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We have developed a straightforward, one-pot, low-temperature hydrothermal method to transform oyster shell waste particles (bCCP) from the species Crassostrea gigas (Mg-calcite, 5 wt% Mg) into hydroxyapatite (HA) micro/nanoparticles. The influence of the P reagents (H 3 PO 4 , KH 2 PO 4 , and K 2 HPO 4 ), P/bCCP molar ratios (0.24, 0.6, and 0.96), digestion temperatures (25-200 °C), and digestion times (1 week-2 months) on the transformation process was thoroughly investigated. At 1 week, the minimum temperature to yield the full transformation significantly reduced from 160 °C to 120 °C when using K 2 HPO 4 instead of KH 2 PO 4 at a P/bCCP ratio of 0.6, and even to 80 °C at a P/bCCP ratio of 0.96. The transformation took place via a dissolution-reprecipitation mechanism driven by the favorable balance between HA precipitation and bCCP dissolution, due to the lower solubility product of HA than that of calcite at any of the tested temperatures. Both the bCCP and the derived HA particles were cytocompatible for MG-63 human osteosarcoma cells and m17.ASC murine mesenchymal stem cells, and additionally, they promoted the osteogenic differentiation of m17.ASC, especially the HA particles. Because of their physicochemical features and biological compatibility, both particles could be useful osteoinductive platforms for translational applications in bone tissue engineering.

Conventional nanocrystal (NC) growth mechanisms have overwhelmingly focused on the final exposed facets to explain shape evolution. However, how the final facets are formed from the initial nuclei or seeds, has not been specifically interrogated. In this concept paper, we would like to concentrate on this specific topic, and introduce the symmetry based kinematic theory (SBKT) to explain the formation and evolution of crystal facets. It is a crystallographic theory based on the classical crystal growth concepts developed to illustrate the shape evolution during the NC growth. The most important principles connecting the basic NC growth processes and morphology evolution are the preferential growth directions and the properties of kinematic waves. On the contrary, the final facets are just indications of how the crystal growth terminates, and their formation and evolution rely on the NC growth processes: surface nucleation and layer advancement. Accordingly, the SBKT could even be applied to situations where non-faceted NCs such as spheres are formed., (© 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology may hold the key to the practical utilization of these materials. An optimized chiral growth method to prepare fourfold twisted gold nanorods is described herein, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges are found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl 4 , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent. From detailed electron microscopy analysis of the crystallographic structures, it is proposed that the dissymmetry results from the development of chiral facets in the form of protrusions (tilted ridges) on the initial nanorods, eventually leading to a twisted shape. The role of cysteine is attributed to assisting enantioselective facet evolution, which is supported by density functional theory simulations of the surface energies, modified upon adsorption of the chiral molecule. The development of R-type and S-type chiral structures (small facets, terraces, or kinks) would thus be non-equal, removing the mirror symmetry of the Au NR and in turn resulting in a markedly chiral morphology with high plasmonic optical activity., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Nature provides numerous biomineral design inspirations for constructing structural materials with desired functionalities. However, large-scale production of damage-tolerant Bouligand structural materials with biologically comparable photonics remains a longstanding challenge. Here, an efficient and scalable artificial molting strategy, based on self-assembly of cellulose nanocrystals and subsequent mineralization