Chromatographic separation simulation of metal-chelating peptides from surface plasmon resonance binding parameters.

Some metal-chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide-metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport-dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental tR with the simulated tR obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of tR were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance.

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

Synthesis, characterization and extraction studies of some metal (II) complexes containing (hydrazoneoxime and bis-acylhydrazone) moieties.

In this study, diacetylmonoximebenzoylhydrazone (L(1)H(2)) and 1,4-diacetylbenzene bis(benzoyl hydrazone) (L(2)H(2)) were synthesized by the condensation of benzohydrazide with diacetyl monoxime and 1,4-diacetylbenzene, respectively. Complexes of these ligands with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) inos were prepared with a metal:ligand ratio of 1:2 for L(1)H(2) ligand, and 1:1 for L(2)H(2) ligand. The ligands and their complexes were elucidated on the basis of elemental analyses CHN, AAS, FT-IR, (1)H- and (13)C NMR spectra, UV-vis spectra and magnetic susceptibility measurements. Results show the L(1)H(2) ligand act as monoanionic O,N,N-tridentate and coordination takes place in the enol form through the oxime nitrogen, the imine nitrogen and the enolate oxygen atoms with a N(4)O(2) donor environment, while the L(2)H(2) ligand act as a dianionic O,N,N,O-tetradentate and coordination takes place in the enol form through the enolate oxygen and the azomethine nitrogen atoms with a N(2)O(2) donor environment. These results are consistent with the formation of mononuclear metal (II) complexes [M(L(1)H)(2)], and binuclear polymeric metal (II) complexes [{M(2)(L(2))}(n)]. The extraction ability of both ligands were examined in chloroform by the liquid-liquid extraction of selected transition metal [Co(2+), Ni(2+), Cu(2+), Zn(2+) and Pb(2+)] cations. The effects of pH and contact time on the percentage extraction of metal (II) ions were studied under the optimum extraction conditions. The (L(1)H(2)) ligand shows strong binding ability toward copper(II) and lead(II) ions, while the (L(2)H(2)) ligand shows strong binding ability toward nickel(II) and zinc(II) ions.

Transition metal cation separations with a resorcinarene-based amino acid stationary phase.

A resorcinarene-based macrocyclic ligand functionalized with alanine and undecyl groups (AUA) was synthesized and applied to ion chromatographic separations. The selectivity and separation of transition metal ions on a column packed with AUA adsorbed onto 55% cross-linked styrene-divinylbenzene resin are presented. The upper and lower rims of the resorcinarene were modified with amino acids and -C(11)H(23) alkyl chains, respectively. The four carboxylic acid groups on the upper rim act as cation-exchangers while the four -C(11)H(23) alkyl chains serve to anchor the ligand to the resin surface by the hydrophobic effect. A systematic study of the effect of different eluent components including non-metal-chelating (HNO(3)) and chelating acids (oxalic acid, succinic acid, dipicolinic acid, and citric acid) on the retention of transition metal ions was investigated. Six metal ions (Mn(2+), Co(2+), Ni(2+), Cd(2+), Cu(2+), and Zn(2+)) were separated on the AUA column within a reasonable time with a single eluent gradient using oxalic acid. The separation is compared to that obtained using a commercial column containing carboxylic acid functional groups. The AUA column containing four preorganized carboxylic acid groups showed selectivity for Cu(2+) when no chelating eluent was present, a selectivity which was not observed with the comparison column.

Separation of selected transition metals by capillary chelation ion chromatography using acetyl-iminodiacetic acid modified capillary polymer monoliths.

Capillary housed laurylmethacrylate-co-ethylene dimethacrylate (LMA-co-EDMA) polymer monoliths were fabricated, functionalised with varying amounts of vinyl azlactone, followed by immobilisation of iminodiacetic acid (IDA), forming a range of acetyl-iminodiacetic acid (AIDA) functionalised monoliths, applied to the chelation ion chromatographic separation of selected transition and heavy metals. A number of monoliths of varying length and ligand density were prepared, resulting in increased cation retention and chromatographic resolution on those displaying the highest capacity. Ligand density and related column capacity were confirmed visually using scanning capacitively coupled contactless conductivity detection (sC(4)D) techniques. Column temperature studies to determine retention mechanism and the effect of temperature on the retention of Mn(II), Cd(II) and Cu(II) was investigated, showing an increase in retention with increased temperature for Cd(II) and Cu(II), whilst a decrease in retention was obtained for Mn(II). Isocratic capillary chelation ion chromatographic separations of Mn(II), Cd(II) and Cu(II) were obtained, with dual peak detection demonstrated using combined on-column C(4)D detection and UV-Visible detection following the post-capillary column reaction of the eluted metals with 4-(2-pyridylazo) resorcinol (PAR).

