US2003055257A1PendingUtilityA1

Water-soluble rhodamine dye conjugates

Assignee: APPLERA CORPPriority: Nov 3, 1999Filed: Oct 24, 2001Published: Mar 20, 2003
Est. expiryNov 3, 2019(expired)· nominal 20-yr term from priority
G01N 2458/00C07H 21/00C09B 11/24C07D 311/80G01N 33/582C07D 491/04C07D 491/06Y10S436/80C07H 19/207
48
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Claims

Abstract

The present invention provides novel, water-soluble, red-emitting fluorescent rhodamine dyes and red-emitting fluorescent energy-transfer dye pairs, as well as labeled conjugates comprising the same and methods for their use. The dyes, energy-transfer dye pairs and labeled conjugates are useful in a variety of aqueous-based applications, particularly in assays involving staining of cells, protein binding, and/or analysis of nucleic acids, such as hybridization assays and nucleic acid sequencing.

Claims

exact text as granted — not AI-modified
We claim:  
     
         1 . A rhodamine dye or a salt thereof, comprising a rhodamine-type parent xanthene ring having attached to the xanthene C9 carbon a phenyl group that is further substituted with an ortho carboxy or ortho sulfonate group or a salt thereof, one to three substituted or unsubstituted aminopyridimnum groups and a substituted or unsubstituted alkylthio, arylthio or heteroarylthio group, said rhodamine dye optionally including one or more linking moieties.  
     
     
         2 . The rhodamine dye of  claim 1  which comprises the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 n is 1, 2, or 3;  
 Y is a rhodamine-type parent xanthene ring attached to the illustrated phenyl group at the xanthene C9 carbon;  
 each R is independently selected from the group consisting of (C 1 -C 6 ) alkyl and heteroalkl, (C 1 -C 20 ) aryl and heteroaryl (C 6 -C 26 ) arylalkyl and heteroalkyl, (C 5 -C 20 ) arylaryl and heteroaryl-heteroaryl, or when taken together, R is (C 4 -C 10 ) alkyldiyl, (C 4 -C 10 ) alkyleno, heteroalkyldiyl and heteroalkyleno;  
 S is sulfuir;  
 Z is (C 1 -C 12 ) alkyl, (C 1 -C 12 ) alkyl substituted with one or more of the same or different W 1  groups, (C 5 -C 20 ) aryl and heteroaryl, and (C 5 -C 20 ) aryl and heteroaryl substituted with one or more of the same or different W 2  groups;  
 W 1  is selected from the group consisting of —X, —R, ═O, —OR, —SR, ═S, —NRR, ═NR, —CX 3 , —CN, —OCN, —SCN, —NCO, —NCS, —NO, —NO 2 , ═N 2 , —N 3 , —S(O) 2 O − , —S(O) 2 OH, —S(O) 2 R, —C(O)R, —C(O)X, —C(S)R, —C(S)X, —C(O)OR, —C(O)O − , —C(S)OR, —C(O)SR, —C(S)SR, —C(O)NRR, —C(S)NRR and —C(NR)NRR;  
 W 2  is selected from the group consisting of —R, —OR, —SR, —NRR, —S(O) 2 O − , —S(O) 2 OH, —S(O) 2 R, —C(O)R, —C(O)X, —C(S)R, —C(S)X, —C(O)OR, —C(O)OF, —C(S)OR, —C(O)SR, —C(S)SR, —C(O)NRR, —C(S)NRR and —C(NR)NRR;  
 each X is independently a halogen; and  
 Y or Z is optionally substituted with L where L is a bond or a linker.  
 
       
     
     
         3 . The rhodamine dye of  claim 2  in which L is selected from a hydrophobic moiety, a charged group, a member of a pair of specific binding molecules, a photo-activatable group and a reactive functional group.  
     
     
         4 . The rhodamine dye of  claim 2  where Z has the form Z 1 —L—R X , or a salt thereof, wherein: 
 Z 1  is (C 1 -C 12 ) alkyldiyl, (C 1 -C 12 ) alkyldiyl independently substituted with one or more of the same or different W 1  groups, or  
 (C 5 -C 14 ) aryldiyl, and aryldiyl, heteroaryldiyl and heteroaryldiyl independently substituted with one or more of the same or different W 2  groups;  
 L is a bond or a linker; and  
 R X  is a reactive functional group.  
 
