Electrospun GelMA fibers and p(HEMA) matrix composite for corneal tissue engineering.

The development of biocompatible and transparent three-dimensional materials is desirable for corneal tissue engineering. Inspired from the cornea structure, gelatin methacryloyl-poly(2-hydroxymethyl methacrylate) (GelMA-p(HEMA)) composite hydrogel was fabricated. GelMA fibers were produced via electrospinning and covered with a thin layer of p(HEMA) in the presence of N,N'-methylenebisacrylamide (MBA) as cross-linker by drop-casting. The structure of resulting GelMA-p(HEMA) composite was characterized by spectrophotometry, microscopy, and swelling studies. Biocompatibility and biological properties of the both p(HEMA) and GelMA-p(HEMA) composite have been investigated by 3D cell culture, red blood cell hemolysis, and protein adsorption studies (i.e., human serum albumin, human immunoglobulin and egg white lysozyme). The optical transmittance of the GelMA-p(HEMA) composite was found to be approximately 70% at 550 nm. The GelMA-p(HEMA) composite was biocompatible with tear fluid proteins and convenient for cell adhesion and growth. Thus, as prepared hydrogel composite may find extensive applications in future for the development of corneal tissue engineering as well as preparation of stroma of the corneal material.

Cryopreservation of a cell-based biosensor chip modified with elastic polymer fibers enabling ready-to-use on-site applications.

An efficient preservation of a cell-based biosensor chip to achieve a ready-to-use on-site system is still very challenging as the chip contains a living component such as adherent mammalian cells. Herein, we propose a strategy called on-sensor cryopreservation (OSC), which enables the adherent cells to be preserved by freezing (-80 °C) on a biosensor surface, such as the light-addressable potentiometric sensor (LAPS). Adherent cells on rigid surfaces are prone to cryo-injury; thus, the surface was modified to enhance the cell recovery for OSC. It relies on i) the integration of elastic electrospun fibers composed of polyethylene vinyl acetate (PEVA), which has a high thermal expansion coefficient and low glass-transition temperature, and ii) the treatment with O2 plasma. The modified sensor is integrated into a microfluidic chip system not only to decrease the thermal mass, which is critical for fast thawing, but also to provide a precisely controlled micro-environment. This novel cryo-chip system is effective for keeping cells viable during OSC. As a proof-of-concept for the applicability of a ready-to-use format, the extracellular acidification of cancer cells (CHO-K1) was evaluated by differential LAPS measurements after thawing. Results show, for the first time, that the OSC strategy using the cryo-chip allows label-free and quantitative measurements directly after thawing, which eliminates additional post-thaw culturing steps. The freezing of the chips containing cells at the manufacturing stage and sending them via a cold-chain transport could open up a new possibility for a ready-to-use on-site system.

Optimization and performance of nitrogen-doped carbon dots as a color conversion layer for white-LED applications.

In this study, green-emitting nitrogen-doped carbon dots (N-CDots) were synthesized and incorporated into drop-cast composite films for use as color conversion layers in a white-LED configuration to generate white light. In order to resolve the red deficiency of this configuration, a commercial red phosphor was integrated into the system. Moreover, the N-CDots were also processed into polymer/N-CDot composite fibers, for which we determined the amount of N-CDots that yielded adequate white-light properties. Finally, we showed that white light with excellent properties could be generated by employing both of the fabricated N-CDot composites either as drop-cast films or composite fibers. Hence, N-CDots provide a promising alternative to inorganic phosphors that are commonly employed in white-LED configurations.

Green fabrication of lanthanide-doped hydroxide-based phosphors: Y(OH)3:Eu3+ nanoparticles for white light generation.

Phosphors can serve as color conversion layers to generate white light with varying optical features, including color rendering index (CRI), high correlated color temperature (CCT), and luminous efficacy. However, they are typically produced under harsh synthesis conditions such as high temperature, high pressure, and/or by employing a large amount of solvent. In this work, a facile, water-based, rapid method has been proposed to fabricate lanthanide-doped hydroxide-based phosphors. In this sense, sub-micrometer-sized Y(OH)3:Eu3+ particles (as red phosphor) were synthesized in water at ambient conditions in ≤60 min reaction time. The doping ratio was controlled from 2.5-20 mol %. Additionally, first principle calculations were performed on Y(OH)3:Eu3+ to understand the preferable doping scenario and its optoelectronic properties. As an application, these fabricated red phosphors were integrated into a PDMS/YAG:Ce3+ composite and used to generate white light. The resulting white light showed a remarkable improvement (≈24%) in terms of luminous efficiency, a slight reduction of CCT (from 3900 to 3600 K), and an unchanged CRI (≈60) as the amount of Y(OH)3:Eu3+ was increased.

