The endophytic strain Xylaria papulis was originated from the stem of Taiwanese Lepidagathis stenophylla C. B. Clarke ex Hayata (Acanthaceae) growing in the Hengchun Peninsula of southern Taiwan. Bioassay-guided fractionation of an EtOAc -soluble fraction of the liquid fermentate of this strain resulted in the isolation of two new isopimarane-type diterpene glycosides compounds, i.e., xylapapusides A & B (1 & 2), along with five previously identified compounds, 3-7. The structures of 1 and 2 were elucidated by detailed spectroscopic analysis including 1H- and 13C-NMR, COSY, HSQC, HMBC, and HR-ESI-MS, while the structures of the known compounds 3-7 were deduced from comparison of their spectral data with those in the literature. The effects of some isolates on the inhibition of NO production in lipopolysaccharide-activated RAW 264.7 murine macrophages were evaluated. Xylapapuside A (1) showed most potent of NO inhibition with E maxvalue of 34.3 μM.

endophytic fungus, Xylaria papulis, Lepidagathis stenophylla, isopimarane-type diterpene glycoside

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6	C7	C8	C9	C10	C11	C12	C13	C14	C15	C16	C17	C18	C19
16	aDGlcp	100.2	73.6	75.2	71.9	73.8	62.8
	Subst	40.4	21.3	43.8	73.1	53.2	23.5	122.2	137.2	53.7	37.4	21.7	38.2	33.9	48.5	45.1	65.6	22.2	23.5	15.1


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6	H7	H8	H9	H10	H11	H12	H13	H14	H15	H16	H17	H18	H19
16	aDGlcp	4.76	3.38	3.62	3.27	3.57	3.67-3.80
	Subst	1.07-1.81	1.34-1.61	1.34-1.77	-	1.43	1.89-2.15	5.37	-	1.74	-	1.34-1.61	1.25-1.61	-	1.92-1.96	1.50-1.61	3.51-3.84	0.81	1.20	0.85


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6	C7/H7	C8/H8	C9/H9	C10/H10	C11/H11	C12/H12	C13/H13	C14/H14	C15/H15	C16/H16	C17/H17	C18/H18	C19/H19
16	aDGlcp	100.2/4.76	73.6/3.38	75.2/3.62	71.9/3.27	73.8/3.57	62.8/3.67-3.80
	Subst	40.4/1.07-1.81	21.3/1.34-1.61	43.8/1.34-1.77		53.2/1.43	23.5/1.89-2.15	122.2/5.37		53.7/1.74		21.7/1.34-1.61	38.2/1.25-1.61		48.5/1.92-1.96	45.1/1.50-1.61	65.6/3.51-3.84	22.2/0.81	23.5/1.20	15.1/0.85

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

C[C@]1(CCO[C@H]2O[C@H](CO)[C@@H](O)[C@H](O)[C@H]2O)CC[C@H]2C(=CC[C@H]3[C@](C)(O)CCC[C@]23C)C1

454.604 g/mol (C₂₅H₄₂O₇)

The endophytic strain Xylaria papulis was originated from the stem of Taiwanese Lepidagathis stenophylla C. B. Clarke ex Hayata (Acanthaceae) growing in the Hengchun Peninsula of southern Taiwan. Bioassay-guided fractionation of an EtOAc -soluble fraction of the liquid fermentate of this strain resulted in the isolation of two new isopimarane-type diterpene glycosides compounds, i.e., xylapapusides A & B (1 & 2), along with five previously identified compounds, 3-7. The structures of 1 and 2 were elucidated by detailed spectroscopic analysis including 1H- and 13C-NMR, COSY, HSQC, HMBC, and HR-ESI-MS, while the structures of the known compounds 3-7 were deduced from comparison of their spectral data with those in the literature. The effects of some isolates on the inhibition of NO production in lipopolysaccharide-activated RAW 264.7 murine macrophages were evaluated. Xylapapuside A (1) showed most potent of NO inhibition with E maxvalue of 34.3 μM.

endophytic fungus, Xylaria papulis, Lepidagathis stenophylla, isopimarane-type diterpene glycoside

13C NMR data:
Linkage	Residue	C1	C2	C3	C4	C5	C6	C7	C8	C9	C10	C11	C12	C13	C14	C15	C16	C17	C18	C19
16	aDManp	101.7	72.3	72.7	68.7	74.7	63.0
	Subst	40.5	19.1	42.0	72.0	50.5	23.5	122.2	137.1	52.7	36.4	21.3	38.3	34.1	48.6	45.3	65.2	22.2	30.8	15.0


