Trace determination of Ag(I) after reduction to Ag nanoparticles and sol–gel entrapment by alginic acid hydrogel

The main goal of this work is development of an effective analytical method for trace determination of Ag(I). The novelty of the Ag(I) preconcentration–determination method is mainly referred to the material and the enrichment–detection process (alginic acid gel phase was employed in a pH-switched sol–gel entrapment/Ag fluorescence detection). Ag(I) was reduced to Ag nanoparticles (AgNPs) and then was enriched by the alginic acid hydrogel phase. Then, the formed gel phase (containing AgNPs) was dissolved in alkali solution prior to Ag detection. The enrichment method was highly compatible with spectrofluorimetry, electrothermal atomic absorption spectrometry (ETAAS) and spectrophotometry. Optimization of the reduction-enrichment procedure was performed employing spectrofluorimetry. The linear working range (LWR) and limit of detection (LOD) for Ag(I) determination were found as 0.1–25 and 0.017 µmol L^??1, respectively. The effects of various anions, cations and organic chemicals on Ag(I) determination were spectrofluorimetrically studied. The applied enrichment-ETAAS Ag(I) determination method showed the LWR and LOD as 0.2–6.9 and 0.05 nmol L^??1, respectively. Also, an enrichment factor equal to 30.3 was obtained for the preconcentration method. The method was successfully applied to determine Ag in different water samples, jewels, antimicrobial suspensions and waste X-ray films. X-ray diffraction, transmission electron microscopy, field emission-scanning electron microscopy and EDX-mapping were also employed to characterize the entrapped AgNPs in the alginic acid gel phase. The complimentary experiments showed the alginic acid gel was also applicable for quantitative recovery of silver from the waste radiographic films.     

新荧光试剂双(2-苯并噻唑重氮氨基)-3,3′,5,5′-四甲基联苯的合成及其分析应用

将3,3′,5,5′-四甲基联苯胺和苯并噻唑类试剂结合, 并引入杂环三氮烯结构, 合成了新荧光试剂双(2-苯并噻唑重氮氨基) 3,3′,5,5′-四甲基联苯(BBTDTMB), 其结构经红外光谱、 核磁共振谱和元素分析证实. 研究结果表明, 在碱性介质中, 该试剂在λex/λem=342 nm/420 nm处产生强荧光, 并且Ag(Ⅰ)对其荧光有很好的猝灭作用, 因而建立了BBTDTMB测定Ag(Ⅰ) 的新荧光分析方法. 该方法的线性范围为1.0～240 μg/L, 检测限为 0.5 μg/L, 应用于人发、 茶叶中的Ag(Ⅰ) 的测定, 结果令人满意.     

Determination of silver(I) ion in water samples by graphite furnace atomic absorption spectrometry after preconcentration with dispersive liquid-liquid microextraction

A method was developed for the determination of silver ion (Ag) by combining dispersive liquid-liquid microextraction preconcentration with graphite furnace atomic absorption spectrometry. Diethyldithiocarbamate was used as a chelating agent, and carbon tetrachloride and methanol as extraction and dispersive solvent. Factors influencing the extraction efficiency of Ag and its subsequent determination were studied and optimized. The detection limit is 12 ng L^?1 (3 s) with an enrichment factor of 132, and the relative standard deviation is 3.5% (n?=?7, at 1.0 ng mL^?1). The method was successfully applied to the determination of trace amounts of Ag in water samples.     

Simultaneous determination of Cu(II) and Ag(I) on SP Sephadex C25 as complexes with 1-phenyl-1,2-propanedione-2-oximethiosemicarbazone by derivative spectrophotometry

A simple, rapid, and sensitive method has been developed for the simultaneous determination of trace amounts of copper and silver using 1-phenyl-1,2-propanedione-2-oximethiosemicarbazone (PPDOT) as a chromogenic reagent. The proposed method was based on retention and preconcentration of the complexes Cu(III)-PPDOT and Ag(I)-PPDOT on a solid phase in acid medium. The complexes were quantitatively retained in the cation exchanger SP Sephadex C25, and the analytical measurements were executed directly in the solid phase by derivative spectrophotometry. In this simultaneous determination, the second derivative and the zero crossing method were used. The determination of copper and silver was carried out to 321.0 and 427.0 nm, respectively. In order to obtain quantitative recoveries of the metal ions, various experimental analytical parameters, such as pH, stirring time, volume, and amount of solid phase, were optimized. The effect of interfering ions on the determination was described. The recovery values for Cu(II) and Ag(I) were found to be > 98%, and the relative standard deviation was < or = 2%. The detection limits (3sigma criterion) for Cu(II) and Ag(I) were found to be 0.9 x 10(-8) and 13 x 10(-8) M, respectively. The developed method was utilized for preconcentration and determination of Cu(II) and Ag(I) in industrial effluents and natural water samples. The results were consistent with those provided by inductively coupled plasma/mass spectrometry.     

