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<!--{{Chembox
{{Chembox
| ImageFile =
| ImageFile = Amavadin.svg
| ImageSize =
| ImageSize = 200px
| IUPACName = bis[''N''-[(1''S'')-1-(carboxy-κO)ethyl]-''N''-(hydroxy-κO)-<small>L</small>-alaninato(2-)-.κN,κO]-vanadium
| IUPACName =
| OtherNames =
| OtherNames =
| Section1 = {{Chembox Identifiers
| Section1 = {{Chembox Identifiers
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| SMILES = }}
| SMILES = }}
| Section2 = {{Chembox Properties
| Section2 = {{Chembox Properties
| Formula = [V{NO[CH(CH<sub>3</sub>)CO<sub>2</sub>]<sub>2</sub>}<sub>2</sub>]<sub>2</sub><sup>-</sup>
| Formula = [V{NO[CH(CH<sub>3</sub>)CO<sub>2</sub>]<sub>2</sub>}<sub>2</sub>]<sup>2-</sup>
| MolarMass = 398.94 g/mol
| MolarMass = 398.94 g/mol
| Appearance = Light blue solution
| Appearance = Light blue in solution
| Density =
| Density =
| MeltingPt =
| MeltingPt =
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| FlashPt =
| FlashPt =
| Autoignition = }}
| Autoignition = }}
}}-->
}}

[[File:Amanita muscaria 3 vliegenzwammen op rij.jpg|thumb| right| ''Amanita muscaria'' contains amavadin]]
[[File:Amanita muscaria 3 vliegenzwammen op rij.jpg|thumb| right| ''Amanita muscaria'' contains amavadin]]
'''Amavadin''' is a [[vanadium]]-containing [[anion]] found in three species of poisonous ''[[Amanita]]'' mushrooms: ''[[Amanita muscaria|A. muscaria]]'', ''A. regalis'', and ''A. velatipes''.<ref name=Berry>Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. “The Structural Characterization of Amavadin.” ''Angew. Chem. Int. Ed.'' 1999, 38:6, pp. 795&ndash;797. {{Cite doi| 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7}}.</ref> Amavadin was first isolated and identified in 1972 by Kneifel and Bayer.<ref>Kneifel, H.; Bayer, E. “Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium anion of ''Amanita muscaria''.” ''J. Am. Chem. Soc.'' 1986, 108:11, pp. 3075&ndash;3077. {{Cite doi|10.1021/ja00271a043}}.</ref> This anion, which appears as a blue solution, is an eight-coordinate vanadium [[complex (chemistry)|complex]].<ref name="Berry" /> A Ca<sup>2+</sup> cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction.<ref name=Berry/> Oxidized amavadin can be isolated as its PPh<sub>4</sub><sup>+</sup> salt. The oxidized form contains vanadium(V), which can be used to obtain an NMR spectrum.<ref name=Hub>Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.;, Hanefeld, U.; Arends, I.W.C.E. “The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium.” ''J. of Inorg. Biochem.'' 2005, 99, pp. 1264&ndash;1267. {{Cite doi|10.1016/j.jinorgbio.2005.02.004}}.</ref>
'''Amavadin''' is a [[vanadium]]-containing [[anion]] found in three species of poisonous ''[[Amanita]]'' mushrooms: ''[[Amanita muscaria|A. muscaria]]'', ''A. regalis'', and ''A. velatipes''.<ref name=Berry>{{cite journal | author = Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. | title = The Structural Characterization of Amavadin | journal = Angew. Chem. Int. Ed. | year = 1999 | volume = 38 | issue = 6 | pages = 795&ndash;797 | doi = 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7}}</ref> Amavadin was first isolated and identified in 1972 by Kneifel and Bayer.<ref>Kneifel, H.; Bayer, E. “Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium anion of ''Amanita muscaria''.” ''J. Am. Chem. Soc.'' 1986, 108:11, pp. 3075&ndash;3077. {{Cite doi|10.1021/ja00271a043}}.</ref> This anion, which appears as a blue solution, is an eight-coordinate vanadium [[complex (chemistry)|complex]].<ref name="Berry" /> A Ca<sup>2+</sup> cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction.<ref name=Berry/> Oxidized amavadin can be isolated as its PPh<sub>4</sub><sup>+</sup> salt. The oxidized form contains vanadium(V), which can be used to obtain an NMR spectrum.<ref name=Hub>{{cite journal | author = Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.;, Hanefeld, U.; Arends, I.W.C.E. | title = The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium | journal = J. of Inorg. Biochem. | year = 2005 | volume = 99 | pages = 1264&ndash;1267 | doi = 10.1016/j.jinorgbio.2005.02.004}}</ref>


