Formation of Ternary Surface Complexes by Adsorption of 2,2'-Bipyridine onto Silica Modified with Copper Ions

The adsorption of 2,2'-bipyridine on a copper-containing silica surface has been studied. The equilibrium of bipyridine binding to surface copper ions are well reproduced by the constants for the formation of ternary surface complexes from an aqueous solution containing copper ions and bipyridine. This indicates clearly that under experimental conditions all reactions are reversible and speciation is controlled by thermodynamics. Copyright 2001 Academic Press.     

Ligand exchange chromatography for analysis and preparative separation of tritium-labelled amino acids

Racemic tritium-labelled amino acids were separated into optical isomers by chromatography on a chiral polyacrylamide sorbent filled with copper ions. The polyacrylamide sorbent is synthesized by Mannich's reaction through the action of formaldehyde and L-phenylalanine upon polyacrylamide Biogel P-4 in an alkali phosphate buffer. Tritiumlabelled amino acids are eluted by a weak alkali solution of ammonium carbonate. Data are presented on the ligand exchange chromatography of amino acids depending on the degree to which the sorbent is filled with copper ions and on the eluent concentration. Conditions are suggested for the quantitative separation of amino acid racemates. Amino acids are isolated from the eluent on short columns filled with sulfonated cation exchanger in the H⁺ form. HPLC on modified silica gel sorbents is also used for the analysis of tritium-labelled optically active amino acids. Amino acids are eluted by a weakly acidic water-methanol solution containing ammonium acetate. UV and scintillation flow type detectors are used.     

The effect of copper ions on adsorption of histamine and histidine on the surface of highly dispersed silica

The effect of copper ions on the adsorption of histamine and histidine on the surface of highly dispersed silica from aqueous solutions is studied. It is shown that the formation of complex particles in solution determines the character of adsorption of these biomolecules. The equilibrium constants of the formation of ternary surface complexes, where silanol groups of silica act as a ligand, are calculated. It is shown that, in such complexes, nitrogen atoms of either histamine or histidine enter into the inner coordination sphere of copper ion.     

用溶出伏安法测定蛋白胨细胞生长液中易变形态铜

采用阳极阶梯溶出伏安法 ,测定了蛋白胨细胞生长液中的易变形态铜 ,并获得了总铜量中易变形态的摩尔分数以及易变形态的表观稳定常数。通过使用交换介质法 ,较好消除了由于蛋白胨细胞生长液中各种氨基酸或其它组分吸附在汞膜表面而引起的干扰     

Adsorption and gas-chromatographic properties of silver-modified silicas

Ag⁰ and Ag(I) nanoparticles are immobilized on the surface of a macroporous silica and amino silica. The adsorption kinetics of a basic dye, methylene blue (MB), from aqueous solutions and the adsorption isotherms of alkyne phenylacetylene from an octane solution are measured. The dependence of the rate constants of MB adsorption on the conditions of immobilization and silver reduction is considered. Silica containing immobilized Ag(I) is shown to have a high adsorption activity with respect to phenyl acetylene. By gas chromatography, it is shown that silver-modified silica has a higher selectivity with respect to alkenes. The reduction of silver on the silica surface and the complexation of silver ions with aminopropyl groups of amino silica lead to a significant decrease in the selectivity of composites.     

Amperometric detection of amino acids with a passivated copper electrode

The amperometric behaviour of a copper electrode towards amino acids is studied by means of a rotating disc electrode. A theoretical model describing the anodic background current in a buffer solution and the increase of the current caused by amino acids is checked experimentally. The influences of the amino acid concentration, the rotation speed of the electrode and the composition of the buffer solution are studied. It is proved that chemical dissolution of a passivating film on the electrode surface, which is enhanced by the complexation reaction between the amino acid and copper(II) ions, is the principle of the phenomena observed. The applicability to flow systems is demonstrated.     

