7 research outputs found
Preparation of Ge@Organosilicon Core–Shell Structures and Characterization by Solid State NMR and Other Techniques
Many core–shell materials
having a protecting outer layer
have lately been proposed. In such materials it is not uncommon that
chemical or thermal stability issues of the core material are resolved
by a proper choice of the shell material. We report here the formation
of core–shell structures by pyrolysis of a mixture of tetraethyl
germanium and tetramethyl silicon at 750 °C in a simple one-step
reaction without the use of catalysts under “RAPET”
conditions. The composite product, germanium–core/organosilicon–shell
(Ge@Organosilicon), is formed in two morphologies, rods and spheroids.
The rods radial distribution is rather narrow while the spheroids
exhibit a broader distribution due to their tendency to agglomerate.
The germanium core phase is crystalline covered by a disordered organosilicon
layer. The contribution of each of the precursors to the final product
is shown by selected-area EDS and solid state NMR spectroscopy and
further corroborated by RAMAN, EPR, and powder X-ray diffraction analysis
Changes to the Disordered Phase and Apatite Crystallite Morphology during Mineralization by an Acidic Mineral Binding Peptide from Osteonectin
Noncollagenous proteins regulate
the formation of the mineral constituent
in hard tissue. The mineral formed contains apatite crystals coated
by a functional disordered calcium phosphate phase. Although the crystalline
phase of bone mineral was extensively investigated, little is known
about the disordered layer’s composition and structure, and
less is known regarding the function of noncollagenous proteins in
the context of this layer. In the current study, apatite was prepared
with an acidic peptide (ON29) derived from the bone/dentin protein
osteonectin. The mineral formed comprises needle-shaped hydroxyapatite
crystals like in dentin and a stable disordered phase coating the
apatitic crystals as shown using X-ray diffraction, transmission electron
microscopy, and solid-state NMR techniques. The peptide, embedded
between the mineral particles, reduces the overall phosphate content
in the mineral formed as inferred from inductively coupled plasma
and elemental analysis results. Magnetization transfers between disordered
phase species and apatitic phase species are observed for the first
time using 2D <sup>1</sup>H–<sup>31</sup>P heteronuclear correlation
NMR measurements. The dynamics of phosphate magnetization transfers
reveal that ON29 decreases significantly the amount of water molecules
in the disordered phase and increases slightly their content at the
ordered-disordered interface. The peptide decreases hydroxyl to disordered
phosphate transfers within the surface layer but does not influence
transfer within the bulk crystalline mineral. Overall, these results
indicate that control of crystallite morphology and properties of
the inorganic component in hard tissue by biomolecules is more involved
than just direct interaction between protein functional groups and
mineral crystal faces. Subtler mechanisms such as modulation of the
disordered phase composition and structural changes at the ordered–disordered
interface may be involved
Multinuclear Magnetic Resonance Spectroscopy and Density Function Theory Calculations for the Identification of the Equilibrium Species in THF Solutions of Organometallic Complexes Suitable As Electrolyte Solutions for Rechargeable Mg Batteries
We
present a multinuclear nuclear magnetic resonance (NMR) and density
functional theory (DFT) study of electrolyte solutions based on organometallic
complexes with aromatic ligands. These solutions constitute a unique
electrolyte family possessing a wide electrochemical window, making
them suitable for rechargeable magnesium batteries. In our previous
study we identified equilibrium species in the solutions based on
a combination of Raman spectroscopy and single-crystal XRD analyses, and herein we extend our studies to include multinuclear
NMR analyses. These solutions are comprised of the metathesis reaction
products of MgCl<sub>2–<i>x</i></sub>Ph<sub><i>x</i></sub> and AlCl<sub>3–<i>y</i></sub>Ph<sub><i>y</i></sub> in various proportions, in THF. In principle,
these reactions involve the exchange of ligands between the magnesium
and the aluminum based compounds, forming ionic species and neutral
molecules, such as Mg<sub>2</sub>Cl<sub>3</sub><sup>+</sup>·6THF,
MgCl<sub>2</sub>·4THF and AlCl<sub>4–<i>y</i></sub>Ph<sub><i>y</i></sub><sup>–</sup> (<i>y</i> = 0–4). The identification of the solution phase
species from the spectroscopic results is supported by spectral analyses
of specially synthesized reference compounds and DFT quantum-mechanical
calculations. The current approach reveals new aspects about the NMR
shift of the organometallic complexes and, in particular, facilitates
differentiation between ionic and neutral species
Structural Analysis of Magnesium Chloride Complexes in Dimethoxyethane Solutions in the Context of Mg Batteries Research
Recently,
MgTFSI<sub>2</sub>/MgCl<sub>2</sub> electrolyte solutions
in dimethoxyethane (DME) have been shown to function as viable electrolyte
solutions for secondary Mg batteries that can facilitate reversible
magnesium deposition/dissolution. MgCl<sub>2</sub> is a crucial component
in these solutions. On its own, however, it is practically insoluble
in DME. Therefore, the fact that it is readily dissolved in MgTFSI<sub>2</sub>/DME solution is remarkable. Addition of MgCl<sub>2</sub> greatly
improves the electrochemical performance of MgTFSI<sub>2</sub>/DME
