LYCOPODIUM ALKALOIDS: XV. STRUCTURE AND MASS SPECTRA OF SOME MINOR ALKALOIDS OF L. FLABELLIFORME

1964 ◽  
Vol 42 (11) ◽  
pp. 2456-2466 ◽  
Author(s):  
S. N. Alam ◽  
K. A. H. Adams ◽  
D. B. MacLean
Keyword(s):  
Mass Spectra ◽  
Physical Evidence ◽  
Lycopodium Alkaloid ◽  
Lycopodium Alkaloids

Hydroxy-des-N-methyl-α-obscurine, C16H24O2N2, has been isolated from L. flabelliforme and a structure assigned to it on the basis of physical evidence. A structure is assigned to Lycopodium alkaloid L.5, which we have named flabellidine, on the basis of physical evidence and its chemical derivation from lycodine. The mass spectra of hydroxy-des-N-methyl-α-obscurine, flabellidine, and flabelline are discussed.

Luciduline: a unique type of Lycopodium alkaloid

1968 ◽  
Vol 46 (23) ◽  
pp. 3631-3642 ◽  
Author(s):  
W. A. Ayer ◽  
N. Masaki ◽  
D. S. Nkunika
Keyword(s):  
Mass Spectra ◽  
X Ray Diffraction ◽  
Complete Structure ◽  
Unique Type ◽  
X Ray ◽  
Physical Evidence ◽  
Weak Bases ◽  
Lycopodium Alkaloid ◽  
New Type

The isolation and determination of the structure of luciduline, C13H21ON, an alkaloid present among the weak bases of Lycopodium lucidulum Michx, is described. Chemical and physical evidence which suggests structure 9 for luciduline is presented. An X-ray diffraction study on O-p -bromobenzoyl-dihydroluciduline confirmed this hypothesis and defined the stereochemistry of the methyl group at C-8. The complete structure of luciduline, including absolute configuration, is thus represented by 1. A possible mode of biosynthesis of luciduline, which is a new type of Lycopodium alkaloid, is discussed. The mass spectra of luciduline and some of its derivatives are interpreted in terms of structure 1.

scholarly journals Confirmation of Indandione Rodenticide Toxicoses by Mass Spectrometry/Mass Spectrometry

1992 ◽  
Vol 4 (4) ◽  
pp. 441-446 ◽  
Author(s):  
W. Emmett Braselton ◽  
Regg D. Neiger ◽  
Robert H. Poppenga
Keyword(s):  
Mass Spectrometry ◽  
High Performance ◽  
Mass Spectra ◽  
Similar Case ◽  
Molecular Ions ◽  
Sample Introduction ◽  
Physical Evidence ◽  
Direct Exposure ◽  
Mass Spectrometry Mass Spectrometry ◽  
Isotope Cluster

Mass spectrometry/mass spectrometry (MS/MS) with collision-activated dissociation (CAD) was utilized to unequivocally distinguish 1,3-indandione rodenticides in 2 cases of anticoagulant toxicosis. Anecdotal evidence provided by the veterinarian in a case involving feedlot cows and physical evidence at the site of occurrence in a similar case involving lambs strongly implicated diphenadione (diphacinone; DP) in both instances. However, high performance liquid chromatography indicated chlorophacinone (CP), not DP, was present in the blood samples obtained from both cows and lambs. Intact 1,3-indandiones exhibit poor gas chromatographic properties, so procedures were developed for analysis by MS/MS using a direct exposure probe for sample introduction. The EI mass spectra of DP and CP contained a base peak at m/z 173, with molecular ions (M+) at m/z 340 and m/z 374 (Cl isotope cluster), respectively. Corresponding MS/MS CAD parent ion spectra of m/z 173 showed an ion of m/z 340 for DP and 374 (Cl cluster) for CP. CAD analysis of the blood extracts showed a parent ion scan of m/z 173 identical to that of CP, with the m/z 374 (Cl cluster). (Additional evidence was obtained by MS/MS examination of the CAD daughter ion spectrum of m/z 374.) Blood extracts from the affected animals revealed CAD daughter ion spectra for m/z 374 identical to that of reference CP. Positive confirmation of CP in both cases led to identification of the source of the toxicant and prevention of further animal exposures.

LYCOPODIUM ALKALOIDS XIII. MASS SPECTRA OF REPRESENTATIVE ALKALOIDS

1963 ◽  
Vol 41 (10) ◽  
pp. 2654-2670 ◽  
Author(s):  
D. B. MacLean
Keyword(s):  
Mass Spectra ◽  
Fragmentation Process ◽  
Structural Types ◽  
Lycopodium Alkaloids

The mass spectra of a number of Lycopodium alkaloids are recorded and schemes proposed for their fragmentation. The loss of the bridge dominates the fragmentation process in the structural types examined.

