Poly(glycidyl methacrylate) beads embedded cryogels for pseudo-specific affinity depletion of albumin and immunoglobulin G

Depletion of high abundant proteins like albumin and immunoglobulin G (IgG) can be beneficial in the analysis of serum proteins. For this purpose, Cibacron Blue F3GA and iminodiacetic acid (IDA)-Cu²⁺ containing poly(glycidyl methacrylate) (PGMA) beads (1.6 µm in diameter) were embedded into the poly(hydroxyethyl methacrylate) (PHEMA) cryogel. The PGMA beads were prepared by dispersion polymerization. The PGMA beads were modified with Cibacron Blue F3GA and iminodiacetic acid (IDA)-Cu²⁺ for simultaneous albumin and IgG depletion, respectively. The PHEMA cryogel was synthesized by free radical polymerization in the presence of the modified PGMA beads. The PHEMA and PHEMA/PGMA composite cryogels were characterized by swelling measurements and scanning electron microscopy (SEM). Protein depletion studies were carried out in a continuous experimental set-up in a stacked column. Albumin adsorption capacity of the PGMA-Cibacron Blue F3GA beads embedded PHEMA cryogel (PHEMA/PGMA-Cibacron Blue F3GA) was 342 mg/g and IgG adsorption capacity of the PGMA-IDA-Cu²⁺ beads embedded PHEMA cryogel (PHEMA/PGMA-IDA-Cu²⁺) was 257 mg/g. The composite cryogels depleted albumin and IgG from human serum with 89.4% and 93.6% efficiency, respectively. High desorption values (over 90% for both modified cryogels) were achieved with 0.05 M phosphate buffer containing1.0 M NaCl.     

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

Supermacroporous cryogel with an average pore size of 10–200 μm 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 23.2 m²/g. The equilibrium swelling ratio of the cryogel is 9.68 g H₂O/g for poly(HEMA–MAGA) and 8.56 g H₂O/g cryogel for PHEMA. The poly(HEMA–MAGA) cryogel disks with a pore volume of 71.6% containing 878 μmol MAGA/g were used in the removal of UO₂²⁺ from aqueous solutions. Adsorption equilibrium of UO₂²⁺ was obtained in about 30 min. The adsorption of UO₂²⁺ ions onto the PHEMA cryogel disks was negligible (0.78 mg/g). The MAGA incorporation significantly increased the UO₂²⁺ adsorption capacity (92.5 mg/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.     

The study of adsorption characteristics Cu and Pb ions onto PHEMA and P(MMA-HEMA) surfaces from aqueous single solution

The adsorption characteristics of Cu²⁺ and Pb²⁺ ions onto poly2-hydroxyethyl methacrylate (PHEMA) and copolymer 2-hydroxyethyl methacrylate with monomer methyl methacrylate P(MMA-HEMA) adsorbent surfaces from aqueous single solution were investigated with respect to the changes in the pH of solution, adsorbent composition (changes in the weight percentage of MMA copolymerized with HEMA monomer), contact time and the temperature in the individual aqueous solutions. The linear correlation coefficients of Langmuir and Freundlich isotherms were obtained. The results revealed that the Langmuir isotherm fitted the experimental results better than the Freundlich isotherm. Using the Langmuir model equation, the monolayer adsorption capacity of PHEMA surface was found to be 0.840 and 3.037 mg/g for Cu²⁺ and Pb²⁺ ions and adsorption capacity of (PMMA-HEMA) was found to be 31.153 and 31.447 mg/g for Cu²⁺ and Pb²⁺ ions, respectively. Changes in the standard Gibbs free energy (ΔG⁰), standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) show that the adsorption of mentioned ions onto PHEMA and P(MMA-HEMA) are spontaneous and exothermic at 293–323 K.     

