US2022290005A1PendingUtilityA1

Coatings with tunable amine density

Assignee: COWPER SCIENCES INCPriority: Nov 9, 2016Filed: May 25, 2022Published: Sep 15, 2022
Est. expiryNov 9, 2036(~10.3 yrs left)· nominal 20-yr term from priority
C08G 65/336C08G 77/26G01N 33/543G01N 33/544C07F 7/1804C08G 77/14B01J 2219/00605C08F 30/08C09D 183/08B05D 1/60C09D 143/04C07F 7/087G01N 33/68
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Claims

Abstract

Molecules or salts thereof are provided, having the structure in Formula I, wherein n 2 and n 4 are the same or different and are independently 1, 2, or 3, and n 3 is 1 to 20; X is oxygen, nitrogen, or sulfur; wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as described herein. Methods are also provided for the synthesis of and use of the provided molecules in applications for diagnostic testing.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . A molecule or salt thereof, having the structure: 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are the same or different and are independently hydrogen, alkyl, alkenyl, aryl, heteroaryl, alkynyl, arylalkyl, arylalkenyl, haloalkyl, cycloalkyl, sulfonamidyl, acyl, or —CO 2 R 8 , wherein R 8  is alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, haloalkyl, cycloalkyl, cycloalkylalkyl, or arylcycloalkylalkyl; or wherein R 1  and R 2  and the N to which they are bound form a ring; or wherein at least one of R 1  or R 2  comprise a nucleoside, nucleotide, polynucleotide, peptide, peptoid, saccharide, polysaccharide, aptamer, or antibody or fragment thereof; 
         R 3 , oriented from N to X, is alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, amino-substituted amidoheteroalkyl, each optionally substituted with an alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, or amino-substituted amidoheteroalkyl; or wherein R 3  is —(CR 9 R 10 CR 11 R 12 ) n — wherein n is 1 to 100, and R 9 , R 10 , R 11 , and R 12  are the same or different and are independently hydrogen, halo, alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, amino-substituted amidoheteroalkyl; or wherein R 3  is 
       
       
         
           
           
               
               
           
         
         
           wherein n 2  and n 4  are the same or different and are independently 1, 2, or 3, and n 3  is 1 to 20; or 
           wherein R 3  is a polymer comprising alkyl, heteroalkyl, amino-substituted alkyl, aminoheteroalkyl, and amidoalkyl; 
         
         X is O, NR 13 , or S, wherein R 13  is hydrogen or alkyl; 
         R 4 , oriented from X to C, is alkyl, alkylether, and alkylthioether, wherein each of alkyl, alkylether, and alkylthioether is optionally substituted with hydroxyl, thiol, amino, or halo; 
         R 5 , R 6 , and R 7  are the same or different and are independently hydrogen, alkyl, silyl, or siloxy; and 
         wherein at least one of R 5 , R 6 , or R 7  optionally further comprises a solid phase. 
       
     
     
         2 . The molecule or salt of  claim 1 , comprising a solid phase. 
     
     
         3 . The molecule or salt of  claim 2 , wherein said solid phase comprises a silicon atom. 
     
     
         4 . A molecule or salt thereof having the structure: 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are the same or different and are independently hydrogen, alkyl, alkenyl, aryl, heteroaryl, alkynyl, arylalkyl, arylalkenyl, haloalkyl, cycloalkyl, sulfonamidyl, acyl, or —CO 2 R 8 , wherein R 8  is alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, haloalkyl, cycloalkyl, cycloalkylalkyl, or arylcycloalkylalkyl; or wherein R 1  and R 2  and the N to which they are bound form a ring; or wherein at least one of R 1  or R 2  comprise a nucleoside, nucleotide, polynucleotide, peptide, peptoid, saccharide, polysaccharide, aptamer, or antibody or fragment thereof; 
         R 3 , oriented from NR 1 R 2  to NH is alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, amino-substituted amidoheteroalkyl, each optionally substituted with an alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, or amino-substituted amidoheteroalkyl ; or wherein R 3  is —(CR 7 R 8 CR 9 R 10 ) n —, wherein n is 1 to 100, and R 7 , R 8 , R 9 , and R 10  are the same or different and are hydrogen, halo, alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, amino-substituted amidoheteroalkyl; or wherein R 3  is 
       
       
         
           
           
               
               
           
         
         
           wherein n 2  and n 4  are the same or different and are independently 1, 2, or 3, and n 3  is 1 to 20; or wherein R 3  is a polymer or dendrimer comprising alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, and amino-substituted amidoalkyl, amidoheteroalkyl, or amino-substituted amidoheteroalkyl; 
         
         R 4 , R 5 , and R 6  are the same or different and are independently hydrogen, alkyl, silyl, or siloxy; 
         (*) is a carbon center, wherein said carbon center is in an R-configuration or S-configuration; and 
         wherein at least one of R 4 , R 5 , or R 6  optionally further comprises a solid phase. 
       
