Slippery Anti-Fouling Surfaces Fabricated from Reactive Polymer Multilayers

Abstract

This invention provides slippery liquid-infused porous surfaces (SLIPS) using nanoporous or microporous and chemically reactive polymer multilayers. This approach permits fabrication of slippery anti-fouling coatings on complex surfaces and provides new means to manipulate the mobilities of contacting aqueous fluids. The results expand the range of tools that can be used to manipulate the behaviors of SLIPS and open the door to new applications of this emerging class of soft materials.

1 - 30 . (canceled) 
     
     
         31 . A method for detecting an analyte, substance, or impurity in a liquid comprising the steps of:
 a) providing a sensor having a first surface area comprising:
 i) a first multilayer film comprising one or more first bilayers, wherein each bilayer of the first multilayer film comprises a first polymer layer in contact with a second polymer layer, where the first multilayer film has nanoscale or microscale porosity and at least a portion of the first multilayer film is functionalized to be hydrophobic; and 
 ii) a hydrophobic oil comprising a thermotropic liquid crystal, wherein the oil coats at least the functionalized portion of the first multilayer film and the oil at least partially fills the pores of at least the functionalized portion of the first multilayer film, and 
   b) providing the liquid to the first surface area;   c) comparing the adhesion of the liquid to the first area to a control sample or known standard of the liquid, wherein the adhesion of the liquid to the first surface area as compared to the control sample or known standard indicates an analyte, substance, or impurity in the liquid.   
     
     
         32 . The method of  claim 31  wherein the hydrophobic oil comprises a mixture of different thermotropic liquid crystals. 
     
     
         33 . The method of  claim 31  wherein the thermotropic liquid crystal comprises a mixture of compounds having the formulas: 
       
         
           
           
               
               
           
         
       
     
     
         34 . The method of  claim 31  wherein the analyte, substance, or impurity is a natural or synthetic amphiphile. 
     
     
         35 . The method of  claim 31  wherein the analyte, substance, or impurity is a bacteria, bacterial endotoxin, or fungus. 
     
     
         36 . The method of  claim 35  wherein the analyte, substance, or impurity is a lipopolysaccharide. 
     
     
         37 . The method of  claim 31  wherein the first multilayer film comprises one or more optionally functionalized PVDMA/PEI bilayers. 
     
     
         38 . The method of  claim 31  wherein the sensor further comprises a second surface area comprising:
 a second multilayer film comprising one or more second bilayers, wherein each bilayer of the second multilayer film comprises a third polymer layer in contact with a fourth polymer layer, where the second multilayer film has nanoscale or microscale porosity, wherein at least a portion of the second multilayer film is functionalized to be hydrophilic; and 
 wherein the method further comprises comparing the adhesion of the liquid to the first and second surface areas to a control sample or known standard of the liquid, wherein a change in the adhesion of the liquid to the first and second surface areas indicates an analyte, substance, or impurity in the liquid. 
 
     
     
         39 . The method of  claim 31  wherein the second multilayer film is functionalized with an amine, hydroxyl group, thiol group, or hydrazine group having the formula R—NH 2 , R—OH, R—SH or R—NHNH 2 , where R is hydrophilic. 
     
     
         40 . The method of  claim 31  wherein the second multilayer film is functionalized with glucamine. 
     
     
         41 . The method of  claim 31  wherein the second surface area is not coated by the hydrophobic oil. 
     
     
         42 . A slippery liquid-infused porous surface (SLIPS) comprising:
 a) a substrate having at least a first surface portion and a second surface portion;   b) a first multilayer film on the first surface portion, the first multilayer film comprising one or more first bilayers, wherein each bilayer of the first multilayer film comprises a first polymer layer in contact with a second polymer layer, where the first multilayer film has nanoscale or microscale porosity and at least a portion of the first multilayer film is functionalized to be hydrophobic; and   c) a hydrophobic oil selected from the group consisting of a silicone oil, a vegetable oil, a mineral oil, a thermotropic liquid crystal, and combinations thereof, wherein the oil coats at least the functionalized portion of the first multilayer film and the oil at least partially fills the pores of at least the functionalized portion of the first multilayer film;   d) a second multilayer film on the second surface portion, the second multilayer film comprising one or more second bilayers, wherein each bilayer of the second multilayer film comprises a third polymer layer in contact with a fourth polymer layer, where the second multilayer film has nanoscale or microscale porosity.   
     
     
         43 . The slippery liquid-infused porous surface of  claim 42  wherein the hydrophobic oil comprises a mixture of different thermotropic liquid crystals. 
     
     
         44 . The slippery liquid-infused porous surface of  claim 42  wherein the thermotropic liquid crystal comprises a mixture of compounds having the formulas: 
       
         
           
           
               
               
           
         
       
     
     
         45 . The slippery liquid-infused porous surface of  claim 42  wherein the second surface portion is not coated by the hydrophobic oil. 
     
     
         46 . The slippery liquid-infused porous surface of  claim 42  wherein at least a portion of the second multilayer film is functionalized to be hydrophilic. 
     
     
         47 . The slippery liquid-infused porous surface of  claim 42  wherein the second multilayer film is functionalized with an amine, hydroxyl group, thiol group, or hydrazine group having the formula R—NH 2 , R—OH, R—SH or R—NHNH 2 , where R is hydrophilic. 
     
     
         48 . The slippery liquid-infused porous surface of  claim 42  wherein the second multilayer film is functionalized with glucamine. 
     
     
         49 . The slippery liquid-infused porous surface of  claim 42  wherein the first polymer layer comprises a functionalized azlactone having the formula: 
       
         
           
           
               
               
           
         
       
       wherein x is 0 or the integers 1 or 2; and each R 1  is independently selected from the group consisting of: hydrogen, alkyl groups, alkenyl groups, alkynyl groups, carbocyclic groups, heterocyclic groups, aryl groups, heteroaryl groups, alkoxy groups, aldehyde groups, ether groups, and ester groups, any of which may be substituted or unsubstituted. 
     
     
         50 . The slippery liquid-infused porous surface of  claim 42  wherein the second polymer layer comprises a primary amine functionalized polymer, an alcohol functionalized polymer, or a thiol functionalized polymer. 
     
     
         51 . The slippery liquid-infused porous surface of  claim 42  wherein at least a portion of residual functional groups in the one or more first bilayers are chemically labile amide/ester-, amide/thioester-, and amide/imine-type bonds.