Cap Nucleation Research Articles

Redefined ion association constants have consequences for calcium phosphate nucleation and biomineralization

Calcium orthophosphates (CaPs), as hydroxyapatite (HAP) in bones and teeth are the most important biomineral for humankind. While clusters in CaP nucleation have long been known, their speciation and mechanistic pathways to HAP remain debated. Evidently, mineral nucleation begins with two ions interacting in solution, fundamentally underlying solute clustering. Here, we explore CaP ion association using potentiometric methods and computer simulations. Our results agree with literature association constants for Ca2+ and H2PO4−, and Ca2+ and HPO42-, but not for Ca2+ and PO43− ions, which previously has been strongly overestimated by two orders of magnitude. Our data suggests that the discrepancy is due to a subtle, premature phase separation that can occur at low ion activity products, especially at higher pH. We provide an important revision of long used literature constants, where association of Ca2+ and PO43− actually becomes negligible below pH 9.0, in contrast to previous values. Instead, [CaHPO4]0 dominates the aqueous CaP speciation between pH ~6–10. Consequently, calcium hydrogen phosphate association is critical in cluster-based precipitation in the near-neutral pH regime, e.g., in biomineralization. The revised thermodynamics reveal significant and thus far unexplored multi-anion association in computer simulations, constituting a kinetic trap that further complicates aqueous calcium phosphate speciation.

ROLE OF NON-COLLAGENOUS PROTEINS IN THE MINERALIZATION OF COLLAGEN FIBRILS: IMPLICATION IN OSTEOARTHRITIS

Purpose: The pathological remodeling of the osteochondral junction is thought to be pivotal in osteoarthritis (OA). It includes alterations in the mineralization state of both cartilage and bone. The biomineralization process is orchestrated by protein-mineral interactions. In bone, the peculiar organization of type I collagen fibrils forms gaps between neighboring collagen molecules, which may be the place where CaP crystals nucleate from an amorphous phase and subsequently grow. This intrafibrillar mineralization process may be directed by highly acidic non-collagenous proteins (SIBLING family proteins, Matrix gla protein (MGP) and fetuin A) which stabilize pre-nucleated clusters and inhibit CaP nucleation in the extrafibrillar spaces.

Effects of polydopamine coatings on nucleation modes of surface mineralization from simulated body fluid

Polydopamine (PDA) has been recently used as a versatile priming layer for further functionalization of a biomaterial surface, particularly in biomimetic mineralization of biomaterials. Yet most of the existing literature is on inorganic substrates and the underlying effects of the PDA layer coatings on the nucleation and mineralization process and the mineral-substrate interface have not been clearly identified. Here we aimed to investigate the effects of the PDA layer on the nucleation and growth and interfacial morphology of calcium phosphate mineral layer (CaP) from 10× simulated body fluid (10× SBF) on polymeric substrates. It is found that the nucleation of CaP on PDA-coated surface favors a mixed “islanding” and planar growth mode (Stranski–Krastanov) while the “islanding” mode (Volmer–Weber) was observed on the surface without PDA. This different early nucleation stage of mineralization was found to correlate with a more “bonded” interface between the mineral layer and the PDA-coated substrates, a slight increase in the interfacial strength and a different delamination mode. This study therefore provided new insights on how polydopamine priming layer influenced the mineralization process and the interface between the mineral layer and the substrate.

Designing Catalysts for Chirality-Selective Synthesis of Single-Walled Carbon Nanotubes: Past Success and Future Opportunity.

A major obstacle for the applications of single-walled carbon nanotubes (SWNTs) in electronic devices is their structural diversity, ending in SWNTs with diverse electrical properties. Catalytic chemical vapor deposition has shown great promise in directly synthesizing high-quality SWNTs with a high selectivity to specific chirality (n, m). During the growth process, the tube-catalyst interface plays crucial roles in regulating the SWNT nucleation thermodynamics and growth kinetics, ultimately governing the SWNT chirality distribution. Starting with the introduction of SWNT growth modes, this review seeks to extend the knowledge about chirality-selective synthesis by clarifying the energetically favored SWNT cap nucleation and the threshold step for SWNT growth, which describes how the tube-catalyst interface affects both the nucleus energy and the new carbon atom incorporation. Such understandings are subsequently applied to interpret the (n, m) specific growth achieved on a variety of templates, such as SWNT segments or predefined molecular seeds, transition metal (Fe, Co and Ni)-containing catalysts at low reaction temperatures, W-based alloy catalysts, and metal carbides at relatively high reaction temperatures. The up to date achievements on chirality-controlled synthesis of SWNTs is summarized and the remaining major challenges existing in the SWNT synthesis field are discussed.

