Use of Silica Gel Chemically Modified with Mercapto Groups for the Extraction, Preconcentration, and Spectroscopic Determination of Palladium

Silica gel chemically modified with mercaptopropyl groups is proposed for the extraction and preconcentration of palladium. This silica gel extracts palladium(II) at an acidity from 6M HCl to pH 4 with distribution ratios at a level of n× 10⁴ g/cm³. Hyphenated procedures for the adsorption–photometric determination of palladium with detection limits of 0.1 g/0.1 g of the adsorbent have been developed. The procedure includes the adsorption preconcentration of palladium, elution by hot (50 ± 5°C) 8% thiourea in 1M HCl, and atomic absorption determination of palladium in the eluate (detection limit is 0.05 g/mL). The procedures were applied to the determination of palladium in standard reference samples of copper–nickel ore and copper concentrate.     

Features of the Sorptive Extraction of Osmium in Different Oxidation States with Silica Gels Chemically Modified with Mercapto and Disulfide Groups

The sorptive extraction of osmium(VIII, VI, IV) from HCl solutions with silica gels chemically modified with mercapto groups (MPS) and disulfide groups (DPDSS) was studied. The recovery of osmium(VIII) from 0.5–4 M HCl is 99 and 25% with the sorption equilibration time 5 and 20 min for MPS and DPDSS, respectively. The equilibration time for the extraction of Os(VI) with MPS is no longer than 1 min. The recovery from 0.1–4 M HCl is up to 99.9%. The recovery of osmium(VI) with DPDSS decreases from 96 and 80% when going from 0.5 M to 4 M HCl. The quantitative extraction of osmium(IV) is attained at 95°C in the presence of tin(II) chloride and the equilibration time 60 min. Without tin(II) chloride, osmium(IV) is not extracted with these sorbents. The difference in the sorption ability of chemically modified silica gels with respect to osmium in different oxidation states can be used for the extraction of osmium(VI) and osmium(IV) and their separate determination directly in the MPS phase with the use of diffuse reflectance spectrometry.     

Molecular Dynamics Simulations of Proteins with Chemically Modified Disulfide Bonds

Proteins that are used as therapeutic drugs act in the extracellular microenvironment. They usually have a small number of intramolecular disulfide bonds to help maintain their tertiary structure in the vascular circulation. In general, most cysteine residues are part of a disulfide bond with free sulfhydrals being uncommon. We have studied whether the site-specific chemical reduction of disulfides and the incorporation of a 3-carbon methylene bridge between the cysteines in interferon-α 2a would change the structure of this protein. Bridging of both of the disulfide bonds of interferon-α 2a was studied using two different molecular simulation protocols: (1) molecular dynamics, and (2) stochastic dynamics. We have shown that the disulfide bonds in interferon-α 2a can be reduced and chemically modified without significantly altering the tertiary structure of the protein. This offers the novel possibility of chemically modifying therapeutically important proteins without affecting their biological properties.     

Sorption of Cobalt as a Nitroso-R-Salt Complex on Silica Gels Modified with Triphenylphosphonium Groups Followed by Determination in the Adsorbent Phase

The adsorption of cobalt(II) was studied on silica gel with chemically bound triphenylphosphonium groups. Cobalt was quantitatively recovered only in the presence of an additional ligand, nitroso-R-salt, in the solution. A sorption–spectrometric procedure was developed for determining cobalt in waters and alloys.     

化学修饰电极富集石墨炉原子吸收法测定痕量金

本文提出用聚丙烯脒硫氰酸盐化学修饰石墨管内壁、电化学预富集石墨炉原予吸收测定Au的分析方法.分析灵敏度提高100倍.应用于矿石中痕量Au的测定,获得了满意的结果.     

