绿槽枝衣的化学成分

从地衣绿槽枝衣（Sulcaria virens）中分离得到一个新的亚油酸异丙叉衍生物,通过波谱学方法包括2D-NMR确定其化学结构为：9,10-O-异丙叉基-（12Z）-十八碳烯酸（1）。同时还得到其它12个已知化合物：（9Z,12Z）-十八碳二烯酸（2）,扁枝衣二酸（3）,（R）-松萝酸（4）,枕酸甲酯（5）,黑茶渍素（6）,virensic acid（7）,abieslactone（8）,3α-羟基羊毛甾-7,24-二烯-26,23R-内酯（9）,蒲公英赛醇（10）,蒲公英赛酮（11）,（22E,24R）-5α,8α-过氧麦角甾-6,22-二烯-3β-醇（12）和2,2′-四氢角鲨烯（13）。     

Bioactivity of secondary metabolites and thallus extracts from lichen fungi

Fungal secondary compounds and total extracts are known to affect growth of bacteria, fungi, and plants. This study tested the effects of purified compounds and total extracts from three lichens on the growth of two plant pathogens, Ophiostoma novo-ulmi ssp. americana and Sclerotinia sclerotiorum. Usnic acid showed no reduction in relative growth rates (RGR), whereas vulpinic acid reduced RGR for both fungi and atranorin reduced RGR of S. sclerotiorum only. However, purified vulpinic acid showed stronger effects than total extracts on fungal growth. The results suggest that these lichens show further promise as a source for bioactive compounds against fungi.     

绿槽枝衣的化学成分

从地衣绿槽枝衣( Sulcaria virens) 中分离得到一个新的亚油酸异丙叉衍生物, 通过波谱学方法包括2D-NMR 确定其化学结构为: 9, 10-O-异丙叉基- (12 Z)-十八碳烯酸(1) 。同时还得到其它12 个已知化合物:( 9 Z, 12 Z )-十八碳二烯酸(2), 扁枝衣二酸(3), ( R ) -松萝酸(4), 枕酸甲酯( 5), 黑茶渍素(6) , virensic acid ( 7), abieslactone (8), 3α-羟基羊毛甾-7, 24-二烯-26, 23 R-内酯(9), 蒲公英赛醇(10 ), 蒲公英赛酮 ( 11 ), (22 E , 24 R )-5α, 8α-过氧麦角甾-6, 22-二烯-3β-醇(12) 和2, 2′-四氢角鲨烯(13)。     

An inducible lactone hydrolase yielding 2,5-diphenyl-3-hydroxy-4-oxo-2-hexendioic acid from pulvinic acid

The metabolism of vulpinic acid by an unclassified soil micro-organism was studied. A new compound, 2,5-diphenyl-3-hydroxy-4-oxo-2-hexendioic acid (DHOHA) was isolated from the reaction mixture of a cell-free preparation and pulvinic acid. The existence of a hydrolase which catalyses the conversion of vulpinic acid to pulvinic acid was detected in cell-free preparation, and an inducible lactone hydrolase capable of converting pulvinic acid to DHOHA was purified 130-fold and characterized. This enzyme had a MW of ca 34 000, a K_m for pulvinic acid at pH optimum (pH 7.0) less than 10 ^{? 6} M, pI = 5.0, and was inhibited by p-chloromercuriphenylsulfonate and diethylpyrocarbonate. The enzyme was highly specific for pulvinic acid. The initial degradative steps proposed for this organism are vulpinic acid → pulvinic acid → DHOHA.     

FACTORS AFFECTING THE TOXICITY OF SEVERAL LICHEN ACIDS: EFFECT OF PH AND LICHEN ACID CONCENTRATION

The effect of pH 5–8 and lichen acid concentration gradients (2.7 times 10⁻² - 2.7 times 10⁻⁶ m ) on the toxicity of the following lichen acids: usnic, lecanoric, evernic, vulpinic, stictic, fumarpro-tocetraric, psoromic, and atranorin, on spores of Funaria hygrometrica was tested. Percent germination and sporeling growth were used as indicators of toxicity. None of the lichen acids were significantly toxic, for either percent germination or sporeling growth at concentrations equal to or below 2.7 times 10⁻⁵ m at pH 7.0, but many of the lichen acids which increased in toxicity at values different from pH 7 may have been toxic at lower concentrations if a different pH was used for the assay. Lichen acid toxicity showed a good correlation with pH for the parameter of spore germination, or sporeling growth, or both. Some lichen acids did not inhibit germination but were effective in retarding sporeling growth, or vice versa. This observation is discussed in relation to changing fatty acids and other lipid composition as germination occurs. Two of the three O-methylated lichen acids (evernic and psoromic) were among the most effective in inhibiting growth over all, but at lower pH values these were less effective than non-O-methylated lichen acids. Stictic, which is also an O-methylated lichen acid, was the least effective inhibitor over all the pH values for both parameters, while vulpinic was the most toxic over all the pH values. The order of relative toxicity for the lichen acids is different, depending on the pH and concentration at which they are tested and depending on the parameter measured. Thus, in an ecological sense, it is difficult to evaluate the adaptive significance of a particular compound or group of compounds without knowing what factors influence the toxicity of those compounds and how these factors vary in the organism's habitat.     