Phosphor-based white LED by various glassy particles: control over luminous efficiency.

Generating white light through a mainstream remote phosphor design suffers from phosphor conversion efficiency loss due to a backscattering of light. Such a loss also reduces luminous efficiency of the resulting white light. To overcome this issue, various glassy scatterers with different morphologies such as glass bubbles, glass beads, and nanosized silica particles were employed as scatterers, together with a fixed amount of yellow phosphor (YAG:Ce3+) and a poly(dimethylsiloxane) (PDMS) matrix. In addition, the simulation of the system validates the rigorous multiple scattering of the incoming light most probably due to refractive index mismatch between the glass bubbles and surrounding PDMS matrix along with the internal reflections.

Polarized emission from CsPbBr3 nanowire embedded-electrospun PU fibers.

Interest in all-inorganic halide perovskites has been increasing dramatically due to their high quantum yield, band gap tunability, and ease of fabrication in compositional and geometric diversity. In this study, we synthesized several hundreds of nanometer long and ∼4 nm thick CsPbBr 3 nanowires (NWs). They were then integrated into electrospun polyurethane (PU) fibers to examine the polarization behavior of the composite fiber assembly. Aligned electrospun fibers containing CsPbBr 3 NWs showed a remarkable increase in the degree of polarization from 0.17-0.30. This combination of NWs and PU fibers provides a promising composite material for various applications such as optoelectronic devices and solar cells.

Integration of Triboluminescent EuD4TEA Crystals to Transparent Polymers: Impact Sensor Application.

Lanthanide-based organometallic materials are well-known candidate triboluminescent (TL) materials that can show bright emission when a mechanical force is applied. These materials are usually in the form of crystalline powders, and it is often useful to integrate these samples into a polymer matrix in order to achieve processability, enabling coating from a solution/molten state or fabrication as a complex-shaped matrix. In this work, micrometer-sized europium tetrakis (dibenzoylmethide) triethylammonium (EuD4TEA) crystals were synthesized and integrated with various transparent polymers (PMMA, PS, PVDF, and PU) using two approaches: (i) blending and (ii) surface impregnation. In the former method, the crystalline particles were molecularly dissolved; therefore, a TL response cannot be achieved. More than 10 wt % TL crystals in the composite is needed to obtain TL signals. However, TL signal was achieved at 2.5 wt % when a composite was prepared by the latter approach. TL intensity shows exponential decay with consecutive mechanical action. The TL emission of PU-based surface impregnated composite expires with long-lived emission, and maximum TL response with respect to applied force was measured between 2.45 and 42.0 N.

Null Extinction of Ceria@silica Hybrid Particles: Transparent Polystyrene Composites.

Scattering of light in optical materials, particularly in composites based on transparent polymer and inorganic pigment nanoparticles, is a chronic problem. It might originate mainly from light scattering because of a refractive index mismatch between the particles and transparent polymer matrix. Thus, the intensity of light is rapidly diminished and optical transparency is reduced. Refractive index matching between the pigment core and the surrounding transparent matrix using a secondary component at the interface (shell) has recently appeared as a promising approach to alter light scattering. Here, CeO2 (ceria) nanoparticles with a diameter of 25 nm are coated with a SiO2 (silica) shell with various thicknesses in a range of 6.5-67.5 nm using the Stöber method. When the hybrid core-shell particles are dispersed into transparent polystyrene (PS), the transmission of the freestanding PS composite films increases over both the ultraviolet (UV) and visible region as the shell thickness increases particularly at 37.5 nm. The increase of transmission can be attributed to the reduction in the scattering coefficient of the hybrid particles. On the other hand, the particles in tetrahydrofuran (THF) absorb over UV and the intensity of absorption shows a systematic decrease as the shell thickness increases. Thus, the silica shell suppresses not only the scattering coefficient but also the molar absorptivity of the core ceria particles. The experimental results regarding the target shell thickness to develop low extinction (scattering + absorption) composites show a qualitative agreement with the predictions of Effective Medium Theory.

Mechanical interlocking between porous electrospun polystyrene fibers and an epoxy matrix.

