Chemically reactive unsymmetrical cyanine dyes and their conjugates

A compound of the formula ##STR44## wherein each R.sup.1 is independently H;

• or an alkyl group having from 1-6 carbons;
• an alkoxy group having from 1-6 carbons;
• or a trifluoromethyl;
• or a halogen;
• or -L-S.sub.c ;
• R.sup.2 is an alkyl group having 1-6 carbons;
• or -L-S.sub.c ;
• X is O, S, Se or NR.sup.15, where R.sup.15 is H or an alkyl group having 1-6 carbons;
• or X is CR.sup.16 R.sup.17 where R.sup.16 and R.sup.17, which may be the same or different, are independently alkyl groups having 1-6 carbons;
• n=0, 1 or 2;
• .psi..sup.- is a compatible counterion;
• Y is --CR.sup.3 .dbd.CR.sup.4 --;
• p and m=0 or 1, such that p+m=1;
• R.sup.5 is an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or R.sup.5 is a cyclic substituent that is an aryl or heteroaryl;
• or a cycloalkyl;
• or R.sup.5 is a TAIL;
• or R.sup.5 is -L-S.sub.c ;
• R.sup.4 is H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or a halogen;
• or an aryl or heteroaryl;
• or a cycloalkyl having 3-10 carbons;
• or --OR.sup.8, --SR.sup.8, --(NR.sup.8 R.sup.9);
• or a TAIL;
• or -L-S.sub.c ;
• where R.sup.8 and R.sup.9, which can be the same or different, are independently alkyl groups having 1-6 carbons;
• or 1-2 alicyclic or aromatic rings;
• or R.sup.8 and R.sup.9 taken in combination are --(CH.sub.2).sub.2 --V--(CH.sub.2).sub.2 -- where V is a single bond, --O--, --CH.sub.2 --, or --NR.sup.10 --, where R.sup.10 is H or an alkyl having 1-6 carbons;
• R.sup.3, R.sup.6 and R.sup.7 are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or -L-S.sub.c ;
• or R.sup.6 and R.sup.7 form a fused aromatic ring such that said compound has the formula ##STR45## wherein R.sup.11, R.sup.12, R.sup.13, and R.sup.14, which may be the same or different, are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or --OR.sup.8, --SR.sup.8, or --(NR.sup.8 R.sup.9);
• or a TAIL;
• or -L-S.sub.c ;
• L is a single covalent bond, or L is a covalent linkage that is linear or branched, cyclic or heterocyclic, saturated or unsaturated, having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• S.sub.c is a conjugated substance;
• TAIL is a heteroatom-containing moiety having the formula LINK-SPACER-CAP;
• wherein
• LINK is a single covalent bond, --O--, --S--, or --NR.sup.20 --;
• where R.sup.20 is H, a linear or branched alkyl having 1-8 carbons, or R.sup.20 is -SPACER'-CAP';
• SPACER and SPACER', which may be the same or different, are covalent linkages, linear or branched, cyclic or heterocyclic, saturated or unsaturated, each having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• CAP and CAP', which may be the same or different, are --O--R.sup.21, --S--R.sup.21, --NR.sup.21 R.sup.22, or --N.sup.+ R.sup.21 R.sup.22 R.sup.23 .psi..sup.- ;
• wherein
• R.sup.21, R.sup.22, and R.sup.23 are independently H, or a linear or branched alkyl or cycloalkyl having 1-8 carbons, optionally further substituted by hydroxy, alkoxy having 1-8 carbons, carboxyalkyl having 1-8 carbons, or phenyl, where phenyl is optionally further substituted by halogen, hydroxy, alkoxy having 1-8 carbons, aminoalkyl having 1-8 carbons, or carboxyalkyl having 1-8 carbons;
• or, one or more of R.sup.21, R.sup.22 and R.sup.23, taken in combination with SPACER or SPACER' or R.sup.20 forms a 5- or 6-membered aromatic, heteroaromatic, alicyclic or heteroalicyclic ring, the heteroatoms selected from O, N or S;
• where .psi..sup.- is a compatible counterion;
• or
• CAP and CAP' are independently ##STR46## where R.sup.21, R.sup.22, R.sup.23, and .psi..sup.- are as defined previously;
• such that at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is -L-S.sub.c ;
• and where more than one of R.sup.1 R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is -L-S.sub.c, each -L-S.sub.c is optionally the same or different;
• provided that when R.sup.5 is -L-S.sub.c and m=1, R.sup.4 is not hydrogen.