Epiphorellic acids 1 and 2, two diaryl ethers from the lichen Cornicularia epiphorella

From the lichen Cornicularia epiphorella two new diaryl ethers, epiphorellic acids 1 and 2, were isolated besides the known compound atranorin. The structures of the new compounds were established by spectroscopic evidence and chemical transformations. The structure of epiphorellic acid 1 was also confirmed by correlation with a known compound.     

Use of lichen secondary metabolites as antifeedants to protect higher plants from damage caused by slug feeding

Extracts of 15 species of lichen were tested for antifeedant properties against the field slug Deroceras reticulation (Müller) (Mollusca: Pulmonata). All but three showed some activity and two of these were from endolithic species. The most effective extract was from Letharia vulpina. The major active compound from this species, vulpinic acid, was tested for dose response, applied as a foliar spray to turnip plants and as a dressing to wheat seeds in laboratory experiments. It provided effective protection against slug feeding under these conditions.     

THE INFLUENCE OF pH AND LICHEN METABOLITES (VULPINIC ACID AND (+) USNIC ACID) ON THE GROWTH OF THE LICHEN PHOTOBIONTTREBOUXIA IRREGULARIS

The quantitative response to two lichen metabolites, vulpinic acid and (+) usnic acid, on biomass production by the photobiontTrebouxia irregularis, isolated from the lichenCladina mitis, was determined experimentally. The presence of usnic acid resulted in inhibition of photobiont growth, and the effect depended on the pH of the culture medium. The concentration effect of usnic acid was observed. The application of vulpinic acid almost completely inhibited the growth ofT. irregularisand no significant differences were found among samples at different medium pH values.     

Light screening in lichen cortices can be quantified by chlorophyll fluorescence techniques for both reflecting and absorbing pigments

Lichens, representing mutualistic symbioses between photobionts and mycobionts, often accumulate high concentrations of secondary compounds synthesized by the fungal partner. Light screening is one function for cortical compounds being deposited as crystals outside fungal hyphae. These compounds can non-destructively be extracted by 100% acetone from air-dry living thalli. Extraction of atranorin from Physcia aipolia changed the lichen colour from pale grey to green in the hydrated state, whereas acetone-rinsed and control thalli were all pale grey when dry. Removal of parietin from Xanthoria parietina changed the colour of desiccated thalli from orange to grey. Colour changes were quantified by reflectance measurements. By a new chlorophyll fluorescence method, screening was assessed as the decrease in incident irradiance (PAR) necessary to reach identical effective quantum yields of PSII (Φ_PSII) in acetone-rinsed and control thalli. Thereby, we estimated a screening efficiency due to cortical atranorin crystals at 61, 38, and 40% of blue, green and red light, respectively, whereas parietin screened 81, 27 and 1% of these wavelength ranges. Removal of atranorin caused similar levels of increased photoinhibition for P. aipolia in blue, green and red light, whereas parietin-deficient thalli of X. parietina exhibited increased photoinhibition with decreasing wavelengths. Atranorin possibly prevents water from entering the spaces between the hyphae in the cortex. The air-filled cavities with white atranorin crystals reflect excess light, whereas the yellow compound parietin absorbs excess light. Thereby, both atranorin and parietin play significant photoprotective roles for symbiotic green algae, but with compound-specific screening mechanisms.     

