Characterization of selenium species in biological extracts by enhanced ion-pair liquid chromatography with inductively coupled plasma-mass spectrometry and by referenced electrospray ionization-mass spectrometry

Kotrebai, Mihály; Bird, Susan Mary; Tyson, Julian F.; Block, Eric; Uden, Peter C.

doi:10.1016/s0584-8547(99)00086-5

Cited by 65 publications

(67 citation statements)

References 28 publications

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“…Comparison of a yeast water extract (not shown) with Figure 1a showed the absence of the major selenomethionine peak, suggesting that it is immobilized, perhaps in proteins; Se-adenosylselenohomocysteine appeared as the major selenium compound. The extraction efficiency and column recovery values of selenium for the enzymatic extracts of yeast were 80-90%, whereas the hot water extraction efficiency was only ∼10% (Uden et al, 1998;Kotrebai et al, 1999). The two identified compounds account for ∼82% of the total selenium in compounds eluting from the enzymatic extract.…”

Section: Methodsmentioning

confidence: 93%

Chemical Speciation Influences Comparative Activity of Selenium-Enriched Garlic and Yeast in Mammary Cancer Prevention

Birringer

Block

et al. 2000

J. Agric. Food Chem.

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270

126

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A recent human intervention trial showed that daily supplementation with selenized yeast (Seyeast) led to a decrease in the overall cancer morbidity and mortality by nearly 50%; past research has also demonstrated that selenized garlic (Se-garlic) is very effective in mammary cancer chemoprevention in the rat model. The goal of this study was to compare certain biological activities of Se-garlic and Se-yeast and to elucidate the differences based on the chemical forms of selenium found in these two natural products. Characterization of organic selenium compounds in yeast (1922 µg/g Se) and garlic (296 µg/g Se) was carried out by high-performance liquid chromatography with inductively coupled plasma mass spectrometry or with electrospray mass spectrometry. Analytical speciation studies showed that the bulk of the selenium in Se-garlic and Se-yeast is in the form of γ-glutamyl-Se-methylselenocysteine (73%) and selenomethionine (85%), respectively. The above methodology has the sensitivity and capability to account for >90% of total selenium. In the rat feeding studies, supplementation of Se-garlic in the diet at different levels consistently caused a lower total tissue selenium accumulation when compared to Se-yeast. On the other hand, Se-garlic was significantly more effective in suppressing the development of premalignant lesions and the formation of adenocarcinomas in the mammary gland of carcinogen-treated rats. Given the present finding on the identity of selenomethionine and γ-glutamyl-Se-methylselenocysteine as the major form of selenium in Se-yeast and Se-garlic, respectively, the metabolism of these two compounds is discussed in an attempt to elucidate how their disposition in tissues might account for the differences in cancer chemopreventive activity.

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Section: Methodsmentioning

confidence: 93%

Chemical Speciation Influences Comparative Activity of Selenium-Enriched Garlic and Yeast in Mammary Cancer Prevention

Birringer

Block

et al. 2000

J. Agric. Food Chem.

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270

126

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“…Although ED is sensitive for compounds with electrochemical active groups, its selectivity is not so good. Element specific detectors, such as atomic emission spectrometry (AES) [11], inductively coupled plasma mass spectrometry (ICP-MS) [12][13][14], atomic absorption spectrometry (AAS) [15,16] or atomic fluorescence spectrometry (AFS) [17][18][19], are the most interesting ones in these respects. ICP-MS offers advantages of easy coupling but the sensitivity is restricted because of the high ionization potential of Se [20].…”

Section: Introductionmentioning

confidence: 99%

Selenium speciation by high-performance anion-exchange chromatography–post-column UV irradiation coupled with atomic fluorescence spectrometry