LYCOPODIUM ALKALOIDS: XVII. MASS SPECTRA OF ANNOTINE AND SOME ANNOTINE DERIVATIVES

1966 ◽  
Vol 44 (5) ◽  
pp. 611-620 ◽  
Author(s):  
D. B. MacLean ◽  
M. Curcumelli-Rodostamo
Keyword(s):  
High Resolution ◽  
Mass Spectra ◽  
Fragmentation Mechanisms ◽  
Lycopodium Alkaloids

The mass spectra of annotine and some of its derivatives are recorded and discussed. Fragmentation mechanisms are proposed to account for the formation of the major peaks in the spectra. The composition of the ions has been verified by measurement of the high-resolution spectra of four of the five compounds. The results lend support to the structure previously proposed for this alkaloid.

Some new Lycopodium alkaloids

1989 ◽  
Vol 67 (6) ◽  
pp. 1077-1086 ◽  
Author(s):  
William A. Ayer ◽  
Gertrude C. Kasitu
Keyword(s):  
Lycopodium Alkaloid ◽  
Lycopodium Alkaloids ◽  
Northern Alberta

The alkaloids of the club moss Lycopodiumobscurum L., collected in Northern Alberta, have been investigated. The known alkaloids lycopodine, lycodine, clavolonine, dihydrolycopodine, O-acetyldehydrolycopodine, flabelliformine, β-lofoline, lycofoline, and des-N-methyl-α-obscurine were isolated and identified, as were the known compounds des-N-methyl-β-obscurine and acrifolinol. α-Obscurine and β-obscurine were not detected. The structures of the previously unreported alkaloids hydroxypropyllycodine (9a), lyconnotinol (11a), lobscurinol (19a), epilobscurinol (19b), and acetyllobscurinol (19c) are presented. Hydroxypropyllycodine (9a) is the first 19-carbon Lycopodium alkaloid reported to date. Its possible biogenetic significance is discussed. The isolation of obscurinine (14) and isoobscurinine (15) are reported and the preparation of obscurinine (15) by treatment of lobscurine (18) with ammonia is described. It is suggested that obscurinine and isoobscurinine are artefacts produced during the isolation process. Keywords: alkaloids, Lycopodium alkaloids, obscurinine, Lycopodiumobscurum, biogenesis.

LYCOPODIUM ALKALOIDS: VII. LYCODOLINE (ALKALOID L.8)

1964 ◽  
Vol 42 (11) ◽  
pp. 2514-2522 ◽  
Author(s):  
W. A. Ayer ◽  
G. G. Iverach
Keyword(s):  
Infrared Spectroscopy ◽  
Mass Spectra ◽  
Optical Rotatory Dispersion ◽  
Rotatory Dispersion ◽  
Optical Rotatory ◽  
Lycopodium Alkaloids

Lycodoline (alkaloid L.8) is shown to have the structure and stereochemistry depicted in II. The transformation of lycodoline into lycopodine is described. The use of infrared spectroscopy in assigning the configuration at C-12 and the nitrogen in these and related alkaloids is described. The effect of the configuration at C-12 on the optical rotatory dispersion spectra and on the mass spectra of lycopodine (I) and 12-epilycopodine (X) is discussesd.

Use of SEM, X-ray analysis and TEM to localize Fe3+ reduction in roots

1988 ◽  
Vol 46 ◽  
pp. 392-393 ◽  
Author(s):  
William P. Wergin ◽  
P. F. Bell ◽  
Rufus L. Chaney
Keyword(s):  
Electron Microscopy ◽  
Root Hairs ◽  
Rapid Reduction ◽  
X Ray ◽  
Physical Evidence ◽  
Transmission Electron ◽  
Young Root ◽  
Insoluble Precipitate ◽  
Uptake And Transport ◽  
Scanning Electron

In dicotyledons, Fe3+ must be reduced to Fe2+ before uptake and transport of this essential macronutrient can occur. Ambler et al demonstrated that reduction along the root could be observed by the formation of a stain, Prussian blue (PB), Fe4 [Fe(CN)6]3 n H2O (where n = 14-16). This stain, which is an insoluble precipitate, forms at the reduction site when the nutrient solution contains Fe3+ and ferricyanide. In 1972, Chaney et al proposed a model which suggested that the Fe3+ reduction site occurred outside the cell membrane; however, no physical evidence to support the model was presented at that time. A more recent study using the PB stain indicates that rapid reduction of Fe3+ occurs in a region of the root containing young root hairs. Furthermore the most pronounced activity occurs in plants that are deficient in Fe. To more precisely localize the site of Fe3+ reduction, scanning electron microscopy (SEM), x-ray analysis, and transmission electron microscopy (TEM) were utilized to examine the distribution of the PB precipitate that was induced to form in roots.

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