Adsorption of transition metal ions from aqueous solutions onto a novel silica gel matrix inorganic-organic composite material.

A novel inorganic-organic composite material silica gel microspheres encapsulated by imidazole functionalized polystyrene (SG-PS-azo-IM) has been synthesized and characterized. This composite material was used to investigate the adsorption of Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II), Hg(II), Pb(II), Pd(II), Pt(II), Ag(I), and Au(III) from aqueous solutions, and the research results displayed that SG-PS-azo-IM has the highest adsorption capacity for Au(III). Langmuir and Freundlich isotherm models were applied to analyze the experimental data, the best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Au(III) is 1.700 mmol/g. The adsorption selectivity, the dynamic adsorption and desorption properties of SG-PS-azo-IM for Au(III) have also been studied. The results showed that SG-PS-azo-IM had excellent adsorption for Au(III) in four binary ions system, especially in the systems of Au(III)-Zn(II) and Au(III)-Cu(II), and almost Au(III) could be desorbed with the eluent solution of 0.5% thiourea in 1 mol/L HCl. Moreover, this novel composite material was used to preconcentrate Au(III) before its determination by flame atomic adsorption spectrometry. In the initial concentration range of 0.10-0.20 microg/mL, multiple of enrichment could reach 5.28. Thus, silica gel encapsulated by polystyrene coupling with imidazole (SG-PS-azo-IM) is favorable and useful for the removal of transition metal ions, and the high adsorption capacity makes it a good promising candidate material for Au(III) removal.

Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.

High-capacity chitosan-based chelating resin for on-line collection of transition and rare-earth metals prior to inductively coupled plasma-atomic emission spectrometry measurement.

High-capacity chitosan-based chelating resin, N-(2-hydroxyethyl)glycine-type chitosan, was synthesized using chloromethyloxirane (CMO) as a cross-linker and a coupling arms and hydroxylethylamine and bromoacetic acid as a synthesizer for the N-(2-hydroxyethyl)glycine chelating moiety. The CMO could bind with both of hydroxyl and amino group of the chitosan resin, and then couple with the chelating moiety. Increasing the amounts of chelating moiety could increase the capacity of the resin toward metal ions. Most transition and rare-earth metals could adsorb quantitatively on the resin at wide pH ranges and could be separated from alkaline and alkaline-earth metals. The resin was packed in a mini-column (40 mm length x 2 mm i.d.) which was installed in a Multi-Auto-Pret system. The Multi-Auto-Pret system coupled with ICP-AES was successfully applied to the determination of transition and rare-earth metals in river water samples.

Removal of transition metal ions from aqueous solutions by adsorption onto a novel silica gel matrix composite adsorbent.

This paper presented the synthesis of a novel composite adsorbent silica gel microspheres encapsulated with 5-sulfosalicylic acid functionalized polystyrene (SG-PS-azo-SSA). It was characterized by titration method, FT-IR (Fourier transform infrared spectrometer), SEM (scanning electron microscope), EDXAS (energy dispersive X-ray analysis system), etc. SG-PS-azo-SSA has been used to investigate the adsorption of Mn(II), Fe(III), Co(II), Ni(II), Zn(II), Cd(II), Hg(II), Pd(II), Cu(II), Ag(I) and Au(III) from aqueous solutions. The research results revealed that SG-PS-azo-SSA has the better adsorption capacity for Cu(II), Ag(I) and Au(III). Langmuir and Freundlich isotherm models were applied to analyze the experimental data and the adsorption of Cu(II), Ag(I) and Au(III) on SG-PS-azo-SSA fitted well to the Langmuir isotherm equation. The obtained maximum adsorption capacity for Cu(II), Ag(I), and Au(III) is 0.472 mmol/g, 0.822 mmol/g and 0.810 mmol/g, respectively. Thus, silica gel encapsulated by 5-sulfosalicyclic acid functionalized polystyrene (SG-PS-azo-SSA) is favorable and useful for the removal of Cu(II), Ag(I) and Au(III) metal ions.

On-line collection/concentration and determination of transition and rare-earth metals in water samples using Multi-Auto-Pret system coupled with inductively coupled plasma-atomic emission spectrometry.

