A convenient synthesis of 3-aryl-5-methylidene-2-thiohydantoins

3-Aryl-5-methylidene-2-thiohydantoins were constructed in one-pot reaction of aryl isothiocyanates and 3-morpholino- alanine in alkaline medium with the subsequent treatment with boiling hydrochloric acid.     

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.     

Highly diastereoselective multicomponent synthesis of polysubstituted 2-hydroxy-2-trifluoromethylpiperidineswith four and five stereogenic centers

The Michael–Mannich cascade cyclization of cyano olefins, ethyl 4,4,4-trifluoro-3-oxobutanoate, aromatic aldehydes and ammonium acetate provides convenient stereoselective formation of ethyl 5,5-dicyano-4,6-diaryl-2-hydroxy-2-(trifluoromethyl)piperidine-3-carboxylates with fourstereogenic centers and dialkyl 4,6-diaryl-5-cyano-2-hydroxy-2-(trifluoromethyl)piperidine-3,5-dicarboxylates with five stereogenic centers. Ammonium acetate plays dual role, acting as a base and as a nitrogen source.     

On pointwise decay rates of time‐periodic solutions to the Navier–Stokes equation

We study the existence of a time‐periodic solution with pointwise decay properties to the Navier–Stokes equation in the whole space. We show that if the time‐periodic external force is sufficiently small in an appropriate sense, then there exists a time‐periodic solution $\{u,p\}$ of the Navier–Stokes equation such that $|{?}^j{u(t,x)|=O(|x|}^{1?n?j})$ and $|{?}^j{p(t,x)|=O(|x|}^{?n?j})(j=0,1,\dots )$ uniformly in $t\in \mathbb{R}$ as $|x|\to \infty$. Our solution decays faster than the time‐periodic Stokes fundamental solution and the faster decay of its spatial derivatives of higher order is also described.     

Theoretical studies on the influence of metallic cations on ring opening of propylene oxide catalyzed by metal-salen complexes

We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH⁻ group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH⁻ group and the Fukui function condensed on the OH⁻ group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts.     

Limitations of the Clausius‐Mossotti function used in dielectrophoresis and electrical impedance studies of biomacromolecules

Dielectrophoresis (DEP) studies have progressed from the microscopic scale of cells and bacteria, through the mesoscale of virions to the molecular scale of DNA and proteins. The Clausius‐Mossotti function, based on macroscopic electrostatics, is invariably employed in the analyses of all these studies. The limitations of this practice are explored, with the conclusion that it should be abandoned for the DEP study of proteins and modified for native DNA. For macromolecular samples in general, a DEP theory that incorporates molecular‐scale interactions and the influence of permanent dipoles is more appropriate. Experimental ways to test these conclusions are proposed.     

Fluid‐structure coupling of linear elastic model with compressible flow models

Cavitation erosion is caused in solids exposed to strong pressure waves developing in an adjacent fluid field. The knowledge of the transient distribution of stresses in the solid is important to understand the cause of damaging by comparisons with breaking points of the material. The modeling of this problem requires the coupling of the models for the fluid and the solid. For this purpose, we use a strategy based on the solution of coupled Riemann problems that has been originally developed for the coupling of 2 fluids. This concept is exemplified for the coupling of a linear elastic structure with an ideal gas. The coupling procedure relies on the solution of a nonlinear equation. Existence and uniqueness of the solution is proven. The coupling conditions are validated by means of quasi‐1D problems for which an explicit solution can be determined. For a more realistic scenario, a 2D application is considered where in a compressible single fluid, a hot gas bubble at low pressure collapses in a cold gas at high pressure near an adjacent structure.     

Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).