Rıdvan Say

BIOSORPTION OF CADMIUM(II), LEAD(II) AND COPPER(II) WITH THE FILAMENTOUS FUNGUS PHANEROCHAETE CHRYSOSPORIUM

The biosorption from artificial wastewaters of heavy metals (Cd(II), Pb(II) and Cu(II)) onto the dry fungal biomass of Phanerochaete chryosporium was studied in the concentration range of 5-500 mg l(-1). The maximum absorption of different heavy metal ions on the fungal biomass was obtained at pH 6.0 and the biosorption equilibrium was established after about 6 h. The experimental biosorption data for Cd(II), Pb(II) and Cu(II) ions were in good agreement with those calculated by the Langmuir model.

Biosorption of Cadmium, Lead, Mercury, and Arsenic Ions by the Fungus Penicillium purpurogenum

The potential use of the fungus Penicillium purpurogenum to remove cadmium, lead, mercury, and arsenic ions from aqueous solutions was evaluated. Biosorption of heavy metal ions reached equilibrium in 4 h. Heavy metal ions binding by Penicillium purpurogenum was clearly pH dependent. Heavy metal loading capacity increased with increasing pH under acidic conditions, presumably as a function of heavy metal speciation and due to the H+ competition at the same binding sites. The adsorption of heavy metal ions reached a plateau value at around pH 5.0. The maximum adsorption capacities of heavy metal ions onto the fungal biomass under noncompetitive conditions were 35.6 mg/g for As(III), 70.4 mg/g for Hg(II), 110.4 mg/g for Cd(II) and 252.8 mg/g for Pb(II). Their adsorption behavior can be described at least approximately with the Langmuir equation. The competitive adsorption capacities of the heavy metal ions were 3.4 mg/g for As(III), 15.8 mg/g for Hg(II), 13.1 mg/g for Cd(II), and 41.8 mg/g for Pb(II) at 50 mmol/L initial concentration of metal ions. The same affinity order on a molar basis was observed under noncompetitive and competitive adsorption conditions, which was as follows: Pb(II)>Cd(II)>Hg(II)>As(III). The equilibrium loading capacity of Pb(II) was greater than that of other metal ions. This fungal biomass showed a preference for binding Pb(II) over Cd(II), Hg(II), and As(III). Elution of heavy metal ions was performed using 0.5 M HCl. The fungus Penicillium purpurogenum could be used for ten cycles for biosorption.

Quartz crystal microbalance based nanosensor for lysozyme detection with lysozyme imprinted nanoparticles

The aim of this study is to prepare quartz crystal microbalance (QCM) nanosensor for the real-time detection of lysozyme. In the first part, the lysozyme imprinted (MIP) nanoparticles were prepared by mini-emulsion polymerization. The MIP nanoparticles were characterized by TEM, zeta-sizer and FTIR-ATR measurements. Particle size was found around 50 nm. The MIP nanoparticles were attached by dropping of nanoparticle solution to gold surface and then, dried at 37°C for 6h. QCM nanosensor was characterized with AFM and ellipsometer. The observations indicated that the nanoparticle film was almost monolayer. The detection limit was found as 1.2 ng/mL. The specificity of the QCM nanosensor was shown by using albumin as a competitor molecule. The results show that the QCM nanosensor has high selectivity and sensitivity with a wide range of lysozyme concentrations in both aqueous solutions (0.2-1500 μg/mL) and natural sources (egg white) (460-1500 ng/mL).

Quantum dot nanocrystals having guanosine imprinted nanoshell for DNA recognition

Molecular imprinted polymers (MIPs) as a recognition element for sensors are increasingly of interest and MIP nanoparticles have started to appear in the literature. In this study, we have proposed a novel thiol ligand-capping method with polymerizable methacryloylamido-cysteine (MAC) attached to CdS quantum dots (QDs), reminiscent of a self-assembled monolayer and have reconstructed surface shell by synthetic host polymers based on molecular imprinting method for DNA recognition. In this method, methacryloylamidohistidine-platinium (MAH-Pt(II)) is used as a new metal-chelating monomer via metal coordination-chelation interactions and guanosine templates of DNA. Nanoshell sensors with guanosine templates give a cavity that is selective for guanosine and its analogues. The guanosine can simultaneously chelate to Pt(II) metal ion and fit into the shape-selective cavity. Thus, the interaction between Pt(II) ion and free coordination spheres has an effect on the binding ability of the CdS QD nanosensor. The binding affinity of the guanosine imprinted nanocrystals has investigated by using the Langmuir and Scatchard methods, and experiments have shown the shape-selective cavity formation with O6 and N7 of a guanosine nucleotide (K(a) = 4.841x10(6) mol L(-1)) and a free guanine base (K(a) = 0.894x10(6) mol L(-1)). Additionally, the guanosine template of the nanocrystals is more favored for single stranded DNA compared to double stranded DNA.