On-line preconcentration and determination of transition and rare-earth metals in water samples was performed using a Multi-Auto-Pret system coupled with inductively coupled plasma-atomic emission spectrometry (ICP-AES). The Multi-Auto-Pret AES system proposed here consists of three Auto-Pret systems with mini-columns that can be used for the preconcentration of trace metals sequentially or simultaneously, and can reduce analysis time to one-third and running cost of argon gas and labor. A newly synthesized chelating resin, ethylenediamine-N,N,N'-triacetate-type chitosan (EDTriA-type chitosan), was employed in the Multi-Auto-Pret system for the collection of trace metals prior to their measurement by ICP-AES. The proposed resin showed very good adsorption ability for transition and rare-earth metal ions without any interference from alkali and alkaline-earth metal ions in an acidic media. For the best result, pH 5 was adopted for the collection of metal ions. Only 5 mL of samples could be used for the determination of transition metals, while 20 mL of samples was necessary for the determination of rare-earth metals. Metal ions adsorbed on the resin were eluted using 1.5 M nitric acid, and were measured by ICP-AES. The proposed method was evaluated by the analysis of SLRS-4 river water reference materials for trace metals. Good agreement with certified and reference values was obtained for most of the metals examined; it indicates that the proposed method using the newly synthesized resin could be favorably used for the determination of transition and rare-earth metals in water samples by ICP-AES.

Investigation of factors affecting adsorption of transition metals on oxidized carbon nanotubes.

Adsorption of nickel, copper, zinc and cadmium from aqueous solutions on carbon nanotubes oxidized with concentrated nitric acid was carried out in single, binary, ternary and quaternary systems. TEM and adsorption of nitrogen were used to determine texture and structural parameters, respectively. The surface chemistry was evaluated using the pH at the point of zero charge, FTIR spectroscopy and XPS analysis. The experimental results showed that all isotherms for Cu(2+)(aq) fit to Langmuir model in each system. On the other hand, the isotherms for Ni(2+)(aq), Cd(2+)(aq) and Zn(2+)(aq) in multi-component systems reveal the effect of competition for adsorption sites seen as a decrease in the amount adsorbed. The uptakes at the equilibrium concentration of 0-0.04 mmol L(-1) in single system and 0-0.15 mmol L(-1) in binary system are in the order Cu(2+)(aq)>Ni(2+)(aq)>Cd(2+)(aq)>Zn(2+)(aq) while for the ternary and quaternary, the order is Cu(2+)(aq)>Cd(2+)(aq)>Zn(2+)(aq)>Ni(2+)(aq). The results indicate that the mechanism of adsorption is governed by the surface features, ion exchange process and electrochemical potential. The latter plays a significant role in multi-component adsorption where redox reactions, not only on the adsorbent surface but also between the adsorbates, are likely to occur.

Novel homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff bases: synthesis, characterization, solvent-extraction and catalase-like activity studies.

Twelve homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff base ligands containing N(4) donor sets have been prepared by employing several steps. The characterization and nature of bonding of the complexes have been deduced from elemental analysis, FT-IR, molar conductivity, magnetic moment measurements and thermal analysis. The three Schiff base ligands were further identified using (1)H and (13)C NMR spectra. All copper(II) complexes are 1:2 electrolytes as shown by their molar conductivities (Lambda(M)) in DMF and paramagnetic. The subnormal magnetic moment values of the di- and tri-nuclear complexes explained by a very strong anti-ferromagnetic interaction. The extraction ability of the ligands has been examined by the liquid-liquid extraction of selected transition metal (Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), Cd(2+), Hg(2+)) cations. The ligands show strong binding ability toward copper(II) ion. Furthermore the homo- and hetero-nuclear copper(II) complexes were each tested for their ability to catalyse the disproportionation of hydrogen peroxide in the presence of the added base imidazole.

Sodium dodecyl sulfate coated poly (vinyl) chloride: an alternative support for solid phase extraction of some transition and heavy metals.