Preparation of ion-imprinted silica gels functionalized with glycine, diglycine, and triglycine and their adsorption properties for copper ions

We report a new procedure for modifying the surface of silica gels with glycine, diglycine, and triglycine in the presence of copper ions to create a new type of copper-imprinted sorbent, which exhibits a high adsorption capacity and selectivity for copper ions. Our results show that copper adsorbed onto the copper-imprinted silica gel is 50% higher than that on nonimprinted silica gel at pH 4.5. The high adsorption capacity observed for the copper-imprinted silica gel is attributed to the stable copper complexes formed with two adjacent glycine, diglycine, or triglycine molecules with proper intermolecular distances obtained from the ion-imprinting procedure. Another possible reason for the high adsorption capacity is that the ion-imprinting procedure prevents the surface from being overcrowded; therefore, copper ions can form very stable 1:1 complexes with immobilized diglycine or triglycine. Interestingly, the imprinting effect is even more pronounced when the adsorption experiments are conducted in the presence of competing metal ions such as magnesium and calcium. The copper-imprinted silica gel exhibits a higher adsorption capacity than does the nonimprinted silica gel for all pH values, even when the concentrations of magnesium and calcium are 50 and 76 times higher than the concentration of copper.     

Enrichment of complexing analytes on a copper-loaded silica surface and on-line coupling with high-performance liquid chromatography, using L-tryptophan and L-tyrosine as model compounds

A chemically modified silica (bisdithiocarbamate) strongly binds copper and has a loading capacity of 0.5 mmol g-1 for the copper ion. This new metal-loaded silica, packed in a short stainless-steel pre-column, is highly selective for the enrichment of two amino acids chosen as model compounds. On-line coupling of this pre-column with an analytical RP-18 column allowed the separation and detection of L-tryptophan and L-tyrosine at parts per billion levels in aqueous media with good accuracy. Separation was achieved by ion-pair chromatography and the solutes were detected by fluorescence. The ions generally present in natural aqueous media did not interfere.     

Simple Free Amino Acid Separation by Reversed-Phase Ion-Pair Liquid Chromatography Using Column Switching Technique

Abstract

Reversed-phase ion-pair liquid chromatography with copper (II) ions (RP-IPC-Cu) was applied to develop a high speed separation of free amino acids. Dynamic gradient elution in RP-IPC-Cu could not achieve this purpose due to base line shift, therefore a column switching technique was used with a combination of different alkyl-bonded silica gel columns under isocratic elution. The flexibility of eluent components makes it easy to realize a rapid separation of a mixture of targeted amino acids.     

The adsorption of amino acids on the surface of highly dispersed silica

The adsorption of arginine, histidine, lysine, and ornithine on the surface of highly dispersed silica from aqueous solutions was studied as a function of pH. The equilibrium constants of the formation of surface complexes were calculated using the Stern model for the electrical double layer. It was shown that the possibility of adsorption of amino acids on the silica surface is determined by the presence of additional basic groups in their molecules.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 733–738.Original Russian Text Copyright © 2004 by Vlasova, Golovkova.     

A Silica Monolithic Column with Chemically Bonded l-Pipecolic Acid as Chiral Stationary Phase for Enantiomeric Separation of Dansyl Amino Acids by CEC–MS

A silica monolithic column chemically modified with l-pipecolic acid as chiral stationary phase has been developed for chiral separation of dansyl amino acids by capillary electrochromatography–mass spectrometry (CEC–MS). The monolithic column was prepared by a sol–gel process and subsequent chemical modification by l-pipecolic acid as chiral selector with 3-glycidoxypropyltrimethoxysilane as spacer. Interestingly, it was found that the l-pipecolic acid-modified monolithic column can hold copper(II) ions tightly after loading Cu(II) ions during column preparation and conditioning and allows CEC separation to be conducted based on chiral ligand exchange with MS detection by a mobile phase without copper ions. It has been demonstrated that the chiral monolithic column operates well for enantioseparation of several dansyl amino acids by CEC–MS.

     

Copper(II)—dialkyldithiocarbamate—silica precolumn for the enrichment of complexing analytes in natural media coupled on-line with liquid chromatography

A chemically modified silica (dialkyldithiocarbamate, DDTC) has been developed which strongly binds copper(II) ion. This metallic surface has been shown to be an effective means for the preconcentration of complexing analytes in natural media (e.g., amino acids chosen as model compounds). The Si-DDTC is more stable than other dithiocarbamate functions previously tested, and no copper or silane leaching occurred with this surface. The possibility of on-line coupling of the enrichment precolumn packed with the copper-loaded silica with an RP-18 analytical column allowed the direct liquid chromatographic analysis of some aqueous media containing amino acids at the 10^?7?10^?9M level and of some complex matrices as urine or blood serum. The total analysis procedure takes not more than 40 min. The method minimizes manipulation errors, contamination, losses and the total analysis time, and enhances the selectivity.     

