Maria Moffa

Local Mechanical Properties of Electrospun Fibers Correlate to Their Internal Nanostructure

The properties of polymeric nanofibers can be tailored and enhanced by properly managing the structure of the polymer molecules at the nanoscale. Although electrospun polymer fibers are increasingly exploited in many technological applications, their internal nanostructure, determining their improved physical properties, is still poorly investigated and understood. Here, we unravel the internal structure of electrospun functional nanofibers made by prototype conjugated polymers. The unique features of near-field optical measurements are exploited to investigate the nanoscale spatial variation of the polymer density, evidencing the presence of a dense internal core embedded in a less dense polymeric shell. Interestingly, nanoscale mapping the fiber Young’s modulus demonstrates that the dense core is stiffer than the polymeric, less dense shell. These findings are rationalized by developing a theoretical model and simulations of the polymer molecular structural evolution during the electrospinning process. This model predicts that the stretching of the polymer network induces a contraction of the network toward the jet center with a local increase of the polymer density, as observed in the solid structure. The found complex internal structure opens an interesting perspective for improving and tailoring the molecular morphology and multifunctional electronic and optical properties of polymer fibers.

Bright Light Emission and Waveguiding in Conjugated Polymer Nanofibers Electrospun from Organic Salt Added Solutions

Light-emitting electrospun nanofibers of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N′-diphenyl)-N,N′-di(p-butyl-oxy-phenyl)-1,4-diaminobenzene)] (PFO–PBAB) are produced by electrospinning under different experimental conditions. In particular, uniform fibers with average diameter of 180 nm are obtained by adding an organic salt to the electrospinning solution. The spectroscopic investigation assesses that the presence of the organic salt does not alter the optical properties of the active material, therefore providing an alternative approach for the fabrication of highly emissive conjugated polymer nanofibers. The produced nanofibers display self-waveguiding of light, and polarized photoluminescence, which is especially promising for embedding active electrospun fibers in sensing and nanophotonic devices.

Organic nanofibers embedding stimuli-responsive threaded molecular components.

While most of the studies on molecular machines have been performed in solution, interfacing these supramolecular systems with solid-state nanostructures and materials is very important in view of their utilization in sensing components working by chemical and photonic actuation. Host polymeric materials, and particularly polymer nanofibers, enable the manipulation of the functional molecules constituting molecular machines and provide a way to induce and control the supramolecular organization. Here, we present electrospun nanocomposites embedding a self-assembling rotaxane-type system that is responsive to both optical (UV–vis light) and chemical (acid/base) stimuli. The system includes a molecular axle comprised of a dibenzylammonium recognition site and two azobenzene end groups and a dibenzo[24]crown-8 molecular ring. The dethreading and rethreading of the molecular components in nanofibers induced by exposure to base and acid vapors, as well as the photoisomerization of the azobenzene end groups, occur in a similar manner to what observed in solution. Importantly, however, the nanoscale mechanical function following external chemical stimuli induces a measurable variation of the macroscopic mechanical properties of nanofibers aligned in arrays, whose Young’s modulus is significantly enhanced upon dethreading of the axles from the rings. These composite nanosystems show therefore great potential for application in chemical sensors, photonic actuators, and environmentally responsive materials.

Microvascular endothelial cell spreading and proliferation on nanofibrous scaffolds by polymer blends with enhanced wettability

The objective of this study is elucidating the mechanisms by which the wettability of nanofibrous electrospun mats varies in polymer blends, and highlighting how this can play a pivotal role in enhancing the viability of cultured microvascular endothelial cells (EC). A functional microvascular network is essential for supplying bioengineered tissues with oxygen and nutrients while removing metabolic wastes. An in vitro pre-vascularization strategy consists of seeding EC on scaffolds, which in turn promotes cells infiltration, adhesion and functionality. We use electrospun poly-L-lactic acid (PLLA) and gelatin (Gel) as prototype materials for realizing nanofibrous scaffolds as bioartificial architectures to improve the proliferation and the functionality of human microvascular ECs (HMEC-1). HMEC-1 seeded on electrospun scaffolds adhere, remain viable, proliferate and positively express the endothelial cell marker CD31 particularly on blend PLLA/Gel fibers, which exhibit wettability enhanced with respect to both the constituent polymers, and are therefore especially promising constructs for promoting the formation of functional endothelial tissue. The wettability characteristics of the blend polymer fibrous scaffolds are modeled and discussed. These results can be valuable for the future design of pre-vascularized scaffolds with enhanced wettability properties for functional tissue engineered implants, with ECs able to form in perspective an effectively functioning vasculature upon implantation.

Distributed Feedback Imprinted Electrospun Fiber Lasers

Imprinted, distributed feedback lasers are demonstrated on individual, active electrospun polymer nanofibers. In addition to advantages related to miniaturization, optical confinement and grating nanopatterning lead to a significant threshold reduction compared to conventional thin-film lasers. The possibility of imprinting arbitrary photonic crystal geometries on electrospun lasing nanofibers opens new opportunities for realizing optical circuits and chips.