Metal Sorption,Solid Phase Extraction and Preconcentration Properties of Two Silica Gel Phases Chemically Modified with 2-Hydroxy-1-Naphthaldehyde

Active silica gel phase (I) was chemically modified to the corresponding amino- (SiNH₂) and chloro- (SiCl) derivatives via silylation reactions. These were used to synthesize two newly modified silica gel phases (II, III) by direct chemical reaction with 2-hydroxynaphthaldehyde (2-HNA). The surface coverage values are 370, 432µmolg^–1 and 320, 355µmolg^–1 for (II) and (III), on the basis of thermal desorption and metal probe testing method, respectively. The metal sorption properties of silica gel phases (II, III) were studied and compared with active silica gel phase (I). The maximum determined metal capacity values were found to be 10–110, 20–290 and 20–370µmolg^–1 for phases I, II and III, respectively. The distribution coefficient values (K_d) were also determined for a series of metal ions, and the results showed that the two new chemically modified phases (II and III) were highly selective for Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺. The potential applications of silica gel phases (II, III) as solid phase extractors for the same five metal ions spiked in drinking tap water (1.000µgmL^–1) were found to give percentage recovery values in the range of 90.2–96.3±4.1–6.3%, while pre-concentration of the same five metal ions spiked in drinking tap water (50.0ngmL^–1) was successfully accomplished with a percentage recovery range of 92.6–95.8±4.8–5.7%.Received December 16, 2002; accepted May 14, 2003 published online September 1, 2003     

Preconcentration and Determination of Copper(II) at a Chemically Modified Electrode Containing Salicylaldehyde Thiosemicarbazone

A chemically modified electrode (CME) containing salicylaldehyde thiosemicarbazone (TSCsal) was evaluated for the ability to preconcentrate copper(II) prior to quantification by voltammetry. The CME has been used for the very sensitive and selective analysis of trace amounts of copper(II). A detection limit of 0.1 ppb was obtained by applying anodic stripping voltammetry with a flow system. The parameters that affect the sensitivity and possible interference by other ions or chelating agents have been examined in detail. The CME exhibits high stability and the response could be reproduced for four preconcentration-determination-renewal cycles [10ppbCu(II)] with a 2.87% relative standard deviation. The proposed method has been applied to the determination of copper(II) in tap water, drinking water, and NASS-3 standard reference sea water samples. The results gave satisfactory recoveries.     

Application of Silica Chemically Modified by Sulfur-Containing Groups to the Separation and Determination of Platinum and Rhenium in Catalysts Based on Aluminum Oxide

Adsorbents based on silica chemically modified by sulfur-containing groups (dithiocarbamate, thiodiazolethiol, mercaptophenyl, and aminobenzothiazole) quantitatively extract (recovery ≥99%) platinum( IV) from solutions ranging from 4 M HCl to pH 6. Under the conditions of the adsorption separation of platinum(IV), rhenium(VII) is not extracted and remains in the solution. The subsequent quantitative (98–99%) adsorption of rhenium(VII) is achieved in the presence of a 1000-fold excess of tin(II) chloride. Adsorption on the surface of adsorbents leads to the formation of platinum(II) complexes with sulfur-containing groups, luminescent at 77 K on irradiation with UV light. The luminescence spectra of surface platinum( II) complexes are located in the region of 550–700 nm. In the adsorption of rhenium(III) in the presence of tin(II) chloride, intensely colored brown complexes of rhenium formed on the surface of adsorbents. Electron paramagnetic resonance showed that, in the surface complexes, rhenium is in the oxidation state 2+. Silicas chemically modified by sulfur-containing groups were used in the development of procedures for the sequential isolation and determination of platinum and rhenium in solutions after the decomposition of aluminum–platinum–rhenium catalysts.     

Flame Atomic Absorption Spectrometric Determination of Gold and Palladium Using Microcolumn On-line Preconcentration and Separation

A microcolumn on-line preconcentration and separation system was developed for the flame atomic absorption spectrometric (FAAS) determination of trace levels of gold and palladium. The analytes were selectively adsorbed onto the microcolumn packed with 2-mercaptothiazole immobilized silica gel (MBTSG) in an acidity range of 0.1 to 6.0M HCl at a sampling flow rate of 4.0mLmin^–1. The analytes adsorbed could be desorbed by a thiourea solution with a flow rate of 2.0mLmin^–1. Most of the common coexisting metal ions at a concentration of 25.0mgmL^–1 and anions at a concentration of 50.0mgmL^–1 did not interfere with the preconcentration and determination of Au and Pd. The limits of detection (LOD), defined as three times the standard deviation of the blank (3), of Au and Pd are 10ngmL^–1 and 26ngmL^–1, respectively, with a preconcentration time of 60s. The relative standard deviation (RSD) is about 2.0% for 0.20µgmL^–1 Au and 0.30µgmL^–1 Pd. With a sample loading time of 30min, 6.7ngmL^–1 Au and 10ngmL^–1 Pd can be preconcentrated quantitatively. A geological sample, an anode slime and a secondary nickel alloy were successfully determined with the proposed method, and the results obtained showed good agreement with the certified values.Received December 23, 2002; accepted May 14, 2003 Published online August 8, 2003     