QUANTITATIVE VARIATION IN VULPINIC AND PINASTRIC ACIDS PRODUCED BY TUCKERMANNOPSIS PINASTRI (LICHEN-FORMING ASCOMYCOTINA,PARMELIACEAE)

Tuckermannopsis pinastri is a lichen species found commonly on rocks and tree branches in boreal and alpine habitats in the northern United States. Members of this species produce three yellow-pigmented phenolic compounds: usnic, pinastric, and vulpinic acids. The objective of our study was to quantify the variation in concentration of the latter two of these compounds in relation to substrate factors, chlorophyll content, and thallus size. Using high-performance liquid chromatography, we analyzed 120 thalli of T. pinastri collected randomly from a single large population located at Spruce Knob, West Virginia. Although individuals were sampled from both tree and rock substrates that differed markedly in light intensity, these environmental factors were not correlated with observed variations in vulpinic or pinastric acid concentrations. Instead, compound concentrations were correlated most closely with thallus size, with small rather than large thalli having the highest concentrations of the two compounds. Small thalli did not have higher concentrations of chlorophylls than large thalli, however, which suggests that the rate of production of secondary compounds by the fungus in T. pinastri is independent of algal biomass. Inasmuch as lichen secondary compounds serve a defensive role against microorganisms and herbivores, our results suggest that small, juvenile thalli are better defended than more mature thalli.     

矮石蕊在东亚的地位

中国和日本有关具粉末状粉芽的矮石蕊(Cladonia humilis)的报导大多数实际上是指本文中描述的新种,黑氏石蕊(Cladonia kurokawae Ahti & S. Stcnroos).其特征是杯体深裂,含有黑茶渍素和富马原岛衣酸.真正的矮石蕊在中国和日本是很少见的;日本的种类中,含有黑茶渍素和波衣酸的两个化学型都存在.     

The antimicrobial activity of extracts of the lichen Cladonia foliacea and its (-)-usnic acid, atranorin, and fumarprotocetraric acid constituents

The antimicrobial activity of the chloroform, diethyl ether, acetone, petroleum ether, and ethanol extracts of the lichen Cladonia foliacea and its (-)-usnic acid, atranorin, and fumarprotocetraric acid constituents against 9 bacteria and fungi has been investigated. The extracts and pure compounds alone were found active against the same bacteria and the same yeasts. Bacillus cereus, Bacillus subtilis, Staphylococcus aureus, Streptococcus faecalis, Proteus vulgaris, Listeria monocytogenes, Aeromonas hydrophila, Candida albicans, and Candida glabrata growth were inhibited. In addition, the MICs of the extracts, (-)-usnic acid, atranorin and fumarprotocetraric acid were determined.     

Evaluation of Antimicrobial Properties of Lichen Substances against Plant Pathogens

Plant pathogens pose major threats on agriculture and horticulture, causing significant economic loss worldwide. Due to the continuous and excessive use of synthetic pesticides, emergence of pesticide resistant pathogens has become more frequent. Thus, there is a growing needs for environmentally-friendly and selective antimicrobial agents with a novel mode of action, which may be used in combination with conventional pesticides to delay development of pesticide resistance. In this study, we evaluated the potentials of lichen substances as novel biopesticides against eight bacterial and twelve fungal plant pathogens that have historically caused significant phytopathological problems in South Korea. Eight lichen substances of diverse chemical origins were extracted from axenic culture or dried specimen, and further purified for comparative analysis of their antimicrobial properties. Usnic acid and vulpinic acid exhibited strong antibacterial activities against Clavibacter michiganensis subsp. michiganensis. In addition, usnic acid and vulpinic acid were highly effective in the growth inhibition of fungal pathogens, such as Diaporthe eres, D. actinidiae, and Sclerotinia sclerotiorum. Intriguingly, the growth of Rhizoctonia solani was specifically inhibited by lecanoric acid, indicating that lichen substances exhibit some degrees of selectivity to plant pathogens. These results suggested that lichen substance can be used as a selective biopesticide for controlling plant disease of agricultural and horticultural significance, minimizing possible emergence of pesticide resistant pathogens in fields.     

Antimicrobial activity of extracts of chemical races of the lichen Pseudevernia furfuracea and their physodic acid, chloroatranorin, atranorin, and olivetoric acid constituents

The antimicrobial activity and the MIC values of the ethanol, chloroform, diethyl ether, and acetone extracts of the chemical races of Pseudevernia furfuracea (var. furfuracea and var. ceratea) and their physodic acid, chloroatranorin, atranorin, and olivetoric acid constituents have been investigated against some microorganisms. Nearly all extracts of both chemical races showed antimicrobial activity against Aeromonas hydrophila, Bacillus cereus, Bacillus subtilis, Listeria monocytogenes, Proteus vulgaris, Staphylococcus aureus, Streptococcus faecalis, Yersinia enterocolitica, Candida albicans, Candida glabrata, Alternaria alternata, Ascochyta rabiei, Aspergillus niger, Fusarium culmorum, Fusarium moniliforme, Fusarium oxysporum, Fusarium solani, and Penicillium notatum. There was no antimicrobial activity of the extracts against Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Pseudomonas syringae, Salmonella typhimurium, Alternaria citri, Alternaria tenuissima, and Gaeumannomyces graminis. Chloroatranorin and olivetoric acid were active against the same microorganisms with few exceptions. Physodic acid was active against about the same bacteria and yeasts and inactive against all of the filamentous fungi tested. Also no activity of atranorin against the filamentous fungi was observed.     

