Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
  • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
  • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
  • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
  • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
  • G01N33/54353—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals with ligand attached to the carrier via a chemical coupling agent
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
  • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
  • C07C311/51—Y being a hydrogen or a carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom

Definitions

• This invention provides compounds that include both a substrate-reactive group and a N-sulfonylaminocarbonyl group.
• the invention also provides articles and methods for immobilizing amine-containing materials to a substrate.
• Amine-containing materials such as amine-containing analytes, amino acids, DNA fragments, RNA fragments, protein fragments, organelles, and immunoglobins immobilized on the surface of a substrate can be used in numerous applications.
• immobilized biological amines can be used for the medical diagnosis of a disease or genetic defect, for biological separations, or for detection of various biomolecules.
• the attachment of amine-containing materials to a substrate is often achieved through the use of a tethering compound.
• a tethering compound usually has two reactive functional groups separated by a linking group. One of the functional groups provides a means for anchoring the tethering compound to a substrate by reacting with a complementary functional group on the surface of the substrate.
• a second reactive functional group can be selected to react with an amine-containing material.
• the second reactive functional group can be, for example, an activated acyl derivative, such as an N- hydroxysuccinimide ester, or a cyclic azlactone.
• An amine-containing material can react with the N-hydroxysuccinimide ester to form a carboxamide resulting in the displacement of an N-hydroxysuccinimide fragment.
• An amine-containing material can react with the cyclic azlactone resulting in an opening of the ring structure.
• tethering compounds that include a group such as an N- hydroxysuccinimide ester or a cyclic azlactone can be highly reactive with primary amine- containing materials, such tethering compounds can suffer from a number of disadvantages. Many of the reactions with biological amines are conducted in dilute aqueous solutions. Under these conditions, the N-hydroxysuccinimide ester functional group is known to undergo rapid hydrolysis. This competing reaction can cause incomplete or inefficient immobilization of the amine-containing materials on the substrate. While cyclic azlactone functional groups are more stable to hydrolysis, cyclic azlactone groups tend to be synthetically incompatible with many groups that could be used to attach the tethering compound to a substrate.
• the compounds include two types of reactive functional groups.
• the first type of reactive functional group is a substrate-reactive group capable of reacting with a complementary functional group on the surface of a substrate resulting in the attachment of a tethering group to the substrate.
• the second type of reactive functional group is a N-sulfonylaminocarbonyl derivative that can react with an amine-containing material by a nucleophilic displacement reaction.
• a connector group is formed between the substrate and the amine-containing material.
• Articles and methods for immobilizing amine-containing materials to a substrate are also provided.
• One aspect of the invention provides compounds that can be attached to a substrate and that can react with an amine-containing material.
• the compounds are of Formula I:
• X 1 is a substrate-reactive functional group selected from a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, disulfide, alkyl disulfide, benzotriazolyl, phosphono, phosphoroamido, phosphato, or ethylenically unsaturated group; Y 1 is a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R 4 is hydrogen or alkyl, or aryl; Z 1 is an alkyl, aryl, or -(CO)R
• the compound of Formula I can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• the substrate reactive group X 1 is an ethylenically unsaturated group and the Y 1 group contains a carbonyl, carbonyloxy, or carbonylimino group that is bonded directly to the ethylenically unsaturated group via the carbonyl group.
• the compounds are according to Formula la: R 5 O O Z 1 H 2 C— C -C — L— Y— C — N-S0 2 R 1 la where R 5 is hydrogen, alkyl, or aryl; L 1 is oxy, -NR 4 - or-C(R 4 ) 2 -, wherein R 4 is hydrogen, alkyl, or aryl; and Y 2 is a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R 4 is hydrogen, alkyl, or aryl.
• the compound can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• Another aspect of the invention provides articles that include a tethering group attached to a substrate.
• the tethering group is the reaction product of the substrate- reactive group X 1 in compounds of Formula I with a complementary functional group on the surface of the substrate to form an ionic bond, covalent bond, or a combination thereof.
• the substrate-attached tethering group has a N-sulfonylaminocarbonyl group capable of reacting with an amine-containing material.
• Yet another aspect of the invention provides a method of immobilizing an amine- containing material to a substrate.
• the method involves preparing a substrate-attached tethering group by reacting the substrate-reactive group X 1 in compounds of Formula I with a complementary functional group on a substrate; and reacting a N- sulfonylaminocarbonyl group of the substrate-attached tethering group with an amine- containing material to form a connector group between the substrate and the amine- containing material.
• the invention also provides a multilayer substrate that includes a polymeric layer, a layer of diamond-like glass, and a layer of diamond-like carbon positioned between the polymeric layer and the diamond-like glass layer.
• a tethering group that includes a N- sulfonylaminocarbonyl group can be attached to the diamond-like glass layer of the multilayer substrate.
• Figure 1 is a confocal micrograph of various concentrations (50 micrograms/ml, 25 micrograms/ml, 12.5 micrograms/ml, and 6.25 micrograms/ml from left to right) of fluorescence labeled mouse IgG immobilized by reacting with N-sulfonylaminocarbonyl tethering groups attached to a substrate.
• Figure 2 is a confocal micrograph showing the capture of Staphylococcus aureus with IgG immobilized on a multilayer substrate of diamond-like glass/diamond-like carbon/polyimide/diamond-like carbon/diamond-like glass.
• Figure 3 is a confocal micrograph showing the exposure of Staphylococcus aureus with a multilayer substrate of diamond-like glass/diamond-like carbon/polyimide/diamond-like carbon/diamond like glass without IgG immobilized to the substrate with a connector group derived from a compound of Formula I.
• Figure 4 is a confocal micrograph showing capture of Staphylococcus aureus with IgG immobilized on a multilayer substrate of polyimide/titanium/gold.
• Figure 5 is a confocal micrograph showing the exposure of Staphylococcus aureus to a multilayer substrate of polyimide/titanium/gold without IgG immobilized to the substrate.
• the first reactive functional group can be used to provide attachment of a tethering group to a surface of a substrate.
• the second reactive functional group is a N-sulfonylaminocarbonyl group that can be reacted with an amine-containing material, particularly a primary aliphatic amine-containing material, to form a carbonylimino-containing connector group.
• the invention also provides articles and methods for immobilizing amine-containing materials to a substrate.
• acyl refers to a monovalent group of formula -(CO)R where R is an alkyl group and where (CO) used herein indicates that the carbon is attached to the oxygen with a double bond.
• acyloxy refers to a monovalent group of formula -O(CO)R where R is an alkyl group.
• acyloxysilyl refers to a monovalent group having an acyloxy group attached to a Si (i.e., Si-O(CO)R where R is an alkyl).
• an acyloxysilyl can have a formula -Si[O(CO)R] 3-n L n where n is an integer of 0 to 2 and L is a halogen or alkoxy. Specific examples include -Si[O(CO)CH 3 ] 3 , -Si[O(CO)CH 3 ] Cl, or -Si[O(CO)CH 3 ]Cl 2 .
• alkoxy refers to a monovalent group of formula -OR where R is an alkyl group.
• alkoxycarbonyl refers to a monovalent group of formula -(CO)OR where R is an alkyl group.
• alkoxysilyl refers to a group having an alkoxy group attached to a Si (i.e., Si-OR where R is an alkyl).
• an alkoxysilyl can have a formula -Si(OR) 3-n (L a ) n where n is an integer of 0 to 2 and L is a halogen or acyloxy.
• alkyl refers to a monovalent radical of an alkane and includes groups that are linear, branched, cyclic, or combinations thereof.
• the alkyl group typically has 1 to 30 carbon atoms. In some embodiments, the alkyl group contains 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
• alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.
• alkyl disulfide refers to a monovalent group of formula -SSR where R is an alkyl group.
• alkylene refers to a divalent radical of an alkane.
• the alkylene can be straight-chained, branched, cyclic, or combinations thereof.
• the alkylene typically has 1 to 200 carbon atoms. In some embodiments, the alkylene contains 1 to
• alkylene refers to a monovalent radical of the compound R-Ar where Ar is an aromatic carbocyclic group and R is an alkyl group.
• aralkylene refers to a divalent radical of formula
• aryl refers to a monovalent aromatic carbocyclic radical.
• the aryl can have one aromatic ring or can include up to 5 carbocyclic ring structures that are connected to or fused to the aromatic ring.
• the other ring structures can be aromatic, non-aromatic, or combinations thereof.
• aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.
• arylene refers to a divalent radical of a carbocyclic aromatic compound having one to 5 rings that are connected, fused, or combinations thereof. In some embodiments, the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromatic ring.
• the arylene group can be phenylene.
• zido refers to a group of formula -N 3 .
• the term “aziridinyl” refers to a cyclic monovalent radical of aziridine having the formula
• R d is hydrogen or alkyl.
• benzotriazolyl refers to a monovalent group having a benzene group fused to a triazolyl group. The formula for a benzotriazolyl group is C 6 E N 3 -.
• carbonyl refers to a divalent group of formula -(CO)-.
• carbonylimino refers to a divalent group of formula -(CO)NR 4 - where R 4 is hydrogen, alkyl, or aryl.
• carbonyloxy refers to a divalent group of formula -(CO)O-.
• carbonyloxycarbonyl refers to a divalent group of formula -(CO)O(CO)-. Such a group is part of an anhydride compound.
• carbonylthio refers to a divalent group of formula -(CO)S-.
• carboxy refers to a monovalent group of formula
• chloroalkyl refers to an alkyl having at least one hydrogen atom replaced with a chlorine atom.
• cyano refers to a group of formula -CN.
• divalent group of formula -S-S- refers to a divalent group of formula -S-S-.
• fluoroalkyl refers to an alkyl having at least one hydrogen atom replaced with a fluorine atom.
• haloalkyl refers to an alkyl having at least one hydrogen atom replaced with a halogen selected from F, Cl, Br, or I.
• Perfluoroalkyl groups are a subset of haloalkyl groups.
• halocarbonyloxy refers to a monovalent group of formula -O(CO)X where X is a halogen atom selected from F, Cl, Br, or I.
• halocarbonyl refers to a monovalent group of formula -(CO)X where X is a halogen atom selected from F, Cl, Br, or I.
• halosilyl refers to a group having a Si attached to a halogen (i.e., Si-X where X is a halogen).
• the halosilyl group can be of formula -SiX 3-n (L b ) n where n is an integer of 0 to 2 and L b is selected from an alkoxy, or acyloxy.