Preconcentration and Determination of Copper（Ⅱ） Using Octadecyl Silica Membrane Disks Modified by 1,5-Diphenylcarhazide and Flame Atomic Absorption Spectrometry

A simple and reproducible method for the rapid extraction and determination of trace amounts of copper（Ⅱ） ions using octadecyl-bonded silica membrane disks modified by 1,5-diphenylcarbazide （DPC） and atomic absorption spectrometry was presented, which was based on complex formation on the surface of the ENVI-18 DISK^TM disks followed by stripping of the retained species by minimum amounts of appropriate organic solvents. The elution was efficient and quantitative. The effect of potential interfering ions, pH, ligand amount, stripping solvent, and sample flow rate were also investigated. Under the optimal experimental conditions, the break-through volume was found to be about 1000 mL providing a preconcentration factor of 400. The maximum capacity of the disks was found to be （255±5） lag for Cu^2＋, and the limit of detection of the proposed method was 5 ng per 1000 mL. The method was applied to the extraction and recovery of copper in different water samples.     

Microcalorimetric Study of Methanol Adsorption on Initial Silica and Silica Modified with Polyfluoroalkyl Groups

The adsorption of methanol on initial silica and modified silica samples containing large mesopores is studied by the adsorption–calorimetric method. The grafted tridecylfluoroalkyl groups have a tilted orientation on the silica and physically screen the part of the surface OH groups that have not been involved in the reaction with a modifier. Adsorbed methanol makes the modifying layer looser, thus facilitating the accessibility of methanol molecules to these hydrophilic adsorption sites. Concentrations of OH groups involved in the chemical interaction with molecules of the modifier, OH groups physically screened by its organofluoric radicals, and OH groups located on the surface areas free of the modifier are quantitatively estimated. An additional silanization of the modified silica leads to coverage of silica surface areas that are free of organofluoric modifier with trimethylsilyl radicals. The heat of interaction between the methanol molecules and silica surface hydroxyl groups is determined; it is equal to 60 kJ/mol. The structure of the modifying organofluoric layer and changes in this structure that resulted from additional silanization of the surface and from the methanol adsorption are discussed.     

Efficient Removal of Pb(II) from Aqueous Medium Using Chemically Modified Silica Monolith

The adsorptive removal of lead (II) from aqueous medium was carried out by chemically modified silica monolith particles. Porous silica monolith particles were prepared by the sol-gel method and their surface modification was carried out using trimethoxy silyl propyl urea (TSPU) to prepare inorganic–organic hybrid adsorbent. The resultant adsorbent was evaluated for the removal of lead (Pb) from aqueous medium. The effect of pH, adsorbent dose, metal ion concentration and adsorption time was determined. It was found that the optimum conditions for adsorption of lead (Pb) were pH 5, adsorbent dose of 0.4 g/L, Pb(II) ions concentration of 500 mg/L and adsorption time of 1 h. The adsorbent chemically modified SM was characterized by scanning electron microscopy (SEM), BET/BJH and thermo gravimetric analysis (TGA). The percent adsorption of Pb(II) onto chemically modified silica monolith particles was 98%. An isotherm study showed that the adsorption data of Pb(II) onto chemically modified SM was fully fitted with the Freundlich and Langmuir isotherm models. It was found from kinetic study that the adsorption of Pb(II) followed a pseudo second-order model. Moreover, thermodynamic study suggests that the adsorption of Pb(II) is spontaneous and exothermic. The adsorption capacity of chemically modified SM for Pb(II) ions was 792 mg/g which is quite high as compared to the traditional adsorbents. The adsorbent chemically modified SM was regenerated, used again three times for the adsorption of Pb(II) ions and it was found that the adsorption capacity of the regenerated adsorbent was only dropped by 7%. Due to high adsorption capacity chemically modified silica monolith particles could be used as an effective adsorbent for the removal of heavy metals from wastewater.     

