Tuning Magnetic and Photophysical Properties of Luminomagnetic Metal-Organic Framework Composites in an Inverse Core-Satellite Structure.

Luminomagnetic composites have been synthesized that allow for an individual tuning of luminescence intensity, chromaticity and magnetization by combination of superparamagnetic, citrate-stabilized iron oxide nanoparticles with the luminescent MOFs 3 ∞ [Ln2 (BDC)3 (H2 O)4 ] (Ln=Eu, Tb; BDC2- =terephthalate). The components are arranged to a concept of inverse structuring compared to previous luminomagnetic composites with MOF@magnetic particle (shell@core) composition so that the luminescent MOF now acts as core and is covered by magnetic nanoparticles forming the satellite shell. Thereby, the magnetic and photophysical properties are individually tuneable between high emission intensity (1.2 ⋅ 106  cps mg-1 ) plus low saturation magnetization (6 emu g-1 ) and the direct opposite (0.09 ⋅ 106  cps mg-1 ; 42 emu g-1 ) by adjusting the particle coverage of the MOF. This is not achievable with a core-shell structure having a magnetic core and a dense MOF shell. The composition of the composites and the influence of different synthesis conditions on their properties were investigated by SEM/EDX, PXRD, magnetization measurements and photoluminescence spectroscopy.

Spray-Dried Photonic Balls with a Disordered/Ordered Hybrid Structure for Shear-Stress Indication.

Optical microscale shear-stress indicator particles are of interest for the in situ recording of localized forces, e.g., during 3D printing or smart skins in robotic applications. Recently developed particle systems are based on optical responses enabled by integrated organic dyes. They thus suffer from potential chemical instability and cross-sensitivities toward humidity or temperature. These drawbacks can be circumvented using photonic balls as shear-stress indicator particles, which employ structural color as the element to record forces. Here, such photonic balls are prepared from silica and iron oxide nanoparticles via the scalable and fast spray-drying technique. Process parameters to create photonic balls with a disordered core and an ordered particle structure toward the exterior of the supraparticles are reported. This hybrid disordered-ordered structure is responsible for a color loss of the indicator particles during shear-stress application because of irreversible structural destruction. By adjusting the primary silica particle sizes, nearly all colors of the visible spectrum can be achieved and the sensitivity of the response to shear stress can be adjusted.

Supraparticles with a Mechanically Triggerable Color-Change-Effect to Equip Coatings with the Ability to Report Damage.

Small scratches and abrasion cause damage to packaging coatings. Albeit often invisible to the human eye, such small defects in the coating may ultimately have a strong negative impact on the whole system. For instance, gases may penetrate the coating and consequently the package barrier, thus leading to the degradation of sensitive goods. Herein, the indicators of mechanical damage in the form of particles are reported, which can readily be integrated into coatings. Shear stress-induced damage is indicated by the particles via a color change. The particles are designed as core-shell supraparticles. The supraparticle core is based on rhodamine B dye-doped silica nanoparticles, whereas the shell is made of alumina nanoparticles. The alumina surface is functionalized with a monolayer of a perylene dye. The resulting core-shell supraparticle system thus contains two colors, one in the core and one in the shell part of the architecture. Mechanical damage of this structure exposes the core from the shell, resulting in a color change. With particles integrated into a coating lacquer, mechanical damage of a coating can be monitored via a color change and even be related to the degree of oxygen penetration in a damaged coating.

Optically Sensitive and Magnetically Identifiable Supraparticles as Indicators of Surface Abrasion.

Identifying and ensuring the integrity of products plays an important role in today's globalized world. Miniaturized information taggants in the packaging surface are therefore required to monitor the product itself instead of applying external labels. Ideally, multiple types of information are stored in such additives. In this work, micrometer-sized core-shell particles (supraparticles) were developed to provide material surfaces with both an identifier and a surface abrasion indication functionality. The core of the supraparticles contains iron oxide nanoparticles that allow identification of the surface with a spectral magnetic code resolved by magnetic particle spectroscopy. The fluorescent silica nanoparticles in the supraparticle shell can be abraded by mechanical stress and resolved by fluorescence spectroscopy. This provides information about the mechanical integrity of the system. The application as surfaces, that contain several types of information in one supraparticle, was demonstrated here by incorporating such bifunctional supraparticles as additives in a surface coating.

A Single Magnetic Particle with Nearly Unlimited Encoding Options.

Communicating objects are demanded for product security and the concepts of a circular economy or the Internet of Nano Things. Smart additives in the form of particles can be the key to equip objects with the desired materials intelligence as their miniaturized size improves applicability and security. Beyond their proposed identification by optical signals, magnetic signals deriving from magnetic particles can hypothetically be used for identification but are to date only resolved roughly. Herein, a magnetic particle-based toolbox is reported, that provides more than 77 billion (77 × 109 ) different magnetic codes, adjustable in one single particle, that can be read out unambiguously, easily, and quickly. The key towards achieving the vast code variety is a hierarchical supraparticle design that is inspired by music: similarly to how the line-up variation of a musical ensemble yields distinguishable overtones, the variation of the supraparticle composition alters their magnetic overtones. By minimizing magnetic interactions, customizable signals are spectrally decoded by the simple method of magnetic particle spectroscopy. A large number of chemically adjustable magnetic codes and the possibility of their remote, contactless detection from within materials is a breakthrough for unexploited labeling applications and pave the way towards materials intelligence.

Supraparticles with silica protection for redispersible, calcined nanoparticles.

Calcination of nanoparticles is always accompanied by undesired sintering. A calcination route preventing hard-agglomeration to bulk lumps, which is transferable to almost any kind of metal oxide nanoparticle, is developed by surrounding targeted nanoparticles by silica nanoparticles within a nanostructured microparticle. After calcination, the desired nanoparticles are regained as a monodisperse sol via silica dissolution.

Core-Satellite Supraparticles To Ballistically Stamp Nanostructures on Surfaces.

Nanostructured surfaces are of great importance in a very wide range of fields. They can be obtained by imprint or deposition techniques. However, these are usually sophisticated to perform. Generally, it is not easy to equip an object/product with a nanostructure after manufacturing. Yet, it would be very beneficial to achieve a modification of an arbitrary surface with a nanostructure of choice at a later stage by an approach that is simple to perform without the need of sophisticated equipment or excessive treatment by physicochemical methods. Herein, such a process is reported, which combines two "old-fashioned" techniques, namely, sandblasting and rubber-stamping, and translates them to the "nanoworld". By creating core-satellite supraparticles via spray-drying, a ballistic core-satellite stamp particle system is obtained, which can be used to easily transfer a wide range of nanoparticles to a great variety of surfaces to equip these with a nanostructure and subsequently advanced properties. These include water-repellant, antifouling, or antidust surfaces. Moreover, it is also demonstrated that the approach can be used to manufacture well-defined nanoimprinted surfaces. Such surfaces showed an improved spreading behavior for aliphatic alcohols, thus making such surfaces, for instance, very susceptible for disinfectants. All in all, the simple technique described herein has a great potential for creating nanostructured surfaces on nearly any surface.