Mihail Mondeshki

Systematical, experimental investigations on LiMgZ (Z = P, As, Sb) wide band gap semiconductors

This work reports on the experimental investigation of wide band gap compounds LiMgZ (Z = P, As, Sb), which are promising candidates for opto-electronics and anode materials for lithium batteries. The compounds crystallize in the cubic (C1b) MgAgAs structure (space group ). The polycrystalline samples are synthesized by solid-state reaction methods. X-ray and neutron diffraction measurements show homogeneous, single-phased samples. The electronic properties are studied using the direct current method. Additionally, UV–Vis diffuse reflectance spectra are recorded in order to investigate the band gap nature. The measurements show that all compounds exhibit semiconducting behaviour with direct band gaps of 1.0–2.3u2009eV depending on the Z element. A decrease in the peak widths in the static 7Li nuclear magnetic resonance spectra with increasing temperature is observed, which can be directly related to an increase in Li ion mobility.

Polysiloxane-Backbone Block Copolymers in a One-Pot Synthesis: A Silicone Platform for Facile Functionalization

Block copolymers consisting exclusively of a silicon-oxygen backbone are synthesized by sequential anionic ring-opening polymerization of different cyclic siloxane monomers. After formation of a poly(dimethylsiloxane) (PDMS) block by butyllithium-initiated polymerization of D3, a functional second block is generated by subsequent addition of tetramethyl tetravinyl cyclotetrasiloxane (D4(V) ), resulting in diblock copolymers comprised a simple PDMS block and a functional poly(methylvinylsiloxane) (PMVS) block. Polymers of varying block length ratios were obtained and characterized. The vinyl groups of the second block can be easily modified with a variety of side chains using hydrosilylation chemistry to attach compounds with Si-H bond. Conversion of the hydrosilylation used for polymer modification was investigated.

Nonclassical crystallization in vivo et in vitro (I): Process-structure-property relationships of nanogranular biominerals

A distinct nanogranular fine structure is shared by a wealth of biominerals from several species, classes and taxa. This nanoscopic organization affects the properties and behavior of the biogenic ceramic material and confers on them attributes that are essential to their function. We present a set of structure-relationship properties that are rooted in the nanogranular organization and we propose that they rest on a common pathway of formation, a colloid-driven and hence nonclassical mode of crystallization. With this common modus operandi, we reveal the most fundamental and wide spread process-structure-property relationship in biominerals. With the recent increase in our understanding of nonclassical crystallization in vitro and in vivo, this significant process-structure-property relationship will serve as a source for new design approaches of bio-inspired materials.

Pseudomorphic transformation of amorphous calcium carbonate films follows spherulitic growth mechanisms and can give rise to crystal lattice tilting

Amorphous calcium carbonate films synthesized by the polymer-induced liquid-precursor (PILP) process convert into crystallographically complex calcite spherulites. Tuning the experimental parameters allows for the generation of crystal lattice tilting similar to that found in calcareous biominerals. This contribution evidences the role of spherulitic growth mechanisms in pseudomorphic transformations of calcium carbonate.

Combining Neopentyllithium with Potassium tert-Butoxide: Formation of an Alkane-Soluble Lochmann–Schlosser Superbase

Mixtures of alkyllithium and heavier alkali-metal alkoxides are often used to form alkyl compounds of heavier alkali metals, but these mixtures are also known for their high reactivity in deprotonative metalation reactions. These organometallic mixtures are often called LiC-KOR superbases, but despite many efforts their constitution remains unknown. Herein we present mixed alkali-metal alkyl/alkoxy compounds produced by reaction of neopentyllithium with potassium tert-butoxide. The key to success was the good solubility and temperature-stability of neopentyl alkali-metal compounds, leading to hexane-soluble mixtures, which allowed handling at ambient temperatures and isolation by crystallization. The compounds in solid state and in solution were identified by X-ray crystallography and NMR spectroscopy as mixtures of lithium/potassium neopentyl/tert-butoxy aggregates of varying compositions Lix Ky Npz (OtBu)x+y-z .

