A new amino acid solorinine [1] having a quaternary ammonium structure that we had previously isolated from the lichen Solorina crocea (L.) Ach., collected in Canada, was contained in all specimens of S. crocea from Europe and North America as well as from Japan. Solorinine was detected in all species of Solorina and Peltigera, both members of the Peltigeraceae; however, it was not detected in species of the Nephromataceae. Another new amino acid, peltigerine [2], isolated from Peltigera praetextata (Florke) Vain., was detected only in species of Peltigera. The structure of peltigerine was determined by spectroscopic methods. All living organisms need water, however, water is difficult obtain under water deficient conditions such as high salinity, drought, or low temperature (Bohnert et al. 1995). Organisms adapt to such environments in numerous ways; accumulation of compatible solutes is one such mechanism. Quaternary ammonium compounds such as glycine betaine are well known to function under water deficient conditions and are found in salt tolerant plants, marine algae, and cyanobacteria (GabbyAzaria et al. 1988; Rhodes & Hanson 1993). Many lichens survive water deficient environments. However, the question, of what mechanisms lichens use remains unanswered. There are a few reports of sugar alcohols as compatible solutes in lichens (Chapman et al. 1994; Feige 1975). Recently, we found a new amino acid, solorinine (2-trimethylamino-4-(3,5-dimethoxy-4hydroxyphenyl)butanoate), (Fig. 1) from Solorina crocea (L.) Ach. (Matsubara et al. 1994). This compound has a quaternary ammonium structure similar to that of glycine betaine. The content of solorinine was about 1 mg g DW-1 (unpublished result), which was equal to that of quaternary ammonium compounds in higher plants (Rhodes & Hanson 1993). These results suggest that solorinine could have a physiological role under water deficient conditions in many species of lichens. Here we report on the distribution of solorinine in lichens of the Peltigerales. Another amino acid, a solorinine analogue, was also isolated and investigated for its distribution. MATERIALS AND METHODS The specimens employed for detection of solorinine are listed in Tables 1-2. Specimens were dried and then stored in the herbarium of Nippon Paint Co. Ltd. (Osaka, Japan) or K chi Gakuen College (Kochi, Japan). Species used are as follows: Nephroma arcticum (L.) Torss., N. bellum (Spreng.) Tuck., N. resupinatum (L.) Ach., N. tropicum (Mill. Arg.) Zahlbr., Peltigera aphthosa (L.) Willd., P. canina (L.) Willd., P. degenii Gyeln., P. dilacerata (Gyeln) Gyeln., P. dolichorrhiza (Nyl.) Nyl., P. elizabethae Gyeln., P. leucophlebia (Nyl.) Gyeln., P. nigripunctata Bitt., P. polydactyla (Neck.) Hoffm., P. praetextata (Fldrke) Vain., P. pruinosa (Gyeln.) Inum., P. rufescens (Weis.) Humb., P. scabrosa Th. Fr., P. spuria (Ach.) DC., Solorina crocea (L.) Ach., S. octospora Arnold, S. platycarpa Hue, S. spongiosa (Sm.) Anzi, and S. saccata (L.) Ach. Each dry lichen thallus (ca 0.5 g) was extracted twice with 100 ml of CHCl3 at room temperature overnight and then twice with 100 ml of MeOH under the same condition. Extraction with CHCl3 was carried out in order to remove constituents of low polarity, which might influence on Rf-values of amino acid derivatives on TLC analysis. Each methanol solution was concentrated under reduced pressure to yield the dried extract. A MeOH extract of each lichen thallus was examined for the presence of solorinine by TLC plate (MERCK DC-Alufolien Kieselgel 60 no. 5553 F254) with high polarity solvent (CHCl3MeOH-HiO, 6:4:1) TLC in comparison with the authentic compound previously isolated (Matsubara et al. 1994). The spot of the quaternary ammonium compound on TLC was clear regardless of the sample freshness, and showed weak violet with both short wave (254 nm) and long wave (365 nm) UV radiation or red after spraying with 10% sulfuric acid and heating at 110oC. Detection of the new amino acid reported in this paper was also done the same way with solorinine using the authentic sample isolated below. Both solorinine and the new amino acid could not 0007-2745/99/196-199$0.55/0 This content downloaded from 207.46.13.115 on Sat, 08 Oct 2016 05:29:28 UTC All use subject to http://about.jstor.org/terms 1999] MATSUBARA ET AL.: NEW AMMONIUM COMPOUNDS 197 +N(CH3)3 N(CH3)2 H3CO .HC O COO H3CO COOH
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