A complex comprising a nucleic acid polymer non-covalently bound to a dye of the formula ##STR47## wherein each R.sup.1 is independently H;

• or an alkyl group having from 1-6 carbons;
• an alkoxy group having from 1-6 carbons;
• or a trifluoromethyl;
• or a halogen;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• R.sup.2 is an alkyl group having 1-6 carbons;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• X is O, S, Se or NR.sup.15, where R.sup.15 is H or an alkyl group having 1-6 carbons;
• or X is CR.sup.16 R.sup.17 where R.sup.16 and R.sup.17, which may be the same or different, are independently alkyl groups having 1-6 carbons;
• n=0, 1 or 2;
• .psi..sup.- is a compatible counterion;
• Y is --CR.sup.3 .dbd.CR.sup.4 --;
• p and m=0 or 1, such that p+m=1;
• R.sup.5 is an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or R.sup.5 is a cyclic substituent that is an aryl or heteroaryl;
• or a cycloalkyl;
• or R.sup.5 is a TAIL;
• or R.sup.5 is -L-R.sub.x ;
• or R.sup.5 is -L-S.sub.c ;
• R.sup.4 is H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or a halogen;
• or an aryl or heteroaryl;
• or a cycloalkyl having 3-10 carbons;
• or --OR.sup.8, --SR.sup.8, --(NR.sup.8 R.sup.9);
• or a TAIL;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• where R.sup.8 and R.sup.9, which can be the same or different, are independently alkyl groups having 1-6 carbons;
• or 1-2 alicyclic or aromatic rings;
• or R.sup.8 and R.sup.9 taken in combination are --(CH.sub.2).sub.2 --V--(CH.sub.2).sub.2 -- where V is a single bond, --O--, --CH.sub.2 --, or --NR.sup.10 --, where R.sup.10 is H or an alkyl having 1-6 carbons;
• R.sup.3, R.sup.6 and R.sup.7 are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• or R.sup.6 and R.sup.7 form a fused aromatic ring such that said compound has the formula ##STR48## wherein R.sup.11, R.sup.12, R.sup.13, and R.sup.14, which may be the same or different, are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or --OR.sup.8, --SR.sup.8, or --(NR.sup.8 R.sup.9);
• or a TAIL;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• each L is a single covalent bond, or L is a covalent linkage that is linear or branched, cyclic or heterocyclic, saturated or unsaturated, having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• R.sub.x is a reactive group;
• S.sub.c is a conjugated substance;
• TAIL is a heteroatom-containing moiety having the formula LINK-SPACER-CAP;
• wherein
• LINK is a single covalent bond, --O--, --S--, or --NR.sup.20 --;
• where R.sup.20 is H, a linear or branched alkyl having 1-8 carbons, or R.sup.20 is -SPACER'-CAP';
• SPACER and SPACER', which may be the same or different, are covalent linkages, linear or branched, cyclic or heterocyclic, saturated or unsaturated, each having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• CAP and CAP', which may be the same or different, are --O--R.sup.21, --S--R.sup.21, --NR.sup.21 R.sup.22, or --N.sup.+ R.sup.21 R.sup.22 R.sup.23 .psi..sup.- ;
• wherein
• R.sup.21, R.sup.22, and R.sup.23 are independently H, or a linear or branched alkyl or cycloalkyl having 1-8 carbons, optionally further substituted by hydroxy, alkoxy having 1-8 carbons, carboxyalkyl having 1-8 carbons, or phenyl, where phenyl is optionally further substituted by halogen, hydroxy, alkoxy having 1-8 carbons, aminoalkyl having 1-8 carbons, or carboxyalkyl having 1-8 carbons;
• or, one or more of R.sup.21, R.sup.22 and R.sup.23, taken in combination with SPACER or SPACER' or R.sup.20 forms a 5- or 6-membered aromatic, heteroaromatic, alicyclic or heteroalicyclic ring, the heteroatoms selected from O, N or S;
• where .psi..sup.- is a compatible counterion;
• or
• CAP and CAP' are independently ##STR49## ;
• where R.sup.21, R.sup.22, R.sup.23 , and .psi..sup.- are as defined previously;
• such that at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is -L-R.sub.x or -L-S.sub.c ;
• and where more than one of R.sup.1 R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is -L-R.sub.x or -L-S.sub.c, each -L-R.sub.x and -L-S.sub.c is optionally the same or different;
• provided that when R.sup.5 is -L-R.sub.x or -L-S.sub.c and m=1, R.sup.4 is not hydrogen.

