Glass transition temperatures and crystallization kinetics of a synthetic, anhydrous, amorphous calcium-magnesium carbonate.

We report the first calorimetric observations of glass transition temperatures and crystallization rates of anhydrous, amorphous calcium-magnesium carbonate using fast scanning differential scanning calorimetry. Hydrous amorphous Ca0.95Mg0.05CO3 · 0.5H2O (ACMC) solid was precipitated from a MgCl2-NaHCO3 buffered solution, separated from the supernatant, and freeze-dried. An aliquot of the freeze-dried samples was additionally dried at 250°C for up to 6 h in a furnace and in a high-purity N2 atmosphere to produce anhydrous ACMC. The glass transition temperature of the anhydrous Ca0.95Mg0.05CO3 was determined by applying different heating rates (1000-6000 K s-1) and correcting for thermal lag to be 376°C and the relaxational heat capacity was determined to be Cp = 0.16 J/(g K). Additionally, the heating rate dependence of the temperature that is associated with the corrected crystallization peaks is used to determine the activation energy of crystallization to be 275 kJ mol-1. A high-resolution transmission electron microscopy study on the hydrous and anhydrous samples provided further constraints on their compositional and structural states. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Formation of Amorphous Iron-Calcium Phosphate with High Stability.

Amorphous iron-calcium phosphate (Fe-ACP) plays a vital role in the mechanical properties of teeth of some rodents, which are very hard, but its formation process and synthetic route remain unknown. Here, the synthesis and characterization of an iron-bearing amorphous calcium phosphate in the presence of ammonium iron citrate (AIC) are reported. The iron is distributed homogeneously on the nanometer scale in the resulting particles. The prepared Fe-ACP particles can be highly stable in aqueous media, including water, simulated body fluid, and acetate buffer solution (pH 4). In vitro study demonstrates that these particles have good biocompatibility and osteogenic properties. Subsequently, Spark Plasma Sintering (SPS) is utilized to consolidate the initial Fe-ACP powders. The results show that the hardness of the ceramics increases with the increase of iron content, but an excess of iron leads to a rapid decline in hardness. Calcium iron phosphate ceramics with a hardness of 4 GPa can be achieved, which is higher than that of human enamel. Furthermore, the ceramics composed of iron-calcium phosphates show enhanced acid resistance. This study provides a novel route to prepare Fe-ACP, and presents the potential role of Fe-ACP in biomineralization and as starting material to fabricate acid-resistant high-performance bioceramics.

Multiscale Reciprocal Space Mapping of Magnetite Mesocrystals.

Mesocrystals are a class of nanostructured material, where a multiple-length-scale structure is a prerequisite of many interesting phenomena. Resolving the mesocrystal structure is quite challenging due to their structuration on different length scales. The combination of small- and wide-angle X-ray scattering (SAXS and WAXS) techniques offers the possibility of non-destructively probing mesocrystalline structures simultaneously, over multiple length scales to reveal their microscopic structure. This work describes how high dynamical range of modern detectors sheds light on the weak features of scattering, significantly increasing the information content. The detailed analysis of X-ray diffraction (XRD) from the magnetite mesocrystals with different particle sizes and shapes is described, in tandem with electron microscopy. The revealed features provide valuable input to the models of mesocrystal growth and the choice of structural motif; the impact on magnetic properties is discussed.

Cross-Linking of Apatite-Gelatin Nanocomposites as the Basis for Dentine Replacement Materials.

A novel approach for the production of a bioinspired dentine replacement material is introduced. An apatite-gelatin nanocomposite material was cross-linked with various cross-linkers. These nanocomposites have a high resemblance to mammalian dentine regarding its composition and properties. A precipitation reaction was used to produce apatite-gelatin nanocomposites as starting materials. Cross-linking of the gelatin has to be performed to produce dentine-like and thus tough and robust apatite-gelatin nanocomposites. Therefore, the efficacy of various protein cross-linkers was tested, and the resulting materials were characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, and EXAFS as well as CHNS analysis and tested for their mechanical performance using Vickers hardness measurements as well as for their dissolution stability in EDTA. Especially glutaraldehyde, proanthocyanidins, and transglutaminase gave promising results with hardness values of up to 63 HV0.2. To further improve the material properties, we combined the effective cross-linker transglutaminase with casein, which led to an improved interconnection between the single nanocomposite platelets. By doing so, a cross-linked composite was obtained, which shows even higher hardness values than does human dentine, at 76 HV0.2. The combination of apatite-gelatin nanocomposites with an effective cross-linker resulted in a bioinspired material with composition and properties close to those of human dentine.

