Electrode array device having an adsorbed porous reaction layer having a linker moiety

1 . An electrode array having an adsorbed porous reaction layer having a linker attached thereto for synthesis comprising:

(a) a plurality of electrodes on a substrate, wherein each of the plurality of electrodes is electronically connected to a computer control system and wherein each electrode of the plurality of electrodes has a surface; and

(b) a porous reaction layer adsorbed onto the surface of each electrode of the plurality of electrodes, wherein the porous reaction layer comprises a chemical species or mixture of chemical specie, wherein the chemical species is selected from the group consisting of monosaccharides, disaccharides, trisaccharides, polyethylene glycol, polyethylene glycol derivative, N-hydroxysuccinimide, formula I, formula II, formula III, formula IV, formula V, formula VI, formula VII, and combinations thereof, wherein formula I is

formula II is

formula III is HOR 4 (OR 5 ) m R 7 formula IV is

formula V is

formula VI is

and formula VII is

wherein in each formula

m is an integer from 1 to 4;

R 1 , R 2 , R 7 , and R 8 are independently selected from the group consisting of hydrogen, and substituted and unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic ring, and polycyclic group, and halo, amide, alkoxy, acyl, acyloxy, oxycarbonyl, acyloxycarbonyl, alkoxycarbonyloxy, carboxy, amino, secondary amino, tertiary amino, hydrazino, azido, alkazoxy, cyano, isocyano, cyanato, isocyanato, thiocyanato, fulminato, isothiocyanato, isoselenocyanato, selenocyanato, carboxyamido, acylimino, nitroso, aminooxy, carboximidoyl, hydrazonoyl, oxime, acylhydrazino, amidino, sulfide, sulfoxide, thiosulfoxide, sulfone, thiosulfone, sulfate, thiosulfate, hydroxyl, formyl, hydroxyperoxy, hydroperoxy, peroxy acid, carbamoyl, trimethyl silyl, nitro, nitroso, oxamoyl, pentazolyl, sulfamoyl, sulfenamoyl, sulfeno, sulfinamoyl, sulfino, sulfo, sulfoamino, hydrothiol, tetrazolyl, thiocarbamoyl, thiocarbazono, thiocarbodiazono, thiocarbonohydrazido, thiocarboxy, thioformyl, thioacyl, thiocyanato, thiosemicarbazido, thiosulfino, thiosulfo, thioureido, triazano, triazeno, triazinyl, trithiosulfo, sulfinimidic acid, sulfonimidic acid, sulfinohydrazonic acid, sulfonohydrazonic acid, sulfinohydroximic acid, sulfonohydroximic acid, and phosphoric acid ester;

R 3 is selected from the group consisting of heteroatom group, carbonyl, and substituted and unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic ring, and polycyclic group;

R 4 and R 5 are independently selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, and hexylene;

R 6 forming a ring structure with two carbons of succinimide and is selected from the group consisting of substituted and unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic ring, and polycyclic group;

R 7 is selected from the group consisting of amino and hydroxyl; and

(c) a linker group attached to the adsorbed porous reaction layer, the linker group comprising:

(i) a bound end, wherein the bound end is covalently linked to the adsorbed porous reaction layer,

(ii) a synthesis end, wherein the synthesis end has a reactive group; and

(iii) a middle section lineally connecting the bound end and the synthesis end, wherein the middle section comprises up to 100 covalently linked monomers, wherein the covalently linked monomers have a substantial ionic charge in an aqueous media, wherein a subsequent group attached to the reactive group is substantially solvated in aqueous media.

2 . The electrode array of claim 1 , wherein the monosaccharide is selected from the group consisting of allose, altrose, arabinose, deoxyribose, erythrose, fructose, galactose, glucose, gulose, idose, lyxose, mannose, psicose, L-rhamnose, ribose, ribulose, sedoheptulose, D-sorbitol, sorbose, sylulose, tagatose, talose, threose, xylulose, and xylose.

3 . The electrode array of claim 1 , wherein the disaccharide is selected from the group consisting of amylose, cellobiose, lactose, maltose, melibiose, palatinose, sucrose, and trehalose The electrode microarray of claim 1 , wherein the triaccharide is selected from the group consisting of raffinose and melezitose.