of amorphous calcium carbonate, is developed to produce biomimetic materials with an exceptional combination of mechanical and photonic properties that are usually mutually exclusive in synthetic materials. These biomimetic composites exhibit tunable mechanics from "strong and flexible", which exceeds the benchmark of natural chiral materials, to "stiff and hard", which is comparable to natural and synthetic counterparts. Especially, the biomimetic composites possess ultrahigh stiffness of 2 GPa in their fully water-swollen state-a value well beyond hydrated crab exoskeleton, cartilage, tendon, and stiffest synthetic hydrogels, combined with exceptional strength and resilience. Additionally, these composites are distinguished by the tunable chiral structural color and water-triggered switchable photonics that are absent in most artificial mineralized materials, as well as unique hydroplastic properties. This study opens the door for a scalable synthesis of resilient biophotonic structural materials in practical bulk form., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Biominerals are unique materials found in many living organisms that often display outstanding functionalities attributed to their mesocrystalline structure. Mesocrystals are nanocrystal superstructures with mutual crystallographic alignment of the building units. One could thus imagine these optimized evolutionary systems as archetypes to fabricate advanced materials. The main advantage of such systems relies on their ability to combine the features of the nanocrystals with those of single crystalline microscopic structures, yielding assemblies with directional, enhanced, and potentially emergent properties. Moreover, fueled by the promises of multifunctional materials with unprecedented and tunable properties, the rational design of mesocrystals assembled from two distinct colloidal nanocrystal ensembles has become a recent focus of research. However, the combination of dissimilar nanocrystals into ordered binary superstructures is still a major scientific challenge due to the nature of the coassembly process.We focus this Account on the growth of tridimensional (3D) binary mesocrystals and the understanding of the self-assembly of two colloidal nanocrystal ensembles with the ultimate goal to serve as a basis for more rational mesocrystal syntheses in the future. The formation of mesocrystals demands nanocrystals with defined surface faceting, the primary factor influencing their oriented self-assembly. Notably, such a process cannot be successfully afforded without functionalized nanocrystals with high and, in many cases, tunable colloidal stability. Besides, the nature and solvation degree of the surface ligand shell influences the effective shape of the nanocrystals and the kinetics of self-assembly. If the assembly is triggered by reducing the colloidal stability with nonsolvents, 3D single-component mesocrystals are often grown. Here, the different magnitude of the van der Waals attraction forces between nanocrystals with differing compositions, dimensions, and morphologies generally favors the segregation and growth of single component mesocrystals. This phenomenon was illustrated during the successful preparation of 3D binary mesocrystals composed of iron oxide and platinum nanocubes. Although the building blocks possessed comparable sizes and were stabilized by similar ligands, the amount of the second component could only be arbitrarily tuned up to some extent, even when the assembly conditions were rationally optimized to achieve 3D binary mesocrystals. Only a small amount of it was effectively incorporated into the matrix of the initial mesocrystal. The 3D binary mesocrystal growth process demands a delicate control over the size, shape, and surface chemistry of the nanocrystals, the solvent nature, and the self-assembly process. Hence, the improvement of our ability to control the synthesis of 3D binary mesocrystalline materials is critical to exploit their potential toward technological applications in catalysis, energy storage, or structural materials.