The influence of transition metal ions on collagen mineralization

The ions in body fluid play an important role in bone formation besides being a synthesizing material. Transition metal ions Co^2 +, Ni^2 +, Zn^2 +, Fe^3 +, Mn^2 +, Cu^2 +, Cd^2 + and Hg^2 + doped hydroxyapatite (HAP)/collagen composites were synthesized successfully in the presence of collagen traces at mild acidic pH for the first time. However, the amount of doped Hg^2 + and Cd^2 + was relatively low. Meanwhile, through soaking the collagen sponge as a template in simulated body fluid (SBF) which contains different transition metal ions (Mn^2 +, Cu^2 +, Ni^2 +, Co^2 +, Cd^2 +, Hg^2 +), bone-like HAP/collagen composites were synthesized. Hg^2 + had a certain inhibitory effect on the formation of HAP crystals on the surface of the collagen sponge while Co^2 + can promote the formation of HAP on the collagen sponge. For both HAP/collagen composites and HAP/collagen sponge, it was found that transition metal ions Mn^2 + had a significant effect on the morphology of HAP particles and could induce to form floc-like HAP particle aggregates.     

PHEMA cryogel for in-vitro removal of anti-dsDNA antibodies from SLE plasma

Supermacroporous poly(2-hydroxyethyl methacrylate) (PHEMA) cryogel carrying DNA was used in the removal of anti-dsDNA antibodies from systemic lupus erythematosus (SLE) patient plasma. The PHEMA cryogel was prepared by bulk polymerization which proceeds in an aqueous solution of monomer frozen inside a plastic syringe. After thawing, the PHEMA cryogel contains a continuous matrix having interconnected macropores of 10–200 μm size. Pore volume in the PHEMA cryogel was 67.5%. Ester groups in the PHEMA structure were converted to imine groups by reacting with poly(ethyleneimine) (PEI) in the presence of NaHCO₃. Amino (? NH₂) content of PEI-modified PHEMA cryogel was determined as 82 mg PEI/g. Then, DNA was attached onto the PHEMA cryogel via amino groups (53.4 mg DNA/g cryogel). Anti-dsDNA-antibody concentration declined significantly from 780 IU/ml to 80 IU/ml with the time. The maximum anti-dsDNA-antibody adsorption amount was 70 × 10³ IU/g. Anti-dsDNA-antibodies could be repeatedly adsorbed and eluted without noticeable loss in the anti-dsDNA-antibody adsorption amount.     

Hydrothermal synthesis of nitrogen-containing carbon nanodots as the high-efficient sensor for copper(II) ions

Preparing high photoluminescent carbon nanodots (CNDs) by facile and low-cost processes have received considerable research interest. In this paper, high photoluminescent nitrogen-containing CNDs have been synthesized by one-step hydrothermal treatment of the pipe tobacco. The dispersion of these CNDs shows a strong blue luminescent emission with a max peak at 450 nm when it is excited at 369 nm. The as-made CNDs can sensitively and selectively detect Cu²⁺ ions compared with Ca²⁺, Mn²⁺, Zn²⁺, Cd²⁺, Pb²⁺ ions, which offers a novel sensing platform for the detection of Cu²⁺ ions.     

Poly(N,N-dimethylaminoethyl methacrylate) modification of activated carbon for copper ions removal

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) functionalization of rice husk-based activated carbon was prepared and its application in the removal of copper ions was investigated. The structural properties of the resulting composite material were characterized by means of N₂ adsorption/desorption, Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA). The obtained composite is observed to hold a relatively large pore diameter of 3.8 nm and high surface area of 789 m² g^?1 with 12 wt% of PDMAEMA coated, which is significant for its use as adsorbent. The ability of the composite material for removing Cu²⁺ from aqueous solution was studied by batch experiments. The adsorption data obeyed the Langmuir isotherms, which revealed that 1 g of the prepared material could adsorb 31.46 mg of Cu²⁺ from its aqueous solution. The PDMAEMA functionalized activated carbon is expected to be used as an efficient adsorbent for removing other heavy metal ions and dyes in water.     

