| Mycotoxins in general:
Mycotoxins are the toxic chemicals produced by fungi for a variety of
reasons. These include to attack or gain access to hosts by helping to
dissolve cell membranes, or as
protective measures against encroaching organisms. The production of
mycotoxins within the fungus depends on food sources and the
particular enzymes of the fungus and other environmental factors.
Mycotoxins are usually not found in spores, but are generally produced
in the next stage, that of mycelium. Many mycotoxins, such as
Mycotoxin T2 (Fusariotoxin) or the Amanita-toxins can be lethal to
animals. Others, such as Psilocybin, are entheogenic, producing
altered states of consciousness that are usually associated with
shamanism/religion. Others, such as the ergot derivatives are used
for migraine and post-partum hemorrhage. Still others, such as penicillin,
Fusaric
acid, and Wortmannin have antibiotic effects, and
Zearalenone with anabolic effects, but which may or may not be beneficial to the
host organism depending on the mode of administration and dose. By definition, only
mycotoxin-producing fungi can be used as mycoherbicides to attack,
colonize and kill plants.
The most-studied mycotoxins in Fusarium are toxic to both plants and
animals. Some have antibiotic properties. The mycotoxins of Pleospora have yet to
be identified, but we know from reports in the lab where it is being
researched that it has toxic effects on humans. After over a decade of work on EN-4 (a
"coca-killing" strain of Fusarium oxysporum forma
specialis erythroxyli),
the USDA has neglected to examine strain EN-4 mycotoxins. And by
ignoring this research, an ARS spokesperson was still able to
repeat the written USDA "talking points" mantra which state
that EN-4 does not produce or contain mycotoxins dangerous to animals or
humans to
various members of the press. This claim is disavowed by her superiors,
such as Eric Rosenquist, who candidly offers that the work on the safety
of EN-4 as a mycoherbicide, including tests on its mycotoxins
--have yet to be done.
In the absence of hard data on mycotoxins present in the Fusarium
oxysporum and Pleospora papaveraceae strains being considered for use as mycoherbicides, we
can only speculate on what these strains may contain. We also must
caution the reader that fungi can produce different toxins and varying amounts of toxins depending on which media they are growing
on, humidity, temperature, and light, among other variables.
Even the USDA has published on this phenomenon: "Cultures
of F. proliferatum established from these samples produced
fumonisins when cultured on rice. They also produced other toxins,
including moniliformin and beauvericin, which were not found in
naturally-infected field samples of rice. It is not known why
moniliformin and beauvericin were not found in field samples. There may
be mechanisms by which viable rice kernels suppress synthesis of
moniliformin and beauvericin by F. proliferatum, that are not
operative in autoclaved rice cultures. A better understanding of the
mechanisms by which mycotoxin production is controlled in Fusarium sp.
may lead to methods to control these compounds in food and feed.".
USDA has yet to persue this research.
However, here, for comparison's sake and taking the aforementioned
caveats about the variability of Fusaria into consideration, we may examine the series of mycotoxins that have been already isolated
from Fusarium oxysporum and other Fusarium species.
Fusarium mycotoxins:
"The genus Fusarium contains important mycotoxin-producing
species that have been implicated in human diseases, such as alimentary
toxic aleukia, Urov or Kashin-Beck disease, Akakabi-byo or scabby grain
intoxication, and esophageal cancer. Many of these mycotoxin-producing
species have also been implicated in several animal diseases, including
hemorrhagic, estrogenic, emetic, and feed refusal syndromes, fescue
foot, degnala disease, moldy sweet potato toxicosis, bean hulls
poisoning, and equine leukoencephalomalacia. The interest in toxigenic
Fusarium species is increasing world-wide due to the discovery of a
growing number of naturally occurring Fusarium mycotoxins that have
practical importance as threats to human and animal health."
quoted from Toxigenic
Fusarium Species by Marasas et alia, Penn State U, 1984
Chemical Names of Fusarium Mycotoxins
from Marasas et al. and other sources
(Toxigenic
Fusarium Species by Marasas et alia, Penn State U, 1984).
Some of the names are redundant, and some
are the result of research in different countries where two or more
names have been given to the same compound, a common phenomenon in
science.
= 4$-3-acetoxy-3",
15-dihydroxy-12,13-epoxytrichothec-9-ene. A similar compound,
monodeacetylanguidin = 4- or 15-acetylscirpentriol.