• heteroalkylene refers to a divalent alkylene having one or more carbon atoms replaced with a sulfur, oxygen, or NR d where R d is hydrogen or alkyl.
• the heteroalkylene can be linear, branched, cyclic, or combinations thereof and can include up to 400 carbon atoms and up to 30 heteroatoms.
• the heteroalkylene includes up to 300 carbon atoms, up to 200 carbon atoms, up to 100 carbon atoms, up to 50 carbon atoms, up to 30 carbon atoms, up to 20 carbon atoms, or up to 10 carbon atoms.
• hydroxy refers to a group of formula -OH.
• isocyanato refers to a group of formula -NCO.
• mercapto refers to a group of formula -SH.
• N-sulfonylaminocarbonyl refers to a divalent entity of formula -SO 2 NZ a (CO)- where Z a is an alkyl, aryl, or part of a group structure.
• oxy refers to a divalent group of formula -O-.
• oxycarbonylimino refers to a divalent group of formula -O(CO)NR 4 - where R 4 is hydrogen, alkyl, or aryl.
• oxycarbonyloxy refers to a divalent group of formula -O(CO)O-.
• the term “oxycarbonylthio” refers to a divalent group of formula -O(CO)S-.
• perfluoroalkyl refers to an alkyl group in which all of the hydrogen atoms are replaced with fluorine atoms. Perfluoroalkyl groups are a subset of fluoroalkyl groups.
• phosphato refers to a monovalent group of formula -OPO 3 H 2 .
• phosphono refers to a monovalent group of formula
• the term “phosphoramido” refers to a monovalent group of formula -NHPO 3 H 2 .
• the term “primary aromatic amino” refers to a monovalent group of formula -ArNH 2 where Ar is an aryl group.
• the term “secondary aromatic amino” refers to a monovalent group of formula -ArNR h H where Ar is an aryl group and R h is an alkyl or aryl.
• the term “tertiary amino” refers to a group of formula -NR 2 where R is an alkyl.
• the term “thio” refers to a divalent group of formula -S-.
• the term “thiocarbonylimino” refers to a divalent group of formula -S(CO)NR 4 - where R 4 is hydrogen, alkyl, or aryl.
• attachment group refers to the group formed by reaction of a substrate-reactive group in a compound according to Formula I with a complementary functional group on the surface of a substrate.
• complementary functional group refers to a group capable of reacting with a recited group to form an ionic bond, covalent bond, or combinations thereof.
• the complementary functional group can be a group on a substrate capable of reacting with group X 1 in Formula I.
• the term "connector group” refers to a group linking a substrate to an immobilized amine-containing material.
• the attachment group is part of the connector group.
• room temperature refers to a temperature of about 20 °C to about 25 °C or about 22 °C to about 25 °C.
• substrate refers to a solid phase support to which the tethering compounds of the invention can be attached.
• the substrates can have any useful form including, but not limited to, thin films, sheets, membranes, filters, nonwoven or woven fibers, hollow or solid beads, bottles, plates, tubes, rods, pipes, or wafers.
• the substrates can be porous or non-porous, rigid or flexible, transparent or opaque, clear or colored, or reflective or non-reflective.
• Suitable substrate materials include, for example, polymeric materials, glasses, ceramics, metals, metal oxides, hydrated metal oxides, or combinations thereof.
• the term "tethering compound” refers to a compound that has two reactive groups. One of the reactive groups (i.e., the substrate-reactive functional group) can react with a complementary functional group on the surface of a substrate to form a tethering group. The other reactive group (i.e., the N-sulfonylaminocarbonyl group) can react with an amine-containing material.
• tethering group refers to a group attached to a substrate that results from the reaction of a tethering compound with a complementary functional group on the surface of the substrate with a tethering compound.
• the tethering group includes a group that can react with an amine-containing material.
• the tethering group includes a N-sulfonylaminocarbonyl group.
• the attachment group is part of the tethering group.
• a curve connecting two groups in a formula indicates that the two groups together form part of a cyclic structure.
• the compounds include both a substrate-reactive group and a N-sulfonylaminocarbonyl group.
• the substrate-reactive group can be used for attachment to a substrate and the N- sulfonylaminocarbonyl group can be reacted with an amine-containing material to form a carbonylimino-containing connector group resulting in the immobilization of the amine- containing material to a substrate. That is, the compounds can be reacted to provide a connector group between a substrate and an amine-containing material.
• the compounds are of Formula I:
• X 1 is a substrate-reactive functional group selected from a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, disulfide, alkyl disulfide, benzotriazolyl, phosphono, phosphoroamido, phosphato, or ethylenically unsaturated group; Y 1 is a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R 4 is hydrogen or alkyl, or aryl; Z 1 is an alkyl, aryl, or -(CO)R
• Formula I can be used, for example, to provide attachment to a substrate by reacting with a complementary functional group on the surface of the substrate. That is, X 1 in compounds of Formula I can react with a complementary functional group to form a substrate-attached tethering group. X 1 can be monovalent or divalent. When X 1 is divalent, r in Formula I is equal to 2 and the compound has the following structure:
• the compound can be symmetrical about X 1 .
• a disulfide is an exemplary divalent X 1 group.
• r in Formula I is equal to 1 and the compound has the following structure:
• Suitable monovalent X 1 groups include a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, disulfide, alkyl disulfide, benzotriazolyl, phosphono, phosphoroamido, phosphato, or ethylenically unsaturated group.
• the X 1 groups typically can react with a complementary functional group on the surface of a substrate to form an ionic bond, covalent bond, or combination thereof.
• Suitable X 1 groups for attachment to the surface of a polymeric substrate include a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, or ethylenically unsaturated group.
• Suitable X 1 groups for attachment to the surface of a gold-containing substrate include mercapto, disulfide, or alkyl disulfide.
• Suitable X 1 groups for attachment to the surface of other metal-containing substrates include benzotriazolyl, phosphono, phosphoroamido, or phosphato groups.
• Suitable X 1 groups for attachment to glass or ceramic-containing substrates as well as to metal oxide-containing or hydrated metal oxide-containing substrates include halosilyl, alkoxysilyl, or acyloxysilyl groups.
• the X 1 group can be an ethylenically unsaturated group.
• These compounds can be, for example, a vinyl compound, a vinyl ester compound, an allyl ester compound, a styrene compound, a vinyl ketone compound, an acrylate compound, a methacrylate compound, and the like.
• These different types of compounds can be formed, for example, by selecting different Y 1 groups.
• the group Y 1 in Formula I can be a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R 4 is hydrogen or alkyl, or aryl.
• the Y 1 group typically does not include peroxide groups (i.e., two oxy groups bonded together).
• Suitable heteroalkylenes usually contain 1 to 400 carbon atoms and up to 30 heteroatoms selected from N, O, S, or combinations thereof.
• Suitable alkylenes usually contain 1 to
• the heteroalkylene and alkylene groups can be linear, branched, cyclic, or combinations thereof.
• the group Y 1 can include an alkylene group as in the following formula: ,1 O I I X (CH 2 ) n - -c- -N- -SO— R' j r where n is an integer of 1 to 100. Exemplary compounds include those where n is an integer no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10.
• the groups X 1 , r, Z 1 , and R 1 are the same as previously defined for Formula I.
• Y 1 includes a first alkylene group that is linked to a second alkylene or a first heteroalkylene group with a group selected from a carbonyl, carbonyloxy, carbonylimino, oxy, thio, or -NR 4 -. Additional alkylene or heteroalkylene groups can be linked to the second alkylene or to the first heteroalkylene group with a group selected from a carbonyl, carbonyloxy, carbonylimino, oxy, thio, or
• Y 1 includes a first heteroalkylene group that is linked to a second heteroalkylene or to a first alkylene group with a group selected from a carbonyl, carbonyloxy, carbonylimino oxy, thio, or -NR 4 -.
• Additional alkylene or heteroalkylene groups can be linked to the second heteroalkylene or to the first alkylene group with a group selected from a carbonyl, carbonyloxy, carbonylimino group, oxy, thio, -NR 4 -.
• compounds can have the following formula: O Z 1 X ⁇ 1 F -(C k H 2k D) — (CH 2 )—C-N— SO— R 1 ] r
• D is oxygen, sulfur, or NH
• m is an integer of 1 to 200
• t is an integer of 0 to 12
• k is an integer of 2 to 4.
• Exemplary compounds include those where m is an integer no greater than 150, no greater than 100, no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10; t is an integer no greater than 10, no greater than 8, no greater than 6, no greater than 4, no greater than 2, or equal to 0; and k is no greater than 3, no greater than 2, or equal to 1.
• the heteroatom D is oxygen and k is equal to 2.
• the groups X 1 , r, Z 1 , and R 1 are the same as previously defined for Formula I.
• the compounds can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• the group Y 1 can include a combination of alkylene and heteroalkylene groups that are separated by a carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof:
• D is oxygen, sulfur, or NH
• n is an integer of 1 to 100
• m is an integer of 1 to 200
• t is an integer of 0 to 12
• k is an integer of 2 to 4
• L is oxygen or NR 4 where R 4 is hydrogen, alkyl, or aryl.
• Exemplary compounds include those where n is an integer no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10; m is an integer no greater than 150, no greater than 100, no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10; t is an integer no greater than 10, no greater than 8, no greater than 6, no greater than 4, no greater than 2, or equal to 0; and k is an integer no greater than 3, no greater than 2, or equal to 1.
• the D group is oxygen and k is equal to 2.
• the groups X 1 , r, Z 1 , and R 1 are the same as previously defined for Formula I.
• the compounds can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• the compound can have one the following formulas:
• D is oxygen, sulfur, or NH
• n is an integer of 1 to 100
• m is an integer of 1 to 200
• p is an integer of 1 to 10
• t is an integer of 0 to 12
• k is an integer of 2 to 4
• L is oxygen or NR 4 where R 4 is hydrogen, alkyl, or aryl.
• Exemplary compounds include those in which n is an integer no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10; m is an integer no greater than 150, no greater than 100, no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10; p is an integer no greater than 8, no greater than 6, no greater than 4, or no greater than 2; t is an integer no greater than 10, no greater than 8, no greater than 6, no greater than 4, no greater than 2, or equal to 0; and k is an integer no greater than 3, no greater than 2, or equal to 1.
• the heteroatom D is oxygen and k is equal to 2.
