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Further occurrence of sulphated carotenoids in lanthella species (Desmospongia)
BiochemicalS~matics ~ d ~olog~ Vol. 1~ N& t p~ ~-5& 198& Pdnted in G ~ Bdtain.
0305-1978/89 $&00+&00 © ~89 Pe~amon Press#c.
Further Occurrence of Sulphated Carotenoids in lanthella Species (Desmospongia)* SlSSELL HERTZBERG~ PATRIClA BERGQUIST$ and SYNNOVE UAAEN-JENSENt tO~an~ C h e m i ~ ~ b o r a t o r ~ Norwegian Institute ~ ~ c h n o ~ g ~ Un~e~ity ~ ~ondh~m, N-7034 Trondheim-NTH, Norw~; ~Depa~me~ ~ Zo~og~ Un~e~i~ ~ Au~lan& Pdv~e Ba~ AucNan& New Zea~nd
~e¥ W o ~ I n d e x - - ~ m i ~ ~ h e ~ a e
~mospong~;
lanthe~ flabelliform~; ~ n ~ d
sulph~es; bastaxanthins.
Abstract--Carotenoid ana~ses of thee isolates of ~n~ella flabelliform~ demon~rated the presence ~ sulphated caroten~ds ~ ~ e ba~axamhin Wpe ~4-90% ~ ~ e total carotenoidL including bastaxanth~ c (m~o~ & ~ ~ n d g ~ew~ Chemosy~em~ic considera~ons a~ made.
and ~s nomenclature is g~en elsewhe~ [10]. The three new spedmens examined represent two colour vadants of ~nthella flabelliformis. The name L flabelliform~ has habitual~ been applied in ~cent I~erature to spedmens of ~nthella which ~ha~ted tempe~te to trop~al A u C t i o n seas from New South Wales no~hward. Recent ~udy of type matedal in Paris (Lama~k collec5ons) indicates that the species name, f/abe//iformis, is correctly applied to the large colour vadable tro~cal species examined here. The southern species requires a new name, but it is not represented in our sam#e& Each of the three isolates not examined before contained strong~ polar carotenoids of the ba~axanthN type (64-90% of the total caroten~d~ (see Table 1). Ba~axanth~ c ~ ) w a s the m~or caroten~d in each isolate (>40% of the total caroten~d~. Polar carotenoids with physical prope~ies compatiMe with the other minor ba~axant~n~ b (1) and d (3), were also encountered. The mo~ polar caroten~d p~sent in isolate A, here referred to as ba~axanthin g (~, was more polar than the other ba~axathins (1-5) and p o s h l y represents a d~ulphate. Ba~axanthin g appeared to have the same chromophore as the other ba~axanthhs and at lea~ one hydroxyl group a c c e s ~ e for acetyla-
Introduc~on Pre~ou~y we have characterized in detail the ~dividual carotenoids of the non-p~ar carotenoid fracSon [1] and of the polar caroten~d fraction [2, 3] of the v e r o n ~ sponge ~nthella basta, The polar carotenoids c o n ~ e d of the novel carotenoid monosu~hates bastaxanthin b (1), c (2), d (3), e (4) and f (5) [2, ~. Subsequently seve~l caroten~d mono- and ~sulphates have been prepared by chem~al syntheses [4-6]. Recently the caroten~d d~ulphate oph~xanthin (6) has been reposed from the echinoderm Ophioderma Iongicaudum [7]. Since carotenoid s~phates have not been encountered in other natural source~ N d u d ~ g other sponges [& 9], the p o s ~ l ~ y that carotenoid sulphates could serve as chemosy~emaSc marke~ for the family lanthellidae was of interest,
