Novel heteroleptic ruthenium (II) complex with DPBPZ derivative for dye-sensitized solar cells

Herein, as Ru(II) complex for the dye-sensitized solar cells (DSSCs), we designed and investigated a novel heteroleptic ruthenium complex [Ru(dcbpy)(dpbpz)(NCS)2] with dpbpz derivative to enhance photovoltaic performance. The density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were used to gain insight into the factors responsible for photovoltaic properties as dye sensitizer. Molecular orbitals analysis confirmed that HOMO of [Ru(dcbpy)2(NCS)2] and [Ru(dcbpy)(dpbpz)(NCS)2] are delocalized over the ruthenium t2g character with sizable contribution from the NCS ligand orbitals. The LUMO of [Ru(dcbpy)2(NCS)2] is localized over the dcbpy moiety. However, LUMO of [Ru(dcbpy)(dpbpz)(NCS)2] is localized over the dpbpz moiety and LUMO + 1 is localized the dcbpy moiety. Overall, the absorption spectrum of the present Ru complex was more broad than that of [Ru(dcbpy)2(NCS)2] known as N3 dye. Especially, absorption band in the region between 500 nm and 600 nm was red-shifted. Moreover, the distance between the HOMO of [Ru(dcbpy)(dpbpz)(NCS)2] and the anchoring moiety is longer than that of [Ru(dcbpy)2(NCS)2]. This means that [Ru(dcbpy)(dpbpz)(NCS)2] have longer charge-separated lifetime than [Ru(dcbpy)2(NCS)2. These results are attributed to the extended pi-conjugation of dpbpz moiety. Therefore, we suggest that newly designed [Ru(dcbpy)(dpbpz)(NCS)2] heteroleptic ruthenium complex would be a good candidate as a dye sensitizer of DSSCs, comparable to [Ru(dcbpy)2(NCS)2].     

Electrogenerated chemiluminescence. 72. Determination of immobilized DNA and C-reactive protein on Au(111) electrodes using tris(2,2'-bipyridyl)ruthenium(II) labels

Anodic electrogenerated chemiluminescence (ECL) with tri-n-propylamine (TPrA) as a coreactant was used to determine DNA and C-reactive protein (CRP) by immobilizations on Au(111) electrodes using tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) labels. A 23-mer synthetic single-stranded (ss) DNA derived from the Bacillus anthracis with an amino-modified group at the 5' end position was covalently attached to the Au(111) substrate precoated with a self-assembled thiol monolayer of 3-mercaptopropanoic acid (3-MPA) in the presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) and then hybridized with a target ssDNA tagged with Ru(bpy)(3)(2+) ECL labels. Similarly, biotinylated anti-CRP species were immobilized effectively onto the Au(111) substrate precovered with a layer of avidin linked covalently via the reaction between avidin and a mixed thiol monolayer of 3-MPA and 16-mercaptohexadecanoic acid on Au(111) in the presence of EDAC and N-hydroxysuccinimide. CRP and anti-CRP tagged with Ru(bpy)(3)(2+) labels were then conjugated to the surface layer. ECL responses were generated from the modified electrodes described above by immersing them in a TPrA-containing electrolyte solution. A series of electrode treatments, including blocking free -COOH groups with ethanol amine, pinhole blocking with bovine serum albumin, washing with EDTA/NaCl/Tris buffer, and spraying with inert gases, were used to reduce the nonspecific adsorption of the labeled species. The ECL peak intensity was linearly proportional to the analyte CRP concentration over the range 1-24 microg/mL. CRP concentrations of two unknown human plasma/serum specimens were measured by the standard addition method based on this technique.     

E.s.r. and i.r. studies of ruthenium (III) hexaamine-exchanged zeolites

The chemistry of Ru(III) hexaamine complex imbedded in zeolite has been investigated by e.s.r., i.r., and other techniques. Zeolite-supported Ru(III)(NH₃)₆ exhibited e.s.r. signal characteristic for four d⁵ low-spin configuration species in an octahedral tetragonally distorted crystal field symmetry. Upon thermal activation, change from axial to orthorhombic symmetry occurred. I.r. analysis in the δNH₃ region also indicated that the symmetry of the NH₃ ligand coordination sphere was lowered upon thermal activation. Activation at temperature higher than 523 K resulted in the formation of RuO_x species. The results will be discussed in terms of rapid hydrolysis of the cationic Ru(III), with the subsequent formation of ruthenium red complexes that were decomposed into ruthenium oxide at higher temperature. The stability of Ru(III)(NH₃)₆ toward hydrolysis depended on the zeolite type used. Finally, we report that the dispersion of the Ru metal, formed upon H₂ reduction, was controlled by the state of the dispersion of the oxidized Ru.     