     
     
         5 . The rhodamine dye of  claim 4  in which Y is selected from:  
       
         
           
           
               
               
           
         
         and a salt thereof, wherein: 
 R 1 and le When taken alone, are independently hydrogen or (C 1 -C 6 ) alkyl;  
 R 3 and R 3′  when taken alone, are independently selected from the group consisting of hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 14 ) aryl and arylaryl, or when taken together is (C 4 -C 6 ) alkyidyl or alkyleno, or when individually taken together with R 2  or R 4  is (C 2 -C 6 ) alkyldiyl or (C 2 -C 6 ) alkyleno;  
 R 4 , when taken alone, is selected from the group consisting of hydrogen and (C 1 -C 6 ) alkyl, or when taken together with R 3  or R 3′  is (C 2 -C 6 ) alkyldiyl or alkyleno;  
 R 5 , when taken alone, is selected from the group consisting of hydrogen and (C 1 -C 6 ) alkyl, or when taken together with R 6  or R 6′  is (C 2 -C 6 ) alkyldiyl or alkyleno;  
 R 6  and R 6′  when taken alone, are selected from the group consisting of hydrogen, (C 1 -C 6 ) alkyl, (C 5 -C 14 ) aryl and arylaryl, or when taken together are (C 4 -C 6 ) alkyldiyl or alkyleno, or when individually taken together with R 5  or R 7  is (C 2 -C 6 ) alkyldiyl or alkyleno;  
 R 7 , when taken alone, is selected from the group consisting of hydrogen and (C 1 -C 6 ) alkyl, or when taken together with le or R 6  is (C 2 -C 6 ) alkyldiyl or alkyleno;  
 R 8 , when taken alone, is selected from the group consisting of hydrogen and (C 1 -C 6 ) alkyl;  
 R 9  indicates the point of attachment to the ortho-carboxyphenyl bottom ring; and  
 R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20  and R 21  are each independently selected from the group consisting of hydrogen and (C 1 -C 6 ) alkyl, or  
 when R 10 , R 11 , R 12  and R 13  taken together are (C 5 -C 14 ) aryleno or (C 5 -C 14 ) aryleno substituted with one or more of the same or different (C 1 -C 6 ) alkyl, or  
 when R 18 , R 19 , R 20  and R 21  taken together are (C 5 -C 14 ) aryleno or aryleno substituted with one or more of the same or different (C 1 -C 6 ) alkyl.  
 
       
     
     
         6 . The rhodamine dye of  claim 5  wherein R 2 , when taken together with R 3  or R 3′  is (C 2 -C 6 ) alkyldiyl or alkyleno.  
     
     
         7 . The rhodamine dye of  claim 6  wherein: 
 alkyl is methanyl, ethanyl or propanyl;  
 aryl is phenyl or naphthyl;  
 arylaryl is biphenyl;  
 alkyldiyl or alkyleno bridges formed by taking R 2  together with R 3  or R 3′ , R 7  together with R 6  or R 6′ , or R 4  together with and R 3  or R 3′ , are ethano, propano, 1,1-dimethylethano, 1,1-dimethylpropano and 1,1,3-trimethylpropano;  
 aryleno bridges formed by taking R 1  together with R 2  are benzo or naphtho;  
 alkyldiyl or alkyleno bridge formed by taking R 3  together with R 3′ , or R 6  together with R 6 , is butano;  
 alkyldiyl or alkyleno bridges formed by taking R 5  together with R 6  or R 6′  are ethano, propano, 1,1-dimethylethano, 1,1-dimethylpropano and 1,1,3-trimethylpropano; and  
 aryleno bridge formed by taking R 10 , R 11 , R 12  and R 13  together, or R 18 , R 19 , R 20  and R 21  together, is benzo.  
 
     
     
         8 . The rhodamine dye of  claim 6  in which L is a bond.  
     