Nested Formation of Calcium Carbonate Polymorphs in a Bacterial Surface Membrane with a Graded Nanoconfinement: An Evolutionary Strategy to Ensure Bacterial Survival.

It is the intention of this study to elucidate the nested formation of calcium carbonate polymorphs or polyamorphs in the different nanosized compartments. With these observations, it can be concluded how the bacteria can survive in a harsh environment with high calcium carbonate supersaturation. The mechanisms of calcium carbonate precipitation at the surface membrane and at the underlying cell wall membrane of the thermophilic soil bacterium Geobacillus stearothermophilus DSM 13240 have been revealed by high-resolution transmission electron microscopy and atomic force microscopy. In this Gram-positive bacterium, nanopores in the surface layer (S-layer) and in the supporting cell wall polymers are nucleation sites for metastable calcium carbonate polymorphs and polyamorphs. In order to observe the different metastable forms, various reaction times and a low reaction temperature (4 °C) have been chosen. Calcium carbonate polymorphs nucleate in the confinement of nanosized pores (⌀ 3-5 nm) of the S-layer. The hydrous crystalline calcium carbonate (ikaite) is formed initially with [110] as the favored growth direction. It transforms into the anhydrous metastable vaterite by a solid-state transition. In a following reaction step, calcite is precipitated, caused by dissolution of vaterite in the aqueous solution. In the larger pores of the cell wall (⌀ 20-50 nm), hydrated amorphous calcium carbonate is grown, which transforms into metastable monohydrocalcite, aragonite, or calcite. Due to the sequence of reaction steps via various metastable phases, the bacteria gain time for chipping the partially mineralized S-layer, and forming a fresh S-layer (characteristic growth time about 20 min). Thus, the bacteria can survive in solutions with high calcium carbonate supersaturation under the conditions of forced biomineralization.

Correction: Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging.

Correction for 'Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging' by Jerome Carnis et al., Nanoscale, 2021, DOI: 10.1039/D1NR01806J.

Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging.

Mesocrystals are nanostructured materials consisting of individual nanocrystals having a preferred crystallographic orientation. On mesoscopic length scales, the properties of mesocrystals are strongly affected by structural heterogeneity. Here, we report the detailed structural characterization of a faceted mesocrystal grain self-assembled from 60 nm sized gold nanocubes. Using coherent X-ray diffraction imaging, we determined the structure of the mesocrystal with the resolution sufficient to resolve each gold nanoparticle. The reconstructed electron density of the gold mesocrystal reveals its intrinsic structural heterogeneity, including local deviations of lattice parameters, and the presence of internal defects. The strain distribution shows that the average superlattice obtained by angular X-ray cross-correlation analysis and the real, "multidomain" structure of a mesocrystal are very close to each other, with a deviation less than 10%. These results will provide an important impact to understanding the fundamental principles of structuring and self-assembly including ensuing properties of mesocrystals.

Podosome-Driven Defect Development in Lamellar Bone under the Conditions of Senile Osteoporosis Observed at the Nanometer Scale.