3-Acetyldeoxynivalenol (= Deoxynivalenol monoacetate) = 3"-acetoxy-7",15-dihydroxy-12,13-epoxytrichothec-9-en-8-one
8-Acetylneosolaniol (= Neosolaniol monoacetate) = 4$,8",
1 5-triacetoxy-3"-hydroxy-1
2,13-epoxytrichothec-9-ene
4- or 15-Acetylscirpentriol. See 4-Acetoxyscirpenediol
Acetyl T-2 toxin = 3",4$,15-triacetoxy-8"-(3-methylbutyry(oxy)-1
2,1 3-epoxytricho-thec-9-ene
Anguidin. See Diacetoxyscirpenol.
Avenacein +1
Beauvericin +2
Butenolide = 4-acetamido-4-hydroxy-2-butenoic-acid -(-lactone.
Calonectrin = 3", 1 5-diacetoxy-12,13-epoxytrichothec-9-ene.
15-Deacetylcalonectrin (= 1 5-De-0-acetylcalonectrin) = 3"-acetoxy-1
5-hydroxy-12,13-epoxytrichothec-9-ene.
Deoxynivalenol (= Rd toxin, = Vomitoxin) = 3",7",15-trihydroxy-12,13-epoxytricho-thec-9-en-8-one
Deoxynivalenol diacetate. See
Diacetyldeoxynivalenol
Deoxynivalenol monoacetate. See 3-Acetyldeoxynjvalenol
Diacetoxyscirpendiol See 7"-Hydroxydiacetoxyscirpenol
Diacetoxyscirpenol (= Anguidin) = 4$,15-diacetoxy-3"-hydroxy12,13-epoxytrjchothec-9-ene.
Diacetoxyscerpentriol See 7",8"-Dihydroxydiacetoxyscirpenol
Diacetyldeoxynivalenol (= Deoxynivalenol diacetate) = 3",15-diacetoxy-7-hydroxy
12,13-epoxytrichothec-9-en-8-one.
Diacetylnivalenol (= Nivalenol diacetate) = 4$,15-diacetoxy-3",7"-dihydroxy-12,13-epoxytrichothec-9-en-8-one
7",8"-Dihydroxydiacetoxyscirpenol
(= Diacetoxyscirpentriol) = 4$,15-diacetoxy-3",7",8"-trihydroxy-12,13-epoxytrichothec-9-ene
Enniatins +1
Fructigenin +1
Fumonisin B1 1 1,2,3-propanetricarboxylic acid
1,-l-[1-(12-amino-4,9,11-trihydroxy-2-methyltridecyl)-2-(1-methylpentyl)
-1,2-ethanediyl]
ester; macrofusine +
Fusarenon. See Fusarenon-X.
Fusarenon-X (=Fusarenon, = Monoacetylnivalenol, = Nivalenol
monoacetate) = 4$-acet oxy-3",7",
15-trihydroxy-12,13-epoxytrichothec9en8one
Fusaric acid (= Fusarinic acid) = 5-butylpicolinic acid.
Fusarinic acid. See Fusaric acid.
F-2. See Zearalenone
HT-2 toxin = l5-acetoxy-3",4$-dihydroxy-8"-(3-methylbutyryloxy)-12$-epoxytricho-thec-9-ene.
7"-Hydroxydiacetoxyscirpenol
(= Diacetoxyscirpendiol) = 4$,15-diacetoxy-3",7"-dihydroxy-12,13-epoxytrichothec-9ene
8"-Hydroxydiacetoxyscirpenol
See Neosolaniol.
1,4-Ipomeadiol = 1-(3-furyI)-1 ,4-pentanediol
Ipomeanine = 1-(3-furyl)-1 ,4-pentanetione.
