Table 1.

NALDI-MS and DIOS-MS detected secondary metabolites from the nanostructured surfaces adjacent to the hypobranchial gland after solvent separation. + Indicates detection within combined spectra.

Compound Class/Compound	Formula	MW	Detected in Solvent Wash				LDI-MS	Major Ions m/z		Major Ions m/z
			Water	Ethanol	Chloroform	Hexane	[M]	NALDI	DIOS	RT (min)	LC-MS
Brominated indoles
Tyrindoxyl sulfate	C9H7BrNO4S2−	337.196	+	+			[M + H]+	337, 339	337, 339	6.52	336, 338
							[M + 4H]+	341, 343	341, 343
Tyrindoxyl	C9H8BrNOS	258.140
Tyrindoleninone	C9H6BrNOS	256.124		+	+		[M]+	256, 258	256, 258	10.96	256, 258
Tyrindolinone	C10H10BrNOS2	304.234		+	+		[M]+	304, 306	-
6-Bromoisatin	C8H4BrNO2	226.029		+	+		[M]+	224, 226	224, 226	6.35	224, 226
Tyriverdin	C18H14Br2N2O2S2	514.264								11.67	511, 513, 515
Tyrian purple (6,6′-Dibromoindigo)	C16H8Br2N2O2	420.060			+		[M + 2H]+	419, 421, 423	419, 421, 423	14.34	417, 419, 421
6,6′-Dibromoindirubin	C16H8Br2N2O2	420.060			+		[M + 2H]+	419, 421, 423	419, 421, 423
Choline esters
Choline	C5H14NO+	104.173	+	+		+	[M]+	104	104
Murexine	C11H18N3O2+	224.284	+	+			[M]+	224	224	1.83	224