A method of forming a nucleic acid complex, comprising

• a) combining a sample that contains or is thought to contain a nucleic acid, with a mixture containing a compound of the formula ##STR50## wherein each R.sup.1 is independently H;
• or an alkyl group having from 1-6 carbons;
• an alkoxy group having from 1-6 carbons;
• or a trifluoromethyl;
• or a halogen;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• R.sup.2 is an alkyl group having 1-6 carbons;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• X is O, S, Se or NR.sup.15, where R.sup.15 is H or an alkyl group having 1-6 carbons;
• or X is CR.sup.16 R.sup.17 where R.sup.16 and R.sup.17, which may be the same or different, are independently alkyl groups having 1-6 carbons;
• n=0, 1 or 2;
• .psi..sup.- is a compatible counterion;
• Y is --CR.sup.3 .dbd.CR.sup.4 --;
• p and m=0 or 1, such that p+n=1;
• R.sup.5 is an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or R.sup.5 is a cyclic substituent that is an aryl or heteroaryl;
• or a cycloalkyl;
• or R.sup.5 is a TAIL;
• or R.sup.5 is -L-R.sub.x ;
• or R.sup.5 is -L-S.sub.c ;
• R.sup.4 is H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or a halogen;
• or an aryl or heteroaryl;
• or a cycloalkyl having 3-10 carbons;
• or --OR.sup.8, --SR.sup.8, --(NR.sup.8 R.sup.9);
• or a TAIL;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• where R.sup.8 and R.sup.9, which can be the same or different, are independently alkyl groups having 1-6 carbons;
• or 1-2 alicyclic or aromatic rings;
• or R.sup.8 and R.sup.9 taken in combination are --(CH.sub.2).sub.2 --V--(CH.sub.2).sub.2 -- where V is a single bond, --O--, --CH.sub.2 --, or --NR.sup.10 --, where R.sup.10 is H or an alkyl having 1-6 carbons;
• R.sup.3, R.sup.6 and R.sup.7 are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• or R.sup.6 and R.sup.7 form a fused aromatic ring such that said compound has the formula ##STR51## wherein R.sup.11, R.sup.12, R.sup.13, and R.sup.14, which may be the same or different, are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or --OR.sup.8, --SR.sup.8, or --(NR.sup.8 R.sup.9);
• or a TAIL;
• or -L-R.sub.x ;
• or -L-S.sub.c ;
• each L is a single covalent bond, or L is a covalent linkage that is linear or branched, cyclic or heterocyclic, saturated or unsaturated, having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• R.sub.x is a reactive group;
• S.sub.c is a conjugated substance;
• TAIL is a heteroatom-containing moiety having the formula LINK-SPACER-CAP;
• wherein
• LINK is a single covalent bond, --O--, --S--, or --NR.sup.20 --;
• where R.sup.20 is H, a linear or branched alkyl having 1-8 carbons, or R.sup.20 is -SPACER'-CAP';
• SPACER and SPACER', which may be the same or different, are covalent linkages, linear or branched, cyclic or heterocyclic, saturated or unsaturated, each having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• CAP and CAP', which may be the same or different, are --O--R.sup.21, --S--R.sup.21, --NR.sup.21 R.sup.22, or --N.sup.+ R.sup.21 R.sup.22 R.sup.23 .psi..sup.- ;
• wherein
• R.sup.21, R.sup.22, and R.sup.23 are independently H, or a linear or branched alkyl or cycloalkyl having 1-8 carbons, optionally further substituted by hydroxy, alkoxy having 1-8 carbons, carboxyalkyl having 1-8 carbons, or phenyl, where phenyl is optionally further substituted by halogen, hydroxy, alkoxy having 1-8 carbons, aminoalkyl having 1-8 carbons, or carboxyalkyl having 1-8 carbons;
• or, one or more of R.sup.21, R.sup.22 and R.sup.23, taken in combination with SPACER or SPACER' or R.sup.20 forms a 5- or 6-membered aromatic, heteroaromatic, alicyclic or heteroalicyclic ring, the heteroatoms selected from O, N or S;
• where .psi..sup.- is a compatible counterion;
• or
• CAP and CAP' are independently ##STR52## ;
• where R.sup.21, R.sup.22, R.sup.23, and .psi..sup.- are as defined previously;
• such that at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is -L-R.sub.x or -L-S.sub.c ;
• and where more than one of R.sup.1 R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is -L-R.sub.x or -L-S.sub.c, each -L-R.sub.x and -L-S.sub.c is optionally the same or different;
• provided that when R.sup.5 is -L-R.sub.x or -L-S.sub.c and m=1, R.sup.4 is not hydrogen;
• and
• b) incubating the sample and mixture for a time sufficient for the compound to associate non-covalently with the nucleic acid in the sample to form one or more nucleic acid complexes.