Mercury removal from synthetic solutions using poly(2-hydroxyethylmethacrylate) gel beads modified with poly(ethyleneimine)

In this study, the Hg2+ adsorption–desorption properties of poly(ethyleneimine) (PEI)-attached poly(2-hydroxyethylmethacrylate) (PHEMA) beads were investigated. Spherical PHEMA beads with an average size of 150–200 μm were obtained by suspension polymerization of 2-hydroxyethylmethacrylate conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, PHEMA beads had a specific surface area of 14.8 m2/g. PEI chains could be covalently attached onto the PHEMA beads with equilibrium binding capacities up to 50 mg PEI/g beads. PEI-attached PHEMA beads were utilized as adsorbent in the adsorption–desorption of Hg2+ ions from synthetic solutions. The adsorption process was fast; 90% of adsorption occurred within 45 min and equilibrium was reached at around 1 h. The maximum Hg2+ adsorption capacity obtained was 1.67 mmol/g at a pH of about pH 5.0. Adsorption behavior can be described at least approximately by the Langmuir equation. The metal-chelating beads can be easily regenerated by 0.1 M HNO3 with higher effectiveness. Adsorption of heavy metal ions from artificial wastewater was also studied. The adsorption capacities were 1.32 mmol/g for Hg2+, 0.34 mmol/g for Ni2+ and 0.42 mmol/g for Cu2+.

Biosorption of inorganic mercury and alkylmercury species on to Phanerochaete chrysosporium mycelium

Abstract The biosorption of inorganic mercury (HgCl2), methyl mercury (CH3HgCl) and ethyl mercury (C2H5HgCl) onto the dry biomass of Phanerochaete chryosponum was studied from aqueous media which concentrations in the range of 5–500 mg l−1. The surface charge density varied with pH, and the concentration of mercury species adsorbed significantly increased from pH 3.0 to maximum levels at pH 8.0. The biosorption of mercury ions by Phanerochaete chrysosporium increased as the initial concentration of Hg(II) ion increased in the adsorption medium. A biosorption equilibrium were established after about 6 h, the adsorbed Hg(II) ion did not significantly change further with time. The dissociation constant (kd) values were 72, 63, and 61 mg l−1 for CH3HgCl, C2H5HgCl and for Hg(II), respectively. The maximum biosorption capacity (qm) at pH 7.0 was 79 mg for CH3HgCI, 67 mg for C2H5HgCl and 61 mg for Hg(II) per g of dried fungal biomass. The affinity order of mercury species was CH3HgCl>C2H5HgCl>and Hg(II).

Adsorption of heavy metal ions onto dithizone-anchored poly (EGDMA-HEMA) microbeads

The dithizone-anchored poly (EGDMA-HEMA) microbeads were prepared for the removal of heavy metal ions (i.e. cadmium, mercury, chromium and lead) from aqueous media containing different amounts of these ions (25-500 ppm) and at different pH values (2.0-8.0). The maximum adsorptions of heavy metal ions onto the dithizone-anchored microbeads from their solutions was 18.3, Cd(II); 43.1, Hg(II); 62.2, Cr(III) and 155.2 mg g(-1) for Pb(II). Competition between heavy metal ions (in the case of adsorption from mixture) yielded adsorption capacities of 9.7, Cd(II); 28.7, Hg(II); 17.6, Cr(III) and 38.3 mg g(-1) for Pb(II). The same affinity order was observed under non-competitive and competitive adsorption, i.e. Cr(III)>Pb(II)>Hg(II)>Cd(II). The adsorption of heavy metal ions increased with increasing pH and reached a plateaue value at around pH 5.0. Heavy metal ion adsorption from artificial wastewater was also studied. The adsorption capacities are 4.3, Cd(II); 13.2, Hg(II); 7.2, Cr(III) and 16.4 mg g(-1) for Pb(II). Desorption of heavy metal ions was achieved using 0.1 M HNO(3). The dithizone-anchored microbeads are suitable for repeated use (for more than five cycles) without noticeable loss of capacity.

Fab fragments imprinted SPR biosensor for real-time human immunoglobulin G detection.

