Rapid sensing of trace ionic substances with the novel porous monolith type ion exchanger

Biological and chemical sensor with a rapid response in microlevel test is required for health and environmental monitor. A novel sensing due to porous ion exchanger with three-dimensional acceptor has been first attempted to develop a high-performance sensor. This porous monolith type ion exchanger has an open-cellular monolith structure with 5–50-μm diameter pores. The trace amount of inorganic ions dissolved in aqueous solutions can be quantitatively determined with the impedance given by the monolith, which attracts and adsorbs the ions rapidly. We have succeeded in detecting ions with a concentration as low as 10⁻⁷ mol. The porous ion exchanger has a potentiality as a high-performance device for biological and chemical sensing. POLYM. ENG. SCI., 47:1666–1670, 2007. © 2007 Society of Plastics Engineers     

Equilibrium studies of phenylalanine and tyrosine on ion-exchange resins

The ion exchange equilibria of amino acids (phenylalanine and tyrosine) on a strong-acid cation exchanger resin (PK220) and on a strong-base anion exchanger resin (PA316) has been investigated. Based on experimental fixed-bed saturations at constant pH, each of the resins was previously screened of a set of three commercial lots with different physical properties. Overall mass balances from the saturation curves enabled to evaluate the linear isotherm constants and its dependence with pH. An equilibrium model that takes into account energetic heterogeneities in ion exchangers was successfully used to correlate binary and multicomponent data.     

Behaviour of boric acid on strong acid cation exchanger in primary water purification cycle of VVER reactors

The aim of this article is to observe anomalous behaviour of strong acid cation (SAC) exchanger in VVER and PWR power plants. This ion exchanger is a part of primary water coolant purification system and shows a non-standard operation in the end of the fuel cycle during high-performance effect. This behaviour consists in process’ changes of potassium cation capture from boric acid solution, which is a major chemical of primary cooling water. The experiments were conducted under laboratory conditions on ion exchanger type DOWEX HCR-S NG and the samples with different concentrations of analytes (K⁺, NH⁴⁺, Li⁺, H₃BO₃) were measured. The results confirmed the anomalous behaviour of ion exchanger during high-performance effect when the potassium ions are captured on SAC due to its size and the lack of boric acid in water coolant. Therefore, the potassium hydroxide must be dosed into the primary water to control the content of alkali metals.     

Linoleic acid oxidation catalyzed by various amino acids and cupric ions in aqueous media

Model systems were designed to study linoleic acid oxidation in the presence and absence of various amino acids with or without cupric ions. The tested amino acids exhibited a potential prooxidant effect in linoleic acid dispersed in aqueous media. The effectiveness of various amino acids on linoleic acid oxidation decreased in the following order: cysteine > serine > tryptophan > phenylalanine > histidine > alanine. The addition of alanine, serine, phenylalanine, histidine, or tryptophan to linoleic acid showed an autocatalytic chain reaction. With cysteine, there was a linear relation between concentration of hydroperoxides and time during the early stages of oxidation. The prooxidative activity of the tested amino acids in general could be attributed to the presence of the a-amino group in the form H₃-N-R. The apparent difference in the prooxidative activity is mainly due to the functional groups attached in the β-carbon atom in the amino acid molecules. The addition of cupric ions at a concentration of 10^-5M to linoleic acid catalyzed with various a-amino acids showed that these amino acids had no significant effect. Increasing the copper concentration from 10^-5M to 10^-3M had the following effects: a shortening of the induction period of linoleic acid catalyzed by amino acids having an aromatic side chain, no effect on the induction period but an increase in the oxidation rate during the propagation step in the model systems catalyzed by alanine and serine, and in the model system containing cysteine a linear increase in the linoleic acid oxidation from the start of the reaction.     