1-Ipomeanol = 1-(3-furyl)-1-hydroxy-4-pentanone
4-lpomeanol = l-(3-furyl)-4-hydroxy4pentanone
Lateritin +1
Lycomarasmin +1
Moniliformin = potassium or sodium salt of
1-hydroxycyclobut-1-ene-3,4-dione
Monoacetoxyscirpenol = 15-acetoxy-3",4$~djhydroxy-12,13-epoxytrichothec-9ene
Monoacetylnivalenol See Fusarenon-X
Monodeacetylanguidin. See 4-Acetoxyscirpenediol
Neosolaniol (= 8"-Hydroxydiacetoxyscirpenol)
= 4$,15-diacetoxy-3"8"-dihydroxy
12,13-epoxytrichothec-9-ene
Neosolaniolacetate See 8-Acetylneosolaniol
Neosolaniol monoacetate. See 8-Acetylneosolaniol
Nivalenol = 3",4$,7",
15-tetrahydroxy-12,13-epoxytrichothec-9-en-8-one
Nivalenol diacetate See Diacetylnivalenol
Nivalenol monoacetate See Fusarenon-X
NT-1 toxin (=T-1 toxin) = 4$,
8"-diacetoxy-3",15-dihydroxy-12,13-epoxytrichothec-9-ene
NT-2 toxin = 4$-acetoxy-3",
8", 1 5-trihydroxy-1 2,1 3-epoxytrichothec-9-ene
Rd toxin See Deoxynivalenol
Sambucynin +1
Scirpentriol = 3",4$,
1 5-trihydroxy-12,13-epoxytrichothec-9-ene
Solaniol See Neosolaniol
T-1 toxin See NT-1 toxin
T-2 toxin = 4$,15-diacetoxy-3"-hydroxy-8"-(3-methylbutyrlyloxy)-12,13-epoxytrichothec-9-ene
Triacetoxyscirpendiol = 4$,8",15-triacetoxy-3",7"-dihydroxy-1
2,1 3-epoxytrichothec-9-ene
Triacetoxyscirpenol = 3",
4$,15-triacetoxy-12,13-epoxytrichothec-9-ene
Vomitoxin See Deoxynivalenol
Yavanicin +1
Zearalenol = 2,4-dihydroxy-6-(6, 1O-dihydroxy-trans-1 -undecenyl)-benzoic
acid :-lactone
Zearalenone = 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-$-resorcylic
acid lactone
+ Other source
+1 N.A.Krasil'nikov,
Soil
Microorganisms and Higher Plants
+2 Abbas
et al.
Mycotoxins
reported from Fusarium oxysporum:
- Diacetoxyscirpenol *
- Diacetylnivalenol *
- 7",8"-Dihydroxydiacetoxyscirpenol
*
- Fumonisin B1 +
- Fusarenon-X *
- Fusaric acid *
- 7"-Hydroxydiacetoxyscirpenol
*
- Moniliformin *
- Neosolaniol *
- T-2 toxin *
- Zearalenone *
* Marasas et
al. Toxigenic
Fusarium Species by Marasas et alia, Penn State U, 1984
Chemistry
and toxicology of the Fusaria mycotoxins:
The mycotoxins produced by Fusarium species are structurally quite varied. Often, there
is a series of closely related compounds which can be identified
as a group, such as the Trichothecenes
which lack nitrogen in their structure and Fumonisins and
Lycomarasmins,
which posses amine functions. Rather than approach
this field by chemical category or structure, we shall resort to an
alphabetical listing of the compounds by their most-used common names,
as registered in the Merck Index, Twelfth Edition, which
we will quote extensively here.
Fusarium mycotoxins may leach into the soil,
causing damage to plants and
animals through leaching even after the
fungus is no longer active. Indeed, a very real risk may be
extrapolated for humans,
also.
Fusaric Acid

Fusaric Acid.
"5-Butyl-2-pyndinecarboxylic acid;
5-butylpicolinic acid. C10H13N02;
mol wt 179.22. C 67.02%, H 7.31%, N 7.82%, 0 17.85%. Antibiotic (wilting
agent) first isolated from the fungus Fusarium heterosporium,
Nees: Yabuta et al., J. Agr. Chem. Soc. Japan 10, 1059
(1934). Isoln from other Fusarium species and from Gibberella
fujikuroi and synthesis: Plattner et al, Helv. Chim. Acta 37,
1379 (1954). Prepn: Hardegger, Nikles, ibid. 39, 505
(1956); 40, 2428 (1957); Schreiber, Adam, Ber. 93, 1848
(1960); Umezawa, Nagatsu, Ger. pat. 2,005,255 (1970 to
Microbiochem. Res. Found.); R. Tschesche, W. Führer, Ber. 111, 3502
(1978). Dopamine-hydroxylase inhibitor and hypotensive activity: Suda et
al., Chem. Pharm. Bull. 17, 2377 (1969); Nagatsu et al,
Biochem. Pharrnacol. 19, 35 (1970). Toxicity study: Ishii et al.
Arzneimittel-Forsch. 25, 55 (1975).
Colorless crystals, mp 96-98°. LD50 orally in mice: 230
mg/kg (Ishii).
Copper Salt, bluish violet crystals from water, mp258-259°." Merck
Index, Twelfth Edition
Fumonisin B1

Fumonisin B1.