Mineralization of plasma treated polymer surfaces from super-saturated simulated body fluids

This study aims to obtain mechanistic understanding of the formation and development of biomedical CaP coating on a model polymer surface of plasma treated polycaprolactone (PCL). Oxygen plasma treatment changed the surface morphology at nanometre scale and introduced negatively charged groups to PCL surface. Nucleation of CaP on the treated PCL surface occurred via two modes of growth, Volmer–Weber and Stranski–Krastanov. EDX and FTIR analysis suggested that the coating progressed from compositions with low Ca/P ratios and solubility to the phases of higher ratios and stability. The results also indicated that CaP clusters formed through Volmer–Weber mode were rich in the CaP phases of the higher Ca/P ratios. This study thus provided mechanistic insights into the coating process of CaP from solution onto functionalized surfaces which could be useful in designing coatings to suit different requirements.

Atomic scale simulation of carbon nanotube nucleation from hydrocarbon precursors.

Atomic scale simulations of the nucleation and growth of carbon nanotubes is essential for understanding their growth mechanism. In spite of over twenty years of simulation efforts in this area, limited progress has so far been made on addressing the role of the hydrocarbon growth precursor. Here we report on atomic scale simulations of cap nucleation of single-walled carbon nanotubes from hydrocarbon precursors. The presented mechanism emphasizes the important role of hydrogen in the nucleation process, and is discussed in relation to previously presented mechanisms. In particular, the role of hydrogen in the appearance of unstable carbon structures during in situ experimental observations as well as the initial stage of multi-walled carbon nanotube growth is discussed. The results are in good agreement with available experimental and quantum-mechanical results, and provide a basic understanding of the incubation and nucleation stages of hydrocarbon-based CNT growth at the atomic level.

Predicting the Chiral Enrichment of Metallic SWCNTs on Ni–Cu Bimetallic Surfaces

Previous modeling and experimental studies have suggested that Cu-based metal catalysts can preferentially produce metallic carbon nanotubes. Here, we explain this selectivity by separately modeling nanotube cap nucleation and nanotube growth on Cu and NixCu1–x surfaces. Cap nucleation is modeled by invoking an epitaxial lattice matching criterion and comparing the binding strengths of different cap chiralities. Nanotube growth on various catalyst surfaces was studied by calculating differences in armchair and zigzag dangling bond energies, relative chemical activity ratios, and nanotube growth rates of different nanotube chiralities. All energies associated with nanotube cap nucleation and armchair and zigzag dangling bond energies were obtained using density functional theory (DFT). We find that certain armchair and zigzag nanotube caps exhibit higher binding strengths than chiral caps, and the stability of the caps on the various surfaces decreases as Ni > Ni0.5Cu0.5 > Cu, in accordance with the respec...

Ion irradiation for improved graphene network formation in carbon nanotube growth

Ion irradiation of carbon nanotubes very often leads to defect formation. However, we have recently shown that Ar ion irradiation in a limited energy window of 10–25eV may enhance the initial cap nucleation process, when the carbon network is in contact with the metal nanocatalyst. Here, we employ reactive molecular dynamics simulations to demonstrate that ion irradiation in a higher energy window of 10–35eV may also heal network defects after the nucleation stage through a non-metal-mediated mechanism, when the carbon network is no longer in contact with the metal nanocatalyst. The results demonstrate the possibility of beneficially utilizing ions in e.g. plasma-enhanced chemical vapour deposition of carbon nanotubes.

