Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Nonlinear frequency response analysis: a recent review and perspectives

The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them.     

HPLC with fluorescence detection assay of perampanel,a novel AMPA receptor antagonist,in human plasma for clinical pharmacokinetic studies

Perampanel (Fycompa®), a novel α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazolepropionic acid (AMPA) receptor antagonist, is registered for the adjunctive treatment of patients (aged ≥12 years) with refractory partial‐onset seizures. To support therapeutic drug monitoring, a simple high‐performance liquid chromatography (HPLC) assay with fluorescence detection was developed to determine perampanel concentrations in human plasma and validated to support clinical trials. Human plasma samples (1.0 mL) were processed by liquid extraction using diethyl ether, followed by chromatographic separation on a YMC Pack Pro C₁₈ column (150 × 4.6 mm i.d., 5 µm) with isocratic elution of acetonitrile–water–acetic acid–sodium acetate (840:560:3:1.8, v/v/v/w) at a flow rate of 1.0 mL/min. Column eluent was monitored at excitation and emission wavelengths of 290 and 430 nm, respectively. The assay was linear (range 1.0–500 ng/mL) and this could be extended to 25 µg/mL by 50‐fold dilution integrity. No endogenous peaks were detected in the elution of analytes in drug‐free blank human plasma from six individuals and no interference was observed with co‐medications tested. Intra‐ and inter‐batch reproducibility studies demonstrated accuracy and precision within the acceptance criteria of bioanalytical guidelines. Validation data demonstrated that our assay is simple, selective, reproducible and suitable for therapeutic drug monitoring of perampanel. Copyright © 2015 John Wiley & Sons, Ltd.     

On a conjecture of Cox and Katz

This note shows that a certain toric quotient of the quintic Calabi-Yau threefold in provides a counterexample to a recent conjecture of Cox and Katz concerning nef cones of toric hypersurfaces. Received: 8 February 2001; in final form: 17 September 2001 / Published online: 1 February 2002     

Monte Carlo study of interfacial silicon suboxide layers and oxidation kinetics

A simple simulation scheme that simultaneously describes the growth kinetics of SiO₂ films at the nanometer scale and the SiO_x/Si interface dynamics (its extent, and spatial/temporal evolution) is presented. The simulation successfully applies to experimental data in the region above and below 10 nm, reproduces the Deal and Grove linear-parabolic law and the oxide growth rate enhancement in the very thin film regime (the so-called anomalous region). According to the simulation, the oxidation is governed mainly by two processes: (a) the formation of a transition suboxide layer and (b) its subsequent drift towards the silicon bulk. We found that it is the superposition of these two processes that produces the crossover from the anomalous oxidation region behavior to the linear-parabolic law.     

Purification and some properties of squalene-2,3-epoxide: lanosterol cyclase from rat liver

Squalene-2,3-epoxide: lanosterol cyclase was purified from rat liver in five steps as a soluble and homogeneous protein. The purified enzyme showed a single band on SDS-polyacrylamide gel electrophoresis with a molecular weight of 75 kD. In its native state it behaved as a homo-dimer. The isoelectric point of 5.5 and the apparent Km value for (3S)-squalene-epoxide of 55 microM were estimated for the cyclase.     

Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations

In order to investigate the relative effects of the differences between the structures and lipophilicities of 1, 10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TA-18-crown-6) and the tetrabenzyl derivative of 1,10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TBTA-18-crown-6) on their extraction-abilities and -selectivities for transition metal cations, constants of the overall extraction (logK _ex) of 1:1 (M:L) complexes, the distribution (K _D) for two diluents (CH₂Cl₂ and CHCl₃) with different dielectric constants have been determined at 25 ± 0.1 °C. The magnitude of logK _ex is largely determined by that of K _D. The equilibrium constants of TA-18-crown-6 have been compared with those of TBTA-18-crown-6. It is found that:(i) logK _ex sequences of TA-18-crown-6 and TBTA-18-crown-6 for transition metals in CH₂Cl₂ lie in order: Fe³⁺ > Cu²⁺ > Mn²⁺ > Co²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺ and Fe³⁺ > Cu²⁺ > Co²⁺ > Mn²⁺ > Ni²⁺ > Cd²⁺ > Zn²⁺ respectively; (ii) the stability sequences of two types of tetra-aza-crown ethers with the transition metal cations in CHCl₃ are the same as follows: Fe³⁺ > Ni²⁺ > Cu²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > Mn²⁺, and (iii) unusual selectivities are observed for transition metal-tetra-aza-crowns, e.g. the high Fe³⁺/M ⁿ⁺ selectivity factors (S_f) of TA-18-crown-6, except for the competitive-extractions for the special case in CHCl₃ of TBTA-18-crown-6, it was found that the Mn²⁺/M ⁿ⁺ values were relatively higher according to the other transition metal cations. A systematic sequence in these two types of solvents is not found for a given transition metal cation in terms of the variation of selectivity with the tetra-aza-crown ethers. The results provide alternatives for the rational design of other specific ligands on the transition metal cations.