Using X-ray scattering, we measured detailed maps of the diffuse scattering intensity distribution and a number of phonon dispersion branches for a single crystal of inorganically formed natural calcite and for high-quality mesocrystals of biogenic calcite from a Mediterranean sea urchin spine. A comparison shows that the known differences in the mechanical properties between the `strong' biogenic and `brittle' abiotic material should be attributed to the mesoscopic architecture of the crystal rather than to a modification of the calcite crystal structure. The data are rationalized by comparing them to the results of ab initio model calculations of lattice dynamics. For the mesocrystal, they are augmented by the evaluation of the faceting of the constituent nanocrystals.

Mesocrystals, which originally was a term to designate superstructures of nanocrystals with a common crystallographic orientation, have now evolved to a materials concept. The discovery that many biominerals are mesocrystals generated a large research interest, and it was suggested that mesocrystals result in better mechanical performance and optical properties compared to single crystalline structures. Mesocrystalline biominerals are mainly found in spines or shells, which have to be mechanically optimized for protection or as a load-bearing skeleton. Important examples include red coral and sea urchin spine as well as bones. Mesocrystals can also be formed from purely synthetic components. Biomimetic mineralization and assembly have been used to produce mesocrystals, sometimes with complex hierarchical structures. Important examples include the fluorapatite mesocrystals with gelatin as the structural matrix, and mesocrystalline calcite spicules with impressive strength and flexibility that could be synthesized using silicatein protein fibers as template for calcium carbonate deposition. Self-assembly of nanocrystals can also result in mesocrystals if the nanocrystals have a well-defined size and shape and the assembly conditions are tuned to allow the nanoparticles to align crystallographically. Mesocrystals formed by assembly of monodisperse metallic, semiconducting, and magnetic nanocrystals are a type of colloidal crystal with a well-defined structure on both the atomic and mesoscopic length scale.Mesocrystals typically are hybrid materials between crystalline nanoparticles and interspacing amorphous organic or inorganic layers. This structure allows to combine disparate materials like hard but brittle nanocrystals with a soft and ductile amorphous material, enabling a mechanically optimized structural design as realized in the sea urchin spicule. Furthermore, mesocrystals can combine the properties of individual nanocrystals like the optical quantum size effect, surface plasmon resonance, and size dependent magnetic properties with a mesostructure and morphology tailored for specific applications. Indeed, mesocrystals composed of crystallographically aligned polyhedral or rodlike nanocrystals with anisotropic properties can be materials with strongly directional properties and novel collective emergent properties. An additional advantage of mesocrystals is that they can combine the properties of nanoparticles with a structure on the micro- or macroscale allowing for much easier handling.

The mollusk shell nacre layer integrates mineral phases with macromolecular components such as intracrystalline proteins. However, the roles performed by intracrystalline proteins in calcium carbonate nucleation and subsequent postnucleation events (e.g., organization of mineral deposits) in the nacre layer are not known. We find that AP7, a nacre intracrystalline C-RING protein, self-assembles to form amorphous protein oligomers and films on mica that further assemble into larger aggregates or phases in the presence of Ca2+. Using solution nuclear magnetic resonance spectroscopy, we determine that the protein assemblies are stabilized by interdomain interactions involving the aggregation-prone T31-N66 C-terminal C-RING domain but are destabilized by the labile nature of the intrinsically disordered D1-T19 AA N-terminal sequence. Thus, the dynamic, amorphous nature of the AP7 assemblies can be traced to the molecular behavior of the N-terminal sequence. Using potentiometric methods, we observe that AP7 protein phases prolong the time interval for prenucleation cluster formation but neither stabilize nor destabilize ACC clusters. Time-resolved flow cell scanning transmission electron microscopy mineralization studies confirm that AP7 protein phases delay the onset of nucleation and assemble and organize mineral nanoparticles into ring-shaped branching clusters in solution. These phenomena are not observed in protein-deficient assays. We conclude that C-RING AP7 protein phases modulate the time period for early events in nucleation and form strategic associations with forming mineral nanoparticles that lead to mineral organization.

The worldwide trend in nanoparticle technology toward increasing complexity must be directly linked to more advanced characterization methods of size, shape and related properties, applicable to many different particle systems in science and technology. Available techniques for nanoparticle characterization are predominantly focused on size characterization. However, simultaneous size and shape characterization is still an unresolved major challenge. We demonstrate that analytical ultracentrifugation with a multiwavelength detector is a powerful technique to address multidimensional nanoparticle analysis. Using a high performance optical setup and data acquisition software, information on size, shape anisotropy and optical properties were accessible in one single experiment with unmatched accuracy and resolution. A dynamic rotor speed gradient allowed us to investigate broad distributions on a short time scale and differentiate between gold nanorod species including the precise evaluation of aggregate formation. We report how to distinguish between different species of single-wall carbon nanotubes in just one experiment using the wavelength-dependent sedimentation coefficient distribution without the necessity of time-consuming purification methods. Furthermore, CdTe nanoparticles of different size and optical properties were investigated in a single experiment providing important information on structure-property relations. Thus, multidimensional information on size, density, shape and optical properties of nanoparticulate systems becomes accessible by means of analytical ultracentrifugation equipped with multiwavelength detection.

Stable monodispersed amorphous calcium carbonate (ACC) nanoparticles can be synthesized in ethanol media by a facile method, and crystallization of ACC is kinetically controlled, resulting in the formation of three polymorphs in a mixed solvent of ethanol-water at different pH values.

