On-line photo-derivatization with flow injection and liquid chromatography-atmospheric pressure electrospray mass spectrometry for the identification of indoles

The application of on-line photochemistry with flow injection (FI) and liquid chromatography (LC) in conjunction with atmospheric pressure electrospray mass spectrometry (LC-APESI-MS) for the identification of similar indole derivatives is reported here. The photo-transformation of the indole compounds is strongly affected by the substituent groups on the aromatic and heterocyclic rings. Upon photolysis for 2.5 min, the mass spectrum of tryptamine (Try) which has no OH substituent on the aromatic ring does not differ greatly from that obtained without photolysis. However, after photolysis of serotonin (Ser) which has one OH group on C5 of the aromatic ring, the mass spectrum indicates the formation of dimers and higher molecular weight ions. The fragmentation pattern of 5-hydroxytryptophol (Phol) without photolysis resembles that of Ser with a base peak of m/z 160. Upon photolysis using MeOH-H₂O (10/90), Phol is found to form a base peak at m/z 375 (100%) and a major peak at m/z 214 (66%) in addition to other ions with lower abundance. Melatonin (Mel) and tryptophan (Phan) upon photolysis are found to form high molecular weight ions with a relative low abundance. The mass spectrum of indole-3-acetic acid (Inaa) with on-line photolysis also shows different ions that are not formed without photolysis.     

在线分离光度法测定痕量金的研究

本提出了一种泡沫塑料柱在线分离富集／β－环糊精－十二烷基苯磺酸钠溶液在线洗脱／硫代米蚩酮光度法测定痕量金的新方法。方法的检测出限是３×１０＾－＾８ｇＡｕ，线性范围是５×１０＾－＾７－８×１０＾－＾６Ａｕ，对于１．０μｇＡｕ进行１１次测定，相对标准偏差小于３．０％。     

Stochastic on-line knapsack problems

Different classes of on-line algorithms are developed and analyzed for the solution of {0, 1} and relaxed stochastic knapsack problems, in which both profit and size coefficients are random variables. In particular, a linear time on-line algorithm is proposed for which the expected difference between the optimum and the approximate solution value isO(log^3/2 n). An(1) lower bound on the expected difference between the optimum and the solution found by any on-line algorithm is also shown to hold.Corresponding author.Partially supported by the Basic Research Action of the European Communities under Contract 3075 (Alcom).Partially supported by research project Models and Algorithms for Optimization of the Italian Ministry of University and Scientific and Technological Research (MURST 40%).     

Determination of rare earth elements in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry

A home made column of commercially available iminodiacetate resin, Muromac A-1 (50–100 mesh) was used to concentrate rare earth elements (REEs) (15 elements: Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in seawater. An automated low pressure flow analysis method with on-line column preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) is described for the determination of REEs in seawater. Sample solutions (adjusted to pH of 3.0) passed through the column. After washing the column with water, the adsorbed elements were subsequently eluted into the plasma with 0.7 M nitric acid. Calibration curves were accomplished by means of purified artificial seawater with a sample loading time of 120 s. Detection limits (DLs) of the on-line column preconcentration/ICP-MS by eight replicate operations were between 0.040 and 0.251 pg ml⁻¹ for REEs in the artificial seawater. The precision was less than 8.9% for REEs and one sample can be processed in 7 min using a 7 ml of sample. The proposed method was applied to determine REEs in coastal seawater of Hiroshima Bay, Japan.     

Supercritical fluid extraction-capillary gas chromatography: On-line coupling with a programmed temperature vaporizer

A simple and versatile system is described for the on-line coupling of SFE to capillary GC. The interfacing consists of a programmed temperature vaporizer (PTV) injector. With this injector it is possible to combine solute trapping, elimination of a high flow of extraction fluid, and quantitative transfer of solutes to the seperation column. The problems caused by impurities in the extraction fluid in on-line SFE-GC are discussed. Simple methods are described for the purification of commercially available carbon dioxide. The trapping efficiency of the PTV injector is studied. Applications of the SFE-PTV-GC system are given for the analysis of polymer anti-degradants, polar compounds, and samples with environmental relevance.     