     
     
         5 . The molecule or salt of  claim 4 , wherein said carbon center is in an R-configuration. 
     
     
         6 . The molecule or salt of  claim 4 , wherein said carbon center is in an S-configuration. 
     
     
         7 . The molecule or salt of any one  claims 4  to  6 , comprising said solid phase. 
     
     
         8 . The molecule or salt of  claim 7 , wherein said solid phase comprises a silicon atom. 
     
     
         9 . The molecule or salt of any one of  claims 4  to  8 , wherein R 3  is alkyl, aminoheteroalkyl, polyamidoaminoalkyl, or polyaminoalkyl. 
     
     
         10 . A molecule or salt thereof having the structure: 
       
         
           
           
               
               
           
         
         wherein: 
         n 1 =1, 2, 3, 4, 5, 6, or 7; 
         n 2  and n 3  are the same or different and are independently about 1 to about 1000; 
         R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20  are the same or different and are hydrogen, alkyl, alkenyl, aryl, heteroaryl, alkynyl, arylalkyl, arylalkenyl, haloalkyl, cycloalkyl, sulfonamidyl, acyl, or —CO 2 R 24 , wherein R 24  is alkyl, alkenyl, aryl, arylalkyl, arylalkenyl, haloalkyl, cycloalkyl, cycloalkylalkyl, or arylcycloalkylalkyl; or wherein R 1  and R 2  and the N to which they are bound, R 3  and R 4  and the N to which they are bound, R 5  and R 6  and the N to which they are bound, R 7  and R 8  and the N to which they are bound, R 9  and R 10  and the N to which they are bound, R 11  and R 12  and the N to which they are bound, R 13  and R 14  and the N to which they are bound, R 15  and R 16  and the N to which they are bound, R 17  and R 18  and the N to which they are bound, and R 19  and R 20  and the N to which they are bound independently optionally form a ring; 
         R 3 , R 4 , and R 5  are the same or different and are independently hydrogen, alkyl, silyl, or siloxy; 
         (*), (**), and (***) are carbon centers, wherein said carbon centers are independently in an R-configuration or S-configuration, or can be achiral centers; 
         (****) is a second carbon center, wherein said second carbon center is in an R-configuration or S-configuration; and 
         wherein at least one of R 21 , R 22 , or R 23  optionally further comprises a solid phase. 
       
     
     
         11 . The molecule of  claim 10 , wherein said carbon center is in an R-configuration. 
     
     
         12 . The molecule of  claim 10 , wherein said carbon center is in an S-configuration. 
     
     
         13 . A molecule or salt of any one of  claims 10  to  12 , comprising a solid phase. 
     
     
         14 . A molecule or salt of  claim 13 , wherein said solid phase comprises a silicon atom. 
     
     
         15 . A method of synthesizing the molecule or salt of any one of  claims 1  to  14 , comprising:
 a. forming an oxygen-silicon covalent bond between a solid substrate and a first molecule comprising:
 i. said silicon at a first end and an epoxide, isocyanate, or thioisocyanate at a second end; 
 b. forming a Y-carbon covalent bond between a carbon atom of said epoxide, isocyanate, or thioisocyanate and a second molecule comprising an amino group; 
 
 wherein Y is nitrogen, oxygen, sulfur, or selenium; 
 wherein said epoxide, isocyanate, or isothiocyanate and said silicon are linked by a group comprising an alkyl, alkylether, or alkylthioether, wherein each of alky, alkylether, or alkylthioether is optionally substituted with hydroxyl, thiol, amino, or halo. 
 
     
     
         16 . The method of  claim 15 , wherein said second molecule is an alkylamine, heteroalkylamine, amino-substituted alkylamine, amino-substituted heteroalkylamine, amidoalkylamine, amidoheteroalkylamine, amino-substituted amidoheteroalkylamine, each optionally substituted with an alkyl, heteroalkyl, amino-substituted alkyl, amino-substituted heteroalkyl, amidoalkyl, amidoheteroalkyl, or amino-substituted amidoheteroalkyl. 
     
     
         17 . The method of  claim 15  or  16 , wherein said forming an oxygen-silicon bond comprises a deposition reaction. 
     