Nanocrystal superstructures of barium carbonate (BaCO(3)) which exhibit unusual morphologies are obtained by the carbon dioxide vapor diffusion technique in the presence of poly(ethylene oxide)-block-eicosa aspartate (PEO-b-Asp(20)). The highly effective bioconjugate acts as a crystal growth modifier over a broad range of concentrations. Instead of commonly observed branched needles, the morphology can be systematically varied along different twinned growth patterns towards well-defined branched dumbbells. Detailed analysis of the crystal substructures with high resolution scanning electron microscopy (HRSEM) and dynamic light scattering (DLS) discloses a potential growth mechanism of the superstructures and reveals the role of the polymeric bioconjugate therein.

Sedimentation analysis of nanoparticle (ZrO(2) and SiO(2)) suspensions of different particle sizes in various solvents as nanoparticle model systems was carried out using interference optics in the analytical ultracentrifuge. The particles differed in their morphology: SiO(2) particles were spherical, whereas ZrO(2) particles were in one case spherical and in the second case non-spherical and spherical. Different analysis programs, based on different principles of data analysis, were used for the evaluation of the size distributions of these particles, viz. SEDFIT [ls-g*(s), c(s)], UltraScan (vHW, 2DSA-MC), SedAnal (dcdt) and VelXLAI (GFL) method and SedAnal, in order to ascertain the benefits and limitations of these analysis methods in characterising the examined nanoparticles.

Mesocrystals are 3D ordered nanoparticle superstructures, often with internal porosity, which receive much recent research interest. While more and more mesocrystal systems are found in biomineralization or synthesized, their potential as material still needs to be explored. It needs to be revealed, which new chemical and physical properties arise from the mesocrystal structure, or how they change by the ordered aggregation of nanoparticles to fully exploit the promising potential of mesocrystals. Also, the mechanisms for mesocrystal synthesis need to be explored to adapt it to a wide class of materials. The last three years have seen remarkable progress, which is summarized here. Also potential future directions of this reaserch field are discussed. This shows the importance of mesocrystals not only for the field of materials research and allows the appliction of mesocrystals in advanced materials synthesis or property improvement of existing materials. It also outlines attractive research directions in this field.

Binary mesocrystals offer the combination of nanocrystal properties in an ordered superstructure. Here, we demonstrate the simultaneous self‐assembly of platinum and iron oxide nanocubes into micrometer‐sized 3D mesocrystals using the gas‐phase diffusion technique. By the addition of minor amounts of a secondary particle type tailored to nearly identical size, shape and surface chemistry, we were able to promote a random incorporation of foreign particles into a self‐assembling host lattice. The random distribution of the binary particle types on the surface and within its bulk has been visualized using advanced transmission and scanning electron microscopy techniques. The 20–40 μm sized binary mesocrystals have been further characterized through wide and small angle scattering techniques to reveal a long‐range ordering on the atomic scale throughout the crystal while showing clear evidence that the material consists of individual building blocks. Through careful adjustments of the crystallization parameters, we could further obtain a reverse superstructure, where incorporated particles and host lattice switch roles. [ABSTRACT FROM AUTHOR]

Post‐polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor‐made materials with superior properties. This concept was adapted to well‐defined block copolymers of the poly(2‐oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water‐soluble, alkyne‐ and alkene‐containing segments were synthesized and orthogonally modified with various low‐molecular weight functional molecules by copper(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) and thiol‐ene (TE) click reactions, respectively. Representative toolkit polymers were used for the synthesis of gold, iron oxide and silica nanoparticles. [ABSTRACT FROM AUTHOR]

Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high‐resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so‐far unsurpassed size‐distribution (PDIc=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes "colloidal" impurities (i.e. nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size‐ and shape‐selective, since mesocrystals show both long‐range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals. [ABSTRACT FROM AUTHOR]