On-line solid-phase extraction with surfactant accelerated on-column derivatization and micellar liquid chromatographic separation as a tool for the determination of biogenic amines in various food substrates

A sensitive method was developed for the determination of biogenic amines at very low levels by combining solid phase extraction (SPE) and derivatization on-line with HPLC. The on-line derivatization and SPE were performed simultaneously on a commercially available ODS guard column, which was installed instead of the filling loop on the HPLC apparatus. Resolution of the peaks and quantification was further enhanced with micellar liquid chromatography and sensitization of the benzene ring absorption at 254 nm. Detection limits of the benzoyl derivatives of biogenic amines were in the vicinity of 0.1 microg L(-)(1), which is even lower than those obtained by fluorescence detection and is unparallel to any other UV approach. The correlation coefficients of determinations were 0.9850-0.9998. The method was applied to the determination of Biogenic amines, that is, putrescine, cadaverine, agmatine, tyramine, tryptamine, phenylethylamine, spermine, spermidine and histamine in fish, chicken, and wine samples. Recovery of the proposed method ranged from 94 to 106%.     

Determination of Dansyl Amino Acids and Oxalate by HPLC with Electrogenerated Chemiluminescence Detection Using Tris(2,2'-bipyridyl)ruthenium(II) in the Mobile Phase

A new electrogenerated chemiluminescence detection method is investigated for use in detection in reversed-phase and reversed-phase ion-pair HPLC with Ru(bpy)(3)(2+) in the mobile phase. In this method, different concentrations of Ru(bpy)(3)(2+) are dissolved in the mobile phase and the HPLC column flushed with the mobile phase for 1 h until the column is saturated with Ru(bpy)(3)(2+). The separated analytes along with Ru(bpy)(3)(2+) pass through an optical-electrochemical flow cell which has a dual platinum electrode held at a potential of 1250 mV vs a Ag/AgCl reference electrode. On the surface of the electrode, Ru(bpy)(3)(2+) is oxidized to Ru(bpy)(3)(3+) which reacts with the analytes to emit light. The retention times, retention orders, detection limits, and linearity in working curves are compared to those obtained with the conventional postcolumn Ru(bpy)(3)(2+) addition method. The retention times for dansyl amino acids with Ru(bpy)(3)(2+) in the mobile phase are longer than those obtained with the postcolumn addition approach. This may be caused by π-to-π interactions between the aromatic groups of the dansyl derivatives and the bipyridyl groups of Ru(bpy)(3)(2+) in the Ru(bpy)(3)(2+)-saturated reversed-phase column. Similarly, oxalate is separated from urine and blood plasma samples by reversed-phase ion-pair HPLC. Plasma samples are obtained using ultrafiltration to remove proteins from whole blood. Retention times for oxalate with the two detection techniques are identical, and detection limits for these techniques are compared.     

Electrogenerated chemiluminescence. 80. C-reactive protein determination at high amplification with [Ru(bpy)3]2+-containing microspheres

Biotinylated anti-C-reactive protein (CRP) species were attached to the surface of streptavidin-coated magnetic beads (MB) and avidin-coated polystyrene microspheres/beads (PSB) entrapping a large number of electrogenerated chemiluminescence (ECL) labels ( approximately 10(9) Ru(bpy)(3)[B(C(6)F(5))(4)](2)/bead) to form anti-CRP<-->MB and Ru(II) subsetPSB/avidin<-->anti-CRP conjugates, respectively. Sandwich-type Ru(II) subsetPSB/avidin<-->anti-CRP CRP anti-CRP<-->MB aggregates were formed when Ru(II) subsetPSB/avidin<-->anti-CRP was mixed with anti-CRP<-->MB conjugates in the presence of analyte CRP. The newly formed aggregates were magnetically separated from the reaction media and dissolved in MeCN containing tri-n-propylamine as an ECL coreactant. ECL was carried out with a potential scan from 0 to 2.8 V vs Ag/Ag(+), and the ECL intensity was found to be proportional to the analyte CRP concentration over the range of 0.010-10 mug/mL. The CRP concentration of an unknown human plasma specimen was measured by the standard addition method based on this technique. Elimination of the nonspecific adsorption of the CRP system with several different blocking agents was also studied, and 2.0% bovine serum albumin was found to be best.     