Results and D~cus~on We now repo~ an analysis of three other isolates of membem of the ~ n t h ~ l ~ a ~ carded out in co,unction with the r e ~ a t l o n of carotenoid s~phates from L bast& Description of L bas~ 5 see *Number He~zbe~ 6 ~ ~ e~sedes ~ (1985) Acta Chem. s ~ p hScan~ a ~ For Numb725. eB r39,
thin, On. ThewasNaBH4con~de~Nyreduc~OnmorePrOdUCt f polaba~axan-t rOf han the correspon~ng reduction product of ba~axanthin
(Received25 Oc~ber 198~
~ 51
52
SISSELLHERTZ~RG,PATRICIBERGQUIST A A N D SYNNOVE UAAEN~EN~N
&~_%o.~~--"'~ "~'~ ;
OH
,~_~V°°~o ,,,,~,V~ °°~ OH
SCHEME1 TABLE1.CAROTEN~D COMPO~ONOFSOMESPEQESOF~NTHLUDAE percemoftotalcarotenoid A B C L~ r m ~ L~be~rm~ Lflabelliform~ Carotenoid (yel~w/pu~ (purple) (purple)
D ~bas~ P~semwo~d. R~s[1,3]
~r°teneunspe~feidZeaxantNn~-~r°tenecarotenoidsn°n-p~ar14101 } t 25
!4
In
10
36
Ba~axa~nbfgeC d
61455 ~'t 75 }t
486190
D~~ ~ sample(~ ~talca~n~dsin%ofd~wt
27 0~6
35 0#06
It is c o n c l u d e d that a high proportion of sul~hated carotenoids of the bastaxanthin tgpe were ~resent in both colour va~ants of [ floOol#formN and thus fa~ these m e t a b ~ e s a ~ e a r to
}} 12475 ~'t 64 19 0~
}501013>'196 38 0~2
cha~cte~zethefamiNNnth~lNa~The#auNNe metab~ forma~on of these carotenoid sul~hates from ~ h g t o ~ a n ~ o n ~ g p e carotenoids has been discussed e l s e w h e ~ [3].
SULPHATED CAROTE~OIDS IN I~HELL~ SPECIES
Experimental Biological materials. All samples were collected ~om Dawes Ree~ Groat Barder Re~, A u ~ l ~ ~&023982~ between 20 and 30 m de~h. H a ~ e ~ A L flabelliform~ ~ellow-purple); h a ~ e ~ B, L flabelliform~ ~urpl~; h a ~ e ~ ~ L flabelliform~ ~urple); and h a ~ e ~ ~ L basta. Physical and chemical methods. These were as described p ~ o u ~ y p - ~ . For quantitative results see Ta~e 1. (A) lan~ella flabelliform~ (yellow-purple) Non~olar carotenoids. By TLC (SiO2, 10% acetone-hexane) these comprised morn than 10 zone~ all had Vis X~a, nm ~cemn~ 445-450. The carotene frac~on had R~=0A9 ~iO 2, hexane); Vis ~ , , nm ~ceton~ (44~, 44~ 473; MS ~9~) m ~ 536 (M~. Zeaxanthin had ~ = 0 ~ 0 ~iO~, 40% ac~one-hexan~; Us X~ex nm ~ c ~ o n ~ H25), 45~ 475; MS (21E m ~ 568 (M~, 550 (M+--18), 476 (M+--92) and prodded upon aceWlation ~ e
~ 20%
MeOH-~OA~
in d ~ e ~
comparison
w~h
NaBH~
~duced 2 wire ~ - - 0 3 ~ Us ~,~ax nm (MeOH) 445. NaBH 4 reduced 3 has ~--038 (SiOz, 15% MeOH-~OA~ [3]. (B) L flabelliform~ (purple) B a s t a x a n ~ b ~). ~ = 0 A 3 ~iO2, 10% MeOH-EOA~; V~
~ , , as for 2. Bastaxanthm c =). ~=0~4 (SiO2, 10% MeOH-~OAc), i n s e p a ~ e ~om a~henSc 2; Vis ~=a, nm (MeOH) 470, 490; MS ~5~) m~E94 (M'+), 576 (M'+-18), 563 (M'+--~ L More polar bastaxanthins. Mass spec~a showed, in gene~L co~amination with b m m ~ a ~ d impurit~s. (C)Lflabelliform~ ~urple) Bastaxanth~ b ~). ~ = 0 A 3 ~iO2, 10% MeOH-~OA~; Vis X ~ nm as for 2. Bastaxanth~ c ~). Rt=0.21 ~iO~, 15%, MeOH-~OAd i n s e p a ~ e ~om a~henQc 2, Vis ~.~ nm (MeOH) 470, 490; MS ~2E) m ~ 594 (M'~, 576 (M'+--18), E63 (M'+-~)
diacetatea 'cetonei~nsepa~Nh eexane);Vi~°~n~×a~maUthen~(aCcetonNSamNeu;nchangedISi 0~'M5S % (M'+-76), ; 488 (M'+ ~6).
