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. Author manuscript; available in PMC: 2017 Jun 20.
Published in final edited form as: Mol Genet Metab. 2016 Sep 28;120(1-2):67–77. doi: 10.1016/j.ymgme.2016.09.005

Table 1.

History of glycosaminoglycan assay.

Year Description First.author(s) Ref.
1856 Discovery of toluidine blue Perkin W.H. [48]
1897 Development of mass spectrometry Thomson J.J. [129]
1956 Use of alcian blue for staining of acidic carbohydrates Mowry et al. [184]
1956 Use of alcian blue for mucopolysaccharidoses Runoe et al. [185]
1969 Development of GAG thin layer chromatography (TLC) Teller et al. [55]
1971 Spot test azure A dye staining of GAGs Berman ER [187]
1974 Analysis of GAGs with DMB Humbel et al. [74]
1974 Separation of urinary GAGs through gas chromatography Murphy et al. [90]
1978 GAG purification with paper chromatography Sato et al. [54]
1983 Separation of GAGs using paper thin chromatography Rajendra V. [53]
1985 HPLC for heparin Rice et al. [92]
1993 ELISA for C4S/C6S/DS Shibutani et al. [123]
1994 ELISA for KS Møller et al. [118]
1996 GAGs through capillary electrophoresis Linhardt et al. [97]
1997 ELISA for HS Najjam et al. [121]
2001 Single GAG measurement by LC-MS/MS Oguma et al. [4547]
2007 Multiple GAG assay in plasma/serum or urine Oguma et al. [146147]
2010 KS levels in plasma of MPS patients Tomatsu et al. [188]
2011 Methanolysis reaction for GAGs Auray-Blais et al.; Zhang et al. [155,158]
2012 ELISA for hyaluronic acid Yang et al. [124]
2012 HPLC-MS/MS for HS Ruijter et al. [186]
2012 Use of non-reducing ends of GAGs as biomarkers Lawrence et al. [154]
2013 Newborn screening for MPS measuring GAGs with LC-MS/MS Tomatsu et al. [150]
2014 Spectrometry for GAGs in cell lines Kiselova et al. [4]
2014 Methanolysis for animal tissue GAGs Trim et al. [159]
2014 Measurement of GAGs in articular cartilage and yellow ligament Osago et al. [152]
2014 Reversed-phase HPLC/MS for GAGs extracts Zhu et al. [145]
2014 Automated high-throughput mass spectrometry for HS Shimada et al. [153]

TLC: thin layer chromatography; GAGs: glycosaminoglycans; DMM: dimethylmethylene blue; HPLC: high performance liquid chromatography; C4S: chondroitin-4sulfate; C6S: chondroitin-6-sulfate; DS: dermatan sulfate; ELISA: enzyme-linked immunosorbent assay; KS: keratan sulfate; HS: heparan sulfate; LC/MS/MS: liquid chromatography tandem mass spectrometry; CSF: cerebrospinal fluid.