Electrode array device having an adsorbed porous reaction layer

Abstract

There is disclosed an electrode array device having an adsorbed porous reaction layer for improved synthesis quality. The array comprises a plurality of electrodes on a substrate, wherein the electrodes are electronically connected to a computer control system. The array has an adsorbed porous reaction layer on the plurality of electrodes, wherein the adsorbed porous reaction layer comprises a chemical species having at least one hydroxyl group. In the preferred embodiment, the reaction layer is sucrose. A method for preparing an electrode array for improved synthesis quality is disclosed. The method comprises a cleaning method and a method of attachment of a reaction layer. The cleaning method comprises a plasma cleaning method and a chemical cleaning method. The reaction layer is attached after cleaning by exposing the microarray to a solution containing the chemical species having at least one hydroxyl group.

1 . An electrode array having an adsorbed porous reaction layer 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; and    R 7  is selected from the group consisting of amino and hydroxyl.    
     
     
         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 . 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, 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 , 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.    
     
     
         8 . The process of  claim 7 , 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.  
     
     
         9 . The process of  claim 7 , wherein the disaccharide is selected from the group consisting of amylose, cellobiose, lactose, maltose, melibiose, palatinose, sucrose, and trehalose  
     
     
         10 . The process of  claim 7 , wherein the triaccharide is selected from the group consisting of raffinose and melezitose.  
     
     
         11 . The process of  claim 7 , 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.  
     
     
         12 . The process of  claim 7 , wherein the polyethylene glycol has a molecular weight from approximately 1,000 to 20,000.  
     
     
         13 . The process of  claim 7 , 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.    
     
     
         14 . The process of  claim 7 , 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.  
     
     
         15 . The process of  claim 7 , 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.    
     
     
         16 . The process of  claim 15 , 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.    
     
     
         16 . The process of  claim 15 , 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.    
     
     
         17 . The process of  claim 15 , 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.    
     
     
         18 . The process of  claim 15 , 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.    
     
     
         19 . The process of  claim 15 , 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.    
     
     
         20 . A process for cleaning an electrode microarray comprising: 
 (a) etching the electrode microarray using a plasma cleaning method; and    (b) cleaning the electrode microarray using a chemical cleaning method.    
     
     
         21 . The process of  claim 20 , wherein the plasma cleaning method comprises: 
 (a 1 ) etching the surface of the electrodes using an argon plasma for from about 2 to about minutes using a power of approximately 600 watts and a pressure of approximately eight millitorr;    (a 2 ) etching the surface of the electrodes 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 3 ) etching the surface of the electrodes 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;    
     
     
         22 . The process of  claim 20 , wherein the chemical cleaning method comprises: 
 (b 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 and the electrodes are electronically attached to a control system;    (b 2 ) pulsing a current for from about 0.01 to about 60 seconds to a first group of electrodes while a second group of electrodes is grounded, wherein the first group and the second group constitute a plurality of electrodes;    (b 3 )-pulsing a current for from about 0.01 to about 60 seconds to the second group of electrodes while the first group of electrodes is grounded; and    (b 4 ) alternating between pulsing a current for from about 0.01 to about 60 seconds to the first group of electrodes while the second group of electrodes is grounded and pulsing a current for from about 0.01 to about 60 seconds to the second group of electrodes while the first group of electrodes remains grounded for a cumulative time of from about 1 to about 60 minutes.    
     
     
         23 . The process of  claim 20 , wherein the chemical cleaning method comprises a hydrogen peroxide cleaning method, wherein the hydrogen peroxide cleaning method comprises contacting a hydrogen peroxide solution with the surface of the electrodes, wherein the hydrogen peroxide solution has a concentration of from about 0.5 to about 10 percent (by volume), wherein contacting time is from about 1 minute to about 24 hours, and wherein the hydrogen peroxide solution temperature is from about 20 to about 95 degrees Celsius.