An epoxy matrix filled with nonwoven mats of porous polystyrene (PS) fibers processed by an electrospinning was compression tested at quasi-static (1 × 10(-3) s(-1)) and high strain (315 s(-1)) rates. The electrospun PS fibers with a diameter between 6 and 9 µm, accommodated spherical pores on the surface with the sizes ranging from 0.1 to 0.2 µm. The filling epoxy matrix with 0.2 wt % PS fibers increased the compressive elastic modulus and compressive strength over those of neat epoxy resin. The microscopic observations indicated that the surface pores facilitated the resin intrusions into the fiber, enhancing the interlocking between resin and fibers, and increased the deformation energy expenditure of the polymer matrix.

Hierarchial coassembly of a cyanine dye in poly(vinyl alcohol) fibrous films by electrospinning.

We report molecular aggregate formation of TTBC (1,1',3,3'-tetraethyl-5,5',6,6'-tetrachlorobenzimidazolocarbocyanine) in submicrometer-sized PVA (poly(vinyl alcohol)) fibers by electrospinning. The formation of the molecular aggregate is examined by solution and instrumental parameters of electrospinning. The precursor solution of PVA/TTBC, in the range of 0.016-0.065 wt % is subjected to electrospinning under an electrical field ranging from 0.95 to 1.81 kV cm(-1). Both randomly deposited and uniaxially aligned fibers are achieved by using two parallel-positioned metal strips as counter electrode. Photoluminescence and polarized Fourier transform infrared spectroscopies are employed to determine spectral properties of the fibers. H-aggregates are formed within the electrospun fibers, regardless of their alignment, and H- and J-type aggregates coexist in the alternative spin-coated and the cast films. A strongly polarized photoluminescence emission is observed in the direction of uniaxially aligned fibers as a result of the orientation of the H-aggregates along the fiber axis. We demonstrate that electrospinning is a process capable of forming and orienting TTBC aggregates during the structural development of the polymer/dye nanofibers. These fibrous films may potentially find applications in optics and electronics.

Hierarchically structured metal oxide/silica nanofibers by colloid electrospinning.

We present herein a new concept for the preparation of nanofibrous metal oxides based on the simultaneous electrospinning of metal oxide precursors and silica nanoparticles. Precursor fibers are prepared by electrospinning silica nanoparticles (20 nm in diameter) dispersed in an aqueous solution of poly(acrylic acid) and metal salts. Upon calcination in air, the poly(acrylic acid) matrix is removed, the silica nanoparticles are cemented, and nanocrystalline metal oxide particles of 4-14 nm are nucleated at the surface of the silica nanoparticles. The obtained continuous silica fibers act as a structural framework for metal oxide nanoparticles and show improved mechanical integrity compared to the neat metal oxide fibers. The hierarchically nanostructured materials are promising for catalysis applications, as demonstrated by the successful degradation of a model dye in the presence of the fibers.

Toward transparent nanocomposites based on polystyrene matrix and PMMA-grafted CeO2 nanoparticles.

The association of transparent polymer and nanosized pigment particles offers attractive optical materials for various potential and existing applications. However, the particles embedded into polymers scatter light due to refractive index (RI) mismatch and reduce transparency of the resulting composite material. In this study, optical composites based on polystyrene (PS) matrix and poly(methyl methacrylate) (PMMA)-grafted CeO(2) hybrid particles were prepared. CeO(2) nanoparticles with an average diameter of 18 ± 8 nm were precipitated by treating Ce(NO(3))·6H(2)O with urea in the presence of a polymerizable surfactant, 3-methacyloxypropyltrimethoxy silane. PMMA chains were grafted on the surface of the nanoparticles upon free radical in situ solution polymerization. While blending of unmodified CeO(2) particles with PS resulted in opaque films, the transparency of the composite films was remarkably enhanced when prepared by PMMA-grafted CeO(2) hybrid particles, particularly those having a PMMA thickness of 9 nm. The improvement in transparency is presumably due to the reduction in RI mismatch between CeO(2) particles and the PS matrix when using PMMA chains at the interface.

Humidity sensing properties of ZnO-based fibers by electrospinning.

Zinc oxide (ZnO) based fibers with a diameter of 80-100 nm were prepared by electrospinning. Polyvinyl alcohol (PVA) and zinc acetate dihydrate were dissolved in water and the polymer/salt solution was electrospun at 2.5 kV cm(-1). The resulting electrospun fibers were subjected to calcination at 500°C for 2h to obtain ZnO-based fibers. Humidity sensing properties of the fiber mats were investigated by quartz crystal microbalance (QCM) method and electrical measurements. The adsorption kinetics under constant relative humidity (RH) between 10% and 90% were explained using Langmuir adsorption model. Results of the measurements showed that ZnO-based fibers were found to be promising candidate for humidity sensing applications at room temperature.

