A sensitive method for the determination of iodine containing diagnostic agents in aqueous matrices using LC-electrospray-tandem-MS detection

Iodinated contrast media belong to the most frequently applied compounds in medicine. They exhibit a high polarity and are very persistent against metabolism by the organism and environmental degradation. A sensitive method for the determination of five iodinated contrast media in aqueous matrices is described. Solid phase extraction utilizing Isolute ENV+ material was used for sample enrichment. The contrast media were partially separated on a RP-C₁₈ column, and detection was achieved using electrospray-tandem MS (API III plus and API 365) allowing the sensitive quantitation of these compounds down to the lower ng/L range. The recovery rates generally exceeded 70%, for spiked surface water as well as tap water. The analytes were detected in native samples such as municipal sewage treatment plant (STP) effluent, the river Rhine and even in tap water.     

A sensitive colorimetric method for the micro determination of iodine in marine water

More than 70% of the earth surface is covered by water bodies. Marine pollution is associated with the discharge of oils, petroleum products, sewage agricultural wastes, pesticides, heavy metals, waste substances and dumping of radioactive waters in sea. This in turn results in hazards to human health, hindrance to aquatic organisms and impairment of quality for use of sea water. Sea water is reported to contain iodine but the concentration varies according to the location and depth. Here a simple and sensitive method is described for the determination of iodine using leucocrystal violet as a reagent in different samples of sea water. The method is based on the oxidation of iodine to iodate with bromine water and the liberation of free iodine from the iodate by addition of potassium iodide in acedic medium. This iodine selectively oxidises leucocrystal violet to form the crystal violet dye. Beer's law is obeyed over the concentration range of 0.04-0.36 ppm of iodine at lambda(max) 592 nm. The dye was further extracted in chloroform. The extracting system obeys Beer's law in the range of 0.008-0.08 ppm at lambda(max) 588 nm.     

Molecular iodine preconcentration and determination in aqueous samples using poly(vinylpyrrolidone) containing membranes

Membranes for preconcentration of molecular iodine were developed by two different routes: (i) UV-grafting of 1-vinyl-2-pyrrolidone in the pores of microporous poly(propylene) host membrane (grafted membrane), and (ii) physical immobilization of preformed poly(vinylpyrrolidone) (PVP) in a plasticized cellulose triacetate matrix to form the polymer inclusion membrane (PVP-PIM). The UV-grafted PVP-membrane was found to be hydrophilic (water uptake capacity = 166 wt.%), while the PVP-PIM was found to be highly hydrophobic (≈2 wt.%). PVP-PIM was found to uptake only I₂ from aqueous sample whereas I₂ and I₃⁻ were sorbed in the grafted membrane. This selectivity of PVP-PIM towards I₂ was attributed to its hydrophobicity that allows only neutral I₂ to interact with PVP in the membrane matrix. Thus, the selective preconcentration and quantitative determination of I₂ in aqueous sample was carried out using PVP-PIM. As PVP-PIM was optically transparent, the characteristic absorbance of PVP–I₂ complex (λ_max = 361 nm) could be used for quantitative determination of I₂ in the membrane. The instrumental neutron activation analysis (INAA) of the I₂-loaded PIM samples indicated that 82% could be sorbed into the PIM samples from the solution within 10 min of equilibration time. This membrane was applied to I₂ determinations in the samples of ¹³¹I radiotracer. The concentration level of iodine species in these samples were in sub-ppb level. Therefore, these samples were ideal for testing the preconcentration efficiency of the membrane towards I₂ by monitoring the radioactivity of ¹³¹I. The amounts of I₂ in the aqueous samples were standardized by conventional solvent extraction of I₂ with the chloroform for validating the preconcentration efficiency of PVP-PIM. The detection limit of I₂ in aqueous samples by INAA hyphenated with PVP-PIM was found to be 0.3 ppb for a sample size of 25 mL.     