Electrogenerated chemiluminescence from R(bpy)3(2+) ion-exchanged in carbon nanotube/perfluorosulfonated ionomer composite films

The electrochemistry and electrogenerated chemiluminescence (ECL) of ruthenium(II) tris(bipyridine) (Ru(bpy)(3)(2+)) ion-exchanged in carbon nanotube (CNT)/Nafion composite films were investigated with tripropylamine (TPA) as a coreactant at a glassy carbon (GC) electrode. The major goal of this work was to investigate and develop new materials and immobilization approaches for the fabrication of ECL-based sensors with improved sensitivity, reactivity, and long-term stability. Ru(bpy)(3)(2+) could be strongly incorporated into Nafion film, but the rate of charge transfer was relative slow and its stability was also problematic. The interfusion of CNT in Nafion resulted in a high peak current of Ru(bpy)(3)(2+) and high ECL intensity. The results indicated that the composite film had more open structures and a larger surface area allowing faster diffusion of Ru(bpy)(3)(2+) and that the CNT could adsorb Ru(bpy)(3)(2+) and also acted as conducting pathways to connect Ru(bpy)(3)(2+) sites to the electrode. In the present work, the sensitivity of the ECL system at the CNT/Nafion film-modified electrodes was more than 2 orders of magnitude higher than that observed at a silica/Nafion composite film-modified electrode and 3 orders of magnitude higher than that at pure Nafion films. The CNT/Nafion composite film-modified GC electrodes also exhibited long-term stability.     

Selective detection of As(III) at the Au(111)-like polycrystalline gold electrode

Selective electrochemical detection of As(III) using a highly sensitive platform based on a Au(111)-like surface is described. The Au(111)-like surface was achieved for the first time by the partial reductive desorption of n-butanethiol (n-BT) from polycrystalline gold (poly-Au), on which a self-assembled monolayer (SAM) of n-BT was formed previously, which allows the selective blockage of the Au(100) and Au(110) surface domains by n-BT while the Au(111) domain remains bare. Square wave anodic stripping voltammetry (SWASV) using the Au(111)-like poly-Au electrode confirms the successful detection of As(III) without any interference from Cu(II). The fabricated electrode is stable and highly sensitive even in the presence of Cu(II), and it shows a linear response for As(III) up to 15 μM. The detection limit (S/N = 3) toward As(III) is 0.28 ppb, which is far below the guideline value given by World Health Organization (WHO). The electrode was applicable for the analysis of spiked arsenic in tap water containing a significant amount of various other ion elements. The results indicate that the Au(111)-like poly-Au electrode could be promising for the electrochemical detection of trace level of As(III) in real samples without any interference from Cu(II).     

Speciation of dissolved iron(III) and iron(II) in water by on-line coupling of flow injection separation and preconcentration with inductively coupled plasma mass spectrometry

A method has been developed for the speciation of trace dissolved Fe(II) and Fe(II) in water by on-line coupling of flow injection separation and preconcentration with inductively coupled plasma mass spectrometry (ICPMS). Selective determination of Fe(III) in the presence of Fe(II) was made possible by on-line formation and sorption of the Fe(III)-pyrrolidinecarbodithioate (PDC) complex in a PTFE knotted reactor over a sample acidity range of 0.07-0.4 mol L(-1) HCl, elution with 1 mol L(-1) HNO3, and detection by ICPMS. Over a sample acidity range of 0.001-0.004 mol L(-1) HCl, the sum of Fe(III) and Fe(II), i.e., Fe(III + II), could be determined without the need for preoxidation of Fe(II) to Fe(III). The concentration of Fe(II) was obtained as the difference between those of Fe(III + II) and Fe(III). With a sample flow rate of 5 mL min(-1) and a 30-s preconcentration time, an enhancement factor of 12, a retention efficiency of 80%, and a detection limit (3s) of 0.08 microg L(-1) were obtained at a sampling frequency of 21 samples h(-1). The relative standard deviation (n = 11) was 2.9% at the 10 microg L(-1) Fe(III) level. Recoveries of spiked Fe(III) and Fe(II) in local tap water, river water, and groundwater samples ranged from 95% to 103%. The concentrations of Fe(III) and Fe(II) in synthetic aqueous mixtures obtained by the proposed method were in good agreement with the spiked values. The result for total iron concentration in the river water reference material SLRS-3 was in good agreement with the certified value. The method was successfully applied to the determination of trace dissolved Fe(III) and Fe(II) in local tap water, river water, and groundwater samples.     