     
         9 . The rhodamine dye of  claim 4  in which R X  is selected from the group consisting of carboxyl, carboxylate, ester and activated ester.  
     
     
         10 . The rhodamine dye of  claim 4  in which Z 1  is selected from the group consisting of (C 1 -C 12 ) alkyleno, (C 1 -C 12 ) alkano, (C 5 -C 10 ) aryldiyl and heteroaryldiyl, phenyldiyl, phena-1,4-diyl, naphthadiyl, naphtha-2,6-diyl, pyridindiyl and purindiyl.  
     
     
         11 . The rhodamine dye of  claim 4  in which Y is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
     
     
         12 . The rhodamine dye of  claim 4  in which L is a bond.  
     
     
         13 . The rhodamine dye of  claim 4  in which R X  is selected from the group consisting of carboxyl, carboxylate, ester and activated ester.  
     
     
         14 . The rhodamine dye of  claim 4  in which Z 1  is selected from the group consisting of (C 1 -C 12 ) alkyleno, (C 1 -C 12 ) alkano, (C 5 -C 10 ) aryldiyl and heteroarylidyl, phenylidyl, phena-14-diyl, naphthadiyl, naphtha-2,6-diyl, pyridindiyl and purindiyl.  
     
     
         15 . The rhodamine dye of  claim 4  which comprises the structure:  
       
         
           
           
               
               
           
         
       
       or a salt thereof.  
     
     
         16 . The rhodamine dye of  claim 15  in which Y is selected from the group consisting of Y-1, Y-2, Y-3 and Y-4.  
     
     
         17 . The rhodamine dye of  claim 15  in which Y is selected from the group consisting of Y-20a, Y-21a, Y-22a, Y-23a, Y-24a, Y-25a, Y-31a, Y-34a, Y-35a, Y-36a, Y-39a, Y-41a, Y-42a, Y-43a, Y-44a, Y-45a and Y-46a.  
     
     
         18 . The rhodamine dye of  claim 2  which has the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 Y 1  is a rhodamine-type parent xanthene ring attach ed to the illustrated phenyl group at the xanthene C9 carbon;  
 L is a bond or linker attached to a xanthene nitrogen atom or a xanthene C4 carbon;  
 n is 1, 2, or 3; and  
 R X  is a reactive functional group.  
 
       
     
     
         19 . The rhodamine dye of  claim 18  in which Y 1  is selected from the group consisting of:  
       
         
           
           
               
               
           
         
         wherein the dashed line at the nitrogen or C4 atom indicates the point of attachment of substituent L.  
       
     
     
         20 . The rhodamine dye of  claim 19  wherein: 
 alkyl is methanyl, ethanyl or propanyl;  
 aryl is phenyl or naphthyl;  
 arylaryl is biphenyl;  
 alkyldiyl or alkyleno bridges formed by taking R 2  together with R 3 , R 4  together with R 3′ , R 5  together with R 6 , or R 7  together with R 6′ , are ethano, propano, 1,1-dimethylethano, 1,1-dimethylpropano and 1,1,3-trimethylpropano;  
 aryleno bridges formed by taking R 10 , R 11 , R 12  and R 13  together or R 18 , R 19 , R 20  and R 21  together are benzo.  
 
     
     
         21 . The rhodamine dye of  claim 18  in which L is selected from the group consisting of (C 1 -C 6 ) alkyldiyl, (C 1 -C 6 ) alkano, (C 5 -C 20 ) aryldiyl, phenyldiyl, phena-1,4-diyl, naphthyldiyl, naphtha-2,6-diyl, naphtha-2,7-diyl, (C 6 -C 26 ) arylalkyldiyl —(CH) i -Φ- and —(CH) i -ψ-, where each i is independently an integer from 1 to 6, φ is (C 5 -C 20 ) aryldiyl, phenyldiyl or phena-1,4-diyl and ψ is naphthyldiyl, naphtha-2,6-diyl or naphtha-2,7-diyl.  
     
     
         22 . The rhodamine dye of  claim 18  in which R X  is selected from the group consisting of carboxyl, carboxylate, ester and activated ester.  
     