Preconcentration and Determination of Chromium Species Using Octadecyl Silica Membrane Disks and Flame Atomic Absorption Spectrometry

A novel and selective method for the fast determination of trace amounts of chromium species in water samples has been developed. The procedure is based on the selective formation of chromium diethyldithiocarbamate complexes at different pH in the presence of Mn(II) as an enhancement agent of chromium signals followed by elution with organic eluents and determination by atomic flame absorption spectrometry. The maximum capacity of the employed disks was found to be (396±3) µg and (376±2) µg for Cr(III) and Cr(VI), respectively. The detection limit of the proposed method is 49 and 43 ng·L^?1 for Cr(III) and Cr(VI), respectively. The proposed method was successfully applied for determination of chromium species Cr(III) and Cr(VI) in different water samples.     

Graphite Furnace Atomic Absorption Spectrometry Determination and On-line Preconcentration of Palladium

Palladium was determined in pharmaceuticals by direct graphite furnace atomic absorption spectrometry (GFAAS) method. The detection limit was 0.1 μg/g in 5% solution; the recovery of 0.5–2.0 μg/g Pd spike was close to 100%. The flow injection GFAAS method was worked out using oxime and iminodiacetic acid ethyl cellulose (IDAEC) microcolumns for preconcentration of Pd in aqueous and 50% methanol solutions. The optimal pH range for preconcentration was 2–5. At 20-fold enrichment the detection limits for Pd were 0.39 μg/liter for oxime cellulose and 0.42 μg/liter for IDAEC.     

火试金富集-电感耦合等离子体发射光谱(ICP-OES)法测定分银渣中的铂、钯

采用火试金富集得到贵金属合粒,经王水溶解,在王水(10%)介质下采用全谱直读电感耦合等离子体发射光谱(ICP-OES)法测定分银渣中铂、钯的含量。方法精密度好,准确度高,铂、钯的加标回收率在98.4%~102%,可以很好地满足分银渣中铂、钯含量的测定。     

Preconcentration and Separation Procedures for the Spectrochemical Determination of Platinum and Palladium

Low concentrations of Pt and Pd in industrial (µgg^–1 level) and environmental samples (ngg^–1 level) together with the complexity of the matrix causing many interferences during the determination of noble metals often require elaboration and application of pre-concentration/matrix separation procedures before detection of the analyte. Different pre-concentration/matrix separation procedures applied prior to the determination of Pt and Pd by atomic spectrometric techniques are reviewed and critically compared taking into account potential interferences. The methods studied are divided into 5 groups including precipitation and coprecipitation, liquid–liquid extraction, solid phase extraction, electrochemical pre-concentration and biosorption. The main analytical problems occuring during sample preparation and storage are discussed.     

Critical Effect of Film Thickness on Preconcentration Electroanalysis with Oriented Mesoporous Silica Modified Electrodes

Electrogenerated silica thin films exhibiting a regular hexagonal packing of vertically‐aligned mesopore channels are promising for preconcentration electroanalysis. This work demonstrates the critical role of film thickness on their sensing performance using paraquat as a model analyte, based on mesoporous silica films prepared by electrochemically assisted self‐assembly performed for various deposition times. Films prepared with too short synthesis times (<10 s) led to deposits covering partially the electrode surface and suffered from rather poor sensing performance. Then, uniformly deposited films were obtained (between 10 and 15 s), and sensitivity rose up by increasing deposition times, whereas some limitations started to occur with much thicker films (>15 s deposition times) as a result of less electrochemically accessible paraquat accumulated far away from the electrode surface and restricted mass transport through the whole film thickness. These limitations were also confirmed on the basis of multi‐layered mesoporous silica films, suggesting a behavior that might be typical for other types of film‐modified electrodes.     

聚乙烯吡啶化学修饰电极预富集-石墨炉原子吸收法测定酒石酸锑钾的研究

本文研究了聚乙烯吡啶(PVP)化学修饰电极预富集——石墨炉原子吸收法测定酒石酸锑钾的方法。结果表明,在 pH 为3.5的 HCl 介质中,酒石酸锑钾浓度在5.4×10~(-8)～2.2×10~(-6)g/ml 范围内,与吸光度值呈良好的线性关系。对1.1×10~(-6)g/ml 的酒石酸锑钾溶液平行测定9次,相对标准偏差为4.9%,最低检测限为1.6×10~(-8)g/ml。17种异离子及有机物不干扰测定,回收率在97～103%之间,结果令人满意。