Abstract A pulsed light emitting diode, coupled with a properly configured spectrometer is implemented in open source analytical ultracentrifugation detection hardware, allowing for spectral acquisition spanning the visible to near infrared. Details of the challenges arising with the new hardware are described, along with the necessary solutions to overcome them. The system is successfully tested with polystyrene and gold nanoparticles, demonstrating effectiveness for different material and particle geometries. Sedimentation coefficient distributions and analytically extracted spectra are presented for the multiwavelength datasets extending into the near infrared. Additionally, deconvolution algorithms are applied as a further demonstration of tools applicable to these datasets and the resolving power possible. The results of gold nanoparticle analysis presented here show effective near infrared spectral acquisition is now possible for multiwavelength analytical ultracentrifugation, opening the door for analysis of many important samples with spectral properties in this range, including rich classes of metal and semiconductor nanoparticles. Graphical abstract Image 1 Highlights • NIR spectral analysis now possible with analytical ultracentrifugation. • Pulsed LEDs provide NIR illumination for multiwavelength AUC. • Gold nanoparticle distributions and spectral properties may be recovered. • Method applicable to a broad range of plasmonic and semi-conductor nanoparticles. [ABSTRACT FROM AUTHOR]

Analytical band centrifugation (ABC) is a powerful tool for the analysis of macromolecules and nanoparticles. Although it offers several advantages over the sedimentation velocity (SV) experiment like a physical separation of the individual components and the possibility to perform chemical reactions, its analysis is still very restricted. Therefore, we investigated the integration of ABC data as an alternative approach, as this results in data similar to SV, which can then be evaluated by many established evaluation programs. We investigated this method using two different test systems, myoglobin as a biopolymer with significant diffusion and 100 nm polystyrene latex as a large particle with negligible diffusion, and found some limiting issues. These are namely, broadening of the initial boundary by diffusion of the sample, which can be taken into account and the dynamic density gradient between the solvent in the sector and the overlaid solution, which deforms the initial band upon movement through the gradient and is currently not taken into account. We show the influence these two factors have on the evaluation and show that it is possible to calculate the time-dependent change in solvent density and viscosity in the AUC cell using the integrated form of Fick’s second law. We conclude that taking the dynamic density gradient into account will open ABC for the sophisticated methods based on the analysis of the whole sedimentation boundary and not just the determination of an average sedimentation coefficient. [ABSTRACT FROM AUTHOR]

Inspired by nature, the synthesis of biohybrid nanocomposites containing inorganic nanoparticles (NPs) and biopolymers such as DNA and peptides as templates offers great potential for a wide range of applications. Using selective recognition schemes of 3D protein spaces for the assembly of magnetic nanocrystals is a challenge with great promise in the field of biomedicine and magnetic data storage. Here we apply the toroidal protein Hcp1 as an interparticle connector for the directed molecular assembly and ferrimagnetic coupling of biohybrid cobalt ferrite NP wires. The resulting biohybrid NP composites show bundles of nanofibers ranging from nano- to the microscale in length verified by TEM, EDX analysis and focused ion beam cut. Their magnetic characterization reveals an increase of the coercive field (+12%) reaching values of high-end Nd2Fe14B bulk magnets, enhanced saturation (+28%) and remanence magnetization (+38%) at 2 K compared to NPs lacking the protein connector. Thus, the combination of the nanoscale alignment of magnetic NPs with the molecular precision of the protein connectors leads to constructive addition of the magnetization reversal energy. This approach can be used to control magnetic properties for the design of materials with enhanced coercivity applicable for magnetic data storage, hyperthermia and theranostics. [ABSTRACT FROM AUTHOR]

Mesocrystals are a fascinating class of crystalline nanostructured materials since they combine the properties of nanoparticles with order on the microscopic or even macroscopic length scale. This tutorial review deals with the structural aspects of mesocrystals as well as their formation mechanisms known so far. The goal is to reach an understanding about what is special about the structuration principles of mesocrystals and their complex structures and what are the possibilities to control their formation processes. [ABSTRACT FROM AUTHOR]

