3D Printable Hybrid Gel Made of Polymer Surface-Modified Cellulose Nanofibrils Prepared by Surface-Initiated Controlled Radical Polymerization (SI-SET-LRP) and Upconversion Luminescent Nanoparticles.

A cellulose nanofibril-based hybrid gel material was developed by grafting the polymerized stearyl acrylate (PSA) and upconversion nanoparticles (UCNPs) onto cellulose nanofibrils (CNFs) via Cu0-mediated radical polymerization (SET-LRP) to create a highly cross-linked CNF system. A two-step strategy was exploited to surface-exchange the ligand of the UCNPs from a hydrophobic ligand (oleic acid) to a hydrophilic small-molecule ligand (2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS) and therefore be suitable for SET-LRP. The characteristics and properties of the hybrid material (UCNP-PSA-CNF) were monitored by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), rheology, X-ray diffraction (XRD), and microscopic analysis. Those characterization techniques prove the efficient modification of the CNF, with the presence of 1.8% UCNPs. The luminescence measurement was carried out using a homebuilt confocal microscope with a 980 nm laser source. The nanostructure of UCNPs and their incorporated CNF species were measured by small-angle X-ray scattering (SAXS). In addition, this CNF-based hybrid gel has decisive rheological properties, such as good viscoelasticity (loss tangent was below 0.35 for the UCNP-PSA-CNF gel, while the PSA-CNF gel reached the highest value of 0.42), shear-thinning behavior, and shape retention, and was successfully applied to three-dimensional (3D) gel printing throughout various 3D print models.

Simple one pot synthesis of luminescent europium doped yttrium oxide Y2O3:Eu nanodiscs for phosphor converted warm white LEDs.

Yttrium oxide (Y2O3) is considered as one of the best host lattices for europium (Eu3+) based red emitting phosphors because of its unit cell and good photo-saturation properties. As a bulk material, it reaches nearly 100% quantum yield. However, providing high quality nanosized materials for the LED industry is still a challenge and not easily accomplished. Within this publication, a simple one pot, non-hydrolytic, solvent-based synthesis method for producing uniform and monodisperse red-emitting europium doped yttrium oxide (Y2O3:Eu) nanoparticles is provided. The synthesis is the cheapest and fastest reported yet, yields up to 80%, and offers good scalability, and the diameter of the produced nanodiscs is tunable from 7 nm to 30 nm. The dispersed nanomaterial shows bright red emission (607 nm) under UV excitation (273 nm) and a higher quantum yield (>30%) compared to other nanosized Y2O3:Eu materials. In order to shift the excitation wavelength towards the visible region we added Tb3+ as the sensitizer. Thereby, it was also possible to tune the emission colour towards orange/yellow. Further, a distorted anisotropic cubic Y2O3 phase is confirmed by XRD analysis, resulting in a distinct change in the intensities of red emission transitions. A calcination step transforms it into a highly crystalline cubic phase, known from the bulk material, and exhibiting a typical emission spectrum.

Bulk-like emission in the visible spectrum of colloidal LiYF4:Pr nanocrystals downsized to 10 nm.

Though Pr3+ doped LiYF4 (LiYF4:Pr3+) bulk crystals are a well-known laser gain material with several radiative transitions, their nanocrystal counterparts have not been investigated with regards to these. Through downsizing to the nanoscale, novel applications are expected, especially in composite photonic devices. For example, nanocrystals in stable colloidal form with narrow size distribution are highly desirable to reduce scattering in such composites. Herein, we synthesized monodispersed LiYF4:Pr3+ nanocrystals having a size of 10 nm resulting in colorless clear stable colloidal dispersions and conducted an extensive optical characterization for the first time. We observed unexpected yet intense emission with excited state lifetimes comparable to bulk crystals in the visible spectrum through excitation at 444 nm and 479 nm. In macroscopic bulk crystals, this emission is only exploitable through excitation of a different, subjacent energy level. A comprehensive comparison to the bulk crystals provides deeper insight into the excitation mechanism and performance of these nanocrystals. The presented results pave the way for developing application-oriented LiYF4:Pr3+ nanocrystals as emitters with tailored properties for quantum optics or biomedical applications.

Effect of the crystal structure of small precursor particles on the growth of ß-NaREF4 (RE = Sm, Eu, Gd, Tb) nanocrystals.

The origin of the narrow particle size distributions obtained in the oleic acid-based synthesis of hexagonal phase ß-NaREF(4) nanocrystals (RE = Sm, Eu, Gd, Tb) has been investigated. Compared to the standard synthesis, the growth conditions were simplified by using small purified particles of either α-NaREF(4) (cubic phase) or ß-NaREF(4) (hexagonal phase) as single-source precursors, thereby avoiding the complications arising from the simultaneous presence of molecular educts and intermediately formed small particles. The study shows that α-phase as well as ß-phase particles grow by Ostwald-ripening but narrow particle size distributions of the ß-NaREF(4) product particles are only obtained when α-phase precursor particles are employed. Since the small particles are also formed as intermediate products in the standard synthesis of ß-NaSmF(4), ß-NaEuF(4), ß-NaGdF(4) and ß-NaTbF(4) particles, their crystal phase is an important parameter to obtain a narrow size distribution in these systems.

An electron paramagnetic resonance spectroscopic investigation on the growth mechanism of NaYF4:Gd nanocrystals.

Doped nanocrystals of NaYF(4) and NaGdF(4) are currently studied as upconversion luminescence markers and magnetic resonance imaging contrast agents. An EPR investigation on the growth mechanism of NaYF(4):Gd and NaGdF(4) nanocrystals showed that these nanomaterials grow in the standard oleic acid-based reaction medium by a dissolution/recrystallization mechanism and not by the aggregation or oriented attachment of smaller particles.

Surface modification of luminescent lanthanide phosphate nanorods with cationic "Quat-primer" polymers.

"Quat-primer" polymers bearing cationic groups were investigated as a surface modifier for Tb-doped cerium phosphate green-emitting fluorescent nanorods (NRs). The NRs were synthesized by a microwave process without using any complex agents or ligands and were characterized with different analytical tools such as X-ray diffraction, transmission electron microscopy, and fluorescence spectroscopy. Poly(ethyleneimine) partially quarternized with glycidyltrimethylammonium chloride was synthesized separately and characterized in detail. (1)H and (13)C NMR spectroscopic studies revealed that the quaternary ammonium group was covalently attached to the polymer. UV-vis spectroscopy was used to examine the stability of the colloidal dispersions of the bare NRs as well as the modified NRs. ζ potential, thermogravimetric analysis, and atomic force microscopy studies were carried out to confirm that the positively charged Quat-primer polymer is adsorbed on the negatively charged surface of the NRs, which results in high dispersion stability. Emission spectra of the modified NRs indicated that there was no interference of the Quat-primer polymer with the fluorescence behavior.