Linoleic Acid Oxidation Catalysed by Various Amino Acids and Cupric Ions in Aqueous Media

Model systems were designed to study the linoleic acid oxidation in the presence and absence of various amino acids and with or without cupric ions. The tested amino acids have shown to possess potential pro-oxidant capacity in linoleic acid dispersed in aqueous media. The effectiveness of various amino acids on linoleic acid oxidation decreased in the following order: cysteine > serine > tryptophan > phenylalanine > histidine > alanine. The addition of alanine, serine, phenylalanine, histidine or tryptophan to linoleic acid have shown features of an autocatalytic oxidation chain reaction. With cysteine, there was a linear relation between concentration of hydroperoxides and time during the early stages of oxidation. The pro-oxidative activity of the tested amino acids in general could be attributed to the presence of the α-amino group in the form H₃-N-R. The apparent difference in the pro-oxidative activity is mainly due to the functional groups attached to β-carbon in the amino acid molecules. The addition of cupric ions at concentration of 10^–5 M to linoleic acid catalysed with various α-amino acids have shown that these amino acids had no significant effect. The increasing copper concentration from 10^–5 to 10^–1 M shortened the induction period of linoleic acid catalysed by amino acids having aromatic side chain, had no effect on the induction period but increased the oxidation rate during the propagation step in the model systems catalysed by alanine and serine and in the model system containing cysteine increased the linoleic acid oxidation linearly from the start of the reaction.     

Chemical imaging sensor and its application to biological systems

The chemical imaging sensor is a semiconductor-based chemical sensor that can visualize the two-dimensional distribution of chemical species in the specimen. One of the prospective applications of the chemical imaging sensor is the visualization of biochemical activities in biological systems. The chemical imaging sensor was successfully applied for the detection of Escherichia coli colonies. For further applications to biological systems, enhanced adhesion of the sample to the sensing surface seems to be indispensable. As a candidate material for biocompatible sensors, porous Si was tested and was found to have a high pH sensitivity of 57.3 mV/pH.     

Nonionic adsorption of aromatic amino acids on a cation-exchange resin

Nonionic adsorption of aromatic amino acids on a cation-exchange resin (Dowex 50W-X8) was studied. At low concentrations, phenylalanine and tyrosine were adsorbed on the resin by monovalent ion-exchange process. Deviation from stoichiometric ion exchange became large as phenylalanine and tyrosine concentrations increased. On the other hand, aliphatic amino acids, glycine and alanine, were adsorbed on the resin by monovalent ion-exchange process. In column breakthrough experiments, the bed capacities for phenylalanine and tyrosine were higher than those for metal ions (Na⁺, Pb²⁺, and Ni²⁺) and the aliphatic amino acids. The increased capacities may be due to nonionic interaction between the aromatic amino acids and the polystyrene resin matrix. The nonionic interaction could be suppressed in 25% ethanol solution.     

Extraction equilibria and separation of phenylalanine and aspartic acid from water with di(2‐ethylhexyl)phosphoric acid

The distribution equilibria of single and binary L ‐phenylalanine and L ‐aspartic acid between water and a kerosene solution of di(2‐ethylhexyl)phosphoric acid (D2EHPA) were studied. It was shown that the distribution ratios of phenylalanine generally increased with increasing aqueous pH (2–5) in the D2EHPA concentration range 0.1–0.5 mol dm^?3, but those of aspartic acid decreased with increasing solution pH. Different reaction stoichiometries were proposed for the extraction of phenylalanine and aspartic acid under the conditions studied. The extraction equilibrium constants were obtained. Competitive extraction in binary systems was more apparent in the pH range where the cationic form of amino acids was not predominant. The present results indicated that selective separation of phenylalanine to aspartic acid was possible with this cationic extractant when they were extracted at higher pH and stripped using higher acidity of HCl solution. Copyright © 2006 Society of Chemical Industry     

Environmentally safe corrosion inhibition of Mg–Al–Zn alloy in chloride free neutral solutions by amino acids

The corrosion inhibition of Mg–Al–Zn alloy was investigated in stagnant naturally aerated chloride free neutral solutions using amino acids as environmentally safe corrosion inhibitors. The corrosion rate was calculated in the absence and presence of the corrosion inhibitor using the polarization technique and electrochemical impedance spectroscopy. The experimental impedance data were fitted to theoretical data according to a proposed electronic circuit model to explain the behavior of the alloy/electrolyte interface under different conditions. The corrosion inhibition process was found to depend on the adsorption of the amino acid molecules on the metal surface. Phenyl alanine has shown remarkably high corrosion inhibition efficiency up to 93% at a concentration of 2 × 10⁻³ mol dm⁻³. The corrosion inhibition efficiency was found to depend on the concentration of the amino acid and its structure. The mechanism of the corrosion inhibition process was discussed and different adsorption isotherms were investigated. The free energy of the adsorption process was calculated for the adsorption of different amino acids on the Mg–Al–Zn alloy and the obtained values reveal a physical adsorption of the inhibitor molecules on the alloy surface.     