Given increasing environmental issues due to the large usage of non-biodegradable plastics based on petroleum, new plastic materials, which are economic, environmentally friendly, and recyclable are in high demand. One feasible strategy is the bio-inspired synthesis of mineral-based hybrid materials. Herein we report a facile route for an amorphous CaCO3 (ACC)-based hydrogel consisting of very small ACC nanoparticles physically cross-linked by poly(acrylic acid). The hydrogel is shapeable, stretchable, and self-healable. Upon drying, the hydrogel forms free-standing, rigid, and transparent objects with remarkable mechanical performance. By swelling in water, the material can completely recover the initial hydrogel state. As a matrix, thermochromism can also be easily introduced. The present hybrid hydrogel may represent a new class of plastic materials, the 'mineral plastics'. [ABSTRACT FROM AUTHOR]

We report an unsurpassed solution characterization technique based on analytical ultracentrifugation, which demonstrates exceptional potential for resolving particle sizes in solution with sub-nm resolution. We achieve this improvement in resolution by simultaneously measuring UV/Vis spectra while hydrodynamically separating individual components in the mixture. By equipping an analytical ultracentrifuge with a novel multi-wavelength detector, we are adding a new spectral discovery dimension to traditional hydrodynamic characterization, and amplify the information obtained by orders of magnitude. We demonstrate the power of this technique by characterizing unpurified CdTe nanoparticle samples, avoiding tedious and often impossible purification and fractionation of nanoparticles into apparently monodisperse fractions. With this approach, we have for the first time identified the pure spectral properties and band-gap positions of discrete species present in the CdTe mixture. [ABSTRACT FROM AUTHOR]

Calcium sulfate is a naturally abundant and technologically important mineral with a broad scope of applications. However, controlling CaSO4 polymorphism and, with it, its final material properties still represents a major challenge, and to date there is no universal method for the selective production of the different hydrated and anhydrous forms under mild conditions. Herein we report the first successful synthesis of pure anhydrite from solution at room temperature. We precipitated calcium sulfate in alcoholic media at low water contents. Moreover, by adjusting the amount of water in the syntheses, we can switch between the distinct polymorphs and fine-tune the outcome of the reaction, yielding either any desired CaSO4 phase in pure state or binary mixtures with predefined compositions. This concept provides full control over phase selection in CaSO4 mineralization and may allow for the targeted fabrication of corresponding materials for use in various areas. [ABSTRACT FROM AUTHOR]

A simple preparation of thermoreversible gelatin-based ferrogels in water provides a constant structure defined by the crosslinking degree for gelatin contents between 6 and 18 wt%. The possibility of varying magnetite nanoparticle concentration between 20 and 70 wt% is also reported. Simulation studies hint at the suitability of collagen to bind iron and hydroxide ions, suggesting that collagen acts as a nucleation seed to iron hydroxide aggregation, and thus the intergrowth of collagen and magnetite nanoparticles already at the precursor stage. The detailed structure of the individual ferrogel components is characterized by small-angle neutron scattering (SANS) using contrast matching. The magnetite structure characterization is supplemented by small-angle X-ray scattering and microscopy only visualizing magnetite. SANS shows an unchanged gelatin structure of average mesh size larger than the nanoparticles with respect to gel concentration while the magnetite nanoparticles size of around 10 nm seems to be limited by the gel mesh size. Swelling measurements underline that magnetite acts as additional crosslinker and therefore varying the magnetic and mechanical properties of the ferrogels. Overall, the simple and variable synthesis protocol, the cheap and easy accessibility of the components as well as the biocompatibility of the gelatin-based materials suggest them for a number of applications including actuators. [ABSTRACT FROM AUTHOR]

An easy design route via simple evaporation is reported for macroscopic mosaic thin films comprising the quaternary system of dl-lysine·HCl, poly(acrylic acid), water, and EtOH. By depositing droplets of the quaternary dispersions onto hydrophilic cover slips, the formation of macroscopic crack-free mosaic mesocrystal thin films are produced. The formation follows a multistage crystallization process, which includes the formation of a polymer-induced liquid-precursor (PILP) phase, the formation of spherulitic thin films, and the recrystallization of mosaic mesocrystal thin films. A slow cooling rate is noted to be beneficial for the mesocrystal thin films, enabling the films to be crack-free and to display low surface roughness at the nanoscale. [ABSTRACT FROM AUTHOR]