A simple and relatively fast approach for developing a solid phase extraction has been described and used for determination of trace quantities of some heavy and transition metal ions with sodium dodecyl sulfate (SDS)-coated poly vinyl chloride (PVC) modified with bis(2-hydroxyacetophenone)-1,4-butanediimine (BHABDI) ligand. The adsorbed ions were stripped from the solid phase by 10 mL of 3M nitric acid as eluent. The eluting solution was analyzed for metals content (cadmium, chromium, cobalt, copper, lead and zinc) by flame atomic absorption spectrometry (FAAS). The main factors such as pH, amount of ligand and PVC, amount and type of surfactant, and condition of eluting solutions on the sorption recovery of metal ions have been investigated in detail. The relative standard deviation was found in the range of 1.0-3.2% for 0.2 microg mL(-1)of metals ions. After optimization of the extraction condition and the instrumental parameters, a detection limit was found to be in the range of 1.2-3.1 microg L(-1), with enrichment factor of 50 was achieved. The method was successfully applied for the determination of these metals contents in real samples with satisfactory results.

Simultaneous separation of inorganic anions and metal-citrate complexes on a zwitterionic stationary phase with on-column complexation.

The retention and separation selectivity of inorganic anions and on-column derivatised negatively charged citrate or oxalate metal complexes on reversed-phase stationary phases dynamically coated with N-(dodecyl-N,N-dimethylammonio)undecanoate (DDMAU) has been investigated. The retention mechanism for the metal-citrate complexes was predominantly anion exchange, although the amphoteric/zwitterionic nature of the stationary phase coating undoubtedly also contributed to the unusual separation selectivity shown. A mixture of 10 inorganic anions and metal cations was achieved using a 20 cm monolithic DDMAU modified column and a 1 mM citrate eluent, pH 4.0, flow rate equal to 0.8 mL/min. Selectivity was found to be strongly pH dependent, allowing additional scope for manipulation of solute retention, and thus application to complex samples. This is illustrated with the analysis of an acidic mine drainage sample with a range of inorganic anions and transition metal cations, varying significantly in their concentrations levels.

Speciation of chromium (III) and chromium (VI) by capillary electrophoresis with contactless conductometric detection and dual opposite end injection.

A sensitive, rapid and inexpensive capillary electrophoretic method for the determination of Cr(III) and Cr(VI) species is presented. The method is based on the dual opposite end injection principle and contactless conductometric detection. The sample containing cationic and anionic species is injected into the opposite ends of the separation capillary and after the high voltage is applied, the analytes migrate towards the capillary center, where the cell of a contactless conductivity detector is placed. The method does not require any sample pretreatment, except dilution with deionized water. The separation of Cr(III), Cr(VI) and other common inorganic anions and cations is achieved in less than 4 min. The parameters of the separation electrolyte solution, such as pH and concentration of L-histidine, were optimized. Best results were achieved with electrolyte solution consisting of 4.5 mM L-histidine, adjusted to pH 3.40 with acetic acid. The detection limits achieved for Cr(III) and Cr(VI) were 10 and 39 microg.L(-1), respectively. The repeatability of migration times and peak areas was better than 0.3% and 2.8%, respectively. The developed method was applied to the analyses of rinse water samples from the galvanic industry. The results for the determination of Cr(III) and Cr(VI) were in good agreement with the results obtained by certified differential spectrophotometric method using diphenylcarbazide (CN 83 0520-40) and with the results for the total chromium concentrations determined by electrothermal atomic absorbance spectrometry (ET-AAS) and inductively coupled plasma-mass spectrometry (ICP-MS).

Atomic wires on furrowed transition metal surfaces.

At low coverages, alkali, alkaline earth, and rare earth layers adsorbed on furrowed transition metal surfaces--such as the Mo(112) surface--demonstrate a quite unusual behavior. In contrast to well-known formation of one-dimensional wires lying in furrows of reconstructed surfaces of semiconductors and noble metals, these metals on the W(112), Mo(112), and Re(1010) surfaces tend to form commensurate linear structures built of monoatomic chains directed across the furrows. Monte-Carlo simulations of the increasing disorder of the chains with increasing temperature provides a transparent presentation of typical fluctuations in such linear structures. Such studies provide insight into the parameters of indirect interaction that are the basis for the formation of the atomic wires. Increasing coverage leads to a one-dimensional compression of the layers along the furrows, which results in dramatic changes in the surface electronic structure as revealed by photoemission ultraviolet photoelectron spectroscopy and electron energy loss (EELS) spectroscopies. Recent low energy electron diffraction, UPS, and electron energy loss spectroscopy data suggest a nonmetal to metal transition in the adsorbed alkaline earth layers when the coverage exceeds 1/2 monolayer and the film structure becomes incoherent with the substrate in direction along the furrows. The NMT in adsorbed layers is discussed in the framework of recent calculations of evolution of the band structure followed from increasing density of the films.