electrolyte solutions. Thus, identifying the species formed in MgTFSI<sub>2</sub>/MgCl<sub>2</sub> solutions is intriguing. In this study,
we implemented a wide variety of analytical tools, including single
crystal X-ray diffraction, multinuclear NMR, and Raman spectroscopy,
to elucidate the structure of these solutions. Various solution species
were determined, and a suitable reaction scheme is suggested
Interfacial Mineral–Peptide Properties of a Mineral Binding Peptide from Osteonectin and Bone-like Apatite
Osteonectin is a regulator of bone
mineralization. It interacts
specifically with collagen and apatite through its N-terminal domain,
inhibiting crystal growth. In this work, we investigated the interface
formed between the mineral and an acidic peptide, ON29, derived from
the protein’s apatite binding domain. The structural properties
of the peptide bound to the mineral and the mineral–peptide
interface are characterized using NMR and computational methods. A
biomaterial complex is formed by precipitation of the mineral in the
presence of the acidic peptide. The peptide gets embedded between
mineral particles, which comprise a disordered hydrated coat covering
apatite-like crystals. <sup>31</sup>P SEDRA measurements show that
the peptide does not affect the overall proximity between phosphate
ions in the mineral. {<sup>15</sup>N}<sup>13</sup>C REDOR measurements
reveal an α-turn in the center of the free peptide, which is
unchanged when it is bound to the mineral. {<sup>31</sup>P}<sup>13</sup>C REDOR and <sup>1</sup>H–<sup>13</sup>C HETCOR measurements
show that Glu/Asp carboxylates and Thr/Ala/Val side chains from ON29
are proximate to phosphate and hydroxyl groups in the mineral phases.
Predictions of ON29’s fold on and off hydroxyapatite crystal
faces using ROSETTA-surface are used to model the molecular conformation
of the peptide and its apatite-binding interface. The models constructed
without bias from experimental results are consistent with NMR measurements
and map out extensively the residues forming an interface with apatitic
crystals
Unique Behavior of Dimethoxyethane (DME)/Mg(N(SO<sub>2</sub>CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub> Solutions
MgÂ(NÂ(SO<sub>2</sub>CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub> (MgTFSI<sub>2</sub>) solutions with dimethoxyethane
(DME) exhibit a peculiar
behavior. Over a certain range of salt content, they form two immiscible
phases of specific electrolyte concentrations. This behavior is unique,
as both immiscible phases comprise the same constituents. Thus, this
miscibility gap constitutes an exceptionally intriguing and interesting
case for the study of such phenomena. We studied these systems from
solutions structure perspective. The study included a wide variety
of analytical tools including single-crystal X-ray diffraction, multinuclei
NMR, and Raman spectroscopy coupled with density functional theory
calculations. We rigorously determined the structure of the MgTFSI<sub>2</sub>/DME solutions and developed a plausible theory to explain
the two-phase formation phenomenon. We also determined the exchange
energy of the “caging” DME molecules solvating the central
magnesium ion. Additionally, by measuring the ions’ diffusion
coefficients, we suggest that the caged Mg<sup>2+</sup> and TFSI<sup>–</sup> move as free ions in the solution. Knowledge of the
arrangement of the solvent/cation/anion structures in these solutions
enables us to explain their properties. We believe that this study
is important in a wide context of solutions chemistry and nonaqueous
electrochemistry. Also, MgTFSI<sub>2</sub>/DME solutions are investigated
as promising electrolyte solutions for rechargeable magnesium batteries.
This study may serve as an important basis for developing further
MgTFSI<sub>2</sub>/ether based solutions for such an interesting use
Unique Behavior of Dimethoxyethane (DME)/Mg(N(SO<sub>2</sub>CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub> Solutions
MgÂ(NÂ(SO<sub>2</sub>CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub> (MgTFSI<sub>2</sub>) solutions with dimethoxyethane
(DME) exhibit a peculiar
behavior. Over a certain range of salt content, they form two immiscible
phases of specific electrolyte concentrations. This behavior is unique,
as both immiscible phases comprise the same constituents. Thus, this
miscibility gap constitutes an exceptionally intriguing and interesting
case for the study of such phenomena. We studied these systems from
solutions structure perspective. The study included a wide variety
of analytical tools including single-crystal X-ray diffraction, multinuclei
NMR, and Raman spectroscopy coupled with density functional theory
calculations. We rigorously determined the structure of the MgTFSI<sub>2</sub>/DME solutions and developed a plausible theory to explain
the two-phase formation phenomenon. We also determined the exchange
energy of the “caging” DME molecules solvating the central
magnesium ion. Additionally, by measuring the ions’ diffusion
coefficients, we suggest that the caged Mg<sup>2+</sup> and TFSI<sup>–</sup> move as free ions in the solution. Knowledge of the
arrangement of the solvent/cation/anion structures in these solutions
enables us to explain their properties. We believe that this study
is important in a wide context of solutions chemistry and nonaqueous
electrochemistry. Also, MgTFSI<sub>2</sub>/DME solutions are investigated
as promising electrolyte solutions for rechargeable magnesium batteries.
This study may serve as an important basis for developing further
MgTFSI<sub>2</sub>/ether based solutions for such an interesting use