==Preparation==
==Preparation==
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==Structure and properties==
==Structure and properties==

⚫
[[Image:AmavadinRevd.png|380 px|thumb|right|The ligand precursor found in amavadin (left), the ligand (center), and H<sub>3</sub> (HIDA, right).]]
The ligand found in amavadin was first synthesized in 1954.<ref>Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. “Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids.” ''J. Am. Chem. Soc.'' 1954, 76:23, pp. 6054&ndash;6058. {{Cite doi| 10.1021/ja01652a057}}.</ref> Amavadin contains vanadium(IV). Initially, amavadin was thought to have a vanadyl, VO<sup>2+</sup>, center. In 1993, it was discovered by crystallographic characterization that amavadin is not a [[vanadyl ion]] compound. Instead, it is an octacoordinated vanadium(IV) complex. This complex is bonded to two tetradentate ligands derived from N-hydroxyimino-2,2'-dipropionic acid, H<sub>3</sub>(HIDPA), ligands.<ref>Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. “The Chemical Nature of Amavadin". ''J. Am. Chem. Soc.'' 1993, 115:2, pp. 807&ndash;808. {{Cite doi| 10.1021/ja00055a073}}.</ref> The ligands coordinate through the nitrogen and the three oxygen centers.
The ligand found in amavadin was first synthesized in 1954.<ref>{{cite journal | author = Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. | title = Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids | journal = J. Am. Chem. Soc. | year = 1954 | volume = 76 | issue = 23 | pages = 6054&ndash;6058 | doi = 10.1021/ja01652a057}}</ref> Amavadin contains vanadium(IV). Initially, amavadin was thought to have a vanadyl, VO<sup>2+</sup>, center. In 1993, it was discovered by crystallographic characterization that amavadin is not a [[vanadyl ion]] compound. Instead, it is an octacoordinated vanadium(IV) complex. This complex is bonded to two tetradentate ligands derived from N-hydroxyimino-2,2'-dipropionic acid, H<sub>3</sub>(HIDPA), ligands.<ref>{{cite journal | author = Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. | title = The Chemical Nature of Amavadin | journal = J. Am. Chem. Soc. | year = 1993 | volume = 115 | issue = 2 | pages = 807&ndash;808 | doi = 10.1021/ja00055a073}}</ref> The ligands coordinate through the nitrogen and the three oxygen centers.


Amavadin is a C<sub>2</sub>-symmetric anion with a 2− charge. The two-fold axis bisects the vanadium atom perpendicular to the two NO ligands. The anion features five chiral centers, one at vanadium and the four carbon atoms having S stereochemistry.<ref name="Berry" /> There are two possible diastereomers for the ligands, (''S'',''S'')-(''S'',''S'')-Δ and (''S'',''S'')-(''S'',''S'')-Λ.
Amavadin is a C<sub>2</sub>-symmetric anion with a 2− charge. The two-fold axis bisects the vanadium atom perpendicular to the two NO ligands. The anion features five chiral centers, one at vanadium and the four carbon atoms having S stereochemistry.<ref name="Berry" /> There are two possible diastereomers for the ligands, (''S'',''S'')-(''S'',''S'')-Δ and (''S'',''S'')-(''S'',''S'')-Λ.
⚫
[[Image:AmavadinRevd.png|380px|thumb|left|The ligand precursor found in amavadin (left), the ligand (center), and H<sub>3</sub> (HIDA, right).]]{{clear-left}}


==Biological function==
The biological function of amavadin is still unknown, yet it has been thought that it uses H<sub>2</sub>O<sub>2</sub> and acts as a peroxidase to aid the regeneration of damaged tissues.<ref name="Hub" /> Amavadin may serve as a toxin for protection of the mushroom.<ref>Garner, C.D.; Armstrong, E.M.; Berry, R.E.; Beddoes, R.L.; Collison, D.; Cooney, J.J.A.; Ertok, S.N.; Helliwell, M. “Investigations of Amavadin.” ''J. of Inorg. Biochem.'' 2000, 80, pp. 17&ndash;20. {{Cite doi|10.1016/S0162-0134(00)00034-9}}.</ref>
The biological function of amavadin is still unknown, yet it has been thought that it uses H<sub>2</sub>O<sub>2</sub> and acts as a [[peroxidase]] to aid the regeneration of damaged tissues.<ref name="Hub" /> Amavadin may serve as a toxin for protection of the mushroom.<ref>{{cite journal | author = Garner, C.D.; Armstrong, E.M.; Berry, R.E.; Beddoes, R.L.; Collison, D.; Cooney, J.J.A.; Ertok, S.N.; Helliwell, M. | title = Investigations of Amavadin | journal = J. of Inorg. Biochem. | year = 2000 | volume = 80 | pages = 17&ndash;20 | doi=10.1016/S0162-0134(00)00034-9}}</ref>