Anisotropy, mesocrystal, nanoparticle, self-assembly, superlattice Keywords: anisotropy; mesocrystal; nanoparticle; self-assembly; superlattice EN anisotropy mesocrystal nanoparticle self-assembly superlattice 1 1 1 01/06/22 20220110 NES 220110 B Binary mesocrystals b demonstrate the combination of nanocrystals from different materials within a highly ordered manner. Cover Picture: 3D Binary Mesocrystals from Anisotropic Nanoparticles (Angew. [Extracted from the article]

Analytical ultracentrifugation (AUC) is a classical absolute technique for polymer analysis. However, it is also a very powerful technique for the characterization of nanoparticles as already established almost 80 years ago by the pioneering work of Svedberg and coworkers. AUC allows for sample fractionation either due to size (sedimentation velocity/sedimentation equil ibrium) or due to the chemical structure expressed as particle density (density gradient). Thus, the direct measurement of particle size resp. particle density distributions is possible with high statistical accuracy and a very high resolution even in complicated mixtures. Beside an introduction to AUC, this article will outline these possibilities for nanoparticles with sizes ranging over the entire colloidal range and also for organic-inorganic hybrid particles, showing the versatility of AUC. Also, a guide to AUC textbooks, internet discussion platforms, and modern free evaluation software is provided. The combination with other techniques such as light scattering or field-flow-fractionation can gain a deep insight into complex hybrid particle mixtures. This points toward future global analysis possibilities for the simultaneous determination of distributions of several particle characteristics such as size and density. [ABSTRACT FROM AUTHOR]

A centrifugal field can provide an external force for the ordering of nanoparticles. Especially with the knowledge from in-situ characterization by analytical (ultra)centrifugation, nanoparticle ordering can be rationally realized in preparative (ultra)centrifugation. This review summarizes the work back to the 1990s, where intuitive use of centrifugation was achieved for the fabrication of colloidal crystals to the very recent work where analytical (ultra)centrifugation is employed to tailor-make concentration gradients for advanced materials. This review is divided into three main parts. In the introduction part, the history of ordering microbeads in gravity is discussed and with the size of particles reduced to nanometers, a centrifugal field is necessary. In the next part, the research on the ordering of nanoparticles in analytical and preparative centrifugation in recent decades is described. In the last part, the applications of the functional materials, fabricated from centrifugation-induced nanoparticle superstructures are briefly discussed. [ABSTRACT FROM AUTHOR]

Nanoparticle gradient materials combine a concentration gradient of nanoparticles with a macroscopic matrix. This way, specific properties of nanoscale matter can be transferred to bulk materials. These materials have great potential for applications in optics, electronics, and sensors. However, it is challenging to monitor the formation of such gradient materials and prepare them in a controlled manner. In this study, we present a novel universal approach for the preparation of this material class using diffusion in an analytical ultracentrifuge. The nanoparticles diffuse into a molten thermoreversible polymer gel and the process is observed in real-time by measuring the particle concentrations along the length of the material to establish a systematic understanding of the gradient generation process. We extract the apparent diffusion coefficients using Fick's second law of diffusion and simulate the diffusion behavior of the particles. When the desired concentration gradient is achieved the polymer solution is cooled down to fix the concentration gradient in the formed gel phase and obtain a nanoparticle gradient material with the desired property gradient. Gradients of semiconductor nanoparticles with different sizes, fluorescent silica particles, and spherical superparamagnetic iron oxide nanoparticles are presented. This method can be used to produce tailored nanoparticle gradient materials with a broad range of physical properties in a simple and predictable way. [ABSTRACT FROM AUTHOR]

