(CH3)-C-13 versus CD3- isotope labeling;
Liquid chromatography-electrospray ionization mass spectrometry;
Quantitative mass spectrometry;
Substituent distribution;
Methyl cellulose;
Oligosaccharide ethers;
SUBSTITUENT DISTRIBUTION;
LIQUID-CHROMATOGRAPHY;
ELECTROSPRAY-IONIZATION;
INTERNAL STANDARDS;
MS;
MATRIX;
METHYLCELLULOSES;
MODEL;
D O I:
10.1007/s00216-023-04622-w
中图分类号:
Q5 [生物化学];
学科分类号:
071010 ;
081704 ;
摘要:
The methyl substitution along and among the polymer chains of methyl cellulose (MC) is commonly analyzed by ESI-MS after perdeuteromethylation of the free-OH groups and partial hydrolysis to cello-oligosaccharides (COS). This method requires a correct quantification of the molar ratios of the constituents belonging to a particular degree of polymerization (DP). However, isotopic effects are most pronounced for H/D since their mass difference is 100%. Therefore, we investigated whether more precise and accurate results could be obtained for the methyl distribution of MC by MS of (CH3)-C-13 instead of CD3-etherified O-Me-COS. Internal isotope labeling with (CH3)-C-13 makes the COS of each DP chemically and physically much more similar, reducing mass fractionation effects, but at the same time requires more complex isotopic correction for evaluation. Results from syringe pump infusion ESI-TOF-MS with (CH3)-C-13 and CD3 as isotope label were equal. However, in the case of LC-MS with a gradient system, (CH3)-C-13 was superior to CD3. In the case of CD3, the occurrence of a partial separation of the isotopologs of a particular DP resulted in slight distortion of the methyl distribution since the signal response is significantly dependent on the solvent composition. Isocratic LC levels this problem, but one particular eluent-composition is not sufficient for a series of oligosaccharides with increasing DP due to peak broadening. In summary, (CH3)-C-13 is more robust to determine the methyl distribution of MCs. Both syringe pump and gradient-LC-MS measurements are possible, and the more complex isotope correction is not a disadvantage.
机构:
Sun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Hong Kong Baptist Univ, Partner State Key Lab Environm & Biol Anal, Dept Chem, Kowloon, Hong Kong, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Jiang, Shuxia
Li, Yongle
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Shenzhen Acad Metrol & Qual Inspect, Shenzhen 518000, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Li, Yongle
Lin, Shuhai
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Hong Kong Baptist Univ, Partner State Key Lab Environm & Biol Anal, Dept Chem, Kowloon, Hong Kong, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Lin, Shuhai
Yang, Hongbo
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Shenzhen Acad Metrol & Qual Inspect, Shenzhen 518000, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Yang, Hongbo
Guan, Xin-yuan
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Univ Hong Kong, Li Ka Shing Fac Med, Dept Clin Oncol, Hong Kong, Hong Kong, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Guan, Xin-yuan
Zhou, Haiyun
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Sun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Zhou, Haiyun
Luan, Tiangang
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Sun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Sun Yat Sen Univ, Sch Life Sci, MOE Key Lab Aquat Prod Safety, Guangzhou 510275, Guangdong, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
Luan, Tiangang
Cai, Zongwei
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Hong Kong Baptist Univ, Partner State Key Lab Environm & Biol Anal, Dept Chem, Kowloon, Hong Kong, Peoples R ChinaSun Yat Sen Univ, Instrumental Anal & Res Ctr, Guangzhou 510275, Guangdong, Peoples R China
机构:
W Virginia Univ, Morgantown, WV 26506 USA
W Virginia Univ, C Eugene Bennett Dept Chem, Morgantown, WV 26506 USAOhio Univ, Dept Chem & Biochem, Ctr Intelligent Chem Instrumentat, Athens, OH 45701 USA
机构:
Birla Inst Technol & Sci, Dept Pharm, Pilani Campus, Pilani 333031, Rajasthan, India
Emami Ltd, R&D Healthcare Div, Med Res, 13 BT Rd, Kolkata 700056, W Bengal, India
All India Inst Med Sci, Dept Obstet & Gynaecol, New Delhi, IndiaBirla Inst Technol & Sci, Dept Pharm, Pilani Campus, Pilani 333031, Rajasthan, India
Dubey, Sunil Kumar
Khadgawat, Rajesh
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Emami Ltd, R&D Healthcare Div, Med Res, 13 BT Rd, Kolkata 700056, W Bengal, IndiaBirla Inst Technol & Sci, Dept Pharm, Pilani Campus, Pilani 333031, Rajasthan, India
Khadgawat, Rajesh
Kachhawa, Garima
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All India Inst Med Sci, Dept Endocrinol & Metab, New Delhi, IndiaBirla Inst Technol & Sci, Dept Pharm, Pilani Campus, Pilani 333031, Rajasthan, India
Kachhawa, Garima
Gupta, Tarang
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All India Inst Med Sci, Dept Endocrinol & Metab, New Delhi, IndiaBirla Inst Technol & Sci, Dept Pharm, Pilani Campus, Pilani 333031, Rajasthan, India