The influence of dissolved organic carbon on sorption of heavy metals on urea-treated pine bark

A previous study showed considerably higher metal adsorption by urea-treated pine bark (UTB) compared to non-treated bark (NTB) at metal adsorption from their individual relatively concentrated solutions. Comparison of the sorption characteristics of the two pine barks at low but environmentally relevant metal concentrations, and investigation of the influence of pH and dissolved organic carbon (DOC) on the sorption process are the aims of the present study. Sorption of Cu²⁺, Ni²⁺, Zn²⁺ and Pb²⁺ on pine bark of the species Pinus sylvestris was measured in multi-metal solutions in the presence and absence of DOC. In the absence of DOC, UTB gave lower residual metal concentrations (2–7 μg/l for copper, 1–5 μg/l for nickel, <0.05 μg/l for zinc and lead) in the range of initial concentrations up to 0.7 mg/l, compared to NTB (6–15 μg/l for copper, 2–24 μg/l for nickel, 2–9 μg/l for zinc, 2–3 μg/l for lead). In the presence of DOC, sorption of Zn, Ni and Pb decreased by up to 75% depending on the DOC concentration. Metal sorption on UTB is less sensitive to pH and more adsorbed metal ions are retained compared to NTB. The potential use of urea-treated bark for treatment of waste water containing DOC and low concentrations of metals is discussed.     

Oriented immobilized anti-LDL antibody carrying poly(hydroxyethyl methacrylate) cryogel for cholesterol removal from human plasma

Low density lipoprotein (LDL) cholesterol is a major ingredient of the plaque that collects in the coronary arteries and causes coronary heart diseases. Among the methods used for the extracorporeal elimination of LDL from intravasal volume, immunoaffinity technique using anti-LDL antibody as a ligand offers superior selectivity and specificity. Proper orientation of the immobilized antibody is the main issue in immunoaffinity techniques. In this study, anti-human β-lipoprotein antibody (anti-LDL antibody) molecules were immobilized and oriented through protein A onto poly(2-hydroxyethyl methacrylate) (PHEMA) cryogel in order to remove LDL from hypercholesterolemic human plasma. PHEMA cryogel was prepared by free radical polymerization initiated with N,N,N′,N′-tetramethylene diamine (TEMED). PHEMA cryogel with a swelling degree of 8.89 g H₂O/g and 67% macro-porosity was characterized by swelling studies, scanning electron microscope (SEM) and blood compatibility tests. All the clotting times were increased when compared with control plasma. The maximum immobilized anti-LDL antibody amount was 63.2 mg/g in the case of random antibody immobilization and 19.6 mg/g in the case of oriented antibody immobilization (protein A loading was 57.0 mg/g). Random and oriented anti-LDL antibody immobilized PHEMA cryogels adsorbed 111 and 129 mg LDL/g cryogel from hypercholesterolemic human plasma, respectively. Up to 80% of the adsorbed LDL was desorbed. The adsorption–desorption cycle was repeated 6 times using the same cryogel. There was no significant loss of LDL adsorption capacity.     

Characterization of an azo-calix[4]arene-based optical sensor for Europium (III) ions

Selective and sensitive optical sensor membranes (optodes) were elaborated to detect cations in aqueous solutions. The sensing films are based on chromogenic calix[4]arene derivatives. The optode membranes were studied using UV/Vis absorption spectroscopy measurements. The sensitivity of the optode has been tested for Pb^2 +, Cd^2 +, Mg^2 + and Eu^3 + ions at pH 6.8. The results showed a good selectivity response towards Eu^3 +. Low selectivity coefficients were observed for Cd^2 + and Mg^2 + where Pb^2 + can be considered as interfering ions. The characteristics of this optode such as response time, regeneration, reproducibility and lifetime are discussed.     

