The preparation of core–sheath fibers by electrospinning is a topic of significant interest for producing composite fibers with distinct core and sheath functionalities. Moreover, in core–sheath fibers, low-molecular-weight substances or nanosized inorganic additives can be deposited in a targeted manner within the core or the sheath. Commonly, for obtaining a core–sheath structure, coaxial electrospinning is used. It requires a coaxial spinneret and suitable immiscible solvents for the inner and outer solutions. The single-nozzle spinneret electrospinning of emulsions can address these issues, but use of a stabilizing agent is needed. A third approach—preparation of core–sheath fibers by single-nozzle spinneret electrospinning of homogeneous blend solutions of two polymers or of a polymer/low-molecular-weight substance—has been much less studied. It circumvents the difficulties associated with the coaxial and the emulsion electrospinning and is thoroughly discussed in this review. The formation of core–sheath fibers in this case is attributed to phase-separation-driven self-organization during the electrospinning process. Some possibilities for obtaining core–double sheath fibers using the same method are also indicated. The gained knowledge on potential applications of core–sheath fibers prepared by single-nozzle spinneret electrospinning of emulsions and homogeneous blend solutions is also discussed.

The conventional approach for preparation of core-sheath fibers is coaxial electrospinning. Single-spinneret electrospinning of emulsions is a much less common method to obtain core-sheath fibers. Core-sheath structure may be generated by electrospinning of homogeneous blend solutions; however, reports on such cases are still scarce. Herein, the preparation of nanofibrous composites from poly(ethylene oxide) (PEO), poly(L-lactide) (PLA) and beeswax (BW) by single-spinneret electrospinning of their homogeneous blend solutions in chloroform is reported. The produced fibers had core/double-sheath structure with a PEO core, PLA inner sheath and BW outer sheath. This original fiber structure was evidenced by transmission electron microscopy, selective extraction of BW or PEO, and X-ray photoelectron spectroscopy. The PLA/BW double sheath led to hydrophobicity of the PEO/PLA/BW mats. The tensile tests revealed that PEO/PLA/BW mats had substantially improved mechanical behavior as compared to PEO, PLA and PEO/BW mats. PEO/PLA/BW mats can be used as drug carriers as evidenced by the one-pot incorporation of the model drug 5-nitro-8-hydroxyquinoline (NQ) into the fibrous materials. Microbiological tests showed that PEO/PLA/BW/NQ had antimicrobial activity. Therefore, the new materials are promising for wound healing applications.

Fibrous materials composed of core–sheath fibers from poly(ethylene oxide) (PEO), beeswax (BW) and 5-nitro-8-hydroxyquinoline (NQ) were prepared via the self-organization of PEO and BW during the single-spinneret electrospinning of a homogeneous blend solution of the partners. Additionally, the application of the same approach enabled the preparation of fibrous materials composed of core–double sheath fibers from PEO, poly(L-lactide) (PLA) and NQ or 5-chloro-7-iodo-8-hydroxyquinoline (CQ), as well as from PEO, poly(ε-caprolactone) (PCL) and NQ. The consecutive selective extraction of BW and of the polyester with hexane and tetrahydrofuran, respectively, evidenced that core–double sheath fibers from PEO/polyester/BW/drug consisted of a PEO core, a polyester inner sheath and a BW outer sheath. In order to evaluate the possibility of the application of fibrous materials from PEO/BW/NQ, PEO/PLA/BW/NQ, PEO/PCL/BW/NQ and PEO/PLA/BW/CQ for plant protection, microbiological studies were performed using both phytopathogenic microorganisms (Pseudomonas corrugata, Fusarium graminearum and Fusarium avenaceum) and beneficial microorganisms (Pseudomonas chlororaphis, Bacillus amyloliquefaciens and Trichoderma asperellum). It was found that the fibrous materials had anti-bacterial and anti-fungal activity against both phytopathogenic and beneficial microorganisms. This is the first report on the activity of fibrous materials loaded with 8-hydroxyquinoline derivatives not only against phytopathogenic but also against beneficial microorganisms that are of importance in agriculture.

Novel multifunctional fibrous materials were prepared by simultaneous dual spinneret electrospinning of two separate solutions differing in composition. This technique allowed for the preparation of materials built of two types of fibers: fibers from poly(vinyl alcohol) (PVA), chitosan (Ch), and rosmarinic acid (RA), and poly(L-lactide) (PLA) fibers containing lidocaine hydrochloride (LHC). Confocal laser scanning microscopy (CLSM) analyses showed that both types of fibers are present on the surface and in the bulk of the new materials. The presence of all components and some interactions between them were proven by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. RA and LHC were in an amorphous state in the fibers, and their presence affected the temperature characteristics and the crystallinity, as detected by differential scanning calorimetry (DSC) and X-ray diffraction analyses (XRD). The presence of PVA/Ch/RA fibers enabled the hydrophilization of the surface of the multifunctional fibrous materials (the water contact angle value was 0°). The newly developed materials demonstrated adequate mechanical properties, making them suitable for use in wound dressing applications. The RA-containing fibrous mats possessed high radical-scavenging activity (ca. 93%), and the combining with LHC led to an enhancement of this effect (ca. 98.5%). RA-containing fibrous mats killed all the pathogenic bacteria S. aureus and E. coli and decreased the titer of fungi C. albicans by ca. 0.4 log for a contact time of 24 h. Therefore, the new materials are prospective as antibacterial and atraumatic functional wound dressings, as systems for local drug delivery, and in medical skincare.

In this study, a hierarchical design strategy is introduced for tuning the release of rosmarinic acid (RA) from electrospun poly(L-lactide) (PLA) fibrous materials via surface engineering with chitosan/hyaluronic acid (Ch/HA) polyelectrolyte complexes (PECs). RA was selectively incorporated within the fiber bulk, the PEC coating, or both, enabling control over its spatial distribution. The PEC coating, formed by sequential dip coating, was shown to act as a diffusion-regulating layer with a dual role—either retarding RA release or promoting rapid initial release when functioning as a surface-associated reservoir. As a result, the release kinetics could be systematically tuned depending on the coating architecture and RA localization. Thorough characterization confirmed successful coating formation, enhanced surface hydrophilicity, and improved mechanical performance. All RA-loaded materials retained high antioxidant activity and exhibited pronounced antibacterial and antifungal effects against Staphylococcus aureus, Escherichia coli, and Candida albicans. This work introduces PEC-modified electrospun systems as a versatile platform for the rational design of multifunctional fibrous biomaterials with controlled release profiles, with potential applications in wound healing and drug delivery.