Profiling of oligosaccharides and polysaccharides in alcoholic beverages using single quadrupole LC-MS

Importance of the Topic

Oligosaccharides and polysaccharides derived from malt and fermentation play a key role in the sensory properties, stability and nutritional quality of beer and related beverages. Comprehensive profiling of these saccharides supports objective taste evaluation, quality control and the discovery of functional or off‐flavor components in both alcoholic and non‐alcoholic products.

Objectives and Study Overview

This study aimed to develop a rapid and sensitive single-run method for simultaneous analysis of malt-derived oligosaccharides (DP1–DP6) and high-molecular-weight polysaccharides (up to DP36) in a range of beer samples. Six beer types (lager, ale, low-malt, soy-protein-fortified, and two non-alcoholic brands) were profiled to compare saccharide content and to classify samples by saccharide pattern using principal component analysis (PCA).

Methodology and Instrumentation

Seven commercial beverages were each diluted 1:10 with water. Separation was performed on a Shodex Asahipak NH2P-40 3E column (250×3.0 mm, 4 µm) using a binary gradient of ammonium bicarbonate solutions and acetonitrile. Flow rate was 0.3 mL/min at 40 °C with 5 µL injections. Detection employed a Shimadzu Nexera XR HPLC coupled to an LCMS-2050 single-quadrupole mass spectrometer in negative ESI/APCI dual ionization mode, SIM acquisition over 40 events. Calibration curves for glucose through maltohexaose exhibited excellent linearity (r2>0.995) and repeatability (<9 %RSD in peak area).

Main Results and Discussion

• All beers except the low‐malt variant contained a complex mixture of malto-oligosaccharides (DP1–DP6) and glucose‐based polymers up to DP36 (approx. MW 5 850).
• PCA separated samples into clusters: lager and ale grouped by high maltose‐derived saccharide content; low-malt and one non-alcoholic beer formed a low-saccharide cluster; the two other non-alcoholic beers clustered by elevated residual glucose and maltose reflecting suppressed fermentation.
• Relative peak area mapping showed beer A and B (lager, ale) rich in DP3–DP8, whereas non-alcoholic E displayed minimal oligosaccharide levels. Non-alcoholic F retained high DP1–DP2 due to deactivated fermentation processes.

Benefits and Practical Applications

• Single-quadrupole LC-MS enables trace-level detection of high-DP saccharides, surpassing conventional RID or ELSD approaches.
• Comprehensive saccharide profiling aids formulation optimization, authenticity testing and process monitoring in brewing and beverage production.
• Rapid analysis supports quality control laboratories in screening a broad range of products for consistency and compliance.

Future Trends and Opportunities

Advances in high-resolution MS and automated data processing will further refine saccharide structural elucidation and quantitation. Coupling this approach with metabolomics and sensory data promises to unlock correlations between saccharide profiles and consumer perception. Expanding to other cereal-based and fermented beverages may reveal unique bioactive polysaccharides and inform functional product development.

Conclusion

A robust, sensitive single-quadrupole LC-MS method was established for simultaneous profiling of oligosaccharides and high-DP polysaccharides in diverse beer samples. The approach delivers detailed saccharide fingerprints, enabling sample classification and practical quality assessments in the beverage industry.

References

• Watabe Y, Hattori T, Iwata N, Terada H, Inohana Y. Profiling of oligosaccharides and polysaccharides in alcoholic beverages using single quadrupole LC-MS. Shimadzu Technical Note.