     
         23 . The rhodamine dye of  claim 18  in which Z is selected from the group consisting of (C 1 -C 12 ) alkyl, (C 1 -C 12 ) alkanyl, (C 5 -C 10 ) aryl and heteroaryl, phenyl, naphthyl, naphth-1-yl, naphth-2-yl, pyridyl and purinyl.  
     
     
         24 . The rhodamine dye of  claim 18  in which Y 1  is selected from the group consisting of:  
       
         
           
           
               
               
           
         
         wherein R 9  and the dash at the nitrogen or C4 atom indicates the point of attachment of L.  
       
     
     
         25 . The rhodamine dye of  claim 18  which has the structure:  
       
         
           
           
               
               
           
         
       
     
     
         26 . The rhodamine dye of  claim 25  in which Y 1  is selected from the group consisting of Y-1b, Y-2b, Y-3b, Y-4b, Y-1c, Y-2c, Y-3c and Y-4c.  
     
     
         27 . The rhodamine dye of  claim 25  in which Y 1  is selected from the group consisting of Y-20b, Y-20c, Y-21b, Y-21c, Y-22b, Y-22c, Y-23b, Y-23c, Y-24b, Y-24c, Y-25b, Y-25c, Y-31b, Y-31c, Y-34b, Y-34c, Y-35b, Y-35c, Y-36b, Y-36c, Y-3b, Y-39b, Y-39c, Y-41c, Y-42b, Y-43b, Y-43c, Y-46b and Y-46c.  
     
     
         28 . An energy-transfer dye pair comprising a donor dye linked to an acceptor dye, wherein the donor dye or the acceptor dye is a compound according to  claim 1  and either or both of said donor and acceptor dyes include an optional linking moiety.  
     
     
         29 . The dye pair of  claim 28  which has the structure:  
       
         
           
           
               
               
           
         
         or a salt thereof, wherein: 
 R 41  is a covalent linkage formed upon reaction between a nucleophile and an electrophile;  
 L″ is a bond or a linker;  
 n is 1,2, or 3; and  
 DD/AD is a donor dye or an acceptor dye which includes a linking moiety.  
 
       
     
     
         30 . The dye pair of  claim 29  in which Y is selected from the group consisting of Y-1, Y-2, Y-3, Y-4, Y-20a, Y-21a, Y-22a, Y-23a, Y-24a, Y-25a, Y-31 a, Y-34a, Y-35a, Y-36a, Y-39a, Y-41a, Y-42a, Y-43a, Y-44a, Y-45a and Y-46a.  
     
     
         31 . The dye pair of  claim 29  in which L is a bond.  
     
     
         32 . The dye pair of  claim 29  in which R 41  has the formula —C(O)NR 45 —, where R 45  is hydrogen or (C 1 -C 6 ) alkyl.  
     
     
         33 . The dye pair of  claim 29  in which Z 1  is selected from the group consisting of (C 1 -C 12 ) alkyleno, (C 1 -C 12 ) alkano, (C 5 -C 10 ) aryldiyl and heteroaryldiyl, phenyldiyl, phena-1,4-diyl, naphthadiyl, naphtha-2,6-diyl, pyridindiyl and purindiyl.  
     
     
         34 . The dye pair of  claim 29  in which L″ is —R 43 —Z 3 —C(O)—R 44 —R 45 —, wherein R 43  is (C 1 -C 6 ) alkyldiyl, preferably (C 1 -C 3 ) alkano, and is bonded to R 42 , where R 42  is O, S or NH; Z 3  is 5-6 membered cyclic alkenyldiyl and heteroalkenyldiyl, (C 1 -C14) aryldiyl and heteroaryldiyl; R 44  is O, S or NH; and R 45  is (C 1 -C 6 ) alkyldiyl, preferably (C 1 -C 3 ) alkano.  
     
     
         35 . The dye pair of  claim 29  in which DD/AD is a fluorescein dye in which the linking moiety is a reactive functional group and wherein L″ is attached to the fluorescein dye at the xanthene C4 carbon.  
     
