PEG-capped, lanthanide doped GdF3 nanoparticles: luminescent and T-2 contrast agents for optical and MRI multimodal imaging

A facile method for the synthesis of water dispersible Er3+/Yb3+ and Tm3+/Yb3+ doped upconverting GdF3 nanoparticles is reported. Strong upconversion emissions are observed in the red (for Er/Yb doped) and near-infrared (for Tm/Yb doped) regions upon laser excitation at 980 nm. The PEG coating ensures a good dispersion of the system in water and reduces the radiationless de-excitation of the excited states of the Er3+ and Tm3+ ions by water molecules. The r(2) relaxivity values are quite high with respect to the common T-2-relaxing agents (22.6 +/- 3.4 mM(-1) s(-1) and 15.8 +/- 3.4 mM(-1) s(-1) for the Tm/Yb and Er/Yb doped samples, respectively), suggesting that the present NPs can be interesting as T-2 weighted contrast agents for proton MRI purpose. Preliminary experiments conducted in vitro, in stem cell cultures, and in vivo, after subcutaneous injection of the lanthanide-doped GdF3 NPs, indicate scarce toxic effects. After an intravenous injection in mice, the GdF3 NPs localize mainly in the liver. The present results indicate that the present Er3+/Yb3+ and Tm3+/Yb3+ doped GdF3 NPs are suitable candidates to be efficiently used as bimodal probes for both in vitro and in vivo optical and magnetic resonance imaging

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Short-Term Morphology Relaxation of Thermoplastic Polyurethane Elastomers after Fast Strain Steps

Strain steps are applied to elastomers in a pneumatic relaxometer and monitored by small-angle X-ray scattering (SAXS). The relaxometer provides a rise time of 13 ms for strain pulses of step height ?e = ±1 in strain. The basic character of the 2D SAXS frames is examined and corresponding invariants Q(t) are analyzed. Three thermoplastic polyurethanes (TPU) of hardness 85 Shore A with different soft segments are studied both unannealed and annealed. The first response of all materials is a fast morphology conversion which finishes within tmc =250 ms. Because it has been untraceable, it is characterized by a settling stroke Q(tmc) - Q(0). The second response is a slow morphology adjustment process which complies with logarithmic relaxation. It is characterized by a relaxation rate DQ = Q(10 t)/Q(t) - 1. Comparison indicates that the nanoscopic morphology relaxation processes appear to have little direct relation to the macroscopic stress relaxation curves. The materials differ with respect to hard-domain morphology stability and morphology recovery. Most unstable is the morphology of the annealed polyether-based material. It forms nanofibrillary entities when strained. © 2020 The Authors. Published by Wiley-VCH Gmb

Short‐Term Morphology Relaxation of Thermoplastic Polyurethane Elastomers after Fast Strain Steps

Strain steps are applied to elastomers in a pneumatic relaxometer and monitored by small‐angle X‐ray scattering (SAXS). The relaxometer provides a rise time of 13 ms for strain pulses of step height Δε = ±1 in strain. The basic character of the 2D SAXS frames is examined and corresponding invariants Q(t) are analyzed. Three thermoplastic polyurethanes (TPU) of hardness 85 Shore A with different soft segments are studied both unannealed and annealed. The first response of all materials is a fast morphology conversion which finishes within $t_{mc}$ =250 ms. Because it has been untraceable, it is characterized by a settling stroke Q($t_{mc}$) − Q(0). The second response is a slow morphology adjustment process which complies with logarithmic relaxation. It is characterized by a relaxation rate D$_Q$ = Q(10 t)/Q(t) − 1. Comparison indicates that the nanoscopic morphology relaxation processes appear to have little direct relation to the macroscopic stress relaxation curves. The materials differ with respect to hard‐domain morphology stability and morphology recovery. Most unstable is the morphology of the annealed polyether‐based material. It forms nanofibrillary entities when strained

Melting, Solidification, and Crystallization of a Thermoplastic Polyurethane as a Function of Hard Segment Content

Thermoplastic polyurethanes (TPU) with varying hard segment contents (HSC) are monitored during melting and solidifying (20 K/min , Tmax = 220 ° C) by small-angle and wide-angle X-ray scattering (WAXS and SAXS). Hard segments: MDI/BD. Soft segments: PTHF1000. The neat materials are injection-molded, having small amorphous hard domains (chord length d⎯⎯h ∼ 35% show sharp Bragg peaks and larger hard domains ( d⎯⎯h > 7 nm ). When heated, small domains melt, but crystallization in the remaining large domains is not detected. Upon cooling, large agglomerates segregate first, which crystallize immediately. Segregation starts for HSC = 42% at 160 °C and for HSC = 75% at 210 °C. When HSC ≤ 30%, the morphologies before and after are similar, but afterward, many hard blocks are dissolved in the soft phase at the expense of the hard domain fraction. In heating and cooling the melts, multiple homogenization and segregation processes are observed, which are explained by the agglomeration of hard blocks of different lengths in the colloidal fluid