The Role of Carboxydothermus hydrogenoformans in the Conversion of Calcium Phosphate from Amorphous to Crystalline State

Two previously unknown modes of biomineralization observed in the presence of Carboxydothermus hydrogenoformans are presented. Following the addition of NaHCO3 and the formation of an amorphous calcium phosphate precipitate in a DSMZ medium inoculated with C. hydrogenoformans, two distinct crystalline solids were recovered after 15 and 30 days of incubation. The first of these solids occurred as micrometric clusters of blocky, angular crystals, which were associated with bacterial biofilm. The second solid occurred as 30–50 nm nanorods that were found scattered among the organic products of bacterial lysis. The biphasic mixture of solids was clearly dominated by the first phase. The X-ray diffractometry (XRD) peaks and Fourier transform infrared spectroscopy (FTIR) spectrum of this biphasic material consistently showed features characteristic of Mg-whitlockite. No organic content or protein could be identified by dissolving the solids. In both cases, the mode of biomineralization appears to be biologically induced rather than biologically controlled. Since Mg is known to be a strong inhibitor of the nucleation and growth of CaP, C. hydrogenoformans may act by providing sites that chelate Mg or form complexes with it, thus decreasing its activity as nucleation and crystal growth inhibitor. The synthesis of whitlockite and nano-HAP-like material by C. hydrogenoformans demonstrates the versatility of this organism also known for its ability to perform the water-gas shift reaction, and may have applications in bacterially mediated synthesis of CaP materials, as an environmentally friendly alternative process.

Quantum chemical simulations reveal acetylene-based growth mechanisms in the chemical vapor deposition synthesis of carbon nanotubes

Nonequilibrium quantum chemical molecular dynamics (QM/MDs) simulation of early stages in the nucleation process of carbon nanotubes from acetylene feedstock on an Fe38 cluster was performed based on the density-functional tight-binding (DFTB) potential. Representative chemical reactions were studied by complimentary static DFTB and density functional theory (DFT) calculations. Oligomerization and cross-linking reactions between carbon chains were found as the main reaction pathways similar to that suggested in previous experimental work. The calculations highlight the inhibiting effect of hydrogen for the condensation of carbon ring networks, and a propensity for hydrogen disproportionation, thus enriching the hydrogen content in already hydrogen-rich species and abstracting hydrogen content in already hydrogen-deficient clusters. The ethynyl radical C2H was found as a reactive, yet continually regenerated species, facilitating hydrogen transfer reactions across the hydrocarbon clusters. The nonequilibrium QM/MD simulations show the prevalence of a pentagon-first nucleation mechanism where hydrogen may take the role of one “arm” of an sp2 carbon Y-junction. The results challenge the importance of the metal carbide formation for SWCNT cap nucleation in the VLS model and suggest possible alternative routes following hydrogen-abstraction acetylene addition (HACA)-like mechanisms commonly discussed in combustion synthesis.

Microscopic mechanisms of vertical graphene and carbon nanotube cap nucleation from hydrocarbon growth precursors

Controlling and steering the growth of single walled carbon nanotubes is often believed to require controlling of the nucleation stage. Yet, little is known about the microscopic mechanisms governing the nucleation from hydrocarbon molecules. Specifically, we address here the dehydrogenation of hydrocarbon molecules and the formation of all-carbon graphitic islands on metallic nanoclusters from hydrocarbon molecules under conditions typical for carbon nanotube growth. Employing reactive molecular dynamics simulations, we demonstrate for the first time that the formation of a graphitic network occurs through the intermediate formation of vertically oriented, not fully dehydrogenated graphitic islands. Upon dehydrogenation of these vertical graphenes, the islands curve over the surface, thereby forming a carbon network covering the nanoparticle. The results indicate that controlling the extent of dehydrogenation offers an additional parameter to control the nucleation of carbon nanotubes.

Effect of Mg Ion Bioactivity on the TiO<SUB>2</SUB> Nano-Network Surface

Magnesium (Mg) ion is well known for improving the Ca-P nucleation and growth. TiO2 nano-network (NT) surface was prepared by alkali-treatment. To introduce the Mg ion to TiO2 NT surface, acrylic acid plasma polymerization was used. Bioactivity of the Mg ions coated samples was evaluated by immersed in simulated body fluid (SBF). Surface morphology and chemical composition of all samples were characterized by SEM, XRD and XPS. Mg ion promotes hydroxyapatite (HA) nucleation and growth on TiO2 NT in SBF and improves crystallinity of HA deposited layer.