• Y 1 can include an arylene group in addition to one or more alkylene groups and one or more heteroalkylene groups.
• the arylene can be bonded directly to the N-sulfonylaminocarbonyl group.
• the arylene group can include up to 30 carbon atoms, up to 24 carbon atoms, up to 18 carbon atoms, up to 12 carbon atoms, or 6 carbon atoms.
• the compounds can have one of the following formulas:
• D is oxygen, sulfur, or NH
• n is an integer of 1 to 100
• m is an integer of 1 to 200
• p is an integer of 1 to 10
• t is an integer of 0 to 12
• k is an integer of 2 to 4
• Ar 1 is an arylene group
• L is oxygen or NR 4 where R 4 is hydrogen, alkyl, or aryl.
• Exemplary compounds include those where n is an integer no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10; m is an integer no greater than
• the groups X 1 , r, Z 1 , and R 1 are the same as previously defined for Formula I.
• the compounds can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• the group Y 1 can be an arylene group as in the following structure:
• Ar 1 is an arylene group.
• Ar 1 is phenylene.
• the groups X 1 , r, Z 1 , and R 1 are the same as previously defined for Formula I.
• the compounds can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• Y 1 can be a single bond.
• Y is a single bond when X 1 is a primary or secondary aromatic amino group.
• R 4 is hydrogen, aryl, alkyl.
• the groups Z 1 and R 1 are the same as previously defined for Formula I.
• the compounds can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• the group Z 1 in some embodiments of Formula I can be alkyl or aryl.
• Z 1 can be a C 1-30 alkyl, a C 1-10 alkyl, or a C 1-6 alkyl.
• Z 1 can be a C 6 - 30 aryl, a C 6-24 aryl, a C 6-18 aryl, or a C 6-12 aryl.
• Formula I
• Z 1 can be a -(CO)R a group that together with R 1 and the groups to which they are attached form a heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group.
• the heterocyclic or heterobicyclic group includes a nitrogen and sulfur heteroatom.
• An exemplary heterocyclic group fused to an aromatic group is shown in the following formula: where X 1 is monovalent or
• R 1 can be an alkyl, fluoroalkyl, perfluoroalkyl, chloroalkyl, aryl, or -NR b R c group where R and R c are each an alkyl or taken together with the nitrogen atom to which they are attached form a four to eight membered heterocyclic group.
• R 1 can be a C 1- o alkyl, a Cno alkyl, or a C 1-6 alkyl. In other embodiments,
• R 1 can be a C 1-30 fluoroalkyl or perfluoroalkyl, a C 1-10 fluoroalkyl or perfluoroalkyl, or a C 1-4 fluoroalkyl or perfluoroalkyl group.
• R 1 can be a C 6-30 aryl, a C 6-18 aryl, or a C 6-12 aryl.
• R 1 can be a phenyl group.
• Exemplary compounds according to Formula I include, but are not limited to, the following:
• the substrate reactive group X 1 is an ethylenically unsaturated group and Y 1 includes a carbonyl, carbonyloxy, or carbonylimino group bonded directly to the ethylenically unsaturated group via the carbonyl group. That is, the compounds are of Formula la:
• R 5 is hydrogen, alkyl, or aryl
• L 1 is oxy, -NR 4 -, or -C(R 4 ) 2 -, wherein R 4 is hydrogen, alkyl, or aryl
• Y 2 is a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R 4 is hydrogen, alkyl, or aryl.
• the compound can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• the compounds of Formula la can be, for example, acrylates (i.e., where R 5 is hydrogen and L 1 is oxy), methacrylates(i.e., where R 5 is methyl and L 1 is oxy), acrylamides (i.e., where R 5 is hydrogen and L 1 is -NR 4 -), methacrylamides (i.e., where R 5 is methyl and L 1 is -NR 4 -), or vinyl ketones (i.e., where L 1 is -C(R4) 2 -).
• D is oxygen, sulfur, or NH
• m is an integer of 1 to 200
• n is an integer of 1 to 12
• k is an integer of 2 to 4.
• the compound can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• m is an integer no greater than 150, no greater than 100, no greater than 80, no greater than 60, no greater than 40, no greater than 20, or no greater than 10.
• Exemplary compounds include those where R 5 is hydrogen or methyl; L 1 is oxy or -NR 4 -; D is oxygen; and k is equal to
• compounds of Formula la can have the following formulas: where the compound can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• Specific examples of compound according to Formula la include, but is not limited to,
• the compounds of Formulas I may be prepared, for example, by reaction of a first compound having a nitrogen-containing group with a second compound that includes a halocarbonyl group. More specifically, the nitrogen-containing group of the first compound includes a nitrogen atom directly bonded to a sulfonyl group as well as to at least one hydrogen atom.
• the first compound can further include a substrate-reactive group X or a group that can be converted to a substrate-reactive group X 1 .
• the substrate- reactive groups do not react, or react slowly, with the halocarbonyl group of the second compound such that the nitrogen-containing group of the first compound reacts preferentially with the halocarbonyl group of the second compound.
• a suitable reaction scheme is shown in Reaction Scheme A. Reaction Scheme A
• the -(CO)Q group can be a halocarbonyl group.
• the groups X 1 , Y 1 , Z 1 , and R 1 can be the same as previously defined for Formula I. Where Z 1 in Formula I is the -(CO)R a and R a combines with R 1 to form a ring structure, the compounds can be prepared using reaction Scheme A'. O Reaction Scheme A'
• R a , R 1 , X 1 , and Y 1 are as previously defined for Formula I.
• the -(CO)Q group can5 be a halocarbonyl group.
• Articles Another aspect of the invention provides articles that include a tethering group attached to a substrate (i.e., a substrate-attached tethering group).
• the substrate-attachedO tethering group is the reaction product of a complementary functional group G on a surface of a substrate with the group X 1 in compounds of Formula I.
• the substrate- attached tethering group has a N-sulfonylaminocarbonyl group that can react with an amine-containing material to form a carbonylimino-containing connector group between a substrate and an amine-containing material.
• the compounds of Formula I5 are those of Formula la.
• the substrate is a solid phase material to which the tethering groups can be attached.
• the substrate is not soluble in a solution used to attach a compound of Formula I to the surface of the substrate.
• a tethering group is attached only to an outer portion of the substrate and a bulk portion of the substrate is not modified during the process of attaching tethering group to the substrate.
• the substrate has groups G distributed throughout the substrate, only those groups in the outer portion (e.g., on or near the surface) are usually capable of reacting with group X 1 of the compounds according to Formula I.
• the substrates can have any useful form including, but not limited to, thin films, sheets, membranes, filters, nonwoven or woven fibers, hollow or solid beads, bottles, plates, tubes, rods, pipes, or wafers.
• the substrates can be porous or non-porous, rigid or flexible, transparent or opaque, clear or colored, and reflective or non-reflective. Suitable substrate materials include, for example, polymeric materials, glasses, ceramics, metals, metal oxides, hydrated metal oxides, or combinations thereof.
• the substrates can have a single layer or multiple layers of material.
• the substrate can have one or more second layers that provide support for a first layer that includes a complementary functional group capable of reacting with the X 1 group in compound of Formula I.
• the first layer is the outer layer of the substrate.
• a surface of a second layer is chemically modified or coated with another material to provide a first layer that includes a complementary functional group capable of reacting with the X 1 group.
• Suitable polymeric substrate materials include, but are not limited to, polyolefins, polystyrenes, polyacrylates, polymethacrylates, polyacrylonitriles, poly(vinylacetates), polyvinyl alcohols, polyvinyl chlorides, polyoxymethylenes, polycarbonates, polyamides, polyimides, polyurethanes, phenolics, polyamines, amino-epoxy resins, polyesters, silicones, cellulose based polymers, polysaccharides, or combinations thereof.
• the polymeric material is a copolymer prepared using a comonomer having a complementary functional group capable of reacting with a group X 1 in compounds according to Formula I.
• the comonomer can contain a carboxy, mercapto, hydroxy, amino, azido, or alkoxysilyl group.
• Suitable glass and ceramic substrate materials can include, for example, sodium, silicon, aluminum, lead, boron, phosphorous, zirconium, magnesium, calcium, arsenic, gallium, titanium, copper, or combinations thereof. Glasses typically include various types of silicate containing materials.
• the substrate includes a layer of diamond-like glass as disclosed in International Patent Application WO 01/66820 Al.
• the diamond-like glass is an amorphous material that includes carbon, silicon, and one or more elements selected from hydrogen, oxygen, fluorine, sulfur, titanium, or copper.
• diamond-like glass materials are formed from a tetramethysilane precursor using a plasma process.
• a hydrophobic material can be produced that is further treated in an oxygen plasma to control the silanol concentration on the surface.
• Diamond-like glass can be in the form of a thin film or in the form of a coating on another layer or material in the substrate.
• the diamond-like glass can be in the form of a thin film having at least 30 weight percent carbon, at least 25 weight percent silicon, and up to 45 weight percent oxygen. Such films can be flexible and transparent.
• the diamond-like glass is the outer layer of a multilayer substrate.
• the second layer (e.g., support layer) of the substrate is a polymeric material and the first layer is a thin film of diamond-like glass.
• the tethering group is attached to the surface of the diamond-like glass.
• the diamond like glass is deposited on a layer of diamond-like carbon.
• the second layer (e.g., support layer) is a polymeric film having a layer of diamond-like carbon deposited on a surface.
• a layer of diamondlike glass is deposited over the diamond-like carbon layer.
• the diamond-like carbon can, in some embodiments, function as a tie layer or primer layer between a polymeric layer and a layer of diamond-like glass in a multilayer substrate.
• the multilayer substrate can include a polyimide or polyester layer, a layer of diamond-like carbon deposited on the polyimide or polyester, and a layer of diamond-like glass deposited on the diamond-like carbon.
• the multilayer substrate includes a stack of the layers arranged in the following order: diamond-like glass, diamond-like carbon, polyimide or polyester, diamond-like carbon, and diamond-like glass.
• Diamond-like carbon films can be prepared, for example, from acetylene in a plasma reactor. Other methods of preparing such films are described U.S. Patent
• Suitable metals, metal oxides, or hydrated metal oxides for substrates can include, for example, gold, silver, platinum, palladium, aluminum, copper, chromium, iron, cobalt, nickel, zinc, and the like.
