Molecular Actuators, and Methods of Use Thereof

Abstract

The synthesis of thiophene based conducting polymer molecular actuators, exhibiting electrically triggered molecular conformational transitions is reported. Actuation is believed to be the result of conformational rearrangement of the polymer backbone at the molecular level, not simply ion intercalation in the bulk polymer chain upon electrochemical activation. Molecular actuation results from π-π stacking of thiophene oligomers upon oxidation, producing a reversible molecular displacement that leads to surprising material properties, such as electrically controllable porosity and large strains. The existence of active molecular conformational changes is supported by in situ electrochemical data. Single molecule techniques have been used to characterize the molecular actuators.

1 - 62 . (canceled) 
     
     
         63 . A method of displacing an object, comprising:
 a) attaching a polymer to a first object and attaching a different position of said polymer to a second object; and   b) applying a potential to said polymer thereby oxidizing or reducing said polymer, resulting in the displacement of said first object wherein said displacement is at least 8% of the distance between the two points of attachment on said polymer to said objects prior to oxidation or reduction of said polymer, wherein said polymer has the following formula:   
       
         
           
           
               
               
           
         
       
       wherein
 A represents independently for each occurrence heteroaryl; 
 x is independently for each occurrence an integer from 2 to 8 inclusive; 
 B represents a bond or 
 
       
         
           
           
               
               
           
         
       
       wherein
 R represents independently for each occurrence H, alkyl, alkaryl, alkenyl, alkynyl, silyl, alkylthio, imino, amido, phosphoryl, phosphonate, phosphine, phosphonamide, carboxyl, carboxamide, keto, alkylsulfonyl, arylsulfonyl, selenoalkyl, formyl, ester, heteroalkyl, cyano, guanidine, amidine, acetal, ketal, aryl, heteroaryl, aralkyl, heteroaralkyl, epoxide, hydroxamic acid, imido, oxime, sulfonamine, sulfonamide, sulfonomate, thioamide, thiocarbamate, urea, thiourea, saturated or mono or poly unsaturated fatty acid, or —(CH 2 ) m —R 80 , or two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —, with the proviso that R is not methyl; 
 R 80  represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group; 
 m is independently for each occurrence an integer in the range 0 to 8 inclusive; and 
 n represents an integer from 2 to about 100. 
 
     
     
         64 . The method of  claim 63 , wherein R represents independently for each occurrence H, alkyl, alkaryl, heteroalkyl, heteroalkaryl, aryl, aralkyl, heteroaryl, or heteroaralkyl, or two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —. 
     
     
         65 . The method of  claim 63 , wherein heteroaryl is selected independently for each occurrence from the group consisting of pyrroles, furans, thiophenes, imidazoles, oxazoles, thiazoles, triazoles, pyrazoles, pyridines, pyrazines, pyridazines, 2,3-dihydrothieno[3,4-b]-1,4-dioxins, and pyrimidines. 
     
     
         66 . The method of  claim 63 , wherein heteroaryl is selected independently for each occurrence from the group consisting of furans, pyrroles, thiophenes, and 2,3-dihydrothieno[3,4-b]-1,4-dioxins. 
     
     
         67 . The method of  claim 63 , wherein R represents independently for each occurrence H, alkyl, alkaryl, heteroalkyl, heteroalkaryl, aryl, aralkyl, heteroaryl, or heteroaralkyl, or two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —; and heteroaryl is selected independently for each occurrence from the group consisting of pyrroles, furans, thiophenes, imidazoles, oxazoles, thiazoles, triazoles, pyrazoles, pyridines, pyrazines, pyridazines, 2,3-dihydrothieno[3,4-b]-1,4-dioxins, and pyrimidines. 
     
     
         68 . The method of  claim 63 , wherein R represents independently for each occurrence H, alkyl, alkaryl, heteroalkyl, heteroalkaryl, aryl, aralkyl, heteroaryl, or heteroaralkyl, or two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —; and heteroaryl is selected independently for each occurrence from the group consisting of furans, pyrroles, thiophenes, and 2,3-dihydrothieno[3,4-b]-1,4-dioxins. 
     
     
         69 . The method of  claim 63 , wherein A is thiophene, B is 
       
         
           
           
               
               
           
         
       
       and R represents independently for each occurrence H, alkyl, alkaryl, heteroalkyl, heteroalkaryl, aryl, aralkyl, heteroaryl, or heteroaralkyl, or two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —. 
     
     
         70 . The method of  claim 63 , wherein A is thiophene, x is 4, B is 
       
         
           
           
               
               
           
         
       
       and two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —. 
     
     
         71 . The method of  claim 63 , wherein A is thiophene, x is 4, B is 
       
         
           
           
               
               
           
         
       
       and R is H. 
     
     
         72 . The method of  claim 63 , wherein A is thiophene, x is 4, B is 
       
         
           
           
               
               
           
         
       
       and R is propyl. 
     
     
         73 . The method of  claim 63 , wherein A is 2,3-dihydrothieno[3,4-b]-1,4-dioxin, B is 
       
         
           
           
               
               
           
         
       
       and R represents independently for each occurrence H, alkyl, alkaryl, heteroalkyl, heteroalkaryl, aryl, aralkyl, heteroaryl, or heteroaralkyl, or two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —. 
     
     
         74 . The method of  claim 63 , wherein A is 2,3-dihydrothieno[3,4-b]-1,4-dioxin, x is 4, B is 
       
         
           
           
               
               
           
         
       
       and two instances of R taken together represent —CH 2 CH 2 OCH 2 (CH 2 OCH 2 ) y CH 2 OCH 2 CH 2 —. 
     
     
         75 - 95 . (canceled)