Analysis of free, mono- and diacetylated polyamines from human urine by LC–MS/MS

Roine, Antti; Auriola, Seppo; Tuokko, Antti; Veskimäe, Erik; Keinänen, Tuomo A.; Lehtimaki, Terho; Oksala, Niku; Vepsäläinen, Jouko

doi:10.1016/j.jchromb.2013.10.009

Cited by 27 publications

(32 citation statements)

References 35 publications

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“…In addition, results concerning diacetylated cadaverine and diacetylated putrescine should be interpreted with caution, because their analysis is only semiquantitative. 7 Although we are not aware of any subsequent studies since the report by Suh et al, 10 on the urinary polyamine profile in ovarian cancer, our results are in accordance with previous experience with other tumors. Patients with non-Hodgkin lymphoma or urogenital cancer (testicular, prostatic, renal, and bladder carcinoma) have been found to have elevated urinary concentrations of DiAcSpm and those with urogenital cancer also of DiAcSpd.…”

Section: Discussionsupporting

confidence: 91%

“…Our LC-MS/MS method optimized for noninvasive and standardized single-run analysis of urine can be used for simultaneous analysis of up to 14 polyamines in free, mono-and diacetylated forms in human urine, without any derivatization. 7 In the present study, however, 1,3-diaminopropane and putrescine were not detectable. In addition, results concerning diacetylated cadaverine and diacetylated putrescine should be interpreted with caution, because their analysis is only semiquantitative.…”

Section: Discussioncontrasting

confidence: 73%

“…26 Although the LC-MS/MS method is very accurate, it is as such not suitable for routine clinical use, at least not for time being. 7 However, if only 1 (DiAcSpm) or a few polyamines need to be analyzed, the analysis could probably be made faster and less expensive to perform. Alternative methods to measure only urinary DiAcSpm in routine clinical practice include an enzyme-linked immunosorbent assay 13,28 or a colloidal gold aggregation procedure.…”

Section: Discussionmentioning

confidence: 99%

“…6 Recently, an optimized LC-MS/MS method has been developed, which allows for a simultaneous analysis of up to 14 polyamines in different forms in urine. 7 The present study was undertaken as a proof of concept study to explore the usefulness of LC-MS/MS in differential diagnostics of ovarian tumors.…”

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confidence: 99%

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Urinary Polyamines as Biomarkers for Ovarian Cancer

Niemi

Roine

Häkkinen

et al. 2017

International Journal of Gynecological Cancer

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ObjectivesElevated concentrations of polyamines have been found in urine of patients with malignant tumors, including ovarian cancer. Previous research has suffered from poorly standardized detection methods. Our liquid chromatography–tandem mass spectrometry (LC-MS/MS) method is capable of simultaneous standardized analysis of most known polyamines. Liquid chromatography–tandem mass spectrometry has not previously been used in the differential diagnostics of ovarian tumors in postmenopausal women.Materials and MethodsIn this prospective study, postmenopausal women (n = 71) presenting with an adnexal mass and, as controls, women with genital prolapse or urinary incontinence scheduled for surgery (n = 22) were recruited in the study. For analysis of the polyamines, a morning urine sample was obtained before surgery. Preoperative serum CA125 concentrations were determined in the study group.ResultsTwenty-three women with benign and 37 with malignant ovarian tumors were eligible. Of all analyzed polyamines, only urinary N1,N12-diacetylspermine showed statistically significant differences between all groups except controls versus benign tumors. N1,N12-diacetylspermine was elevated in malignant versus benign tumors (P < 0.001), in high-grade versus low malignant potential tumors (P < 0.001), in stage III to IV versus stage I to II cancers (P < 0.001), and even in early-stage cancer (stage I–II) versus benign tumors (P = 0.017). N1,N12-diacetylspermine had better sensitivity (86.5%) but lower specificity (65.2%) for distinguishing benign and malignant ovarian tumors than CA125 with a cut-off value of 35 kU/L (sensitivity, 75.7%; specificity, 69.6%).ConclusionsUrinary N1,N12-diacetylspermine seems to be able to distinguish benign and malignant ovarian tumors as well as early and advanced stage, and low malignant potential and high-grade ovarian cancers from each other, respectively.

