Polymers containing poly(ester amides) and agents for use with medical articles and methods of fabricating the same

Abstract

Polymers containing poly(ester amides) and agents for use with medical articles and methods of fabricating the same are disclosed. The medical article generally comprises an implantable substrate having a coating, and the coating contains a polymer comprising a polymeric product of a reaction comprising a polyol, a polycarboxylic acid, an amino acid and an agent.

1 . A polymer represented by a formula:  
     
       
         
         
             
             
         
       
       wherein A comprises  
       
         
           
           
               
               
           
         
       
       B comprises  
       
         
           
           
               
               
           
         
       
       where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 3  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 2  and R 4  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 6  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained and branched aliphatic radicals;  
       L 1  is an optional linkage connecting said A to said B;  
       X is optionally an agent;  
       L 2  is optionally a linkage connecting X to said polymer;  
       n and m are integers not equal to 0;  
       provided that if (i) said R 1 , R 3  and R 5  are independently selected straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (ii) said R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; (iii) R 6  is a pentylene radical; and, (iv) said X is a straight-chained or branched saturated aliphatic radical having from 1-6 carbon atoms, a phenyl radical, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and, (v) said m and n are integers not equal to 0; then, said L 2  cannot be  
       
         
           
           
               
               
           
         
       
       when the carbon of said L 2  is attached to either C 1  or C 5  of the pentylene radical, R 6 ;  
       provided further that if (i) said R 1  and R 5  are unsubstituted, straight-chained octyl radicals; (ii) said R 3  is an unsubstituted, straight-chained butyl radical; (iii) said R 2  and R 4  are unsubstituted t-butyl radicals; (iv) said R 6  is a pentylene radical; and (v) said X is TEMPO; then, said L 2  cannot be  
       
         
           
           
               
               
           
         
       
       when the carbon of said L 2  is attached to either C 1  or C 5  of the pentylene radical, R 6 , and the nitrogen of said L 2  is attached to C 1  of the TEMPO;  
       and provided further that if (i) said R 1  and R 5  are straight-chained-butyl or straight-chained-hexyl radicals; (ii) said R 3  is a straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (iii) said R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; (iv) said R 6  is a pentylene radical; (v) said X is TEMPO and L 2  is  
       
         
           
           
               
               
           
         
       
       or said X is rapamycin and said L 2  is  
       
         
           
           
               
               
           
         
       
       then, said R 1  and R 5  cannot be substituted with epoxy groups.  
     
   
   
       2 . The polymer of  claim 1 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations-thereof.  
   
   
       3 . The polymer of  claim 1 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       4 . The polymer of  claim 1 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolirnus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, and any derivatives, salts and combinations thereof.  
   
   
       5 . The polymer of  claim 4 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       6 . The polymer of  claim 4 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       7 . The polymer of  claim 4 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       8 . The polymer of  claim 4 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       9 . The polymer of  claim 1 , wherein said L 2  is selected from a group consisting of anhydrides, ketals, acetals, orthoesters and all-aromatic carbonates.  
   
   
       10 . The polymer of  claim 1 , wherein said polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n, m and r are integers not equal to 0.  
     
   
   
       11 . The polymer of  claim 1 , wherein said polymer is represented by the formula:  
     
       
         
         
             
             
         
       
       wherein n and m are integers not equal to 0.  
     
   
   
       12 . The polymer of  claim 1 , wherein said polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein m and n are integers not equal to 0.  
     
   
   
       13 . A polymer represented by a formula:  
     
       
         
         
             
             
         
       
       wherein A comprises  
       
         
           
           
               
               
           
         
       
       B comprises  
       
         
           
           
               
               
           
         
       
       where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 3  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 2 , R 4 , and R 7  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 6  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained and branched aliphatic radicals;  
       L 1  is an optional linkage connecting said A to said B;  
       X is optionally an agent;  
       L 2  is optionally a linkage connecting X to said polymer; and  
       n and m are integers not equal to 0.  
     
   
   
       14 . The polymer of  claim 13 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       15 . The polymer of  claim 14 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       16 . The polymer of  claim 13 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       17 . The polymer of  claim 16 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       18 . The polymer of  claim 16 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       19 . The polymer of  claim 16 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       20 . The polymer of  claim 16 ,.wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       21 . The polymer of  claim 13 , wherein said L 2  is selected from a group consisting of amides, esters, anhydrides, ketals, acetals, orthoesters and all-aromatic carbonates.  
   
   
       22 . The polymer of  claim 13 , wherein said polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n, m and r are integers not equal to 0.  
     