     
         18 . The method of  claim 17 , wherein said deposition reaction is performed in the gas phase. 
     
     
         19 . The method of  claim 18 , wherein said deposition reaction comprises a chemical vapor deposition reaction. 
     
     
         20 . The method of  claim 19 , wherein said chemical vapor deposition reaction occurs at an elevated temperature. 
     
     
         21 . The method of  claim 20 , wherein said elevated temperature is at least about 100° C., 110° C., 120° C., 130° C., 140° C., or 150° C. 
     
     
         22 . The method of any one of  claims 15  to  21 , wherein step b further comprises the use of a diluent. 
     
     
         23 . The method of  claim 22 , wherein said diluent is an alcohol. 
     
     
         24 . The method of  claim 23 , wherein said alcohol is isopropyl alcohol. 
     
     
         25 . The method of any one of  claim 15  or  24 , wherein said first molecule is 3-glycidoxypropyltrimethoxysilane (GPTMS). 
     
     
         26 . The method of any one of  claims 15  to  25 , wherein said second molecule is ethylenediamine (EDA), (ethylenedioxy)bis(ethylamine) (EDBA), tris (2-aminoethyl)amine (TAEA), polyamidoamine (PAMAM), or polyallylamine (PAAm). 
     
     
         27 . The method of  claim 26 , wherein said second molecule is PAAm. 
     
     
         28 . The method of  claim 27 , wherein said PAAm has an average molecular weight of from about 1 KDa to about 100 KDa. 
     
     
         29 . The method of any one of  claims 15  to  28 , wherein said second molecule has a boiling point of from about 100° C., to 300° C. 
     
     
         30 . The method of any one of  claims 15  to  29 , further comprising coupling said amino group to a protected amino acid or salt thereof. 
     
     
         31 . The method of  claim 30 , wherein said protected amino acid is a tert-butyl carbamate (Boc)- or 9-fluorenylmethyl carbamate (Fmoc)-protected amino acid. 
     
     
         32 . The method of  claim 30  or  31 , wherein said amino acid is glycine. 
     
     
         33 . An amino coating comprising two or more molecules or salts of any one of  claims 1  to  14 . 
     
     
         34 . A method of tuning the amino group density of the amino coating of  claim 33 . 
     
     
         35 . An array comprising at least 2 molecules or salts of any one of  claims 1  to  14 . 
     
     
         36 . The array of  claim 35 , wherein said array comprises a density of said amino groups from about 1×10 10  groups per cm 2  to about 1×10 14  groups per cm 2 . 
     
     
         37 . The array of  claim 35  or  36 , wherein said molecules or salts are stereoenriched or a racemate. 
     
     
         38 . The array of any one of  claims 35  to  37 , wherein said molecules or salts have an enantiomeric excess of at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100%. 
     
     
         39 . The array of any one of  claims 35  to  38 , wherein at least some of said molecules or their salts form a coating, wherein said coating has a thickness of from about 1 angstrom to about 25 angstroms. 
     
     
         40 . The array of any one of  claims 35  to  39 , wherein said molecules or their salts are cross-linked. 
     
     
         41 . The array of any one of  claims 35  to  40 , further comprising instructions for use. 
     
     
         42 . A method of making an array, comprising associating the molecule or salt of any one of  claims 1  to  14  with a substrate. 
     
     
         43 . A method of making an array, comprising the method of any one of  claims 20  to  32 . 
     
     
         44 . The method of  claim 42  or  43 , wherein said array comprises a density of said amino groups from about 1×10 10  groups per cm 2  to about 1×10 14  groups per cm 2 . 
     
     
         45 . The method of any one of  claims 42  to  44 , comprising tuning the density of said amino groups on said array. 
     
     
         46 . A kit, comprising the molecule or salt of any one of  claims 1  to  14  and instructions for use. 
     
     
         47 . A kit, comprising the array of any one of  claims 35  to  41  and instructions for use. 
     
     
         48 . The kit of  claim 46  or  47 , further comprising a binding moiety. 
     
     
         49 . The kit of  claim 48 , wherein said binding moiety comprises an antibody. 
     
     
         50 . The kit of  claim 48  or  49 , wherein said binding moiety emits a signal. 
     
     
         51 . A method of making a kit, comprising forming the kit with the molecule or salt of any one of  claims 1  to  14 . 
     
     
         52 . A molecule or salt thereof made by the process of any one of  claims 15  to  32 . 
     
     
         53 . An array made by the process of any one of  claims 42  to  45 .

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