~0E) m~E52 (M~, 592 (M+--60~ B a s t a x a n ~ d. ~ = 0 2 9 ~iO 2, 15% MeOH-~OA~ Bastaxanth~ b ~). ~ = 0 A 3 (SiO2, 10% MeOH-~OAc), Vis insepam~e ~om authentic ~ Vis Xr~,xnm 47~ 49~ X ~ nm ~ c ~ o n ~ as ~ r 2. Bastaxanth~ f ~) or g ~). ~ < 0 2 (SiO2, 15% MeOHBastaxanth~ c ~). ~=034 ~iO2, 10% MeOH-~OAc), ~OA~, insufficient for fu~her studies. i n s e p a ~ e from an authentic sample; Us ~ , nm (MeOH) 470, 490; MS ~0E) m ~ 59~ (M'~, 576 (M'+-18), 488 (D)Lbasta (M'+-106), 470 (M'+ 1 0 6 ~ ; ~H NMR ~00 MHz, CD~OD), Bastaxanth~ b ~). c ~), d ~) and e N) were o~ained as 0~6s ( M e - I ~ L 138s and 121s (Me--16,17), 1A8s (Me--IE), reference compounds as pm~ou~y described [~ ~. 1~2s (Me--l~, 2~0s (Me-20~E,2EL 432s ~H2--19), 6~8d Bastaxanthin g ~) ~pmsemed a minor c o n ~ u e n ~ ~ - 7 ' L 6 3 6 ~ m (olefin~ H), Z36d ~ - E ) . ~ e p a ~ b ~ ~om 7 ex Sponge 1A. AceW~don provided 2-diacetate, ~ = 0 2 6 (SiO2, 5% MeOH-EOA~ of unchanged Vis X~,x; MS ~0E) m ~ 618 Acknowledgements--We thank Clive W i ~ n s o ~ formerly (M'+-60), 558 (M'+--60-6~; ~H NMR (100 MHz, CDzOD) $ RRIME Dee Wh~ for the collec~ons. ~ssel He~zbe~ was 1~4s ( M e - I E L 136s and 1~9s (Me-16,17), 1A8s (Me--IE~ supposed by a mseamh grant ~om the Norweg~n 192s (Me--18), 2~0s (Me--19,20,203, 2~3s (OAcL 423 (non- Resea~h Coun~l of S~ence and Human~es to Synn~ve ~WI~ CH2OA~, 6 3 - 6 ~ m (olefin~ HL 738d (H-EL ~aaemJensen. AI~I~ oxida~on with p - c h ~ n i l of 2 prodded ~ e l~al, ~ = 0 2 2 ~5% MeOH-~OA~; Us ~ , , nm (MeOH) 49~ References Reduction of 2 w~h NaBH4 in MeOH gave the tetroL 1. RamdahL ~ Ka~auska~ R, Be~quist, R and Liaaeni n s e p a ~ e by TLC ~iO2, 15% MeOH-~OAc), from an Jensen, S~(19~)Biochem. Sys~EcoLg,~l. authentic sam~e ex L bas~; Vis ~ nm (MeOH) 33~ H2~, 2. He~zbe~, S~ Ramda~, T., Johanse~ J. E. and Liaaen443, 472. Jensen, S. ~983) Ac~ Chem. Scand. B3Z 267 Bastaxanth~ d ~). ~ = 0 A 6 ~0% MeOH-~oAc), morn 