• the metal-containing material can be alloys such as stainless steel, indium tin oxide, and the like.
• a metal-containing material is the top layer of a multilayer substrate.
• the substrate can have a polymeric second layer and a metal containing first layer.
• the second layer is a polymeric film and the first layer is a thin film of gold.
• a multilayer substrate includes a polymeric film coated with a titanium-containing layer and then coated with a gold-containing layer. That is, the titanium layer can function as a tie layer or a primer layer for adhering the layer of gold to the polymeric film.
• a silicon support layer is covered with a layer of chromium and then with a layer of gold. The chromium layer can improve the adhesion of the gold layer to the silicon layer.
• the surface of the substrate typically includes a group capable of reacting with a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, disulfide, alkyl disulfide, benzotriazolyl, phosphono, phosphoroamido, phosphato, or ethylenically unsaturated group.
• the substrate includes a group capable of reacting with the group X 1 in compounds of Formula I (i.e., the substrate includes a complementary functional group to the group X 1 ).
• Substrates can include a support material that is treated to have an outer layer that includes a complementary functional group.
• the substrate can be prepared from any solid phase material known to have groups capable of reacting with X 1 and is not limited to the following examples of suitable materials.
• a carboxy group or a halocarbonyl group can react with a substrate having a hydroxy group to form a carbonyloxy-containing attachment group.
• substrate materials having hydroxy groups include, but are not limited to, polyvinyl alcohol, corona-treated polyethylene, hydroxy substituted esters of polymethacrylates, hydroxy substituted esters of polyacrylates, and a polyvinyl alcohol coating on a support material such as glass or polymer film.
• a carboxy group or a halocarbonyl group can also react with a substrate having a mercapto group to form a carbonylthio-containing attachment group.
• substrate materials having a mercapto group include, but are not limited to, mercapto substituted esters of polyacrylates, mercapto substituted esters of polymethacrylates, and glass treated with a mercaptoalkylsilane.
• a carboxy group or a halocarbonyl group can react with a primary aromatic amino group, a secondary aromatic amino group, or a secondary aliphatic amino group to form a carbonylimino-containing attachment group.
• substrate materials having aromatic primary or secondary amino groups include, but are not limited to, polyamines, amine substituted esters of polymethacrylate, amine substituted esters of polyacrylate, polyethylenimines, and glass treated with an aminoalkylsilane.
• a halocarbonyloxy group can react with a substrate having a hydroxy group to form an oxycarbonyloxy-containing attachment group.
• substrate materials having hydroxy groups include, but are not limited to, polyvinyl alcohol, corona-treated polyethylene, hydroxy substituted esters of polymethacrylates, hydroxy substituted esters of polyacrylates, and a polyvinyl alcohol coating on a support material such as glass or polymer film.
• a halocarbonyloxy group can also react with a substrate having a mercapto group to form an oxycarbonylthio-containing attachment group.
• substrate materials having a mercapto group include, but are not limited to, mercapto substituted esters of polymethacrylates, mercapto substituted esters of polyacrylates, and glass treated with a mercaptoalkylsilane.
• a halocarbonyloxy group can react with a substrate having a primary aromatic amino group, a secondary aromatic amino group, or a secondary aliphatic amino group to form an oxycarbonylimino-containing attachment group.
• substrate materials having aromatic primary or secondary amino groups include, but are not limited to, polyamines, amine substituted esters of polymethacrylate, amine substituted esters of polyacrylate, polyethylenimines, and glass treated with an aminoalkylsilane.
• a cyano group can react with a substrate having an azido group to form a tetrazinediyl-containing attachment group.
• substrates having azido groups include, but are not limited to, a coating of poly(4-azidomethylstyrene) on a glass or polymeric support.
• Suitable polymeric support materials include polyesters, polyimides, and the like.
• a hydroxy group can react with a substrate having isocyanate group to form an oxycarbonylimino-containing attachment group.
• Suitable substrates having isocyanate groups include, but are not limited to, a coating of 2-isocyanatoethylmethacrylate polymer on a support material.
• Suitable support materials include glass and polymeric materials such as polyesters, polyimides, and the like.
• a hydroxy group can also react with a substrate having a carboxy, carbonyloxycarbonyl, or halocarbonyl to form a carbonyloxy-containing attachment group.
• Suitable substrates include, but are not limited to, a coating of acrylic acid polymer or copolymer on a support material or a coating of a methacrylic acid polymer or copolymer on a support material.
• Suitable support materials include glass and polymeric materials such as polyesters, polyimides, and the like.
• Other suitable substrates include copolymers of polyethylene with polyacrylic acid, polymethacrylic acid, or combinations thereof.
• a mercapto group can react with a substrate having isocyanate groups.
• Suitable substrates having isocyanate groups include, but are not limited to, a coating of 2-isocyanatoethylmethacrylate copolymer on a support material.
• Suitable support materials include glass and polymeric materials such as polyesters, polyimides, and the like.
• a mercapto group can also react with a substrate having a halocarbonyl group to form a carbonylthio-containing attachment group.
• Substrates having halocarbonyl groups include, for example, chlorocarbonyl substituted polyethylene.
• a mercapto group can also react with a substrate having a halocarbonyloxy group to form an oxycarbonlythio-containing attachment group.
• Substrates having halocarbonyl groups include chloroformyl esters of polyvinyl alcohol.
• a mercapto group can react with a substrate having an ethylenically unsaturated group to form a thioether-containing attachment group.
• Suitable substrates having an ethylenically unsaturated group include, but are not limited to, polymers and copolymers derived from butadiene.
• An isocyanate group can react with a substrate having a hydroxy group to form a oxycarbonylimino-containing attachment group.
• substrate materials having hydroxy groups include, but are not limited to, polyvinyl alcohol, corona-treated polyethylene, hydroxy substituted esters of polymethacrylates or polyacrylates, and a polyvinyl alcohol coating on glass or polymer film.
• An isocyanate group can also react with a mercapto group to form a thiocarbonylimino-containing attachment group.
• substrate materials having a mercapto group include, but are not limited to, mercapto substituted esters of polymethacrylates or polyacrylates and glass treated with a mercaptoalkylsilane.
• an isocyanate group can react with a primary aromatic amino group, a secondary aromatic amino group, or a secondary aliphatic amino group to form a urea- containing attachment group.
• Suitable substrates having a primary or secondary aromatic amino group include, but are not limited to, polyamines, polyethylenimines, and coatings of an aminoalkylsilane on a support material such as glass or on a polymeric material such as a polyester or polyimide.
• An isocyanate group can also react with a carboxy to form an O-acyl carbamoyl- containing attachment group.
• Suitable substrates having a carboxylic acid group include, but are not limited to, a coating of an acrylic acid polymer or copolymer or a coating of a methacrylic acid polymer or copolymer on a glass or polymeric support.
• Copolymers include, but are not limited to, copolymers that contain polyethylene and polyacrylic acid or polymethacrylic acid.
• Suitable polymeric support materials include polyesters, polyimides, and the like.
• a halosilyl group, an alkoxysilyl group, or an acyloxysilyl group can react with a substrate having a silanol group to form a disiloxane-containing attachment group.
• Suitable substrates include those prepared from various glasses, ceramic materials, or polymeric material.
• These groups can also react with various materials having metal hydroxide groups on the surface to form a silane-containing linkage.
• Suitable metals include, but are not limited to, silver, aluminum, copper, chromium, iron, cobalt, nickel, zinc, and the like.
• the metal is stainless steel or another alloy.
• Polymeric material can be prepared to have silanol groups.
• commercially available monomers with silanol groups include 3-(trimethoxysilyl)propyl methacrylate and 3-aminoproplytrimethoxysilane available from Aldrich Chemical Co., Milwaukee, WI.
• An azido group can react, for example, with a substrate having carbon-carbon triple bond to form triazolediyl-containing attachment groups.
• An azido group can also react with a substrate having nitrile groups to form a tetrazenediyl-containing attachment group.
• Substrates having nitrile groups include, but are not limited to, coatings of polyacrylonitrile on a support material such as glass or a polymeric material. Suitable polymeric support material includes polyesters and polyimides, for example.
• Other suitable substrates having nitrile groups include acrylonitrile polymers or copolymers and
• 2-cyanoacrylate polymers or copolymers An azido group can also react with a strained olefinic group to form a triazolinyl- containing attachment group.
• Suitable substrates have a strained olefinic group include coatings that have pendant norbornenyl functional groups.
• Suitable support materials include, but are not limited to, glass and polymeric materials such as polyesters and polyimides.
• An aziridinyl group can react with a mercapto group to form a ⁇ - ammoalkylthioether-containing attachment group.
• substrate materials having a mercapto group include, but are not limited to, mercapto substituted esters of polymethacrylates or polyacrylates and glass treated with a mercaptoalkylsilane. Additionally, an aziridinyl group can react with a carboxy group to form a ⁇ - aminoalkyloxycarbonyl-containing attachment group.
• Suitable substrates having a carboxy include, but are not limited to, a coating of a acrylic acid polymer or copolymer, or a coating of a methacrylic acid polymer or copolymer on a glass or polymeric support.
• Copolymers include, but are not limited to, copolymers that contain polyethylene and polyacrylic acid or polymethacrylic acid.
• Suitable polymeric support materials include polyesters, polyimides, and the like.
• a haloalkyl group can react, for example, with a substrate having a tertiary amino group to form a quaternary ammonium-containing attachment group.
• Suitable substrates having a tertiary amino group include, but are not limited to, polydimethylaminostyrene or poly imethylaminoethylmethacrylate.
• a tertiary amino group can react, for example, with a substrate having a haloalkyl group to form a quaternary ammonium-containing attachment group.
• Suitable substrates having a haloalkyl group include, for example, coatings of a haloalkylsilane on a support material.
• Support materials can include, but are not limited to, glass and polymeric materials such as polyesters and polyimides.
• a primary aromatic amino or a secondary aromatic amino group can react, for example, with a substrate having an isocyanate group to form a oxycarbonylimino- containing attachment group.
• Suitable substrates having isocyanate groups include, but are not limited to, a coating of a 2-isocyanatoethylmethacrylate polymer or copolymer on a glass or polymeric support.
• Suitable polymeric supports include polyesters, polyimides, and the like.
• a primary aromatic amino or a secondary aromatic amino group can also react with a substrate containing a carboxy or halocarbonyl group to form a carbonylimino- containing attachment group.