Single Nanogranules Preserve Intracrystalline Amorphicity in Biominerals

We revisit the ultrastructural features of different calcareous biominerals and identify remarkable similarities: taxonomically very distant species show a common nanogranular structure, even if different extracellular secretion patterns are employed or calcium carbonate polymorphs formed. By these analyses, we elucidate the locus of the small fraction of intracrystalline organic matrix revealing its intergranular character and localize the intracrystalline amorphous calcium carbonate moiety commonly found in mesocrystalline biominerals and provide a first explanation for the pathway by which it is preserved.

Anhydrous Amorphous Calcium Oxalate Nanoparticles from Ionic Liquids: Stable Crystallization Intermediates in the Formation of Whewellite

The mechanisms by which amorphous intermediates transform into crystalline materials are not well understood. To test the viability and the limits of the classical crystallization, new model systems for crystallization are needed. With a view to elucidating the formation of an amorphous precursor and its subsequent crystallization, the crystallization of calcium oxalate, a biomineral widely occurring in plants, is investigated. Amorphous calcium oxalate (ACO) precipitated from an aqueous solution is described as a hydrated metastable phase, as often observed during low-temperature inorganic synthesis and biomineralization. In the presence of water, ACO rapidly transforms into hydrated whewellite (monohydrate, CaC2 O4 ⋅H2 O, COM). The problem of fast crystallization kinetics is circumvented by synthesizing anhydrous ACO from a pure ionic liquid (IL-ACO) for the first time. IL-ACO is stable in the absence of water at ambient temperature. It is obtained as well-defined, non-agglomerated particles with diameters of 15-20u2005nm. When exposed to water, it crystallizes to give (hydrated) COM through a dissolution/recrystallization mechanism.

(1-Adamantyl)methyl Glycidyl Ether: A Versatile Building Block for Living Polymerization

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers.

Hydrothermal growth mechanism of SnO2 nanorods in aqueous HCl

Abstract Rutile-type nanorods of SnO2 were obtained in a one-pot hydrothermal synthesis starting from SnCl4·5H2O and HCl in a temperature range between 200 and 240°C. Although the nanorods are polydisperse, the average length of the nanorods could be adjusted from 13 to 65 nm by varying of the reaction temperature. The resulting anisotropic nanocrystals were characterized using powder X-ray diffraction (PXRD), (high resolution-) transmission electron microscopy (HR-TEM), and selected area electron diffraction (SAED). The particle growth proceeds via a dissolution-recrystallization process with soluble [SnCl5(H2O)]− intermediates, as confirmed by PXRD, Raman spectroscopy, and magic angle spinning nuclear magnetic resonance (MAS-NMR).

27Al NMR Study of the pH Dependent Hydrolysis Products of Al2(SO4)3 in Different Physiological Media

Soluble inorganic aluminium compounds like aluminium sulfate or aluminium chloride have been challenged by the European Chemical Agency to induce germ cell mutagenicity. Before conducting mutagenicity tests, the hydrolysis products in water and in physiological solutions should be determined as a function of the concentration and pH. We used different 27Al NMR spectroscopic techniques (heteronuclear Overhauser effect spectroscopy (HOESY), exchange spectroscopy (EXSY), diffusion ordered (DOSY)) in this work to gain the information to study the aluminium species in solutions with Al2(SO4)3 concentrations of 50.0, 5.0, and 0.5 g/L and their pH and time dependent transformation. At low pH, three different species were present in all physiological solutions and water: [Al(OH)n(H2O)6 − n](3 − n)+ (n = 0–2), [Al(H2O)5SO4]+, and [Al2(OH)2(H2O)8]4+. Increasing pH reduced the amounts of the two monomer species, with a complete loss at pH 5 for solutions with a concentration of 50.0 g/L and at pH 4 for solutions with a concentration of 5.0 g/L. The dimer species [Al2(OH)2(H2O)8]4+ is present in a pH range between 3 and 6. Less symmetric oligomeric and probably asymmetric aluminium species are formed at pH of 5 and 6. The pH value is the driving force for the formation of aluminium species in all media, whereas the specific medium had only minor effect. No conclusive information could be obtained at pH 7 due to signal loss related to fast quadrupole relaxation of asymmetric aluminium species. A slight reduction of the content of the symmetric aluminium species due to the formation of oligomeric species was observed over a period of 6 weeks. Reference 27Al NMR experiments conducted on saturated water solutions of AlCl3 and those with a concentration of 50 g/L show that the type of salt/counter ion at the same concentration and pH influences the hydrolysis products formed.