nanoparticles was conducted by Fourier transform infrared spectroscopy (FTIR), elemental analysis, scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), transmission electron microscopy (TEM) and zeta size analysis. The SPR sensor was prepared by gold surface modification of the sensor with UA-imprinted poly(HEMA-MAC)-Fe3+ nanoparticles. Characterization of the SPR sensor surface was performed with atomic force microscopy (AFM), contact angle (CA) and optic profilometer measurements. UA sensing ability of the prepared sensor was determined by interacting UA solutions in different concentrations (0.5-40 mg/L) with the SPR sensor. The limit of detection (LOD) and limit of quantification (LOQ) values for the prepared SPR sensor were calculated as 0.247 and 0.825 mg/L for aqueous solution, respectively. The UA-imprinted sensor was also used for UA detection in urine. The results showed the SPR sensor has high selectivity and sensitivity for UA

Vinyl imidazole carrying metal-chelated beads for reversible use in yeast invertase adsorption

Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) [poly(EGDMA-VIM)] hydrogel (average diameter 150-200 mu m) was prepared copolymerizing ethylene glycol dimethacrylate (EGDMA) with n-vinyl imidazole (VIM). Poly(EGDMA-VIM) beads had a specific surface area of 59.8 M-2/g. Poly(EGDMA-VIM) beads were characterized by swelling studies and scanning electron microscope (SEM). Cu2+ ions were chelated on the poly(EGDMA-VIM) beads (452 mu mol Cu2+/g), then the metal-chelated beads were used in the adsorption of yeast invertase in a batch system. The maximum invertase adsorption capacity of the poly(EGDMA-VIM)-Cu2+ beads was observed as 35.2 mg/g at pH 4.5. The adsorption isotherm of the poly(EGDMA-VIM)-Cu2+ beads can be well fitted to the Langmuir model. Adsorption kinetics data were tested using pseudo-first- and -second-order models. Kinetic studies showed that the adsorption followed a pseudo- second-order reaction. The value of the Michaelis constant K-m of invertase was significantly larger upon adsorption, indicating decreased affinity by the enzyme for its substrate, whereas V-max was smaller for the adsorbed invertase. The optimum temperature for the adsorbed preparation of poly(EGDMA-VIM)-CU2+- invertase at 50 degrees C, 10 degrees C higher than that of the free enzyme at 40 degrees C. Storage stability was found to increase with adsorption. Adsorbed invertase retains an activity of 82% after 10 batch successive reactions, demonstrating the usefulness of the enzyme-loaded beads in biocatalytic applications

Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) beads for heavy metal removal

Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) [poly(EGDMA-VIM)] hydrogel (average diameter 150-200 mum) was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) with n-vinyl imidazole (VIM). The copolymer hydrogel bead composition was characterized by elemental analysis and found to contain 5 EGDMA monomer units each VIM monomer unit. Poly(EGDMA-VIM) beads had a specific surface area of 59.8 m(2)/g. Poly(EGDMA-VIM) beads were characterized by swelling studies and scanning electron microscopy (SEM). These poly(EGDMA-VIM) beads with a swelling ratio of 78% were used for the heavy metal removal studies. Chelation capacity of the beads for the selected metal ions, i.e., Cd(II), Hg(II) and Pb(II) were investigated in aqueous media containing different amounts of these ions (10-750 mg/l) and at different pH values (3.0-7.0). Chelation rate was very fast. The maximum chelation capacities of the poly(EGDMA-VIM) beads were 69.4 mg/g for Cd(H), 114.8 mg/g for Pb(II) and 163.5 mg/g for Hg(II). The affinity order on molar basis was observed as follows: Hg(H) > Cd(II) > Pb(II). Chelation behavior of heavy metal ions could be modelled using both the Langmuir and Freundlich isotherms. pH significantly affected the chelation capacity of VIM incorporated beads. Chelation of heavy metal ions from synthetic wastewater was also studied. The chelation capacities are 45.6 mg/g for U(II), 74.2 mg/g for Hg(H) and 92.5 mg/g for Pb(II) at 0.5 mmol/l initial metal concentration. Regeneration of the chelating-beads was easily performed with 0.1 M HNO3. These features make poly(EGDMA-VIM) beads potential candidate adsorbent for heavy metal removal: (C) 2003 Elsevier B.V. All rights reserved