F(ab) fragments imprinted surface plasmon resonance (SPR) chip was prepared for the real-time detection of human immunoglobulin G (IgG). In order to attach polymerization precursor on SPR chip, the SPR chip surface was modified with allyl mercaptan. F(ab) fragments of the IgG molecules were prepared by papain digestion procedure and collected by fast protein liquid chromatography (FPLC) system using Hi-Trap_r Protein A FF column. The collected F(ab) fragments were complexed with histidine containing specific monomer, N-methacryloyl-l-histidine methyl ester (MAH). Molecular imprinted polymeric nanofilm was prepared on SPR chip in the presence of ethylene glycol dimethacrylate and 2-hydroxyethylmethacrylate. The template molecules, F(ab) fragments, were removed from the polymeric nanofilm using 1M NaCl solution (pH: 7.4, phosphate buffer system). The molecular imprinted SPR chip was characterized by contact angle, atomic force microscopy and Fourier transform infrared spectroscopy. By the real-time IgG detection studies carried out using aqueous IgG solutions in different concentrations, the kinetics and isotherm parameters of the molecular imprinted SPR chip-IgG system were calculated. To show selectivity and specificity of the molecular imprinted SPR chip, competitive kinetic analyses were performed using bovine serum albumin (BSA), IgG, F(ab) and F(c) fragments in singular and competitive manner. As last step, IgG detection studies from human plasma were performed and the measured IgG concentrations were well matched with the results determined by enzyme-linked immunosorbent assay (ELISA). The results obtained with the molecular imprinted SPR chip were well fitted to Langmuir isotherm and the detection limit was found as 56 ng/mL. In the light of the results, we can conclude that the proposed molecular imprinted SPR chip can detect IgG molecules from both aqueous solutions and complex natural samples.

Production of surface plasmon resonance based assay kit for hepatitis diagnosis.

Hepatitis B surface antibody (HBsAb) imprinted poly(hydroxyethyl methacrylate-N-methacryloyl-L-tyrosine methyl ester) (PHEMAT) film on the surface plasmon resonance (SPR) sensor chip was prepared for diagnosis of HBsAb in human serum. Gold SPR chip surface was modified with allyl mercaptane and, then, HBsAb-imprinted PHEMAT film was formed on the chip surface. Surface characterization of the non-modified, allyl mercaptane modified and HBsAb-imprinted PHEMAT SPR chips were investigated with contact angle, atomic force microscopy (AFM). Kinetic studies were performed using HBsAb positive human serum. In order to determine the kinetic and binding constants, Scatchard, Langmuir, Freundlich and Langmuir-Freundlich models were applied to experimental data. Scatchard curve shows that HBsAb imprinted SPR chip has some surface heterogeneity, SPR chip obeyed the Langmuir adsorption model. The maximum detection limit was 208.2 mIU/mL. K(A) and K(D) values are 0.015 mIU/mL and 66.0 mL/mIU, respectively. Control experiments of the SPR chip were performed using non-immunized, HBsAb negative serum. The control experiment results show that SPR chip does not give any noticeable response to HBsAb negative serum.

Molecular imprinting based composite cryogel membranes for purification of anti-hepatitis B surface antibody by fast protein liquid chromatography.

In the present study, we have focused our attention to prepare molecular imprinted composite cryogel membranes for purification of hepatitis B surface antibody (anti-HBs) by fast protein liquid chromatography. Before the preparation of the molecular imprinted composite cryogel membranes (MI-CMs) by free radical polymerization at sub-zero temperature, we have synthesized and characterized the anti-HBs imprinted particles. Then, the cryogel membranes (CMs) were characterized by swelling test, scanning electron microscopy and Fourier transform infrared spectroscopy. Prior to chromatographic purification studies, the effective parameters on the anti-HBs adsorption process were evaluated by investigating the dependency of the adsorption capacity on flow-rate, anti-HBs concentration, contact time and ionic strength. The maximum anti-HBs adsorption capacity was calculated as 701.4 mIU/g CM. The selectivity of the MI-CMs was shown by competitive adsorption of anti-HBs, total anti-hepatitis A antibody (anti-HAV) and total immunoglobulin E (IgE) adsorption studies. The MI-CMs have relative selectivity coefficients as 5.45 for anti-HBs/total anti-HAV and 9.05 for anti-HBs/total IgE, respectively. The phosphate buffer solution (pH 7.4) containing 1.0M NaCl was used for elution, almost completely, of adsorbed anti-HBs molecules. The MI-CMs could be used many times without any significant decrease in the adsorption capacity. The chromatographic purification performances of the MI-CMs were also investigated. The chromatographic parameters such as capacity and separation factors, the theoretical plate number and resolution of the MI-CMs were calculated as 5.48, 6.02, 1153.9, and 1.72 for anti-HBs molecules, respectively. As a conclusion, we can say that the MI-CMs could be used for specific purification of anti-HBs from anti-HBs positive human plasma.