2,5-巯基-1,3,4-硫代二氮唑自组装金电极测定银(I)

制备了2,5-巯基-1,3,4-硫代二氮唑(DMTD)自组装单分子层修饰金电极,用电化学阻抗谱进行了表征,研究了Ag(I)在该电极上的电化学行为并用差分脉冲阳极溶出伏安法对其进行了测定。结果表明,DMTD/Au电极能显著提高Ag(I)测定的灵敏度和选择性,Ag(I)浓度在9.4×10-7～8.0×10-6mol/L范围内,氧化峰电流与Ag(I)呈现良好的线性关系,检出限为2×10-7 mol/L。该自组装电极可用于水样的测定。     

Determination of Iodide and Idoxuridine at a Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Modified Glassy Carbon Electrode

The detection limit (about 0.017 μg mL^?1) for voltammetric determination of iodide (peak at +0.87 V vs. Ag/AgCl at pH 2) at a glutaraldehyde‐cross‐linked poly‐L ‐lysine modified glassy carbon electrode involving oxidation to iodine was found to be several orders of magnitude lower than that for the voltammetric determination on a bare glassy carbon electrode. This method was applied successfully to the determination of iodide in two medicinal formulations. Idoxuridine was determined indirectly at the same electrode by accumulating it first at ?0.8 V vs. Ag/AgCl. At this potential the C? I bond in the adsorbed idoxuridine is reduced giving iodide, which is then determined at the modified electrode. The method was successfully applied to the determination of idoxuridine in a urine sample.     

Analytical applications of the o-dianisidine-persulfate reaction: Kinetic determination of silver and cobalt

A kinetic method for the silver determination based on the catalytic effect of Ag(I) on the oxidation of o-dianisidine by persulfate at pH = 4.5 in the presence of 1,10-phenanthroline is proposed. Ag(I) can be determined by measuring the absorbance of the reaction product at 450 nm, using the fixed time method. Co(II) does not have a catalytic effect in the reaction, but in the simultaneous presence of silver and cobalt the reaction shows an induction period the length of which is related to the Ag/Co molar ratio. As a consequence, two new methods for the determination of cobalt and silver using the induction period method are proposed. The two methods for silver are applied to the determination of silver in lead.     

On-line separation and preconcentration of silver ion on amidino-thiourea immobilized glass beads packing in flow injection analysis with atomic absorption spectrometric detection.

Amidino-thiourea immobilized glass beads (AGB I) were prepared and used as the microcolumn packing for the flow injection (FI) on-line separation and preconcentration of Ag(I) coupled with atomic absorption spectrometry (AAS) determination. Base metal ions and anions with a concentration of 2.0 mg mL(-1) had no interference with the determination of Ag(I). The limit of detection (LOD) of Ag(I) for a preconcentration time of 60 s with a sampling flow rate of 5.0 mL min(-1) for 40.0 ng mL(-1) of Ag(I) were 0.50 ng mL(-1) with the peak-height absorbance mode and 1.26 ng mL(-1) with the peak-area absorbance mode, respectively. The relative standard deviations (RSD) of 7 replicate determinations were 0.9% and 0.7% for the peak-height absorbance (H) and the peak-area absorbance (A), respectively. The method was successfully applied to the determination of Ag(I) in ore samples.     

Determination of silver(I) by electrothermal-AAS in a microdroplet formed from a homogeneous liquid-liquid extraction system using tetraspirocyclohexylcalix[4]pyrroles.

A simple and efficient method for the selective separation and preconcentration of Ag+ using homogeneous liquid-liquid extraction was developed. Tetraspirocyclohexylcalix[4]pyrrole (TSCC4P) was synthesized and investigated as a suitable selective complexing ligand for Ag+. Zonyl FSA (FSA) was applied as a phase-separator agent under mild pH conditions. Under the optimal conditions ([TSCC4P] = 3.4 x 10(-4) M, [THF] = 25.0% v/v, [FSA] = 1.25% w/v, and pH = 4.5), 5 microg of Ag+ in 6.0 ml aqueous phase could be extracted quantitatively into 20 microl of the sedimented phase. The maximum concentration factor was 300-fold. The limit of detection of the proposed method was 0.005 ng/ml. The reproducibility of the proposed method was at most 3.5%. The influence of the pH, type and volume of the water-miscible organic solvent, concentration of FSA, concentration of the complexing ligand and the effect of different diverse ions on the extraction and determination of Ag+ were investigated. The proposed method was applied to the extraction and determination of Ag+ in different water samples.     