Synthesis of N-acyl amino acids and correlation of structure with surfactant properties of their sodium salts

The effect of structural variation in fatty acid and amino acid moieties on surfactant properties of sodium salts of N-acyl condensates of amino acids was investigated. Pure N-acyl leucines and N-lauroyl condensates of different amino acids were synthesized and neutralized. Among the N-acyl leucinates, N-lauroyl leucinate exhibited optimum properties and compared well with sodium lauryl sulfate (SLS). Among the salts of Nα-lauroyl amino acids, Nα-lauroyl lysinate was found comparable to SLS. Salts of Nα-lauroyl condensates of leucine, tryptophan, phenylalanine and proline showed good wetting ability; proline also displayed high calcium ion tolerance. Salts of N-lauroyl tyrosine and phenylalanine exhibited good foaming ability. N-Lauroyl aspartate showed inferior properties compared to SLS in spite of having an additional carboxylic group. HCT Communication No. 2525.     

离子色谱-直接电导法同时测定常见氨基酸和无机阳离子

采用阳离子交换色谱-直接电导法测定部分常见氨基酸和无机阳离子,以酒石酸和吡啶二羧酸溶液为淋洗液,利用阳离子色谱系统等度洗脱,通过对色谱分析条件的优化,无需衍生化即可同时测定谷氨酸、丙氨酸、甲硫氨酸、亮氨酸、苯丙氨酸、赖氨酸及Na+, NH4+, K+, Ca2+和Mg2+. 选择12 min内出峰的5种氨基酸和3种无机阳离子进行定量分析,结果表明,其相对标准偏差RSDn=5≤4.690%,标准曲线的线性相关系数不低于0.9984,检出限在0.27~10.34 mg/L之间. 以建立的方法测定味精等电母液中的氨基酸,结果显示,氨基酸的回收率为88.7%~107.2%.     

Convergent Total Synthesis of the Complex Non-Ribosomal Peptide Polytheonamide B

Polytheonamide B, isolated from the Japanese marine sponge Theonella swinhoei, is by far the largest non-ribosomal peptide known to date, and displays potent cytotoxicity. Its 48 amino acid residues include a variety of non-proteinogenic D - and L -amino acids, and the chiralities of these amino acids alternate in sequence. These structural features induce the formation of a stable β^6.3-helical structure in the hydrophobic environment, giving rise to an overall tubular structure of 45 Å in length. In a biological setting, this fold is believed to transport cations across the lipid bilayer through a pore with an inner diameter of 4 Å, thereby acting as an ion channel. In this account, we describe in detail our total synthetic route to polytheonamide B. The total synthesis relies on a combination of four key stages: synthesis of eight non-proteinogenic amino acids and an N-terminus moiety, a solid phase assembly of four fragments of polytheonamide B, three Ag⁺-mediated couplings of the fragments, and finally, acid-promoted global deprotection. The generality and modularity of the developed strategy will enable future studies of the chemical and biological properties of this unusual ion-channel-forming peptide and its synthetic analogues.     

Preparation and Impedance Analysis of Biodegradable Polymer Polyvinyl Alcohol with Amino Acid,Arginine

Biodegradable polymers have an innumerable use in the field of biomedicine, especially in drug delivery system. Polyvinyl alcohol is one of the biodegradable polymer used as a carrier for drug delivery. Amino acids are necessary for maintaining good health for human beings. The present study focuses on the interaction between polyvinyl alcohol and amino acids. An effort is being taken to prepare polymer membrane based on polyvinyl alcohol complexed with different concentration of arginine, a type of amino acids using water as solvent by solution-casting technique. The amphorousity and complex formation between polyvinyl alcohol and Arignine have been confirmed by X-ray diffraction and FTIR spectroscopy, respecticvely. The thermal behavior of PVA–arginine complexes has been analyzed by differential scanning calorimetry. From AC impedance spectroscopy, ion transport mechanism has been investigated in detail. By using Almond and West formulisms, the parameter such as ion hopping frequency ω_p, has been calculated. The polymer membrane 75 Mwt% PVA:25 Mwt% arginine has the highest ionic conductivity as 1.97 × 10^?6 S cm^?1 at ambient temperature.     