   
   
       23 . A polymer represented by a formula:  
     
       
         
         
             
             
         
       
       wherein A comprises  
       
         
           
           
               
               
           
         
       
       and B comprises  
       
         
           
           
               
               
           
         
       
       where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 3  and R 8  are selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 2 , R 4 , R 7  and R 9  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       L 1  is an optional linkage connecting said A to said B;  
       X is optionally an agent;  
       L 2  is optionally a linkage connecting X to said polymer; and  
       n and m are integers not equal to 0.  
     
   
   
       24 . The polymer of  claim 23 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       25 . The polymer of  claim 24 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       26 . The polymer of  claim 23 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       27 . The polymer of  claim 26 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       28 . The polymer of  claim 26 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       29 . The polymer of  claim 26 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       30 . The polymer of  claim 26 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       31 . The polymer of  claim 23 , wherein said L 2  is selected from a group consisting of amides, esters, anhydrides, ketals, acetals, orthoesters and all-aromatic carbonates.  
   
   
       32 . The polymer of  claim 23 , wherein said polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n and m are integers not equal to 0.  
     
   
   
       33 . A medical article comprising an implantable substrate comprising a coating, wherein said coating comprises a block-copolymer comprising at least one block of poly(ester amide) and at least one block of a polymeric agent.  
   
   
       34 . The medical article of  claim 33 , wherein said polymeric agent is a biobeneficial agent selected from a group consisting of heparin, hyaluronic acid, poly(ethylene glycol), a graft copolymer of poly(L-lysine) and poly(ethylene glycol), and copolymers and combinations thereof.  
   
   
       35 . A polymer comprising a poly(ester amide) that is a polymeric product of a reaction comprising a polyol, a polycarboxylic acid, an amino acid, and an agent (X); 
 provided that said polymeric product is not                          where (i) R 1 , R 3  and R 5  are independently selected straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (ii) R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and (iii) X is a straight-chained or branched saturated aliphatic radical having from 1-6 carbon atoms, a phenyl radical, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and, (iv) m and n are integers not equal to 0; and    provided further that said polymeric product is not                          where n and m are integers not equal to 0; and    provided further that said polycarboxylic acid is not 2,3-epoxysuccinic acid, 3,4-epoxyadipic acid or a diepoxyadipic acid, where the amino acid chosen to link with said X is lysine, and said X is 4-amino-TEMPO or rapamycin.    
   
   
       36 . The polymer of  claim 35 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       37 . The polymer of  claim 36 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       38 . The polymer of  claim 35 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       39 . The polymer of  claim 38 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       40 . The polymer of  claim 38 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       41 . The polymer of  claim 38 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       42 . The polymer of  claim 38 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       43 . A coating for a medical article comprising the polymer of  claim 1 .  
   
   
       44 . A coating for a medical article comprising the polymer of  claim 13 .  
   
   
       45 . A coating for a medical article comprising the polymer of  claim 23 .  
   
   
       46 . A coating for a medical article comprising the polymer of  claim 35 .  
   
   
       47 . A medical article comprising the polymer of  claim 1 .  
   
   
       48 . A medical article comprising the polymer of  claim 13 .  
   
   
       49 . A medical article comprising the polymer of  claim 23 .  
   
   
       50 . A medical article comprising the polymer of  claim 35 .  
   
   
       51 . A stent comprising a coating, wherein said coating comprises a polymer represented by a formula:  
     
       
         
         
             
             
         
       
       wherein A comprises  
       
         
           
           
               
               
           
         
       
       B is selected from a group consisting of  
       
         
           
           
               
               
           
         
       
       where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 3  and R 8  are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 2 , R 4 , R 7  and R 9  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;  
       R 6  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained and branched aliphatic radicals;  
       L 1  is an optional linkage connecting said A to said B;  
       n and m are integers not equal to 0;  
       provided that B is not  
       
         
           
           
               
               
           
         
       
       where (i) said R 1 , R 3  and R 5  are independently selected straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (ii) said R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and (iii) said R 6  is a carboxyl-substituted, pentylene radical;  
       and provided further that B is not  
       
         
           
           
               
               
           
         
       
       where (i) said R 1  and R 5  are epoxy-substituted, straight-chained-butyl or straight-chained-hexyl radicals; (ii) said R 3  is a straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (iii) said R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and (iv) said R 6  is a carboxyl-substituted, pentylene radical.  
     
   
   
       52 . The stent of  claim 51 , wherein said coating further comprises an agent that may be blended or connected to said coating.  
   