     
         36 . The dye pair of  claim 29  which has the structure:  
       
         
           
           
               
               
           
         
         wherein, R 50  is a carboxyl, a salt, ester or activated ester thereof.  
       
     
     
         37 . The dye pair of  claim 36  in which Y is selected from the group consisting of Y-1, Y-2, Y-3, Y-4, Y-20a, Y-21a, Y-22a, Y-23a, Y-24a, Y-25a, Y-31a, Y-34a, Y-35a, Y-36a, Y-39a, Y-41 a, Y-42a, Y-43a, Y-44a, Y-45a and Y-46a.  
     
     
         38 . The dye pair of  claim 28  which has the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 R 41  is a covalent linkage formed upon reaction between a nucleophile and an electrophile;  
 L″ is a bond or a linker;  
 n is 1, 2, or 3; and  
 DD/AD is a donor dye or an acceptor dye which includes a linking moiety.  
 
       
     
     
         39 . The dye pair of  claim 38  in which Y 1  is selected from the group consisting of Y-1b, Y-2b, Y-3b, Y-4b, Y-1c, Y-2c, Y-3c, Y-4c, Y-20b, Y-20c, Y-21b, Y-21c, Y-22b, Y-22c, Y-23b, Y-23c, Y-24b, Y-24c, Y-25b, Y-25c, Y-31b, Y-31c, Y-34b, Y-34c, Y-35b, Y-35c, Y-36b, Y-36c, Y-37b, Y-39b, Y-39c, Y-41c, Y-42b, Y-43b, Y-43c, Y-46b and Y-46c.  
     
     
         40 . The dye pair of  claim 38  in which L is (C 1 -C 6 ) alkyldiyl or (C 1 -C 3 ) alkano.  
     
     
         41 . The dye pair of  claim 38  in which R 41  is an amide of the formula —C(O)NR 45 , where R 45  is hydrogen or (C 1 -C 6 ) alkyl.  
     
     
         42 . The dye pair of  claim 38  in which Z is selected from the group consisting of (C 1 -C 12 ) alkyl, (C 1 -C 12 ) alkanyl, (C 5 -C 10 ) aryl and heteroaryl, phenyl, naphthyl, naphth-1yl, naphth-2-yl, pyridyl and purinyl.  
     
     
         43 . The dye pair of  claim 38  in which L″ is —R 43 —Z 3 —C(O)—R 44 —R 45 —, wherein R 43  is (C 1 -C 6 ) alkydiyl, preferably (C 1 -C 3 ) alkano, and is bonded to R 42 , where R 42  is O, S or NH; Z 3  is 5-6 membered cyclic alkenyldiyl and heteroalkenyldiyl, (C 5 -C 14 ) aryldiyl and heteroaryldiyl; R 44  is O, S or NH; and R 45  is (C 1 -C 6 ) alkyldiyl, preferably (C 1 -C 3 ) alkano.  
     
     
         44 . The dye pair of  claim 38  in which DD/AD is a fluorescein dye in which the linking moiety is a reactive group R X  and wherein L″ is attached to the fluorescein dye at the xanthene C5 carbon.  
     
     
         45 . The dye pair of  claim 38  which has the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 Y 1  is selected from the group consisting of Y-20b, Y-20c, Y-21b, Y-21c, Y-22b, Y-22c, Y-23b, Y-23c, Y-24b, Y-24c, Y-25b, Y-25c, Y-31b, Y-31c, Y-34b, Y-34c, Y-35b, Y-35c, Y-36b, Y-36c, Y-37b, Y-39b, Y-39c, Y-41c, Y-42b, Y-43b, Y-43c, Y-46b and Y-46c; and  
 R 50  is a carboxyl, a salt, ester or activated ester thereof.  
 
       
     
     
         46 . The dye pair of  claim 45  in which Y 1  is selected from the group consisting of Y-1b, Y-2b, Y-3b, Y-4b, Y-1c, Y-2c, Y-3c, Y-4c, Y-20b, Y-20c, Y-21b, Y-21c, Y-22b, Y-22c, Y-23b, Y-23c, Y-24b, Y-24c, Y-25b, Y-25c, Y-31b, Y-31c, Y-34b, Y-34c, Y-35b, Y-35c, Y-36b, Y-36c, Y-37b, Y-39b, Y-39c, Y-41c, Y-42b, Y-43b, Y-43c, Y-46b and Y-46c.  
     