4 . The electrode array of claim 1 , wherein the polyethylene glycol derivative is selected from the group consisting of diethylene glycol, tetraethylene glycol, polyethylene glycol having primary amino groups, 2-(2-aminoethoxy) ethanol, ethanol amine, di(ethylene glycol) mono allyl ether, di(ethylene glycol) mono tosylate, tri(ethylene glycol) mono allyl ether, tri(ethylene glycol) mono tosylate, tri(ethylene glycol) mono benzyl ether, tri(ethylene glycol) mono trityl ether, tri(ethylene glycol) mono chloro mono methyl ether, tri(ethylene glycol) mono tosyl mono allyl ether, tri(ethylene glycol) mono allyl mono methyl ether, tetra(ethlyne glycol) mono allyl ether, tetra(ethylene glycol) mono methyl ether, tetra(ethylene glycol) mono tosyl mono allyl ether, tetra(ethylene glycol) mono tosylate, tetra(ethylene glycol) mono benzyl ether, tetra(ethylene glycol) mono trityl ether, tetra(ethylene glycol) mono 1-hexenyl ether, tetra(ethylene glycol) mnon 1-heptenyl ether, tetra(ethylene glycol) mono 1-octenyl ether, tetra(ethylene glycol) mono 1-decenyl ether, tetra(ethylene glycol) mono 1-undecenyl ether, penta(ethylene glycol) mono methyl ether, penta(ethylene glycol) mono allyl mono methyl ether, penta(ethylene glycol) mono tosyl mono methyl ether, penta(ethylene glycol) mono tosyl mono allyl ether, hexa(ethylene glycol) mono allyl ether, hexa(ethylene glycol) mono methyl ether, hexa(ethylene glycol) mono benzyl ether, hexa(ethylene glycol) mono trityl ether, hexa(ethylene glycol) mono 1-hexenyl ether, hexa(ethylene glycol) mono 1-heptenyl ether, hexa(ethylene glycol) mono 1-octenyl ether, hexa(ethylene glycol) mono 1-decenyl ether, hexa(ethylene glycol) mono 1-undecenyl ether, hexa(ethylene glycol) mono 4-benzophenonyl mono 1-undecenyl ether, hepta(ethylene glycol) mono allyl ether, hepta(ethylene glycol) mono methyl ether, hepta(ethylene glycol) mono tosyl mono methyl ether, hepta(ethylene glycol) monoallyl mono methyl ether, octa(ethylene glycol) mono allyl ether, octa(ethylene glycol) mono tosylate, octa(ethylene glycol) mono tosyl mono allyl ether, undeca(ethylene glycol) mono methyl ether, undeca(ethylene glycol) mono allyl mono methyl ether, undeca(ethylene glycol) mono tosyl mono methyl ether, undeca(ethylene glycol) mono allyl ether, octadeca(ethylene glycol) mono allyl ether, octa(ethylene glycol), deca(ethylene glycol), dodeca(ethylene glycol), tetradeca(ethylene glycol), hexadeca(ethylene glycol), octadeca(ethylene glycol), benzophenone-4-hexa(ethylene glycol) allyl ether, benzophenone-4-hexa(ethylene glycol) hexenyl ether, benzophenone-4-hexa(ethylene glycol) octenyl ether, benzophenone-4-hexa(ethylene glycol) decenyl ether, benzophenone-4-hexa(ethylene glycol) undecenyl ether, 4-flourobenzophenone-4′-hexa(ethylene glycol) allyl ether, 4-flourobenzophenone-4′-hexa(ethylene glycol) undecenyl ether, 4-hydroxybenzophenone-4′-hexa(ethylene glycol) allyl ether, 4-hydroxybenzophenone-4′-hexa(ethylene glycol) undecenyl ether, 4-hydroxybenzophenone-4′-tetra(ethylene glycol) allyl ether, 4-hydroxybenzophenone-4′-tetra(ethylene glycol) undecenyl ether, 4-morpholinobenzophenone-4′-hexa(ethylene glycol) allyl ether, 4-morpholinobenzophenone-4′-hexa(ethylene glycol) undecenyl ether, 4-morpholinobenzophenone-4′-tetra(ethylene glycol) allyl ether, and 4-morpholinobenzophenone-4′-tetra(ethylene glycol) undecenyl ether.

5 . The electrode array of claim 1 , wherein the polyethylene glycol has a molecular weight of approximately 1,000 to 20,000.

6 . The electrode array of claim 1 , wherein the electrodes surface is made from a material is selected from the group consisting of platinum, gold, semiconductor, indium tin oxide, and carbon and combinations thereof.

7 . The electrode array of claim 1 , wherein the reactive group is selected from the group consisting of amino, hydroxyl, and carboxyl.

