ABSTRACT
Controllable synthesis of homochiral nano/micromaterials has been a constant challenge for fabricating various stimuli-responsive chiral sensors. To provide an avenue to this goal, we report electrospinning as a simple and economical strategy to form continuous homochiral microfibers with strain-sensitive chiroptical properties. First, electrospun homochiral microfibers from self-assembled cadmium sulfide (CdS) quantum dot magic-sized clusters (MSCs) are produced. Highly sensitive and reversible strain sensors are then fabricated by embedding these chiroptically active fibers into elastomeric films. The chiroptical response on stretching is indicated quantitatively as reversible changes in magnitude, spectral position (wavelength), and sign in circular dichroism (CD) and linear dichroism (LD) signals and qualitatively as a prominent change in the birefringence features under cross-polarizers. The observed periodic twisted helical fibrils at the surface of fibers provide insights into the origin of the fibers' chirality. The measurable shifts in CD and LD are caused by elastic deformations of these helical fibrillar structures of the fiber. To elucidate the origin of these chiroptical properties, we used field emission-electron microscopy (FE-SEM), atomic force microscopy (AFM), synchrotron X-ray analysis, polarized optical microscopy, as well as measurements to isolate the true CD, and contributions from photoelastic modulators (PEM) and LD. Our findings thus offer a promising strategy to fabricate chiroptical strain-sensing devices with multiple measurables/observables using electric-field-assisted spinning of homochiral nano/microfibers.
ABSTRACT
This paper describes the effects of both solvent and copolymer block lengths on the stability of electrospun poly(lactic acid)/poly(lactic acid)-b-poly(ethylene glycol) (PLA/PLA-b-PEG) and PLA/PLA-b-PEG-Biotin fibers in water. By tailoring the block length of copolymers PLA-b-PEG, water stability of electrospun fibers is improved over fibers reported previously. The solvent used also influenced the stability and hydrophilicity of resulting fibers. Fibers formed using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) have greater water stability, but less PEG at the surface of fibers than fibers spun from dimethylformamide (DMF). Attaching biotin to the end of PLA(3600)-b-PEG(2000) and spinning from DMF resulted, initially, in 7.6% of the total biotin incorporated into the fiber, assuming every PEG terminal had one biotin attached (1.1 mg of biotin per gram of fiber) available at the fibers' surface. In addition, PLA/PLA(3600)-b-PEG(2000)-Biotin spun from DMF hindered biotin migration to the aqueous phase, leaving 2% of the incorporated biotin remaining at the surface of fibers after 7 days of water exposure. The water wicking ability of DMF spun fibers also increased significantly with the biotin attachment to the PEG terminal. While HFIP spun fibers lost little biotin from fibers, there was no detectable surface available biotin, indicating biotin was at the interior. With biotin and PEG at the interior of the fibers spun from HFIP, the water wicking remained the same for PLA/PLA(3600)-b-PEG(2000) spun samples and decreased for PLA/PLA(5700)-b-PEG(1000). The dissimilarities observed in water wicking for HFIP spun samples are primarily the result of differences in fiber morphology.
Subject(s)
Biotin/chemistry , Biosensing Techniques , Hydrophobic and Hydrophilic Interactions , Polyesters , Polymers , WaterABSTRACT
In this work, biotin surface functionalized hydrophilic non-water-soluble biocompatible poly(lactic acid) (PLA) nanofibers are created for their potential use as biosensors. Varying concentrations of biotin (up to 18 weight total percent (wt %)) were incorporated into PLA fibers together with poly(lactic acid)-block-poly(ethylene glycol) (PLA-b-PEG) block polymers. While biotin provided surface functionalization, PLA-b-PEG provided hydrophilicity to the final fibers. Morphology and surface-available biotin of the final fibers were studied by Field Emission Scanning Electron Microscopy (FESEM) and competitive colorimetric assays. The incorporation of PLA-b-PEG block copolymers not only decreased fiber diameters but also dramatically increased the amount of biotin available at the fiber surface able to bind avidin. Finally, fiber water stability tests revealed that both biotin and PLA-b-PEG, migrated to the aqueous phase after relatively extended periods of water exposure. The functional hydrophilic nanofiber created in this work shows a potential application as a biosensor for point-of-care diagnostics.
ABSTRACT
The interface tension of a smectic liquid crystal with respect to a surrounding ionic surfactant solution is investigated at concentrations above and below the critical micelle concentration (cmc). A simple measurement technique has been developed recently [Phys. Chem. Chem. Phys., 2013, 15, 7204], based on the geometrical analysis of the shape of smectic bubbles in water that are deformed by the buoyancy of trapped air bubbles. After preparation of the smectic membranes in the solution, we measure both the time dependence of their dynamic interface tension as well as the asymptotically reached static tension values. These are established about 15 minutes after the membrane preparation. At large enough concentrations of the surfactant (above the critical micelle concentration), the interface tension drops to 6 mN m(-1). At the lowest possible surfactant concentrations in our experiment, the equilibrium tension reaches 20 mN m(-1), which is almost equal to the smectic surface tension respective to air. The tension of a freshly drawn film exceeds this value by far.