Solid phase extraction of ultra-trace amounts of Ag+ by using octadecyl silica membrane disks modified with a new fulvalen derivative.

A simple method for the rapid extraction and determination of ultra-trace amounts of Ag+ ions using octadecyl-bonded silica membrane disks modified with a recently synthesized fulvalen (tetramethyltetrathiafulvalen) (TMTTF) and graphite furnace atomic absorption spectrometry is presented. The extraction efficiency and influence of the flow rate, pH, nature of the counter ion and type and the least amount of eluent for the stripping of Ag+ from disks and breakthrough volume were evaluated. The maximum capacity of the membrane disks modified by 5 mg of TMTTF used was found to be 482 +/- 6 micrograms Ag+. The detection limit of the proposed method is 1.0 ng/dm3. The method was applied to the recovery of Ag+ ions from different synthetic and water samples.     

铋试金法测定高铋物料中的银

火法试金最常用的为铅试金,当物料中铋的质量百分含量15%时,铅试金分析方法测定银量结果精密度差,且结果偏低。实验中研究了铋试金测定高铋铅阳极泥中银量的方法、铋试金和铅试金方法过程对比、铋试金方法中杂质元素Sb,Cu,As,Ni,Pb的干扰、铋试金过程中铋扣直接溶解滴定和铋扣灰吹二次试金方法对比。通过多家单位对精密度和加标回收率的考察,相对标准偏差(RSD)在0.33%~0.84%,加标回收率在96.38%~100.62%,方法准确、可靠。     

基于纳米银对鲁米诺-铁氰化钾化学发光体系的增敏作用测定硫酸特布他林

基于纳米银对鲁米诺-K3Fe(CN)6化学发光体系的显著增敏作用,建立了流动注射化学发光检测硫酸特布他林的新方法.运用透射电子显微镜(TEM)对所制备的纳米银进行了表征.化学发光光谱和紫外吸收光谱显示将纳米银注入鲁米诺-K3Fe(CN)6体系后,未生成新的发光物质.考察了鲁米诺,K3Fe(CN)6,NaOH以及纳米银浓度对化学发光体系的影响,在优化的实验条件下,该方法对硫酸特布他林检测的线性范围是1.0×10-9～2.0×10-5 g/L(r=0.9935),检出限为1×10-10 g/L,相对标准偏差为3.6%(C=1.0×10-6 g/L, n=11).本方法应用于硫酸特布他林片剂含量的测定,回收率为98.5%～102.5%,并与药典方法进行了比较,结果基本一致.     

纳米银增敏化学发光体系测定间苯二酚

采用柠檬酸钠包覆化学还原法制备纳米银粒子,将该纳米银粒子加入到碱性鲁米诺-铁氰化钾化学发光体系,体系的化学发光强度明显增强,而间苯二酚的加入能抑制该体系的化学发光,据此建立了流动注射化学发光法定量分析痕量间苯二酚的新方法.考察了鲁米诺、铁氰化钾、氢氧化钠以及纳米银浓度对化学发光体系的影响.在优化的实验条件下,该方法测定...     

Electrochemical Metalloimmunoassay Based on Enlargement of Gold Nanoparticle Label Treated with Ag Enhancement System

A novel sensitive electrochemical immunoassay with colloidal gold as the antibody labeling tag and subse-quent signal amplification by silver enhancement is described. Colloidal gold was treated by a light-sensitive silver enhancement system which made silver deposit on the surface of colloidal gold(form Au/Ag core-shell structure), followed by the release of the metallic silver atoms anchored on the antibody by oxidative dissolu-tion of them in an acidic solution and the indirect determination of the dissolved Ag ions by anodic stripping voltamrnetry(ASV) at a carbon fiber microelectrode. The electrochemical signal is directly proportional to the amount of analyte(goat IgG) in the standard or a sample, The method was evaluated by means of a non-competitive heterogeneous immunoassay of immunoglobulin G(IgG) with a concentration as low as 0. 2 ng/mL. The high performance of the method is related to the sensitive ASV determination of silver( I ) at a car-bon fiber microelectrode and to the release of a large number of Ag^ ions from each silver shell anchored on the analyte (goat IgG).     