8 . The electrode array of claim 1 , wherein the plurality of covalently linked monomers is selected from the group consisting of DNA, RNA, and amino acids having ionic side chains and combinations thereof.

9 . The electrode array of claim 1 , wherein the plurality of covalently linked monomers is selected from the group consisting of deoxyadenylate, deoxyguanylate, deoxycytidylate, and deoxythymidylate and combinations thereof.

10 . The electrode array of claim 1 , wherein the plurality of covalently linked monomers is selected from the group consisting of adenylate, guanylate, cytidylate, and uridylate, and combinations thereof.

11 . A process for forming an electrode array device having a plurality of electrodes wherein each electrode has a surface, and a porous reaction layer adsorbed to the surface for improved synthesis quality comprising:

(a) providing a plurality of electrodes on a substrate, wherein each of the plurality of electrodes is electronically connected to a computer control system and wherein each electrode of the plurality of electrodes has a surface; and

(b) adsorbing a porous reaction layer on the surface of each electrode of the plurality of electrodes, wherein the porous reaction layer comprises a chemical species, wherein the chemical species is selected from the group consisting of monosaccharides, disaccharides, trisaccharides, polyethylene glycol, polyethylene glycol derivative, N-hydroxysuccinimide, formula I, formula II, formula III, formula IV, formula V, formula VI, formula VII, and combinations thereof, wherein formula I is

formula II is

formula III is HOR 4 (OR 5 ) m R 7 , formula IV is

formula V is

formula VI is

and formula VII is

wherein in each formula m is an integer from 1 to 4;

R 1 , R 2 , R 7 , and R 8 are independently selected from the group consisting of hydrogen, and substituted and unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic ring, and polycyclic group, and halo, amide, alkoxy, acyl, acyloxy, oxycarbonyl, acyloxycarbonyl, alkoxycarbonyloxy, carboxy, amino, secondary amino, tertiary amino, hydrazino, azido, alkazoxy, cyano, isocyano, cyanato, isocyanato, thiocyanato, fullminato, isothiocyanato, isoselenocyanato, selenocyanato, carboxyamido, acylimino, nitroso, aminooxy, carboximidoyl, hydrazonoyl, oxime, acylhydrazino, amidino, sulfide, sulfoxide, thiosulfoxide, sulfone, thiosulfone, sulfate, thiosulfate, hydroxyl, formyl, hydroxyperoxy, hydroperoxy, peroxy acid, carbamoyl, trimethyl silyl, nitro, nitroso, oxamoyl, pentazolyl, sulfamoyl, sulfenamoyl, sulfeno, sulfinamoyl, sulfino, sulfo, sulfoamino, hydrothiol, tetrazolyl, thiocarbamoyl, thiocarbazono, thiocarbodiazono, thiocarbonohydrazido, thiocarboxy, thioformyl, thioacyl, thiocyanato, thiosemicarbazido, thiosulfino, thiosulfo, thioureido, triazano, triazeno, triazinyl, trithiosulfo, sulfinimidic acid, sulfonimidic acid, sulfinohydrazonic acid, sulfonohydrazonic acid, sulfinohydroximic acid, sulfonohydroximic acid, and phosphoric acid ester,

R 3 is selected from the group consisting of heteroatom group, carbonyl, and substituted and unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic ring, and polycyclic group;

R 4 and R 5 are independently selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, and hexylene;

R 6 forms a ring structure with two carbons of succinimide and is selected from the group consisting of substituted and unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic ring, and polycyclic group; and

R 7 is selected from the group consisting of amino and hydroxyl;

(c) attaching a linker group to the adsorbed porous reaction layer, wherein the linker group comprises:

(i) a bound end, wherein the bound end is covalently linked to the adsorbed porous reaction layer;

(ii) a synthesis end, wherein the synthesis end has a reactive group; and

(iii) a middle section lineally connecting the bound end and the synthesis end, wherein the middle section comprises up to 100 covalently linked monomers, wherein the covalently-linked monomers have a substantial ionic charge in an aqueous media, wherein a subsequent group attached to the reactive group is substantially solvated in aqueous media.

12 . The process of claim 11 , wherein the monosaccharide is selected from the group consisting of allose, altrose, arabinose, deoxyribose, erythrose, fructose, galactose, glucose, gulose, idose, lyxose, mannose, psicose, L-rhamnose, ribose, ribulose, sedoheptulose, D-sorbitol, sorbose, sylulose, tagatose, talose, threose, xylulose, and xylose.

