Computational characterization of magneto-electric composites: the role of ferroelectric pre-polarization

The interaction between electric and magnetic fields enables smart devices which can find applications in sensor technology and data storage. Materials showing magneto-electric (ME) coupling combine different ferroic characteristics. In the present contribution we focus on composites, which combine ferroelectric and ferromagnetic phases due to strain couplings, such that they generate a strain-induced ME coupling. We derive a two-scale homogenization approach for the determination of effective properties in consideration of microscopic morphologies. Furthermore, we demonstrate the strong influence of ferroelectric polarization states on the ME-coefficient by modeling the switching of remanent polarizations on the microscale. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simulation of Atomic Force Microscopy for investigating BaTiO3 and LiMn2O4 nanostructures based on Phase Field Approach

Atomic Force Microscopy (AFM) probes the surface features of specimens using an extremely sharp tip scanning the sample surface while the force is applied. AFM is also widely used for investigating the electrically non-conductive materials by applying an electric potential on the tip. Piezoresponse Force Microscopy (PFM) and Electrochemical Strain Microscopy (ESM) are variants of AFM for different materials. Both PFM and ESM signals are obtained by observing the displacement of the tip when applying electric fields during the scanning process. The PFM technique is based on converse piezoelectric effect of ferroelectrics and the ESM technique is based on electrochemical coupling in solid ionic conductors. In this work, two continuum-mechanical formulations for simulation of PFM and ESM are discussed. In the first model, for PFM simulation, a phase field approach based on the Allen-Cahn equation for non-conserved order parameters is employed for ferroelectrics. Here, the polarization vector is chosen as order parameter. Since ferroelectrics have highly anisotropic properties, this model accounts for transversely isotropic symmetry using an invariant formulation. The polarization switching behavior under the electric field will be discussed with some numerical examples. In the simulation of ESM, we employ a constitutive model based on the work of Bohn et al. [8] for the modeling of lithium manganese dioxide LiMn₂O₄ (LMO). It simulates the deformation of the LMO particle according to an applied voltage and the evolution of lithium concentration after removing a DC pulse. The modeling results are compared to experimental data. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Incommensurate Phase in Λ-cobalt (III) Sepulchrate Trinitrate Governed by Highly Competitive N−H⋅⋅⋅O and C−H⋅⋅⋅O Hydrogen Bond Networks**

Phase transitions in molecular crystals are often determined by intermolecular interactions. The cage complex of [Co(C₁₂H₃₀N₈)]³⁺ ⋅ 3 NO₃⁻ is reported to undergo a disorder-order phase transition at T_c1 ≈133 K upon cooling. Temperature-dependent neutron and synchrotron diffraction experiments revealed satellite reflections in addition to main reflections in the diffraction patterns below T_c1. The modulation wave vector varies as function of temperature and locks in at T_c3≈98 K. Here, we demonstrate that the crystal symmetry lowers from hexagonal to monoclinic in the incommensurately modulated phases in T_c1<T<T_c3. Distinctive levels of competitions: trade-off between longer N−H⋅⋅⋅O and shorter C−H⋅⋅⋅O hydrogen bonds; steric constraints to dense C−H⋅⋅⋅O bonds give rise to pronounced modulation of the basic structure. Severely frustrated crystal packing in the incommensurate phase is precursor to optimal balance of intermolecular interactions in the lock-in phase.     

Method development for mono- and disaccharides monitoring in cell culture medium by capillary and microchip electrophoresis

The rapidly growing, competitive biopharmaceutical market requires tight bioprocess monitoring. An integrated, automated platform for the routine online/at-line monitoring of key factors in the cell culture medium could greatly improve process monitoring. Mono- and disaccharides, as the main energy and carbon source, are one of these key factors. A CE-LIF method was developed for the analysis of several mono- and disaccharides, considering requirements and restrictions for analysis in an integrated, automated monitoring platform, such as the possibility for miniaturization to microchip electrophoresis. Analysis was performed after fluorescent derivatization with 8-aminopyrene-1,3,6-trisulfonic acid. The derivatisation reaction and the separation BGE were optimized using design of experiments. The developed method is applicable to the complex matrix of cell culture medium and proved transferable to microchip electrophoresis.     