A simple evaporation method for the preparation of mosaic mesocrystal thin films is studied by Helmut Cölfen and co‐workers. As reported on page 1547, the multistep process starts with the formation of a polymer–induced liquid–precursor phase, followed by the formation of spherulitic thin films and their recrystallization into mesocrystal thin films. The image shows a polarized light (Abrio) image of a mesocrystalline thin film of dl‐lysine·HCl. [ABSTRACT FROM AUTHOR]

In the nacre or aragonite layer of the mollusk shell, proteomes that regulate both the early stages of nucleation and nano-to-mesoscale assembly of nacre tablets from mineral nanoparticle precursors exist. Several approaches have been developed to understand protein-associated mechanisms of nacre formation, yet we still lack insight into how protein ensembles or proteomes manage nucleation and crystal growth. To provide additional insights, we have created a proportionally defined combinatorial model consisting of two nacre-associated proteins, C-RING AP7 (shell nacre, Haliotis rufescens) and pseudo-EF hand PFMG1 (oyster pearl nacre, Pinctada fucata), whose individual in vitro mineralization functionalities are well-documented and distinct from one another. Using scanning electron microscopy, flow cell scanning transmission electron microscopy, atomic force microscopy, Ca(II) potentiometric titrations, and quartz crystal microbalance with dissipation monitoring quantitative analyses, we find that both nacre proteins are functionally active within the same mineralization environments and, at 1:1 molar ratios, synergistically create calcium carbonate mesoscale structures with ordered intracrystalline nanoporosities, extensively prolong nucleation times, and introduce an additional nucleation event. Further, these two proteins jointly create nanoscale protein aggregates or phases that under mineralization conditions further assemble into protein-mineral polymer-induced liquid precursor-like phases with enhanced ACC stabilization capabilities, and there is evidence of intermolecular interactions between AP7 and PFMG1 under these conditions. Thus, a combinatorial model system consisting of more than one defined biomineralization protein dramatically changes the outcome of the in vitro biomineralization process. [ABSTRACT FROM AUTHOR]

Biomimeticorganic–inorganic composite materials were fabricatedvia one-step self-organization on three hierarchical levels. The organiccomponent was a polyoxazoline with pendent cholesteryl and carboxyl(N-Boc-protected amino acid) side chains that wasable to form a chiral nematic lyotropic phase and bind to positivelycharged inorganic faces of Laponite. The Laponite particles formeda mesocrystalline arrangement within the liquid-crystal (LC) polymerphase upon shearing a viscous dispersion of Laponite nanoparticlesand LC polymer in DMF. Complementary analytical and mechanical characterizationtechniques (AUC, POM, TEM, SEM, SAXS, μCT, and nanoindentation)covering the millimeter, micrometer, and nanometer length scales revealthe hierarchical structures and properties of the composite materialsconsisting of different ratios of Laponite nanoparticles and liquid-crystallinepolymer. [ABSTRACT FROM AUTHOR]

The principle of polymer-controlled crystallization of inorganic materials has been successfully transferred to functional aromatic organic dyes, in this instance 3,4,9,10-perylenetetracarboxylic acid potassium salt (PTCAPS), after its single-crystal structure was determined. The cationic double hydrophilic block copolymer poly(ethylene glycol)-block-branched-poly(ethyleneimine) (PEG-b-PEI) was used as the polymer additive to modify the crystallization of PTCAPS. Ultralong hierarchically structured PTCAPS microbelts with constant width and thickness of each individual belt have been fabricated. The belts are a mesocrystalline assembly of primary nanoparticles with high-energy anionic {001} faces stabilized by polymer complexation. Polarization microscopy, X-ray diffraction, optical absorption spectra, and fluorescence spectra indicate the favorable orientation of the 1D microbelts in the close-stacking direction and reveal a specific 1 D superstructure fluorescence. Electrical conductivity measurements performed on a single nanobelt disclose in the doped state a remarkably high electronic conductivity and further demonstrate extended, wirelike π-π interactions along the [020] long axis of the belts. Together with the very large length of the belts and their organic-organic hybrid nanostructure, this makes these organic wires potentially interesting for the field of nano-/micro-optoelectronics. [ABSTRACT FROM AUTHOR]