Conductive oligomers attached to electrodes and nucleoside analogs
The invention relates to nucleic acids covalently coupled to electrodes via conductive oligomers. More particularly, the invention is directed to the site-selective modification of nucleic acids with electron transfer moieties and electrodes to produce a new class of biomaterials, and to methods of making and using them.
1. A conductive oligomer comprising an ethyl-pyridine protected sulfur atom.
2. A conductive oligomer comprising a trimethylsilylethyl protected sulfur atom.
3. A composition comprising a conductive oligomer covalently attached to a CPG (controlled pore glass)-nucleoside, wherein said conductive oligomer has the formula:
wherein
Y is an aromatic group;
n is an integer from 1 to 50;
g is either 1 or zero;
e is an integer from zero to 10; and
m is zero or 1;
wherein when g is 1, B—D is selected from acetylene, alkene, substituted alkene, amide, azo, esters, thioesters, —CH═N—, —CR═N—, —N═CH— and —N═CR—, —SiH═SiH—, —SiR═SiH—, —SiR═SiH—, and —SiR═SiR—, —SiH═CH—, —SiR═CH—, —SiH═CR—, —SiR═CR—, CH═SiH—, —CR═SiH—, —CH═SiR—, and —CR═SiR—, wherein R is a substitution group; and
wherein when g is zero, e is 1 and D is carbonyl or a moiety comprising oxygen, sulfur, nitrogen or phosphorus.
4. A composition comprising a phosphoramidite nucleoside covalently attached to a conductive oligomer, said phosphoramidite nucleoside further comprising a covalently attached metallocene ligand, wherein said conductive oligomer has the formula:
wherein
Y is an aromatic group;
n is an integer from 1 to 50;
g is either 1 or zero;
e is an integer from zero to 10; and
m is zero or 1;
wherein when g is 1, B—D is selected from acetylene, alkene, substituted alkene, amide, azo, esters, thioesters, —CH═N—, —CR═N—, —N═CH— and —N═CR—, —SiH═SiH—, —SiR═SiH—, —SiR═SiH—, and —SiR═SiR—, —SiH═CH—, —SiR═CH—, —SiH═CR—, —SiR═CR—, CH═SiH—, —CR═SiH—, —CH═SiR—, and —CR═SiR—, wherein R is a substitution group; and wherein when g is zero, e is 1 and D is carbonyl or a moiety comprising oxygen, sulfur, nitrogen or phosphorus.
5. A composition according to claim 4 wherein said nucleoside comprises a ribose and said metallocene is covalently attached to the 2′ position of said ribose.
6. A composition according to claim 4 wherein said metallocene is covalently attached to the base of said nucleoside.
7. A composition according to claim 4 wherein said metallocene is ferrocene.
8. A composition comprising a deoxynucleotide triphosphate covalently attached to a conductive oligomer, said deoxynucleotide triphosphate further comprising a covalently attached metallocene ligand, wherein said conductive oligomer has the formula:
wherein
Y is an aromatic group;
n is an integer from 1 to 50;
g is either 1 or zero;
e is an integer from zero to 10; and
m is zero or 1;
wherein when g is 1, B—D is selected from acetylene, alkene, substituted alkene, amide, azo, esters, thioesters, —CH═N—, —CR═N—, —N═CH— and —N═CR—, —SiH═SiH—, —SiR═SiH—, —SiR═SiH—, and —SiR═SiR—, —SiH═CH—, —SiR═CH—, —SiH═CR—, —SiR═CR—, CH═SiH—, —CR═SiH—, —CH═SiR—, and —CR═SiR—, wherein R is a substitution group; and wherein when g is zero, e is 1 and D is carbonyl or a moiety comprising oxygen, sulfur, nitrogen or phosphorus.
9. A composition according to claim 8 wherein said metallocene is ferrocene.
10. An electrode comprising:
a) a monolayer comprising a passivation agent layer comprising conductive oligomers, wherein said conductive oligomer having the formula:
wherein
Y is an aromatic group;
n is an integer from 1 to 50;
g is either 1 or zero;
e is an integer from zero to 10; and
m is zero or 1;
wherein when g is 1, B—D is selected from acetylene, alkene, substituted alkene, amide, azo, esters, thioesters, —CH═N—, —CR═N—, —N═CH— and —N═CR—, —SiH═SiH—, —SiR═SiH—, —SiR═SiH—, and —SiR═SiR—, —SiH═CH—, —SiR═CH—, —SiH═CR—, —SiR═CR—, CH═SiH—, —CR═SiH—, —CH═SiR—, and —CR═SiR—, wherein R is a substitution group; and wherein when g is zero, e is 1 and D is carbonyl or a moiety comprising oxygen, sulfur, nitrogen or phosphorus; and,
b) at least one nucleic acid covalently attached to said electrode with a spacer, wherein said spacer is an insulator.
11. An electrode comprising:
a) a monolayer comprising a passivation agent layer comprising conductive oligomers and insulators, wherein said conductive oligomer having the formula:
wherein
Y is an aromatic group;
n is an integer from 1 to 50;
g is either 1 or zero;
e is an integer from zero to 10; and
m is zero or 1;
wherein when g is 1, B—D is selected from acetylene, alkene, substituted alkene, amide, azo, esters, thioesters, —CH═N—, —CR═N—, —N═CH— and —N═CR—, —SiH═SiH—, —SiR═SiH—, —SiR═SiH—, and —SiR═SiR—, —SiH═CH—, —SiR═CH—, —SiH═CR—, —SiR═CR—, CH═SiH—, —CR═SiH—, —CH═SiR—, and —CR═SiR—, wherein R is a substitution group; and wherein when g is zero, e is 1 and D is carbonyl or a moiety comprising oxygen, sulfur, nitrogen or phosphorus; and,
b) at least one nucleic acid covalently attached to said electrode with a spacer.