ABSTRACT
Unlike conventional colloids showing random mobility because of Brownian motion, active colloids contain nanomotors that translate chemical or physical triggers into directed movement. Whereas the acceleration of such particles works well, it is difficult to decelerate them by request. Compared to the existing literature on microscaled swimmers/robots, the main question of the current paper is whether nanoscaled colloids (<100 nm) can also be actively controlled despite the stronger relevance of rotational diffusion at such dimensions. We developed nanoparticles comprising two independent mechanisms for propulsion: a chemical engine associated with a Janus-type modification of organosilica nanoparticles and physical locomotion because of a superparamagnetic core inside these particles. Both triggers can be used independently to initiate the particles' directed and anisotropic movement. The magnetic forces can be tuned, most importantly concerning the angle defining the chemical acceleration. Superposition and a boost state are adopted for a parallel alignment. However, when the magnetic field acting on the particles is turned to an antiparallel orientation, a rapid deceleration can be observed, and the colloids halt.
ABSTRACT
Postsynthetic exchange (PSE) is a key technique for integrating sensitive linkers into metal-organic frameworks (MOFs). Despite its importance, investigations into linker distributions have primarily focused on micrometer-sized crystals due to the analytical limitations, leaving nanoparticles less explored, although they are commonly synthesized and used in applications. In particular, the emergence of core-shell nanostructures via PSE has shown potential for applications in CO2 adsorption and selective catalysis. This study addresses this gap by investigating the formation of core-shell structures on nanoparticles under diffusion-controlled PSE conditions. By analyzing volume-to-surface ratios and conducting time-dependent experiments, we confirmed that these conditions facilitate the development of core-shell architectures. We also developed a straightforward method to calculate the minimum incorporation depth using basic parameters such as particle size and the total amount of incorporated linker. The accuracy of our approach was validated against data obtained from transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy. These findings enhance the understanding of PSE in MOF nanoparticles and open up promising avenues for developing advanced MOF core-shell structures for various applications.
ABSTRACT
Small molecule structures and their applications rely on good knowledge of their atomic arrangements. However, the crystal structures of these compounds and materials, which are often composed of fine crystalline domains, cannot be determined with single-crystal X-ray diffraction. Three-dimensional electron diffraction (3D ED) is already becoming a reliable method for the structure analysis of submicrometer-sized organic materials. The reduction of electron beam damage is essential for successful structure determination and often prevents the analysis of organic materials at room temperature, not to mention high temperature studies. In this work, we apply advanced 3D ED methods at different temperatures enabling the accurate structure determination of two phases of Pigment Orange 34 (C34H28N8O2Cl2), a biphenyl pyrazolone pigment that has been industrially produced for more than 80 years and used for plastics application. The crystal structure of the high-temperature phase, which can be formed during plastic coloration, was determined at 220 °C. For the first time, we were able to observe a reversible phase transition in an industrial organic pigment in the solid state, even with atomic resolution, despite crystallites being submicrometer in size. By localizing hydrogen atoms, we were even able to detect the tautomeric state of the molecules at different temperatures. This demonstrates that precise, fast, and low-dose 3D ED measurements enable high-temperature studies the door for general in situ studies of nanocrystalline materials at the atomic level.
ABSTRACT
Structure-property relationships in ordered materials have long been a core principle in materials design. However, the introduction of disorder into materials provides structural flexibility and thus access to material properties that are not attainable in conventional, ordered materials. To understand disorder-property relationships, the disorder - i.e., the local ordering principles - must be quantified. Local order can be probed experimentally by diffuse scattering. The analysis is notoriously difficult, especially if only powder samples are available. Here, we combine the advantages of three-dimensional electron diffraction - a method that allows single crystal diffraction measurements on sub-micron sized crystals - and three-dimensional difference pair distribution function analysis (3D-ΔPDF) to address this problem. In this work, we compare the 3D-ΔPDF from electron diffraction data with those obtained from neutron and x-ray experiments of yttria-stabilized zirconia (Zr0.82Y0.18O1.91) and demonstrate the reliability of the proposed approach.