   
       53 . A method for fabricating a medical article comprising an implantable substrate, wherein said method comprises: 
 (a) preparing a polymer represented by a formula:                          wherein A comprises                          B comprises                          where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 3  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 2  and R 4  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 6  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained and branched aliphatic radicals;    L 1  is an optional linkage connecting said A to said B;    X is optionally an agent;    L 2  is optionally a linkage connecting X to said polymer;    n and m are integers not equal to 0;    provided that if (i) said R 1 , R 3  and R 5  are independently selected straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (ii) said R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; (iii) said R 6  is a pentylene radical; and, (iv) said X is a straight-chained or branched saturated aliphatic radical having from 1-6 carbon atoms, a phenyl radical, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and, (v) said m and n are integers not equal to 0; then, said L 2  cannot be                          when the carbon of said L 2  is attached to either C 1  or C 5  of the pentylene radical, R 6 ;    provided further that if (i) said R 1  and R 5  are unsubstituted, straight-chained octyl radicals; (ii) said R 3  is an unsubstituted, straight-chained butyl radical; (iii) said R 2  and R 4  are unsubstituted t-butyl radicals; (iv) said R 6  is a pentylene radical; and (v) said X is TEMPO; then, said L 2  cannot be                          where the carbon of said L 2  is attached to either C 1  or C 5  of the pentylene radical, R 6 , and the nitrogen of said L 2  is attached to C 1  of the TEMPO;    and provided further that if (i) said R 1  and R 5  are straight-chained-butyl or straight-chained-hexyl radicals; (ii) said R 3  is a straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (iii) said R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; (iv) said R 6  is a pentylene radical; (v) said X is TEMPO and L 2  is                          where the carbon of said L 2  is attached to either C 1  or C 5  of the pentylene radical, R 6 , and the nitrogen of said L 2  is attached to C 1  of the TEMPO,    or said X is rapamycin and said L 2  is                          when the carbon of said L 2  is attached to either C 1  or C 5  of the pentylene radical, R 6 ; then, said R 1  and R 5  cannot be substituted with epoxy groups; and    (b) forming a coating comprising the polymer on at least a portion of an implantable substrate.    
   
   
       54 . The method of  claim 53 , wherein said medical article is a stent.  
   
   
       55 . The method of  claim 53 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       56 . The method of  claim 55 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       57 . The method of  claim 53 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       58 . The method of  claim 57 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       59 . The method of  claim 57 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       60 . The method of  claim 57 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       61 . The method of  claim 57 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       62 . The method of  claim 53 , wherein said L 2  is selected from a group consisting of amides, esters, anhydrides, ketals, acetals, orthoesters and all-aromatic carbonates.  
   
   
       63 . The method of  claim 53 , wherein the polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n, m and r are integers not equal to 0.  
     
   
   
       64 . The method of  claim 53 , wherein the polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n and m are integers not equal to 0.  
     
   
   
       65 . The method of  claim 53 , wherein the polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n and m are integers not equal to zero.  
     
   
   
       66 . A method for fabricating a medical article comprising: 
 (a) preparing a polymer represented by a formula:                          wherein A comprises                          B comprises                          where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 3  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 2 , R 4 , and R 7  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 6  is selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained and branched aliphatic radicals;    L 1  is an optional linkage connecting said A to said B;    X is optionally an agent;    L 2  is optionally a linkage connecting X to said polymer;    n and m are integers not equal to 0; and    (b) forming a coating comprising the polymer on at least a portion of an implantable substrate.    
   
   
       67 . The method of  claim 66 , wherein said medical article is a stent.  
   
   
       68 . The method of  claim 66 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       69 . The method of  claim 68 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       70 . The method of  claim 66 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       71 . The method of  claim 70 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       72 . The method of  claim 70 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       73 . The method of  claim 70 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       74 . The method of  claim 70 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       75 . The method of  claim 66 , wherein said L 2  is selected from a group consisting of amides, esters, anhydrides, ketals, acetals, orthoesters and all-aromatic carbonates.  
   
   
       76 . The method of  claim 66 , wherein the polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n, m and r are integers not equal to zero.  
     
   
   
       77 . A method for fabricating a medical article comprising: 
 (a) preparing a polymer represented by a formula:                          wherein A comprises                          B comprises                          where R 1  and R 5  are optional and are independently selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 3  and R 8  are selected from a group consisting of substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    R 2 , R 4 , R 7  and R 9  are independently selected from a group consisting of hydrogen; substituted, unsubstituted, hetero-, straight-chained, branched, cyclic, saturated and unsaturated aliphatic radicals; and substituted, unsubstituted, and hetero-aromatic radicals;    L 1  is an optional linkage connecting said A to said B;    X is optionally an agent;    L 2  is optionally a linkage connecting X to said polymer;    n and m are integers not equal to 0; and    (b) forming a coating comprising the polymer on at least a portion of an implantable substrate.    
   