A new simple sensitive differential pulse polarographic method for the determination of acrylamide in aqueous solution

A new simple sensitive differential pulse polarographic (DPP) method was investigated for the determination of acrylamide (AA) directly in a neutral aqueous solution. The AA showed a well-defined and well-resolved peak in pure aqueous LiCl at −1.84 V in the potential range from −1.6 V to −1.97 V at nitrogen pressure of 0.5 kg cm⁻². Among the various electrolytes studied, the AA showed good DPP response in the presence of LiCl and tetra methyl ammonium iodide, while it showed poor response in the presence of tetra butyl ammonium hydroxide and tetra butyl ammonium bromide due to their strong adsorption on the surface of electrode which hindered its reduction. The effect of LiCl concentration, the cyclic voltammetric response and the drop time study showed that AA exhibited an irreversible adsorptive electrochemical behavior. The good electrochemical response in pure aqueous medium suggested that hydrogen bonding might be involved which may favor the electrode reaction. Under optimized conditions, the peak current was linear in the entire concentration range from 0.2 mg L⁻¹ to 20 mg L⁻¹ with the correlation coefficient of R² = 0.9998. The method showed good reproducible results with R.S.D. of 0.3% (n = 16). The detection limit (LOD) was 27 μg L⁻¹. The influence of various interfering agents was also studied. The method was applied successfully for the quantification of AA in water samples without any interference effect from alkali metals.     

A highly sensitive method for the determination of adriamycin and adriamycinol in human plasma using HPLC with fluorimetric detection

Summary A simple and very sensitive HPLC method, for the simultaneous determination in human plasma of adriamycin and its metabolite adriamycinol, is described. Plasmas from patients were stored frozen. Thawed samples were extracted by absorption of anthracyclin onto a small C18 column. After evaporation of the eluate and reconstitution of the residue with methanol (100L), 30 to 40L of the mixture were injected into the chromatograph. Separation was obtained using an RP 8 column with a mobile phase of formate buffermethanol-acetonitrile (502327, v/v). A spectrofluorimeter was used as detector. The limit of sensitivity of the assay was 50 pcg/ml of plasma.     

A sensitive method for the determination of tritium in urine

An analytical procedure was developed for the determination of tritium in urine. The content of contaminants in urine after treatment is reduced markedly so that no influence is expected on tritium measurements by a liquid scintillation counter. The established analytical procedure was successfully applied for urine from the general public in Japan.     

A new method for the determination of complexing agents in river water using HPLC

 An HPLC-method is described for the rapid and sensitive determination of NTA, EDTA and DTPA in surface and ground water at the sub-μg/L level. The analytes are enriched on anion-exchange cartridges, eluted with formic acid and analyzed on RP 8 columns within 6 min. Recoveries for EDTA and NTA were 110% resp. 94% at an interlaboratory test. They are significantly lowered when higher amounts of sulfate are present in the sample. Reproducibility and comparability with other methods are investigated. The new technique is faster than the well known GC-analysis. Received: 11 March 1996/Revised: 10 June 1996/Accepted: 21 June 1996     

A new method for the determination of complexing agents in river water using HPLC

 An HPLC-method is described for the rapid and sensitive determination of NTA, EDTA and DTPA in surface and ground water at the sub-μg/L level. The analytes are enriched on anion-exchange cartridges, eluted with formic acid and analyzed on RP 8 columns within 6 min. Recoveries for EDTA and NTA were 110% resp. 94% at an interlaboratory test. They are significantly lowered when higher amounts of sulfate are present in the sample. Reproducibility and comparability with other methods are investigated. The new technique is faster than the well known GC-analysis. Received: 11 March 1996/Revised: 10 June 1996/Accepted: 21 June 1996     

A one-step highly sensitive method for DNA detection using dynamic light scattering

A one-step homogeneous DNA detection method with high sensitivity was developed using gold nanoparticles (AuNPs) coupled with dynamic light scattering (DLS) measurement. Citrate-protected AuNPs with a diameter of 30 nm were first functionalized with two sets of single-stranded DNA probes and then used as optical probes for DNA detection. In the presence of target DNA, the hybridization between target DNA and the two nanoparticle probes caused the formation of nanoparticle dimers, trimers, and oligomers. As a result, the nanoparticle aggregation increased the average diameter of the whole nanoparticle population, which can be monitored simply by DLS measurement. A quantitative correlation can be established between the average diameter of the nanoparticles and the target DNA concentration. This DLS-based assay is extremely easy to conduct and requires no additional separation and amplification steps. The detection limit is around 1 pM, which is 4 orders of magnitude better than that of light-absorption-based methods. Single base pair mismatched DNAs can be readily discriminated from perfectly matched target DNAs using this assay.     