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Section: Discussionsupporting

confidence: 91%

Section: Discussioncontrasting

confidence: 73%

Section: Discussionmentioning

confidence: 99%

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confidence: 99%

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Urinary Polyamines as Biomarkers for Ovarian Cancer

Niemi

Roine

Häkkinen

et al. 2017

International Journal of Gynecological Cancer

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“…In addition, an extra extraction or manual cleanup step to remove derivatization agent after derivatization was required such as liquid-liquid extraction which may lead to a depletion of polyamines [7]. Solidphase extraction (SPE) including SPE online which was used frequently in recent years could not omit the derivatization step before or after SPE either [10], and for high-throughput screenings SPE are really high cost. In this present work, the derivatization and SPE were not used and the pretreatment was minimized to protein precipitation step only.…”

Section: Sample Preparationsmentioning

confidence: 99%

Quantification of free polyamines and their metabolites in biofluids and liver tissue by UHPLC-MS/MS: application to identify the potential biomarkers of hepatocellular carcinoma

Liu

Xie

et al. 2015

Anal Bioanal Chem

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Polyamines and their N-acetylated metabolites are potential biomarkers in the diagnosis and therapeutic evaluation of cancer. Thus, we present here an ultra high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of 6 free, 3 monoacetylated, and 2 diacetylated polyamines without derivatization. The major improvement of this method is the use of 0.2 % perfluoroheptanoic acid methanol in the pretreatment step to achieve protein precipitation and 0.0125 % perfluoroheptanoic acid in the mobile phase to achieve analyte separation within 9 min. The established analytical method was validated with plasma, urine, and liver tissue and applied to determine plasma, urine, and liver tissue samples from healthy rats, hepatocellular carcinoma rats, and administrated rats successfully. Results indicated free polyamines such as putrescine mainly existed in liver tissue but more polar N-acetylated metabolites such as N (1),N (12)-diacetylspermine seemed to exist in biological fluid. After carcinogenesis, the levels of polyamines were increased, but the elevated levels of polyamines and their metabolites tended to decrease when administrated with anticancer drug. The method provided a more versatile manner for clinical application in the diagnosis and therapeutic evaluation of hepatocellular carcinoma.

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Aliphatic Polyamine Oxidation Reaction Mechanism at Boron‐doped Microcrystalline and Ultrananocrystalline Diamond Electrodes

2015

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The oxidation reaction mechanism of several aliphatic polyamines was studied using diamond electrodes with different doping levels and non‐diamond carbon impurity content. The important roles of surface boron and localized non‐diamond carbon sites in the polyamine oxidation reaction mechanism were confirmed. A well defined oxidation peak was seen for all the amines that was dependent on the onset potential for water discharge. Epox shifted negative and the ipox increased with increasing solution pH. ipox also increased with increasing boron doping level or surface boron site density. FIA‐EC analysis revealed a reproducible response for the aliphatic polyamines in a binary solvent (7/93 %) acetonitrile/borate buffer, pH 11.2. Optimum signal‐to‐background ratios for the aliphatic polyamines were seen at potentials between 650 and 670 mV.

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Analysis of free, mono- and diacetylated polyamines from human urine by LC–MS/MS

Cited by 27 publications

References 35 publications

Urinary Polyamines as Biomarkers for Ovarian Cancer

Urinary Polyamines as Biomarkers for Ovarian Cancer

Quantification of free polyamines and their metabolites in biofluids and liver tissue by UHPLC-MS/MS: application to identify the potential biomarkers of hepatocellular carcinoma

Aliphatic Polyamine Oxidation Reaction Mechanism at Boron‐doped Microcrystalline and Ultrananocrystalline Diamond Electrodes

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