   
       78 . The method of  claim 77 , wherein said medical article is a stent.  
   
   
       79 . The method of  claim 77 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate), sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       80 . The method of  claim 79 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       81 . The method of  claim 77 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       82 . The method of  claim 81 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       83 . The method of  claim 81 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       84 . The method of  claim 81 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       85 . The method of  claim 81 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.  
   
   
       86 . The method of  claim 77 , wherein said L 2  is selected from a group consisting of amides, esters, anhydrides, ketals, acetals, orthoesters and all-aromatic carbonates.  
   
   
       87 . The method of  claim 77 , wherein the polymer is represented by a formula:  
     
       
         
         
             
             
         
       
       wherein n and m are integers not equal to zero.  
     
   
   
       88 . A method for fabricating a medical article comprising: 
 (a) preparing a polymer comprising a poly(ester amide), wherein said preparing comprises combining a polyol, a polycarboxylic acid, an amino acid, and an agent (X);    provided that said polymer is not                          where (i) R 1 , R 3  and R 5  are independently selected straight-chained or branched saturated aliphatic radicals having from 2-20 carbon atoms; (ii) R 2  and R 4  are independently selected straight-chained or branched saturated aliphatic radicals having from 1-6 carbon atoms, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one unsaturated carbon-carbon bond, straight-chained or branched aliphatic radicals having from 2-6 carbon atoms and at least one carbon-carbon triple bond, phenyl radicals, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and (iii) X is a straight-chained or branched saturated aliphatic radical having from 1-6 carbon atoms, a phenyl radical, an ortho-fused bicyclic carbocyclic radical having 6-10 carbon atoms and at least one aromatic ring, or hydrogen; and, (iv) m and n are integers not equal to 0;    provided further that said polymer is not                          where n and m are integers not equal to 0;    provided further that said polycarboxylic acid is not 2,3-epoxysuccinic acid, 3,4-epoxyadipic acid or a diepoxyadipic acid, where the amino acid chosen to link with said X is lysine, and said X is 4-amino-TEMPO or rapamycin; and    (b) forming a coating comprising the polymer on at least a portion of an implantable substrate.    
   
   
       89 . The method of  claim 88 , wherein said preparing further comprises producing a poly(ester amide) with all amino end-groups for conjugating to said agent.  
   
   
       90 . The method of  claim 88 , wherein said preparing further comprises producing a poly(ester amide) with all carboxyl end-groups for conjugating to said agent.  
   
   
       91 . The method of  claim 88 , wherein said medical article comprises a stent.  
   
   
       92 . The method of  claim 88 , wherein said X is a biobeneficial agent selected from a group consisting of poly(alkylene glycols), poly(N-vinyl pyrrolidone), poly(acrylamide methyl propane sulfonic acid), poly(styrene sulfonate)i sulfonated dextran; polyphosphazenes, poly(orthoesters), poly(tyrosine carbonate), hyaluronic acid, heparin and any derivatives, analogs, homologues, congeners, salts, copolymers and combinations thereof.  
   
   
       93 . The method of  claim 92 , wherein the biobeneficial agent is hyaluronic acid, heparin, poly(ethylene glycol), or any derivatives, analogs, homologues, congeners, salts, copolymers or combinations thereof.  
   
   
       94 . The method of  claim 88 , wherein said X is a bioactive agent selected from a group consisting of a free radical scavenger, a nitric oxide donor, rapamycin, everolimus, tacrolimus, paclitaxel, docetaxel, estradiol, clobetasol, idoxifen, tazarotene and any prodrugs, metabolites, analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       95 . The method of  claim 94 , wherein the free radical scavenger is selected from a group consisting of 2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-amino-2,2′,6,6′-tetramethyl-1-piperinyloxy, free radical; 4-hydroxy-2,2′,6,6′-tetramethyl-piperidene-1-oxy, free radical; 2,2′,3,4,5,5′-hexamethyl-3-imidazolinium-1-yloxy methyl sulfate, free radical; 16-doxyl-stearic acid, free radical; superoxide dismutase mimic; and, any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       96 . The method of  claim 94 , wherein the free radical scavenger is TEMPO or any analogs, homologues, congeners, derivatives, salts or combinations thereof.  
   
   
       97 . The method of  claim 94 , wherein the nitric oxide donor is selected from the group consisting of S-nitrosothiols, nitrites, N-oxo-N-nitrosamines, substrates of nitric oxide synthase, diazenium diolates and any analogs, homologues, congeners, derivatives, salts and combinations thereof.  
   
   
       98 . The method of  claim 94 , wherein the bioactive agent is rapamycin, everolimus, tacrolimus, or any prodrug, metabolite, analog, congener, derivative, salt or combinations thereof.