Molecular Fingerprints Of Hemoglobin On A Nanofilm Chip

Hemoglobin is an iron carrying protein in erythrocytes and also an essential element to transfer oxygen from the lungs to the tissues. Abnormalities in hemoglobin concentration are closely correlated with health status and many diseases, including thalassemia, anemia, leukemia, heart disease, and excessive loss of blood. Particularly in resource-constrained settings existing blood analyzers are not readily applicable due to the need for high-level instrumentation and skilled personnel, thereby inexpensive, easy-to-use, and reliable detection methods are needed. Herein, a molecular fingerprints of hemoglobin on a nanofilm chip was obtained for real-time, sensitive, and selective hemoglobin detection using a surface plasmon resonance system. Briefly, through the photopolymerization technique, a template (hemoglobin) was imprinted on a monomeric (acrylamide) nanofilm on-chip using a cross-linker (methylenebisacrylamide) and an initiator-activator pair (ammonium persulfate-tetramethylethylenediamine). The molecularly imprinted nanofilm on-chip was characterized by atomic force microscopy and ellipsometry, followed by benchmarking detection performance of hemoglobin concentrations from 0.0005 mg mL−1 to 1.0 mg mL−1. Theoretical calculations and real-time detection implied that the molecularly imprinted nanofilm on-chip was able to detect as little as 0.00035 mg mL−1 of hemoglobin. In addition, the experimental results of hemoglobin detection on the chip well-fitted with the Langmuir adsorption isotherm model with high correlation coefficient (0.99) and association and dissociation coefficients (39.1 mL mg−1 and 0.03 mg mL−1) suggesting a monolayer binding characteristic. Assessments on selectivity, reusability and storage stability indicated that the presented chip is an alternative approach to current hemoglobin-targeted assays in low-resource regions, as well as antibody-based detection procedures in the field. In the future, this molecularly imprinted nanofilm on-chip can easily be integrated with portable plasmonic detectors, improving its access to these regions, as well as it can be tailored to detect other proteins and biomarkers.PubMedWoSScopu

Microcontact imprinted surface plasmon resonance sensor for myoglobin detection

In this study, we prepared surface plasmon resonance (SPR) sensor using the molecular imprinting technique for myoglobin detection in human serum. For this purpose, we synthesized myoglobin imprinted poly(hydroxyethyl methacrylate-N-methacryloyl-t-tryptophan methyl ester) [poly(HEMA-MATrp)] nanofilm on the surface of SPR sensor. We also synthesized non-imprinted poly(HEMA-MATrp) nanofilm without myoglobin for the control experiments. The SPR sensor was characterized with contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, and ellipsometry. We investigated the effectiveness of the sensor using the SPR system. We evaluated the ability of SPR sensor to sense myoglobin with myoglobin solutions (pH 7.4, phosphate buffer) in different concentration range and in the serum taken from a patient with acute myocardial infarction. We found that the Langmuir adsorption model was the most suitable for the sensor system. The detection limit was 87.6 ng/mL. In order to show the selectivity of the SPR sensor, we investigated the competitive detection of myoglobin, lysozyme, cytochrome c and bovine serum albumin. The results showed that the SPR sensor has high selectivity and sensitivity for myoglobin

Immobilization of alpha-amylase on Cu2+ chelated poly(ethylene glycol dimethacrylate-n-vinyl imidazole) matrix via adsorption

Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) [poly(EGDMA-VIM)] hydrogel (average diameter 150-200 pm) was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) with n-vinyl imidazole (VIM). The copolymer hydrogel bead composition was characterized by elemental analysis and found to contain 5 EGDMA monomer units each VIM monomer unit. Poly(EGDMA-VIM) beads had a specific surface area of 59.8 m(2)/g. Poly- (EGDMA-VIM) beads were characterized by swelling studies and SEM. Cu2+ ions were chelated on the poly(EGDMA-VIM) beads, then these beads were used in the adsorption of alpha-amylase from Aspergillus Oryzae in batch system. The maximum alpha-amylase adsorption capacity of the poly(EGDMA-VIM)-Cu2+ beads was observed as 38.9 mg/g at pH 4.0. The K-m values for immobilized alpha-amylase (poly(EGDMA-VIM)-Cu2+) (22.5 mM) was higher than that of free enzyme (15.8 mM). Storage stability was found to increase with immobilization. It was observed that enzyme could be repeatedly adsorbed and desorbed without significant loss in adsorption capacity or enzyme activity