Simple Engineering of Polymer-Nanoparticle Hybrid Nanocapsules

International audienceA general method to generate hybrid hollow capsules is reported. The process is based on the stabilization of solvent droplets by nanoparticles, in macroscopically miscible mixtures of tetrahydrofuran (THF) and water. After addition of a crosslinking polymer and removal of the solvent core, capsules of diameter ca 100 nm are obtained. This novel strategy does not require the use of block copolymers. In contrast, most methods reporting the formation of hybrid nanocapsules incorporate nanoparticles into block-copolymer polymersomes or use nanoparticles tethered with block-copolymers. The nanocapsules were characterized using a full set of techniques including nanoparticle tracking analysis, electron microscopy and liquid phase atomic force microscopy. Our results show that the vesicular shape of the nanocapsules is templated by the liquid droplets. Nanocapsules were prepared from quantum dots, gold nanoparticles, superparamagnetic iron oxide nanoparticles and mixtures of particles. The entrapment of a fluorescent dye was also demonstrated. Thus, nanocapsules with dual properties (e.g., magnetic and fluorescent) are easily obtained. Interestingly, the magnetic nanocapsules enable magnetic resonance imaging contrast enhancement of tumors in vivo

Wide‐Angle Scattering Halo Analysis and the Evolution of Oriented Amorphous Structure after Elongation Jumps in Some Elastomers

Amorphous and low-crystallinity thermoplastic polyurethane elastomers are shot back and forth between two elongation levels ($\epsilon=$0.2 and $\epsilon=$1.2) and observed between the excitations for 10 s using wide-angle X-ray scattering (WAXS) (50 Hz). For orientation analysis, the fiber patterns are projected, expanded in multipoles, and discussed as a function of relaxation time. Normalized WAXS suggests that the oriented halo observed during extension is predominantly due to selective extinction of unfavorably oriented probes (chain bundles). During retraction, neighborhoods and thus clusters are restored. Discussed are the relaxation curves depending on material and the number of load cycles. The separation of the halo into narrow rings introduces “bundle airiness” as a second coordinate. The now bivariate cluster density is the product of two univariate functions. Its factor “airiness distribution” seems to be a material property which is not changed by annealing. In contrast, the bivariate preferred orientation is not product-separable. Especially with harder materials it shows two bundle ensembles of different airiness. Interactions between the ensembles explain complex trajectories of the orientation–relaxation curves. The formation of the additional airier oriented component is inhibited by annealing in most of the materials studied. In contrast, multiple load changes promote its formation

Thermoplastic polyurethanes with varying hard segment components. Mechanical performance and a filler crosslink conversion of hard domains as monitored by SAXS

When monitoring tensile tests of thermoplastic polyurethanes TPU by small angle X ray scattering SAXS we find a filler to crosslink conversion of hard domain function. Its strength is related to the chemical composition and governs the mechanical performance of the TPUs. Acting as fillers, the domains provide a high modulus of elasticity. Once the domains take load, they lose their filler function and the material gains in extensibility. All the five machine cast TPUs have soft segments from PTHF 1000 and a hard segment content amp; 8776; 45 . The hard segments are built from different diisocyanates DI and diols chain extenders, CE . The base material has hard segments made from 1,4 butanediol BD and methylene diphenyl diisocyanate MDI . Two other TPUs contain as DIs either the hydrogenated, isomeric MDI H12MDI or hexamethylene diisocyanate HDI , respectively. In two other materials the CE is varied. Here the BD is replaced by either the shorter 1,3 propanediol PD or by the longer 1,6 hexanediol HD . A morphological model is fitted to the SAXS data. It returns nanoscopic parameters, e.g. discriminating between the total Vt and the crosslinked Vx volume of hard domains. Fillers are Vf Vt amp; 8722;Vx. Results show that Vf domains can be converted into Vx domains. Hydrogenation of the aromatic base DI does not change Vt, but Vx lags behind. Young s modulus is higher filler function, high Vf , but the material breaks earlier low Vx . Generally, Vt increases for small strains strain induced domains, SIDs and decreases for strain gt;1. SIDs start as fillers. When MDI is replaced by HDI the formation of SIDs is boosted leading to strain induced hardening only at low strain. At higher strain the modulus lowers conversion Vf amp; 8594; Vx . Only in this material are so many domains converted that Vx increases during stretching. The material breaks late. The long CE increases the average distance between crosslink domains and narrows the distribution of the distances. With the medium CE domains appear less stable at low strai