While self-assembly is relatively well-known and widely used to form hierarchical structures and thin film coatings,controlled assembly is less known and utilized.Our prior work has demonstrated the concept of control...While self-assembly is relatively well-known and widely used to form hierarchical structures and thin film coatings,controlled assembly is less known and utilized.Our prior work has demonstrated the concept of controlled assembly of macromolecules such as star polymers[molecular weight(M_(w))∼383 kDa,hydrodynamic radius R∼13.8 nm]in droplets.This work extends this concept to smaller molecules,in this case,poly(ethylene glycol)bis-tetrazine(PEGbisTz,M_(w) 8.1 kDa,R∼1.5 nm).The key to controlled molecular assembly is to first deliver ultrasmall volumes(sub-fL)of solution containing PEG-bisTz to a substrate.The solvent evaporates rapidly due to the minute volume,thus forcing the assembly of solute,whose overall size and dimension are dictated by the initial liquid geometry and size.Using prepatterned surfaces,this work revealed that the initial liquid shape can be further tuned,and we could control the final assembly of solute such as PEGbisTz molecules.The degree of control was demonstrated by varying the micropatterns and delivery conditions.This work demonstrated the validity of controlled assembly for PEG-bisTz and enables three-dimensional(3D)nanoprinting of functional materials.The technology has promising applications in nanophotonics,nanoelectronics,nanocomposite materials,and tissue engineering.展开更多
基金supported by the National Science Foundation(nos.CHE-1808829 and DMR 1809612)National Institutes of Health(no.R01DC014461)the United States,and the Gordon and Betty Moore Foundation.
文摘While self-assembly is relatively well-known and widely used to form hierarchical structures and thin film coatings,controlled assembly is less known and utilized.Our prior work has demonstrated the concept of controlled assembly of macromolecules such as star polymers[molecular weight(M_(w))∼383 kDa,hydrodynamic radius R∼13.8 nm]in droplets.This work extends this concept to smaller molecules,in this case,poly(ethylene glycol)bis-tetrazine(PEGbisTz,M_(w) 8.1 kDa,R∼1.5 nm).The key to controlled molecular assembly is to first deliver ultrasmall volumes(sub-fL)of solution containing PEG-bisTz to a substrate.The solvent evaporates rapidly due to the minute volume,thus forcing the assembly of solute,whose overall size and dimension are dictated by the initial liquid geometry and size.Using prepatterned surfaces,this work revealed that the initial liquid shape can be further tuned,and we could control the final assembly of solute such as PEGbisTz molecules.The degree of control was demonstrated by varying the micropatterns and delivery conditions.This work demonstrated the validity of controlled assembly for PEG-bisTz and enables three-dimensional(3D)nanoprinting of functional materials.The technology has promising applications in nanophotonics,nanoelectronics,nanocomposite materials,and tissue engineering.