3. He~zbe~, S, Johansen, J. E, Ramda~, G~ Bo~h, G. and polar than 2 (R~=0.51) and ~sepaB~e from 3 ex L bas~; Uaaen-Jensen, S. ~98~ Biochem. SysL Ecol. ~, 267 Vis X=,, nm (MeOH) 47~ H90); MS ~00~, m ~ 596 (M'+), 581 4. Ramdahl, • and ~aaen~ense~ S. ~980) Ac~ Chem. (M'+ 15),490 (M'~ 106). Scan~ B34, 773. Bastaxan~ g (~. ~ = 0 3 9 ~iO~, 20% MeOHEtOAc), 5. He~zbe~, S. and ~aaemJense~ S. (198~ Ac~ Chem. ~ 0 3 8 ~iO2, 15% MeOH-~OA~ pm~nged deve~pment, Scan~ B39, 629. in cochmm~og~phy ~ w~h authenSc ba~axanthin f ~) 6. He~zbe~, S, Be~e~ H. and UaaemJense~ S. ~98~ Ac~ with ~ = 0 . ~ ; Vis X=a~ nm (MeOH) 465, sligh~y bathoChem. Scan~B39, 725. chmm~al~ s h ~ e ~ b ~ same s p e ~ l shape as 2; MS ~0~) 7 ~Auria. M. V., R ~ R. and M ~ L ~98~ ~trahedron nomcon~u~v~ Le~ 2 ~ 18~. Ac~n prodded 7-A~ ~=0.74 ~iO~, 20% 8. L~aen-Jensen, S, R e n ~ m , B~ Ramdahl, ~ Hal~nswe~ MeOH-~OA~ in d~ect comparison wkh 7 (~=03~. 7-Ac M. and Be~quist, R R. (1982) Biochem. SysL EcoL 10, 162. was pa~y conve~ed ~ 7 upon a~a~ne h y d m ~ 9. Matsun~ ~ (1985) PureAppL Chem. 57, 659. NaBH4-reduction in EtOH gave reduced 7; ~=031 ~iO2, 10. Bergquist, RR.~980) N . Z ~ Z o o l . ~ 4 4 3 .
0305-1978/89 $&00+&00 © ~89 Pe~amon Press#c.
Further Occurrence of Sulphated Carotenoids in lanthella Species (Desmospongia)* SlSSELL HERTZBERG~ PATRIClA BERGQUIST$ and SYNNOVE UAAEN-JENSENt tO~an~ C h e m i ~ ~ b o r a t o r ~ Norwegian Institute ~ ~ c h n o ~ g ~ Un~e~ity ~ ~ondh~m, N-7034 Trondheim-NTH, Norw~; ~Depa~me~ ~ Zo~og~ Un~e~i~ ~ Au~lan& Pdv~e Ba~ AucNan& New Zea~nd
~e¥ W o ~ I n d e x - - ~ m i ~ ~ h e ~ a e
~mospong~;
lanthe~ flabelliform~; ~ n ~ d
sulph~es; bastaxanthins.
Abstract--Carotenoid ana~ses of thee isolates of ~n~ella flabelliform~ demon~rated the presence ~ sulphated caroten~ds ~ ~ e ba~axamhin Wpe ~4-90% ~ ~ e total carotenoidL including bastaxanth~ c (m~o~ & ~ ~ n d g ~ew~ Chemosy~em~ic considera~ons a~ made.