• Suitable substrates include, but are not limited to, acrylic or methacrylic acid polymeric coatings on a support material.
• the support material can be, for example, glass or a polymeric material such as polyesters or polyimides.
• Other suitable substrates include copolymers of polyethylene and polymethacrylic acid or polyacrylic acid.
• a disulfide or an alkyl disulfide group can react, for example, with a metal surface to form a metal sulfide-containing attachment group.
• Suitable metals include, but are not limited to gold, platinum, palladium, nickel, copper, and chromium.
• the substrate can also be an alloy such an indium tin oxide or a dielectric material.
• a benzotriazolyl can react, for example, with a substrate having a metal or metal oxide surface.
• Suitable metals or metal oxides include, for example, silver, aluminum, copper, chromium, iron, cobalt, nickel, zinc, and the like.
• the metals or metal oxides can include alloys such as stainless steel, indium tin oxide, and the like.
• a phosphono, phosphoroamido, or phosphato can react, for example, with a substrate having a metal or metal oxide surface.
• Suitable metals or metal oxides include, for example, silver, aluminum, copper, chromium, iron, cobalt, nickel, zinc, and the like.
• the metals or metal oxides can include alloys such as stainless steel, indium tin oxide, and the like.
• An ethylenically unsaturated group can react, for example, with a substrate having an alkyl group substituted with a mercapto group. The reaction forms a heteroalkylene- containing attachment group.
• Suitable substrates include, for example, mercapto- substituted alkyl esters of polyacrylates or polymethacrylates.
• An ethylenically unsaturated group can also react with a substrate having a silicon surface, such as a silicon substrate formed using a chemical vapor deposition process.
• silicon surfaces can contain -SiH groups that can react with the ethylenically unsaturated group in the presence of a platinum catalyst to form an attachment group with Si bonded to an alkylene group.
• an ethylenically unsaturated group can react with a substrate having a carbon-carbon double bond to form an alkylene-containing attachment group.
• substrates include, for example, polymers derived from butadiene.
• Other ethylenically unsaturated groups include those in Formula la that are bonded to a carbonyl, carbonyloxy, or carbonylimino group.
• the resulting compounds can have, for example, an acryloyl, acrylamido, or vinyl ketone group that can react with a substrate having a hydroxy group to form an oxycarbonylethyleneoxy-containing attachment group, an iminocarbonylethyleneoxy-containing attachment group, or a carbonylethyleneoxy- containing attachment group, respectively.
• substrate materials having hydroxy groups include, but are not limited to, polyvinyl alcohol, corona-treated polyethylene, hydroxy substituted esters of polymethacrylates, hydroxy substituted esters of polyacrylates, and a polyvinyl alcohol coating on a support material such as glass or polymer film.
• a (meth)acryloyl, (meth)acrylamido, or vinyl ketone group can also react with a substrate having a mercapto group to form an oxycarbonylethylenethio-containing attachment group, an iminocarbonylethylenethio-containing attachment group, or a carbonylethylenethio-containing attachment group, respectively.
• substrate materials having a mercapto group include, but are not limited to, mercapto substituted esters of polymethacrylates, mercapto substituted esters of polyacrylates, and glass treated with a mercaptoalkylsilane.
• a acryloyl, acrylamido, or vinyl ketone group can also react with a substrate having a primary aromatic amino group, a secondary aromatic amino group, or a secondary aliphatic amino group to form an an oxycarbonylethyleneimino-containing attachment group, an iminocarbonylethyleneimino-containing attachment group, or a carbonylethyleneimino-containing attachment group, respectively.
• substrate materials having aromatic primary or secondary amino groups include, but are not limited to, polyamines, amine substituted esters of polymethacrylate, amine substituted esters of polyacrylate, polyethylenimines, and glass treated with an aminoalkylsilane.
• a (meth)acryloyl, (meth)acrylamido, or vinyl ketone group can react with a substrate having an azido group to form an oxycarbonyltriazolinyl-containing attachment group, an iminocarbonyltriazolinyl-containing attachment group, a carbonyltriazolinyl-containing attachment group, respectively.
• substrates having azido groups include, but are not limited to, a coating of poly(4- azidomethylstyrene) on a glass or polymeric support. Suitable polymeric support materials include polyesters, polyimides, and the like.
• the compounds of Formula I can undergo a self-assembly process when contacted with a substrate.
• self-assembly refers to process in which a material can spontaneously form a monolayer of substrate-attached tethering groups when contacted with a substrate.
• compounds having a disulfide or alkyl disulfide group for X 1 can undergo a self-assembly process when exposed to a gold substrate.
• compounds having a halosilyl group for X 1 can undergo a self-assembly process when exposed to a diamond-like glass or glass substrate.
• Formula ⁇ can represent the articles of the invention:
• Formula II represents a tethering group attached to a substrate.
• the tethering group is derived from a compound according to Formula I.
• the group U 1 is the attachment group formed by reaction of X 1 in a compound according to Formula I with a complementary functional group on the surface of a substrate.
• the groups Y 1 and R 1 are the same as previously defined for Formula I. That is, the article includes: a substrate; and a substrate-attached tethering group that includes a reaction product of a complementary functional group G on a surface of the substrate with a compound of
• X 1 is a substrate-reactive functional group selected from a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, disulfide, alkyl disulfide, benzotriazolyl, phosphono, phosphoroamido, or phosphato; Y 1 is a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R 4 is hydrogen, alkyl,
• these articles which are a subset of the articles of Formula ⁇ , include a substrate, and a substrate- attached tethering group.
• the substrate-attached tethering group is the reaction product of a complementary functional group G on the surface of the substrate with a compound of Formula la.
• the tethering group can be unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof.
• Formulas II and Ila show only one tethering group attached to the substrate; however, more than one tethering group can be attached to the substrate if there are more than one reactive group G on the substrate. Further, the substrate can have excess G groups on the surface of the substrate that have not reacted with a tethering compound.
• Groups on a substrate i.e., groups G
• groups G capable of reacting with X 1 groups in compounds according to Formula I include, but are not limited to, hydroxy, mercapto, primary aromatic amino group, secondary aromatic amino group, secondary aliphatic amino group, azido, carboxy, carbonyloxycarbonyl, isocyanate, halocarbonyl, halocarbonyloxy, silanol, and nitrile.
• the attachment of tethering groups to the surface of a substrate i.e., formation of the substrate-attached tethering groups of Formulas II
• the N-sulfonylaminocarbonyl group in the tethering group has reacted with an amine-containing material.
• a carbonylimino-containing connector group is formed resulting in the immobilization of an amine-containing material to the substrate.
• the amine-containing material can react with a N-sulfonylaminocarbonyl group of the substrate-attached tethering group of Formula II.
• the amine-containing materials are biomolecules such as, for example, amino acid, peptide, DNA, RNA, protein, enzyme, organelle, immunoglobin, or fragments thereof.
• the amine-containing material is a non- biological amine such as an amine-containing analyte.
• the amine-containing material (H 2 N-T) can react with the substrate-attached tethering group of Formula II by a nucleophilic substitution reaction to produce a substrate immobilized amine-containing material of Formula III:
• U 1 is the attachment group formed by reacting X 1 of a compound according to Formula I with a complementary functional group on the surface of the substrate; T is the remainder of the amine-containing material; and Y 1 and R 1 are the same as previously defined for Formulas I and II.
• H 2 N-T is any suitable primary amine-containing material.
• H 2 N-T is a biomolecule.
• the substrate immobilized amine-containing material of Formula HI can be of Formula Ilia for the tethering groups of Formula Ila:
• the substrate immobilized amine-containing material of Formula Ilia is a subset of Formula III.
• the presence of the immobilized amine can be determined, for example, using mass spectroscopy, contact angle measurement, infrared spectroscopy, and ellipsometry. Additionally, various immunoassays and optical microscopic techniques can be used if the amine-containing material is a biologically active material. Other materials can be bound to the amine-containing material.
• a complementary RNA or DNA fragment can hybridize with an immobilized RNA or DNA fragment.
• an antigen can bind to an immobilized antibody or an antibody can bind to an immobilized antigen.
• a bacterium such as Staphylococcus aureus can bind to an immobilized biomolecule.
• Method of immobilizing amine-containing material to a substrate Another aspect of the invention provides methods for immobilizing an amine- containing material to a substrate.
• the method involves preparing a substrate-attached tethering group by reacting a complementary functional group on the surface of the substrate with the substrate-reactive group X 1 in compounds of Formula I; and reacting a N-sulfonylaminocarbonyl group of the substrate-attached tethering group with an amine- containing material to form a carbonylimino-containing connector group between the substrate and the amine-containing material.
• the method of immobilizing an amine-containing material to a substrate is shown in Reaction Scheme B for a monovalent X 1 .
• H N-T is any suitable amine-containing material.
• H 2 N-T is a biomolecule. The method involves: selecting a compound of Formula I
• X 1 is a substrate-reactive functional group selected from a carboxy, halocarbonyl, halocarbonyloxy, cyano, hydroxy, mercapto, isocyanato, halosilyl, alkoxysilyl, acyloxysilyl, azido, aziridinyl, haloalkyl, tertiary amino, primary aromatic amino, secondary aromatic amino, disulfide, alkyl disulfide, benzotriazolyl, phosphono, phosphoroamido, phosphato, or ethylenically unsaturated group; Y 1 is a single bond or a divalent group selected from an alkylene, heteroalkylene, arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, -NR 4 -, or combinations thereof, wherein R a is hydrogen, alkyl, or aryl; Z 1 is an alkyl, aryl, or -(CO)
• the connector group is a divalent group of formula -U 1 -Y 1 -(CO)-NH- (the divalent group between the substrate and the group T in Formula III).
• the attachment group is part of the connector group.
• the N-sulfonylaminocarbonyl group of the substrate- attached tethering group reacts with an amine-containing material to form a connector group of formula -U 1 -(CO)-L 1 -Y 2 -(CO)-NH- (the divalent group between the substrate and the group T in Formula III).
• the attachment group is part of the connector group.
• the compounds of the invention can be used, for example, for immobilizing amine-containing material.
• the amine-containing material is an amine-containing analyte.
• the amine-containing materials are biomolecules such as, for example, amino acids, peptides, DNA, RNA, protein, enzymes, organelles, immunoglobins, or fragments thereof.
• Immobilized biological amine- containing materials can be useful in the medical diagnosis of a disease or of a genetic defect.