ABSTRACT
Using colloidal particles as models to understand processes on a smaller scale is a precious approach. Compared to molecules, particles are less defined, but their architecture can be more complex and so is their long-range interaction. One can observe phenomena that are unknown or much more difficult to realize on the molecular level. The current paper focuses on particle-based surfactants and reports on numerous unexpected properties. The main goal is creating an amphiphilic system with responsiveness in surface activity and associated self-organization phenomena depending on applying an external trigger, preferably a physical field. A key step is the creation of a Janus-type particle characterized by two types of dipoles (electric and magnetic) which geometrically stand orthogonal to each other. In a field, one can control which contribution and direction dominate the interparticle interactions. As a result, one can drastically change the system's properties. The features of ferrite-core organosilica-shell particles with grain-like morphology modified by click chemistry are studied in response to spatially isotropic and anisotropic triggers. A highly unusual aggregation-dissolution-reaggregation sequence w as discovered. Using a magnetic field, one can even switch off the amphiphilic properties and use this for the field-triggered breaking of multiphase systems such as emulsions.
ABSTRACT
Continuous-rotation 3D electron diffraction methods are increasingly popular for the structure analysis of very small organic molecular crystals and crystalline inorganic materials. Dynamical diffraction effects cause non-linear deviations from kinematical intensities that present issues in structure analysis. Here, a method for structure analysis of continuous-rotation 3D electron diffraction data is presented that takes multiple scattering effects into account. Dynamical and kinematical refinements of 12 compounds-ranging from small organic compounds to metal-organic frameworks to inorganic materials-are compared, for which the new approach yields significantly improved models in terms of accuracy and reliability with up to fourfold reduction of the noise level in difference Fourier maps. The intrinsic sensitivity of dynamical diffraction to the absolute structure is also used to assign the handedness of 58 crystals of 9 different chiral compounds, showing that 3D electron diffraction is a reliable tool for the routine determination of absolute structures.
ABSTRACT
Many pathogenic bacteria are getting more and more resistant against antibiotic treatment and even become up to 1.000× times more resilient in the form of a mature biofilm. Thus, one is currently prospecting for alternative methods for treating microbial infections, and photodynamic therapy is a highly promising approach by creating so-called reactive oxygen species (ROS) produced by a photosensitizer (PS) upon irradiation with light. Unfortunately, the unspecific activity of ROS is also problematic as they are harmful to healthy tissue as well. Notably, one knows that uncontrolled existence of ROS in the body plays a major role in the development of cancer. These arguments create need for advanced theranostic materials which are capable of autonomous targeting and detecting the existence of a biofilm, followed by specific activation to combat the infection. The focus of this contribution is on mesoporous organosilica colloids functionalized by orthogonal and localized click-chemistry methods. The external zone of the particles is modified by a dye of the Hoechst family. The particles readily enter a mature biofilm where adduct formation with extracellular DNA and a resulting change in the fluorescence signal occurs, but they cannot cross cellular membranes such as in healthy tissue. A different dye suitable for photochemical ROS generation, Acridine Orange, is covalently linked to the surfaces of the internal mesopores. The spectral overlap between the emission of Hoechst with the absorption band of Acridine Orange facilitates energy transfer by Förster resonance with up to 88% efficiency. The theranostic properties of the materials including viability studies were investigated in vitro on mature biofilms formed by Pseudomonas fluorescens and prove the high efficacy.
ABSTRACT
Determination of lattice parameters from 3D electron diffraction (3D ED) data measured in a transmission electron microscope is hampered by a number of effects that seriously limit the achievable accuracy. The distortion of the diffraction patterns by the optical elements of the microscope is often the most severe problem. A thorough analysis of a number of experimental datasets shows that, in addition to the well known distortions, namely barrel-pincushion, spiral and elliptical, an additional distortion, dubbed parabolic, may be observed in the data. In precession electron diffraction data, the parabolic distortion leads to excitation-error-dependent shift and splitting of reflections. All distortions except for the elliptical distortion can be determined together with lattice parameters from a single 3D ED data set. However, the parameters of the elliptical distortion cannot be determined uniquely due to correlations with the lattice parameters. They can be determined and corrected either by making use of the known Laue class of the crystal or by combining data from two or more crystals. The 3D ED data can yield lattice parameter ratios with an accuracy of about 0.1% and angles with an accuracy better than 0.03°.
ABSTRACT
This study made use of a recently developed combination of advanced methods to reveal the atomic structure of a disordered nanocrystalline zeolite using exit wave reconstruction, automated diffraction tomography, disorder modelling and diffraction pattern simulation. By applying these methods, it was possible to determine the so far unknown structures of the hydrous layer silicate RUB-6 and the related zeolite-like material RUB-5. The structures of RUB-5 and RUB-6 contain the same dense layer-like building units (LLBUs). In the case of RUB-5, these building units are interconnected via additional SiO4/2 tetrahedra, giving rise to a framework structure with a 2D pore system consisting of intersecting 8-ring channels. In contrast, RUB-6 contains these LLBUs as separate silicate layers terminated by silanol/sil-oxy groups. Both RUB-6 and RUB-5 show stacking disorder with intergrowths of different polymorphs. The unique structure of RUB-6, together with the possibility for an interlayer expansion reaction to form RUB-5, make it a promising candidate for interlayer expansion with various metal sources to include catalytically active reaction centres.