13 . The process of claim 11 , wherein the disaccharide is selected from the group consisting of amylose, cellobiose, lactose, maltose, melibiose, palatinose, sucrose, and trehalose

14 . The process of claim 11 , wherein the triaccharide is selected from the group consisting of raffinose and melezitose.

15 . The process of claim 11 , wherein the polyethylene glycol derivative is selected from the group consisting of diethylene glycol, tetraethylene glycol, polyethylene glycol having primary amino groups, 2-(2-aminoethoxy) ethanol, ethanol amine, di(ethylene glycol) mono allyl ether, di((ethylene glycol) mono tosylate, tri(ethylene glycol) mono allyl ether, tri(ethylene glycol) mono tosylate, tri(ethylene glycol) mono benzyl ether, tri(ethylene glycol) mono trityl ether, tri(ethylene glycol) mono chloro mono methyl ether, tri(ethylene glycol) mono tosyl mono allyl ether, tri(ethylene glycol) mono allyl mono methyl ether, tetra(ethlyne glycol) mono allyl ether, tetra(ethylene glycol) mono methyl ether, tetra(ethylene glycol) mono tosyl mono allyl ether, tetra(ethylene glycol) mono tosylate, tetra(ethylene glycol) mono benzyl ether, tetra(ethylene glycol) mono trityl ether, tetra(ethylene glycol) mono 1-hexenyl ether, tetra(ethylene glycol) mnon 1-heptenyl ether, tetra(ethylene glycol) mono 1-octenyl ether, tetra(ethylene glycol) mono 1-decenyl ether, tetra(ethylene glycol) mono 1-undecenyl ether, penta(ethylene glycol) mono methyl ether, penta(ethylene glycol) mono allyl mono methyl ether, penta(ethylene glycol) mono tosyl mono methyl ether, penta(ethylene glycol) mono tosyl mono allyl ether, hexa(ethylene glycol) mono allyl ether, hexa(ethylene glycol) mono methyl ether, hexa(ethylene glycol) mono benzyl ether, hexa(ethylene glycol) mono trityl ether, hexa(ethylene glycol) mono 1-hexenyl ether, hexa(ethylene glycol) mono 1-heptenyl ether, hexa(ethylene glycol) mono 1-octenyl ether, hexa(ethylene glycol) mono 1-decenyl ether, hexa(ethylene glycol) mono 1-undecenyl ether, hexa(ethylene glycol) mono 4-benzophenonyl mono 1-undecenyl ether, hepta(ethylene glycol) mono allyl ether, hepta(ethylene glycol) mono methyl ether, hepta(ethylene glycol) mono tosyl mono methyl ether, hepta(ethylene glycol) monoallyl mono methyl ether, octa(ethylene glycol) mono allyl ether, octa(ethylene glycol) mono tosylate, octa(ethylene glycol) mono tosyl mono allyl ether, undeca(ethylene glycol) mono methyl ether, undeca(ethylene glycol) mono allyl mono methyl ether, undeca(ethylene glycol) mono tosyl mono methyl ether, undeca(ethylene glycol) mono allyl ether, octadeca(ethylene glycol) mono allyl ether, octa(ethylene glycol), deca(ethylene glycol), dodeca(ethylene glycol), tetradeca(ethylene glycol), hexadeca(ethylene glycol), octadeca(ethylene glycol), benzophenone-4-hexa(ethylene glycol) allyl ether, benzophenone-4-hexa(ethylene glycol) hexenyl ether, benzophenone-4-hexa(ethylene glycol) octenyl ether, benzophenone-4-hexa(ethylene glycol) decenyl ether, benzophenone-4-hexa(ethylene glycol) undecenyl ether, 4-flourobenzophenone-4′-hexa(ethylene glycol) allyl ether, 4-flourobenzophenone-4′-hexa(ethylene glycol) undecenyl ether, 4-hydroxybenzophenone-4′-hexa(ethylene glycol) allyl ether, 4-hydroxybenzophenone-4′-hexa(ethylene glycol) undecenyl ether, 4-hydroxybenzophenone-4′-tetra(ethylene glycol) allyl ether, 4-hydroxybenzophenone-4′-tetra(ethylene glycol) undecenyl ether, 4-morpholinobenzophenone-4′-hexa(ethylene glycol) allyl ether, 4-morpholinobenzophenone-4′-hexa(ethylene glycol) undecenyl ether, 4-morpholinobenzophenone-4′-tetra(ethylene glycol) allyl ether, and 4-morpholinobenzophenone-4′-tetra(ethylene glycol) undecenyl ether.