Light-Sensitive Phenacyl Crosslinked Dextran Hydrogels for Controlled Delivery**

Stimuli-responsive soft materials enable controlled release of loaded drug molecules and biomolecules. Controlled release of potent chemotherapeutic or immunotherapeutic agents is crucial to reduce unwanted side effects. In an effort to develop controlled release strategies that can be triggered by using Cerenkov luminescence, we have developed polymer hydrogels that can release bovine serum albumin and immunoglobulin G by using light (254 nm–375 nm) as a trigger. We describe the synthesis and photochemical characterization of two light sensitive phenacyl bis-azide crosslinkers that are used to prepare transparent self-supporting hydrogel patches. One crosslinker was designed to optimize the overlap with the Cerenkov luminescence emission window, bearing an π-extended phenacyl core, resulting in a high quantum yield (14 %) of photocleavage when irradiated with 375 nm light. We used the extended phenacyl crosslinker for the preparation of protein-loaded dextran hydrogel patches, which showed efficient and selective dosed release of bovine serum albumin or immunoglobulin G after irradiation with 375 nm light. Cerenkov-triggered release is as yet inconclusive due to unexpected side-reactivity. Based on the high quantum yield, efficient release and large overlap with the Cerenkov window, we envision application of these photosensitive soft materials in radiation targeted drug release.     

Comprehensive Characterization of Shredded Lithium-Ion Battery Recycling Material

Herein we report on an analytical study of dry-shredded lithium-ion battery (LIB) materials with unknown composition. Samples from an industrial recycling process were analyzed concerning the elemental composition and (organic) compound speciation. Deep understanding of the base material for LIB recycling was obtained by identification and analysis of transition metal stoichiometry, current collector metals, base electrolyte and electrolyte additive residues, aging marker molecules and polymer binder fingerprints. For reversed engineering purposes, the main electrode and electrolyte chemistries were traced back to pristine materials. Furthermore, possible lifetime application and accompanied aging was evaluated based on target analysis on characteristic molecules described in literature. With this, the reported analytics provided precious information for value estimation of the undefined spent batteries and enabled tailored recycling process deliberations. The comprehensive feedstock characterization shown in this work paves the way for targeted process control in LIB recycling processes.     

Polycations Stabilised by Borosulfates: [Au3Cl4][B(S2O7)2] and the One-Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)

(SO₄)-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au₃Cl₄][B(S₂O₇)₂] and [Au₂Cl₄][B(S₂O₇)₂](SO₃) were obtained by solvothermal reaction with SO₃, and the electronic properties were investigated by means of density functional theory–based calculations. [Au₃Cl₄][B(S₂O₇)₂] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au₂Cl₄][B(S₂O₇)₂](SO₃) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy.     

Formation of cellulose microspheres and nanocrystals from mildly carboxylated fibers

Cellulose - The ultrastructure of mildly carboxylated swollen tracheids from which cellulose microspheres and cellulose nanocrystals (CNC) were formed was investigated. A mild etherification of...     

FeIII in a high-spin state in bis(5-bromosalicylaldehyde 4-ethylthiosemicarbazonato-κ3O,N1,S)ferrate(III) nitrate monohydrate,the first example of such a cationic FeIII complex unit

The synthesis and crystal structure (100 K) of the title compound, [Fe(C₁₀H₁₁BrN₃OS)₂]NO₃·H₂O, is reported. The asymmetric unit consists of an octahedral [Fe^III(HL)₂]⁺ cation, where HL^? is H-5-Br-thsa-Et or 5-bromosalicylaldehyde 4-ethylthiosemicarbazonate(1?) {systematic name: 4-bromo-2-[(4-ethylthiosemicarbazidoidene)methyl]phenolate}, a nitrate anion and a noncoordinated water molecule. Each HL^? ligand binds via the thione S, the imine N and the phenolate O atom, resulting in an Fe^IIIS₂N₂O₂ chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. This [Fe(HL)₂](anion)·H₂O compound contains the first known cationic Fe^III entity containing two salicylaldehyde thiosemicarbazone derivatives. The Fe^III ion is in the high-spin state at 100 K. In addition, a comparative IR spectroscopic study of the free ligand and the ferric complex is presented, demonstrating that such an analysis provides a quick identification of the degree of deprotonation and the coordination mode of the ligand in this class of metal compounds. The variable-temperature magnetic susceptibility measurements (5–320 K) are consistent with the presence of a high-spin Fe^III ion with a zero-field splitting D = 0.439 (1) cm^?1.