1H NMR data:
Linkage	Residue	H1	H2	H3	H4	H5	H6	H7	H8	H9	H10	H11	H12	H13	H14	H15	H16	H17	H18	H19
16	aDManp	4.72	3.77	3.68	3.60	3.53	3.71-3.83
	Subst	1.00-1.86	1.38-1.81	1.36-1.72	-	1.15-1.17	1.97-2.11	5.36	-	1.63-1.65	-	1.33-1.55	1.21-1.55	-	1.91-1.94	1.49-1.52	3.49-3.84	0.81	1.15	1.03


1H/13C HSQC data:
Linkage	Residue	C1/H1	C2/H2	C3/H3	C4/H4	C5/H5	C6/H6	C7/H7	C8/H8	C9/H9	C10/H10	C11/H11	C12/H12	C13/H13	C14/H14	C15/H15	C16/H16	C17/H17	C18/H18	C19/H19
16	aDManp	101.7/4.72	72.3/3.77	72.7/3.68	68.7/3.60	74.7/3.53	63.0/3.71-3.83
	Subst	40.5/1.00-1.86	19.1/1.38-1.81	42.0/1.36-1.72		50.5/1.15-1.17	23.5/1.97-2.11	122.2/5.36		52.7/1.63-1.65		21.3/1.33-1.55	38.3/1.21-1.55		48.6/1.91-1.94	45.3/1.49-1.52	65.2/3.49-3.84	22.2/0.81	30.8/1.15	15.0/1.03

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

C[C@]1(CCO[C@H]2O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]2O)CC[C@H]2C(=CC[C@@]3(C)[C@@](C)(O)CCC[C@]23C)C1

468.631 g/mol (C₂₆H₄₄O₇)

The endophytic strain Xylaria papulis was originated from the stem of Taiwanese Lepidagathis stenophylla C. B. Clarke ex Hayata (Acanthaceae) growing in the Hengchun Peninsula of southern Taiwan. Bioassay-guided fractionation of an EtOAc -soluble fraction of the liquid fermentate of this strain resulted in the isolation of two new isopimarane-type diterpene glycosides compounds, i.e., xylapapusides A & B (1 & 2), along with five previously identified compounds, 3-7. The structures of 1 and 2 were elucidated by detailed spectroscopic analysis including 1H- and 13C-NMR, COSY, HSQC, HMBC, and HR-ESI-MS, while the structures of the known compounds 3-7 were deduced from comparison of their spectral data with those in the literature. The effects of some isolates on the inhibition of NO production in lipopolysaccharide-activated RAW 264.7 murine macrophages were evaluated. Xylapapuside A (1) showed most potent of NO inhibition with E maxvalue of 34.3 μM.

endophytic fungus, Xylaria papulis, Lepidagathis stenophylla, isopimarane-type diterpene glycoside

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

C[C@]1(CCO[C@H]2O[C@H](CO)[C@@H](O)[C@H](O)[C@@H]2O)CC[C@H]2C(=CC[C@H]3[C@](C)(O)CCC[C@]23C)C1

454.604 g/mol (C₂₅H₄₂O₇)

Sparassis crispa is a medicinal mushroom containing high 6-branched 1,3-β-D-glucan (sparan) content, which exhibits immune-mediated antitumor activity. In the present study, we investigated the stimulating effect of sparan on phenotypic and functional maturation of dendritic cells (DCs). Phenotypic maturation was confirmed by the elevated expressions of CD40, CD80, CD86, and MHC-I/II molecules. Functional activation was proved by increased cytokine production of IL-12, IL-1β, TNF-α, and IFN-α/β, enhanced IL-2 production and proliferation of allogenic T cells, and decreased endocytosis. The role of toll-like receptor 4 (TLR4) as a membrane receptor of sparan was proved by the impaired maturation of DCs generated from bone marrow cells of tlr4-/- knock-out mice and TLR4-mutated C3H/HeJ mice, and by using anti-MD-2/TLR4 neutralizing antibody. Sparan increased phosphorylation of ERK, p38, and JNK, and enhanced nuclear translocation of NF-ΚB p50/p65 in DCs. These results indicate that sparan activates DCs via MAPK and NF-ΚB signaling pathways, which are signaling molecules downstream of TLR4.

polysaccharides, Toll-like receptor 4, dendritic cells, Sparassis crispa, Sparan

There is only one chemically distinct structure:

SVGMWSMILES3D molIonize

 

[*]O[C@@H]1[C@@H](O)[C@H]([*])O[C@H](CO[C@@H]2O[C@H](CO)[C@@H](O)[C@H](O)[C@H]2O)[C@H]1O

324.282 g/mol (C₁₂H₂₀R₂O₁₀, R = next and previous repeats, not counted in mol weight)