Remote fluorescence imaging of dynamic concentration profiles with micrometer resolution using a coherent optical fiber bundle

Dynamic concentration profiles within the diffusion layer of an electrode were imaged in situ using fluorescence detection through a multichannel imaging fiber. In this work, a coherent optical fiber bundle is positioned orthogonal to the surface of an electrode and is used to report spatial and temporal micrometric changes in the fluorescence intensity of an initial fluorescent species. The fluorescence signal is directly related to the local concentration of a redox fluorescent reagent, which is electrochemically modulated by the electrode. Fluorescence images are collected through the optical fiber bundle during the oxidation of tris(2,2'-bipyridine)ruthenium(II) to ruthenium(III) at a diffusion-limited rate and allow the concentration profiles of Ru(II) reagent to be monitored in situ as a function of time. Tris(2,2'-bipyridine)ruthenium(II) is excited at 485 nm and emits fluorescence at 605 nm, whereas the Ru(III) oxidation state is not fluorescent. Our experiments emphasize the influence of two parameters on the micrometer spatial resolution: the numerical aperture of optical fibers within the bundle and the Ru(II) bulk concentration. The extent of the volume probed by each individual fiber of the bundle is discussed qualitatively in terms of a primary inner-filter effect and refractive index gradient. Experimentally measured fluorescence intensity profiles were found to be in very good agreement with concentration profiles predicted upon considering planar diffusion and thus validate the concept of this new application of imaging fibers. The originality of this remote approach is to provide a global view of the entire diffusion layer at a given time through one single image and to allow the time expansion of the diffusion layer to be followed quantitatively in real time.     

Development of a cloud point extraction-spectrofluorimetric method for trace copper(II) determination in water samples and parenteral solutions

A simple and efficient cloud point extraction-spectrofluorimetric method for the determination of copper(II) in different samples has been proposed. The procedure is based on the oxidation of thiamine with copper(II) to form highly fluorescent thiochrome, its extraction to Triton X-114 micelles and spectrofluorimetric determination. The variables affecting the analytical performance were studied and optimized. The calibration graphs using the preconcentration system for copper were linear over the range 1.0-250 ng ml-1 with limit of detection of 0.29 ng ml-1. Relative standard deviation for five replicate determinations of copper at 100 ng ml-1 concentration level was 2.12%. Average recoveries between 94 and 105% were obtained for spiked samples. The method has been applied to water samples and parenteral solutions and the amounts of copper found are very similar to those obtained by a standard method.     

Selective detection of biogenic amines using capillary electrochromatography with an on-column derivatization technique

A selective detection method for biogenic amines present in highly complex matrixes was devised by employing both electrokinetic injection and on-column-derivatization capillary electrochromatographic methods. The on-column derivatization capillary electrochromatography system was evaluated by use of a capillary column (total length of 45 cm, effective length of 25 cm) fabricated using a 100-mcirom (i.d.) fused-silica capillary tube packed with 5-microm (i.d.) ODS particles that were tolerant of an alkaline environment. The column was filled with a run buffer consisting of a derivatization reagent, o-phthalaldehyde/2-mercaptoethanol, in a mixture of borate buffer (pH 10). After electrokinetic injection of a mixture of five biogenic amines (histamine, serotonin, tyramine, putrescine, cadaverine) as a test sample, the free amines entered into the anodic site of the capillary column and started to travel along the column, during which time the analytes reacted with the derivatization reagent, separated out, and were detected with an absorbance at 340 nm when high voltage was applied to the column. When this system was applied to a mixture containing 5 biogenic amines and 17 amino acids, the 5 biogenic amines plus arginine selectively entered into the capillary with the electrokinetic injection and were observed on the electrochromatogram, but none of the amino acids lacking arginine were detected. The designated method was also tested for its ability to determine the presence of biogenic amines in the crude extracts obtained from two types of aged fish.     

Redox hydrogel-based amperometric bienzyme electrodes for fish freshness monitoring

This work presents the design and optimization of amperometric biosensors for the determination of biogenic amines (e.g., histamine, putrescine, cadaverine, tyramine, cystamine, agmatine, spermidine), commonly present in food products, and their application for monitoring of freshness in fish samples. The biosensors were used as the working electrodes of a three-electrode electrochemical cell of wall-jet type, operated at -50 mV vs Ag/AgCl, in a flow injection system. Two different bienzyme electrode designs were considered, one based on the two enzymes [a newly isolated and purified amine oxidase (AO) and horseradish peroxidase (HRP)] simply adsorbed onto graphite electrodes, and one when they were cross-linked to an Os-based redox polymer. The redox hydrogel-based biosensors showed better biosensors characteristics, i.e., sensitivity of 0.194 A M-1 cm-2 for putrescine and 0.073 A M-1 cm-2 for histamine, and detection limits (calculated as three times the signal-to-noise ratio) of 0.17 microM for putrescine and 0.33 microM for histamine. The optimized redox hydrogel-based biosensors were evaluated in terms of stability and selectivity, and were used for the determination of total amine content in fish samples kept for 10 days in different conditions.     