Cadmium removal out of human plasma using ion-imprinted beads in a magnetic column

The aim of this study is to utilize ion-imprinted magnetic beads in the selective removal of Cd²⁺ ions out of human plasma overdosed with Cd²⁺ ions. The Cd²⁺ imprinted magnetic poly(HEMA-MAC) (mPHEMAC-Cd²⁺) beads were produced by suspension polymerization in the presence of magnetite Fe₃O₄ in a nano-powder form. The template Cd²⁺ ions could be reversibly detached from the matrix to form mPHEMAC-Cd²⁺ beads using 0.1 M thiourea solution. The specific surface area of the mPHEMAC-Cd²⁺ beads was found to be 24.7 m²/g. The MAC and Fe₃O₄ contents of the mPHEMAC-Cd²⁺ beads were found to be 41.8 µmol/g polymer and 8.2% on the average. The Cd²⁺ adsorption capacity of mPHEMAC-Cd²⁺ columns decreased drastically from 48.8 µmol/g to 20.0 µmol/g as the flow rate is increased from 0.50 ml/min to 3.0 ml/min. The maximum adsorption capacity of the mPHEMAC-Cd²⁺ beads was determined to be 48.8 µmol Cd²⁺/g on the average. The relative selectivity coefficients of the mPHEMAC beads for Cd²⁺/Pb²⁺ and Cd²⁺/Zn²⁺ were 22.6 and 160.7 times greater than those of the non-imprinted magnetic PHEMAC (mPHEMAC) beads, respectively. The mPHEMAC-Cd²⁺ beads are reusable for many times with no significant decrease in their adsorption capacities.     

Adsorption intrinsic kinetics and isotherms of lead ions on steel slag

Batch experiments were carried out to investigate the kinetics of adsorption of lead ions by steel slag on the basis of the external diffusion, intra-particle diffusion and adsorption reaction model (pseudo-first-order, pseudo-second-order). The results showed that the controlling step for the adsorption kinetics changed with the varying experimental parameters. When the particle size of steel slag was larger than 120 mesh, intra-particle diffusion of Pb²⁺ was the controlling step, and when the initial concentration of Pb²⁺ was less than 150 mg L^?1 or the shaking rate was lower than 150 rpm, external diffusion of Pb²⁺ was promoted. Contrary to the former experimental conditions the adsorption reaction was the controlling step, and the adsorption followed second-order kinetics, with an adsorption rate constant of 13.26 g mg^?1 min^?1. The adsorption isotherm of Pb²⁺ with steel slag followed the Langmuir model, with a correlation coefficient of 0.99.     

Reliable synthesis of bismuth nanoparticles for heavy metal detection

A reliable and facile pathway is described here for preparing high-quality bismuth nanoparticles. Combined with hydrothermal method and confined growing effect of polymer, bismuth nanoparticles with uniform size and shape were obtained with remarkable productivity. The nanoparticles is proved to be pure Rhombohedral structure Bi crystals with R-3m space group and the diameter of the nanoparticles is about 80 nm with a quite narrow particle size distribution. Those bismuth nanoparticles were predicted to grow from a rolling process by sheet-like Bi nanocrystal intermediates. The obtained bismuth nanoparticles were used to prepare modified electrode for the detection of Cd²⁺ and Pb²⁺ in water solution by stripping analysis. Compared with naked glassy carbon electrodes, the modified electrode showed two obvious responses at −0.85 V and −0.62 V, corresponding to the reduction process of Pb²⁺ and Cd²⁺ and this well-resolved stripping response can be observed when the concentration is as low as 10 μg/L, indicating potential application in electroanalysis for environmental inspection.     

Development of novel naphthalimide-functionalized magnetic fluorescent nanoparticle for simultaneous determination and removal of Hg2+

Mercury (Hg) commonly found in the global environment poses a serious threat to the environment and human health because of its durability, easy transference and high biological accumulation. So, great attention has been paid to the quantification and removal of mercury. Herein, we present the synthesis and properties of a novel naphthalimide-functionalized magnetic fluorescent nanoparticle for simultaneous determination and removal of Hg²⁺. The proposed nanoparticle showed a good linear relation (Y = −29.12216X + 363.2597, correlation coefficient of R² = 0.9952) between the fluorescence intensity at 540 nm and the concentration of Hg²⁺ varying from 0.1 μmol/L to 4.5 μmol/L. Additionally, our proposed nanoparticle exhibited excellent Hg²⁺-selectivity over other metal ions, which was ascribed to the formation of imide-Hg-imide complexes. The removal of Hg²⁺ from contaminated water samples was achieved by the aggregation-induced sedimentation (AIS) strategy. Moreover, the suspended magnetic nanoparticle could be removed by external magnetic field, and the secondary pollution was avoided.     