Addition of carbon tetrachloride to olefins in the presence of copper complexes with polyfunctional ligands chemically immobilized on the surface of silica

Homogeneous and heterogeneous catalysts containing copper complexes with amino alcohols and hydroxy amino acids were synthesized. Heterogenized systems were immobilized on the surface of silica by covalent bonding of the hydroxyl groups of ligands to the silanol groups of silica. The resulting complexes were active in the reactions of CCl₄ addition to multiple bonds of olefins. In the case of 1-octene, the activity of heterogeneous catalysts was an extremal function of metal concentration on the surface, whereas a symbatic relationship was observed for a chlorinated olefin (allyl chloride). The above effects were explained by the participation of different copper complexes, in particular, of different nuclearity, in reactions with different olefins.Translated from Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 80–84.Original Russian Text Copyright © 2005 by Smirnov, Tarkhanova, Kokorin, Gantman, Tsvetkov     

Modification of Surface Forces by Metal Ion Adsorption

Abstract

Sorption of ions may lead to variations in interparticle forces and, thus, changes in the stability of colloidal particles. Chemical interactions between metal ions and colloidal particles modify the molecular structure of the surface, the surface charge, and the electrical potential between colloidal particles. These modifications to the surface and to the electrical double layer due to metal ion sorption are reflected in the interaction force between a particle and another surface, which is measured in this study by atomic force microscopy (AFM). Specifically, AFM is used to investigate the sorption of copper ions from aqueous solutions by silica particles. The influence of metal ion concentration and solution ionic strength on surface forces is studied under transient conditions. Results show that as the metal ion concentration is decreased, charge reversal occurs and a longer period of time is required for the system to reach equilibrium. The ionic strength has no significant effect on sorption kinetics. Furthermore, neither metal concentration nor ionic strength exhibits any effect on sorption equilibria, indicating that for the experimental conditions used in this study, the surface sites of the silica particle are fully occupied by copper ions.     

Simultaneous Determination of Tyrosine and Histidine by Differential Pulse Cathodic Stripping Voltammetry Using H‐point Standard Addition Method in Tap and Seawater

H‐point standard addition method (HPSAM) has been applied for simultaneous determination of tyrosine and histidine in trace levels using copper ions by adsorptive cathodic stripping voltammetry. The amino acids‐Cu(II) complexes were accumulated onto the surface of a hanging mercury drop electrode for 40 s. The reduction peaks of preconcentrated complexes were used for simultaneous determination of amino acids in the range 8.0–180 and 30–1100 nM for tyrosine and histidine respectively. The effect of various parameters such as pH, concentration of copper, accumulation time and scan rate on the selectivity were studied. Under the optimized conditions the method was successfully applied for determination of tyrosine and histidine in synthetic and real samples.     

Utilizing reversible copper(II) peptide coordination in a sequence-selective luminescent receptor

Although vast information about the coordination ability of amino acids and peptides to metal ions is available, little use of this has been made in the rational design of selective peptide receptors. We have combined a copper(II) nitrilotriacetato (NTA) complex with an ammonium-ion-sensitive and luminescent benzocrown ether. This compound revealed micromolar affinities and selectivities for glycine- and histidine-containing sequences, which closely resembles those of copper(II) ion peptide binding: the two free coordination sites of the copper(II) NTA complex bind to imidazole and amido nitrogen atoms, replicating the initial coordination steps of non-complexed copper(II) ions. The benzocrown ether recognizes the N-terminal amino moiety intramolecularly, and the significantly increased emission intensity signals the binding event, because only if prior coordination of the peptide has taken place is the intramolecular ammonium ion-benzocrown ether interaction of sufficient strength in water to trigger an emission signal. Intermolecular ammonium ion-benzocrown ether binding is not observed. Isothermal titration calorimetry confirmed the binding constants derived from emission titrations. Thus, as deduced from peptide coordination studies, the combination of a truncated copper(II) coordination sphere and a luminescent benzocrown ether allows for the more rational design of sequence-selective peptide receptors.     