ABSTRACT
Electron diffraction tomography (EDT) has gained increasing interest, starting with the development of automated electron diffraction tomography (ADT) which enables the collection of three-dimensional electron diffraction data from nano-sized crystals suitable for ab initio structure analysis. A basic description of the ADT method, nowadays recognized as a reliable and established method, as well as its special features and general applicability to different transmission electron microscopes is provided. In addition, the usability of ADT for crystal structure analysis of single nano-sized crystals with and without special crystallographic features, such as twinning, modulations and disorder is demonstrated.
ABSTRACT
Nanoscaled porous materials such as zeolites have attracted substantial attention in industry due to their catalytic activity, and their performance in sorption and separation processes. In order to understand the properties of such materials, current research focuses increasingly on the determination of structural features beyond the averaged crystal structure. Small particle sizes, various types of disorder and intergrown structures render the description of structures at atomic level by standard crystallographic methods difficult. This paper reports the characterization of a strongly disordered zeolite structure, using a combination of electron exit-wave reconstruction, automated diffraction tomography (ADT), crystal disorder modelling and electron diffraction simulations. Zeolite beta was chosen for a proof-of-principle study of the techniques, because it consists of two different intergrown polymorphs that are built from identical layer types but with different stacking sequences. Imaging of the projected inner Coulomb potential of zeolite beta crystals shows the intergrowth of the polymorphs BEA and BEB. The structures of BEA as well as BEB could be extracted from one single ADT data set using direct methods. A ratio for BEA/BEB = 48:52 was determined by comparison of the reconstructed reciprocal space based on ADT data with simulated electron diffraction data for virtual nanocrystals, built with different ratios of BEA/BEB. In this way, it is demonstrated that this smart interplay of the above-mentioned techniques allows the elaboration of the real structures of functional materials in detail - even if they possess a severely disordered structure.
ABSTRACT
Poly(triazine imide) with incorporated lithium chloride has recently attracted substantial attention due to its photocatalytic activity for water splitting. However, an apparent H/Li disorder prevents the delineation of structure-property relationships, for example, with respect to band-gap tuning. Herein, we show that through a combination of one- and two-dimensional, multinuclear solid-state NMR spectroscopy, chemical modelling, automated electron diffraction tomography, and an analysis based on X-ray pair distribution functions, it is finally possible to resolve the H/Li substructure. In each cavity, one hydrogen atom is bound to a bridging nitrogen atom, while a second one protonates a triazine ring. The two lithium ions within each cavity are positioned between two nitrogen atoms of neighbouring triazine rings. The thereby induced local dipole moments cause slight buckling of the framework and lateral displacements of the Cl- ions at a coherence length below 2â nm. Nevertheless, the average structure conforms to space group P21 21 21 . In this way, we demonstrate that, in particular, the above-mentioned techniques allow for smart interplay in delineating the real structure of PTI/LiCl.
ABSTRACT
The M2O-Al2O3-WO3 (M = alkaline metals) system has attracted the attention of the scientific community because some of its members showed potential applications as single crystalline media for tunable solid-state lasers. These materials behave as promising laser host materials due to their high and continuous transparency in the wide range of the near-IR region. A systematic investigation of these phases is nonetheless hampered because it is impossible to produce large crystals and only in a few cases a pure synthetic product can be achieved. Despite substantial advances in X-ray powder diffraction methods, structure investigation on nanoscale is still challenging, especially when the sample is polycrystalline and the structures are affected by pseudo-symmetry. Electron diffraction has the advantage of collecting data from single nanoscopic crystals, but it is frequently limited by incompleteness and dynamical effects. Automated diffraction tomography (ADT) recently emerged as an alternative approach able to collect more complete three-dimensional electron diffraction data and at the same time to significantly reduce dynamical scattering. ADT data have been shown to be suitable for ab initio structure solution of phases with large cell parameters, and for detecting pseudo-symmetry that was undetected in X-ray powder data. In this work we present the structure investigation of two hitherto undetermined compounds, K5Al(W3O11)2 and NaAl(WO4)2, by a combination of electron diffraction tomography and precession electron diffraction. We also stress how electron diffraction tomography can be used to obtain direct information about symmetry and pseudo-symmetry for nanocrystalline phases, even when available only in polyphasic mixtures.