Synthesis and characterization of poly(hydroxyethyl methacrylate-N-methacryloyl-(l)-glutamic acid) copolymer beads for removal of lead ions

N-methacryloyl-(l)-glutamic acid (MAGA) was synthesized using methacryloyl chloride and l-glutamic acid methyl ester as a metal-complexing ligand and/or comonomer. MAGA was characterized by FTIR and NMR. Spherical beads with an average diameter of 150–200 μm were obtained by suspension polymerization of MAGA and 2-hydroxyethyl methacrylate (HEMA) performed in an aqueous dispersion medium. Poly(HEMA-MAGA) beads were characterized by swelling studies, surface area measurements and elemental analysis. Poly(HEMA-MAGA) beads have a specific surface area of 56.7 m²/g. Poly(HEMA-MAGA) beads were used in the removal studies of Pb²⁺ ions. Adsorption equilibrium was achieved in about 60 min. The adsorption of Pb²⁺ ions onto PHEMA beads was negligible (0.38 mg/g). The MAGA incorporation into the polymer structure significantly increased the lead adsorption capacity (348 mg/g). The adsorption of Pb²⁺ ions increased with increasing pH and reached a plateau value at around pH 5.0. Competitive adsorption of heavy metal ions from synthetic wastewater was also studied. The adsorption capacities are 42.5 mg/g for Pb²⁺, 26.8 mg/g for Hg²⁺ and 17.6 mg/g for Cd²⁺ at 0.5 mmol/l metal concentration. Consecutive adsorption and elution operations showed the feasibility of repeated use for poly(HEMA-MAGA) chelating beads.     

Silanized polymeric nanoparticles for DNA isolation

The aim of this study is to prepare silanized polymeric nanoparticles for DNA isolation. Polymeric p(HEMA)-IMEO-PBA nanoparticles around 85.7 nm diameter, was obtained by surfactant free emulsion polymerization for DNA isolation. Synthesized nanoparticles for characterization studies were realized scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Zeta-size. Surface area, average particle size and size distribution were also performed. The surface area of synthesized silanized polymeric nanoparticles was 2460 m²/g. Synthesized polymeric nanoparticles were silanized with 3-(2-imidazoline-1-yl)propyl (triethoxysilane) (IMEO). After that, phenylboronic acid (PBA) which is DNA specific ligand were covalently binded to silanized polymeric nanoparticles. The amount of DNA adsorbed onto the p(HEMA)-IMEO-PBA nanoparticles first increased and then reached a saturation value at around 14.0 mg/mL of DNA concentration. The maximum adsorption was 672.41 mg/g silanized polymeric nanoparticles in the optimum adsorption medium. The maximum DNA adsorption was achieved at 4 °C. The overall recovery of DNA was calculated as 95%. In repetitive adsorption–desorption circles, it is observed not being important decrease in DNA adsorption capacities. The results were shown that silanized polymeric nanoparticles can be a good alternative for DNA isolation.     

Determination of ultratrace levels of lead (II) in water samples using a modified carbon paste electrode based on a new podand