• the immobilized amine-containing materials can also be used for biological separations or for detection of the presence of various biomolecules. Additionally, the immobilized amine-containing materials can be used in bioreactors or as biocatalysts to prepare other materials.
• the substrate-attached tethering groups can be used to detect amine-containing analytes.
• Biological amine-containing materials often can remain active after attachment to the substrate (i.e., the articles according to Formula III can include biologically active amine-containing materials immobilized to the substrate).
• an immobilized antibody can bind with antigen or an immobilized antigen can bind to an antibody.
• An amine-containing material can bind to a bacterium.
• the immobilized amine-containing material can bind to a Staphylococcus aureus bacterium
• the immobilized amine-containing material can be a biomolecule that has a portion that can specifically bind to the bacterium.
• the articles prepared by attaching the compounds of the invention to a substrate typically have improved hydrolytic stability compared to previously known articles prepared using a tethering compound that is a derivative of N-hydroxysuccinimide.
• the compounds and the substrate-attached tethering groups of the invention can typically be used in aqueous systems.
• a carbonylimino-containing connector group is formed that results in the immobilization of the amine-containing material to the substrate (i.e., substrate immobilized amine- containing materials according to Formulas III).
• the rate of reaction of amine-containing materials with the N-sulfonylaminocarbonyl groups of the substrate-attached tethering groups is typically faster than the rate of hydrolysis of the N-sulfonylaminocarbonyl group. That is, immobilization of amine-containing materials occurs at a faster rate than the hydrolysis reactions.
• the amine-containing materials are not easily displaced once immobilization to a substrate has occurred due to the formation of a covalent carbonylimino bond.
• Aqueous buffer solutions were obtained from Sigma Aldrich Co., Milwaukee, WI or were prepared by known methods.
• HSA and conjugated and unconjugated IgG i.e., Immunoglobulin G
• the IR and 1H NMR spectra of each product formed in the Preparative Examples and Examples were consistent with the assigned structure.
• CHES buffer refers to an aqueous solution of 2- (cyclohexylamino)ethanesulfonic acid
• DLC refers to a diamond-like carbon coating prepared as described
• DG refers to a diamond-like glass coating prepared as described
• DMF refers to N,N-dimethylformamide
• ELISA refers to enzyme-linked immunoabsorbent assay
• FITC- ALBUMIN refers to fluorescein-labeled bovine serum albumin, which was obtained as a 2mg/mL solution in bicarbonate buffer from Sigma- Aldrich Corp., St.
• HSA human serum albumin
• S A-HRP streptavidin conjugated with horseradish peroxidase, which was obtained from Jackson ImmunoResearch Laboratories, Inc., West Grove, PA
• ABTS 2, 2'-azino-di-(3-ethylbenzthiazoline-6-sulfonate), which was obtained in kit form from KPL Inc., Gaithersburg, MD
• PBS phosphate buffered saline which has a pH of about 7.4
• SDS sodium dodecyl sulfate
• 'TWEEN 20 refers to polyoxyethylene(20) sorbitan monolaurate.
• AutoEL ellipsometer available from Rudolph Technologies, Inc., Flanders, NJ
• ellipsometric constants were determined by extrapolation of self assembled monolayers of 1-mercaptohexadecane, 1-mercaptododecane, and 1-mercaptooctane.
• the ellipsometric thicknesses of the monolayers were estimated by using a three-layer model and by assuming the refractive index of 1.46 for the monolayer.
• Methylamine is introduced from a cylinder via a stainless steel tube that is connected to a valve on the reactor.
• the reactor is periodically weighed, and methylamine is added until 20g have been added.
• Trifluoromethanesulfonylfluoride is then introduced into the reactor from a cylinder via a stainless steel tube until 97.9 g have been added.
• the pressure reactor is then sealed and is placed in a motorized rocker and is rocked and allowed to warm to room temperature. After a period of about 6 hours after the reactor reaches room temperature, it is slowly vented to the atmosphere by opening the valve.
• the product residue is washed with 10 weight percent aqueous HCl and the organic phase is then dried over MgSO 4 .
• the mixture is filtered and the solvent is removed from the filtrate using a rotary evaporator to afford the product.
• Preparative Example 2 Preparation of
• Preparative Example 8 Preparation of a multilayer substrate of DLG-DLC-polyimide- DLC-DLG
• a Model 2480 parallel-plate capacitively coupled reactive ion etcher obtained from PlasmaTherm, St. Russia, FL was used to deposit a diamond-like glass (DLG) coating using a tetramethylsilane plasma onto a diamond-like carbon coating (DLC).
• the DLC coating was deposited using an acetylene plasma with the Model 2480 reactive ion etcher onto a polyimide film.
• An approximately 20 cm by 30 cm sample of polyimide film available under the trade designation "KAPTON E” from E.I. du Pont de Nemours & Co., Wilmington, DE) was affixed to the powered electrode of the ion etcher using 3M 811 Adhesive Tape from
• the ion etcher chamber was closed and the chamber was pumped to a pressure of 0.67 Pa (0.005 Torr).
• Oxygen gas was introduced into the chamber at a flow rate of 500 standard cm 3 per minute, and the pressure of the chamber was maintained at 6.7Pa (0.050Torr). Plasma was ignited and was sustained at a power of 2000 W for 15 seconds.
• the oxygen gas flow was then terminated and the chamber was allowed to pump to a pressure of 0.67 Pa (0.005 Torr).
• Acetylene gas was then introduced into the chamber at a flow rate of 200 standard cm 3 per minute, and the pressure of the chamber was maintained at 2 Pa (0.015 Torr). Plasma was ignited and was sustained at a power of 1600 W for 10 seconds.
• acetylene gas was then terminated and the chamber was allowed to pump to a pressure of 0.67 Pa (0.005 Torr).
• Oxygen gas was again introduced into the chamber at a flow rate of 500 standard cm 3 per minute and, the pressure of the chamber was maintained at 20 Pa (0.15 Torr). Plasma was ignited and was sustained at a power of 300 W for 10 seconds.
• tetramethylsilane gas was introduced into the chamber at a flow rate of 150 standard cm 3 per minute.
• the chamber pressure was maintained at 20 Pa (0.15 Torr). Plasma was ignited and was sustained at a power of 300 W for 12 seconds.
• the flow of tetramethylsilane gas was terminated.
• SELECTED from VWR Scientific, West Chester, PA was treated in a plasma chamber according to the method of Preparative Example 8 to sequentially deposit layers of DLC and DLG onto one side of the glass microscope slide.
• Preparative Example 10 Preparation of a multilayer substrate of polyimide-titanium- gold Sequential layers of titanium and gold were deposited by electron beam evaporation onto polyimide film. A 10 cm by 15 cm sample of polyimide film (available under the trade designation "KAPTON E” from E. I. Du Pont de Nemours & Co.,
• Preparative Example 12 Preparation of acid chloride functionalized poly(methylmethacrylate-co-methacrylic acid) beads
• Poly(methylmethacrylate-co-methacrylic acid) beads available under the trade designation "MCI GEL CQK3 IP” from Mitsubishi Chemical Corp., Tokyo, Japan) (20 g) were combined with cyclohexane (66 g) and thionyl chloride (8.3 g) in a round bottom flask fitted with a magnetic stir bar, a reflux condenser and a source of nitrogen gas. The mixture was heated under reflux for 6 hours, during which time nitrogen gas was slowly passed through the apparatus. The mixture was then allowed to cool to room temperature and filtered- The beads were washed with cyclohexane and were then dried under a stream of nitrogen gas overnight to afford the product.
• Preparative Example 13 Preparation of hydroxyl functionalized poly(methylmethacrylate-co-methacrylic acid) beads
• the acid chloride functionalized poly(methylmethacrylate-co-methacrylic acid) b beads of Preparative Example 12 (20.43 g) were combined with 2-(2-aminoethoxy)ethanol (40.0 g) in a round bottom flask fitted with a magnetic stir bar. The mixture was stirred overnight at room temperature and then the beads were filtered and washed with methanol. The beads were then dried under a stream of nitrogen gas overnight to afford the product.
• Example 1 Preparation of
• a mixture of sodium saccharin dihydrate (1.0 g) and toluene (approximately 15 mL) was magnetically stirred and boiled under reflux in a round bottom flask fitted with a Dean-Stark trap and a reflux condenser. After 6 hours, the mixture was allowed to cool to room temperature and the volatile components were removed using a rotary evaporator. The entire portion of this material was combined with dry acetone (5.6 g) and succinoyl chloride (2.57 g) in a round bottom flask. The mixture was magnetically stirred at room temperature for 30 minutes after which time it was filtered. The filtrate was concentrated using a rotary evaporator.
• N-phenyltrifluoromethylsulfonamide (2.2 g) and N,N- diisopropylethylamine (1.3 g) in dry THF (25 mL) is added to a stirred solution of 10- undecenoyl chloride (2.0 g) in dry THF (25 mL).
• the solution is stirred overnight at room temperature and then the volatile components are removed using a rotary evaporator and then a high vacuum pump.
• a solution of this material is then made in methylene chloride (30 g) in 125 mL screw cap bottle.
• Platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisilane complex in xylenes is diluted with methylene chloride to a concentration of approximately 1.5 weight percent, and 3 drops of this solution are added to the bottle.
• the bottle is then sealed and is heated to 60 °C in a water bath. After 18 hours, the mixture is allowed to cool to room temperature and additional platinum complex solution (1 drop) is added.
• the bottle is again sealed and is heated at 60 °C for an additional 24 hours.
• the mixture is then cooled to room temperature and the volatile components are removed using a rotary evaporator to afford the product.
• Solid sodium saccharin (0.38 g) was added at room temperature to a magnetically stirred solution of the chlorocarbonyl containing product of Preparative Example 6 (0.75 g) in dry acetone (4.1 g). After mixing overnight, the mixture was poured into deionized water in a beaker and the resultant solid was filtered and dried overnight in a vacuum oven at room temperature and 66.7 Pa (0.5 mm Hg) to afford 0.60 g of product.
• Example 12 Attachment of a N-sulfonylaminocarbonyl containing tethering group to a gold-coated silicon substrate
• a 250-micromolar solution of the disulfide containing product of Example 10 in acetone was prepared.
