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Polymer fibers are currently exploited in tremendously importanttechnologies. Their innovative properties are mainly determined by the behaviorof the polymer macromolecules under the elongation induced by externalmechanical or electrostatic forces, characterizing the fiber drawing process.Although enhanced physical properties were observed in polymer fibers producedunder strong stretching conditions, studies of the process-induced nanoscaleorganization of the polymer molecules are not available, and most of fiberproperties are still obtained on an empirical basis. Here we reveal theorientational properties of semiflexible polymers in electrospun nanofibers,which allow the polarization properties of active fibers to be finelycontrolled. Modeling and simulations of the conformational evolution of thepolymer chains during electrostatic elongation of semidilute solutionsdemonstrate that the molecules stretch almost fully within less than 1 mm fromjet start, increasing polymer axial orientation at the jet center. Thenanoscale mapping of the local dichroism of individual fibers by polarizednear-field optical microscopy unveils for the first time the presence of aninternal spatial variation of the molecular order, namely the presence of acore with axially aligned molecules and a sheath with almost radially orientedmolecules. These results allow important and specific fiber properties to bemanipulated and tailored, as here demonstrated for the polarization of emittedlight.

The conformational evolution of elongated polymer solutions tailors the polarization of light-emission from organic nanofibers