The degradation mechanism of human trabecular bone harvested from the central part of the femoral head of a patient with a fragility fracture of the femoral neck under conditions of senile osteoporosis was investigated by high-resolution electron microscopy. As evidenced by light microscopy, there is a disturbance of bone metabolism leading to severe and irreparable damages to the bone structure. These defects are evoked by osteoclasts and thus podosome activity. Podosomes create typical pit marks and holes of about 300-400 nm in diameter on the bone surface. Detailed analysis of the stress field caused by the podosomes in the extracellular bone matrix was performed. The calculations yielded maximum stress in the range of few megapascals resulting in formation of microcracks around the podosomes. Disintegration of hydroxyapatite and free lying collagen fibrils were observed at the edges of the plywood structure of the bone lamella. At the ultimate state, the disintegration of the mineralized collagen fibrils to a gelatinous matrix comes along with a delamination of the apatite nanoplatelets resulting in a brittle, porous bone structure. The nanoplatelets aggregate to big hydroxyapatite plates with a size of up to 10 x 20 µm2. The enhanced plate growth can be explained by the interaction of two mechanisms in the ruffled border zone: the accumulation of delaminated hydroxyapatite nanoplatelets near clusters of podosomes and the accelerated nucleation and random growth of HAP nanoplatelets due to a nonsufficient concentration of process-directing carboxylated osteocalcin cOC.

Nonclassical Recrystallization.

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.

Crystals of Benzamide, the First Polymorphous Molecular Compound, Are Helicoidal.

The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X-ray diffraction reveal a complex lamellar structure of benzamide form II needle-like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non-classical morphologies.

Inorganic Porous Bulk Discs as a Matrix for Thin-Layer Chromatography and Translucent Hard Composite Materials.

Magnesium-stabilized amorphous calcium carbonate (Mg-ACC), amorphous magnesium calcium silicate hydrate (MCSH), and hydroxyapatite (HAp) are prepared by a precipitation method. By cold-pressing these particles, it is possible to produce porous bulk discs with a narrow pore size distribution. These porous inorganic discs (Mg-ACC, MCSH, and HAp) are investigated as stationary phases to study the chromatographic behavior and adsorption ability of rhodamine B, methylene blue, and ribonuclease. The adsorption affinities of different biomolecules can be easily observed and evaluated through this method. Furthermore, by infiltrating fabricated opaque porous discs with benzyl ether, which has a similar refractive index as the used inorganic particles (Mg-ACC, MCSH, and HAp), their optical properties significantly change and the discs become translucent. Moreover, by infiltrating the MCSH discs with a light-curing polymer, translucent composites with good surface hardness are fabricated. By doping particles with ions such as Ni2+, Co2+, Fe3+, and Eu3+, the color and UV-visible spectrum of the bulk discs can be adjusted. Typically, by using iron-doped MCSH particles as the inorganic matrix, nanocomposites, which show a steep UV-absorption edge at 400 nm, are fabricated. Our work provides a simple and economical method to evaluate the affinity of biomolecules to inorganic materials and a novel way to fabricate translucent hard composite materials. The fabricated nanocomposite discs show a great UV shielding effect and superior surface hardness compared to polymethyl methacrylate and commercial sunglasses, suggesting their potential as new sunglass materials.

Comparison of long-term outcomes between open and laparoscopic Thal fundoplication in children.

OBJECTIVES: In recent years laparoscopic fundoplication is increasingly performed in pediatric surgery. The aim of this study was to compare the long-term outcomes between open and laparoscopic Thal fundoplication in children. METHODS: This retrospective study includes children who underwent a Thal fundoplication between 3/1997 and 7/2009. The minimum follow-up time to enter the study was 2 years; the overall median follow-up was 77 months (range, 29-176 months). RESULTS: A total of 101 patients were included, of which 47 underwent an open and 54 a laparoscopic Thal. Intraoperative problems, early postoperative complications, time to establish enteral feeds and length of stay did not differ among both groups. The mean duration of surgery was significantly less in the open group (OPG) (108.0 (± 7.72) versus 144.1 (± 6.36) minutes; p=0.001) and this was mainly attributed to patients with neurological problems. Severe dysphagia requiring endoscopy was observed in 10 patients, but this did not differ significantly between groups (n=2 in the OPG vs. n=8 in the laparoscopic group (LAPG); p=0.10). Overall 12 patients (11.9%) (6 in each group) required a redo-fundoplication after a median of 18.7 months (range, 6-36 months). In the whole study group, 80 patients (79.2%) were classified as having surgical results being excellent, good or satisfactory and this did not differ significantly between groups. CONCLUSIONS: In the long-term open and laparoscopic Thal fundoplication have similarly good outcomes. The laparoscopic approach can be considered as an alternative, however there is not a clear superiority compared with the open counterpart.