Confining single Er3+ ions in sub-3 nm NaYF4 nanoparticles to induce slow relaxation of the magnetisation.

Molecular systems known as single-molecule magnets (SMMs) exhibit magnet-like behaviour of slow relaxation of the magnetisation and magnetic hysteresis and have potential application in high-density memory storage or quantum computing. Often, their intrinsic magnetic properties are plagued by low-energy molecular vibrations that lead to phonon-induced relaxation processes, however, there is no straightforward synthetic approach for molecular systems that would lead to a small amount of low-energy vibrations and low phonon density of states at the spin-resonance energies. In this work, we apply knowledge accumulated over the last decade in molecular magnetism to nanoparticles, incorporating Er3+ ions in an ultrasmall sub-3 nm diamagnetic NaYF4 nanoparticle (NP) and probing the slow relaxation dynamics intrinsic to the Er3+ ion. Furthermore, by increasing the doping concentration, we also investigate the role of intraparticle interactions within the NP. The knowledge gained from this study is anticipated to enable better design of magnetically high-performance molecular and bulk magnets for a wide variety of applications, such as molecular electronics.

Stimulus-Responsive Nanoconjugates Derived from Phytoglycogen Nanoparticles.

Plant-derived phytoglycogen nanoparticles (PhG NPs) have the advantages of size uniformity, dispersibility in water, excellent lubrication properties, and lack of cytotoxicity; however, their chemical functionalization may lead to loss of NP structural integrity. Here, we report a straightforward approach to the generation of PhG NP conjugates with biologically active molecules. Hydrogen bonding of bovine serum albumin with electroneutral PhG NPs endows them with additional ligand binding affinity and enables the electrostatically governed attachment of methotrexate (MTX), a therapeutic agent commonly used in the treatment of cancer and arthritis diseases, to the protein-capped NPs. We showed stimuli-responsive release of MTX from the PhG-based nanoconjugates under physiological cues such as temperature and ionic strength. The results of this study stimulate future exploration of biomedical applications of nanoconjugates of PhG NPs.

Phytoglycogen Nanoparticles: Nature-Derived Superlubricants.

Phytoglycogen nanoparticles (PhG NPs), a single-molecule highly branched polysaccharide, exhibit excellent water retention, due to the abundance of close-packed hydroxyl groups forming hydrogen bonds with water. Here we report lubrication properties of close-packed adsorbed monolayers of PhG NPs acting as boundary lubricants. Using direct surface force measurements, we show that the hydrated nature of the NP layer results in its striking lubrication performance, with two distinct confinement-controlled friction coefficients. In the weak- to moderate-confinement regime, when the NP layer is compressed down to 8% of its original thickness under a normal pressure of up to 2.4 MPa, the NPs lubricate the surface with a friction coefficient of 10-3. In the strong-confinement regime, with 6.5% of the original layer thickness under a normal pressure of up to 8.1 MPa, the friction coefficient was 10-2. Analysis of the water content and energy dissipation in the confined NP film reveals that the lubrication is governed by synergistic contributions of unbound and bound water molecules, with the former contributing to lubrication properties in the weak- to moderate-confinement regime and the latter being responsible for the lubrication in the strong-confinement regime. These results unravel mechanistic insights that are essential for the design of lubricating systems based on strongly hydrated NPs.

Corrosion of One-Step Superhydrophobic Stainless-Steel Thermal Spray Coatings.

As most superhydrophobic coatings are made of soft materials, the need for harder, more robust films is evident in applications where erosional degradation is of concern. The work herein describes a methodology to produce superhydrophobic stainless-steel thermal spray coatings using the high-velocity oxygen fuel technique. Due to the use of a kerosene fuel source, a carbon-rich film is formed on the surface of the thermal spray coatings, lowering the surface energy of the high-energy metallic substrates. The thermal spray process generates a hierarchical micro-/sub-micro-structure that is needed to sustain superhydrophobicity. The effect of spray parameters such as particle velocity and temperature on the coating's hydrophobicity state was explored, and a high particle velocity was shown to cause superhydrophobic characteristics. The coatings were characterized using scanning electron microscopy, profilometry, X-ray photoelectron spectroscopy, static water contact angle measurements, water droplet roll-off measurements, and water droplet bouncing tests. The corrosion behavior of the coatings was studied using potentiodynamic polarization measurements in order to correlate water repellency with corrosion resistance; however, all coatings demonstrated active corrosion without passivation. This study describes an interesting phenomenon where superhydrophobicity does not guarantee corrosion resistance and discusses alternative applications for such materials.