Structurally Characterized Cationic Silver(I) and Ruthenium(II)carbene complexes of 1,2,3-Triazol-5-ylidenes

A novel 1,3,4-substituted 1,2,3-triazolium salt was found to function as an effective precursor for the synthesis of the first structurally characterized cationic silver(I) and ruthenium(II)carbene complexes of overall 1:2 ligand-to-metal stoichiometry. The Ag(I) complex crystallized in the form of an eight silver atom-containing cluster, whereas the Ru(II) complex proved to be a discrete species and was found to be capable of initiating the ring-opening metathesis polymerization of norbornene upon activation with (trimethylsilyl)diazomethane.     

Microcolumn separation of amine metabolites in the fruit fly

Electrophoretic resolution of 14 biogenic amines and metabolites with similar mobilities is addressed by employing micellar electrokinetic capillary chromatography coupled to amperometric electrochemical detection. The present study describes the optimization of separation conditions to achieve resolution of analytes of biological significance within 20 min in a single separation. They include dopamine, epinephrine, norepinephrine, octopamine (OA), L-3, 4-dihydroxyphenylalanine, tyramine (TA), and serotonin as well as metabolites 5-hydroxyindolacetic acid, 3,4-dihydroxyphenylacetic acid, homovanillic acid, and 3-methoxytyramine in addition to N-acetylated metabolites including N-acetyldopamine, N-acetyloctopamine (naOA), and N-acetylserotonin. The optimized conditions used result in excellent reproducibility and predictable peak shifting, thus enabling identification of several metabolites along with their biogenic amine precursors in biological samples, specifically from the fruit fly Drosophila melanogaster. The separation method is sensitive, selective, and quantitative as demonstrated by its capacity to detect changes in TA, OA, and naOA present in the head homogenates of the Canton-S and mutant inactive(1) Drosophila lines. Quantitative analysis of metabolites in conjunction with their biogenic amine precursors in a single separation offers tremendous potential to understand the physiological processes and underlying mechanisms mediated by various biogenic amines in Drosophila and other animals.     

Extraction and separation of Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid solutions with selected cyanamides as novel extractants

Three structurally related novel extractants namely: N,N-dihexylcyanamide (DHCY), N,N-di(2-ethylhexyl)cyanamide (DEHCY) and N,N-di-octylcyanamide (DOCY) were synthesized in our laboratory and characterized by different techniques. The general method for synthesizing these extractants was based on the reaction of relevant secondary amines with cyanogen bromide in presence of sodium acetate anhydride. Their extracting ability in toluene as a diluent for Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid media has been studied. The extraction of hydrochloric acid was studied also. Pd(II) was strongly extracted by these extractants at low hydrochloric acid concentrations and the extraction decreased with increasing hydrochloric acid concentration while the reverse was obtained in the extraction of Pt(IV), Fe(III) and Zn(II). Under similar extraction conditions Cu(II) and Ag(I) were found poorly extracted. Hydrochloric acid was extracted only in its high concentration region. A systematic investigation has been carried out on the extraction of Pd(II) using two of the synthesized extractants. Pd(II) was extracted as a solvated complex with the composition, metal:chloride ion:extractant=1:2:2. The extracted species were studied also using IR spectra.     