and ~s nomenclature is g~en elsewhe~ [10]. The three new spedmens examined represent two colour vadants of ~nthella flabelliformis. The name L flabelliform~ has habitual~ been applied in ~cent I~erature to spedmens of ~nthella which ~ha~ted tempe~te to trop~al A u C t i o n seas from New South Wales no~hward. Recent ~udy of type matedal in Paris (Lama~k collec5ons) indicates that the species name, f/abe//iformis, is correctly applied to the large colour vadable tro~cal species examined here. The southern species requires a new name, but it is not represented in our sam#e& Each of the three isolates not examined before contained strong~ polar carotenoids of the ba~axanthN type (64-90% of the total caroten~d~ (see Table 1). Ba~axanth~ c ~ ) w a s the m~or caroten~d in each isolate (>40% of the total caroten~d~. Polar carotenoids with physical prope~ies compatiMe with the other minor ba~axant~n~ b (1) and d (3), were also encountered. The mo~ polar caroten~d p~sent in isolate A, here referred to as ba~axanthin g (~, was more polar than the other ba~axathins (1-5) and p o s h l y represents a d~ulphate. Ba~axanthin g appeared to have the same chromophore as the other ba~axanthhs and at lea~ one hydroxyl group a c c e s ~ e for acetyla-
Introduc~on Pre~ou~y we have characterized in detail the ~dividual carotenoids of the non-p~ar carotenoid fracSon [1] and of the polar caroten~d fraction [2, 3] of the v e r o n ~ sponge ~nthella basta, The polar carotenoids c o n ~ e d of the novel carotenoid monosu~hates bastaxanthin b (1), c (2), d (3), e (4) and f (5) [2, ~. Subsequently seve~l caroten~d mono- and ~sulphates have been prepared by chem~al syntheses [4-6]. Recently the caroten~d d~ulphate oph~xanthin (6) has been reposed from the echinoderm Ophioderma Iongicaudum [7]. Since carotenoid s~phates have not been encountered in other natural source~ N d u d ~ g other sponges [& 9], the p o s ~ l ~ y that carotenoid sulphates could serve as chemosy~emaSc marke~ for the family lanthellidae was of interest,
Results and D~cus~on We now repo~ an analysis of three other isolates of membem of the ~ n t h ~ l ~ a ~ carded out in co,unction with the r e ~ a t l o n of carotenoid s~phates from L bast& Description of L bas~ 5 see *Number He~zbe~ 6 ~ ~ e~sedes ~ (1985) Acta Chem. s ~ p hScan~ a ~ For Numb725. eB r39,
thin, On. ThewasNaBH4con~de~Nyreduc~OnmorePrOdUCt f polaba~axan-t rOf han the correspon~ng reduction product of ba~axanthin
(Received25 Oc~ber 198~
~ 51
52
SISSELLHERTZ~RG,PATRICIBERGQUIST A A N D SYNNOVE UAAEN~EN~N
&~_%o.~~--"'~ "~'~ ;
OH
,~_~V°°~o ,,,,~,V~ °°~ OH
SCHEME1 TABLE1.CAROTEN~D COMPO~ONOFSOMESPEQESOF~NTHLUDAE percemoftotalcarotenoid A B C L~ r m ~ L~be~rm~ Lflabelliform~ Carotenoid (yel~w/pu~ (purple) (purple)
D ~bas~ P~semwo~d. R~s[1,3]
~r°teneunspe~feidZeaxantNn~-~r°tenecarotenoidsn°n-p~ar14101 } t 25
!4
In
10
36
Ba~axa~nbfgeC d
61455 ~'t 75 }t
486190
D~~ ~ sample(~ ~talca~n~dsin%ofd~wt
27 0~6
35 0#06
It is c o n c l u d e d that a high proportion of sul~hated carotenoids of the bastaxanthin tgpe were ~resent in both colour va~ants of [ floOol#formN and thus fa~ these m e t a b ~ e s a ~ e a r to
}} 12475 ~'t 64 19 0~
}501013>'196 38 0~2
cha~cte~zethefamiNNnth~lNa~The#auNNe metab~ forma~on of these carotenoid sul~hates from ~ h g t o ~ a n ~ o n ~ g p e carotenoids has been discussed e l s e w h e ~ [3].