A sensitive spectrophotometric method for the determination of desloratadine in tablets

A simple, rapid, and sensitive visible spectrophotometric method was developed, for the first time, for analysis of desloratadine (DE) in tablets. The method is based on the deep-blue colored TCNQ*- radical anion formed by interaction of the drug (n-donor) with 7,7,8,8-tetracyanoquinodimethane (TCNQ, pi-acceptor) in acetonitrile at ambient temperature. Optimum conditions for the reaction were investigated, absorbances were read at 843 nm, and the linearity range for concentrations of DE was found to be 1.5-13 microg/mL. The reaction product remains stable up to 8 h when kept at room temperature in the dark. The developed method was validated and successfully applied to the determination of DE in tablets. The tablets were also analyzed with a column liquid chromatography method reported in literature. The results from both methods were statistically compared by t- and F-tests. No significant difference was found for the means and standard deviations at 95% confidence level. Accuracy was examined through recovery studies. Being very simple and reliable, the method can be recommended for routine quality control analysis of DE in tablets.     

A sensitive method for the determination of nitroamines in alcoholic beverages

Summary Nitrosamines in alcoholic beverages and malted barley were analysed by adsorption from the gas phase onto a porous polymer trap of Chromosorb 104 and subsequent desorption of the trapped compounds directly to a gas chromatograph fitted with glass capillary column and alkali-FID. The detection limit for NDMA was 0.05 g/l in beer samples and 0.3 g/kg in malted barley.Presented at the 14th International Symposium on Chromatography London, September, 1982     

铟的灵敏光度测定法

我国对微量铟的显色反应研究得较少.最常用的是碱性染料萃取光度法,但操作冗繁而且苯的毒性较大.因此寻找灵敏度高而又能在水相测定铟的新方法是很有必要的. 用苯荧光酮(2,3,7-三羟基-9-苯基-6-荧光酮,PF)作显色剂的胶束增溶分光光度法已应用于锗、钼、锡、镓等的测定,但用类似的方法测铟则尚未见报道.我们的实验证明,在pH为7.7～8.9的醋酸-氢氧化铵缓冲介质中,铟与PF及氯化十六烷基吡啶(OPC)生成玫瑰红色的三元配合物,其配合比为In(III):PF:CPC=1:2:2,表观稳定常数为8.6×10~(10),摩尔吸收系数达1.28×10~5.提出用乙酸乙酯萃取分离杂质.利用本显色反应测定微量铟,方法灵敏且稳定,准确度和精密度均较好.     

A sensitive method for the ultraviolet spectrophotometric determination of chloride

A new method for the determination of chloride ion is based on the formation of phenylmercury(II) chloride, its extraction into chloroform and reaction with sodium diethyldithiocarbamate to form phenylmercury(II) diethyldithiocarbamate. This complex has spectral maxima at 257 and 297 nm. either of which can he used for quantitative purposes. The molar absorptivities are 21.3·10³ and 6.5·10³ respectively. referred to the chloride ion. The method is especially suitable for the determination of trace amounts of chloride in aqueous solution and has been applied to samples of drinking water. Amounts of chloride in the range 0.04 0.32 p.p.m. can be determined in 250-ml aqueous samples with an average relative mean error of 12%. The method can be used also for bromide and iodide, and for organomercury(11) compounds. Interferences are minimal and the method compares favourably with the standard mercury(II) thiocyanate procedure.     