==References==
==References==

Revision as of 17:11, 29 September 2010

Amavadin
Names
IUPAC name
bis[N-[(1S)-1-(carboxy-κO)ethyl]-N-(hydroxy-κO)-L-alaninato(2-)-.κN,κO]-vanadium
Identifiers
Properties
[V{NO[CH(CH3)CO2]2}2]2-
Molar mass 398.94 g/mol
Appearance Light blue in solution
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Amanita muscaria contains amavadin

Amavadin is a vanadium-containing anion found in three species of poisonous Amanita mushrooms: A. muscaria, A. regalis, and A. velatipes.[1] Amavadin was first isolated and identified in 1972 by Kneifel and Bayer.[2] This anion, which appears as a blue solution, is an eight-coordinate vanadium complex.[1] A Ca2+ cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction.[1] Oxidized amavadin can be isolated as its PPh4+ salt. The oxidized form contains vanadium(V), which can be used to obtain an NMR spectrum.[3]

Preparation

The formation of amavadin begins with the formation of two tetradentate ligands.[3]

2 HON(CH(CH3)CO2H)2 + VO2+ → [V{NO[CH(CH3)CO2]2}2]2− + H2O + 4 H+

Structure and properties

The ligand found in amavadin was first synthesized in 1954.[4] Amavadin contains vanadium(IV). Initially, amavadin was thought to have a vanadyl, VO2+, center. In 1993, it was discovered by crystallographic characterization that amavadin is not a vanadyl ion compound. Instead, it is an octacoordinated vanadium(IV) complex. This complex is bonded to two tetradentate ligands derived from N-hydroxyimino-2,2'-dipropionic acid, H3(HIDPA), ligands.[5] The ligands coordinate through the nitrogen and the three oxygen centers.

Amavadin is a C2-symmetric anion with a 2− charge. The two-fold axis bisects the vanadium atom perpendicular to the two NO ligands. The anion features five chiral centers, one at vanadium and the four carbon atoms having S stereochemistry.[1] There are two possible diastereomers for the ligands, (S,S)-(S,S)-Δ and (S,S)-(S,S)-Λ.

The ligand precursor found in amavadin (left), the ligand (center), and H3 (HIDA, right).

Biological function

The biological function of amavadin is still unknown, yet it has been thought that it uses H2O2 and acts as a peroxidase to aid the regeneration of damaged tissues.[3] Amavadin may serve as a toxin for protection of the mushroom.[6]

References

  1. ^ a b c d Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. (1999). "The Structural Characterization of Amavadin". Angew. Chem. Int. Ed. 38 (6): 795–797. doi:10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  2. ^ Kneifel, H.; Bayer, E. “Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium anion of Amanita muscaria.” J. Am. Chem. Soc. 1986, 108:11, pp. 3075–3077. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi:10.1021/ja00271a043, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with |doi=10.1021/ja00271a043 instead..
  3. ^ a b c Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.;, Hanefeld, U.; Arends, I.W.C.E. (2005). "The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium". J. of Inorg. Biochem. 99: 1264–1267. doi:10.1016/j.jinorgbio.2005.02.004.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. ^ Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. (1954). "Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids". J. Am. Chem. Soc. 76 (23): 6054–6058. doi:10.1021/ja01652a057.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. ^ Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. (1993). "The Chemical Nature of Amavadin". J. Am. Chem. Soc. 115 (2): 807–808. doi:10.1021/ja00055a073.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  6. ^ Garner, C.D.; Armstrong, E.M.; Berry, R.E.; Beddoes, R.L.; Collison, D.; Cooney, J.J.A.; Ertok, S.N.; Helliwell, M. (2000). "Investigations of Amavadin". J. of Inorg. Biochem. 80: 17–20. doi:10.1016/S0162-0134(00)00034-9.{{cite journal}}: CS1 maint: multiple names: authors list (link)
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