SULPHATED CAROTE~OIDS IN I~HELL~ SPECIES
Experimental Biological materials. All samples were collected ~om Dawes Ree~ Groat Barder Re~, A u ~ l ~ ~&023982~ between 20 and 30 m de~h. H a ~ e ~ A L flabelliform~ ~ellow-purple); h a ~ e ~ B, L flabelliform~ ~urpl~; h a ~ e ~ ~ L flabelliform~ ~urple); and h a ~ e ~ ~ L basta. Physical and chemical methods. These were as described p ~ o u ~ y p - ~ . For quantitative results see Ta~e 1. (A) lan~ella flabelliform~ (yellow-purple) Non~olar carotenoids. By TLC (SiO2, 10% acetone-hexane) these comprised morn than 10 zone~ all had Vis X~a, nm ~cemn~ 445-450. The carotene frac~on had R~=0A9 ~iO 2, hexane); Vis ~ , , nm ~ceton~ (44~, 44~ 473; MS ~9~) m ~ 536 (M~. Zeaxanthin had ~ = 0 ~ 0 ~iO~, 40% ac~one-hexan~; Us X~ex nm ~ c ~ o n ~ H25), 45~ 475; MS (21E m ~ 568 (M~, 550 (M+--18), 476 (M+--92) and prodded upon aceWlation ~ e
~ 20%
MeOH-~OA~
in d ~ e ~
comparison
w~h
NaBH~
~duced 2 wire ~ - - 0 3 ~ Us ~,~ax nm (MeOH) 445. NaBH 4 reduced 3 has ~--038 (SiOz, 15% MeOH-~OA~ [3]. (B) L flabelliform~ (purple) B a s t a x a n ~ b ~). ~ = 0 A 3 ~iO2, 10% MeOH-EOA~; V~
~ , , as for 2. Bastaxanthm c =). ~=0~4 (SiO2, 10% MeOH-~OAc), i n s e p a ~ e ~om a~henSc 2; Vis ~=a, nm (MeOH) 470, 490; MS ~5~) m~E94 (M'+), 576 (M'+-18), 563 (M'+--~ L More polar bastaxanthins. Mass spec~a showed, in gene~L co~amination with b m m ~ a ~ d impurit~s. (C)Lflabelliform~ ~urple) Bastaxanth~ b ~). ~ = 0 A 3 ~iO2, 10% MeOH-~OA~; Vis X ~ nm as for 2. Bastaxanth~ c ~). Rt=0.21 ~iO~, 15%, MeOH-~OAd i n s e p a ~ e ~om a~henQc 2, Vis ~.~ nm (MeOH) 470, 490; MS ~2E) m ~ 594 (M'~, 576 (M'+--18), E63 (M'+-~)
diacetatea 'cetonei~nsepa~Nh eexane);Vi~°~n~×a~maUthen~(aCcetonNSamNeu;nchangedISi 0~'M5S % (M'+-76), ; 488 (M'+ ~6).
~0E) m~E52 (M~, 592 (M+--60~ B a s t a x a n ~ d. ~ = 0 2 9 ~iO 2, 15% MeOH-~OA~ Bastaxanth~ b ~). ~ = 0 A 3 (SiO2, 10% MeOH-~OAc), Vis insepam~e ~om authentic ~ Vis Xr~,xnm 47~ 49~ X ~ nm ~ c ~ o n ~ as ~ r 2. Bastaxanth~ f ~) or g ~). ~ < 0 2 (SiO2, 15% MeOHBastaxanth~ c ~). ~=034 ~iO2, 10% MeOH-~OAc), ~OA~, insufficient for fu~her studies. i n s e p a ~ e from an authentic sample; Us ~ , nm (MeOH) 470, 490; MS ~0E) m ~ 59~ (M'~, 576 (M'+-18), 488 (D)Lbasta (M'+-106), 470 (M'+ 1 0 6 ~ ; ~H NMR ~00 MHz, CD~OD), Bastaxanth~ b ~). c ~), d ~) and e N) were o~ained as 0~6s ( M e - I ~ L 138s and 121s (Me--16,17), 1A8s (Me--IE), reference compounds as pm~ou~y described [~ ~. 