"1,2,3-propanetricarboxylic acid
1,-l-[1-(12-amino-4,9,11-trihydroxy-2-methyltridecyl)-2-(1-methylpentyl)
-1,2-ethanediyl]
ester; macrofusine; F B1. C34H59NO15
mol wt 721.84. C 56.57%, H 8.24%, N 1.94%, 0 33.25%. Most prevalent of a
family of mycotoxins produced by Fusarium moniliforme, a common
mold associated with corn; also isolated from other Fusarium
species. Isolation: W.C. A. Gelderblom et al, Appl. Environ.
Microbiol. 54, 1806 (1988). Structure elucidation of family:
S. C. Bezuidenhout et al., Chem. Commun. 1988, 743. Causative
agent of pulmonary edema in pig: L. R. Harrison et al, J. Vet. Diagn.
Invest. 2, 217 (1990). Association of B1, B2
with human esophageal cancer: J. P. Rheeder et al, Phytopathology
82, 353 (1992). Metabolism: G. S. Shephard et al, Toxicon.
30, 768 (1992). Toxicity and carcinogenicity in rat: W.C. A. Gelderblom et
al, Carcinogenesis 12, 1247 (1991). Toxicology in pig: W. H.
Haschek et al, Mycopathologia 117, 83 (1992). LC determn
in corn of B series fumonisins: M.E. Stack, R. M. Eppley, J. Assoc.
Offic. Anal Chem. 75, 834 (1992); P. A. Murphy et al., J.
Agric. Food Chem. 41, 263 (1993). Review of animal toxicoses:
P. F. Ross et al., Mycopathologia 117, 109-114
(1992). Review: W. P. Norred, J. Toxicol Environ. Health 38,
309-328 (1993)." Merck
Index, Twelfth Edition
Also see: NC-129 Fusarium mycotoxins in cereal grains
and:
Reduction of Fusarium Mycotoxins as
concerns in Agricultural Commodities.
and:
Fumonisin
in US corn: Corn toxin examined in border birth defects: Diet may have put
Hispanics at risk
T-2 Toxin, Fusariotoxin,
Mycotoxin T-2

T-2Toxin.
"(3",4$,8")-12,13,-Epoxytrichothec-9-ene-3,4,8,15-tetrol
4,15-diacetate 8-(3-methylbutanoate); 3"
-hydroxy -4$, 15-diacetyloxy-8"-(3-methylbutyryloxy)-12,13-epoxy
-)9 -tricothecene; 8"-(3-methylbutyryloxy)-4$,
I 5-diacetoxyscirp-9-en-3"-ol;
fusariotoxin T-2; insariotoxin; mycotoxin T-2; NSC-138780. C24H34O9;
mol wt 466.53. C 61.79%, H 7.35%, 0 30.87%. Trichothecene mycotoxin
isolated from Fusarium tricinctum: J. R. Bamburg et al,
Tetrahedron 24, 3329 (1968). Physicochemical data: A. E.
Pohland et al, Pure Appl. Chem. 54, 2119 (1982). Synthesis:
M.C. Wani et al., J. Org. Chem. 52, 3468 (1987).
Biosynthetic study: F. Van Middlesworth et al., J. Org. Chem. 55,
1237 (1990). Toxicology studies: W. F. 0. Marasas et al., Toxicol. Appl.
Pharmacol. 15, 471 (1969); H. B. Schiefer, D. S. Hancock,
ibid. 76, 464 (1984); D. A. Creasia et al, Fund. Appl.
Toxicol 14, 54 (1990). Implicated as a chemical warfare agent
in Southeast Asia with nivalenol, q.v.: N. Wade, Science 214, 34
(1981); R. T. Rosen, J. D. Rosen, Biomed Mass Spectrum. 9,
443 (1982). Review: Developments in Food Science vol. 4, Y.
Ueno, Ed., entitled "Trichothecenes: Chemical, Biological and
Toxicological Aspects" (Kodansha Ltd. and Elsevier, New York, 1983)
310 pp. Review of pharmacokinetics and metabolism: B. Yagen, M. Bialer, Drug
Metab. Rev. 25, 281-323 (1993).
Crystals, mp l51-152°. ["]26/D
= 15° ( c = 2.58 in ethanol). Freely soluble in ethyl alcohol, ethyl
acetate, chloroform, DMSO and other organic solvents; slightly soluble in
petroleum ether; very slightly soluble in water. LD50 orally in
female rats: 4.0 mg/kg (Marasas). LD50 (mg/kg) in mice: 5.2 i.p.,
4.2 i.v.; in rats: 7.0 intragastric, 0.9-1.3 i.p., 0.9 iv., 2.0 s.c.; in
guinea pigs: 3.0-4.0 orally, 5.3 intragastric, 1.0 i.m., 1.0-2.0 i.v., 1.0-2.0
s.c.; in pigs: 5.0 orally, 3.0 iv. (Yagen, Bailer).