• a 1 cm by 1 cm portion of a gold-coated silicon wafer was immersed in the solution for 30 minutes, after which time it was removed and was rinsed sequentially with ethanol and methanol and was then dried by directing a stream of nitrogen gas over the treated gold surface for approximately 1 minute.
• the ellipsometric thickness on the gold side of the multilayer substrate was determined to be 18 Angstroms.
• Example 13 Attachment of a N-sulfonylaminocarbonyl containing tethering group to multilayer substrate of glass-DLC-DLG A 1-millimolar solution of the trichlorosilyl containing product of Example 11 in methylene chloride was prepared. A multilayer substrate of glass-DLC-DLG, the product of Preparative Example 9, was immersed in this solution for 30 minutes, after which time it was rinsed with methylene chloride and was dried by directing a stream of nitrogen gas over the treated gold surface for approximately 1 minute. The static advancing contact angle of deionized water on the surface resulting from the attachment of tethering groups to the DLG substrate layer was determined to be 63 degrees.
• Example 14 Attachment of a N-sulfonylaminocarbonyl containing tethering group to a multilayer DLG-DLC-polyimide-DLC-DLG substrate
• a 1 millimolar solution of the trichlorosilyl product of Example 11 in methylene chloride was prepared.
• the static advancing contact angle of deionized water on a surface resulting from attachment of the tethering groups to the DLG substrate layer was determined to be 63 degrees.
• Example 15 Attachment of a N-sulfonylaminocarbonyl containing tethering group to a multilayer polyimide-titanium-gold substrate
• a 1 millimolar solution of the disulfide product of Example 10 in acetone was prepared.
• a sample a polyimide-titanium-gold multilayer substrate, approximately 2.5 cm by 7 cm, the product of Preparative Example 10, was immersed in this solution for 30 minutes, after which time both sides were rinsed with acetone and the sample was dried by directing a stream of nitrogen gas over the gold surface for approximately 1 minute each.
• the static advancing contact angle of deionized water on the surface resulting from attachment of the tethering groups to the gold substrate layer was determined to be
• Examples 16-17 Immobilization of lysine with N-sulfonylaminocarbonyl containing group attached to a gold coated silicon substrate
• Two 1 cm by 1 cm samples of the product of Example 12 (a N- sulfonylaminocarbonyl containing tethering group attached to a gold-coated silicon substrate) were immersed in a 1 millimolar solution of lysine in carbonate buffer.
• One of the samples (Example 16) was removed from the buffer after 30 minutes and was rinsed with deionized water.
• the ellipsometric thickness was determined as described above.
• the second sample (Example 17) was removed from the buffer after 90 minutes and was rinsed with deionized water before the ellipsometric thickness was determined.
• the data are given in Table 1 for the thickness of the layer attached to the gold substrate surface.
• Comparative Example 1-2 Immobilization of lysine with N-acyloxysuccinimide- containing tethering group attached to a gold-coated silicon substrate
• Two 1 cm by 1 cm samples of the product of Preparative Example 11 (N- acyloxysuccinimide containing tethering group attached to a gold-coated silicon substrate) were immersed in a 1 millimolar solution of lysine in carbonate buffer.
• One of the samples was removed from the buffer after 30 minutes (Comparative Example 1) and was rinsed with deionized water.
• the ellipsometric thickness was determined as described above.
• the second sample (Comparative Example 2) was removed from the buffer after 90 minutes and was rinsed with deionized water before the ellipsometric thickness was determined.
• the data are given in Table 1 for the thickness of the layer attached to the gold substrate surface.
• Example 18 Immobilization of fluorescent labeled IgG with a N-sulfonylaminocarbonyl containing tethering group attached to a multilayer substrate of glass-DLC-DLG Fluorescent labeled mouse IgG was reconstituted by mixing 0.55 mL of deionized water to give a solution of the IgG with a concentration of 2 mg/mL. This solution was diluted with CHES buffer to a IgG concentration of 50 ⁇ g/mL. Successive dilutions were made to give samples with IgG concentrations of 50 ⁇ g/mL, 25 ⁇ g/mL, 12.5 ⁇ g/mL, and 6.25 ⁇ g/mL.
• the slide was analyzed using a Model GeneTAC UC-4 scanner (available from Genomic Solutions, Inc., Ann Arbor, MI).
• the results, shown in Figure 1, indicate that the fluorescent labeled mouse IgG is bound to the surface of the substrate.
• Qualitative fluorescence intensity is highest with the most concentrated fluorescent labeled IgG sample and lowest with the least concentrated IgG sample.
• Example 19 Capture of Staphylococcus aureus with immobilized IgG on multilayer substrate of DLG-DLC-polyimide-DLC-DLG Rabbit IgG specific to Staphylococcus aureus (rabbit anti Staphylococcus aureus, obtained from Accurate Chemical & Scientific Corp., Westbury, NY) was used at a concentration of 4.52 mg/mL. This solution was diluted with CHES buffer to give a solution with a concentration of the IgG of 50 ⁇ g/mL.
• a 1 cm by 1 cm sample of the product of Example 14 (N-sulfonylaminocarbonyl containing tethering group attached to a multilayer substrate of DLG-DLC-polyimide-DLC-DLG; that is, the substrate was polyimide coated on both sides with a layer of DLC and then a layer of DLG) was immersed in this solution for 30 minutes after which time it was washed sequentially with PBS buffer, PBS buffer containing 0.05 weight percent TWEEN 20, and PBS buffer. The sample with immobilized IgG was then allowed to dry in air at room temperature for approximately 1 hour.
• a solution of acridine orange in deionized water at a concentration of lOmg/mL was diluted to a concentration of 0.1 mg/mL with deionized water.
• a 500 microliter aliquot of this solution was mixed in a centrifuge tube with a 500 microliter aliquot of a suspension of Staphylococcus aureus in PBS buffer at a concentration of 10 9 colony forming units per milliliter (cfu/mL). This mixture was allowed to stand at room temperature for 15 minutes, after which time it was mixed using a laboratory vortex mixer and was then centrifuged at 8000 rpm.
• the supernatant liquid was removed using a pipette and the bacteria were washed three times by adding 500 microliters of deionized water to the tube, mixing the contents using the vortex mixer, centrifuging the tube at 8000 rpm, and removing the supernatant liquid.
• the bacteria were then dispersed in PBS buffer by adding 500 microliters of buffer to the centrifuge tube and mixing the contents by using the vortex mixer.
• the concentration of S. aureus in the buffer was 10 9 colony forming units per milliliter (10 9 cfu/mL).
• the substrate with immobilized IgG was then affixed to a glass microscope slide using double-sided adhesive tape (available from 3M Company, St.
• Comparative Example 3 Exposure of Staphylococcus aureus to multilayer substrate of DLG-DLC-polyimide-DLC-DLG A 1 cm by 1 cm sample of the substrate of Preparative Example 8 (multilayer substrate of DLG-DLC polyimide film-DLC-DLG) was immersed CHES buffer for 30 minutes after which time it was washed sequentially with PBS buffer, PBS buffer containing 0.05 weight percent TWEEN 20, and PBS buffer. The substrate was then allowed to dry in air at room temperature for approximately 1 hour. The substrate was then immersed in a suspension of Staphylococcus aureus and was then rinsed and immersed in a 1 weight percent aqueous paraformaldehyde solution as described in Example 19. The sample was analyzed by confocal microscopy using an Olympus Model FV-300 confocal microscope (available from Leeds Precision hie, Minneapolis, MN). The results are shown in Figure 3.
• Examples 20-35 ELISA using a multilayer substrate of DLG-DLC-polyimide-DLC-
• DLG having attached N-sulfonylaminocarbonyl containing tethering groups For each of Examples 20-35, a 1 cm by 1 cm sample of the product of Example 14 (a multilayer substrate of DLG-DLC-polyimide-DLC-DLG with attached N- sulfonylaminocarbonyl containing tethering groups) was placed in a sterile culture tube that contained CHES buffer (1 mL) and various concentrations of the antibody anti-human mouse IgG. Four tubes each contained a concentration of anti-human mouse IgG in CHES buffer of 5 ⁇ g/mL, 10 ⁇ g/mL, 2O ⁇ g/mL, or 50 ⁇ g/mL.
• Each tube was shaken on a laboratory shaker for an exposure time of 5, 10, 30, or 60 minutes.
• the buffer was removed from each tube using a pipette and then the substrate immobilized IgG sample in each tube was washed three times with PBS buffer that contained 0.05 weight percent
• TWEEN 20 To each tube there was then added 1.5 mL of a solution of 2 weight percent nonfat dry milk powder (available under the trade designation "NESTLE CARNATION NONFAT DRY MILK POWDER” from Nestle USA, Glendale, CA) in PBS buffer. Each tube was placed on the shaker for 1 hour after which time the solution was removed using a pipette and then the sample in each tube was washed three times with PBS buffer that contained 0.05 weight percent TWEEN 20. A 1 mL aliquot of a solution of biotin-conjugated human IgG in PBS buffer, at a concentration of 4 ⁇ g/mL, was then added to each tube.
• 2 weight percent nonfat dry milk powder available under the trade designation "NESTLE CARNATION NONFAT DRY MILK POWDER” from Nestle USA, Glendale, CA
• PBS buffer that contained 0.05 weight percent TWEEN 20.
• the tubes were placed on the shaker for 1 hour after which time the solution was removed using a pipette and then the sample in each tube was washed three times with PBS buffer that contained 0.05 weight percent TWEEN 20.
• the tubes were placed on the shaker for 30 minutes, after which time the solution was removed from each tube using a pipette. Then the sample film in each tube was washed three times with PBS buffer that contained 0.05 weight percent TWEEN 20.
• Examples 36-41 Immobilization of lysine to a N-sulfonylaminocarbonyl containing compound attached to a multilayer substrate of glass-DLC-DLG
• Six samples of the product of Example 13 (a N-sulfonylaminocarbonyl containing tethering group to attached to a multilayer substrate of Glass-DLC-DLG) having a static advancing contact angle of deionized water of 63 degrees, were immersed in a 30 millimolar solution of lysine in CHES buffer. A sample was removed at time intervals, as shown in Table 3, and was washed with CHES buffer and dried under stream of nitrogen gas. The contact angle was then measured for the layer attached to the DLG surface of the multilayer substrate as described above. The data are shown in Table 3.