A compound of the formula ##STR53## wherein X is O or S;

• R.sup.2 is an alkyl group having 1-6 carbons;
• n=0, 1 or2;
• .psi..sup.- is a compatible counterion;
• R.sup.4 is an aryl or heteroaryl that is optionally substituted by halogen, alkyl, perfluoroalkyl, amino, alkylamino, dialkylamino, alkoxy or carboxyalkyl, each alkyl group having 1-6 carbons;
• or is substituted by TAIL;
• or is substituted by -L-R.sub.x ;
• R.sup.5 is an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• an aryl or heteroaryl;
• or R.sup.5 is a TAIL;
• or R.sup.5 is -L-R.sub.x ;
• R.sup.3, R.sup.6 and R.sup.7 are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or R.sup.6 and R.sup.7 form a fused aromatic ring such that said compound has the formula ##STR54## wherein R.sup.11, R.sup.12, R.sup.13, and R.sup.14, which may be the same or different, are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or an alkoxy having 1-6 carbons;
• or --OR.sup.8, --SR.sup.8, or --(NR.sup.8 R.sup.9) where R.sup.8 and R.sup.9, which can be the same or different, are independently alkyl groups having 1-6 carbons;
• or 1-2 alicyclic or aromatic rings;
• or R.sup.8 and R.sup.9 taken in combination are --(CH.sub.2).sub.2 --V--(CH.sub.2).sub.2 -- where V is a single bond, --O--, --CH.sub.2 --, or --NR.sup.10 --, where R.sup.10 is H or an alkyl having 1-6 carbons;
• or a TAIL;
• L is a single covalent bond, or L is a covalent linkage that is linear or branched, cyclic or heterocyclic, saturated or unsaturated, having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• R.sub.x is a reactive group;
• TAIL is a heteroatom-containing moiety having the formula LINK-SPACER-CAP;
• wherein
• LINK is a single covalent bond, --O--, --S--, or --NR.sup.20 --;
• where R.sup.20 is H, a linear or branched alkyl having 1-8 carbons, or R.sup.20 is -SPACER'-CAP';
• SPACER and SPACER', which may be the same or different, are covalent linkages, linear or branched, cyclic or heterocyclic, saturated or unsaturated, each having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• CAP and CAP', which may be the same or different, are --O--R.sup.21, --S--R.sup.21, --NR.sup.21 R.sup.22, or --N.sup.+ R.sup.21 R.sup.22 R.sup.23 .psi..sup.- ;
• wherein
• R.sup.21, R.sup.22, and R.sup.23 are independently H, or a linear or branched alkyl or cycloalkyl having 1-8 carbons, optionally further substituted by hydroxy, alkoxy having 1-8 carbons, carboxyalkyl having 1-8 carbons, or phenyl, where phenyl is optionally further substituted by halogen, hydroxy, alkoxy having 1-8 carbons, aminoalkyl having 1-8 carbons, or carboxyalkyl having 1-8 carbons;
• or, one or more of R.sup.21, R.sup.22 and R.sup.23, taken in combination with SPACER or SPACER' or R.sup.20 forms a 5- or 6-membered aromatic, heteroaromatic, alicyclic or heteroalicyclic ring, the heteroatoms selected from O, N, S;
• where .psi..sup.- is a compatible counterion;
• or
• CAP and CAP' are independently ##STR55## where R.sup.21, R.sup.22, R.sup.23, and .psi..sup.- are as defined previously.

