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Comparison of Mumijo (Shilajit) and Humic Acids (HA) Chemical
Composition Using FTICR Mass-Spectrometry
Gleb Vladimirov1, Alexey Kononikhin1, Erast Kunenkov2,Irina Perminova2, Igor Popov1,
Andrey Garmash2, Eugene Nikolaev1
1The Institute for Biochemical Physics Russian Academy of Science, Moscow, Russia,
2Department of Chemistry, Lomonosov Moscow State University, 119992, Moscow, Russia
Keywords: humic, mumijo, mumie, shilajit, FTICR mass-spectrometry
Humic substances (HS) are complex mixtures formed during decay of plant and
animal materials. HS are generically classified into fulvic and humic acid fractions
according to their solubility properties. The particular features of HS are polydispersity and
extreme structural heterogeneity. The biological effects of humic substances can be
different, depending on their chemical structure and physicochemical properties. Chemical
composition, structure, and functional groups can vary greatly, depending on the origin
and age of the humic substance and the conditions of the humification process (humidity,
aeration, temperature, mineral microenvironment, etc.) (1). Mumijo has been used in
traditional medicine for thousands of years, but there are only a few research devoted to
the investigation of humic substances from mumijo.
2. MATERIALS AND METHODS
We used well characterized samples of Suwannee River fulvic and humic acids of
the International Humic Substances Society (IHSS). Kyrgyz mumijo from drugstore were
used for analysis without further purification. All experiments were performed on a
commercial mass-spectrometer 7 Tesla Finnigan LTQ FT (Thermo Electron, Bremen,
Germany) equipped with electrospray ion source (Finnigan Ion Max Source). Mumijo
samples were dissolved in 1:4 water-acetonitrile solution and analyzed using electrospray
ionization both in positive and negative modes. For accurate molecular mass
measurements FTICR mass spectra were acquired using selected ion monitoring (SIM)
scanning with 100 Da mass range.
For interpretation of FTICR data Kendrick and van Krevelen diagrams were used (2).
All FTICR mass spectra were also processed using FIRAN software for determination of
stoichometric formulas (2).
3. RESULTS AND DISCUSSION
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Figure 1 Van Kleveren diagram for kyrgyz mumijo and Suwannee River fulvic acid
Comparison of kyrgyz mumijo with fulvic acid (FA) shown on figure 1. It was found
both mumijo and fulvic acid contain a lot of ions tending to form groups in certain region of
van Krevelen diagram. This may be interpreted like these substances were formed in
stochastic synthesis process and consists of molecules which are close one to each other
in their functional composition and differ only by simple structural modifications (e.g.,
carbon chain length, a number of double bonds, oxidation level). Kyrgyz mumijo seems to
differ from humic substances by higher H/C ratio and lower O/C ratio.
Comparison of mumijo composition determined by mass spectrometry with
composition of humic substances gives advance in understanding of mumijo origin and its
relation with humic substances. Both of these substances seems to be formed from
organic remains in slightly different conditions, so, processes which take place during
mumijo formation may be very similar to processes of HS formation.
1. Schepetkin I., Khlebnikov A., Shin Young Ah, Sang Woo, Choon-Soo Jeong, O. Klubachuk,
Byoung Kwon 2003 J. Agric. Food Chem., 51 (18), 5245 -5254.
2. Kunenkov, E.V., Kononikhin, A.S., Perminova, I.V., Garmash, A.V., Nikolaev, E.N., Popov, I.A.
2006. Abstracts of the First Int. Symposium on Ultrahigh Resolution Mass Spectrometry for the
Molecular level Analysis of Complex (BioGeo)Systems, 6-7 Nov. 2006, GSF,