Liang

Shu-min

Zhang

et al. 2006

Journal of Chromatography A

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A technique for the speciation of selenomethylcysteine (SeMeCys), selenocystine (SeCys), selenite [Se(IV)] and selenomethionine (SeMet) was established in this paper using high-performance anion-exchange chromatography coupled with atomic fluorescence spectrometry (HPAEC-AFS). Analytes were separated on an AminoPac PA10 column and then digested by on-line ultraviolet (UV) irradiation, which destroyed organic compound structure. Hydride generation was used as an available sample introduction technique for atomic fluorescence detection. The detection limits of four compounds were 1-5 g/L (250 L injection, 10 times of the baseline noise). The relative standard deviations (RSDs), calculated from seven consecutive injections of 100 g/L standard mixtures, were from 2 to 4%. Selenious yeast tablet, which had been proposed as selenium supplement, and human urine collected from a volunteer were analyzed. Good spiked recoveries from 86 to 103% were obtained.

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“…Five selenium species and several unknown peaks were observed in selenium-enriched garlic, onion, and broccoli [22,23]. Several seleno-analogues of sulfur-containing amino acids and their derivatives have been identified in terrestrial plants, especially in so-called "selenium accumulator plants" [24][25][26]. Among the six organoselenium compounds detected in seagull eggs the major compounds were selenocysteine and selenocystamine [27].…”

Section: Species Of Interestmentioning

confidence: 99%

“…Ion-exchange and reversed-phase HPLC have been mainly applied to the separation of Se(IV), Se(VI), selenomethionine, and selenocysteine (for an exhaustive list of references see [17,18,55]). In recent studies a large number of synthetic organoselenium compounds were used [24][25][26].…”

Section: Hplc With Selenium-specific Detectionmentioning

confidence: 99%

“…Retention and separation of selenoamino acids can be increased by using an ion-pairing reagent: trifluoroacetic acid [17,20] or octanesulfonate [79]. In particular, perfluorinated carboxylic acids offer good resolution and should be given preference for the characterization of samples containing many seleno compounds [23][24][25]. Another possibility is the derivatization of the selenoamino acids to N-2,4-dinitrophenyl derivatives by reaction with 2,4-dinitrofluorobenzene [17] Despite the fact that, in theory, SE-HPLC separation should be based on the molecular weights of the analytes, secondary adsorption and ion-exchange effects apparently play an important role, and separation of small compounds with similar molecular masses can be achieved in addition to the possibility of the detection of selenoproteins [20].…”

Section: Detection Of Small Seleno Compounds By Hplc-icp Msmentioning

confidence: 99%

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Species-selective determination of selenium compounds in biological materials (Technical Report)

Łobiński

Edmonds

Suzuki

et al. 2000

Pure and Applied Chemistry

157

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Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the need for formal IUPAC permission on condition that an acknowledgmentMembership of the Commission during the preparation of this report (1997)(1998)(1999) Species-selective determination of selenium compounds in biological materials (Technical Report)Abstract: There is substantial evidence of the complexity of selenium speciation in living organisms and of the importance of the selective determination of the particular species of this element in order to understand its metabolism and biological significance in clinical chemistry, biology, toxicology, and nutrition. The state-of-the-art of analytical techniques available for this purpose is critically evaluated with particular emphasis on the element-selective detection and identification of the detected selenium compounds. Whereas there are a number of techniques available that are able to detect various selenium species in living organisms selectively, few techniques exist that are able to identify and to characterize the species detected.

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Characterization of selenium species in biological extracts by enhanced ion-pair liquid chromatography with inductively coupled plasma-mass spectrometry and by referenced electrospray ionization-mass spectrometry

Cited by 65 publications

References 28 publications

Chemical Speciation Influences Comparative Activity of Selenium-Enriched Garlic and Yeast in Mammary Cancer Prevention

Chemical Speciation Influences Comparative Activity of Selenium-Enriched Garlic and Yeast in Mammary Cancer Prevention

Selenium speciation by high-performance anion-exchange chromatography–post-column UV irradiation coupled with atomic fluorescence spectrometry

Species-selective determination of selenium compounds in biological materials (Technical Report)

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