Graphene–Ruthenium(II) Complex Composites for Sensitive ECL Immunosensors

Non‐covalent modi?cation method has been proven as an effective strategy for enhancing the chemical properties of graphene while the structure and electronic properties of graphene can be retained. This work describes a novel strategy to fabricate a solid‐state electrochemiluminescent (ECL) immunosensor based on ruthenium(II) complex/3,4,9,10‐perylenetetracarboxylic acid (PTCA)/graphene nanocomposites (Ru‐PTCA/G) for sensitive detection of α‐fetoprotein (AFP). It is found that immobilization of PTCA and reduction of GO can be simultaneously achieved in one‐pot synthesis method under alkaline condition and moderate temperature, forming PTCA/G nanocomposites. Further covalent attachment of ruthenium(II) complex to the PTCA assembled on graphene sheets produces the functional Ru‐PTCA/G nanocomposites which show good electrochemical activity and ca. 21 times higher luminescence quantum efficiency than the adsorbed derivative ruthenium(II) complex. The Ru‐PTCA/G nanocomposites based solid‐state ECL sensor exhibits high stability toward the determination of tripropylamine (TPA) coreactant. In addition, a new ECL immunosensor based on steric hindrance effect is fabricated by cross‐linking α‐fetoprotein antibody (anti‐AFP) with chitosan covered on Ru‐PTCA/G composites modi?ed electrode for detection of cancer biomarker AFP. This ECL immunosensor shows an extremely sensitive response to AFP in a linear range of 5 pg·mL^‐1–10 ng·mL^‐1 with a detection limit of 0.2 pg·mL^‐1. The present approach is effective for various molecules immobilization and may become a promising technique for biomolecular detection.     

A single calibration graph for the direct determination of ascorbic and dehydroascorbic acids by electrogenerated luminescence based on Ru(bpy)(3)2+ in aqueous solution

Ascorbic (H2A) and dehydroascorbic (DA) acids were for the first time directly determined in a single chromatographic run by means of the tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)2+) based electrogenerated chemiluminescence (ECL) detection. For the first time, it was demonstrated that DA, a nonelectroactive compound, is ECL active and is responsible for the ECL behavior of H2A. This fact, together with the lack of a DA standard, suggested the use of a calibration graph obtained for H2A, for determining both analytes. The proven ECL activity of DA, together with literature data relative to the standard redox potentials of the different species coming from H2A, led to a reconsideration of the proposed ECL reaction mechanism for H2A. The role of the OH- ion in the reaction mechanism of the two analytes appeared to be crucial. H2A and DA could be separated by a suitable C18-reversed-phase HPLC column using an aqueous 30 mM H3PO4 solution as the mobile phase. The optimal ECL response was achieved by polarizing the working electrode at 1.150 Vvs SCE (standard calomel electrode) (oxidation diffusion limiting potential for both H2A and Ru(bpy)(3)2+). The Ru(bpy)(3)2+ solution, at pH 10 for carbonate buffer, was mixed to the eluent solution in a postcolumn system, obtaining, still at pH 10, the final 0.25 mM Ru(bpy)(3)2+ concentration. The detection limit found for the two analytes was 1 x 10(-7) M. The method was successfully applied to the determination of the analytes in a commercially available orange fruit juice.     

Oxygen gas sorption of Mn(II) complex salts of ethylene ionomer with various organic amines

Manganese(II) (Mn(II)) complex salts of poly(ethylene-co-methacrylic acid) (EMAA) were produced from a precursor Mn(II) salt of EMAA and eight different kinds of organic amines, and their oxygen-gas (O2) sorption behavior was investigated using visible absorption and infrared spectroscopies. It was found that the Mn(II) complex salts exhibit a selective O2 sorption during ageing at room temperature in air and release sorbed O2 molecules from ionic aggregates of the Mn(II) complex ions above 343 K in vacuo. From these results, the relationship between the O2 sorption behaviour and the chemical structure of amines is discussed.     

Tris(2-aminoethyl) amine functionalized silica gel for solid-phase extraction and preconcentration of Cr(III), Cd(II) and Pb(II) from waters

A new tris(2-aminoethyl) amine (TREN) functionalized silica gel (SG-TREN) was prepared and investigated for selective solid-phase extraction (SPE) of trace Cr(III), Cd(II) and Pb(II) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Identification of the surface modification was characterized and performed on the basis of FT-IR. The separation/preconcentration conditions of analytes were investigated, including effects of pH, the shaking time, the sample flow rate and volume, the elution condition and the interfering ions. At pH 4, the maximum adsorption capacity of Cr(III), Cd(II) and Pb(II) onto the SG-TREN were 32.72, 36.42 and 64.61 mg g(-1), respectively. The adsorbed metal ions were quantitatively eluted by 5 mL of 0.1 mol L(-1) HCl. Common coexisting ions did not interfere with the separation. According to the definition of International Union of Pure and Applied Chemistry, the detection limits (3sigma) of this method for Cr(III), Cd(II) and Pb(II) were 0.61, 0.14 and 0.55 ng mL(-1), respectively. The relative standard deviation under optimum conditions is less than 4.0% (n=11). The application of this modified silica gel to preconcentration trace Cr(III), Cd(II) and Pb(II) of two water samples gave high accurate and precise results.