16 . The process of claim 11 , wherein the polyethylene glycol has a molecular weight from approximately 1,000 to 20,000.

17 . The process of claim 11 , wherein the step of adsorbing the porous reaction layer further comprises:

(b 1 ) contacting a treatment solution to the microarray for from about 1 minute to about 1 month, wherein the treatment solution comprises the chemical species and a solvent capable of dissolving the chemical species, wherein the chemical species has a concentration of approximately 0.001 to 5 molar, wherein the temperature of the treatment solution is approximately 0 to 90 degrees celcius.

18 . The process of claim 11 , wherein the surface of each electrode of the plurality of electrodes is selected from the group consisting of platinum, gold, semiconductor, indium tin oxide, and carbon and combinations thereof.

19 . The process of claim 11 , wherein the reactive group is selected from the group consisting of amino, hydroxyl, and carboxyl.

20 . The process of claim 11 , wherein the plurality of covalently linked monomers is selected from the group consisting of DNA, RNA, and amino acids having ionic side chains and combinations thereof.

21 . The process of claim 11 , wherein the plurality of covalently linked monomers is selected from the group consisting of deoxyadenylate, deoxyguanylate, deoxycytidylate, and deoxythymidylate and combinations thereof.

22 . The process of claim 11 , wherein the plurality of covalently linked monomers is selected from the group consisting of adenylate, guanylate, cytidylate, and uridylate, and combinations thereof.

23 . The process of claim 11 , wherein the plurality of covalently linked monomers is selected from the group consisting of lysine, arginine, histidine, aspartic acid, glutamic acid, phospho-serine, phospho-threonine, phosphor-tyrosine, asparagine, and glutamine.

24 . The process of claim 1 1, wherein the step of providing the plurality of electrodes further comprises:

(a 1 ) etching the electrode surfaces using a plasma cleaning method; and

(a 2 ) cleaning the electrode surfaces using a chemical cleaning method.

20 . The process of claim 24 , wherein the plasma cleaning method further comprises:

(a 1.1 ) exposing the electrode microarray to an argon plasma plasma for approximately two to six minutes.

25 . The process of claim 24 , wherein the plasma cleaning method further comprises:

(a 1.1 ) exposing the electrode microarray to a sulfur hexafluoride plasma plasma for approximately two to six minutes.

26 . The process of claim 24 , wherein the plasma cleaning method comprises:

(a 1.1 ) etching the electrode microarray using an argon plasma for from about 2 to about 4 minutes using a power of approximately 600 watts and a pressure of approximately eight millitorr;

(a 1.2 ) etching the electrode microarray using an oxygen plasma for from about 5 to about 7 minutes using a power of approximately 500 watts and a pressure of approximately 50 millitorr; and

(a 1.3 ) etching the electrode microarray using an argon plasma for from about 8 to about 12 minutes using a power of approximately 600 watts and a pressure of approximately eight millitorr.

27 . The process of claim 24 , wherein the chemical cleaning method further comprises an electrochemical cleaning method, wherein the electrochemical cleaning method comprises:

(a 2.1 ) contacting a sulfuric acid solution with the surface of the electrodes, wherein the sulfuric acid solution has a concentration of approximately 0.01 to 5 molar,

(a 2.2 ) pulsing a current for approximately 0.01 to 60 seconds to a first group of electrodes while a second group of electrodes is grounded, wherein each electrode is in the first group of electrodes or the second group of electrodes;

(a 2.3 ) pulsing a current for approximately 0.01 to 60 seconds to the second group of electrodes while the first group of electrodes is grounded; and

(a 2.4 ) alternating between pulsing a current for approximately 0.01 to 60 seconds to the first group of electrodes while the second group of electrodes is grounded and pulsing a current for approximately 0.01 to 60 seconds to the second group of electrodes while the first group of electrodes remains grounded for a cumulative time of approximately 1 to 60 minutes.

28 . The process of claim 24 , wherein the chemical cleaning method further comprises a hydrogen peroxide cleaning method comprising:

(a 2.1 ) contacting a hydrogen peroxide solution with the surface of the electrodes, wherein the hydrogen peroxide solution has a concentration of approximately 0.5 to 10 percent (by volume), wherein the contacting time is from about 1 minute to about 24 hours, and the hydrogen peroxide solution temperature is approximately 20 to 95 degrees Celsius.