Interaction of supramolecular centers of silica surface with aromatic amino acids

Surface grafting of β-cyclodextrin onto aminopropylsilica has been carried out under mild conditions using 1,1'-carbonyldiimidazole as an activator. The obtained β-cyclodextrin-silica has been characterized by means of chemical and IR spectral analysis. Adsorption of para-aminobenzoic and para-aminosalicylic acids onto the surface of hydroxylated silica, aminopropylsilica, and silica with chemically attached β-cyclodextrin moieties has been studied in relation to duration of contact, equilibrium concentration, and solution pH. Chemical immobilization of β-cyclodextrin onto silica surface improves adsorption parameters for aromatic amino acids. The well-known mathematical models for the kinetic and equilibrium adsorption processes have been used, and the main adsorption parameters have been calculated. Kinetic curves of aromatic amino acids adsorption correspond to the model of pseudo-second order reaction. The major contribution to the equilibrium adsorption of para-aminobenzoic and para-aminosalicylic acids onto β-cyclodextrin-containing silica is due to the formation of surface inclusion complexes between grafted oligosaccharide molecules and aromatic amino acids.     

Potentiometric detection in ion chromatography using a metallic copper indicator electrode

Summary A metallic copper electrode housed in a suitable flowcell is shown to be a sensitive and versatile potentiometric detector for ion chromatography. This electrode may be used for direct or indirect detection of many inorganic anions and cations and also for organic acids. In the direct detection mode, electrode response is based on either complexation of copper ions at the electrode surface by eluted species, or on oxidation and reduction reactions for eluted species which are strong oxidants or reductants. Direct detection is therefore applicable to such species as amino acids, organic acids, chloride, bromide, iodide, chlorate, bromate and iodate. Indirect detection is possible for anions which do not complex copper ions, provided a copper complexing ligand (such as phthalate) is used in the eluent; cations which complex this ligand are also detectable. Indirect detection may be used for species such as nitrite, nitrate, acetate, formate, succinate, benzoate, alkaline earth ions and transition metal ions. Electrode calibration relationships are discussed and sample separations are presented, together with some typical detection limits attainable in the direct and indirect detection modes.Presented in part at a National Symposium on Ion Chromatography, held at the University of New South Wales, Kensington, Australia, Nov. 21, 1984.     

Reactions of excited states of phenoxazin-3-one dyes with amino acids

The interaction with amino acids of the excited states of the N-oxide resazurin and its deoxygenation product resorufin, has been studied in aqueous solution at pH 7.5. Steady-state and time-resolved studies show that the fluorescence is quenched by amino acids. Complexation of the dyes in the ground state with aromatic amino acids was also observed. The singlet quenching is attributed to electron transfer from the amino acids to the excited dye based on the dependence of the bimolecular rate constants with the ionization potential of quenchers. Flash photolysis experiments allowed determination of the quenching rate constants for the triplet deactivation of dyes by several amino acids, as well as the characterization of the transients formed in the process. These data show that the triplet is also deactivated by an electron transfer process. However, the deactivation of the N-oxide dye by tryptophan can be described by a hydrogen atom transfer. The protolytic dissociation constants of the dye radical ions are reported. The irradiation of rezasurin in the presence of amino acids leads to deoxygenation of the dye to give resorufin. This process involves the triplet excited state of resazurin and is efficient only in the presence of amino acids containing the -SH group.     

Ternary surface complexes in silica-Ni2+ ions-2,2′-dipyridyl systems

The adsorption of complexes of nickel ions with an organic base (2,2′-dipyridyl) at an interface between silica and an aqueous electrolyte solution has been considered in terms of the theory of complexation. It has been shown that, on the silica surface, ternary complexes are formed, in which nickel ions are bonded to silanol groups. The equilibrium constants of the reactions of ternary surface complex formation have been calculated from the adsorption curves describing the pH dependences of nickel ion and dipyridyl adsorption.