电位法研究弱碱性树脂D354吸附游离无机酸的行为

以D354弱碱性阴离子交换树脂为吸附剂,吸附低浓度的盐酸、硝酸和硫酸,采用电位法对吸附过程进行在线跟踪,利用固-液界面吸附动力方程,求取表观吸附速率常数.重点研究D354树脂与无机酸在三元体系的固-液吸附行为,讨论了NaCl和KCl作为外加盐对吸附速率的影响,寻找其吸附过程的规律.     

Synthesis and Characterization of Anionic Exchange Resins with a Gradient in Polymer Composition for the PS-co-DVB/PDEAMA-co-DVB System

Summary Anionic exchange resins with a gradient in polymer composition were prepared in two stages. After P(S-co-DVB) suspension beads were obtained, N,N-diethylaminoethyl methacrylate monomer was let to diffuse into the beads at 25 °C, and immediately photopolymerized to fix the gradient polymer composition with high surface concentration of ion exchanger. Chemical composition through the radial position was estimated by means of a mathematical algorithm and using UV spectroscopy. Resin characterization included particle size distribution, “settled” density and total anion exchange capacity, following ASTM D-2187. Values were compared with a porous commercial resin (Amberlite IRA900RF Cl). Since non porous structure with high ion exchange capacity resins were obtained, useful resins for ion exchange with long term stability can be prepared with this methodology.     

Antioxidant activity of amino acid sodium and potassium salts in vegetable oils at frying temperatures

Previous studies reported that several amino acids had strong antioxidant activity in vegetable oils under frying conditions. In this study, amino acids were converted to their sodium or potassium salts, and a heating study was conducted with 5.5 mM amino acid salts in soybean oil (SBO) at 180°C. Sodium salts of amino acids including alanine, phenylalanine, and proline and disodium glutamate had significantly stronger antioxidant activity than the corresponding amino acids, and potassium salts had stronger antioxidant activity than sodium salts. Potassium salts of alanine and phenylalanine more effectively retained tocopherols in SBO than the corresponding amino acids during heating. Phenylalanine potassium salt had stronger antioxidant activity than phenylalanine in other vegetable oils including olive, high oleic soybean, canola, avocado, and corn oils. Phenylalanine potassium salt at 5.5 mM more effectively prevented oil oxidation than tert-butyl hydroquinone, a synthetic antioxidant, at its legal concentration limit (0.02%) indicating its feasibility as a new antioxidant for frying.     

EDTA-stannic(IV)iodate: preparation, characterization and its analytical applications for metal content determination in real and synthetic samples

A new organic–inorganic cation exchanger EDTA-stannic(IV)iodate was synthesized. The materials possess good chemical and thermal stability. The exchanger was characterized on the basis of X-ray, TGA, FTIR, UV–Visible spectrophotometery and SEM studies. ion exchange capacity, pH titration, elution and distribution studies were also carried out to determine the primary ion exchange properties of the material. The SEM study confirms the fibrous nature of the material. The exchanger behaves as a monofunctional cation exchanger with ion exchange capacity of 1.30 meq/g for Na⁺ ions. The material can perform well upto the temperature of 500 °C and retains the 76.4% of ion exchange capacity. The material is fairly stable in dilute solutions of some common mineral acids, bases and organic solvents. The differential selectivity of metal ions on EDTA-stannic(IV)iodate has been utilized to perform analytically and industrially important binary separations.     