Caution: May be
highly irritating to skin and mucous nembranes. Direct contact may cause
extensive inflammation and tissue necrosis (Marasas). Topical exposure has
lead to systemic toxicity and death in experimental animals (Scheiffer,
Hancock)." Merck
Index, Twelfth Edition
Lycomarasmin

Lycomarasmine.
"
N-[2-[(2-Amino-2-oxoethyl)-amino]-2-carboxyethyl]-L-aspartic acid;
Welkstoff. C9H15N3O7; mol wt
277.23. C 38.99%, H 5.45%, N 15.16%, O 40.40%. Antibiotic peptide
(tomato-wilting agent) produced by the fungus Fusarium lycopersici.
Isoln: Plattner. Clauson-Kaas, Helv. Chim. Acta 28, 188
(1945). Structure: eldem. Experientia 1, 195 (1945); Hardegger
et al, Helv. Chim. Acta 46, 60 (1963).
Crystals, dec 227-229°. [" ]20/D
- 42° to -48° (aq. Soln at pH7). Acid reaction. Sparingly sol in water;
freely sol in dil acids or alkalies." Merck
Index, Twelfth Edition
Nivalenol

Nivalenol.
"(3",4B, 7")-1
2,13-Epoxy-3,4,7,15-tetra-hydroxytrichothec-9-en -8-one;
3",4$,7",
I 5-tetrahydroxyscirp-9-en-8-one. C15H20O7; mol wt 312.32. C 57.69%, H 6.45%,
0 35.86%. Trichothecene mycotoxin isolated from Fusarium nivale: T.
Tatsuno et al., Chem. Pharm. Bull. 16, 2519 (1968). Structure: eidem,
Tetrahedron Letters 1969, 2823. Toxicology: T. Tatsuno, Cancer Res. 28,
2393(1968). Implicated as a chemical warfare agent in Southeast Asia with
T-2 toxin, q.v.: N. Wade, Science 214, 34 (1981); R.T. Rosen, J. D.
Rosen, Biomed. Mass Spectrom. 9, 443(1982).
Crystals, mp 222-223° (dec). ["]24/D
+21.54° (c = 1.3 in ethanol). uv max (methanol): 218 nm (,
6300). Slightly sol in water; sol in polar organic solvents. LD50
i.p. in mice: 40 :g/1O g (Tatsuno).
Caution: Potential
symptoms of overexposure include fever, nausea, vomiting, diarrhea,
leukopenia, bleeding, sepsis; necrotic lesions of skin and mucosa. See M. J.
Ellenhorn, D. G. Barceloux in Medical Toxicology: Diagnosis and Treatment
of Human Poisoning (Elsevier, New York, 1988) pp. 1312-1314."
Merck
Index, Twelfth Edition
Vomitoxin

Vomitoxin.
"12,13.Epoxy-3,7,15-trihydroxytrichothec-9-en-8-one;
deoxynivalenol; dehydronivalenone. C15H20O6;
mol wt 296.32. C 60.80%, H 6.80%, 0 32.40% Isoln of the trichothecene
mycotoxin from Fusarium roseum and structure: N. Morooka et al,
J. Food Hyg. Soc Japan 13, 368 (1972); T. Yoshizawa, N.
Morooka, Agr. Biol. Chem 37, 2933 (1973). Isoln from F.
graminearum R. F. Vesonder et al, Appl. Microbiol. 26,
1008 (1973); eidem, Appl. Environ. Microbiol. 31, 280
(1976). Emetic and refusal activity in swine: D. M. Forsyth et al.,
ibid. 34, 547 (HPLC analysis: G. A. Bennett et al, J. Am.
Oil Chem Soc. 58, 1002A (1981). Implicated as a chemical warfare agent
with nivalenol, q.v. in Southeast Asia: N. Wade, Science 214,
34 (1981).
Fine needles from ethyl acetate + petr ether, mp
151-153°. [a]25/D+6.35 (c=0.07 in ethanol) uv maxd (ethanol): 218 nm (e
4500). LD50 i.p. in male, female mice (mg/kg): 70.0, 76.7 (Yoshizawa,
Marooka)." Merck
Index, Twelfth Edition
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