More than four decades ago, Brochard and de Gennes proposed that colloidal suspensions of ferromagnetic particles in nematic (directionally ordered) liquid crystals could form macroscopic ferromagnetic phases at room temperature. The experimental realization of these predicted phases has hitherto proved elusive, with such systems showing enhanced paramagnetism but no spontaneous magnetization in the absence of an external magnetic field. Here we show that nanometre-sized ferromagnetic platelets suspended in a nematic liquid crystal can order ferromagnetically on quenching from the isotropic phase. Cooling in the absence of a magnetic field produces a polydomain sample exhibiting the two opposing states of magnetization, oriented parallel to the direction of nematic ordering. Cooling in the presence of a magnetic field yields a monodomain sample; magnetization can be switched by domain wall movement on reversal of the applied magnetic field. The ferromagnetic properties of this dipolar fluid are due to the interplay of the nematic elastic interaction (which depends critically on the shape of the particles) and the magnetic dipolar interaction. This ferromagnetic phase responds to very small magnetic fields and may find use in magneto-optic devices.
We have studied the response of ferromagnetic liquid crystals to external magnetic and electric fields, and compared it to the usual response of nematic liquid crystals (NLCs). We have observed effects, which are not present in a pure NLC and are a consequence of the coupling between the nematic director and the magnetization. The electro-optic effect, which is in the ferromagnetic phase the same as in the pure NLC, is accompanied by a converse magnetoelectric effect. The magneto-optic effect differs completely from the one observed in the pure NLC, where it is a quadratic effect and it only appears when a magnetic field larger than a critical field is applied perpendicular to the director. In the ferromagnetic NLC in addition to the response to the perpendicular field, there is also a qualitatively different response to the parallel field. Contrary to the pure NLC no critical field needs to be exceeded for the system to respond to a perpendicular field, but a critical field needs to be exceeded to observe a response to the field parallel to the director and antiparallel to the magnetization. The critical field is in this case two orders of magnitude smaller than the critical field of the magnetic Frederiks transition in the pure NLC. The experimental observations are well described by a simple macroscopic theory.
The dissolution of upconverting AYF4:Yb,Tm (A = Na or K) nanoparticles (UCNPs) in aqueous media was systematically studied. UCNPs with a cubic structure and sizes of between 10 and 33 nm were synthesized solvothermally in ethylene glycol at 200 °C. The UCNPs of both compositions showed an upconversion fluorescence emission characteristic of Tm(3+). The effects of the A cation, the particle size, the temperature, the pH, and the composition of the aqueous medium on the dissolution of the UCNPs were evaluated. The degree of dissolution was determined from the fraction of dissolved fluoride (F(-)) using potentiometry. Unexpectedly, the composition of aqueous media had the most significant effect on the dissolution of the UCNPs. The highest degree of dissolution and rate were measured for the phosphate-buffered saline (PBS), which can be explained by the formation of stable lanthanide compounds with phosphates. The degree of dissolution was much lower in water and in the phthalate buffer, which was attributed to the release of F(-) as a result of the hydrolysis of the UCNPs' surfaces.
In a proof-of-concept study, we assessed different analytical and spectroscopic parameters for stability screening of differently sized β-NaYF:20 mol % Yb, 2 mol % Tm upconversion nanoparticles (UCNPs) exemplarily in the bioanalytically relevant buffer phosphate buffered saline (PBS; pH 7.4) at 37 and 50 °C. This included the potentiometric determination of the amount of released fluoride ions, surface analysis with X-ray photoelectron spectroscopy (XPS), and steady-state and time-resolved fluorescence measurements. Based on these results, the luminescence lifetime of the 800 nm upconversion emission was identified as an optimum parameter for stability screening of UCNPs and changes in particle surface chemistry.
The hydrothermal treatment of an appropriate suspension of Ba and Fe hydroxides in the presence of a large excess of OH(-) results in the formation of Ba hexaferrite at temperatures as low as 150 degrees C. This low formation temperature enables the synthesis of uniform, ultrafine Ba hexaferrite nanoparticles. These nanoparticles have a disc-like shape, approximately 10 nm wide, but only approximately 3 nm thick. When the temperature of the hydrothermal treatment is increased, large platelet Ba hexaferrite crystals appear as a consequence of secondary re-crystallization (Ostwald ripening). In this work, this undesired process of secondary re-crystallization has been evaluated. We show that the secondary re-crystallization can be totally suppressed with the use of an oleic acid surfactant. The addition of oleic acid enabled the synthesis of uniform, ultrafine nanoparticles at temperatures up to 240 degrees C. The nanoparticles were hydrophobic and could be suspended in nonpolar liquids to form relatively concentrated ferrofluids. Such stable suspensions of hexaferrite nanoparticles will be technologically important, especially as precursors for the preparation of new nanostructured materials, for example nanocomposites or nanostructured ceramic films.
The unique photoluminescent properties of upconversion nanoparticles (UCNPs) have attracted worldwide research interest and inspired many bioanalytical applications. The anti‐Stokes emission with long luminescence lifetimes, narrow and multiple absorption and emission bands, and excellent photostability enable background‐free and multiplexed detection in deep tissues. So far, however, in vitro and in vivo applications of UCNPs are restricted to the laboratory use due to safety concerns. Possible harmful effects may originate from the chemical composition but also from the small size of UCNPs. Potential end users must rely on well‐founded safety data. Thus, a risk to benefit assessment of the envisioned combined therapeutic and diagnostic (“theranostic”) applications is fundamentally important to bridge the translational gap between laboratory and clinics. The COST Action CM1403 “The European Upconversion Network—From the Design of Photon‐Upconverting Nanomaterials to Biomedical Applications” integrates research on UCNPs ranging from fundamental materials synthesis and research, detection instrumentation, biofunctionalization, and bioassay development to toxicity testing. Such an interdisciplinary approach is necessary for a better and safer theranostic use of UCNPs. Here, the status of nanotoxicity research on UCNPs is compared to other nanomaterials, and routes for the translation of UCNPs into clinical applications are delineated.
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