Chemical variation within and between individuals of the lichenized ascomycete Tephromela atra

HPLC-analysis was used to determine the concentrations of the lichen compounds alectoronic acid (depsidon), -collatolic acid (depsidon) and atranorin (depsid) in the lichenized ascomycete Tephromela atra (syn. Lecanon atra) (Hudson) Hafeliner from limestone walls on the Baltic island of Öland, Sweden. In 24 individuals of T. atra sampled on a stone wall, the pre-reproductive and reproductive tissue did not differ in the concentrations of alectoronic acid, collatolic acid and atranorin. The concentrations of the three lichen compounds were inter-correlated in the reproductive tissue, but not in the pre-reproductive tissue. Single individuals of T. atra ranged in area covered from 10.1 to 147.4 cm² (mean: 38.5 cm²; N=24); 38.6% of this area was pre-reproductive tissue. However, the concentrations of the three lichen compounds were correlated neither with the total area covered by the lichen nor with the percentage of pre-reproductive tissue. This suggests that the concentrations of the lichen compounds do not change with increasing size (age) of the lichen. Analysis of specimens of T. atra from eight localities revealed a significant variation in lichen compounds (range between localities: alectoronic acid 0.60–3.26 μg/mg lichen dry weight (DW); collatolic acid 2.14–11.59 μg/mg lichen DW; atranorin 0.58–4.16 μg/mg lichen DW). The level of grazing observed in the lichens differed significantly among localities. However, no correlations between the concentrations of the three lichen compounds and the grazing damage to the lichens were found.     

Phenolic constituents from the lichen Parmotrema stuppeum (Nyl.) Hale and their antioxidant activity

Lichen, Parmotrema stuppeum (P. stuppeum) was successively extracted with benzene and acetone. Both the extracts were fractionated on 1% oxalic acid impregnated silica gel column to obtain four phenolic compounds. The structures of compounds were identified by 1H and 13C NMR spectra as methyl orsenillate, orsenillic acid, atranorin and lecanoric acid respectively. Antioxidant activity of benzene extract, acetone extract and isolated compounds were evaluated in a beta-carotene-linoleate model system. The pure compounds showed moderate antioxidant activity. This is the first report on the isolation and characterisation of compounds from the lichen P. stuppeum as well as on their antioxidant activity.     

Photosynthetical and nutritional implications in the accumulation of phenols in the lichen Pseudevernia furfuracea

By supplying acetate, glucose or DCMU to Pseudevernia furfuraceathallus, it has been found that the accumulation of the depside atranorin is independent of the photosynthetic activity but is repressed by glucose. In this last condition, lecanoric acid is alternatively produced.     

Lepraria atlantica,a new species from the British Isles

Abstract:Lepraria atlantica is described as new from acidic rocks in the British Isles; it contains porphyrilic acid, cf. rangiformic acid or rarely cf. roccellic acid, and atranorin. It differs from L. cacuminum in the diffuse, powdery thallus. It is morphologically similar to L. jackii, but differs in the possession of porphyrilic acid.     

Lichen biodeterioration of the Convento de la Peregrina, Sahagún, Spain

Lichen encrustations from Diploschistes scruposus involved in the biodeterioration of the 13th Century Convento de la Peregrina in Sahagún Spain, have been analyzed using Raman spectroscopy. The vibrational spectra are characteristic of calcium oxalate monohydrate, beta-carotene, chlorophyll, and para-depside phenolic acids such as atranorin, lecanoric acid, and diploschistesic acid. The destructive colonization of the monumental stonework is highlighted and evidence presented for deleterious lichen invasion of the wall paintings inside the Convent.     

The occurrence of lichen phenolics in the photobiont cells of Evernia prunastri

Photobiont cells of Evernia prunastri were isolated by filtration through a bed of Sepharose 2B. Algal preparations did not contain fungal contamination, as revealed by the absence of mannitol. Isolated photobionts contain the four Evernia phenolics, although repeated superficial washes with polyvinylpyrrolidone remove from these cells 81% atranorin, 51% chloroatranorin, 94% evernic acid and 82% usnic acid.