     
         47 . A labeled nucleoside/tide or nucleoside/tide analog comprising the rhodamine dye of  claim 2  where Z has the form Z 1 —L—R 46 —L′—NUC, wherein: 
 R 46  is a linkage formed by reaction between an electrophile and a nucleophile; and —L′—NUC taken together has the structure:  
                     
 wherein:  
 B is a nucleobase;  
 L′ is (C 1 -C 20 ) alkyldiyl and heteroalkyldiyl, (C 1 -C 20 ) alkyleno and heteroalkyleno, (C 2 -C 20 ) alkyno and heteroalkyno, or (C 2 -C 20 ) alkeno and heteroalkeno;  
 R 70  and R 71 , when taken alone, are each independently selected from the group consisting of hydrogen, hydroxyl and a moiety which blocks polymerase-mediated template-directed polymerization, or when taken together form a bond such that the illustrated sugar is 2′,3′-didehydroribose; and  
 R 72  is selected from the group consisting of hydroxyl, a phosphate ester having the formula  
                     
 where a is an integer from 0 to 2, and a phosphate ester analog, or a salt thereof.  
 
     
     
         48 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47  where Z has the form Z 1 —L—R 41 —L″—DD/AD—L 3 —R 46 —L′—NUC, or a salt thereof, wherein: 
 R 41  is a covalent linkage formed upon reaction between a nucleophile and an electrophile;  
 L″ is a bond or a linker;  
 DD/AD is a donor dye or an acceptor dye which includes a linking moiety; and.  
 L 3  is a bond or a linker.  
 
     
     
         49 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47  where Y has the form Y 1 —R 41 —L″—DD/AD—L 3 —R 46 —L′—NUC, or a salt thereof wherein: 
 Y 1  is Y-1, Y-2, Y-3, or Y-4;  
 R 41  is a covalent linkage formed upon reaction between a nucleophile and an electrophile;  
 L″ is a bond or a linker;  
 DD/AD is a donor dye or an acceptor dye which includes a linking moiety; and.  
 L 3  is a bond or a linker.  
 
     
     
         50 . A labeled nucleoside/tide or nucleoside/tide analog of  claim 47  where Y has the form Y 1 —R 41 —L″ 13  DD/AD and Z has the form Z 1 —L—R 46 —L′—NUC, or a salt thereof; wherein: 
 Y 1  is Y-1, Y-2, Y-3, or Y-4;  
 R 41  is a covalent linkage formed upon reaction between a nucleophile and an electrophile;  
 L″ is a bond or a linker;  
 DD/AD is a donor dye or an acceptor dye which includes a linking moiety; and  
 Z 1  is (C 1 -C 12 ) alkyldiyl, (C 1 -C 12 ) alkyldiyl independently substituted with one or more of the same or different W 1  groups, (C 5 -C 14 ) aryldiyl, and (C 5 -C 14 ) aryldiyl, heteroaryldiyl and heteroaryldiyl independently substituted with one or more of the same or different W 2  groups.  
 
     
     
         51 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47 ,  48 ,  49  or  50  which is enzymatically incorporatable.  
     
     
         52 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47 ,  48 ,  49  or  50  which is a terminator.  
     
     
         53 . The lableled nucleoside/tide or nucleoside/tide analog of  claim 47 ,  48 ,  49  or  50  which is enzymatically extendable.  
     