Dithizone derivatives as sensitive water soluble chromogenic reagents for the ion chromatographic determination of inorganic and organo-mercury in aqueous matrices

Water-soluble sulfonate and the novel carboxylate analogues of dithizone, combined with ion interaction chromatography on a Dionex Acclaim 120 C18 silica column (250 x 4.6 mm id) with an eluent consisting of 10 mM tetrabutylammonium bromide and 60:40 methanol:water, have been developed as highly sensitive chromogenic ligands for the quantitative isocratic determination of inorganic and organo-mercury compounds in aqueous matrices in under 12 min. Using an optimised post column reagent system containing 0.65 mM dye, 0.5% Triton X-100 and 50 mM sodium hydroxide, good linearity (0-7.5 mg L(-1) R2 > 0.999), reproducibility using peak area measurements (RSD 0.69-1.38%, n = 8), and limits of detection (4-12 microg L(-1)) were achieved for methyl mercury, inorganic mercury and phenyl mercury.     

A new routine method for determination of iodine in plant materials

A new method is suggested for determination of iodine in grass and crop samples. The sample is decomposed with sulphuric, nitric and perchloric acids. Iodine is determined in the diluted digest. The method is excellent for routine work, being faster and simpler than previous nethods.     

A sensitive and selective detection method for thiol compounds using novel fluorescence probe

In this work, a sensitive and selective detection method based on fluorescence resonance energy transfer (FRET) was developed for analyzing thiol compounds by using a novel fluorescent probe. The new fluorescent probe contains a disulfide bond which selectively reacts with nucleophilic thiolate through the thiol-disulfide exchange reaction. An obvious fluorescence recovery can be observed upon addition of the thiol compound in the fluorescent probe solution due to the thiol-disulfide exchange reaction and the destruction of FRET. This novel probe was successfully used to determine dithiothreitol (DTT), glutathione (GSH) and cysteine (Cys). The limits of detection (LOD) were 2.0 μM for DTT, 0.6 μM for GSH, and 0.8 μM for Cys. This new detection method was further investigated in the analysis of compound amino acid injection.     

Flow-assisted automated solid-phase microextraction for the determination of chloroethers in aqueous matrices

In this study a method of flow-assisted automated solid-phase microextraction (FA-SPME) was developed for the determination of organic pollutants in aqueous samples. A CTC Combi-PAL autosampler coupled with gas chromatography–mass spectrometry (GC–MS) was used to automate the entire extraction process. In this method, the SPME fibre was exposed to 100 mL of sample in a direct immersion mode for 10 min. After exposure, the fibre was desorbed at the injection port of GC–MS. To demonstrate the applicability of FA-SPME, chloroethers were selected as model compounds. Good linear correlation was found over a concentration range of 0.5–100 µg/L. The detection limits of the method were determined between 0.02 and 0.05 µg/L with the coefficients of determination (R²) from 0.9980 to 0.9996. The relative standard deviations (RSDs) of the FA-SPME for three sequential FA-SPME analyses were determined to be in the range between 1.2% and 6.2% (n = 3). The applicability of the method was assessed by means of recovery studies and satisfactory values for all compounds were obtained. This optimised method was used in the analysis of water and human urine samples to show the matrix effect on FA-SPME. This FA-SPME/GC–MS is substantially faster and suitable for the routine continuous flow-mode environmental monitoring applications.     

A novel and highly sensitive catalytic method with oscillopolarographic detection for the determination of ultratrace amounts of iridium

Iridium(IV) has a strong catalytic effect on the slow redox reaction between Malachite Green and periodate ion in pH 4.2 acetate buffer solution at 100 degrees , and Malachite Green exhibits a sensitive single-sweep oscillopolarographic wave at -0.65 V vs. SCE. This provides the basis for a novel and highly sensitive and selective catalytic method with oscillopolarographic detection for iridium. The effect of pH, potassium periodate and Malachite Green concentrations, reaction temperature and reaction time and other variables are investigated. The detection limit is 8 ng/l. with a fixed-reaction time of 10 min. A linear calibration graph from 24 to 1600 ng/l. is obtained. Possible interferences by co-existing ions are examined.