Diameter and chiral angle distribution dependencies on the carbon precursors in surface-grown single-walled carbon nanotubes

Carbon nanotubes grown from discrete Fe-containing nanoparticles dispersed on a silicon nitride transmission electron microscope grid were systematically studied. The (n,m) indices of produced single-walled carbon nanotubes (SWNTs) were deduced from their electron diffraction patterns. Relatively small diameter SWNTs with a narrow diameter distribution (0.7-1.6 nm) were produced using CO as the carbon source at 800 °C, while large diameter SWNTs ranging from 1.0 nm to 4.7 nm were synthesized when using CH(4) as the carbon source. The chiral angle distributions of the SWNTs produced from different carbon sources are also different, which are attributed to the preferred cap nucleation associated with the carbon feed rate on the catalyst instead of carbon nanotube growth kinetics. Furthermore, growth of carbon laminar nanoclusters inside carbon nanotubes was achieved at a higher growth temperature, suggesting that dissociated carbon diffuses across the nanoparticle during the nanotube growth process.

QM/MD Simulation of SWNT Nucleation on Transition-Metal Carbide Nanoparticles

The mechanism and kinetics of single-walled carbon nanotube (SWNT) nucleation from Fe- and Ni-carbide nanoparticle precursors have been investigated using quantum chemical molecular dynamics (QM/MD) methods. The dependence of the nucleation mechanism and its kinetics on environmental factors, including temperature and metal-carbide carbon concentration, has also been elucidated. It was observed that SWNT nucleation occurred via three distinct stages, viz. the precipitation of the carbon from the metal-carbide, the formation of a "surface/subsurface" carbide intermediate species, and finally the formation of a nascent sp(2)-hybidrized carbon structure supported by the metal catalyst. The SWNT cap nucleation mechanism itself was unaffected by carbon concentration and/or temperature. However, the kinetics of SWNT nucleation exhibited distinct dependences on these same factors. In particular, SWNT nucleation from Ni(x)C(y) nanoparticles proceeded more favorably compared to nucleation from Fe(x)C(y) nanoparticles. Although SWNT nucleation from Fe(x)C(y) and Ni(x)C(y) nanoparticle precursors occurred via an identical route, the ultimate outcomes of these processes also differed substantially. Explicitly, the Ni(x)-supported sp(2)-hybridized carbon structures tended to encapsulate the catalyst particle itself, whereas the Fe(x)-supported structures tended to form isolated SWNT cap structures on the catalyst surface. These differences in SWNT nucleation kinetics were attributed directly to the relative strengths of the metal-carbon interaction, which also dictates the precipitation of carbon from the nanoparticle bulk and the longevity of the resultant surface/subsurface carbide species. The stability of the surface/subsurface carbide was also influenced by the phase of the nanoparticle itself. The observations agree well with experimentally available data for SWNT growth on iron and nickel catalyst particles.

The Effect of Polymeric Substances on Apatite Reactivity in the Presence of a Freshwater Cyanobacterium

Marine cyanobacteria have evolved phosphate uptake systems to live where P is limiting. Ultimately, P derives from apatite in rocks but little is known about apatite solubilization by cyanobacteria. Fluorapatite (FAP) was added to a P-free culture medium with and without Anabaena, as well as in cell-free supernatant to test reports that the cyanobacterium Anabaena PCC 7120 enhances the dissolution of fluorapatite (FAP). Anabaena, a fresh-water organism, is an analogue to harder-to-grow marine cyanobacteria. The initial abiotic release rate ratios (Ca/P) are significantly higher than the similar stoichiometric ratio of apatite. The majority of the “missing” P in abiotic experiments is sorbed to precipitates formed from Fe added as a nutrient to the culture medium. In contrast to literature reports, Ca release from FAP in the presence of Anabaena or culture supernatant was lower than abiotic release. However, Anabaena cultures aggregate and cells attach to the FAP when P-limited. Adhesion is explained by surface charge rather than P content because significant adhesion on boehmite occurred in similar experiments. X-ray photoelectron spectroscopic (XPS) analysis of the FAP surface after incubation with Anabaena is consistent with sorbed proteins that promote adhesion. These released polymers are also inferred to complex with Ca during dissolution, contributing to nucleation of Ca-P precipitates in experiments with cells or supernatant. These experiments emphasize that for Anabaena growing under P-limited conditions, polymeric material is important for cellular adhesion to mineral particles and for the concentration of phosphate as Ca-or Fe-complexes or nanoparticles.