Visual detection of silver(I) ions by a chromogenic reaction catalyzed by gold nanoparticles

We report on a novel method for visual detection silver(I) ion. It is based on the finding that Ag(I) ions are rapidly reduced by hydroquinone to form a shell of silver on the surface of gold nanoparticles (AuNPs) which act as catalysts for this reaction. This leads to a color change from red to yellow which can be seen with bare eyes. This scheme is sensitive and highly specific for Ag(I) ions. The detection limits are 5 μM for visual inspection and 1 μM for photometric readout, respectively. The method was successfully applied to the determination of Ag(I) ions in spiked lake water and soil.

Separation and preconcentration of Ag(I) in aqueous samples by flotation as an ion-associate using iodide and ferroin followed the determination by flame atomic absorption spectrometry

A simple method for separation/preconcentration and determination of Ag(I) in aqueous samples is described. The method is based on formation of an ion-associate between Ag(I)-iodide complex and ferroin, which can be floated at the interface of the aqueous/n-heptane phases. The flotation process was carried out using 500-ml aliquot of the aqueous solution and the floated layer was dissolved in 5 ml of 1 M HNO3 containing methanol (50% v/v) as the solvent. The Ag(I) content was then determined by flame atomic absorption spectrometry (FAAS). The method so could be considered as an enrichment process, was achieved to a quantitative feature, when the pH of the solution was adjusted to 4 and the concentrations of iodide and ferroin were about 3.2 x 10(-4) M and 6.25 x 10(-5) M, respectively. The LOD and RSD (n = 7) were obtained 1.0 x 10(-8) M and 2.4%, respectively. It was found that a large number of cations and anions even at high considerably foreign ion/Ag(I) ratios were not interfered. The method was applied satisfactorily to recovery of Ag(I) from different aqueous samples.     

活性炭吸附及离子交换富集分离-分光光度法测定水中痕量银

建立了用活性炭对水中痕量银进行预富集的新方法。结果表明,pH=1.0时,活性炭能对水中被抗坏血酸还原后的痕量银进行吸附富集,而Cu(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)、Al(Ⅲ)、Bi(Ⅲ)和Sb(Ⅲ)等常见阳离子不被吸附,用K2S2O8将吸附在活性炭上的单质银氧化解脱后,用Mg(NO3)2辅助置换洗脱,可用分光光度法测定。该法在8～50μg/L银(Ⅰ)范围内加标回收率为93.2～97.1%。同时还研究了活性炭对银的吸附行为,提出了活性炭表面上被氧化的Ag(Ⅰ)和Mg(Ⅱ)有离子交换作用。应用该法测定自来水中痕量银,结果令人满意。     

Determination of lead and silver in copper blister by isotope excited X-ray fluorescence

The energy dispersive X-ray fluorescence method of Pb and Ag determination in metallic copper is described. Radioisotopic sources of⁵⁷Co and²⁴¹Am/target have been used for excitation and Si(Li) and hyperpure Ge spectrometers for spectra analysis. The standard deviation of Pb and Ag determination for a single measurement is 0.015 and 0.012%, respectively.     

The determination of copper ions based on sensitized chemiluminescence of silver nanoclusters

We report on the first application of novel, water-soluble and fluorescent silver nanoclusters (Ag NCs) in a chemiluminescent (CL) detection system. A method has been developed for the determination of copper(II) ion that is based on the fact that the weak CL resulting from the redox reaction between Ce(IV) ion and sulfite ion is strongly enhanced by the Ag NCs and that the main CL signals now originate from Ag NCs. UV-visible spectra, CL spectra and fluorescent (FL) spectra were acquired to investigate the enhanced CL mechanism. It is proposed that the electronic energy of the excited state intermediate SO₂* that originates from the CL reaction is transferred to Ag NCs to form an electronically excited NC whose emission is observed. In addition, it is found that copper(II) is capable of inhibiting the CL of the nanoclusters system, but not if other common metal ions are present. The detection of copper(II) is achieved indirectly by measuring the CL intensity of Ag NCs. Under the optimized experimental conditions, a linear relationship does exist between the intensity of CL and the concentrations of copper(II) in the range of 0.2?nM to 0.1?m??. The detection limit is 0.12?nM. The method is applied to the determination of copper(II) ion in tap water with satisfactory results.

聚1,8-萘二胺修饰玻碳电极溶出伏安法测定银的研究

采用电化学聚合的方法制备了聚1,8-萘二胺修饰玻碳电极,建立了开路富集-阳极溶出测定痕量Ag~+的方法.优化了各种实验参数(如富集底液的pH,富集时间等),并考察了其它离子的干扰影响.在最佳实验条件下,银在0.0008～0.1 mg·L~(-1)浓度范围内与溶出峰电流成良好的线性关系,检出限为0.0005 mg·L~(-1).该法用于实际水样中痕量银的测定,效果良好.