Effect of alkali metal hydroxides on the morphological development and optical properties of ceria nanocubes under hydrothermal conditions.

Nanocrystalline cerium(LV) oxide (CeO2, ceria) particles were produced via the hydrothermal treatment of cerium nitrate hexahydrate with various alkali metal hydroxides (MOH: M = Li, Na, K). Experimental conditions such as [MOH], reaction temperature, and reaction time were studied. Particle morphology as well as size of crystallites was precisely controlled by choice of experimental conditions. While rod-shaped particles were obtained at 120 degrees C, well-defined nanocubes were formed at higher temperatures regardless of the choice of MOH. Examination of particle growth kinetics, in the final stages of crystallization, showed that particle growth rate is controlled by two different mechanisms. Grain boundary diffusion controls the particle growth in the presence of NaOH with an activation energy of 113.8 kj/mol and surface diffusion for LiOH ad KOH with the activation energy of 43.0-150.9 kj/mol, respectively. In addition, the particles exhibit strong violet and blue emissions at 400 nm and 370 nm. The former emission originates from excitation of a wide band gap of CeO2. The latter one is attributed to the trivalency of the cerium ion and appears to be sensitive to all the experimental conditions studied. Both extending reaction time and increasing temperature reduce the intensity of the 370 nm emission and increase the intensity of the 400 nm emission.

Sorption efficiency of chitosan nanofibers toward metal ions at low concentrations.

Chitosan fibers showing narrow diameter distribution with a mean of 42 nm were produced by electrospinning and utilized for the sorption of Fe(III), Cu(II), Ag(I), and Cd(II) ions from aqueous solutions. The ion concentrations in the supernatant solutions were determined using inductively coupled plasma-mass spectrometry (ICP-MS). The filtration efficiency of the fibers toward these ions was studied by both batch and microcolumn methods. High efficiency in sorption of the metal ions was obtained in the both methods. The effects of sorbent amount (0.10-0.50 mg), shaking time (15-120 min), initial metal ion concentration (10.0-1000.0 µg·L(-1)), and temperature (25 and 50 °C) on the extent of sorption were examined. The sorbent amount did not significantly alter the efficiency of sorption; however, shaking time, temperature, and metal ion concentration were found to have a strong influence on sorption. By virtue of its mechanical integrity, the applicability of the chitosan mat in solid phase extraction under continuous flow looks promising.

Formation of pseudoisocyanine J-aggregates in poly(vinyl alcohol) fibers by electrospinning.

Submicrometer diameter, light emitting fibers of poly(vinyl alcohol) (PVA) doped with pseudoisocyanine (1,1'-diethyl-2,2'-cyanine bromide, PIC) dye were prepared by electrospinning. A horizontal setup was employed with a stationary collector consisting of two parallel-positioned metal strips separated by a void gap. Formation of uniaxially aligned and randomly deposited fibers in electrospun films was confirmed by microscopy. Photoluminescence (PL) spectroscopy is used to evaluate spectral properties of both types of fibers doped with PIC. While PIC molecules were individually dispersed in PVA solution, they assemble into J-aggregates upon electrospinning when the weight fraction of PIC molecules is above 2.5 wt %. The formation of J-aggregates was observed in both randomly deposited and uniaxially aligned electrospun fibers. Moreover, the fibers aligned uniaxially showed a high degree of polarized emission (PLparallel/PLperpendicular=10), arising from the orientation of J-aggregates along the fiber axis. On the other hand, isotropic emission of J-aggregates was observed from the fibers deposited randomly. As a conclusion, electrospinning was found to be an efficient and a practical method to form highly oriented J-aggregates dispersed into polymer fibers. To the best of our knowledge, it is the first time formation of J-aggregates (a bottom-up approach) and electrospinning (a top-down approach) is successfully combined.

Investigation of Oxygen Permeation through Composites of PMMA and Surface-Modified ZnO Nanoparticles.

Oxygen permeabilities of nanocomposite films consisting of poly(methyl methacrylate) (PMMA) and different amounts of spherical zinc oxide (ZnO) nanoparticles were determined to investigate the barrier effect of this material with respect to particle content. A method was applied which is based on quenching of an excited phosphorescent dye by oxygen. Possible effects of the nanoparticles on the response of the dye molecules were investigated and were ruled out.