Combined Nano‐ and Micro‐Scale Topographic Cues for Engineered Vascular Constructs by Electrospinning and Imprinted Micro‐Patterns

The major cause of synthetic vessel failure is thrombus and neointima formation. To prevent these problems the creation of a continuous and elongated endothelium inside lumen vascular grafts might be a promising solution for tissue engineering. Different micro- and nano-surface topographic cues including grooved micro-patterns and electrospun fibers have been previously demonstrated to guide the uniform alignment of endothelial cells (ECs). Here, with a very simple and highly versatile approach we combined electrospinning with soft lithography to fabricate nanofibrous scaffolds with oriented fibers modulated by different micro-grooved topographies. The effect of these scaffolds on the behavior of the ECs are analyzed, including their elongation, spreading, proliferation, and functioning using unpatterned random and aligned nanofibers (NFs) as controls. It is demonstrated that both aligned NFs and micro-patterns effectively influence the cellular response, and that a proper combination of topographic parameters, exploiting the synergistic effects of micro-scale and sub-micrometer features, can promote EC elongation, allowing the creation of a confluent ECs monolayer in analogy with the natural endothelium as assessed by the positive expression of vinculin. Combining different micro- and nano-topographic cues by complementary soft patterning and spinning technologies could open interesting perspectives for engineered vascular replacement constructions.

Conformational Evolution of Elongated Polymer Solutions Tailors the Polarization of Light-Emission from Organic Nanofibers.

Polymer fibers are currently exploited in tremendously important technologies. Their innovative properties are mainly determined by the behavior of the polymer macromolecules under the elongation induced by external mechanical or electrostatic forces, characterizing the fiber drawing process. Although enhanced physical properties were observed in polymer fibers produced under strong stretching conditions, studies of the process-induced nanoscale organization of the polymer molecules are not available, and most of fiber properties are still obtained on an empirical basis. Here we reveal the orientational properties of semiflexible polymers in electrospun nanofibers, which allow the polarization properties of active fibers to be finely controlled. Modeling and simulations of the conformational evolution of the polymer chains during electrostatic elongation of semidilute solutions demonstrate that the molecules stretch almost fully within less than 1 mm from jet start, increasing polymer axial orientation at the jet center. The nanoscale mapping of the local dichroism of individual fibers by polarized near-field optical microscopy unveils for the first time the presence of an internal spatial variation of the molecular order, namely the presence of a core with axially aligned molecules and a sheath with almost radially oriented molecules. These results allow important and specific fiber properties to be manipulated and tailored, as here demonstrated for the polarization of emitted light.

Surface-enhanced Raman spectroscopy in 3D electrospun nanofiber mats coated with gold nanorods

AbstractNanofibers functionalized by metal nanostructures and particles are exploited as effective flexible substrates for surface-enhanced Raman scattering (SERS) analysis. Their complex three-dimensional structure may provide Raman signals enhanced by orders of magnitude compared to untextured surfaces. Understanding the origin of such improved performances is therefore very important for pushing nanofiber-based analytical technologies to their upper limit. Here, we report on polymer nanofiber mats which can be exploited as substrates for enhancing the Raman spectra of adsorbed probe molecules. The increased surface area and the scattering of light in the nanofibrous system are individually analyzed as mechanisms to enhance Raman scattering. The deposition of gold nanorods on the fibers further amplifies Raman signals due to SERS. This study suggests that Raman signals can be finely tuned in intensity and effectively enhanced in nanofiber mats and arrays by properly tailoring the architecture, composition, and light-scattering properties of the complex networks of filaments. Graphical abstractEnhancement of Raman signals by electrospun nanofiber mats

Controlled Atmosphere Electrospinning of Organic Nanofibers with Improved Light Emission and Waveguiding Properties

Electrospinning in controlled nitrogen atmosphere is developed for the realization of active polymer nanofibers. Fibers electrospun under controlled atmospheric conditions are found to be smoother and more uniform than samples realized by conventional electrospinning processes performed in air. In addition, they exhibit peculiar composition, incorporating a greatly reduced oxygen content during manufacturing, which favors enhanced optical properties and increases emission quantum yield. Active waveguides with optical losses coefficients lowered by 10 times with respect to fibers spun in air are demonstrated through this method. These findings make the process very promising for the highly controlled production of active polymer nanostructures for photonics, electronics and sensing.

Core–Shell Electrospun Fibers Encapsulating Chromophores or Luminescent Proteins for Microscopically Controlled Molecular Release

Core-shell fibers are emerging as interesting microstructures for the controlled release of drugs, proteins, and complex biological molecules, enabling the fine control of microreservoirs of encapsulated active agents, of the release kinetics, and of the localized delivery. Here we load luminescent molecules and enhanced green fluorescent proteins into the core of fibers realized by coaxial electrospinning. Photoluminescence spectroscopy evidences unaltered molecular emission following encapsulation and release. Moreover, the release kinetics is microscopically investigated by confocal analysis at individual-fiber scale, unveiling different characteristic time scales for diffusional translocation at the core and at the shell. These results are interpreted by a two stage desorption model for the coaxial microstructure, and they are relevant in the design and development of efficient fibrous systems for the delivery of functional biomolecules.