A compound of the formula ##STR56## or of the formula ##STR57## wherein each R.sup.1 is independently H;

• or an alkyl group having from 1-6 carbons;
• an alkoxy group having from 1-6 carbons;
• or a trifluoromethyl;
• or a halogen;
• or -L-R.sub.x ;
• R.sup.2 is an alkyl group having 1-6 carbons;
• or -L-R.sub.x ;
• X is O, S, Se or NR.sup.15, where R.sup.15 is H or an alkyl group having 1-6 carbons;
• or X is CR.sup.16 R.sup.17 where R.sup.16 and R.sup.17, which may be the same or different, are independently alkyl groups having 1-6 carbons;
• n=0, 1 or 2;
• R.sup.5 is an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or R.sup.5 is a cyclic substituent that is an aryl or heteroaryl;
• or a cycloalkyl;
• or R.sup.5 is a TAIL;
• or R.sup.5 is -L-R.sub.x ;
• R.sup.4 is NR.sup.19 ;
• where R.sup.19 is an alkyl group having 1-6 carbons;
• or an alicyclic or aromatic ring;
• or R.sup.19 is -SPACER-CAP;
• or R.sup.19 is -L-R.sub.x ;
• R.sup.3, R.sup.6 and R.sup.7 are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or -L-R.sub.x ;
• or R.sup.6 and R.sup.7 form a fused aromatic ring such that said compound has the formula ##STR58## or the formula ##STR59## wherein R.sup.11, R.sup.12, R.sup.13, and R.sup.14, which may be the same or different, are independently H;
• or an alkyl that is saturated or unsaturated, linear or branched, having 1-6 carbons;
• or --OR.sup.8, --SR.sup.8, or --(NR.sup.8 R.sup.9), where R.sup.8 and R.sup.9, which can be the same or different, are independently alkyl groups having 1-6 carbons;
• or 1-2 alicyclic or aromatic rings;
• or R.sup.8 and R.sup.9 taken in combination are --(CH.sub.2).sub.2 --V--(CH.sub.2).sub.2 -- where V is a single bond, --O--, --CH.sub.2 --, or --NR.sup.10 --, where R.sup.10 is H or an alkyl having 1-6 carbons;
• or a TAIL;
• or -L-R.sub.x ;
• L is a single covalent bond, or L is a covalent linkage that is linear or branched, cyclic or heterocyclic, saturated or unsaturated, having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• R.sub.x is a reactive group;
• TAIL is a heteroatom-containing moiety having the formula LINK-SPACER-CAP;
• wherein
• LINK is a single covalent bond, --O--, --S--, or --NR.sup.20 --;
• where R.sup.20 is H, a linear or branched alkyl having 1-8 carbons, or R.sup.20 is -SPACER'-CAP';
• SPACER and SPACER', which may be the same or different, are covalent linkages, linear or branched, cyclic or heterocyclic, saturated or unsaturated, each having 1-16 nonhydrogen atoms selected from the group consisting of C, N, P, O and S, such that the linkage contains any combination of ether, thioether, amine, ester, amide bonds;
• or single, double, triple or aromatic carbon--carbon bonds;
• or phosphorus-oxygen, phosphorus-sulfur bonds, nitrogen--nitrogen or nitrogen-oxygen bonds;
• or aromatic or heteroaromatic bonds;
• CAP and CAP', which may be the same or different, are --O--R.sup.21, --S--R.sup.21, --NR.sup.21 R.sup.22, or --N.sup.+ R.sup.21 R.sup.22 R.sup.23 .psi..sup.- ;
• wherein
• R.sup.21, R.sup.22, and R.sup.23 are independently H, or a linear or branched alkyl or cycloalkyl having 1-8 carbons, optionally further substituted by hydroxy, alkoxy having 1-8 carbons, carboxyalkyl having 1-8 carbons, or phenyl, where phenyl is optionally further substituted by halogen, hydroxy, alkoxy having 1-8 carbons, aminoalkyl having 1-8 carbons, or carboxyalkyl having 1-8 carbons;
• or, one or more of R.sup.21, R.sup.22 and R.sup.23, taken in combination with SPACER or SPACER' or R.sup.20 forms a 5- or 6-membered aromatic, heteroaromatic, alicyclic or heteroalicyclic ring, the heteroatoms selected from O, N or S;
• where .psi..sup.- is a compatible counterion;
• or
• CAP and CAP' are independently ##STR60## where R.sup.21, R.sup.22, R.sup.23, and .psi..sup.- are as defined previously.