     
         54 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47  in which L′ is selected from the group consisting of: 
 propargyl, where the terminal sp carbon is covalently attached to nucleobase B and the terminal methylene (sp 3 ) carbon is covalently attached to F x ; and  
 —C≡C—CH 2 —O—CH 2 —CH 2 —NR 47 —R 48 —, where R 47  is hydrogen or (C 1 -C 6 ) alkyl and R 48  is —C(O)—(CH 2 ) r —, —C(O)—CHR 49 —, —C(O)—C≡C—CH 2 — or —C(O)-φ-(CH 2 ) r —, where each r is independently an integer from 1 to 5 and φ is C 6  aryldiyl orheteroaryldiyl and R 49  is hydrogen, (C 1 -C 6 ) alkyl or a side chain of an encoding or non-encoding amino acid, and where the terminal sp carbon is covalently attached to nucleobase B and the other terminal group is covalently attached to F x .  
 
     
     
         55 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 48  or  claim 49  in which L 3  is a bond, R 46  the formula —C(O)—NHR 51 , where R 51  is hydrogen or (C 1 -C 6 ) alkyl.  
     
     
         56 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47  in which nucleobase B is a purine, a 7-deazapurine, an 8-aza, 7-deazapurine, a pyrimidine, a normal nucleobase or a common analog of a normal nucleobase.  
     
     
         57 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47  or  claim 48  in which Y is selected from the group consisting of Y-1, Y-2, Y-3 and Y-4.  
     
     
         58 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 47  or  claim 48  in which Y is selected from the group consisting of Y-20a, Y-21a, Y-22a, Y-23a, Y-24a, Y-25a, Y-31a, Y-34a, Y-35a, Y-36a, Y-39a, Y-41a, Y-42a, Y-43a, Y-44a, Y-45a and Y-46a.  
     
     
         59 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 49  or  claim 50  in which Y 1  is selected from the group consisting of Y-1b, Y-2b, Y-3b, Y4b, Y-1c, Y-2c, Y-3c and Y-4c.  
     
     
         60 . The labeled nucleoside/tide or nucleoside/tide analog of  claim 49  or  claim 50  in which Y 1  is selected from the group consisting of Y-20b, Y-20c, Y-21b, Y-21c, Y-22b, Y-22c, Y-23b, Y-23c, Y-24b, Y-24c, Y-25b, Y-25c, Y-31b, Y-31c, Y-34b, Y-34c, Y-35b, Y-35c, Y-36b, Y-36c, Y-37b, Y-39b, Y-39c, Y-41c, Y-42b, Y-43b, Y-46b and Y-46c.  
     
     
         61 . A polynucleotide labeled with a rhodamine dye according to  claim 1  or an energy-transfer dye pair according to  claim 28 .  
     
     
         62 . A method of generating a labeled primer extension product, comprising the step of enzymatically extending a primer-target hybrid in the presence of a mixture of enzymatically-extendable nucleotides capable of supporting continuous primer extension and a terminator, wherein said primer or said terminator is labeled with a rhodamine dye according to  claim 1  or an energy-transfer dye pair according to  claim 28 .  
     
     
         63 . The method of  claim 62  in which the terminator has the structure:  
       
         
           
           
               
               
           
         
         wherein R 70  and R 71 , when taken alone, are each independently selected from the group consisting of hydrogen, halide, and any moiety which blocks polymerase-mediated template-directed polymerization.  
       
     
     
         64 . The method of  claim 62  in which the terminator is a mixture of four different terminators, one which terminates at a template A, one which terminates at a template G, one which terminates at a template C and one which terminates at a template T or U.  
     
     
         65 . The method of  claim 62  in which each of the four different terminators is labeled ith a different, spectrally-resolvable fluorophore.  
     
     
         66 . A labelled rhodamine dye-polypeptide conjugate comprising the rhodamine dye of  claim 1  and a polypeptide, wherein the polypeptide is selected from the group consisting of a peptide, a protein, and an antibody.  
     
     
         67 . A method of detecting a rhodamine dye-antibody conjugate, in which said conjugate is a rhodamine dye-antibody conjugate according to  claim 66 , comprising the steps of: 
 (a) binding the conjugate to a peptide or protein, and    (b) detecting the rhodamine dye-antibody conjugate bound to the peptide or protein.    
     
     
         68 . The method of  claim 67  in which the conjugate is bound to the peptide or protein in the presence of a second antibody specific for binding said peptide or protein.  
     
     
         69 . The method of  claim 68  in which the second antibody is bound to a solid bead or particle.

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