A new podand of 1,1′-thiobis(naphthalene-2,1-diyl)bis(2-aminobenzoate) (TNBA) was synthesized and used as a suitable carrier for construction of Pb²⁺ modified carbon paste electrode (CPE). The effects of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dioctyl pththalate (DOP), dibutyl phthalate (DBP) and paraffin oil were studied. The best performance was obtained with a matrix composition of CPE with a DOP/graphite powder/TNBA weight percent ratio of 35/60.5/4.5. The sensor exhibits significantly enhanced selectivity toward Pb²⁺ ion over the concentration range 8.0 × 10^? 8 to 1.0 × 10^? 2 mol L^? 1 with a lower detection limit of 5.0 × 10^? 8 mol L^? 1 and a Nernstian slope of 29.0 ± 0.2 mV decade^? 1 of lead activity. It has a fast response time of 8 s with a working pH range from 3.5 to 7. The interaction between TNBA and Pb²⁺ was studied spectrophotometrically and it exhibits that the stoichiometry of the complex is 1:1 in acetonitrile solution. Finally, the electrode was satisfactorily used as an indicator electrode in complexometric titration of Pb²⁺ with EDTA and in direct determination of lead in various water samples.     

Optical sensor based on 1,3-di(2-methoxyphenyl)triazene for monitoring trace amounts of mercury(II) in water samples

A new optical sensor for highly sensitive and selective determination of mercury(II) ion in aqueous solutions is developed. The mercury sensing membrane was prepared by incorporating 1,3-di(2-methoxyphenyl)triazene (MPT) as chromoionophore in the plasticized PVC membrane containing tris(2-ethylhexyl)phosphate (TEHP) as plasticizer. The proposed sensor displays a wide linear range of 9.0 × 10^?10–2.5 × 10^?7 M with a low detection limit of 2.0 × 10^?10 M in aqueous solutions at pH 4.0. This sensor has a relatively fast response time of less than 5 min. In addition to high stability and reproducibility, it shows a unique selectivity towards Hg²⁺ ion with respect to common coexisting cations. The sensor can readily be regenerated by exposure to a solution of sodium iodide (0.01 M). The proposed optode was applied to the determination of Hg²⁺ in water samples.     

Designing and synthesis of bis(2,4-dihydroxybenzylidene)-1,6-diaminohexane and its efficient application as neutral carrier for preparation of new copper selective electrode

A new copper carbon paste electrode (CPE) based on incorporation bis(2, 4-dihydroxybenzyliden)-1,6-diaminohexane (DHBDAH) in graphite powder matrix has been described. The influence of variables including an amount of graphite, sodium tetraphenylborate (NaTPB), DHBDAH and nujol on the Cu²⁺ carbon paste electrode response was studied and optimized. The optimum carbon paste composition was set as follows, graphite powder: NaTPB: Nujol: DHBDAH with amount of 150:2.3:30:4 mg, respectively. At the optimum conditions, the potential response is linear over the concentration range of 5.0 × 10^? 8 to 1.0 × 10^? 1 mol L^? 1 with a Nernstian slope of 29.5 ± 1.1 mV per decade of Cu²⁺ ion concentration. The good performance of electrode such as low detection limit of (LOD) (4 × 10^? 8 mol L^? 1), wide applicable pH range (2.5–5.5), fast response time (?10 s) and adequate shelf life (69 days) indicate the utility of the proposed electrode for evaluation of Cu²⁺ ion content in various analysis. Due to moderate potentiometric selectivity coefficients of proposed electrode obtained by fixed interference method (FIM) and separate solution method (SSM), the proposed electrode successfully can be applied for the determination of Cu²⁺ ions content in some real samples.     

Sensitive detection of mercury (II) ion using water-soluble captopril-stabilized fluorescent gold nanoparticles

In our work, a simple, facile, and green method was developed for the synthesis of water-soluble and well-dispersed fluorescent gold nanoparticles (Au NPs) within 5 min, using captopril as a capping agent. The as-prepared Au NPs showed strong emission at 414 nm, with a quantum yield of 5.5%. The fluorescence of the Au NPs can be strongly quenched by mercury (II) ion (Hg^2 +) due to the stronger interactions between thiolates (RS^?) and Hg^2 +. It was applied to the detection of Hg^2 + in water samples in the linear ranges of 0.033–0.133 μM and 0.167–2.500 μM, with a detection limit of 0.017 μM. Therefore, the as-prepared Au NPs can meet the requirement for monitoring Hg^2 + in environmental samples.