1~2s (Me--l~, 2~0s (Me-20~E,2EL 432s ~H2--19), 6~8d Bastaxanthin g ~) ~pmsemed a minor c o n ~ u e n ~ ~ - 7 ' L 6 3 6 ~ m (olefin~ H), Z36d ~ - E ) . ~ e p a ~ b ~ ~om 7 ex Sponge 1A. AceW~don provided 2-diacetate, ~ = 0 2 6 (SiO2, 5% MeOH-EOA~ of unchanged Vis X~,x; MS ~0E) m ~ 618 Acknowledgements--We thank Clive W i ~ n s o ~ formerly (M'+-60), 558 (M'+--60-6~; ~H NMR (100 MHz, CDzOD) $ RRIME Dee Wh~ for the collec~ons. ~ssel He~zbe~ was 1~4s ( M e - I E L 136s and 1~9s (Me-16,17), 1A8s (Me--IE~ supposed by a mseamh grant ~om the Norweg~n 192s (Me--18), 2~0s (Me--19,20,203, 2~3s (OAcL 423 (non- Resea~h Coun~l of S~ence and Human~es to Synn~ve ~WI~ CH2OA~, 6 3 - 6 ~ m (olefin~ HL 738d (H-EL ~aaemJensen. AI~I~ oxida~on with p - c h ~ n i l of 2 prodded ~ e l~al, ~ = 0 2 2 ~5% MeOH-~OA~; Us ~ , , nm (MeOH) 49~ References Reduction of 2 w~h NaBH4 in MeOH gave the tetroL 1. RamdahL ~ Ka~auska~ R, Be~quist, R and Liaaeni n s e p a ~ e by TLC ~iO2, 15% MeOH-~OAc), from an Jensen, S~(19~)Biochem. Sys~EcoLg,~l. authentic sam~e ex L bas~; Vis ~ nm (MeOH) 33~ H2~, 2. He~zbe~, S~ Ramda~, T., Johanse~ J. E. and Liaaen443, 472. Jensen, S. ~983) Ac~ Chem. Scand. B3Z 267 Bastaxanth~ d ~). ~ = 0 A 6 ~0% MeOH-~oAc), morn 3. He~zbe~, S, Johansen, J. E, Ramda~, G~ Bo~h, G. and polar than 2 (R~=0.51) and ~sepaB~e from 3 ex L bas~; Uaaen-Jensen, S. ~98~ Biochem. SysL Ecol. ~, 267 Vis X=,, nm (MeOH) 47~ H90); MS ~00~, m ~ 596 (M'+), 581 4. Ramdahl, • and ~aaen~ense~ S. ~980) Ac~ Chem. (M'+ 15),490 (M'~ 106). Scan~ B34, 773. Bastaxan~ g (~. ~ = 0 3 9 ~iO~, 20% MeOHEtOAc), 5. He~zbe~, S. and ~aaemJense~ S. (198~ Ac~ Chem. ~ 0 3 8 ~iO2, 15% MeOH-~OA~ pm~nged deve~pment, Scan~ B39, 629. in cochmm~og~phy ~ w~h authenSc ba~axanthin f ~) 6. He~zbe~, S, Be~e~ H. and UaaemJense~ S. ~98~ Ac~ with ~ = 0 . ~ ; Vis X=a~ nm (MeOH) 465, sligh~y bathoChem. Scan~B39, 725. chmm~al~ s h ~ e ~ b ~ same s p e ~ l shape as 2; MS ~0~) 7 ~Auria. M. V., R ~ R. and M ~ L ~98~ ~trahedron nomcon~u~v~ Le~ 2 ~ 18~. Ac~n prodded 7-A~ ~=0.74 ~iO~, 20% 8. L~aen-Jensen, S, R e n ~ m , B~ Ramdahl, ~ Hal~nswe~ MeOH-~OA~ in d~ect comparison wkh 7 (~=03~. 7-Ac M. and Be~quist, R R. (1982) Biochem. SysL EcoL 10, 162. was pa~y conve~ed ~ 7 upon a~a~ne h y d m ~ 9. Matsun~ ~ (1985) PureAppL Chem. 57, 659. NaBH4-reduction in EtOH gave reduced 7; ~=031 ~iO2, 10. Bergquist, RR.~980) N . Z ~ Z o o l . ~ 4 4 3 .