流动注射在线共沉淀HG-AFS测定痕量铅

建立了流动注射在线共沉淀HG-AFS测定痕量铅的分析方法。方法基于铅在碱性介质中与氢氧化镁共沉淀，沉淀收集在锥形沉淀腔中，用HCl溶洗沉淀和NaBH4反应，产生的氢化物被载气引入原子化器中进行测定。测定铅的RSD为3％(5ng/mL，n=10)，检出限为0．01ng。检出限较直接进样降低了11倍。对国家标准物质中铅的测定结果与标准值相符。     

Determination of Trace Molybdenum in Biological Matrices by Neutron Activation Analysis

Based on consecutive extractions using bismuth diethyldithiocarbamate and thallium diethyldithiocarbamate as reagents, molybdenum was selectively and highly enriched from biological matrices, and then subjected to neutron activation analysis. Most of interfering elements, e.g., Na, K, Br, P, Fe, U, etc. were simultaneouly removed and the preconcentrated samples always showed only the r rays from molybdenum after neutron bombardment. Thus, molybdenum in the biological matrices could be accurately determined.     

Molecularly-imprinted polypyrrole-modified stainless steel frits for selective solid phase preconcentration of ochratoxin A

A molecularly-imprinted polymer (MIP) was prepared by electropolymerization of pyrrole (Py) onto a stainless steel frit, using ochratoxin A (OTA) as the template, in order to make a micro solid phase preconcentration (SPP) device. The OTA template was removed with 1% triethylamine (TEA) in methanol. Compared to non-imprinted polypyrrole (PPy), the molecularly-imprinted polypyrrole (MIPPy) enhanced the selective binding of OTA. The percentage recovery improved from 0 to 40% when the OTA sample solution was acidified with 1 M HCl (1% by volume). At a flow rate of 0.2 mL/min, maximum OTA binding was reached in 6 min after a total loading of 3.2 ng OTA. Final elution of the OTA was analyzed by high performance liquid chromatography (HPLC) with fluorescence detection, using 20:80 v/v acetonitrile–ammonia buffer (NH₄Cl/NH₃, 20 mM, pH 9.2) as the mobile phase. The MIPPy-SPP-HPLC results clearly demonstrated that the MIPPy-SPP device afforded selective preconcentration of OTA from red wine samples, at OTA concentration levels as low as 0.05 ppb, prior to HPLC analysis.     

Comparative study of 8-hydroxyquinoline derivatives as chelating reagents for flow-injection preconcentration of cobalt in a knotted reactor

8-Hydroxyquinoline (HQ), 2-methyl-8-hydroxyquinoline (CH₃-HQ), 5,7-dichloro-2-methyl-8-hydroxyquinoline (Cl₂-CH₃-HQ), 5,7-dibromo-8-hydroxyquinoline (Br₂-HQ), 5-sulfo-7-iodo-8-hydroxyquinoline (ferron) and 5-sulfo-8-hydroxyquinoline (SO₃H-HQ) were compared as chelating reagents for on-line sorption preconcentration of cobalt in a knotted reactor (KR) precoated with the reagent. The results obtained with the different HQ derivatives reveal those properties of the chelating reagent responsible for the processes taking place in the KR. The influence of hydrophobicity, acidity, stability of the cobalt chelate and type of substituents in the HQ ring system on the separate steps of the flow injection (FI) preconcentration procedure are discussed. According to the performance characteristics of the different HQ derivatives, the most important parameters for on-line preconcentration in a KR are the hydrophobicity of the reagent and the stability of the chelate complex with the analyte.     

On-line SFE-GC for determination of PCBs in human milk and blood serum

On-line coupled supercritical fluid extraction and gas chromatography (SFE-GC) has been utilized for the determination of PCBs and other organochlorine compounds in human milk and blood serum. The procedure involved preconcentration of the sample on C₁₈-silica sorbent in an extraction cell: after precipitation of the proteins up to 20 ml of human milk was concentrated on 0.5 g of sorbent. Serum (up to 5 ml) was applied to the C₁₈ material without pretreatment. Basic alumina was utilized as a selective adsorbent for lipids in the on-line SFE-GC system. The method was used to analyze milk and serum spiked with 0.5 and 10 ng of Aroclor 1260 and the results compared with those obtained by liquid–liquid extraction of serum.