• Examples 42-46 Immobilization of HSA to a gold-coated silicon substrate with N- sulfonylaminocarbonyl containing tethering groups
• Five samples of the product of Example 12 (N-sulfonylaminocarbonyl containing tethering group attached to a gold-coated silicon substrate) were immersed in a 10 micromolar solution of HSA in carbonate buffer at pH 9.6. A sample was removed at time intervals, as shown in Table 4, and was washed sequentially with deionized water, ethanol, and methanol and was then dried under a stream of nitrogen gas. The ellipsometric thickness was then measured as described above and was compared to the thickness of the product of Example 12 (18 Angstroms). That is, the thickness of the layer attached to the gold surface of the substrate was measured. The data are shown in Table 4.
• Comparative Examples 4-7 Binding of HSA to a N-acyloxysuccinimide-containing tethering group attached to a gold-coated silicon substrate
• Four samples of the product of Preparative Example 11 (N-acyloxysuccinimide containing tethering groups attached to a gold-coated silicon substrate) were immersed in a 10 micromolar solution of HSA in carbonate buffer at pH 9.6. A sample was removed at time intervals, as shown in Table 5, and was washed sequentially with deionized water, ethanol and methanol and was then dried under a stream of nitrogen gas. The ellipsometric thickness was then measured as described above and was compared to the thickness of the film as prepared as described in Preparative Example 11 (17 Angstroms). That is, the thickness of the layer attached to the gold surface of the substrate was measured. The data are shown in Table 5.
• Example 47 Attachment of a N-methyl-trifluoromethanesulfonamide containing tethering group to a gold-coated silicon substrate
• a 1 cm by 1 cm portion of a gold-coated silicon wafer was immersed in the solution for 30 minutes, after which time it was removed and was rinsed sequentially with ethanol and methanol and was then dried by directing a stream of nitrogen gas over the treated gold surface for approximately 1 minute.
• the ellipsometric thickness was determined to be 17 Angstroms and the static advancing contact angle of deionized water on the surface resulting from the attachment of the tethering groups to the gold substrate layer was determined to be 79 degrees.
• Example 48 Attachment of a N-phenyl-trifluoromethanesulfonamide containing tethering group to a gold-coated silicon substrate
• a 1 cm by 1 cm portion of a gold-coated silicon wafer was immersed in the solution for 30 minutes, after which time it was removed and was rinsed sequentially with ethanol and methanol and was then dried by directing a stream of nitrogen gas over the treated gold surface for approximately 1 minute.
• the ellipsometric thickness was determined to be 23 Angstroms and the static advancing contact angle of deionized water on the surface resulting from the attachment of the tethering groups to the gold substrate layer was determined to be 73 degrees.
• Example 49 Immobilization of 1-aminododecane with N- methyltrifluoromethanesulfonamine-containing group attached to a gold coated silicon substrate
• a lcm by lcm sample of the product of Example 47 (a N- methyltrifluoromethanesulf onamide containing tethering group attached to a gold-coated silicon substrate) was immersed in a 1 millimolar solution of 1-aminododecane in ethanol. The sample was removed from the solution after 2 hours and was rinsed sequentially with ethanol and methanol and was then dried under a stream of nitrogen gas. The ellipsometric thickness was determined to be 21 Angstroms and the static advancing contact angle of deionized water on the surface was determined to be 86 degrees.
• Example 50 Immobilization of didodecylamine with N- methyltrifluoromethanesulfonamine-containing group attached to a gold coated silicon substrate
• a lcm by lcm sample of the product of Example 47 (a N- methyltrifluromethanesulfonamide containing tethering group attached to a gold-coated silicon substrate) was immersed in a 1 millimolar solution of didodecylamine in ethanol.
• the sample was removed from the solution after 2 hours and was rinsed sequentially with ethanol and methanol and was then dried under a stream of nitrogen gas.
• the ellipsometric thickness was determined to be 19 Angstroms and the static advancing contact angle of deionized water on the surface was determined to be 78 degrees.
• Example 51 Immobilization of 1-aminododecane with N- phenyltrifluoromethanesulfonamine-containing group attached to a gold coated silicon substrate
• a lcm by lcm sample of the product of Example 48 (a N- phenyltrifluromethanesulfonamide containing tethering group attached to a gold-coated silicon substrate) was immersed in a 1 millimolar solution of 1-aminododecane in ethanol.
• the sample was removed from the solution after 2 hours and was rinsed sequentially with ethanol and methanol and was then dried under a stream of nitrogen gas.
• the ellipsometric thickness was determined to be 26 Angstroms and the static advancing contact angle of deionized water on the surface was determined to be 78 degrees.
• Example 52 Immobilization of didodecylamine with N- phenyltrifluoromethanesulfona ⁇ ne-containing group attached to a gold coated silicon substrate
• a lcm by lcm sample of the product of Example 48 (a N- phenyltrifluromethanesulfonamide containing tethering group attached to a gold-coated silicon substrate) was immersed in a 1 millimolar solution of didodecylamine in ethanol.
• the sample was removed from the solution after 2 hours and was rinsed sequentially with ethanol and methanol and was then dried under a stream of nitrogen gas.
• the ellipsometric thickness was determined to be 23 Angstroms and the static advancing contact angle of deionized water on the surface was determined to be 78 degrees.
• Example 53 Capture of Staphylococcus aureus with immobilized IgG on multilayer substrate of polyimide-titanium-gold Rabbit IgG specific to Staphylococcus aureus (rabbit anti Staphylococcus aureus, obtained from Accurate Chemical & Scientific Corp., Westbury, NY) was used at a concentration of 4.52 mg/mL. This solution was diluted with CHES buffer to give a solution with a concentration of the IgG of 50 ⁇ g/mL.
• Example 15 N-sulfonylaminocarbonyl containing tethering group attached to a multilayer substrate of polyimide-titanium-gold as described in Preparative Example 10.
• PBS buffer PBS buffer containing 0.05 weight percent TWEEN 20
• PBS buffer PBS buffer
• the sample with immobilized IgG was then allowed to dry in air at room temperature for approximately 1 hour.
• a solution of acridine orange in deionized water at a concentration of lOmg/mL obtained from Molecular Probes, Inc., Eugene, OR
• a 500 microliter aliquot of this solution was mixed in a centrifuge tube with a 500 microliter aliquot of a suspension of Staphylococcus aureus in deionized water at a concentration of 10 9 colony forming units per milliliter (cfu/mL).
• This mixture was allowed to stand at room temperature for 15 minutes, after which time it was mixed using a laboratory vortex mixer and was then centrifuged at 8000 rpm.
• the supernatant liquid was removed using a pipette and the bacteria were washed three times by adding 500 microliters of deionized water to the tube, mixing the contents using the vortex mixer, centrifuging the tube at 8000 rpm, and removing the supernatant liquid.
• the bacteria were then dispersed in PBS buffer by adding 500 microliters of buffer to the centrifuge tube and mixing the contents by using the vortex mixer.
• the concentration of S. aureus in the buffer was 10 9 colony forming units per milliliter (10 9 cfu/mL).
• the substrate with immobilized IgG was then affixed to a glass microscope slide using double-sided adhesive tape (available from 3M Company, St. Paul, MN) and this construction was immersed in the suspension of S. aureus in PBS buffer for 1 hour.
• the sample was then washed sequentially with PBS buffer, PBS buffer containing 0.05 weight percent TWEEN 20, and PBS buffer.
• the sample was then immersed in a 1 weight percent aqueous solution of paraformaldehyde for 15 minutes, after which time it was washed with deionized water.
• the sample was analyzed by confocal microscopy using an
• Comparative Example 8 Exposure of Staphylococcus aureus to multilayer substrate of polyimide -titanium-gold A 1 cm by 1 cm sample of the substrate of Preparative Example 10 (multilayer substrate of polyimide film-titanium-gold) was immersed CHES buffer for 30 minutes after which time it was washed sequentially with PBS buffer, PBS buffer containing 0.05 weight percent TWEEN 20, and PBS buffer. The substrate was then allowed to dry in air at room temperature for approximately 1 hour. The substrate was then immersed in a suspension of S. aureus and was then rinsed and immersed in a 1 weight percent aqueous paraformaldehyde solution as described in Example 53.
• Example 54 Attachment of a N-sulfonylaminocarbonyl containing tethering group to a substrate of poly(methylmethacrylate-co-methacrylic acid) beads
• the hydroxyl functionalized beads of Preparative Example 13 (2.0 g) were combined with NMP (15 mL) in a round bottom flask that was fitted with a magnetic stir bar.
• the acid chloride product of Example 2 (0.19 g) in NMP (5 mL) was added to the flask.
• Example 55 Immobilization of FITC-albumin with a N-sulfonylaminocarbonyl containing tethering group attached to poly(methylmethacrylate-co-methacrylic acid) beads
• the poly(methylmethacrylate-co-methacrylic acid) beads with the N- sulfonylaminocarbonyl containing tethering group of Example 54 (50 mg) was combined with a solution of FITC-albumin (1 mL) in a centrifuge tube. The tube was placed on a laboratory rocker for 45 minutes.
• the beads were then washed by centrifuging the tube, decanting the supernatant liquid and then adding PBS buffer having a pH of 7.2 (lmL), again centrifuging the tube and again decanting the supernatant liquid. This washing with PBS buffer was repeated for a total of four washing cycles to afford beads that were yellow-orange in color. The color of the beads thus obtained was compared to the color of the beads of Example 54 that were not treated with FITC-albumin, which were white in color.
• the concentrate was slowly added to a stirred suspension of dry Na saccharin (31.29 g) in dry acetone (250 mL) chilled in an ice bath. The mixture was stirred overnight and allowed to warm to room temperature. The mixture was filtered. The filtrate was concentrated and slurried in chloroform, and then filtered again. The filtrate was concentrated, diethyl ether was added, and the precipitate was isolated by filtration and dried under a stream of nitrogen gas to give the desired product. Yield: 40.5 grams.
• Example 58 Preparation of A solution of 2-hydroxyethyl methacrylate (15.3 g), glutaric anhydride (14.08 g), and triethyl amine (19.08 g) in dry THF (114.9 mL) were stirred overnight at room temperature in a glass reaction vessel. The solution was concentrated using a rotary evaporator and the residue was dissolved in EtOAc (400 ⁇ _L). The organic phase was washed successively with deionized water and saturated aqueous NaCl and then dried over MgSO 4 . The solution was filtered, treated with thionyl chloride (16.9 g) and DMF (3 drops) in a glass reaction vessel.

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