Nutrient Composition of Larval Nectar Secretions from Three Species of Myrmecophilous Butterflies

A comparative chemical analysis of the larval nectar secretions and hemolymph from three unspecifically and facultatively ant-attended lycaenid species (Polyommatus coridon, P. icarus, and Zizeeria knysna) was performed by using high-performance liquid chromatography techniques. Sucrose was the main sugar component in all three species. In half of the samples of P. coridon, it was accompanied by glucose, whereas other sugars occurred only rarely. In P. icarus and Z. knysna, melezitose was the second-most important component, followed by fructose and glucose. Total sugar contents were 43.6 ± 14.8 g/l (mean ± SD) for P. coridon, 74.2 g/l for P. icarus, and 68.3 ± 22.6 g/l for Z. knysna. Up to 14 different identified amino acids were found in P. coridon nectar, with a total content of 9.7 ± 3.4 g/l. Leucine was always the major component (contributing 50% of overall amino acid content). Other important amino acids were tyrosine, proline, arginine, and phenylalanine. P. icarus nectar contained up to six amino acids with a total content of 1.2 g/l, dominated by tyrosine and phenylalanine. Z. knysna nectar contained alanine and proline, with only 0.3 ± 0.17 g/l total content. In the hemolymph of all species, up to 16 different amino acids occurred relatively regularly, with histidine dominating, followed by serine and proline. The amino acid pattern in hemolymph was considerably different from that of the nectar secretions. Larval diet weakly influenced P. coridon nectar sugars, and with a semisynthetic diet, a more homogeneous amino acid pattern was detected. Comparison with reports from other lycaenid species shows that secretions rich in amino acids are related to intimate, often obligate ant associations, whereas facultative, unspecific myrmecophiles rely on carbohydrates.     

Amino Acids 785, 787 of the Na+/H+ Exchanger Cytoplasmic Tail Modulate Protein Activity and Tail Conformation

The mammalian Na⁺/H⁺ exchanger isoform 1 (NHE1) is a plasma membrane protein ubiquitously present in humans. It regulates intracellular pH by removing an intracellular proton in exchange for an extracellular sodium. It consists of a 500 amino acid membrane domain plus a 315 amino acid, regulatory cytosolic tail. Here, we investigated the effect of mutation of two amino acids of the regulatory tail, Ser⁷⁸⁵ and Ser⁷⁸⁷, that were similar in location and context to two amino acids of the Arabidopsis Na⁺/H⁺ exchanger SOS1. Mutation of these two amino acids to either Ala or phosphomimetic Glu did not affect surface targeting but led to a slight reduction in the level of protein expressed. The activity of the NHE1 protein was reduced in the phosphomimetic mutations and the effect was due to a decrease in Vmax activity. The Ser to Glu mutations also caused a change in the apparent molecular weight of both the full-length protein and of the cytosolic tail of NHE1. A conformational change in this region was indicated by differential trypsin sensitivity. We also found that a peptide containing amino acids 783–790 bound to several more proximal regions of the NHE1 tail in in vitro protein interaction experiments. The results are the first characterization of these two amino acids and show that they have significant effects on enzyme kinetics and the structure of the NHE1 protein.     

Cr(VI)‐containing wastewater treatment by means of ion exchange on weak‐ and strong‐base anion exchangers

The aim of this research work was a thermodynamic and kinetic study of the retention of Cr(VI) ions from a K₂CrO₄ solution on macroporous weak‐ and strong‐base anion exchangers, Lewatit M 64 A and Lewatit MP 500 A, respectively. Also, the correlations among the ion‐exchange rate, the retention capacity of Cr(VI), and some process parameters were established. The parameters studied mainly were the concentration of Cr(VI) ions and the type of the counterions coupled with active groups from the anion exchangers. The results led to the conclusion that, for the Lewatit M 64 A resin, there is the following order of the Cr(VI) retention capacity: RCl > R₂SO₄ > ROH, while for the strong‐base anion exchanger, the retention capacity for the Cr(VI) ions is different: ROH > RCl > R₂SO₄. In the Cl^? form, both anion exchangers have the same retention‐capacity values. On the other side, the weak‐base anion exchanger in SO and OH^? forms presents the lowest retention‐capacity values. The process kinetics also presents some differences: for the Lewatit M 64 A resin, the ion‐exchange rate has lower values, especially in the OH^? form. This result is attributed to the increase of the OH^? ion concentration in the solution and its presence hinders the dissociation of the active groups of a weak‐base anion exchanger. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2093–2098, 2002